BE655181A - - Google Patents

Description

  

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  * 'Process for the preparation of high molecular weight compounds containing poly (oxyalkylene) groups. "
It is known to react polyvalent ethers of [alpha] .ss-hydrochlorides or of glycidyl containing poly (oxalkylene) groups with ammonia or with monovalent amines, optionally in the presence of alkalis, to obtain [ still soluble alpha] ss-amino alcohols, which have a relatively low molecular weight and contain poly- (oxalkylene) groups or with polyvalent amines to obtain insoluble resins. Likewise, insoluble resins crosslinked in reacting polyvalent α-amino alcohols containing poly (oxalkylene) groups

   with polyvalent epoxies or ce.µ-

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 EMI2.1
 polyvalent hydrochlorides, in the presence of alkalis. In addition, have already described the preparation of still soluble high molecular weight polyvalent amines which contain poly- groups.
 EMI2.2
 (oxalkylenes) and which are free of hydroxyl groups, by reaction of polyvalent esters of compounds containing poly- (oxethylene) groups with ammonia and / or polyvalent primary amines, especially at high temperatures and in the absence of water.



   However, the applicant has found that it is possible to obtain
 EMI2.3
 high molecular weight aa3-hydrinos, which contain pcly- (oxalkylenes) groups and which constitute interesting new O1 compounds, as well as from these compounds α {3-amino..alcohols , by reacting epichlorohydrin, the dichlorohydrins of lycerol and / or polyvalent 4-p-hydrochlorides, optionally in the presence of water and / or solvents, with ammonia and / or hydrazine and / or sodium sulphide and / or 'compounds containing in their molecule at least two functions such as primary or secondary amino groups or phenolic or mercapto groups, in quantities which are insufficient for the total exchange of all chlorine atoms reagents present, in
 EMI2.4
 : ,,: "r-²m.:, $) 1f1 '":

  "at the mo18v. ùn -or all the parteJUltras réao% 1o <nels tt, together contain at least 40% of their total weight of groups, 1> <,. 'oly-toxalkylenes), in the presence of alkalis, at most up to 'at the i, i * <iaii6ation,. and, if necessary, by doing "the $, f! 1:' oduite, ::; ".; 1rt: if \ 'eS, to:! High molecular weight thus formed, which -cont: 1 .tain poly- (oxalkylene) groups and which still carry.



  ,,. roRps., 4 '<chlorhyci. & s ayes epichlorohydrin and / or iug, 1, ...



    'ààéÀ4'amÀÉniao and / or hydrazine and / or primary amines' and / u. ,, .. <-. =, ': -. h ...> i
 EMI2.5
 1 1 ¯1. aJ.ca.3.s.



  .....>. , ....... # <a1u xcàuàx.ne k 1 e * ààK. bzz ru: ui, will t lgquel,> Ijm
 EMI2.6
 or all of the reaction partners together must contain dh3 poly (oxalkylene) groups in an amount corresponding to E1.t (t) '"t', minus! s0% of the quantity of their weight, the QUantitf5? QUiSQ s! .. iÎW'i.²j

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 poly- (oxalkylene) groups may be contained a) either only in the components of [alpha] ss-chlorhydri- es, b) or only in the components bearing amino, phenolic or mercapto groups, c) or both in the two reaction partners.



   The minimum quantity of poly (oxalkylene) groups required (in g) is given by the expression: 0.4 x sum of the weights of the reaction partners (in g).



   The molecular weights of the reaction partners containing poly (oxalkylene) groups should be in the range of 250 to about 12,000, preferably 300 to 6,000.



   In case a), the a.p-chlorohydrins which can be used, bearing poly- (oxalkylene) groups, must contain at least two a.p-chlorohydrin radicals.



   These compounds can be obtained, for example, from [alpha] ss-epoxy halohydrins with compounds which are able to react with them in the presence of Friedel and Crafts catalysts and which contain, in their molecule, au at least two hydroxyl groups and at least 40% poly (oxalkylene) groups. They can also be prepared according to the process described in French patent application P.V. N 991,070 of October 12, 1963 for: "High molecular weight compounds, usable in particular as adjuvants for textiles".

   The basic oxalkylates (polyoxyalkylation product) required for this purpose can be prepared by co- or polyaddition or by reaction, for example, of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, phenoxypropene oxide - instead of pure compounds, it is also possible to use mixtures of several alkylene oxides - in corresponding amounts with, for example, polyvalent alcohols, primary amines, polyvalent secondary amines, alkanolamines

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 primary or secondary, thiodiglycol, polyvalent mercaptans, polyvalent phenols, aminophenols, polyvalent carboxylic acids, and phenol-, hydroxy- acids,

   amino- or mercapto-carboxylic acids.



