BE548065A - - Google Patents

Description

       

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   The invention relates to an improved process for the preparation of alkali metal, alkaline earth metal and tertiary aromatic amine salts, ester and amide compounds from carboxylic acids and amino- or hydroxy-alkanesulfonic acids.



   It is well known to react fatty acids, fatty acid chlorides and fatty acid esters with 2-amino- or 2-hydroxy-alkanesulfonic acids and their alkali metal salts to produce surface active substances. anionic agents usable as wetting, cleaning, softening and dispersing agents. In US Pat. No. 1,932,180 various processes are described for preparing such surfactant substances.

   The processes fall into three categories in which (1) a free fatty acid is mixed,

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 dissolved in an aliphatic amine, with an amino-alkanesulfonic acid (taurine) and then heated to boiling, (2) an alkyl ester of fatty acid is heated with the sodium salt of an amino-alkane- sulfonic acid, and (3) treating a carboxylic acid chloride in aqueous medium with a 2-amino-alkanesulfonic acid in the presence of caustic soda. The latter process is that which is mainly employed in the preparation of surfactants sold under the name "Igepons".



  The preparation of the carboxylic acid chloride used as an intermediate is not only dangerous, but it is time consuming and expensive since phosphorus trichloride is used which is an expensive product. Further, when the acid chloride is treated with a taurine or a taurine salt, an anionic agent is obtained which contains a considerable amount of salt, i.e. sodium chloride, the- which is highly detrimental when the anionic surfactant is employed in bar soap formulations comprising builders. The presence of sodium chloride is the reason why some commonly sold "igepons" have high hygroscopicity. The removal of free salt from "Igepons" is very expensive.



   Reaction of a ras acid with a slight excess of taurine in accordance with the teachings of the aforementioned patent results in poor yields. The use of equivalent amounts of the reactants in this reaction results in a considerable decomposition of the taurine. In order to overcome these drawbacks, it has been proposed in this field to obtain a product free of salt by the supposed condensation of taurine. one mole of a fatty acid with one mole of a taurine salt at a temperature of about 220 ° C, but this has not been found to be an advantage over the acid chloride process.

   Time; dehydration may be reduced if the temperature, following

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 the fatty acid employed, is repidemnet pertée to 250-260 C $ or Plas towards the end of the reaction, while employing a vacuum close to
15 mm mercury. However, in this latter case, a small amount of the fatty acid distils along with the water formed during the dehydration reaction.

   To promote the. dehydration reaction, about 10% anhydrous sodium sulfate can be added to the reaction mixture. After the distillation of the fatty acid and the water formed, the final product after cooling is a solid mixture of soap capable of being ground.



   It has been found that the drawbacks inherent in the foregoing processes can be easily overcome by using a process which eliminates the preparation and use of fatty acid chloride, which uses a much shorter reaction time, and which provides a product free of fatty acids. salt. In principle, the process consists of heating a carboxylic acid with an alkali metal, alkaline earth metal or tertiary amine salt of a taurine or a 2-hydroxy-alkanesulfonic acid in the presence of 'a compound containing boron as a catalyst, under reduced pressure or in an inert atmosphere.

   An essential and in fact critical feature of the process is that the carboxylic acid should be used in excess of the theoretical molar amount, for example in an amount of 1.2 to about 10.0 moles and preferably 1.5. to 2.0 moles of carboxylic acid per mole of a salt of a taurine or a salt of a 2-hydroxy-alkanesulfonic acid. The use of a compound containing boron as a catalyst is necessary to obtain a rapid reaction. All salts are converted into the final product free of any mineral salt.

   A salt-free product can also be prepared at a molar ratio of 2 carboxylic acid to 1 salt of a taurine or salt of a 2-hydroxy-alkanesulfonic acid. As one uses an acid exoùs '!'

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 monocarboxylic, the final product will necessarily have a certain amount of free carboxylic acid, but not a mineral salt.

   Therefore, the end product is particularly suitable for formulations of the bar soap type with builders, in skin creams, lotions, ointments, and in food products as foaming agents, and for other uses where the presence of of an inorganic acid salt of an alkali metal, an alkaline earth metal or a tertiary is undesirable, as will be evidenced below.



   The reaction temperature, depending on the carboxylic acid used and the desired reaction time, can be from 200 to 320 C. This latter temperature range is used for a short reaction time, for example less than 5 minutes, while for a longer reaction time, for example 2 hours, a temperature range of 220-260 ° C. is used. The condensation or esterification reaction can be carried out either under reduced pressure, or in an inert atmosphere.



  When using reduced pressures, preference is given to absolute pressures of 10 to 2CO mm Hg. Pressures less than 10 mm Hg can be used if the fatty acid is not too volatile. The vacuum will therefore depend on the volatility of the carboxylic acid and the reaction temperature. If the reaction is to proceed at atmospheric pressure, an inert gas such as nitrogen is passed through the reaction mixture to facilitate the removal of the water formed.



   Water can also be removed by using a water-immiscible solvent such as xylene, toluene, chloroenzene, dichlorobenzene, chlorinated hydrocarbons, alkylbenzenes, alkylnaphthalene, etc. The use of immiscible solvents has the disadvantage of a higher cost due to the expense of recovery and loss of sol.

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 EMI5.1
 is-; -. '. ... ¯. ,.: 't's the speed of J' <'::, cfic.z- cjt ;; .. f: .8C-l (.C, ..ï.'. 2.iwW%. -.., i : in most Ç2vs' .'..- '::. Li7 of acids 81: 1Í "ÔllicltlOS d-, 1; .1'" B f: .. 0: / 2. f.> - -: .



