EP0093361B1 - Quaternary alkoxyalkyl-ammonium compounds, preparation and use thereof - Google Patents

Abstract

Novel quaternary alkoxyalkylammonium compounds of the formula 1 <IMAGE> in which R denotes C8-C20-, preferably C12-C18-, alkyl or C8-C20-, preferably C12-C18-, alkenyl, R1, R'1 and R''1, which can be identical or different, denote methyl, ethyl or benzyl and at least one of the radicals R1, R'1 and R''1 denotes a group of the formula -(CSH2SO)xH, R2 and R3, which can be identical or different, denote methyl, ethyl or benzyl, a denotes 0 or 1, b denotes 0 or 1, of which either a or b has to be=1, m denotes 0 or 1, n denotes 2 or 3, p denotes 1, 2 or 3, S denotes 2 or 3, x denotes 1, 2, 3 or 4, and A denotes a halide, methosulfate, ethosulfate or methophosphate ion. These compounds are used as retarders and leveling agents in the dyeing of polyacrylonitrile and acid-modified polyester fibers.

Description

It is known that the coloring of polyacrylonitrile fibers and of anionically modified polyester fibers with cationic or basic dyes depends to a large extent on the speed with which the dyes are drawn onto the fiber.

It is also known that in these cases, uniform colorations are usually only obtained when they are carried out in the presence of leveling agents known under the term "retarders". In fact, in the absence of retarders, the dye uptake (or the rate of dyeing) is very rapid and consequently irregular. The use of retarders makes it possible to slow down the rate at which the dyes are drawn up, which results in more regular and uniform coloring.

A distinction is usually made between permanent and temporary retarders. The permanent retarders are usually very effective. In competition with the dyes, they bond firmly to the fibers. They are therefore only used in low concentrations and their amount must be calculated precisely by taking into account the saturation factors of the dyes and the fiber (true technical equivalents). This type of retarders has the disadvantage that, in the event of an overdose, it does not allow the dye liquor to be completely depleted in the bath, or that it makes it difficult to over-dye already-dyed goods made from polyacrylonitrile fibers or anionically modified polyester fibers in cases in which a further, subsequent dyeing is necessary is. The aforementioned permanent retarders generally consist of quaternary ammonium salts, the best known of which is lauryldimethylbenzylammonium chloride.

The temporary retarders, on the other hand, consist of various products that have a less pronounced ionic charge than the aforementioned. Therefore, the temporary retarders connect to the fiber in a more labile manner. Their connection to the active groups of the fiber is such that they can be displaced by the dye, since this has more pronounced ionic properties. In other words, in contrast to the permanent retarders, the temporary retarders block the active centers of the fiber to a lesser extent. As is known, the temporary retarders are used in relatively high concentrations and cannot guarantee complete uniformity of the coloring under all application conditions.

The task was therefore to develop new products that simultaneously combine the advantages of the two types of retarders without having their disadvantages.

worin R C₈-C₂₀-, vorzugsweise C₁₂-C₁₈-Alkyl oder C₈-C₂₀-, vorzugsweise C₁₂-C_1a-Alkenyl,

• R_l, R', und R"_i, die gleich oder verschieden sein können, Methyl, Ethyl oder Benzyl und mindestens einer der Reste R₁, R', und R"₁ eine Gruppe der Formel -(C_SH_2S0)_XH,
• R₂ und R₃, die gleich oder verschieden sein können, Methyl, Ethyl oder Benzyl,
• a 0 oder 1, b 0 oder 1, wobei entweder a oder b = 1 sein muß, m 0 oder 1, n 2 oder 3, p 1, 2 oder 3, s 2 oder 3, x 1,2,3 3 oder 4 und A ein Halogen-, Methosulfat-, Ethosulfat- oder Methophosphat-Ion bedeuten.