   In order to prepare the polyvalent [alpha] ss-hydrochlorides, it is also possible, for example, to react epichlorohydrin with known primary or secondary amines which do not have a high molecular weight and contain poly groups. - (oxalkylenes), or with corresponding alpha; .ss-amino alcohols or with polyvalent mercaptans containing poly (oxethylene) groups, for example those obtained by heating corresponding thiosulphates with mineral acids.

   To obtain suitable [alpha] ss-hydrochlorins, condensation products which contain several phenolic groups and which are obtained from mono- or polyvalent phenols, formaldehyde and oxethylated phenols can also be reacted. 'aromatic amines, with epichlorohydrin in the presence of alkalis.



   In addition to at least two [alpha] ss-chlorohydrin radicals and a sufficient quantity of poly (oxalkylene) groups, the suitable substances may also contain other functions, for example tertiary or quaternary amino groups and / or acidic groups, such as phosphonate, carboxyl, sulfonate, sulfone, carboxylam, carbamic ester, urea or dye radicals.



   As primary or secondary amines, polyvalent and devoid of poly (oxalkylene) groups, which can be reacted according to a) with the polyvalent [alpha] s-chlohydrins, it is possible to envisage, for example, aliphatic or aromatic polyvalent amines. , such as ethylene-diamine, diethylene-triamine, triethylene-tetramine, polyethylene-imines, 1 * 2-propylene diamine, dipropylene-triamine, hexamethylene-diamine, piperazine, phenylene-diamine, benzidine, 4.4'-diaminodiphenyl-methane or-propane, and naphthylene diamines.

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   As the aminophenols, there may be mentioned, for example, o-, m- and p-aminophenols, as well as the various amino-naphthols also containing more than one phenolic or amino group.



   Particularly suitable polyvalent phenols are, for example, hydroquinone, resorcinol, phloroglucinol, 4,4'-dihydroxy-diphenyl-propane, bis- or polyfunctional naphthols. Substances bearing mercapto groups and showing polyfunctional behavior with respect to [alpha] ss-chlorohydrines, can be, for example, sodium sulphide, aliphatic or aromatic polyvalent mercapto compounds, such as for example 1.2. -dimercapto-ethane or di-thiophenols, aminomercapto compounds such as 1-amino-2-mercapto-ethane, various mercapto-phenols and / or mercapto-naphthols.



   The compounds of all the classes mentioned above can also contain, besides at least two reactive groups, other functions, such as basic ter- 'flary or quaternary nitrogen atoms, azo groups, radicals. dyes, acidic radicals such as carboxyl, sulphonate, phosphonate, sulphone, carboxylamide or coarse carbamic esters.



   In case b), in which the required poly (oxalkylene) groups are found only in compounds which carry more than one primary or secondary amino group, or phenolic and / or mercapto groups, amines can be used, such as those obtainable from polyvalent esters of polyvalent oxalkylates and excess ammonia and / or primary amines or polyvalent ethers [alpha] ss-amino-hydroxy- or [alpha] ss-mercapto-hydroxy-propyl of substances containing poly- (oxalkylene) groups, which can be prepared from the corresponding propyl ethers of [alpha] ss-chlohydrin with ammonia and / or primary amines,

   or through the corresponding thiosulfuric esters. As substances containing poly- (oxalkylene) groups and several phenolic groups, the products

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 of condensation already mentioned and obtained from polyvalent phenols, formaldehyde and oxyethylates of phenols or aromatic amines.



   The polyvalent [alpha] ss-hydrochlorines and devoid of polyoxallene groups, which can be reacted according to b) with these compounds, in addition to epichlorohydrin and glycerol dichlorohydrins can be obtained from polyalcools aliphatics, such as ethylene glycol, glycerol, trimethylol-propane, triethanolamine, pentaerythritol, sorbitol, polyglycerols and at least 2 moles of epichlorhydrin, in the presence of Friedel-Crafts catalysts, or from primary or secondary polyamines, such as ethylene-diamine, 1.2-propylene-diamine, diethylene-triamine, 1.5-naphthylene-diamine, 4.4'-diamio-diphenyl-methane, o -, m- and p-aminophenols, polyphenols, such as 4.4'-dihydroxy-diphenylpropane, polymercaptans,

   aminomercaptan or mercapto-phenols, which is reacted with at least 2 moles of epichlorohydrin. All these [alpha] ss-chlohydrins can, on the other hand, additionally carry other functional groups.



   In case c), it is possible to react with each other, on the one hand, the polh- [alpha] ss-hydrochlorides containing polyoxalkylene residues described under a) and, on the other hand, the substances described under b), containing poly "(oxalkylene) groups and several primary and / or secondary, phenolic and./or mercapto amino groups, in the presence of alkalis, such as sodium or potassium hydroxides, sodium carbonate, methylate sodium, etc ***
Since polyglycidyl compounds easily pass to the insoluble state by reacting with polyfunctional compounds carrying amino, phenolic and / or mercapto groups,

   the proportion of added alkali is of particular importance during the formation of intermediate products to

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 high molecular weight, still containing hydrochloride groups. Only a judicious dosage of the alkali agents allows only a fraction of the epoxy groups which can theoretically be obtained: are produced and continue to react, in such a way that it is possible to capture intermediates of high molecular weight and still soluble . The proportion between the added alkali or reactive epoxy groups which result from this addition and the amino, phenolic or mercapto groups which react with the latter can vary from 0.5 to 2.0.