  G .1¯¯. as indicated above, the molar ratio of reactants consists of a 180th: ['e:': 00S molar carboxylic acid, preferably of the order of 20pl to 100 molar excess of carboxylic acid per mole of alkali metal salt, from Y: h :::. 2-
 EMI5.2
 alkaline earth or tertiary amine of a taurine or a
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 acid 2 - '= dro: ßr-a, lcarwe-sulFoni iue.



  From D.êl: 8, if a mixture of tauride acyl salt and carboxylic acid soap (high soap content) is desired, additional fatty acid can be used to arrive at the composition.
 EMI5.4
 final tion. Thus, 10 moles or more of acid can be used.
 EMI5.5
 carboxylic together with 1.0 mole of taurine, after <ll1tÚ treated with an appropriate alkaline azeiit to obtain fJ ,, 1].



  Above 100 of excess carboxylic acid, the cost of the final product is slightly increased by more crUl1cl8 on requirements.
 EMI5.6
 calories and higher losses of carboxylic acid.



  Therefore it is preferable to use the carbon acid.
 EMI5.7
 boxylic in the range of a molar eXCOiJ between 20 "'and 50. In some cases it takes a do 100jl of ocrbo acid.",: - licl110 to reduce the viscosity of the laÙl'i.11; C ds reaction .



  The reaction time will depend on the temperature of the iL'5rict'i-J> 1 and the rate of water removal. In order to have the l1: oill: -l1l '= -] .l'; "ftl, .tutu, it was preferable to have a short reaction in teups confessing the use of a high temperature. However, we can 8 [J1pl ( ) "or a long duration (10 reaction with temperatures balms to have t1; 1 good 7: '3: 1ç' :::::? el't 0n final product.

   Tic? 1; nt, z> z; 11 cotto oiri '> 1 "> 0'jo, can it extend, -" ,,., ...-,' Jl <':', -, - 4.riodt: \ "J .. '' l 'r' (1 'j.)"' "'R ;, not 10'" y, '\' '' '' <! T ,, ", '(\' 1.1 '0" uses .i. = ,, high temperatures, on., R> .jt "1" "Y'CI' the reaction.; Ii space do 15" ( "('\ n 1r' r. -. 2: .is,; 'Gß'Vis Le, Jor, 1'>;> iJ containing '.ii2 1J'c" "' '' 't L 1 d; ( 'o "'! (" "('.,.!.,.," ".)"' 1 '!'

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 represents 0.01 to 10% of the weight of the reactants, preferably 0.1 to 3% It will be noted that the nature or the character of the compound containing boron does not matter; indeed, any compound which can form boric acid or boric acid dehydration products when employed in the process of the present invention is also applicable.

   Compounds of this kind are boric acid, borax, fluoboric acid and its salts, and the adducts of boron fluoride with diethyl ether, water, lower alcohols such as methanol, ethanol, propanol, eto, ammonia and various aliphatic and aromatic amines: ethylamine, aniline, carboxylic acids such as for example acetic acid, propionic acid, benzoic acid, l ' stearic acid, etc., amides like acetamide, propionamide, etc., phenols, thiophenol, cresols, naphthols, etc. It is believed that the boron-containing compound acts both as a coordination type molecule and as a dehydration catalyst.

   It has not, however, been determined whether the catalysis takes place on the catalyst particles or whether some part of the catalyst dissolves in the reaction mixture. Whatever phenomenon occurs, the presence of a boron-containing compound as a catalyst in the process of the present invention is essential in that it considerably accelerates the rate of reaction and enables the reaction to be effected. continuous process. In addition, the catalyst prevents the decomposition of taurine.



  This is of great importance since the decomposition of taurine considerably increases the cost of the process and imparts a bad odor to the product. For practical reasons, preference is given to the use of boric acid since the latter is readily available and inexpensive.



   It is also known that boric acid dehydrates to

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 EMI7.1
 force .f. ': J "c ^ O lß U.ts 1: .1. c'2ï â tz.t, iLil4'â.¯'¯t .., .. ¯ is3 the i.ei-1 .c; 1, oz.L, .. <i)
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 and retort in the present reaction no appreciable catalysis occurs below 180 C, it is possible that
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 iiB, 0 ",, r) 2: 5 'or one of' :: .... - ..- t;., are the vivelai.5 catalysts.



  C01: I: 0 examples of acids arbo :: 3, liclu8 ±: 1 which can be used d <: :( ':; the condensation or esterification reaction, one can u; i' :) yo1 'any carboxylic acid with at least 6 1¯ito;.: e, .J carbon, whether saturated, i: 021-; C, t.tl.r G', aliphatic, arOd; J .tic or cycloaliphatic, the maturity and character of the acid being irrelevant as long as it contains a carboxylic acid group.

   The acids of this type which can be used are in particular the following: caproic acid, caprylic acid,
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 pelarconic acid, capric acid, auric acid, 211 water; fl'ifJtiÇLue, palmitic acid, stearic acid, oleic acid, linoleic acid, acid of talle oil acids; 1.'l2wile of tall h3, lrog6n8G, acids [; ra: 3 of tallow 1.ijr: lro- 5énÓ, naphthenic acids, abietic acids, al1 :: yl-benzoic acids ” retorts doclÓcy1bcnzoiquc acid, n0113'lbenz0 lçy, e, octylbensoic acid, .7.ii acids ;; r1 - ix .: ah-toxic C #; Jl1e nonylnarh- acid :;

  olQ1.e, acids from alcohols and oxo aldehydes, acids from oxidized petroleum fractions, etc. It is also possible to use mixtures of acids of various natural vegetable oils and
 EMI7.5
 animal 00:.:;:;: 8 olive, tallow, castor oil, 'Cl'ta2ELC: II de, coconut, soybean, cottonseed,
 EMI7.6
 ucahuba, linseed, fish oils co: .2.ae

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 EMI8.1
 uorne, ie herring, from:.; a1} :: 'Edell, etc, from l'11:' foot island of '-o ... lM- fO c -: - Ir "," - At ... ......, ...- :. ï! ":); on .... ,,: r; .s of 1" "0" '' '-' ,, \ '' 1- = 1 1.-1 -.- r-.C '., "From: 2.pok, from c :::

  ..L'levis, mustard, rubber seed, rapeseed, crta2G, Sé8Qe, etc.