The invention thus relates to new quaternary alkoxyalkylammonium compounds of the formula 1

wherein RC ₈ -C ₂₀ -, preferably C ₁₂ -C ₁₈ alkyl or C ₈ -C ₂₀ -, preferably C ₁₂ -C _1a alkenyl,

• R ₁ , R ', and R " _i , which may be the same or different, methyl, ethyl or benzyl and at least one of the radicals R ₁ , R', and R" ₁ a group of the formula - (C _S H _2S 0) _X H,
• R ₂ and R ₃ , which may be the same or different, methyl, ethyl or benzyl,
• a 0 or 1, b 0 or 1, where either a or b must be 1, m 0 or 1, n 2 or 3, p 1, 2 or 3, s 2 or 3, x 1,2,3 3 or 4 and A represent a halogen, methosulfate, ethosulfate or methophosphate ion.

The following may be mentioned as alkyl groups under the meaning of R:

Decyl, undecyl- (1), undecyl- (4), dodecyl- (1), tridecyl- (1), tetradecyl- (1), tetradecyl- (6), pentadecyl- (1), hexadecyl- (8), Heptadecyl- (1), heptadecyl- (9), octadecyl- (1) or stearyl, monodecyl- (1), 5-propyl-decyl- (1), 3-propyltri-decyl- (1) and eicosyl. Examples of unsaturated aliphatic groups (C ₈ -C ₂₀ ) represented by R in the above formula are the following:

Decen (1) -yl, Decen- (9) -yl, Dodecen- (9) -yl (1), Hexadecen- (9) -yl (1), Octadecen- (6) -yl (1), Octadecen- (9) -yl (1) and octadecen (11) -yl (1). Preferred radicals R are: decyl, dodecyl- (1), tridecyl- (1), tetradecyl- (1), hexadecyl- (1), stearyl and decen- (1) -yl.

Also preferred are those radicals R which are derived from naturally occurring fats, such as, for example, tallow fatty alkyl, coconut fatty alkyl, soybean oil alkyl, palm oil alkyl or the like. Since these naturally occurring fats are mixtures of compounds with different chain lengths, the radical R in these cases is accordingly a mixture of alkyl or alkenyl groups with different chain lengths.

In the context of the present invention, the terms "product of formula (1)" include "Retarders and / or leveling agents of formula (1)", "Product of the present invention", and "Retarders and / or leveling agents of the present invention" both a single compound falling under formula (1) and a mixture of two or more compounds of formula (1), as can also be seen from the examples.

The retarders and / or leveling agents of the present invention are capable of blocking the fiber enough to guarantee normal dye uptake. At the same time, they are able to slowly detach from the fiber if there is an excess of dye in the dyeing liquor or an accidental overdosing of the retarder and / or leveling agent. The new retarder and / or leveling agent is used in the dyeing of polyacrylonitrile fibers and anionically modified polyester fibers by the methods which are generally known for permanent retarders.

The optimal amount of retarders and / or leveling agents to be added to the dye liquor is to be calculated by taking into account the saturation factors of the fiber to be dyed and the dyes used, as is generally known to the person skilled in the art in this field. If, in addition to the retarders and / or leveling agents of the formula 1, retarders of known type are also added to the process according to the present invention, these retarders should always be present in a smaller amount compared to the compounds according to the invention.

The material to be dyed, which consists of polyacrylonitrile or anionically modified polyester fibers, can be in different stages of processing, e.g. as yarn, tops (special cuts of the yarn), Tows (special cuts of the fabric), fabric or knitted fabric. The aqueous dye liquor contains the necessary amount of dye, electrolytes, any additives (wetting agents, anti-foaming agents and the like) and a lot of retarders and / or leveling agents of the formula 1. The respective amounts depend on the saturation factor of the fiber, the dye or the dyes, the substantivity of the dye or dyes and the characteristics of the dyeing equipment used. The liquor ratio is usually between 1: 1 and 1: 200, preferably between 1: 2 and 1:40.