   When all of the reaction partners are water soluble, the reaction is preferably carried out in water. When one or both of the components are not soluble in water, it is advantageous to add a hydrophilic solubilizing agent, for example of the type of low molecular weight aliphatic mono- or polyalcohols, ketones. or ethers, such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, polyethylene glycols, triethanol amine, tetrahydrofuran. dioxane, methyl ethyl ketone,. acetone, dimethyl sulfoxide, dimethyl formamide, methylpyrrolidone, etc. It is however also possible to use hydrophobic solvents, such as aliphatic or aromatic hydrocarbons, halogenated or not, esters, ethers, etc.

   In many cases, the reaction can also take place in the absence of solvent or water.



   It is possible to bring the two partners together first! reactions and initiate the reaction by adding the calculated amount of alkali. It is also possible to first mix one of the components with the alkali and then add the second component. However, care must always be taken to ensure that the reaction does not lead to insoluble resins before all the necessary substances are present.



   But, even when all the components, partners,

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 Reactions and alkali are combined, the reaction conditions must be chosen: concentration, temperature, proportions of reaction partners, quantity of alkali, so as to always remain in control of the reaction. To follow the evolution of the condensation, the measurements of cloud points of the mixtures of the product of the reaction with, for example, solutions of salts such as sodium chloride, sodium sulphate, etc., and / or viscosity determinations, for example by measuring resistance to agitation, have proved successful.

   Once the desired degree of condensation has been reached or when resinification begins to occur, which in most cases can be recognized by a marked increase in viscosity, the reaction should be stopped immediately. of crosslinking, preferably by lowering the pH below 7, for example by adding dilute hydrochloric acid (alcoholic) and lowering the temperature.



   In some cases there is an advantage to be determined by means of testing? preliminary conditions of the reaction and, above all, the temperature. The most favorable reaction times, for which the progress of the condensation can be easily monitored, are, for example, from about 1 to 20 hours. It is only at the end of this time that the resinification must begin, for example. As a result, the temperatures are between about 1 and 140. It is advantageous to operate between approximately
20 and 80.



   The new high molecular weight intermediates, still containing [alpha] .ss-chlohydiene residues obtainable by controlled precondensation, are soluble in water and / or in hydrosilic organic solvents. The addition of an alkali causes their crosslinking, giving in most cases insoluble resins, and they can be used as intermediate products or as adjuvants in the textile industry.

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   By reacting with additional amounts of epichlohydrin, preferably at a pH of approximately 7.5 to 11.5, under mild reaction conditions, for example 4 temperatures of about 10 to 60, it is possible to introduce other [alpha] .ss-chlohydrin groups in high molecular weight "intermediates" already containing [alpha], ss-chlohydrin groups. In this way, in a large number of cases, the crosslinking power of the products is further increased.



   In order to convert into high molecular weight substances containing poly- (oxalkylene) and [alpha] .ss-amino-hydroxyl groups, the above-mentioned intermediates still containing [alpha] .ss-hydrochloride groups or the products of reaction thereof with additional amounts of epichlorohydrin, it is necessary to treat them with ammonia, hydrazine (hydrate) 'and / or primary and / or secondary amines, and with an amount of at least sufficient alkali so that all the [alpha] .ss-hydrochloride groups still present are transformed into [alpha], ss-amino-hydroxyl residues, via the epoxy groups which are truly capable of reacting with the bases organic.

   In order to avoid the occurrence of other crosslinking reactions resulting in the formation of insoluble resinous fractions, it is necessary, in most cases, for there to be an excess, in particular of ammonia, hydrazine (hydrate), primary amines and / or polyvalent amines. Once again, the most favorable reaction temperature has been found to be between 20 'and 80.



   The excess ammonia, hydrazine (hydrate) or amines can be removed, depending on the nature of the base, advantageously by blowing, by distillation, optionally under reduced pressure or by using steam. of water, by salting-out and / or by separation by means of solvents. As a result, the amines,

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 primary or secondary, which can also carry other functions, which can be easily separated, are particularly
 EMI10.1
 appropriate.

   The non-volatile, high molecular weight.-Amino alcohols remaining in the residue, containing polyo residues. xalkylenes, having primary, secondary or tertiary amino groups, are also all soluble in water and / or in hydrophilic solvents, and they can find application as adjuvants in the textile industry.

