JPS607640B2 - New phosphorus-containing compound - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel phosphorus-containing compound.

More specifically, the present invention relates to a phosphorus-containing compound that can be used as a copolymerization component for producing polyester and has the property of imparting flame retardance to the resulting polyester.
In recent years, from a standpoint of respect for humanity, the need to make various molded products, including fibers, flame retardant has been emphasized, and various efforts have been made.

Many studies have been conducted to impart flame retardancy to molded articles manufactured from linear polyester, and various methods have been proposed. Among these methods, if the industrial standpoint is taken into consideration, the process of manufacturing the elutriation molded product is easy.

The method of copolymerization by adding a flame retardant imparting substance to the system during polyester production has been proposed because the various properties of the resulting molded product are not impaired and the flame retardant performance does not deteriorate due to post-processing of the molded product. considered to be the most advantageous. Many phosphorus compounds having an ester-forming functional group have been proposed as the flame retardant imparting substance.

However, these phosphorus compounds that have been proposed so far are supplied to the high-temperature, long-time reaction system of so-called transesterification (or esterification) single polycondensation to produce polyester, so they are thermally decomposed in the reaction system. However, the flame-retardant polyester produced by the copolymerization method described above has disadvantages such as causing oxidation, scattering from the reaction system, and undesirable phenomena such as gelation and coloring of the resulting polyester. A suitable phosphorus compound for obtaining phosphorus has not yet been found. Taking the above circumstances into consideration, the present inventors conducted extensive research in order to obtain a phosphorus compound that can impart excellent flame retardancy to polyester and is stable under the conditions for producing polyester. The present invention has now been completed.

That is, the present invention is a novel phosphorus compound represented by the following general formula.

However, in the formula, R1 and R2 are the same or different groups, and are a hydrocarbon group having 1 to 18 carbon atoms, which may or may not contain a halogen atom, and R3 and R5 are hydrogen atoms or groups having 1 to 8 carbon atoms. The lower alkyl groups, R6 and R7, are each represented by -COOR8, R8 is an organic group having 1 to 18 carbon atoms containing or not containing a hydrogen atom or a hydroxy group, and R6 and R7 form a ring through You may.

Or n represents 0 or 1-3.

Note that the above hydrocarbon group may be substituted with a halogen atom such as a chlorine atom or a bromine atom.

Specific examples of the phosphorus compound represented by the general formula [1] include the following. (1,2-dicarboxyethyl)dimethylphosphine oxide, (1,2-
dimethoxycarbonylethyl) dimethylphosphine oxide, (1,2-diethoxycarbonylethyl)dimethoxyphosphine oxide, (1,2-diphenoxycarbonylethyl)dimethylphosphine oxide, [1,2
...di(8-hydroxyethoxycarbonyl)ethyl]dimethylphosphine oxide, (1,2-dicarpoxyethyl)diethylphosphine oxide, (1,2-dicarboxyethyl)methylphenylphosphine oxide, (
1,2-dicarboxyethyl) diphenylphosphine oxide, (1,2-dicarboxy2-methyl-ethyl)dimethylphosphine oxide, (2,3-dicarboxypropyl)dimethylphosphine oxide, (2,3-dimethoxycarbonyl) propyl)dimethylphosphine oxide, [2,3-di(3-hydroxyethoxycarbonyl)propyl]dimethylphosphine oxide, (2.
3-dicarboxypropyl) diphenylphosphine oxide, and compounds of the following formula. The phosphorus-containing compound of the present invention can be produced based on the method shown below. That is, it can be easily produced by reacting di/hydrocarbon phosphine oxide with an unsaturated compound having an ester-forming functional group.
Examples of the above-mentioned unsaturated compounds include maleic acid, fumaric acid, itaconic acid, and acid anhydrides. It is preferable to carry out the reaction between dino-hydrocarbon phosphine oxide and the above-mentioned unsaturated compound so that the molar ratio of the former to the latter is approximately 1:1, but it is also possible to use a slight excess of either one. good. As an example of the method for producing the phosphorus-containing compound of the present invention, when using diethylphosphine oxide and dimethyl itaconate as starting materials, the starting materials are mixed at room temperature and then mixed under an inert gas atmosphere. The desired substance can be produced by heating and heating at a temperature of 100 qo or more, preferably 120 to 2000C. Note that when carrying out the reaction, it is often preferable to use a metal alkoxide such as sodium methoxide, sodium ethoxide, potassium ethoxide, or the like as a catalyst in order to increase the reaction rate. Furthermore, in order to suppress side reactions, lower alcohols such as methanol, ethanol, isopropanol, and n-butanol, and glycols such as ethylene glycol, propanediol, and butanediol may be present in the reaction system. As mentioned above, the phosphorus-containing compound of the present invention is very useful for producing a key-fired polyester having excellent properties when added to a polyester production system. In particular, the phosphorus-containing compound of the present invention hardly causes thermal decomposition or gelation even under the high temperatures of the polyester production system, and therefore the flame-retardant polyester obtained has excellent color tone.
In addition, there is almost no difference in mechanical properties from those produced without using the phosphorus-containing compound of the present invention.