Thanks to their good solubility, the retarders and / or leveling agents of the invention can be added directly to the dye liquor. The dyeing liquor is heated to a temperature of between 80 and 110 ° C and so long that complete exhaustion of the dye is guaranteed. This period is usually between 20 and 120 minutes. The amount of retarders and / or leveling agents is generally between 0.1 and 4% by weight, based on the material to be colored. The pH of the dye liquor is adjusted to values between 1 and 7, preferably between 3 and 6.

With the method of the present invention, completely uniform dyeings are obtained with optimal exhaustion of the dye liquor. It is also possible to carry out overdyeing or to completely exhaust the dyeing liquor, even in the event of accidental overdosing of the retarder and / or leveling agent. However, this overdose must not exceed the amount necessary to fully saturate the fiber by more than 30-50%. It should be emphasized that if dyes are used which are only substantive to a small extent, the concentration of the retarder and / or leveling agent in the dyeing liquor can be reduced in order to avoid excessively long dyeing times.

worin

• R einen aliphatischen gesättigten oder ungesättigten Rest mit 10 - 20 Kohlenstoffatomen,
• R^I im statistischen Mittel 0 - 20 % Wasserstoff und 100 - 80 % Methyl oder Äthyl,
• X^e ein Äquivalent eines Anions,
• n die Zahlen 1 oder 2 und m die Zahlen 0 oder 1 darstellen. Diese Produkte sind aber temporäre Retarder mit den dieser Klasse von Retardern eigenen Nachteilen. In den folgenden Beispielen 9, 10 und 11 werden einige typische Vertreter dieser Retarder den Retardern und/oder Egalisiermitteln dieser Erfindung gegenübergestellt.

DE-OS 2 633 138 describes a process for the production of level dyeings on polyacrylonitrile or acid-modified polyester fibers by treating this material with basic dyes using leveling agents of the formula (2),

wherein

• R is an aliphatic saturated or unsaturated radical with 10-20 carbon atoms,
• R ^I on average 0 - 20% hydrogen and 100 - 80% methyl or ethyl,
• X ^{e is} an equivalent of an anion,
• n represents the numbers 1 or 2 and m represents the numbers 0 or 1. However, these products are temporary retarders with the disadvantages inherent in this class of retarders. In Examples 9, 10 and 11 below, some typical representatives of these retarders are compared to the retarders and / or leveling agents of this invention.

mit Alkylierungsmitteln umgesetzt. Die Umetzung erfolgt in einem wäßrigen Mittel oder in einem organischen Lösungsmittel in Gegenwart von Alkali. Beispiele von zweckmäßigen organischen Lösungsmitteln sind niedere aliphatische Alkohole, Äther, vor allem zyklische Äther, wie Tetrahydrofuran oder Dioxan und Benzolderivate, wie Benzol, Toluol, Xylol und chlorierte Benzole. Als Alkalien kann man vor allem Alkalihydroxyde und Alkalicarbonate nennen. Vorzugsweise arbeitet man in einem wäßrigen Medium in Gegenwart von Natriumhydroxyd.The retarders and / or leveling agents of the present invention can be prepared as described in "Cationic Surfactants ", edited by Eric Jungermann, Marcel Dekker Inc., New York (1970), p. 29. For this purpose, compounds of the formula (3)

implemented with alkylating agents. The reaction takes place in an aqueous medium or in an organic solvent in the presence of alkali. Examples of suitable organic solvents are lower aliphatic alcohols, ethers, especially cyclic ethers such as tetrahydrofuran or dioxane and benzene derivatives such as benzene, toluene, xylene and chlorinated benzenes. Alkali can be mentioned above all as alkali hydroxides and alkali carbonates. It is preferred to work in an aqueous medium in the presence of sodium hydroxide.