   In particular, when they contain several primary or secondary amino groups, they also represent useful intermediates or crosslinking agents, since they can be modified in different ways by means of a large number of functional substances, capable of reacting with primary or secondary amino groups and can be converted by means of the corresponding polyfunctional compounds into insoluble crosslinked resins.



   The following examples are intended to illustrate the present invention; they cannot in any way limit it. the scope.



    EXAMPLE 1:
 EMI10.2
 From 600 g of polyethylene glycol, with a molecular weight of 600, is prepared, by reacting 223 g of 70-80 epichlorohydrin, aveq as catalyst, 5 g of boron trifluoride etherate, a bischlorhydrin ether which is trans-
 EMI10.3
 form, at a temperature of 2 to 30, by means of 284 g of 24% aqueous ammonia with the addition of 276 g of a 33% sodium hydroxide solution, followed by subsequent removal by distillation of the 'excess ammonia, in a 40% solution which contains essential
 EMI10.4
 ¯>; ¯ E-'zt le: compound of formula ...,: ../ ::: {\ - .: 't \ -1 n $! J, .. = oxj,>:

   ,>,; x.; :: â:;:. Ha .. c2.cxo.c, We mix bzz0, g of a 40% solution of the diamine thus prepared with 320 g of bischlorhydrin ether at 100 %

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      described above and slowly dropwise introduced into the mixture, at a temperature of 25 to 30, a rolation of 35 g of caustic soda in 50 ml of water. Stirring is continued, at 25-30, until the contents of the container have become so viscous that they rise up the agitator. With the immediate addition of about 18% hydrochloric acid, the pH is adjusted to 6 by means of a glass electrode and the product is diluted with water to a concentration of 30-40%.

   An aqueous, viscous and practically colorless solution is obtained.



   535 g of a 40% solution of the polyamine still containing [alpha] .ss-chlohydrin groups are mixed with 720 ml of 24% aqueous ammonia. A solution of 24 g of caustic soda in 60 ml of water was added dropwise over 30 minutes at room temperature, then the mixture was continued to stir for 1 hour at 60. Then separated by distillation under near-! reduction, water and excess ammonia, until no ammoniacal odor is noticed. In this way, a solution of about 24 to 40% of a polyfunctional high molecular weight amino-polyethylene glycol is obtained.



   Similar products are obtained if, instead of starting from a polyethylene glycol having an average molecular weight of 600, one starts from polyethylene glycols having an average molecular weight of 300, 400, 1,000, 2,000 or 6,000, react until the beginning of resinification the various bis ... hydrochlorinic ethers with the bis (amino-alcohols) which can be obtained from them, and that they are converted by means of ammonia into the corresponding poly (ap-amino-alcohols).



    EXAMPLE 2:
10 g of 24% ammonia is added to a solution in 60 ml of water of 80.3 g of a reaction product of one mole of polyethylene glycol, having a molecular weight of 600, with 2, 2 moles of epichlorohydrin. Then introduced dropwise, at a temperature of 30 to 40, 8.8 g of caustic soda in solution.

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 tion in 15 ml of water. After stirring for about 3 to about 40 hours, the contents of the container begin to rise up the stirrer. By immediate addition of hydrochloric acid, the pH is adjusted to 4.0 by means of a glass electrode. 187 g of about 40% viscous and almost colorless solution are obtained.



   Heated to 60 60 g thereof with 25 g of monoethanolamine, then 1.2 g of a 33% sodium hydroxide solution is added and the mixture is stirred for 1 hour at 60. 1 excess of amino alcohol under reduced pressure (water pump) with continuous addition of water. About 50% solution of the poly- (α-amino alcohol) remains.



  EXAMPLE 3;
The pH of 249 g of an approximately 40% solution of the intermediate product in accordance with Example 1, containing
 EMI12.1
 again α-hydrochloride groups, based on a polyethylene glycol having a molecular weight close to 2,000, 15.0 g of ethylene di-amine are added thereto, then the mixture is brought dropwise to 50 , a solution of 2.3 g of caustic soda in 5 ml of water. Stirring of the reaction mixture is continued for 1 hour at the same temperature. The excess ethylene diamine is removed under reduced pressure with the addition of water. 229 g of a solution are obtained
 EMI12.2
 tion of about 40% poly (a.s-amino-alcohol).



   An analogous product is obtained by replacing the ethylenediamine with 11.5 g of aniline and by using the same operating procedure; roof.



    EXAMPLE 4:
191.0 g of a 40% aqueous solution, essentially containing the compound of formula
 EMI12.3
 NX22 "22Y13" 2 '22

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 with a solution of 26.2 g of the reaction product of one mole
 EMI13.1
 of glycerol with 3 moles of epichlorohydrin in 50 ml of isopropanol, then added dropwise to the mixture, to 40 × 9 8 # 0 of caustic soda dissolved in 10 ml of water. After condensa- '
 EMI13.2
 At 400 for about 1.5 hours the contents of the container rise up the stirrer. The pH is then adjusted to 5 using hydrochloric acid.

