JPH0247997B2 - RINSANESUTERUNOSEIZOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing phosphoric esters. It has been known for a long time to produce a phosphoric ester by reacting an organic hydroxyl compound and phosphoric anhydride under substantially anhydrous conditions, but it is said that in this method the reaction temperature is preferably as low as possible: for example. "Phosphorous and Its Compounds" Volume (Interscience)
Published by Publishers, Inc. 1961) 1227 pages contain 30~
Maintaining a temperature of 80 °C, in this temperature range the composition of the product is not very affected by the reaction temperature, lower temperatures are advantageous to obtain lighter colored products, and temperatures close to 100 °C are significantly It is stated that decomposition occurs, and Japanese Patent Publication No. 12524/1984 states that it is necessary to maintain the temperature below 110°C, and that temperatures exceeding 110°C tend to discolor and produce dark-colored products. Publication No. 125797 requires the reaction to be carried out at a reaction temperature (T) that satisfies T≦75/(M-1.3) (M is the molar ratio of alcohol to phosphoric anhydride), and at temperatures above the above, the appearance of the phosphoric acid ester salt may change. It is stated that the material becomes sticky and the occurrence of roller wrapping during the spinning process increases, making it impossible to expect the desired performance. However, as a result of various studies, the present inventor found that
The inventors have discovered that by raising the temperature of the reaction system to a temperature higher than that conventionally used, a phosphoric acid ester having performance superior to conventional products can be obtained, contrary to expectations, and the present invention has been achieved. That is, in producing a phosphoric ester by reacting an organic hydroxyl compound and phosphoric anhydride under substantially anhydrous conditions, the present invention sets the molar ratio of the organic hydroxyl compound and phosphoric anhydride to 23 to 4, and the reaction This is a method for producing phosphoric acid ester, which is characterized by raising the temperature of the system to 115°C or higher. The phosphoric anhydride used in the present invention is generally commercially available as a substantially anhydrous granular powder represented by the general formula P ₂ O ₅ or as a dried fine powder (for example, Nippon Kagaku Kogyo Co., Ltd. and Rasa Kogyo Co., Ltd.). (manufactured by) can be used. In the present invention, organic hydroxyl compounds include alkylene oxide adducts of higher alcohols and active hydrogen atom-containing compounds. Higher alcohols include alcohols with 6 or more carbon atoms: usually 6 to 36 carbon atoms (preferably 8 to 22 carbon atoms)
saturated or unsaturated natural or synthetic aliphatic alcohols with straight and/or branched chains (e.g. hexyl alcohol, octyl alcohol,
2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol,
Oleyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyl octadecanol, JP 49-127000, JP 54-125797
Synthetic alcohol described in JP-A No. 50-194,
(higher alcohol mixtures having side chains, etc.), and alicyclic alcohols having 6 to 8 carbon atoms (for example, cyclohexanol, cycloheptanol). The alkylene oxide adduct of a compound containing an active hydrogen atom is prepared by adding at least 1 alkylene oxide to 1 mole of the compound having at least one active hydrogen atom.
It is a compound with a structure obtained by adding moles. Examples of active hydrogen atom-containing compounds include alcohols (for example, the above-mentioned higher alcohols and alcohols having 5 or less carbon atoms, such as methanol, ethanol, n
-, i-propanol, butanol, amyl alcohol, cyclobutanol, etc.; polyols such as ethylene glycol, propylene glycol,
butanediol, hexanediol, etc.), phenols [phenol, cresol, etc.; alkylphenol, e.g. carbon number 4-20, preferably 6-18
Substituted phenols such as alkyl groups (butyl-, amyl-, octyl-, nonyl-, decyl-, dodecyl-, oleyl-, octadecyl-, etc.), cresol, etc.], carboxylic acids (e.g., higher carbon atoms having 6 to 22 carbon atoms) Fatty acids such as caprylic acid, 2-ethylhexanoic acid, lauric acid, oleic acid, stearic acid, isostearic acid, erucic acid, behenic acid, etc.) acid amides, mercaptanic acid, amines, castor oil and its derivatives, mono- and di- Examples include glycerides. The alkylene oxide has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms: ethylene oxide, propylene oxide, 1.2-, 2.3-, 1.3- or 1.4
-butylene oxide; and combination systems thereof (random and block). Specific examples of active hydrogen atom-containing compounds and alkylene oxide adducts thereof include those described in Japanese Patent Publication No. 32-6615, Japanese Patent Publication No. 38-12524, and Japanese Patent Publication No. 49-127000. Among the organic hydroxyl compounds, preferred are higher alcohols; and alkylene oxide adducts (especially ethylene oxide and/or propylene oxide adducts) of active hydrogen-containing compounds having a hydrocarbon group having 6 or more carbon atoms (especially an aliphatic hydrocarbon group). thing). Particularly preferred are higher alcohols. In the production method of the present invention, the molar ratio of the organic hydroxyl compound to phosphoric anhydride (the number of moles of the organic hydroxyl compound per 1 mole of P ₂ O ₅ ) is 2.3.
