KR890000799B1 - Process for the preparation of phosphine sulfites - Google Patents

Abstract

Novel phosphinsulfides (I)[R1=halogen, H, Me; n=0-5; A-R2= CH2CH2COOH, CH2OH, CH2OCH2, CH2OH, CH2CH2COOCH2CH2OH; B-R3= CH2CH2OH were prepd.. Thus, a mixt. of 142g phenylphosphinic acid and 32g sulfur in 100ml EtOH and 200ml toluene was refluxed for 3hr at 70≰C and cooled to 5≰C. The resulting ppt. was washed with 100ml hexane over 3 times, dried, and reacted with a mixt. of 72g acrylic acid and 130g ethylenglycol for 3hr at 110≰C with stirring and the reaction mixt. was vacuum-evapd. at 10mmHg to give (I)[A-R2=CH2CH2COOCH2CH2OH, B-R3=CH2CH2OH, R1=H, n=1).

Description

Process for preparing phosphine sulfide compound

The present invention relates to a process for preparing phosphine sulfide compounds.

In particular, the present invention relates to a method for producing a novel phosphine sulfide compound capable of exerting a flame retardant synergistic effect of phosphorus and sulfur by mixing and copolymerizing in the production process of a polymer such as polyester.

A method of blending a halogen-based or phosphorus-based compound such as bromine in the treatment of the surface of the molded product or in the production of the molded product (Japanese Patent Application Laid-Open No. 50-10052, 53-98355, Special Office 56-32335) or copolymerization (Japanese Patent Application Center 52-31211). , 5638596, Japanese Patent Application Laid-Open No. 57-212251, and EPO 092 868).

However, conventional halogen or phosphorus compounds mainly used for imparting flame retardancy, when introduced into a copolyester reaction system, deactivates the catalyst and lowers the degree of polymerization, causing side reactions such as formation of ether bonds, gelation, and the like. Low friction resistance to frictional sweating cannot provide continuous function.

The present inventors have been able to solve the above-mentioned problems, and while searching for a compound which is expected to have excellent flame retardant effect by using a small amount, the inventors have found a compound represented by the following general formula (IV) and have completed the preparation method thereof.

Wherein R ₁ is selected from a halogen atom, a hydrocarbon group of 1-10 carbon atoms and R ₂ , R ₃ , and R ₂ , R ₃ are the same or different groups and are selected from a hydrogen atom or a monovalent ester-forming functional group. And A and B are each an organic residue of 0-10, and n represents an integer of 0-5.

The compound may be prepared by addition reaction of an alkyl or hydroxy alkyl ester of phenylphosphinic acid or phenylphosphinic acid with an unsaturated compound having formaldehyde or ester forming group, followed by substitution with sulfur. You can enumerate things like

In the first step of the present invention, phenylphosphinic acid or an ester compound thereof is mixed with sulfur to reflux in a mixed solvent such as methanol, toluene or benzene, or directly added without sulfur to melt to prepare a substituent of sulfur. The desired phosphine sulfide compound is prepared through addition reaction of the sulfur substituent with an unsaturated compound having formaldehyde or ester forming group. It is also possible to carry out the addition reaction of phenylphosphinic acid or its ester compound with an unsaturated compound having formaldehyde or ester-forming group first, followed by the substitution with sulfur, or by the addition reaction and the substitution reaction simultaneously. Formaldehyde used in the present invention may be used in aqueous solution of formarin, paraformaldehyde or other types of monomers, and unsaturated compounds include carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid or their anhydrides and esterified products. Although it is preferable to select, it is also possible to use oxycarboxylic acid or unsaturated alcohols.

Phenylphosphinic acid and its ester compounds used as starting materials of the invention can be obtained from dichlorophenyl phosphine and water or alcohols. (Houben Wey 1, XII, I, Page 294,322).

When producing flame-resistant polyester using the phosphorus and sulfur compounds of the present invention, it is preferable to add phosphorus and sulfur atom content in the produced polyester to 500-50,000 ppm, and the phosphorus and sulfur compounds are added to the polyester. The method of adding to the production system is not particularly limited. That is, when prepared by the transesterification method of the dicarboxylic acid diester and the diol, the phosphorus and sulfur compounds may be added during the transesterification reaction, or may be added before the polycondensation reaction or in the initial stage of the polycondensation reaction. It may also be added in any esterification step in the production of polyester by ester method of dicarboxylic acid and diol.