   Heated to 60 85 g of the solution
 EMI13.3
 at 28 thus obtained with 100 g of a 40% methylamine solution, then 7 g of a sodium hydroxide solution at 33 are added dropwise. After 1 hour of additional stirring and separation by distillation, with the addition of water , from the excess amine we obtain
 EMI13.4
 a colorless 33% solution of the corresponding poly (a.-amino-alcohol).



  EXAMPLE 5
 EMI13.5
 Heated to 60 ° with 20 g of diethylamine, 185 g of a rez0% solution of an intermediate product, still containing c-ch2orhydrin groups, obtained as described in Example 1 from a polyethylene glycol having a molecular weight close to 1000, and, after the dropwise addition of a solution of 5.5 g of caustic soda in 15 ml of water, stirring is continued for 1 hour at 60 . The excess amine is removed under reduced pressure by introducing dropwise water,
 EMI13.6
 so that a solution of about 40 µ of the poly- (a.pamino-alcohol) remains.



  EXAMPLE 6; A solution of 1-
 EMI13.7
 anereapto-2-amino-ethane, prepared from 2.4 g of the compound of the formula
 EMI13.8
 

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 and a solution of 0.9 g of caustic soda in 10 ml of water, at the same time as 10 g of 50% sodium hydroxide solution so that the pH of the reaction mixture remains in the region of 9 - 10, at
 EMI14.1
 200 g of a 40% solution of an a.-hydrochloride polyether prepared from one mole of a triethanolamine oxethoxide having a molecular weight of 1,500 and 5 moles of epichlorhydri-
 EMI14.2
 ne, obtained with a boron trifluoride catalyst,

   precondoned by post-heating up to the limit of water solubility. After about 90 minutes of continuous post-condensation at 60, the contents of the vessel begin to rise up the agitator, indicating the start of resinification. The pH is adjusted to 5.0 by the addition of hydrochloric acid and thus a solution is obtained.
 EMI14.3
 tion at 35; 5.

   For the conversion to poly- (a.-amino-alcohol) t, the pH is adjusted to 7 by means of sodium hydroxide solution and 73 g of diethylamine are added to the solution. A solution of 5 g of caustic soda in 10 ml of water is then added dropwise at 30. Stirring is continued for 1 hour at 50 and the mixture is separated by distillation, with suction with a water pump and adding drip water, diethylamine in excess, until the real du no longer smells of amine.

   There remains a solution
 EMI14.4
 aqueous, ent, 4.rvn 39 in * 1 !! El, 1PItl: 34 g of an adduct obtained are mixed with. nioycen and a tri boron fluoride catalyst, from one mole s.ûxypyopyl4t having a molecular weight of 6'lql and
 EMI14.5
 \ "1tes epichlorohydrin, containing virtually no 'XTt.' .5 .i'Ï epoxy, with 0 m of isopropanol and 15.2 g of a ce * ¯p-amino- w:,> ,.,,; .âos obtained from 1 mole of tripropylene glycol, from 2.2 @
 EMI14.6
 1, iie and excess aqueous ammonia with> '9lÉs' to be heated, the>'; cp "" beyond to JO.

   A solution of 4 g of caustic soda in 100 ml of methanol is then added dropwise, stirring is continued for 1 hour at 50, after which the alcohols are removed by '

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 distillation with water pump suction. After a heater
 EMI15.1
 subsequent fage of a haui'e, 0 ,,, lra. u. ° t, âaot, crnre. begins to rise along the stirrer, the pH is adjusted to 7 using a 10% solution of hydrochloric acid in methanol.
 EMI15.2
 Is then introduced at a temperature of 40 to 10.4 m, gaseous to saturation, while providing dropwise a solution of 4 g of caustic soda in 100 ml of methanol. The mixture is then heated to 50 and stirring is continued for.



  1 hour. The excess ammonia is removed under reduced pressure and the reaction product, which is not soluble in water, is taken up in isopropanol.



    EXAMPLE 8
200 g of the solution are mixed at room temperature.
 EMI15.3
 tion at about 40 l of the polyether-ap-hydrochloride described in Example 6 with a solution in 10 ml of water of 7.2 g of a commercial sodium sulphide, containing water of crystallization, and heat to 50, after adjusting the pH to 9. After about 30 minutes, resinification begins to occur.



  From this point on, the pH of the reaction mixture is adjusted to 7 using approximately 18% hydrochloric acid. To 143 g of the 28% solution thus obtained, 44 g of diethylamine is added, and the mixture is heated to 50 while adding dropwise a solution of 2.8 g of caustic soda in 5 ml of water. After continuing to stir for 1 hour, the excess amine is separated off by distillation under reduced pressure with the addition of water.
 EMI15.4
 



  An approximately 31% solution of the corresponding poly (ce S-amino alcohol) remains.



