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  • 专利说明
  • 权利要求
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    • 专利摘要:
    1. METHOD FOR OBTAINING SURFACE-ACTIVE SUBSTANCES WeiModey. Phosphoric anhydride alcohols when heated followed by neutralization of the resulting alkylphosphoric acids with a base, characterized in that, in order to improve the quality of the target products, tetraethylammonium or benzyltriethylammonium hydroxide is used as a base in alcohol. 2. A method according to claim 1, characterized in that alcohols are used as alcohols, carry alcohols fractions, ethoxylated Alcohols or chemical mixtures of alcohols with polyethylene glycol mol. m. 200-1500. 3. Method according to paragraphs. 1 and 2, of which it is due to the fact that the interactions (the action of alcohols with phosphoric anhydride is carried out at 55-b C.
    公开号:SU1122664A1
    申请号:SU823500646K
    申请日:1982-07-07
    公开日:1984-11-07
    发明作者:Станислав Николаевич Харьков；Наталья Михайловна Румянцева；Владимир Павлович Кабанов；Александр Сергеевич Чеголя
    申请人:Всесоюзный научно-исследовательский институт синтетических волокон；
    IPC主号:
    专利说明:

    yu go
    The invention relates to the chemistry of phosphorus compounds, namely, to an improved method for the preparation of surfactants, which Moryv finds use as wetting antistatic agents in the production and processing of chemical fibers. A known method for the preparation of sodium, potassium and ammonium salts of alkylphosphoric acids by the interaction of higher alcohols C1Dyl ethoxylated 2J alcohols with phosphoric anhydride by heating to 60-110 ° C, followed by neutralization of the alkylphosphoric acid esters with aqueous solutions of bases. The substances obtained by these methods have surface-active properties (6–30–36 mN / m) and are antistatic agents for chemical wipocons (the specific electrical resistance of the polyamide filament has a linear density of 29, tex 10 0m-cm). However, the first of the above methods are salts, which are wax-like Ksgt paste-like substances. Cosistens alkyl phosphates derived from ethoxylated alcohols vary somewhat, although in this case salts are either pasty substances or viscous syrups. It should also be noted that in either case, the obtained salts contain from 10 to 20% by weight of water (depending on the neutralization of the base concentration, after the final substance, if necessary, the salts are powdery substances , which have rather high (lOO-ISO C, depending on the radical length of the starting alcohol) melting temperatures. The closest to the technical essence and the achieved result to the proposed method is the method of obtaining surface-active substances by the interaction of phosphorus anhydride with an equimolar mixture of alcohols and polyethylene glycol with a molecular weight of 200-1500 at 60-70 0 followed by neutralization of the obtained alkylphosphoric acids with an aqueous solution of C3 base. The alkyl phosphates obtained by the known method have good surface activity (surface tension of aqueous solutions 6 30-36 ), dissolves in water and in some solvents, they have a p 10 0m-cm. However, they contain up to 20 wt.% of water, which is difficult to remove, since the products foam heavily, and after removing water, the products are oh waxy or pulverulent refractory material. Further use of salts of alkylphosphoric acids in the form of waxes, powders is associated with certain difficulties, since the powders, for example, are hygroscopic, show a tendency to dusting and caking. To obtain stable emulsions from solid preparations, additional equipment and additional energy are required to melt the preparations. In the production and processing of chemical fibers, it is also recommended that liquid preparations be used as sizing agents and antistatic agents to prevent the formation of raids on the headset of torsion, warping and filling machines. The aim of the invention is to improve the quality of surfactants. The goal of delivery is achieved in that according to the method of preparing surfactants, the alcohol is reacted with phosphoric anhydride, followed by neutralization of the resulting alkylphosphoric acids with an alcohol solution of tetraethylamine FUNI or benzyltriethylammonium hydroxide. As alcohols, it is desirable to use alcohols, mixtures of alcohols fractions, ethoxylated alcohols or equimolar mixtures of alcohols fraction of polyethylene glycol with mol.m. 200-1500. The