  The salts. Of acids 2-r = # iiro-a = 11; & - ze- # ilfoniq'àes and acids -¯; G .. -.v. ¯G, ''? E -, - ^. Tt = O 1Ç1t8. ^ -. which is condensed with the aforementioned carboxylic acids are characterized by the following general formulas:
 EMI8.2
 in which 3 represents hydrogen, a methyl or ethyl radical, R1 represents hydrogen or a hydrocarbon radical having 1 to 20 carbon atonies, for example a radical
 EMI8.3
 methyl, ethyl, propyl, butyl, amyl, hexyl, cyclol1e :::: yl, phenyl, iieptyl, octal, dodecyl, oleyl, linoleyl, stearyl, abietinyl, etc, and l;

  1 represents an alkaline earth metal, for example calcium, .r.1aC; llésiura, baryt1ill, un = alkali metal, for example lithium, sodium, potassium, or a tertiary amine, for example la, trioctylamine, 1T, 1T-diphenylm.ethylaP.line, 1¯; , - 11? '1t tïlrlOCt2 "C.c''lE.tTïalln8, etc.

   Highly hindered secondary amines can also be employed, particularly those which do not easily break down amides with fatty acids.
 EMI8.4
 CO: i ': J "' TIe examples of 2-amino-alkane-sulfonic acids and 2-ï ;;,? Roj; - a ':. C.ne-w.lioniemes that are r '- 7ir in the form of their salts with the above carboxylic acids to form anionic surfactants, the following
 EMI8.5
 are typical: 2-amino-alkane-sulfoninue3 taurine acids c <l ..L v2:;:;, rllle.



  17-mcthyltaurine:; -. '; Let: Wlc1i tc:. Urine

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 EMI9.1
 IT-etl1;) rltaurine IT-br Oy j 't, u: C'1ne R-isoDroT7ltaurine 1: T-butyl tc.urine 11-isobutyltaurine .1-tert.butl, l-taurine H-amyltaurine
 EMI9.2
 : i-he ;;: yl taurine 11-cyclohe: .- yi-aurine N-phenyltaurine I; epty 1 tiL¯rine I'-o c t;

  ltaurine N-dod8cyltaurine 1,7-oleyltaurine N-linoleyltaurine
 EMI9.3
 11-stear yltalIne N-abietinyltaurine 1T-dihydr oa'aietinyltaurine N-aethyl-2-methyltaurine T7-methyl.-2-ethyltaurine TT-.methyl-1, 2 -dim, ethyltaurine 2-hydroxy-alkane- acids sulfonic acid isethionic acid 2-hydroxy-propane-sulfonic acid 2-hydroxy-2-butane-sulfonic acid 2-hydroxy-l-butane-sulfonic acid
 EMI9.4
 The 2-amino-alkanesulfonic acids and the 2-.liydroxy-alkali-sulfonic acids above are used in the form of their salts of sodium, potassium, calcium, magnesium, etc., or of salts of secondary amines. or tertiary.

   The salts are easily prepared by neutralizing the acid with an equivalent amount of an alkali metal or alkaline earth metal hydroxide or carbonate, or of secondary or tertiary aliphatic or aromatic amines, such as for example
 EMI9.5
 11, lT-diplienylmethylalnirie trioctylamine Ts, rl-dimet11r1octadécJlamiYie N, N-dioctadecylethylamine 2T, T5-dihewadecylmethylar.vine.



  The taurine salts and the 2-hydroy-alkane-sulfonic acid salts can be used in the form of aqueous solutions or dry powders. In the first case, water is removed during the reaction in the presence of carboxylic acid. The carboxylic acid helps stabilize the taurines. In the absence of carboxylic acid, heating taurines at high temperature

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 causes the release of an amine or ammonia to force di- or tritaurins:

   
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   In view of the high yields obtained by the process of the present invention, it is believed that the following reactions occur in addition to the main reaction of carboxylic acid with taurine.
 EMI10.2
 where R2 represents an aliphatic or alicyclic radical.



   Likewise, tritaurine can react to form one anionic anide molecule, two anionic ester molecules and one water molecule.



   The products obtained by this process are valuable anionic surfactants and they have various commercial uses. The most striking property of these products is their great activity at surfaces and interfaces, which favors their use in a wide field of technical applications. Through

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   example,

     they can be used as wetting, foaming or washing upstreams in the treatment and manufacture of textiles, to convert liquid or solid substances which
 EMI11.1
 in themselves are insoluble in water (by t: .a) 12 hydrocarbons, higher alcohols, hulls, fats, waxes and resins) in creamy emulsions, clear solutions or stable dispersions fine, for charring, for dyeing, for pasting dyes, for processing
 EMI11.2
 fulling, finishing, i1 tem ents:

  1prgllation and bleaching as cleaning agents in hard water, in tanning and mordanting processes, for dyeing acetate rayon with insoluble dyes, for preparing dyes in finely divided form, for powdery dyes dispersible, for the production of foam in fire extinguishers, as an agent for improving the absorbency of fibrous bodies, and as an auxiliary agent in the softening of hides and skins.