    . EXAMPLE 9:
One mole of a polyethylene glycol having a molecular weight of 600 is taken up in 80 ml of water in 80.3 g of the product of the reaction with 2.2 moles of epichlorohydrin, then, after addition of 8 , 2 g of diethylene triamine, is added dropwise to

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 drop, at 20 ', a solution of 8.8 g of caustic soda in 15 ml of water. After 90 minutes of stirring at 25-30, the reaction mixture begins to become very viscous. Hydrochloric acid at% is then added until the pH drops to 4, and a 36% solution is obtained.



   88 g of this solution and 20 g of benzylamine are mixed at room temperature, then 8 g of a 33% sodium hydroxide solution are added dropwise to this mixture. The mixture is continued to stir at room temperature for 1 hour, then the excess amine is removed by distillation under reduced pressure with the addition of water. There is a 24% solution left.



  EXAMPLE 10
In a mixture of 112 g of the reaction product of a; polyethylene glycol having a molecular weight of 600 with 2.2 moles of epichlorohydrin, having an epoxy residue content practically
 EMI16.1
 completely zero, and 23.8 g of 1 ..- diar.no-diphdnylmdthane are introduced dropwise at 50.2.8 g of caustic soda dissolved in 15 ml of water. After 4 hours of stirring at 80, the reaction mixture becomes highly viscous and its pH is then adjusted to 5.5 using hydrochloric acid. The solution is 38%.



   As the free base is insoluble in water, the viscous substance which precipitates is dissolved in dioxane when the pH is adjusted to 7. After addition of 50 g of diethylamine, a mixture of 50 g is added dropwise at 50. solution of 11.2 g of caustic soda in 15 ml of water and, after continuing stirring for 1 hour, the excess amine is removed by distillation under reduced pressure. The amine produced is obtained at 77%; it is not soluble in water, but can however be taken up in acids and in hydrophilic solvents.



  EXAMPLE 11:
To 88.3 g of a condensation product of one mole of polyethylene glycol having a molecular weight of 600 with 2.2

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 moles of epichlorohydrin are added dropwise, at 50, a solution of 18.2 g of 4,4'-dihydroxy-diphenylpropane and 6.4 g of caustic soda in 70 ml of water, and sufficient addition is added. - sodium hydroxide solution so that the pH remains constantly at 11.



  After stirring for about 4 hours at 80 ', the product becomes highly viscous, so the pH is adjusted to 7 with 18% acid, hydrochloric acid, and 100 ml of hydrochloric acid are added at room temperature. 24% ammonia. 6.4 g of caustic soda dissolved in 15 ml of water are then added dropwise at 50-60, after which stirring is continued for 1 hour. The excess ammonia is removed by distillation under reduced pressure. A colorless and highly viscous residue remains, at about 77%, which is insoluble in water, sparingly soluble in acid; dilute acetic, but which is on the other hand easily soluble in dioxane.



  EXAMPLE 12
100 g of a 40% solution of the intermediate, still containing [alpha] .ss-hydrochloride groups, described in Example 1, is mixed with 40 g of 80% hydrazine hydrate. 50.10 ml of a 2N sodium hydroxide solution are introduced dropwise, then stirring is continued for 15 minutes. There is then a separation into two layers. The highly viscous phase containing the poly - ([alpha] .ss-amino-alcohol) weighs 76 g; it is taken up in 100 g of water.



    EXAMPLE 13:
283.6 g of the reaction product of aniline are heated to 80 under a nitrogen atmosphere with 14 moles of ethylene oxide, 37.6 g of phenol and 86.6 g of a. 30% formaldehyde solution. 82.6 g of 64% sulfuric acid was added dropwise over 2 minutes, then the mixture was continued to stir for
1 hour to 100.



   To the condensation product thus obtained, containing in its molecule several phenolic and poly-oxethylene groups,

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 270 ml of water are added and the pH is adjusted to 10 by means of 130 g of 33% sodium hydroxide solution. The lower layer of saline solution is separated in a separatory funnel. 30.74.1 g of the upper phase, at approximately 75%, are mixed with 250 g of the 40% solution of the polyether [alpha] .ss-hydrochloride described in Examples 6 and 8 and 25 ml of lye. of 2N soda. The water is then removed from the mixture by distillation under reduced pressure, after which said mixture is heated.

   At 130, the reaction product begins to move up the stirrer. The condensation is stopped and the pH adjusted to 4 by immediate addition of 30 ml of 2N hydrochloric acid. The highly viscous solution thus obtained is about 79%. 83 g of this solution i are mixed with 109.5 ml of water, 25 g of diethylamine and 12.5 g of 2N sodium hydroxide solution, the mixture is heated to 60 and maintained at this temperature for 10 minutes. The excess amine is then removed by entrainment with water vapor under reduced pressure with the addition of water. About 40% solution of the poly - ([alpha] .ss-aminoalcohol) remains.