interaction of alcohols with phosphoric anhydride is preferably carried out at 55-60C. Alcohols containing not less than 6 and not more than 10 carbon atoms in the alkyl radical are used for the reaction, as with a lower content of carbon atoms, the surface activity of the substances decreases, and with a higher content, the substances are solid waxes and the solubility in water is significantly reduced. The proposed method for the preparation of surfactants is carried out as follows: alcohols are placed in a reactor supplied with a stirrer, nitrogen feed is fed in, heated before and phosphoric anhydride is added with stirring. After the end of the dosage of phosphoric anhydride, the mixture is stirred for another 4 hours at 3W-C. The solvent is distilled off. Output after neutralizing quantitative. Liquid anhydrous products are readily soluble in water, alcohol, benzene, chloroform, CC, possessing good surface-active and antistatic properties. Example 1 In a three-neck flask equipped with a meogalka, a nitrogen inlet and a thermometer, 102.2 g (1 M) of n-hexyl alcohol are labeled. At 40 ° C and with stirring, 71 g (0.5 M) of phosphorus pentoxide is added. The rate of P-O addition is determined by the temperature of the reaction mixture (rie above). After the total amount of PgOy is added, the re-stirring is continued for another 4 hours. The resulting alipiphosphoric acid is filtered from pieces of un-reacted phosphoric anhydride (yield 98% relative to the original alcohol) and titrated. The content in the reaction mixture monoi dialkylphosphoric acids: - 31 and 47 wt.%, Respectively. The resulting acids are neutralized with alcoholic solution of tetraethylammonium hydroxide to pH, the solvent (ethanol) is distilled off. A yellowish liquid is obtained (quantitative), readily soluble in water, benzene, chloroform, and ether. The refractive index and surface-active properties of tetrathylammonium alkyl phosphate based on n-hexanol are given in Table. f. Example 2. In a three-neck flask equipped with a stirrer, a nitrogen inlet and a thermometer, 118 g (1 M) synthetic alcohols of the fraction (hydroxyl number of alcohols 475-480) are placed. 71 g (0.5 M) phosphorus pentoxide is added with stirring. The rate of addition of P.O. is limited by the temperature of the reaction mixture (not above). After adding the entire amount, stirring is continued for another 4 hours. The resulting acid is filtered from pieces of unreacted phosphoric anhydride (yield 96% relative to the starting alcohol) and rubbed. The content in the reaction mixture of mono - and dialkylphosphoric acids: 32 and 49 wt.%, Respectively. The resulting alkyl phosphoric acids are neutralized with an alcohol solution of tetraethylammonium hydroxide to pH, the solvent (ethanol) is distilled off. A light brown liquid is obtained (quantitative yield), readily soluble in water, alcohol, chloroform, CCt, benzene. The properties of tetraethylammonium alkyl phosphate based on alcohols fraction are given in table. 1. Example 3. In a three-necked flask equipped with a stirrer, a nitrogen inlet and a thermometer, 83.5 g (0.31 M) of the C, –Ca fraction alcohols were placed. oceanized with three moles of ethylene oxide (hydroxyl number of ethoxylated alcohols 190230). At 40 ° C and stirring, 22 g (0.155 M) of phosphorus pentoxide are added at such a rate that the temperature of the reaction mixture does not exceed 60 ° C. After adding the total amount of Py Oy, stirring is continued for another 4 hours, it is filtered from pieces of unreacted phosphoric anhydride (yield 92% relative to the initial alcohol) and titrated: the content of monoalkylphosphoric acid in the reaction mixture is 26.1% by weight dialkliphosphoric acid, 47.1 May. % The acids are then neutralized with an alcohol solution of tetraethyl ammonium hydroxide to pH 7-1, the solvent (ethanol) is distilled off. A light-brown liquid is obtained (quantitative yield), readily soluble in water, alcohol, benzene, chloroform and CC1. Properties of the drug are given in table. Example 4. Under the conditions of Example 3, an alkylphosphoric acid based on alcohols fraction ethoxylated with three moles of ethylene oxide is obtained. The content of mono- and dialkiphosphoric acids is the same as in Example 3. The acid is neutralized with an alcohol solution of benzyltristilammonium hydroxide until the solvent is distilled off. A liquid of yellow-brown color is obtained (the yield is quantitative), well