JPS60209594A - Bis(beta-carboxyethyl)isobutyl, sec-butyl and tert-butylphosphine oxide and polyamide containing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION U.S. Pat. Nos. 4,032,517 and 4;
092.31) No. 2 is 1 In the formula Otsu, Z is an alkyl group having 1 to 4 carbon atoms, and r and S are each an integer of 2 or 3, as a group of the formula Phosphorus has been published since ancient times, indicating the presence of fibers in the capital. However, the only compounds specifically disclosed and exemplified in the above patents are methyl and ethyl derivatives, ie, derivatives where Z is methyl or ethyl.

In the present invention, a copolyamide is prepared from a compound consisting of bis(, &-carboxyethyl isobutylphosphine oxide, a compound consisting of bis(β-carboxyethyl)sec.butylphosphine oxide, or a compound consisting of bis(β-carboxyethyl)-1-butylphosphine oxide. are produced, the fibers produced therefrom have lower hygroscopicity and more High flexibility (fl
It was found that it exhibits

Furthermore, in the present invention, when the following new method is used for production, the bis(carboxyethyl)alkylphosphine oxides of A'IjI can be produced more cheaply and with a smaller amount of contaminating salts present. I found this out.

The present invention relates to compounds having the formula: wherein 几 is a SeC, butyl, isobutyl or t-butyl group.

The present invention also provides a polymethylene of from 4 to 12 carbon atoms, consisting essentially of (JO t , where 几 is as defined above and R1 and R2 are individually ζ), m
- a fiber consisting of repeating units selected from the group consisting of phenylene and p-phenylene and containing units b) in an amount sufficient to provide from about 0.5% to about 7.0% by weight of phosphorus; Concerning the produced copolyamide.

Furthermore, the present invention provides a catalyst stage 1. R3PH, + 2CH, = CHCO, R,
−-→RsP[(CH+)tCOtRJz Stage 2- Rs”[(CHt)tcOtR+:lt+
H20 101'sP[(CH++)tcO2"4]z11 acid R# 3, R, P[(C)I2)2CO,R4)2+
H,0-+1 R,P((CH2),CO,H]2 In the formula, ■(4 is an alkyl group of 1 to 4 carbon atoms.) In the formula , 几3 is an alkyl group having from 2 to 6 carbon atoms.

Step 1 employs the acrylate ester as a solvent solution in an inert hydrocarbon bath medium such as toluene, heptane, etc. in the presence of a free radical generating catalyst such as azobisisobunalonitrile, at a temperature of about 50°C to about 50°C. It is carried out at a temperature of 110°C, preferably from about 70°C to about 95°C.

Stage 2 oxidation is from about 50°C to about 80°C, preferably about 6
It is carried out using a dilute (e.g. 10 to 740%) aqueous solution of an oxidizing agent such as hydrogen peroxide at temperatures ranging from 0°C to about 70°C. The reaction is complete in 1-5 hours. The resulting phosphine oxide is recovered from the mixture as an oil by distillation of the solvent and water.

Step 3 involves hydrolyzing the phosphine oxide from Step 2 using a very dilute (ie 1-10%) aqueous acid solution. Acid, hydrochloric acid, etc. can be used. Hydrolysis is carried out under reflux for 5 to 10 hours, preferably 6 to 8 hours. Upon cooling, the desired product is recovered as a crystalline solid. Purification can be carried out by recrystallization from water.

The copolyamides of the present invention can be made by condensation of difunctional polyamide-forming reactants, such as diamines and dicarboxylic acids, described in the above-identified patents, which are incorporated herein by reference.

Generally, the above unit a) is a dicarboxylic acid having the formula l-1020(CH2),1CO,H, where n is an integer from 4 to 12, H,N(CH2) nNH.

where n is as defined above, unit b) is present during the condensation reaction and the copolyamide polymer chain width ranges from about 0.5% to about 7% by weight. .0 wt. phosphorus is produced.

The copolyamides of the present invention provide fibers with improved processing properties, mechanical properties (i.e. elongation, elastic modulus, etc.) and are made from methyl and ethyl bis(carboxyethyl) phosphine oxides as one of the components. It has lower hygroscopicity than other fibers.

It is to be understood that the following examples are set forth for illustrative purposes only and are not intended to limit the invention in any way other than as described within the scope of the appended patents. Parts and percentages are by weight unless otherwise indicated.

Example 1 A solution of 688 parts of methyl acrylate in 285 parts of toluene was prepared at 74-93°C in the presence of 450 parts of 80% isobutylphosphine and 3.9 parts of an (azobisisobutyronitrile) reaction initiator. The reaction was allowed to proceed for 7 hours. The resulting isobutylbis(carbomethoxyethyl)phosphine was oxidized using 600 parts of a 25% aqueous hydrogen peroxide solution (10% excess). The reaction was completed within 2-3 hours at 65 DEG C. and the phosphine oxide formed was separated from the mixture as an oil after distillation of toluene and water.

The recovered phosphine oxide was hydrolyzed in 4 liters of a 5% sulfuric acid aqueous solution by Kokichi in a rapid flow for 7 hours.