    EXAMPLE 14:
50.3 g of the reaction product of one mole of polyethylene glycol having a molecular weight of 300 are mixed, and
2.2 moles of epichlorohydrin, with 127.0 g of a 40% solution of the product of the action of excess ammonia and alkali on the above-mentioned condensation product, containing about two groups [alpha] .ss-chlohydriqnes, then is added dropwise to the mixture at room temperature, 8.8 g of caustic soda dissolved in 15 ml of water. Immediately after the end of the addition of the lye, a mixture of 2 ml of the reaction product with 9 ml of a 10% sodium chloride solution remains transparent even if heated to 100.

   After 30 minutes of stirring at 30, a cloud point can already be determined.



   This point is 86; after a total of 60 minutes, it drops to 76, after 90 minutes, to 74 and after 120 minutes.

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 tes, at 72-73. With further stirring for 30 minutes at 40, a cloud point of 70 is observed and the reaction mixture begins to rise up the stirrer. 150 ml of a solution are immediately added. 24% ammonia and a solution of 8.8 g of caustic soda in 15 ml of eua is then introduced dropwise. Stirring is continued for 1 hour at 50%, then the excess ammonia is removed with distillation under reduced pressure with the addition of water to give an approximately 26% solution of the poly - ([alpha] ss-amino-alcohol).



  ¯EXAMPLE¯¯13:
52.8 g of a 100% [alpha] .ss-amino alcohol obtained by means of excess ammonia and alkali from the polyether [alpha] are dissolved in 50 ml of isopropanol. ss-hydrochlorinic described in Example 6, then added dropwise, at 50, first 4.2 g of epichlorohydrin, and then 2 g of caustic soda dissolved in 5 ml of water. After continuing to stir for 1 hour at
50, the alcohol is removed by distillation under reduced pressure, the same amount of water is added and the mixture is further stirred for about
1 hour to 50 minutes, until the contents of the container have become highly viscous.

   Then immediately added, without isolating the high molecular weight intermediate product, 100 ml of an aqueous solution of methylamine at about 40%, then again 2 g of caustic soda dissolved in 5 ml of water. After another hour of stirring at 50, the excess amine is removed by distillation under reduced pressure with the addition of water. An about 35% solution of the corresponding high molecular weight poly - ([alpha] .ss-amino alcohol) is obtained.



   EXAMPLE 16:
56.6 g of the condensation product described in Example 7, obtained from one mole of oxypropylated glycerol, having a molecular weight of 670, and 3.3 moles of epichlorhydrin, are stirred with 80 ml. of isopropanol, 4.8 g of piperazine dissolved in 45 ml of isopropanol are added, and the mixture is introduced dropwise

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 drop at 50 in the mixture 6 g of caustic soda dissolved in 50 ml of methanol. After one hour, the alcohols are distilled off under reduced pressure and the product is maintained for 4 hours at 120. A further 1.7 g of piperazine dissolved in 10 ml of isopropanol are then added to 50 and, after distilling off the alcohol, stirring is continued for 2 hours at 120.

   The reaction mixture thus becomes viscous at 50. Alons are added 100 g of n-butylamine and introduced
6 g of caustic soda dissolved in 50 ml of methanol, stirring is continued for 1 hour, then the excess amine is removed by distillation under reduced pressure. A 100% poly- ([alpha] .ss-amino alcohol) is obtained, which is very viscous, is insoluble in water, but gives transparent solutions with, for example, dilute aqueous acetic acid, l ethanol, butyl acetate or benzene.



   EXAMPLE 17:
Under a stream of nitrogen and while distilling off the water produced by the reaction, 140 g of dipropylene-triamine, 139 g of azelaic acid and 166 g of dimerized oleic acid are stirred for 3 hours. and a half to 150 and for 1 hour
3/4 to 165 - 175, It separates in all by distillation 34 ml of water. Add to 120, 50 ml of water and, at 90 and slowly,
360 ml of ethanol. This gives about a 50% solution.



   26 g of this alcoholic aqueous solution are mixed with
50% of the condensation product obtained, containing several groups; pes amino and amido, with 20 g of a condensation product
100%, obtained from one mole of a polyethylene glycol having a molecular weight of 600, and 2.2 moles of epichlorohydrin, and
25 g of isopropanol. It is introduced dropwise over 2 minutes, to '
50, in this mixture, '4.7 g of a 33% sodium hydroxide solution, then heated under reflux for 34 minutes. At the end of this time, the contents of the container rise along the agitator.

   The formation of insoluble resinous portions was prevented and the pl 'was adjusted to between 6.5 and 7.0 by immediate addition of chlorine acid.