In addition, when producing a flame-retardant polyester using the phosphorus-containing compound of the present invention, it is desirable that the phosphorus atom content in the obtained polyester be at least 50%. Further, the phosphorus-containing compound of the present invention can be added at the start of a so-called transesterification reaction or esterification reaction for producing a polyester to produce a desired flame-retardant polyester. EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not necessarily limited to these Examples. In the examples, parts represent parts by weight.

Example 1 380 parts of diethylphosphine oxide and 566 parts of primary dimethyl itaconate reagent were placed in a reaction vessel, and after purging with nitrogen, the reaction vessel was immersed in 100 oo of oil and heated for 120 minutes under an oil pressure. Made it react.

After the reaction is complete, the reaction product is distilled under reduced pressure to obtain the desired product (2
- 767 parts of 3-dimethoxycarbonylpropyl)diethylphosphine oxide (compound A) were obtained. The obtained compound A is a colorless and transparent liquid at room temperature with a boiling point of 169-171°C/0.2 side Hg, and its infrared absorption spectrum is 29
50, 17351437, 137 stop 1300, 1203
116fu, 1035100fu, 817 and 765hada-1 had maximum absorption values, respectively. Also during CDC13,
The NMR value of compound A measured at 6000 is 6.3,
6.7, 6.5-7.3, 7.7-8.5, 8.55
8.6fu 8.8 8.92, 9.6.

Furthermore, the elemental analysis values are from Pill. 70%, C=49.
95%, H=8.03% and theoretical value P=11.72%
, C=49.99%, H=8.01%.
The acid value calculated by titrating the ethanol solution with a 1/1 normal aqueous hydrochloric acid solution using a phenolphthalein indicator was 0.04 q'k9, which was 95% of 1/2 normal potassium hydroxide. saponified with ethanol solution,
The saponification value calculated by titrating with 1/2 N hydrochloric acid aqueous solution using a phenolphthalein indicator is 7.5 q.
/k9 (theoretical value 7.57 eq/kg). Example 2 58 parts of di-propylphosphine oxide and 68.4 parts of the reagent primary dimethyl itaconate were placed in a reaction vessel, and after purging with nitrogen, the reaction vessel was immersed in 120 qo of oil, and the mixture was heated to 150 qo. The mixture was heated for a minute to react.

After the reaction is complete, the reaction product is distilled under reduced pressure to obtain the desired product (2
- 84 parts of 3-dimethoxycarponylpropyl) di-n-propylphosphine oxide (compound B) was obtained. The obtained compound B is a colorless and transparent liquid at room temperature with a boiling point of 177-179°C/0.1 Yanagi Hg, and its infrared absorption spectrum is 2980, 1735, 14351370, 1200,
Maximum absorption values were found at 1160, 1079, 1030, and 835ka-1, respectively. Also, CDC18, 600
The NMR value of Compound B measured at 0 is 6.10 6.
21, 6.4-7.3 7.35-8.6, 8.6-9
．． It was 1. Furthermore, its elemental analysis value is P=10.42
%, C=53.43%, H=8.65%, theoretical value P=10.60%, C=53.41%, H=8.62%
It was a good match.