Phosphorus and sulfur compounds of the present invention not only impart excellent flame resistance to polymers such as polyamide, polystyrene, polyacrylonitrile and polyester, but also have a chemical structure similar to that of the basic skeleton of polyester, especially when added to polyester. It has good compatibility and does not cause pyrolysis or gelation even at high temperatures, and can achieve the flame retardancy synergistic effect of phosphorus and sulfur atoms together with the flame retardancy of phosphorus and sulfur atoms, so that it is possible to use an amount less than that of conventional flame retardants. The adverse effects on the physical properties and color tone of the resulting polyester molded article are hardly seen, and various excellent flame resistant molded articles can be produced. In addition, the compound of the present invention is a common phosphine sulfide-based compound having a high chemical activity functional group can be used as sterilization, the production of pesticides, additives for ignition control of gasoline, heat stabilizer of pvc and the like.

The present invention is explained in more detail by the following examples.

Example 1

In a 500 ml three-necked flask equipped with a reflux cooling stirrer, 142 g of phenylphosphinic acid and 32 g of sulfur were mixed, followed by adding 200 ml of methanol 100 ml toluene, stirring for 3 hours in a 70 ° C. hot water bath, and cooling to 5 ° C. to obtain white crystals. . The precipitate thus obtained was filtered, washed three times with 100 ml of hexane, dried, and then mixed with 72 g of acrylic acid and 130 g of ethylene glycol, and maintained at 110 ° C., followed by stirring for 3 hours to collect the outflowing water. After most of the water has flowed out, the reaction system is maintained in a vacuum of 10 mmHg and the remaining unflowed volatiles are removed to obtain the compound (e) having viscosity at room temperature.

Elemental Analysis:

Theoretic value: C; 49.06, H; 5.97, P; 9.75, S; 10.06

Found: C; 48.05, H; 5.01, P; 9.99, S; 9.87

Infrared spectroscopy; Nuclear magnetic resonance analysis (ppm: δ);

νOH 3470 cm ^-1 7.20-8.00 (5 H, m, phenyl)

νCO 1710 cm ^-1 4.00-4.20 (8 H, m, -CH ₂ -O)

νPC 1440cm ^-1 2.00-2.20 (2 H, t, P-CH ₂ )

νPS 1150 cm ^-1 2.10-2.30 (2 H, t, CH ₂ -CO)

Example 2

142 g of phenylphosphinic acid was melted in a 500 ml three-necked flask equipped with a reflux cooling stirrer to maintain 140 ° C., and 33 g of paraformaldehyde was slowly added over 30 minutes to maintain the temperature of the reaction product not exceeding 160 ° C. After further stirring for 1 hour, the reaction mixture was cooled to room temperature and dissolved by adding 100 ml of methanol and 100 ml of benzene, and 32 g of sulfur was added thereto to maintain the temperature of the solution at 70 ° C. and refluxed for 5 hours, and then cooled to 5 ° C. White crystals are obtained. The crystals were filtered, washed three times with 100 ml of hexane, and dried to obtain the compound (b) having a melting point of 135 ° C.

Elemental Analysis:

Theoretic value: C; 44.68, H; 4.79, P; 16.49, S; 17.02

Found: C; 43.79, H; 4.90, P; 15.51, S; 16.52

Infrared spectroscopy; Nuclear magnetic resonance analysis (ppm: δ);

νOH 3470c m ^-1 7.20-8.00 (5H, m, phenyl)

νPC 1440cm ^-1 3.90 (2H, d, P-CH ₂ )

νPS 1150 cm ^-1 4.45 (2H, s, OH)

Example 3

In Example 2, a compound obtained by reacting with methanol and benzene while maintaining the temperature at 100-110 ° C. instead of using a solvent of methanol and benzene was obtained. The same results as in Example 2 were obtained.

Claims (2)

A method for preparing a phosphine sulfide compound of the following formula (II) by reacting a phenylphosphinic acid of the following formula (I) or an unsaturated compound having a reactive derivative, sulfur and an ester forming group thereof.

In the above formula, R ₁ is a halogen atom or CH ₃ and n is an integer of 1-2. AR ₂ is -CH ₂ CH ₂ COOH, -CH ₂ OH, -CH ₂ OCH ₂ CH ₂ OH or -CH ₂ CH ₂ COOCH ₂ CH ₂ OH, BR ₃ is -CH ₂ CH ₂ OH, or H and n Is 1-2. The method of claim 1, wherein maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, anhydrides thereof, esters or oxycarboxylic acids or unsaturated alcohols are used as the unsaturated compound having an ester forming group.