   In addition, these products are valuable emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 2,4-D, toxaphene, chlordane, dormant sprays or mineral oil, sulfate sprays. nicotine, methoxychlor, etc. and they are effective dispersing agents for pesticide powders, such as those which contain the aforementioned toxicants.



  In addition, these products are useful for use as additives to petroleum products, for example fuel oils, lubricating oils, greases, and as additives to water or brine used for the recovery of petroleum. from oil-bearing strata by employing techni-
 EMI11.3
 C7 v üe.>: .E;: lo: - "c.ce.



   Other useful uses are in metal cleaning compositions, cleaning compositions.

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 dry, as additives to rubber latexes, as knot inhibitors for synthetic rubber latex exhaustions, as skimming flotation agents, as additives for road construction materials, as air entraining agents for concrete or cement as additives to asphalt compositions, as plasticizers and modifiers for vinyl plastics, alkyd resins, phenol-aldehyde resins and other types of polymer-type plastics,

   for incorporation in adhesives, paints, linoleum, for use in binding agents used in various insulating and building materials, as auxiliary refining agents in wood digesters to prepare pulp, as additives to pulp pulp in pounding operations to prevent foaming and also to facilitate the pounding operation in papermaking, and as auxiliary agents in the preparation of viscose syrup.



   The products are also useful as emulsifiers for emulsion polymerization, as auxiliary mercerizing agents. wetting agents, rewetting agents, dispersing agents, detergents, penetrating agents, softening agents, calcareous soap dispersants, dishwashing agents, antistatic agents, disinfectants, insecticides, moth repellants, bactericides, fungicides and biocides. They are valuable as anti-fog agents for use on glass and other surfaces where the build-up of aqueous mist is harmful. They are useful in the rayon industry as additives to syrup or to the spinning bath and as auxiliary clarifying agents for viscose rayon.

   They are useful in hydraulic fluids to improve viscosity characteristics.



   The products are of special interest in breaking the

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 petroleum emulsions. They can be used to break up crude oil and saltwater depletions as obtained from oil wells, or to prevent oil-in-water type emulsions from oil-in-water. acidification of oil wells by introducing the agent into the well, or to break or prevent depletions which would result from a water drowning process in order to recover oil from the oil strata.

     They can also be used to break up emulsions that are encountered in the petroleum refining process.



   They are of interest as corrosion inhibitors, as rust inhibitors, in the protection of metals and especially ferrous metals, in acid pickling baths, in acidic cleaning compositions and in galvanizing baths.

   Other useful uses are as solvents in dissolving compositions, retort agents (the cleaning of paint brushes, as additives to lacquers and varnishes, retort lubricants, as greases and as stopping agents.



   Laize la products, preparation of skin creams, lotions, ointments and other cosmetic preparations such as permanent waving products at home, shaving creams, shampoos, toothpaste, etc. can be used. They can also be used in food products as foaming agents, emulsifying agents and softening agents.



   They can also be used in soil conditioning, as auxiliaries in grinding, rolling or cutting metals, either in aqueous solution, in emulsions or in oils, as auxiliaries for fixing dyes on leather and on natural or synthetic fibers, as auxiliary dye leveling agents

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 fibers, as auxiliary agents in the stability of the growth of plants,

   as an additive to cite to improve the strength of the resulting concrete or to improve its hardening time or its resistance to freezing and thawing or chipping, and finally as auxiliary maturing agents and as penetrating agents for use in entrainers.



   The following examples will further explain the nature of the improved process, which, however, should not be construed as being limited to these examples. The parts given are all expressed by weight.



   The following two examples in which the reactive components are used, but however in the absence of a catalyst, are given for comparison. Example 1 can be viewed as indicating optimum reaction conditions when no catalyst is used. Example 2 shows the mediocre yields obtained without a catalyst at high temperature.



    Example 1.



   In a 250 cc three-nozzle balloon. provided with a stirrer, a stopper and an outlet connected to a vacuum suction, 11.8 parts of dry sodium salt of methyltaurine and 26.4 parts of stearic acid are placed. The flask is then placed in an oil bath which is thermostatically controlled at 220 ° C., and maintained at this temperature for 10 hours while stirring and maintaining it under vacuum by suction. The product (which is melted at 220 ° C.) is cooled and the fragile waxy tan-colored mass is cut into chips.

   The weight of the final product is 36.3 parts, and its analysis indicates an activity of 65%. This corresponds to a 90% conversion of methyltaurine to the sodium salt of N-stearoyltaurine.



   The product analysis is established following the following:

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N-stearoyl-taurine sodium salt anionic surfactant "IGepon" 65% stearic acid 26.9 sodium methyltaurine salt 1.5% decomposition product of stearic acid 3.7% remaining (by difference) 2, 9%
The determination of the active anionic surfactant in the preceding analysis is carried out by the methylene blue method described in nature 160, 759 (1947) and in TranseFaraday Soc.

   44, 226-239 (1948) The determination of stearic acid is carried out by extraction with petroleum ether and titration of the residue of petroleum ether. The sodium methyltaurine salt is determined by titration of the solution which has been extracted with petroleum ether to remove fatty acid, and the other components (by difference) are determined from the weight of the residue of the petroleum ether. petroleum by subtracting stearic acid.



  Example 2.