Also, the acid value is 0.028eq'k9, and the saponification value is 6.78.
eq/k9 (theoretical value 6.8 eq'k9). Example 3 106 parts of diethylphosphine oxide and 144 parts of reagent-grade dimethyl fumarate were placed in a reaction vessel, and after purging with nitrogen, the reaction vessel was immersed in 100 qo of oil, and heated for 12 qo under an oil bath. and reacted.

After the reaction is completed, the reaction product is distilled under reduced pressure to obtain the desired product (1.
126 parts of 2-dimethoxycarbonylethyl) diethylphosphine oxide (compound C) were obtained. The obtained compound C is a colorless and transparent liquid at room temperature with a boiling point of 142 to 144 cm and 0.15 skin Hg, and its infrared absorption spectrum is 29
60, 1730, 1437, 1410, 1865, 13
23, 1210, 1160, 1080, 1030, 10
00, 855, 835, 76 & Desk-1 had maximum absorption values, respectively. In addition, the NMR 1 value of compound C measured at 70qo in CDC13 is 6.15 6.2, 6.
The absorption ranged from $ to 7.15, and from 7.66 to 9.06. Furthermore, its elemental analysis values are P=12.30%, C=4
8.04%, H=7. paper%, theoretical value P=12.3
8%, C=48.00%, H=7.65%, which showed good agreement.

Also, the acid value is 0.040eq'k9, and the saponification value is 7.95.
eq'kg (theoretical value 7.9 stages q/k9). Example 4 121 parts of di-n-butylphosphine oxide and 137 parts of reagent grade diethyl itaconate were placed in a reaction vessel, and after purging with nitrogen, the reaction vessel was immersed in 120 qo of oil.
The reaction was carried out by heating for 180 minutes under the trunk of a fly.

After the reaction is complete, the reaction product is distilled under reduced pressure to obtain the desired product (2
208 parts of 13-diethoxycarbonylpropyl)jetylphosphine oxide (Compound D) were obtained. The obtained compound D was a colorless and transparent liquid at room temperature with a boiling point of 191 to 199°C/0.1 side Hg. Its elemental analysis value is P=9.0
0%, C=58.64%, H=9.51%, theoretical value P=8.89%, C=58.60%, H=9.48%
It was a good match. In addition, the acid value is 0.03 q/k9, and the saponification value is 5.7 q'k9 (theoretical value 5.74 eq'k9).
Met. Infrared spectrum is 2970, 2940, 28
80, 1738, 1470, 1380, 1350, 13
05, 1200, 11651097, 1037, 905
862, 83fu and 995 skin-1 respectively have maximum absorption values, and the N of compound D measured at 60oC in CDC13.
1 value of MR is 5.33-5.86.2-7.05 7.
It was 35-9.1. Reference Example 1 50 parts of dimethyl terephthalate, 36 parts of ethylene glycol, phosphorus-containing compound obtained in Example 1 AI7.8
parts, 0.035% by weight of zinc acetate, 0.005% by weight of cobalt acetate and 0.03% by weight of dimethyl terephthalate.
A mixture consisting of 0% by weight of amorphous germanium dioxide was charged into a reactor and heated at 150 to 23,000 for 140 minutes to perform a transesterification reaction.

Claims (1)

[Claims] 1. A novel phosphorus-containing compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, R^1 in the formula
, R^2 are the same or different groups, and have 1 to 18 carbon atoms, which may or may not contain a halogen atom.
hydrocarbon group, R^3 to R^5 are hydrogen atoms or lower alkyl groups having 1 to 8 carbon atoms, R^6 and R^7 are each represented by -COOR^3, and R^8 is a hydrogen atom. Alternatively, it is an organic group having 1 to 18 carbon atoms that may or may not contain a hydroxy group, and R^6 and R^7 may form a ring via ▲There are numerical formulas, chemical formulas, tables, etc.▼. Moreover, n represents 0 or 1-3. ].