soluble in water, alcohol, benzene, CCB. The properties of the preparation are given in Table. Example 5. In a three-necked flask equipped with a stirrer, an input for nitrogen and a thermometer, put 118 g (1 M) synthetic alcohols of the CjC fraction (hydroxyl number of alcohols 475-480), 400 g (1 M), polyethylene glycol (average throxyl the number is 280). While stirring, 142 g (1 M) of phosphorus pentoxide are added. The rate of addition of PR is divided by the temperature of the reaction mixture (not higher). After adding the total amount of P-Og, stirring is continued for another 4 hours. The reaction mixture is filtered from pieces of unreacted phosphoric anhydride (yield 95% relative to the original alcohol) and titrated to determine the content of mono and dialkyl phosphoric acids of 30.1 and 48.5 wt.%, Respectively. The resulting mixture is neutralized with an alcohol solution of benzyl three-ammonium hydroxide to pH 7-1, the solvent (ethanol) is distilled off. A yellow liquid is obtained (quantitative yield) readily soluble in water, ether, acetone, chloroform, CCb4. The refractive index and surface-active properties are listed in Table. 1. Example 6. A 158.3 g (1 M) n-decyl alcohol is placed in a three-neck flask with a stirrer with a thermometer and an inlet for nitrogen. At 40 ° C and stirring, 71 g (0.5 M) of phosphoric anhydride is added. After adding the total amount of P205, transfer is continued for another 4 hours at 55-60 ° C. The resulting acids filter out, yield 97% relative to the starting alcohol and titrate: mono-a: lkylphosphoric acid 29.4 May. % dialkyl phosphoric acid 50.1 wt.%. The acids are neutralized with an alcohol solution of benzyltriethylammonium hydroxide to pH 7-1, the solvent (ethanol) is distilled off. A light brown liquid is obtained (quantitative yield), readily soluble in water, acetone, chloroform,. Properties of the drug are given in table.1. Example 7. Under conditions of Example 5, alkylphosphoric acid based on alcohols of fraction L and polyethylene glycol (PE) 200 is obtained. The content of mono- and dialkylphosphoric acids is the same as in Example 5. The mixture obtained is neutralized with an alcohol solution of tetraztilammonium hydroxide to pH 7-1 the solvent (ethanol) is distilled off. A yellow liquid is obtained (quantitative), readily soluble in water, ether, acetone, chloroform, p 1.4620; 6 28.2-10-3 n / m; KKM of 1,8 kg / m. Example 8. Under the conditions of Example 3, alkylphosphoric acid is obtained on the basis of alcohols of the fraction and polyethylene glycol 1500. The content of monoalkylphosphoric acid is 32.5 wt.%, Dialkylphosphoric acid is 45.7 wt.%. The resulting mixture is neutralized with an alcoholic solution of tetraethylammonium hydroxide until the solvent (ethanral) is distilled off. A light-brown liquid is obtained (quantitative yield), readily soluble in water, acetone, chloroform, 1.4803; 6 building 35.240-3 n / m; CMC 2.1 kg / mz Example 9 (comparative). In a flask equipped with a stirrer, a thermometer, 118 g (1 M) of synthetic alcohols fraction (hydroxyl number of alcohols 475-480) and 400 g (1 M) polyethylene glycol (average hydroxyl number 280) are placed, heated to 60-70 C and with stirring 142 g (1 M) of P2 Su are added. After adding the total amount "0d. the reaction mixture is incubated at 60-70 ° C for 4 hours. The resulting viscous syrup (monoalkyl phosphoric acid content is 30.5 wt.%, dialkyl phosphoric acid is 48.3 wt.%) is neutralized with 70% aqueous KOH solution to. A product is obtained, which is a paste containing 10-15% by weight of water, which dissolves well in water, ethanol, chloroform, CC. The surface-active properties of the obtained preparation are given in table. 1 in comparison with the properties of the products obtained.
    Table 1
    CeH ,, (C2H5) 4
    G
    Is he
    + (SbN1zO) rR-oG C2H5)
    about
    RO-PCopN C2H5) jt +
    about
    Ii.
    -f-t- (RO) 2 F-0 mCzH5) y 1.4503 26.1 R-radical of alcohols fraction С –CO
    Ko4s ОЖЖС2Н5Уг + О
     4- (RO) rP-Ob N C, H5)
    R-radical hydroxyethyl, ovated with 3 moles of oxide, ethylene alcohol C-C fraction,
    0 -
    Ro4cJ - (CjHjljKCHj.
    4® .t, 472935,9
    + {RO) (CjH5) 3HCHj5 -H
    R-radical of oxylethylated 3 moles of ethylene oxide of the C – C fraction
    ABOUT -
    RO-PCJ (,
    II
    ROP-0 t z "s41 CHjQJ 1.498026.9
    5-10 (CH2CH2Q), HJ
    R-radical alcohols fraction
    28.5
    3.2
    3.3
    1,3
    at .