Preferred alkylating agents are methyl or ethyl halides, preferably chloride, dimethyl or diethyl sulfate or trimethyl or triethyl phosphate. The alkylation reaction is generally carried out at temperatures between 55 and 100 ° C, preferably between 80 and 95 ° C. If complete quaternization is desired, it is advisable to use an excess of alkylating agents. After the alkylation, the excess alkylating agent can be removed from the reaction mixture by evaporation, e.g. if you use alkyl halides. It is also possible to use e.g. with alkyl halides, add alkylating agent under pressure until the vapor pressure of the alkylating agent is established in the reaction vessel at the reaction temperature. If, on the other hand, you do not want complete quaternization, you can also work with a deficit of alkylating agents. In this case, compounds of the formula (1) are obtained, where either a or b = 0. The amount of alkali used in the alkylation is at least equivalent to the amount of alkylating agent consumed, and generally a slight excess of alkali is used. After the alkylation reaction has ended, the excess alkali is neutralized by adding an acid. The following examples serve to better illustrate the invention. Unless otherwise stated, the parts are parts by weight.

example 1 N'-alkyl-N ', N "-trihydroxyethyl-N'-N" -dibenzylpropylenediammonium chloride

448 parts (moles) of N'-alkyl-N'-N "-trihydroxyethylpropylenediamine (" alkyl "is a linear aliphatic chain derived from hydrogenated tallow, which is a mixture of octadecyl, hexadecyl, tetradecyl radicals) at 85 ° 100 parts of water and 65 parts of 30% sodium hydroxide are added to form a homogeneous paste, 252 parts of benzyl chloride are slowly added between 60-95 ° C., preferably between 80-85 ° C.

The reaction is exothermic and the addition of benzyl chloride must therefore be adjusted so that the temperature does not exceed 95-98 ° C to avoid foaming caused by boiling the water at 100 ° C. It is best to work in a reaction vessel with a reflux condenser. It is also possible to work in a closed apparatus under light pressure. The pH must be kept between 2 and 7, preferably between 4 and 7. The reaction is stopped by heating to 80-100 ° C, better between 90-98 ° C, until the benzyl chloride has completely disappeared. This gives 680-690 parts of the desired product at a concentration of 100% by weight, the product has a melting point of 80-95 ° C.

Example 2 N'-dodecyl-N'-N "-trihydroxyethyl-N'-N" -di-benzylpropylenediammonium chloride

As described in Example 1, 1200 parts of water and 65 parts of 30% sodium hydroxide are added to 374 parts (1 mol) of N'-dodecyl-N'-N "-trihydroxyethylpropylenediamine at 80 ° C. to form a homogeneous paste. 252 parts Benzyl chloride (2 moles) are between 60 - 95 ° C, preferably between 80 - 90 ⁰ C. added and at a temperature of 95-98 ° C (exothermic) the pH of the reaction mixture is kept between 1 and 7, preferably between 4 and 7. To complete the reaction, 250 parts of water are distilled off, thereby removing about 10 parts of benzyl alcohol which had formed in the course of the reaction.

About 1640 parts of liquid product with a solids content of 38% are obtained.

Example 3

Mixture of N'-octadecenyl-N'-N "-trihydroxyethyl-N'-N" -dibenzylpropylenediammonium chloride, N'-octadecenyl-N'-N "trihydroxyethyl-N'-monobenzylpropyleneammonium chloride and N'-Octadecenyt-N'-N" - Trihydroxyäthyl-N "-monobenzylpropylenammoniumchlorid.

As described in Example 2, 456 parts (1 mol) of N'-octadecenyl-N'-N "-trihydroxyethyl-propylenediamine at 60-90 ° C, preferably at 70-80 ° C, 1200 parts of water and 60 parts of 30% Sodium hydroxide is added to form a homogeneous paste, 189 parts (1.5 moles) of benzyl chloride are then added between 50-95 ° C., preferably between 80-90 ° C. (exothermic reaction), and 200 parts of water are used to complete the reaction Distilled off, which contain 8-10 parts of benzyl alcohol which has formed in the course of the reaction, gives approximately 1697 parts of an aqueous solution with a content of the reaction product of 38%.