The number is 4 or less, preferably 2.5 to 3.5, more preferably 2.7 to 3.3. If the above molar ratio is lower than 2.3, the same conditions (temperature) as in the present invention
If the reaction is carried out, the decomposition of the organic hydroxyl compound will be significant, and the product will become sticky, increasing the amount of wrapping around the rollers during the spinning process and deteriorating the antistatic properties. Moreover, when the molar ratio is larger than 4, a large amount of unreacted organic hydroxyl compound remains, which increases smoke generation and deteriorates antistatic properties, which is not preferable. In the present invention, the reaction between the organic hydroxyl compound and phosphoric anhydride is carried out under substantially anhydrous conditions (the amount of water is 1% or less in the reaction system, 1 mol or less per 1 mol of P ₂ O ₅ ). The organic hydroxyl compound and the phosphoric anhydride can be added and mixed using conventional methods and conditions; usually, the phosphoric anhydride is gradually added to the liquid organic hydroxyl compound. The addition of phosphoric anhydride may be carried out at any temperature below 100° C. as long as the organic hydroxyl compound is in a liquid state. If this temperature exceeds 100°C, there are problems such as the reactants are likely to be colored or a rapid reaction may occur, creating a danger. After adding the entire amount of phosphoric anhydride while maintaining the temperature at 100° C. or lower, stirring may be further continued at the same temperature (for example, for 30 minutes to 5 hours) if necessary. According to the present invention, a reaction system (phosphoric acid esterification product) in which phosphoric anhydride is dispersed (dissolved, reacted) in an organic hydroxyl compound at a temperature below 100°C is
The temperature is raised to over 115℃. Preferably 118~
The temperature is raised to 200°C, particularly preferably 120 to 160°C.
Heat treatment at 115°C or higher produces remarkable effects (antistatic properties under low humidity, smoke-emitting properties,
(improvement of roller winding at high temperatures), and such effects cannot be achieved at lower temperatures. The time for heat treatment at 115° C. or higher varies depending on the heating temperature, but is generally 30 minutes to 15 hours, preferably 1 to 10 hours. When raising the temperature to 115℃ or higher, do so in an inert gas (nitrogen, etc.) atmosphere (especially while blowing an inert gas into the reaction system).