   In a beaker are placed 36.8 parts (0.2 equivalent based on the amino group) of crude sodium salt of methyltaurine and 85.2 parts (0.3 mole) of stearic acid. Heat the contents of the beaker until melted and shake well. 6.66 parts of the stirred mixture is placed in a 20 cm test tube and the contents are heated for 10 minutes.
 EMI15.1
 a bath of Vood metal which is set to 300 "0, while keeping the contents of the tube under an absolute pressure of 25 mm of mercury /
The product is analyzed by the methylene blue method as in Example 1. The percentage of conversion to salt
 EMI15.2
 sodium of ¯; - ,, tearo-1-taurine is 52, Jµ 'with respect to. the initial amino group content.

   We obtain 9g; '¯ from the excess tL50ric: ue, .'cide ¯gras (determine rar ētr2.ction with 6thei

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 of petroleum and titration at 12 caustic welds).



  This example clearly shows that despite the higher temperature at. which one would expect a faster reaction, a poorer yield is obtained.



   The following examples will show the improved results obtained by the process in which a compound containing boron is used as a catalyst.



    Example 3.



   This example is similar to Example 1 except for the addition of boric acid as a catalyst and the reaction time which is much shorter.



   The following materials are mixed well and melted in a beaker by stirring at 140 ° C: 36.8 parts (0.2 mole) of powdered sodium salt of methyltaurine (incompletely dried) 85.2 parts (0.3 mole) of stearic acid and 3.66 parts of boric acid. 7.44 parts of the melt are added to a test tube and placed under the vacuum of a water pump, of the order of 20 to 30 mm Hg absolute pressure. The test tube is placed in an oil bath set at 220 ° C. for 2 hours. Vigorous evolution of water occurs during the reaction period.



   Analysis for the anionic surfactant component by the methylene blue method will show that the product contains 0.01055 moles of anionic surfactant. This corresponds to a conversion of 89.1; of methyltaurine as a surfactant.



  The product has a light tan color; the product appears almost white when ground to a powder.



    'Example 4.



   Stearic acid and methyltaurine powder (sodium salt) are mixed in the ratio of 1.5 :: ales of stearic acid per mole of methyltaurine loss. To 5.89 parts of the mixture in a glass container is added 0.18 part

 <Desc / Clms Page number 17>

 
 EMI17.1
 of boric acid and the nulanje - <:; 1-1 -! "llt 21F '- QC is heated for 1S minutes under an absolute pressure of 25 1;, 1 of ... crcu- -É * 1 . t .., - con.Jei # 1ion d = e ± 1 ', 4ii <)., t; "' \" "'l..L' -'''- '' i '" Or.:1 ': \ i ria Cn obtains a conversion of 97.4' ho - .; thyltaunue adjent surfactant # 1: iioni j "ae, from aprj 1 ';. # :: i yz c;.,: -. blue 1,:;

   methylene. si ?, extract the acid -r, - s and titrate it. The titratior. against that we recover 99 :. ' ; the acid not having rcaji. A similar reaction of a.rail-c = tio;.: Ec #. ": - e callc given plus =: 2 ..: - :, maie Bans boric acid eo: .r # -9 catalyst, reveals a significant decomposition of ethyltaurine 26 GC, resulting in a dark product obtained in low yield.



  Iemrle.



  Danc a balloon with four tubes of 500 C1: 13, cjxi;: i of a d.1-a condenser (descending) and è, 't: I t3:, Crl'; C) l; t (::: bre, 66 parts (0.3 uole) of coconut black acids are introduced 'entrain & s, 5 6, 83 parts (C, 2 ii: o 1;) G. e powder of netliyltaurine (2 7, 4.o "', ucfhyltaurine according to the titratable amino group) and 5.3-4 parts of boric acid cli, imiçue ;; # e: t pure (5j.1 of the charge).



  The contents (flask 8, lu2-23210) were heated for one hour while stirring under 20 µl absolute pressure.
 EMI17.2
 



  99.72 parts of a light tan product are obtained.
 EMI17.3
 



  Analysis for the anionic surfactant content by the methylene blue method indicates 1.96 µl: lol per serum, or 97, Ci conversion. in tonsioactive feeling. The product foams well in water and disperses hard soaps well (use of ol.éafe de in hard water).



  : ExeElpl, 6.



  In a 2-liter flask 1,: 1:.: Have an efficient stirrer,
 EMI17.4
 a thermometer and an air condenser leading to a tube
 EMI17.5
 Aspiration under vacuum, 423 parts (1.5 soles) of olic acid c: hil: LÎQ:>. 8: <: pure, 17C, 3 parts (1.0 equivalent of CrouJ: 8 ai-liro) de -, cook partially dried raw taurine '(which contains a little sodium salt of isethionic acid) and

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 EMI18.1
 i7, v parties to tc.C..¯v -......... -r1- .. ,, "'" "' :: \ ùa .........., l - -1- oy "0" l, 1) L ..: "" \ t. -: 'we heat the content el.-...' '-: .. i O = 2 scuj -,' it leaves -Lel è. Z50 C and it is maintained for 2 hours at 25G-25SoC under an absolute pressure of 35 ¯Or 3.3: .¯, .rcLSx'e. E final product weighing 569) 5 sometimes is a solid o. ....: .. (:). r8 ::::: n: t brown when allowed to cool to room temperature.

   The analysis for the anionic surfactant by la. i = ôftod, e with ncthylene blue indicates 1.79 :::! Ülli: '!. 01e8 by This corresponds to 1é2'e, :: G'ilt more than 100% of yield when multiplied by the weight of the product final (1.02% of surfactant from 1.0 equivalent of taurine). The product against a good dispersing power of calcareous soaps.



    Example 7.