Example 4

10 g of polyacrylonitrile yarn are boiled for 60 minutes in 400 cc of water, which in solution 0.25 g / l of the commercial dye Basic Red 18 C.J. No. 11085, 0.25 g / I of the retarder from Example 1 and 1 g / 1 acetic acid.

A completely uniform coloring is obtained and the exhaustion of the dye present in the bath is slow and gradual, while the same treatment in the absence of the retarder leads to an uneven coloring and to a rapid exhaustion of the dye bath.

Example 5

The procedure described in Example 4 is repeated by increasing the cooking time to 90 minutes and increasing the concentration of the retarder to 0.35 g / l.

A completely uniform coloring of the same intensity as that obtained in Example 4 is obtained.

If, instead of the retarder and / or leveling agent according to the invention, equivalent amounts of a cationic retarder of the known type, consisting of dodecyl-N-dimethyl-benzylammonium chloride, are used, this leads to a coloration in lighter shades and to an insufficient exhaustion of the dye present in the dyeing liquor .

Example 6

• - Faktor des Farbstoffs = 0,3
• - Faktor der Faser = 2,1
• - Freier zu sättigender Faktor = 2,1-0,3 = 1,8
• - Faktor des Retarders = 0,55
• - einzusetzende Quantität des
  Retarders = 1,8:0,55 = 3,27 kg

100 kg of polyacrylonitrile fibers with a saturation factor of 2.1 are dyed in a box-shaped system in 2000 liters of dyeing liquor containing 2 kg of acetic acid, 1 kg of dye CI Basic Blue 69 of very high substantivity and 3.27 kg of the retarder of the present invention in 38%. solution, prepared according to Example 2, according to the following calculation contains:

• - factor of the dye = 0.3
• - factor of the fiber = 2.1
• - Free factor to be saturated = 2.1-0.3 = 1.8
• - Retarder factor = 0.55
• - Quantity of the to be used
  Retarders = 1.8: 0.55 = 3.27 kg

The dyeing carried out with a cooking time of 45 minutes leads to a gradual and complete exhaustion of the dye liquor and to a completely uniform blue dyeing of the fiber.

Example 7

10 g of polyacrylonitrile fibers are treated for 30 minutes in 400 cc of boiling water, which in solution contains 0.5 g / l of the dye C.I. Basic Yellow 11, No. 48055, containing 0.25 g / l of the retarder of the present invention prepared according to Example 1 and 1 g / l of acetic acid.

10 g of the same fiber are treated in an analogous manner, but with the equivalent weight of lauryldimethylbenzylammonium chloride.

After drying and conditioning, the fibers are dyed the same as the fibers dyed with the retarder and / or leveling agent of the present invention, but show a higher antistatic value than those dyed with the conventional retarders.

Example 8

10 g of polyacrylonitrile fibers with a saturation factor of 2.1 are boiled for 4-5 minutes in a dyeing liquor which consists of 400 cc water, 0.1 g of the dye C.I. Basic Red J8 No. 11085, 0.25 g retarder, produced according to Example 2, and 0.5 g acetic acid.

Another 10 g of this fiber are dyed in the same way in the presence of the same amount of the retarder prepared according to Example 3.

The process gives a uniform dyeing of the fiber, but the dye pull-up rate is different in both cases, as the table below shows:

The numbers in the table represent the dye content in the dye liquor at the various times, expressed as a percentage, based on the initial amount (100%).

The table shows that the quaternization of all two nitrogen atoms in the molecule of the retarder and / or leveling agent of the formula (1) has a greater retarding effect.

Example 9

100 kg of polyacrylonitrile fibers are dyed in a dye liquor, which is composed as follows:

The process is carried out by heating the dye liquor to 98 ° C., the temperature being allowed to rise by 1 ° C./minute and the dye liquor being kept at the boiling temperature for one hour. (Curve 1 in FIG. 1)

In the same way, 100 kg of polyacrylonitrile fibers are also dyed using the same amount of a conventional retarder (dimethyl-coco-benzylammonium chloride). (Curve 2 in FIG. 2)

In both cases, completely level colorations are obtained. In contrast, the rate at which the dye is drawn up proves to be very different, as can be seen from the graphic representation in FIG.