Preferably, heating is performed. When carrying out the method of the present invention, if necessary, hypophosphorous acid, phosphorous acid, or a salt or ester thereof (for example, those described in Japanese Patent Publication No. 12524/1982)
The reaction can also be carried out in the presence of color inhibitors such as. The timing, method, and amount of addition may be the same as those described in the above publication. The products according to the invention can be supplied in the free acid form (unneutralized) or in the form neutralized to the appropriate pH with various basic compounds (salts). Cations that form salts include alkali metals, alkaline earth metals, other metals, ammonium and organic amines, and specific examples thereof include those described in Japanese Patent Publication No. 12524/1983. Among these, preferred are alkali metals (sodium, potassium). According to the present invention, the phosphoric ester obtained by setting the molar ratio of the organic hydroxyl compound and phosphoric anhydride to 2.3 to 4 and increasing the temperature of the reaction system to 115°C or higher is different from the phosphoric ester obtained by the conventional method (the same molar ratio is 2.3 to 4). (in comparison to those that do not raise the temperature above 115℃)
It has excellent antistatic properties and low smoke generation under low humidity conditions (for example, 35 to 50% RH), and has effects such as less winding around rollers under high humidity conditions (for example, 70 to 85% RH) in the spinning process. Conventionally, it has been said that lower temperatures are preferable, and that temperatures exceeding 110°C cause decomposition and discoloration, while temperatures exceeding 75/(M-1.3) (M is the molar ratio of alcohol to phosphoric anhydride) increase roller wrapping. Therefore, it is completely unexpected that the method of the present invention in which the temperature is raised to a higher temperature would produce the above-mentioned excellent effects. Although it is not clear why the above-mentioned difference in effect occurs between the temperature raised to 115°C or higher according to the present invention and the conventional method in which the temperature is not raised, each peak of the chart in GPC (gel permeation chromatography) is not clear. The position of 115℃ appears shifted to the higher molecular weight side in the former than in the latter.
By raising the temperature above, a condensed phosphoric ester with high thermal stability and higher molecular weight (higher degree of condensation) is generated in the product (phosphoric ester), thereby producing the above-mentioned effects. is thought to be played. Furthermore, if the molar ratio of organic hydroxyl compound to phosphoric anhydride is less than 2.3 and the temperature is raised to 115°C or higher, undesirable side reactions such as decomposition and dehydration condensation of the hydroxyl compound will occur, which will reduce the above-mentioned effects of the present invention. is not obtained, and there is a lot of roller wrapping, resulting in poor antistatic properties. The phosphoric acid ester (salt) obtained by the present invention is
Because it has the above-mentioned effects, various fibers (especially polyamide, polyester, acrylic,
Oil treatment agent for synthetic fibers such as polypropylene and polyvinyl fiber, especially oil agent for spinning and drawing process,
It is useful as a spinning oil, and also as an antistatic agent (for synthetic resins), a lubricant (metal lubricants, etc.), an emulsifier (for agricultural chemicals, cosmetics, emulsion polymerization, etc.), and a cleaning agent (for various detergents, dry cleaning, etc.) is also useful. The phosphoric acid ester (salt) obtained by the present invention is
When used as a fiber treatment agent, it can be used in combination with various smoothing agents and various surfactants, if necessary. Such substances include smoothing agents such as mineral oils, animal and vegetable oils, fatty acid esters, waxes, silicones, and higher alcohols; nonionic surfactants such as alkylene oxide adducts of higher alcohols, fatty acids, and alkylamines; and alkyl sulfates. , alkyl ether sulfates, sulfonates, other phosphates, fatty acid soaps; cationic surfactants such as quaternary ammonium salts; amphoteric surfactants such as alkyl betaines. can. These acid combination ratios can be varied depending on the processing purpose, required performance, processing method, etc. An example of the blending amount is as follows. Phosphate ester (salt) according to the invention: 20-100% (preferably 40-80%
%) Smoothing agent component: 0-50% (preferably 10-40%) Other surfactants: 0-80% (preferably 10-50%)
%) The oil agent containing the phosphoric acid ester (salt) according to the present invention and, if necessary, a leveling agent component and other surfactants, can be applied to fibers in a conventional manner, for example in the form of an emulsion emulsified with water ( The concentration of the oil agent is usually 0.1 to 10% by weight) or in the form of water-free (crude oil or organic solvent solution), and is added to the synthetic fiber manufacturing process by known lubricating methods such as roller lubricating, immersion lubricating, or spray lubricating. Can be refueled at any location. Alternatively, after applying the treatment agent by the immersion oiling method, the treated fibers can be subjected to dry heat treatment, and then re-oiled again by the spraying method. It can be applied at various stages such as the spinning process, the process immediately before drawing, and the drawing process; the fibers can be in various forms, such as filament yarn (multifilament yarn) - staple, undrawn yarn - drawn yarn, etc. Can be mentioned. The amount of oil applied can vary over a wide range depending on the processing purpose, etc., but in general, the amount is usually 0.05 to 3% as solid content, preferably 0.08 to 0.3% by weight based on the fiber.