   In a 4-liter resin container, fitted with an efficient stirrer, a thermometer and an air condenser connected to a vacuum pipe, 607.7 parts (3.3 equi-
 EMI18.2
 total amino group vals) of spray-dried -., ethylturium sodium salt, 1347.9 parts (4.95 equivalents) of crass acids. tallow and 39.1 parts (0.645 mole) of boric acid. The mixture is heated with stirring under partial vacuum at 225 C, and then for 2 hours at 225 C. The product is
 EMI18.3
 a hard solid tan color on cooling. Analysis indicates an 87% conversion of the total amino group in the starting taurine to anionic surfactant.



  Example 8.



   In a test tube one places 1.57 parts (0.01 mole) of
 EMI18.4
 Sodium 2-hydroxy-ethane-sulfonate a. 95, 4.26 parts (0.015%) of stearic acid and 0.1 .. part of borj CJ.l1.G.



  The test tube is then placed in a bath (: 'oil set at 2 ° C. C. A vacuum of 20 ..¯ .: mercury is made in the tube a eC8c.i and the vacuum is maintained while heating the tube ( 1 ::: .. nc the bath for 2 hours. There occurs an i .. ::.:>. Zer. ::: vijoureu-x

 <Desc / Clms Page number 19>

   (water value) during this period. The yield of tan-colored solid is 5.623 parts.



   The contents of the tube were cooled and analyzed by the method instead of methylene. 1.650 millimoles of anionic surfactant are found per gram of sample. This corresponds to a 92.8% conversion of the 2-hydorxyethanesulfonic acid salt.



   We run a second experiment identical to the previous one, except that we do not add. boric acid. The yield is 5.70 parts of product. There are 0.3056 millimoles of anionic compound per part of product (conversion of 17.4% of sodium 2-hydroxyethane-sulfonate to surfactant compound) Example 3.



   An equivalent of methyltaurine (powder) and 1.5 equivalents of refined tall oil are heated at 250 ° C. in the presence of 12 parts of boric acid for 2 hours under an absolute pressure of 25 mm of mercury, which gives a crude anionic surfactant.



  Example 10.



   An equivalent of taurine sodium salt and 1.5 equivalents of commercially available naphthenic acids are heated for 2 hours at 250 ° C., under an absolute pressure of 25 mm of mercury and in the presence of 10 parts of boric acid, this which gives a mixture of anionic surfactant: naphthenic acids.



  Example 11.



   One equivalent of aqueous sodium butyltaurine salt is concentrated to a paste in vacuo. and 1.5 equivalents of lauric acid and 0.2 moles of boric acid are added. The mixture is heated until it becomes liquid and the pressure is gradually reduced to 35 mm of mercury while heating to 220 C.



  The mixture is stirred under an absolute pressure of 35 mm sea.

 <Desc / Clms Page number 20>

 
 EMI20.1
 cur2 during z 1 *,:,;. == while .i: J.¯;: C.2: t la ... y C :. i's t i,.:. ; .2C 1; L0 l "": - 'cli t ± 1 = eī1 ± ¯ = ni <= 1 3 l' e ::. T l1C¯1 :: i "Ll: G;: ol": io :. ::: r.:; :: ..: t, ::. m¯¯6.¯¯ "¯1 '.. 12.



  -C-3 l; .11 recÍ? I2;: -:.:. # 1 = lsii = e Ge 4 -3-tjY. * GSy 1.112- d. 'i; ± ë:; it: their efficient, .d,' 1 === t¯tC3¯'¯.: 0: .. t = '2 and i'Llx2 CCi2i: 1''¯? L¯I '... ir cort (± 1 = ia to urge and has a vacuum line), or place 1.3û5 parts (5 "' C2 ..0 'c, .C') of palnitic acid, 652 parts ('7,' 7 ;; '7 total anine group or 2 Q group a :: 1 -il secondary) sodium salt of: zet ;; 3rltaJrixie spray-dried, and 40 parts (C, ° 6 The 11 {l8.nce was heated to 225 C while reducing the pressure Gr ::;, d: L.èClle :: 19nt to 15-25 mm Hg. On .t; 1 tE ; then the = .; els, n¯ùe 1; 225 C for 2 hours The final product, which}? 8Se 1950.4 parts, e = Jt poured onto flat trays for solidification.

   The product which has a very light tan color is then ground in a hammer mill, and a very lightly colored powder is obtained. Analysis for the anionic surfactant by the methylene blue method indicates a conversion of 92.8% by
 EMI20.2
 relative to the total amino group in 1116tllyl taurine. Z'al2o.lrw; for fatty acid by titration with caustic soda, petroleum ether extracts indicate that 60% of the theoretical excess fatty acid is recovered.



    'Example 13.



   36.9 parts (0.2 equivalent
 EMI20.3
 of group x: 1in) of se ::!, sodium of methyltaurine and a5.2 ± 1 parts (0.3 mole) of st6e.riclue acid. We heated the contents of the beaker until it melted and we s, rite well. We place 6 parts of. :: l-'C ::: 'i té and C, 2.2 part of boric acid (] [: 1.1 j a tube e282.i of 2C em. C "i; .¯ . -3r.:..,8:; er40: '": cl ... t 10 ¯zr Ü te :; le t! -1 ../ e è..1S an oil bath :::: , é: l 23C C under an absolute pressure of 25 ..: .. of ¯Pr C ,: T '. 0 ;. analyzes the rc :: ¯:. "! i 1'; by 1 ::. 4: C: tl10d 3: blue .e '..thylnc scared' 1 1 .-;, ß-. ¯ and we

 <Desc / Clms Page number 21>

 
 EMI21.1
 the oil extract to determine the, = ::;, = itii; 15 <1 d '# = ciàe 1 = fi; -r rCUrr8.



