Synthetic Tannins, Their Synthesis, Industrial Production and Application Part 14

Leathers tanned with these mixtures were more or less dark coloured according to the amounts used of solvenol and the consequent solubilisation of the phlobaphenes.

A similar effect, though of opposite nature from a tanning standpoint, is exhibited by sulphonates on certain colloidal dark coloured substances. A phenolsulphonic acid, which had been overheated during sulphonation and subsequently condensed (crude Neradol), imparted a conspicuous greyish-brown colour to the leather; samples of this crude product were then partly neutralised with varying amounts of alkali, and these samples (containing increasing quant.i.ties of salts) tested for tannin and colour effects. It was found that the more highly neutralised samples imparted a darker colour to the solutions, but these dark products did not deposit the dark impurities on the pelt. One may therefore a.s.sume that tannoid substances are colloidally suspended, and when converted into true solutions are incapable of being fixed in insoluble form by the pelt.

Just as, by adding Neradol D to a tanning extract, the phlobaphenes are solubilised and a dark coloured extract results, it is also possible to remove the mechanically deposited phlobaphenes and oxidised tannins from the finished leather, and, as a consequence, lighten the colour of the leather. For practical purposes, bleaching with Neradol D is carried out by brus.h.i.+ng over the darkly coloured leather with a 2-3 Be. solution of Neradol D, and then rinsing well with water, in order to remove the solubilised tannin. A lighter colour may also be obtained by immersing the leather in a liquor of the strength mentioned above for several hours, and then rinsing with water, but by this procedure not only the surface tannin is removed, but also tannin from the leather substance itself; this method is therefore not suitable for heavy leathers which are sold by weight.

The advantage of employing Neradol D as a bleach in this way is to be found in the fact that, on the one hand, the bleaching sulphonic acid attacks the leather to a much slighter extent than is the case with inorganic acids usually employed for this purpose; on the other hand, the method of brus.h.i.+ng the sulphonic acid on the leather only introduces small amounts of sulphonic acid in the leather, thus lessening the harmful effects of acids upon leather. Furthermore, the common methods of using alkalies as tannin-solubilising agents with the consequent running off and waste of alkaline tan liquors are here subst.i.tuted by a method leaving liquors rich in tannin and Neradol, and which may be used in the ordinary procedure of tannage.

Since Neradol D contains neutral sodium sulphate (about 3 per cent.), and the latter, by precipitating colouring matters present in tan liquors, may slightly bleach these, it was of interest to determine whether the sodium sulphate plays any part in the bleaching effected by Neradol. Mixtures of chestnut and quebracho extracts were prepared, to which were added:--

(1) 5 per cent. Neradol D.

(2) 5 per cent. Neradol D. free from Na_2SO_4.

(3) 15 Per cent. sodium sulphate (corresponding to above Neradol D).

These mixtures were allowed to act upon pelt alongside of comparison tests using quebracho and chestnut extracts only, the strength of the liquors in all cases being 1.5 Be; the pelt was left in the solution till tanned through. The following results were obtained:--

(1) Quebracho tanned leather was darker; no difference in colour by chestnut extract.

(2) Similar to (I).

(3) Same colour as given by the original extracts.

This experiment demonstrates that absence of sodium sulphate in the mixture is without influence on the colour of the resulting leather, and that an addition of sodium sulphate to natural extracts does not affect the colour imparted by them to pelt

5. Effect of Neradol D on Pelt

Being a sulphonic acid derivative, the chemical const.i.tution of Neradol is obviously considerably different from that of the natural tannins, and the question has been asked: Will Neradol D, in its concentrated form, attack the hide substance?[Footnote 1: _Collegium_, 1913, 521, 487.] Bearing in mind that concentrated extracts of vegetable tannins in some circ.u.mstances effect a "dead" tannage (_cf_. case-hardening) and hence reduce their practical value, and that for this reason it is impossible to allow either concentrated extracts or concentrated Neradol D to act upon pelt, the author still decided to carry out some experiments in this direction. Concentrated Neradol D (33 Be.) and strong aqueous solutions of this material in strengths of--

30 25 20 15 10 5 3 1 Be.

were therefore allowed to remain in contact with pelt for a period of ten days, when the pelts were taken out and washed in running water for twenty-four hours, and then dried. The resultant leathers possessed the following properties:--

33 Be. solution: completely gelatinised.[Footnote 2]

30 " " " [Footnote 2]

25 " two-thirds gelatinised; surface tanned.

20 " one third gelatinised; surface "dead" tanned.