From this graph it can be seen that the rate at which the dye is drawn up at cooking temperature is much lower when using the retarder in accordance with the present invention. This is an advantage over the conventional permanent retarders, since the complete exhaustion of the dye is obtained with greater constancy in the rate of pulling up.

Example 10

10 g of polyacrylonitrile fibers are treated for 75 minutes while boiling in 400 cc of water containing 0.2 Basic Red 46 dye, 0.4 g of retarder according to Example 2 and 0.4 cc of acetic acid.

Another 10 g of the same fiber are treated in parallel in a dyeing liquor which is prepared like the first, but contains 0.4 g of a tallow fat propylene diamine quaternized with dimethyl sulfate as a retarder.

Other samples of the same fiber are treated in the same way by bringing the amount of the two retarders to 0.6 g.

The speed at which the dye is drawn up is shown in the graphical representation in Figure 2. (Curves 1a and 1b according to the invention, curves 2a and 2b with product according to the prior art) The differences in the speed at which the dye is drawn up show a greater retarder activity for the product according to the invention an analog product, but with other R ₁ residues and with quaternization by dimethyl sulfate instead of benzyl chloride.

Example 11

The procedure is as given in Example 10 using a reaction product of 2.5 mol of ethylene oxide and 1 mol of stearylamine as a retarder. This product is a commercially available temporary retarder.

The rate at which the dye is drawn onto the fiber is shown in the graph in FIG. 3. (Curves 1a and 1b with the product according to the invention, curves 2a and 2b with the product according to the prior art) The differences in the rate of absorption of the dye on the fiber show that the retarder and / or leveling agent of the present invention follows the course of the dyeing gives a greater regularity.

At higher concentrations, the retarder and / or leveling agent of the present invention proves that it has remarkable temporary characteristics.

Example 12

10 g of polyacrylonitrile fibers are boiled for 30 minutes in a dyebath of 400 cc of water, which contains 0.50 g of retarder - according to Example 2. After this treatment, the fibers are washed in water at 40 ° C for 10 minutes and then boiled for 45 minutes in a dyebath containing 0.25 g of Basic Red 18 and 0.5 cc of acetic acid.

In parallel, another 10 g of fiber is also treated for 45 minutes at the boiling temperature in a dyebath of 400 cc of water which contains 0.50 g of retarder according to Example 2, 0.25 g of Basic Red 18 and 0.5 cc of acetic acid.

The speed at which the dye is drawn onto the fiber is practically the same for both types of treatment. This proves the permanence of the compounds according to the invention, since a temporary retarder would be eliminated during the intermediate washing, while it is clear from the parallel winding speeds that the retarder is firmly and completely attached to the fiber.

Claims (3)

1. A process for preparing new quaternary alkoxyalkylammonium compounds of the formula

in which R denotes C₈-C₂₀-, preferably C₁₂-C₁₈-, alkyl or C₈-C₂₀-, preferably C₁₂-C₁₈-, alkenyl,

R₁, R'₁ and R"₁, which can be identical or different, denote methyl, ethyl or benzyl and at least one of the radicals R₁, R'₁ and R" denotes a group of the formula -(C_SH_2SO)xH,

R₂ and R₃, which can be identical or different, denote methyl, ethyl or benzyl,

a denotts 0 or 1, b denotes 0 or 1, of which either a or b has to be = 1, m denotes 0 or 1, n denotes 2 or 3, p denotes 1, 2 or 3, S denotes 2 or 3, x denotes 1, 2, 3 or 4, and A denotes a halide, methosulfate, ethosulfate or methophosphate ion, which process comprises quarternizing a compound of the formula

with an alkylating agent.

2. The use of a compound as claimed in claim 1, as a retarder and leveling agent in the dyeing of polyacrylonitrile and anionically modified polyester fibers.

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