Upon cooling, the product isobutylbis(β-carboxyethyl)phosphine oxide was released as a white crystalline solid.
% yield and purified by recrystallization from water, melting point 186-187°C. 31PNMR chemical shift; 52.2 ppm0 Example 2 Sec, butylbis(β-carboxyethyl)phoSeC
, 592 parts of butylphosphine (85% purity) were reacted with 860 parts of methyl acrylate containing 4.9 parts of azobis(Invaleroni IJ) at 67-100°C for 3.5 hours. The reaction product Sec, butylbis(carbomethoxyethyl)phosphine, was reacted with a 10% molar excess of hydrogen peroxide (25% solution) at 60° C. for 2 hours to obtain the corresponding phosphine oxide. After hydrolysis of the latter with dilute sulfuric acid and recrystallization from water, sec, butyl bis(
β-carboxyethyl)phosphine oxide was obtained.

Melting point: 134°C. 31PNMR chemical shift; 5
7.3 ppm0 Example 3 860 parts of methyl acrylate was mixed with 4 parts of t-butylphosphine.
The method of Example 1 was repeated except that 52 parts were reacted. 4.9 parts of azobis-1-isovaleronitrile was used as a catalyst. The liquid reaction product was oxidized to give t-butylbis(carbomethoxyethyl)phosphine oxide, which was then hydrolyzed. Product t-butylbis(β
-carboxyethyl)phosphine oxide has a melting point of 17
Separated on an off-white crystalline solid having a temperature of 4°C. 31PNMR chemical shift; 60.1pI)m
Q Example 4 Using the method of Example 1, isopentylphosphine was
It was made to react with ethyl acrylate at 0-90 degreeC, and isopentyl bis (carboethoxyethyl) phosphine was obtained. The latter is oxidized with hydrogen peroxide and hydrolyzed with dilute aqueous hydrochloric acid to give the corresponding acid, isopentyl bis(
β-carboxyethyl)phosphine oxide was obtained.

Example 5 Hexylbis (β
- preparing carboxyethyl)phosphine from hexylphosphine and butyl acrylate to obtain phosphine;
Subsequent oxidation and acid catalyzed hydrolysis yielded the desired product.

Example 6 A mixture of 180 parts of adipic acid hexamethylene diamine salt and 62.3 parts of bis(β-carboxyethyl)inbutylphosphine oxide was heated to 200 to 200 parts in an autoclave.
200-250°C under nitrogen atmosphere at 250 psi
Copolymerization was carried out at The water condensate was removed and the polymer melt was extruded through a multi-hole spinneret into yarn, which was drawn into fibers. The yarn includes repeating units of the formula: The fibers are non-hygroscopic and exhibit excellent flexibility.

Example 7 According to the method of Example 6, 180 parts of adipic acid hexamethylene diamine salt and bis(β-carboxyethyl) se
c. A polyamide fiber was produced by copolymerizing 68 parts of butylphosphine oxide. The fiber is essentially that of Example 6.
It showed the same properties as the fibers.

Example 8 Again according to the method of Example 6, a polyamide fiber containing repeating units produced from bis(β-carboxyethyl)-1-butylphosphine oxide was produced. Again, the fibers exhibited improved flexibility and were non-hygroscopic.

Claims (1)

[Claims] In the formula, R is sec, butyl group, isobutyl group, or t-
A compound characterized by having the formula, which is a butyl group. 2. The compound according to claim 1, wherein R is sec, butyl group. 3. The compound according to claim 1, wherein R is an isobutyl group. 4. The compound according to claim 1, wherein R is a t-butyl group. 5, essentially 0 111 a) -C-R, -C-NH-R2-NH- and in the formula, R is sec, butyl group, isobutyl group or t
-butyl group and 1 and 2 are each selected from the group consisting of polymethylene, m-phenylene and p-phenylene having from 4 to 12 carbon atoms. , a fiber-forming copolyamide comprising units b) in an amount sufficient to provide from about 0.5% to about 7.0% by weight phosphorus. 6. Claim 5, in which R is sec, butyl group
Copolyamides as described in Section. 6. The copolyamide according to claim 5, wherein 7.1 is an isobutyl group. 8. The copolyamide according to claim 5, wherein R is a t-butyl group. 6. The copolyamide according to claim 5, wherein 9, lt, and R3 are polymethylene groups. 10. The copolyamide of claim 9, wherein R, is a tetramethylene group and R2 is a hexamethylene group. 11. Copolyamide according to claim 5 in the form of fibers. 12, R, PH, (7) where R3 is an alkyl group having from 2 to 6 carbon atoms, CH, == cHco2a, (II) where R4 is an alkyl ester having the formula, which is an alkyl group of 1 to 4 carbon atoms, is reacted at a temperature in the range of about 50°C to about 110°C in the presence of a radical-forming catalyst, aP[(CHz)t C0tR+)t (1) and oxidizing the compound of formula (Ill) in the presence of an oxidizing agent at a temperature in the range of about 50 to 80°C. wherein the compound of formula (IV) is hydrolyzed under reflux conditions in the presence of a dilute aqueous solution of an acid and the resulting compound is recovered; , 16 is an alkyl group having 2 to 6 carbon atoms. [1, Claim 1, wherein Rs is an isobutyl group]
The method described in 2Jjm.・ 14, ■1. 13. The method of claim 12, wherein sec is a butyl group. 15, Claim 1, in which R3 is a t-butyl group
The method described in Section 2. 13. The method according to claim 12, wherein 16, R, is a methyl group.