It is. The oil agent containing the phosphoric acid ester (salt) according to the present invention is an oil agent that has excellent antistatic properties at low humidity and less roll-up at high humidity. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. [In the following, parts indicate parts by weight, and percentages indicate percent by weight (unless otherwise specified). ] Example 1 558 parts (3 moles) of lauryl alcohol in 40 to 60 parts
142 parts (1 mol) of phosphoric anhydride was gradually added over a period of about 1 hour while stirring at a temperature of .degree. Thereafter, the temperature was raised while passing nitrogen gas, and the reaction was carried out at 120-130° for 8 hours. The product is a slightly yellow transparent liquid at a temperature of 40℃ and has an acid value.
220 and bound phosphoric acid 21. Comparative example 1 Same as above, the reaction temperature was set to 50 with the raw material and reaction molar ratio.
The reaction was carried out at ~60°C for 8 hours. The product temperature is 40℃
It was a slightly yellow liquid with a slightly cloudy appearance, and had an acid value of 206.6 and a bound phosphoric acid value of 20.5. The phosphoric acid esters obtained in Example 1 and Comparative Example 1 were neutralized with a caustic soda aqueous solution to adjust the pH to 7 (measured with a 1% aqueous solution). These phosphoric acid ester salts were subjected to performance tests for smoke generation, electrical resistance, generated electrostatic voltage, and roller winding according to the following test methods. The results are shown in Table-1.

[Table] Test method (1) Smoke-emitting property A 10% aqueous solution of the sample was spread uniformly into a thin film on a circular metal container with a diameter of 45 mm, and the film was heated to a specified temperature.
Measure the amount of smoke generated when heated to 200℃ using a digital dust meter (manufactured by Shibata Kagakukiki). The numerical value indicates an integrated value for 3 to 6 minutes after the start of heating, and the smaller the value, the less smoke is produced. (2) Electrical resistance The sample was oiled at 0.1% on a polyester table (1.5d.38mm) using the immersion oiling method.
After adjusting the humidity of this formula cotton overnight at 20℃ and 40% RH to reach an equilibrium moisture content, measure the surface leakage electrical resistance of 10g of the sample cotton using a super megohmmeter SM-5 model (manufactured by Toa Denpa). . (4) Generated charged voltage (a) Card test 300g of sample cotton treated and conditioned as described in (2) above was spun using a small flat card (spinning speed 15 m/min), and the generated charged voltage on the web was measured by current collector potential difference. Measure with a device. Temperature and humidity: 20°C, 40% RH (b) Draw test 280g of the above carded sliver is repeatedly drawn twice using a small Schare type drawing machine, and the electrostatic voltage generated in the web is measured using a current collector potentiometer. do. Temperature and humidity 20℃, 40%RH (5) Roller winding Sliver that has been drawn twice is 80% at 27℃
After adjusting the humidity all day and night under RH conditions to reach the equilibrium moisture content, it is drawn using a small Schare type drawing machine (with the clearer on the rubber side removed) and the number of times it is wrapped around a rubber roller is measured. The sliver is
Use 100grain/6yd for 2000m. Temperature and humidity 27℃,
80%RH Example 2 A reaction was carried out in the same manner as in Example 1 using 502.2 parts (2.7 mol) of lauryl alcohol and 142 parts (1 mol) of phosphoric anhydride. The product was a slightly yellow transparent liquid at a temperature of 40°C, with an acid value of 234 and a bound phosphoric acid of 23.3. Comparative Example 2 Same raw materials and reaction molar ratio as above, reaction temperature 50-60
The reaction was carried out at ℃ for 8 hours. The product is a pale yellow liquid with a slight haze at a temperature of 40℃, an acid value of 225, and bound phosphoric acid.
It was 23.0. The phosphoric acid esters obtained in Example 2 and Comparative Example 2 were neutralized in the same manner as in Example 1, and their performance was evaluated. The results are shown in Table-2.