  : conversion = c'O '7 ;; ("2-LZ-ot M- jroup r.;. ii:.> o toti, 1 in crude taurine. from acid recovery == ri-x = 9SjJ By titr '=; tioi =. é; caustic soda extracts petroleum ether.
 EMI21.2
 



  'I; = e second e :: periance e ± fe <e-tu. e oo: -.:;. # e described j1 Es above gives a Ge 99 conversion according to the blue method do: #, 'tl = yléne. Other possible catalysts are used 0t compared with CO! ": D00S contains: 1, al1t boron in the condensation reaction between stearic acid and> 6th.3rlta.;: Rine. The results obtained are reproduced. in the following table: TABLE
 EMI21.3
 Catalyst quantity to be µ '(conversion a, el1t tcnsiocatalyst x for 2 hours- active .wi0? .L.i.¯ res at 225 C. (1110 10 1: [iii.



  ¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯ - x has 280 C. ¯¯¯
 EMI21.4
 
<tb>
<tb>. nil <SEP> nil <SEP> 75 <SEP> '<SEP> 58
<tb> <SEP> boric acid <SEP> 2% <SEP> 91 <SEP> 99
<tb>
 
 EMI21.5
 NaIISO. iT1ilIZ Q j 2il,) \): Je ::: 0 '"' =: 0 2 ;. ' 77 110
 EMI21.6
 
<tb>
<tb> A12O3 <SEP> 2% <SEP> 74 <SEP> 57
<tb> <SEP> sodium <SEP> phosphate <SEP> 2% <SEP> 80 <SEP> 61
<tb>
 
 EMI21.7
 y.r <l 2 67 47.5:; llCl .., 2µJ "68 5 ± 310r- (.: il .. cel) 2 72 57 301 '\:' :: 2f 33
 EMI21.8
 
<tb>
<tb> B2O3 <SEP> 2%
<tb>
 
 EMI21.9
 K ........ "1-" "" '' ''; : ..: -1 L .. ¯ "1'0-; 'c' ci3 't'fi'" 'r''j i; 1 ii, r 1 (") - ,, - 4 -1, ¯, 1> ù e y. Or; 1 1 =. E 1 2::. ::}: lt [...:; 'lill ( ; 1.z <; = to.



  It rossor-t '¯, t-'¯ = :: 1'::. t; t: ... -1; 3 :::: ': l;: .. c: l; j: J t c .......:] one obi - =., w 1-: ; ..: ..: -; "'.: ill" r; -...': '' '' {21 L, ...: 1.:.:. '': ';' ..: .''... "'1 (;.:. .. :::.:. Lc.i) 1.1: co: - .. rc;.;, J CO.d-

 <Desc / Clms Page number 22>

 holding boron as a catalyst, and that the percentage conversion of the coreactants to anionic surfactant is efficient for short periods at high temperatures, and for long periods at low temperatures.



  Example 14.
 EMI22.1
 



  J / lC -I 12l0lecule -. ::; ralJID.G of sodium salt of N-ethyltaurine powder is mixed with 0, 2 grarmie of capriqul acid and 1.5 g of boric acid, and everything is heated. stirring at 225 C.



  The pressure is gradually reduced to 100 mm Hg absolute pressure over an hour, then heated for 1.5 hours while stirring under 100 mm Hg absolute pressure. The final product which contains some unreacted capricum gives an excellent foaming solution in water.



  Example 15.



   To 5.08 parts of an aqueous solution containing 0.01 mol
 EMI22.2
 Of sodium salt of 11-but-Tltl, -Urine, 4.26 parts (0.015%) of stearic acid and 0.12 part (0.002 mole) of boric acid are added. The suspension is heated in a test tube
 EMI22.3
 100 0 under vacuum, until almost all of the water is removed. The tube is then placed in an oil bath set at 280 C. The contents of the tube are placed under the vacuum of a water pump (absolute pressure of 20 to 30 mm of mercury) then it is heated in the bath for 10 minutes. Remove the tube from the bath; the weight of the product obtained is 6.209 parts.



   A second identical experiment is carried out, except that no boric acid catalyst is used. Analysis of the two products by the methylene blue method shows that the reaction product catalyzed with boric acid contains almost twice as much anionic surfactant as the product resulting from the reaction carried out in the absence of acid.

 <Desc / Clms Page number 23>

 
 EMI23.1
 boric.



  "" - :: '! oT1Y \ l e 16.



  A C, 1 Cy ', lVielî t - = ..: ye de c' -? t2'01: -'C: x Oß t'¯1e-r.-31:. 'i0ilt te of sodiwi we add 0.2 Q.1.Üvalent - = rc ::: the of 0010rhau0 of wood. The mixture is stirred at 260 0 for 3 hours under an absolute pressure of 25 mm of mercury. The product gives detergent solutions with low foaming power in water.



  Example 17.
 EMI23.2
 



  A 1.697 r; of crude I-ethyltaurine calcium salt (containing 0.01: nolÉCttle-ro,: T'r-thylt.arine calcium salt), in a test tube, 4.26 g (0.015 mole) are added. stearic acid and 0.12 (C, 002 mole) Doric acid. We heat
 EMI23.3
 for 10 minutes ::, elo.::1t:':lall're in an oil bath r6, '': 1é et 280 C while maintaining the contents of the tube under a vacuum of 20 to 30 mm of mercury of absolute pressure. The reaction product poses 5.498 g.



   A second experiment identical to the present is carried out. except that we do not use boric acid.