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 18% hydric. Then 60 g of stearylamine, 100 ml of isopropanol and 2.5 g of 33% sodium hydroxide solution are added, the mixture is stirred for 90 minutes at 50 minutes, another 1 g of 33% sodium hydroxide solution is added and stirring is continued for 35 minutes at 50 at a pH ranging from 10.5 to 11 (measured on Special Merck indicator paper soaked in water).

   The isopropanol is then removed under reduced pressure (water pump) and the excess stearylamine is removed by shaking repeatedly, at about 60, with a gasoline fraction boiling between 60 and 95. The residue is insoluble in water, but forms, with a mixture consisting of 100 g of dioxane, 100 g of acetic acid and 20 g of water, a very viscous solution slightly colored yellow, which can be obtained. dilute without limitation with a 2: 1 mixture of dioxane and water.



    EXAMPLE 18:
170 g of a 40% solution of the intermediate product according to Example 1, still containing primary or secondary amino groups and [alpha] .ss-chlohydrin groups, are mixed at room temperature with 170 ml of water, and the pH is adjusted to 10.0.



   Then 8.3 g of epichlorohydrin are added dropwise at 25 to 30 over three minutes, and the mixture is further stirred at 25 to 30 and at a pH of r. from 9.9 to 10.2. The whole is then separated into two portions.



   Using 2N hydrochloric acid, the pH of one of the halves is brought to 4.0. A colorless solution of about 29% of a high molecular weight [alpha] .ss-chlorohydrin is obtained, the [alpha] .ss-chlohydrin content of which is increased relative to the starting material.



   At a temperature of 25 to 30, 24 g of a 24% ammonia solution are added to the other half and 12 g of 33% sodium hydroxide solution are added dropwise over 5 minutes. The pH rises under these conditions to about 13. Stirring is continued for a further 40 minutes to about 40, then the ammonia is removed by

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 excess by distillation under reduced pressure with the addition of dropwise water. The remaining solution of the corresponding [alpha] .ss-amino alcohol is about 32%.



    EXAMPLE 19:
64.5 g of a condensation product having a practically zero content of epoxy groups, obtained in the presence of boron triflucride etherate from a poly-1,2-n-butylene- are taken up in 50 ml of dioxane. glycol having an average molecular weight of 1,000 and 3 moles of epichlorohydrin, 6.0 g of hexamethylene tetramine dissolved in 50 ml of dioxane are added, and the mixture is introduced dropwise at 50.4, 4 g of caustic soda dissolved in 45 ml of mathanol. After having . Stirring continued for 1 hour, the alcohols were distilled off under reduced pressure and the reaction mixture heated for 3 hours at 120.

   At the end of this time, the contents of the container begin to rise up the agitator. The mixture is cooled to 50, 100 ml of isopropanol are added and 4.6 g of epichlorohydrin at pH 9-10 (measured on special Marck indicator paper soaked in water) are introduced dropwise.



   Stirring is continued for 1 hour and the alcohol is removed by distillation under reduced pressure. The highly viscous residue is taken up in 70 ml of isopropanol, the pH is adjusted to 7 using alcoholic hydrochloric acid and the mixture is separated. sodium chloride which precipitated. After addition of 58.5 g of NN-diethyl-ethylene-diamine and 4.4 g of caustic soda dissolved in 48 ml of methanol, the mixture is stirred for 1 hour at 50 and the excess amine is removed by distillation. under reduced pressure with water supply. Sufficient isopropanol is added to the residue to obtain a viscous solution of about 40%.



  EXAMPLE 20;
To 100 g of the 40% solution of the high molecular weight intermediate product according to Example 1, 1.9 g of 80% hydrazine hydrate and 7.2 g of a sodium hydroxide solution are added. soda

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33%. After stirring for 1 hour at 50. the excess of amine is removed by evaporation under reduced pressure with the addition of water.



   An approximately 30% solution of the poly - ([alpha] .ss-amino-alcohol) remains. corresponding.

 

Claims (1)

ABSTRACT The present invention comprises in particular: A process for the preparation of new high molecular weight [alpha] .ss-hydrochlorides containing poly-oxalkylene groups, as well as. [alpha] .ss-amino-alcohols obtainable from said compounds, process according to which one reacts .between them, optionally in the presence of water and / or solvents, epichlorohydrin, glycerol dichlorohydrins and / or poly- (ap-chlorohydrins), with amounts insufficient to cause an integral exchange of all the reactive chlorine atoms present, of ammonia and / or of hydrazine and / or of sodium sulfide and / or of compounds having at least 2 free functions of the type of primary or secondary amino groups, phenolic or mercapto, one of the reaction partners at least or all, {\ of said partners having to contain polyoxalkylene residues in an amount of at least 40% of the sum of their weight, in the presence of alkali, throughout more until the start of resinification, and, optionally, the epichlorohydrin and / or excess ammonia and / or primary or secondary amines are still allowed to act in the presence of alkali on the products high molecular weight intermediates thus obtained, bearing polyoxalkylene groups and also α-hydrochloride groups.