15 " pelt was gla.s.sy throughout.

10 " rather cracky leather, but well tanned.

5 " normal tannage.

3 " " "

1 " " "

[Footnote 2: Impossible to subject the pieces to a proper was.h.i.+ng out.]

The interiors of the leathers obtained from the 25 and 20 Be. solutions were completely gelatinised; this may be accounted for by a.s.suming that the surface was "dead" tanned, and that hence the free dissociated sulphonic acid diffused into the leather, towards which it exhibited hydrolysing rather than a tannoid effect with the consequent result described above. Above 10 Be. the effect is more that of an acid with concentrations below 10 Be.--the only ones of technical importance--however, no ill-effects may be observed.

For tanning purposes, Neradol D solutions of 2 Be. are quite satisfactory, and it has been found [Footnote 1: _Technik.u.m_, 1913, 80, 324.] that solutions of this strength do not dissolve out any protein of the hide. [Footnote 2: The translator cannot agree with the author on this point. He has, for instance, found that solutions of a.n.a.lytical strength dissolve considerable amounts of hide substance, and his practical experience confirms results arrived at in the laboratory.]

A purely Neradol D tanned leather may be produced by immersing a bated pelt, free from lime, in a 2 Be. Neradol D liquor for about four days; the resultant leather being nearly white and otherwise very similar to a leather tanned with vegetable tanning materials.

The main application of Neradol D is in admixture with vegetable tanning materials; especially in the early stages of tannage is this substance of value, since by its use not only a light coloured leather surface is obtained, but its presence prevents a subsequent dead tannage when strong vegetable tan liquors are applied, and it also imparts strength to the grain layer. It is thus possible to shorten the time consumed by the tanning process by employing Neradol D in the manner described.

A further explanation as to why the tanning process is considerably hastened by using Neradol D, either alone or in conjunction with natural tannins, is afforded by the fact that though Neradol D quickly penetrates the grain, it is but "loosely" fixed by the latter, _i.e._, it is not deposited to such an extent that it would prevent penetration of the vegetable tannins. In the case of a mixture of Neradol D and vegetable tannins, the former quickly diffuses into the pelt and fixes the fibres, thus facilitating penetration of the vegetable tannins.

This a.s.sumption is justified in view of the speed with which Neradol D completely penetrates and tans the pelt, since Neradol D containing acids and salts exhibits effects similar to those of a pickle.

6. Reactions of Neradol D with Iron and Alkalies

A special characteristic of Neradol D tannage is the sensitiveness of the latter to the action of iron and alkalies. The active principle of Neradol D being free dicresylmethanedisul-phonic acid, which is easily neutralised by lime, ammonia, and amino-acids and hence rendered inactive for tanning purposes, it is essential that the pelt prior to tannage with Neradol D should be completely delimed, bated, and freed from all const.i.tuents possessing alkaline reaction. It is, however, possible to regenerate Neradol D liquors contaminated with alkali or partly neutralised by the addition of small quant.i.ties of organic (formic, acetic, lactic, and butyric) or inorganic (hydrochloric or sulphuric) acids,_i.e._, the dicresyl-methanedisulphonic acid is again partly liberated, and this procedure is always preferred where the tanning process does not allow of a complete deliming of the pelt prior to introducing the latter into a Neradol D liquor. If, on the other hand, such liquors are kept properly, and the addition of acid referred to kept up, they will remain active for weeks and need only strengthening up with the requisite quant.i.ty of Neradol prior to introducing fresh pack.

The sensitiveness to alkalies of Neradol D is considerably greater than in the case of natural tannins, and it appears that a vegetable tan liquor neutralised with lime will not even surface-tan when acting upon pelt and will neither impart a dark colour to the leather nor remove from it any appreciable amount of protein. Similarly, a Neradol D liquor neutralised with lime exerts no tanning action, but in contradistinction to the vegetable tan liquor similarly treated, will impart a blue or blackish-blue colour to the pelt, from which it removes larger quant.i.ties of protein. The author examined two such liquors relating to their contents of tanning matters and protein and obtained the following results:--

Reaction. Bark. Tans. Non-Tans Insol. Proteins

Per Per Per Per Cent. Cent. Cent. Cent.

Vegetable Slightly 12 0 2.93 0.35 0.01 tan alkaline liquor

Neradol " " 10 0 4.43 0.17 0.17

These figures do not only show the higher protein contents of the Neradol D liquor, but do also show higher contents in soluble non-tannins, which consist mainly of lime (2.12 per cent.) and sodium salts (1.8 per cent.), thus establis.h.i.+ng the fact of the sensitiveness of Neradol D to alkalies in addition to its lime-solubilising effects.