   Analysis of the two products by the methulene blue method shows that the boric acid catalyzed product contains about twice as much anionic surfactant as the uncatalyzed product. Example 18.
 EMI23.4
 



  At 0.01 Mole of 3 - ;: ztlyl; ': sodium zino-2.-butane-sul'onate (sodium salt of I: - ^ t.yl-; 1., 2.-di: n thyl .tc.urïne) in a test tube, 0.02 mole of dod cylnenzoicue acid and 0.002 mole of boric diacid are added. The mixture is heated in an oil bath at 250 C for 2 hours, retaining the contents of the tube.
 EMI23.5
 under one? ' absolute pressure of 20 to .35 1i = 1 of mercury. The product ,
 EMI23.6
 reaction gives a strong Y..101ss solution in water.



  : 8xe ::: y. On 19.



  At 0,01 ::: 010 of 3-iljr.rOt¯2¯bvtû, .. re-sli'On.atr in a tube

 <Desc / Clms Page number 24>

 
 EMI24.1
 test we add to, Q '5 ::' C <: '3 "! ..' Ciè..8 - = j..i, <#fi i:" c 3t C, QQ12 key of boric acid. C3 .: c: .c.uff. 3 tube p-at 15.: ...: Lt20 in oil bath kept 2µ'il. Z, in:.: Ai -. Te -. Iant the i = xtw <.R of the tub: .eus' a vacuum of e 2 ± 1. 5C: - ..: 2: ": ¯8: iei 'e -ii' 1.; Y #> <. Zi 1 o i .: il. Roiue rour facilitate e'ii = 1. ;; tion of i 'e *, #. + i = - =,;, ± "=. if 1 .; i <lc.;> tioii douue a solution seen 3S e- ..



  = -. ,: -, -. q 2 c Da: z5 un tuLe assai on -> lz; ce î, l- ± = (S, ± ?.: io: .e) of 2- .lJ, -.... .: ...:;,. VV-I..J 1; .. \ ........ ':; :: ;; c ",.: - L.;:' I ..;,:,. \ J, ut: ...... J - \ .. J¯¯v + iÉth3rltav, rine e.grge = se 24.3. ' .-ct-lve, 4.25 = (E, Q? -5 "0" of ni-2 acid, ul-1, aurine 1-4, .Ji- .. :: .. \, ; lJ ....... \ ..; ..,,., Lv -.J \ ...., V ...- .. / -L \ :; ..L \ ... t 01 "'".,. ,,:. "" 1. "uli sertéarigūe and 0.1µ .1 = Il'û, Ca2 ¯.iole) of boric acid. In the second tube we place the n31.:es "r'0 '::"' 1 of reagents, enough that one .l.1J .....- t, .i'-e the -. J.¯l¯¯ ,; ' ..joz ""; oL., - "....... VJ" "................." '' l, O.let boric acid. Qn cl; i #, '1.1 è both tubes .. .l. = - n # an oil bath cl 100 C until the water distillation is slow.



  Then we put the tubes in a bin,} '1 ::. 1;, i10 S tcur6'o.ture constant recite 1' µ1 C. C = a. c :: c: .1.1f:;: 'e the tubes in the imile bath for 2 hours under an absolute pressure of 5C zLt of mercury.



  The second tube turns black and shows a significant loss of weight. The product in the first tube 8;.:; T (: 0 co-: ¯lcur brown
 EMI24.2
 and contains 50µ1. in addition to before anionic surfactant than the product in the second tube.
 EMI24.3
 where I IT 1? 17 D I 1 J, <'T - r i.
 EMI24.4
 
 EMI24.5
 h1 0C pr.égar> tioré 'eC + .tàii <t' s, # oe14.e; <, és.i, a.ctéProcess for the preparation of esters and 81ides, characterized in that Ch.iiu , ± 'e 1, a temperature of 2CO?. J2Q 'i and under a pressure 1 ±: ùàI'ïEà1 e "1;.' Il '% igiio: 1 - atmospheric, iii-ic r) ress -'- oii -....- 1 .. -'- '11 --- t .....

   Jo. h.lJ: "'" "in the presence of a ccter-ant compound .1 ,,: boron co ..-' .. e catalyst, ei-i pr (::: Sellce ........ , ........'- J "" '' '' '' '... v ", Js-¯ ...... U J ....... G Vf¯ .. .U ........ J.ú -'- "1,2 a la, o Tfloles of a carboylic acid with at least 1,2 atoms 10,0 -orles ¯ ...-. .......... -.J> ¯..¯U> wJJo.-4./ c .... f C ::: .. \, o1, ..... Çl .. .......... carbon, selected from the group consisting of aliphatic and alkyl carboxylic acids, with -.- iole of an alhane-sulfo.iiq -.- e acid salt selected 1. # ¯Il ± the class consisting of C "'5 -?' - responding to the following òr-. -The following:

   

 <Desc / Clms Page number 25>

 
 EMI25.1
 where R represents a member selected from the group consisting of hydrogen and lower alkyl groups, R1 represents a number selected from the group consisting of hydrogen and a hydrocarbon radical having 1 to 20 carbon atoms, and M represents a salt-forming group selected from the class consisting of: alkali metals and alkaline earth metals.



   2. - The method of claim 1, characterized in that due the alkanesulfonic acid salt is the sodium salt of taurine:
3. - Method according to claim 1, characterized in that the alkanesulfonic acid salt is the sodium salt of N-methyltaurine.



   4. A method according to claim 1, characterized in that the alkanesulfonic acid salt is the sodium salt of N-ethyltaurine.



   5. - Process according to claim 1, characterized in that the alkanesulfonic acid salt is the sodium salt of isethionic acid.



   G.- A method according to claim 1, characterized in that the alkanesulphonic acid salt is the sodium salt of 2-hydroxy-propanesulphonic acid.