    , c, H «0-PCj - (C, H ,, NCH,
    O 4- (C, H, 0) -POP (C, H,), ICN,
    ABOUT
    PI
    RO-P-OK RO-P-0 (, 01. "I II6 6 9
    OKOKR-radical alcohols fraction. Thus, liquid anhydrous substances are obtained by a tethered method (as opposed to substances by a known method containing up to 15 May.% Water), which are not inferior in surface-active properties to known compounds. The proposed and known methods are determined by antistatic properties. For this purpose, bX-hnye aqueous solutions of substances are prepared and these solutions process the polyamide complex thread of linear density 29 tex. The treated filament is kept in a climate according to GOST 10681-63 for 24 hours, then, under the same conditions, its electrical resistance is determined on a YES-1 instrument (according to GOST 19806-74). The technical capabilities of this device make it possible to measure the electrical resistivity (f) of samples with p ohm-cm, while the processing of fiber with products obtained by the proposed method reduces p with ohm "see. (for neobrabyu
    1,122664 Continued table. I
    33.4
    2.2
    4830
    Past 6, 31 TaHHOiro fibers) to a VO OHtCM value, i.e. by 3–4 orders of magnitude of the electrical resistivity for a product obtained by means of a test method 10 LM “cm, {Taksh obrvYyM And by this indicator, nojiyneHKbtev products are not inferior to the known. Since the production and processing of chemical fibers in razystak cfdfffutK imeioT place is quite high 1 "W1" of the treatment, it is necessary to know how they will conduct one or another drug under temperature exposure, whether it will completely vyropatb wan will form all-agar , which is undesirable "s, and kk.rbrazom these can be removed In table. 2 {The data presented are presented in a short run of coke with a method of tioc Tb and shemsfapicheskie. properties are neither; TR, treated with 62 aqueous solutions of the obtained products in comparison with the product obtained by the known process with Stearox-6. ic, H "o-p4f K (C2H,) o and Dry ko1 - | - (CeH | 50) f PT IJWCCjHsU brown
    .0
    (C2H5) jrО
    + (CO) s4-0 LS2N5)
    R-radical alcohols fraction
    (C2H5) 4l
    0
    n
    i-h
    + (nO) 2 -P-o - NiC2H5) J;
    R-radical of ethoxylated 3 moles of ethylene oxide Alcohols C- | Cd
    O {RO-PCjj tC, H5), HCH,
    about .
     + (CO) -R-OM (CrH5KSN,
    R-radical of ethoxylated 3 mol of ethylene oxide fraction
    table 2
    Wool, sm21, 5
    10 chenny water
    ten
    Dry yellow-water, wetted with water vat 19.8
    Dry light-17.7 watts dipped in c. brown. water Wool wetted with 20.2 water s.
     I O CHjjCHjOljHJ K radical of alcohols fraction
    C7-S
    about
    1 s, y) 7PC ° YCLs1,), NcHg
    Dry,
    o light + (,, 0) 4-P-o (C, Hs) | WCHj brown
    and
    RO-PCJJ NIC, H,)
    Sticky, lightly
    (Sn, Sn, o) ,.
    | Ro4.- "yellowish 21.3
    R-radical alcohols fraction
    C-Se
    .c, H, ui;
    , 01, cH, o) ,, “| - IKIC.H,),}
    R-radical of alcohols of the fraction Sticky dark to RO-P-OK- RO-P-O (CHgCH O 1H nevy fi black OKrK R-radical. Alcohols of the CzI fraction
    Stearox-6 C, (Adhesive
    black 58.5
    Continued table. 2
    n d Wetted with water
    Removed by washing with chloroform
    Deleted
    washing
    ten
    ten
    chloroform
    Removed by repeated chloroform and mechanical
    impact 10 is removed by mechanical action and multiple. washing with chloroform 15117.266 As can be seen from the data table. 2, the products obtained by the proposed method, have .3-5.5 times less coking ability compared with the product obtained by the known method, and with Stearox-6. Nagar (residues) after heating the products at high temperatures are easily removed without much energy. О 416 Thus, the proposed method allows to obtain substances that are not inferior to the known products in surface-active and antistatic properties. In addition, the proposed method allows to improve the quality of surfactants, namely, to reduce the coking ability and to obtain them in the form of liquid, anhydrous preparations. .
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR PRODUCING SURFACE-ACTIVE SUBSTANCES by the interaction of alcohols with phosphoric anhydride when heated, followed by neutralization of the formed alkylphosphoric acids with a base, characterized in that, in order to improve the quality of the target products, tetraethipammonium hydroxide or benzyltriethylammonium hydroxide is used as a base.
    [2]
    2. The method according to π. 1, with the fact that alcohols C ^ -C 1 0 alcohols, alcohol mixtures of the C ^ -Cg fraction, ethoxylated alcohols or equimolar mixtures of C ^ -C 10 alcohols with polyethylene glycol with pier m. ' 200-1500.
    [3]
    3.
    lead
    The method according to PP. 1 and 2, distinguished by the fact that the interaction of alcohols with phosphoric anhydride at 55-60 in C.
    1 1122664
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SU823500646A|SU1122663A1|1982-07-07|1982-07-07|Quaternary ammonium salts of alkylphosphoric acids as antistatic surfactants|
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