[Table] Example 3 A reaction was carried out in the same manner as in Example 1 using 613.8 parts (3.3 mol) of lauryl alcohol and 142 parts (1 mol) of phosphoric anhydride. The product was a slightly yellow transparent liquid at a temperature of 40°C, with an acid value of 212 and a bound phosphoric acid of 19.5. Comparative Example 3 Using the same raw materials and reaction molar ratio as above, the reaction temperature was 50~
The reaction was carried out at 60°C for 8 hours. The product was transparent and slightly yellow at a temperature of 40°C, with an acid value of 210 and bound phosphoric acid of 19.2. The phosphoric acid esters obtained in Example 3 and Comparative Example 3 were neutralized in the same manner as in Example 1, and their performance was evaluated. The results are shown in Table-3.

[Table] Example 4 A reaction was carried out in the same manner as in Example 1 using 639 parts (3 moles) of myristyl alcohol and 142 parts (1 mole) of phosphoric anhydride. The product was a slightly yellow transparent liquid at a temperature of 50°C, with an acid value of 200 and bound phosphoric acid of 18.6. Comparative Example 4 Same raw materials and reaction molar ratio as above, reaction temperature 60
The reaction was carried out at ~70°C for 8 hours. The product is a pale yellow liquid with a slight haze at a temperature of 50℃, and an acid value of 188.
The combined phosphoric acid was 18.0. The phosphoric acid esters obtained in Example 4 and Comparative Example 4 were neutralized in the same manner as in Example 1, and their performance was evaluated. The results are shown in Table-4.

[Table] Example 5 726 parts (3 moles) of cetyl alcohol at 60-70℃
142 parts (1 mole) of phosphoric anhydride was gradually added to the mixture at a temperature of about 1 hour while stirring. Thereafter, the temperature was raised while nitrogen gas was passed through the mixture, and the reaction was carried out at 120 to 130°C for 8 hours. The product is a pale yellow liquid at a temperature of 60℃ and has an acid value.
168.4 and bound phosphoric acid 17.8. Comparative Example 5 Using the same raw materials and reaction molar ratio as above, the reaction temperature was 90~
The reaction was carried out at 100°C for 8 hours. The product was a pale yellow liquid at a temperature of 60°C, with an acid value of 16.4 and a bound phosphoric acid of 17.6. The phosphoric acid esters obtained in Example 5 and Comparative Example 5 were neutralized in the same manner as in Example 1, and their performance was evaluated. The results are shown in Table-5.

[Table] Example 6 Dovanol 23 (synthetic alcohol with 12 or 13 carbon atoms)
A reaction was carried out in the same manner as in Example 1 using 627 parts (3 moles) and 142 parts (1 mole) of phosphoric anhydride. The product was a slightly yellow transparent liquid at a temperature of 40°C, with an acid value of 229 and bound phosphoric acid of 22.1. Comparative Example 6 Using the same raw materials and reaction molar ratio as above, the reaction temperature was 50~
The reaction was carried out at 60°C for 8 hours. The product was a pale yellow liquid with a slightly cloudy appearance at a temperature of 40°C, with an acid value of 217.4 and bound phosphoric acid of 21.0. The phosphoric acid esters obtained in Example 6 and Comparative Example 6 were neutralized in the same manner as in Example 1, and their performance was evaluated. The results are shown in Table-6.

[Table] As shown in the above results, it is clear that the production method of the present invention is superior to the conventional method.

Claims (1)

[Claims] 1. In producing a phosphoric ester by reacting an organic hydroxyl compound and phosphoric anhydride under substantially anhydrous conditions, the molar ratio of the organic hydroxyl compound and phosphoric anhydride is set to 2.3 to 4, A method for producing a phosphoric ester, which further comprises raising the temperature of the reaction system to 115°C or higher. 2. The production method according to claim 1, wherein the organic hydroxyl compound is at least one selected from the group consisting of higher alcohols and alkylene oxide adducts of active hydrogen atom-containing compounds.