The sensitiveness towards alkalies is also noticeable on a large scale where the tanpits have been built of cement; though the pelt may be quite free from lime, the Neradol D is quickly neutralised by the cement, with results similar to those enumerated above.

The blue coloured soluble compound of Neradol D and iron salts, to which frequent reference has been made, is very important from a practical standpoint. Whereas the catechol tannins (_i.e._, fir, gambir, hemlock, cutch, mangrove, and quebracho) are coloured black, those of the pyrogallol cla.s.s (_i.e._, algarobilla, dividivi, valonea, gallotannic acid, myrabolams, and sumac) bluish-black, and the "mixed" tannins (_i.e._, canaigre, oak, and mimosa bark) bluish-purple by iron alum, Neradol D is coloured a pure blue. How sensitive this reaction is, the following comparative a.n.a.lyses ill.u.s.trate: to each litre of tan liquor containing 4 gm. tanning matter prepared from (_a_) quebracho extract and (_b_) Neradol D, 10 c.c. of a 10 per cent. iron alum solution were added, the solutions heated to 100 C., cooled and filtered, and the colour of the filtrates and the weight of the precipitates determined:--

(_a_) Quebracho solution: light reddish-brown filtrate, 3.22 gm.

precipitate.

(_b_) Neradol solution: deep blue filtrate, 0.02 gm. precipitate.

Hence, on adding a soluble iron salt to a solution of a natural tannin, most of the tanning matter is precipitated; the colour of the filtrate, however, is much the same as that of the original solution. A Neradol D liquor similarly treated gives no precipitate, but is coloured blue throughout. The filtrates from the above solutions were allowed to act upon pelt, and the following observations were made:--

(_a_) The light reddish-brown filtrate from the quebracho liquor exhibited no well-defined tanning effect on pelt, to which it imparted a light brown colour.

(_b_) On the other hand, the deep blue filtrate from the Neradol D liquor exhibited well-defined tanning effects, and imparted a deep blue colour to the pelt.

For practical purposes, the sensitiveness of Neradol D to iron is not only remarkable because any contact with iron particles will colour the liquor (and hence the pelt) blue, but also because the slight amount of iron always present in cement renders the use of cement pits prohibitive where Neradol D liquors are used.

This intense blue coloration might have made possible a colorimetric estimation of Neradol D. The author has investigated this possibility, using different concentrations of Neradol D liquors to which a solution of iron ammonium alum was added, and found that when, at certain concentrations, the maximum blue colour had been obtained, it was still possible to increase the quant.i.ty of Neradol without the intensity of the colour being affected. Addition of a little alkali tends at first to darken the blue colour, more alkali changes the blue colour to brown and yellow, successive additions of a weak organic acid (_e.g._, acetic acid) rapidly lighten the blue colour. Since industrially used Neradol D liquors always contain varying quant.i.ties of acid and may be neutral or even slightly alkaline, it must be considered impossible to make any use of such a colorimetric estimation for practical purposes.

7. Reagents Suitable for Demonstrating the Various Stages of Neradol D Tannage

The extent to which tannage with Neradol D proceeds on the surface and within the pelt may be judged from the feel of the skin, but such a method is totally unsuited to any but a practical tanner. A suitable and reliable reagent is indigotine (B.A.S.F.), which clearly distinguishes tanned and untanned layers of the pelt. If, for instance, a 1-2 per cent, solution of indigotine is brought into contact with a fresh cut on a pelt, and the latter subsequently washed with warm water, the indigotine is only retained by the untanned parts; a leather tanned with Neradol D is therefore only coloured by indigotine to the extent to which it has combined with the Neradol. [Footnote: According to Seel and Sander (_Zeits. f. ang. Chem._, 1916, 333), basic dyestuffs are also very suitable for demonstrating tanned parts of the pelt.]

Another reagent is const.i.tuted by iron ammonium sulphate; the extent of the penetration of Neradol D, which gives an intense blue coloration with iron salts, into the leather may be determined by was.h.i.+ng the pelt treated with Neradol D, making a cut, again was.h.i.+ng and treating the cut with a few drops of a weak solution of iron ammonium sulphate. Those parts of the pelt which have been converted into leather then appear deep blue; on the other hand, those which have been in contact with Neradol D, but have not yet been converted into leather, are light blue. Those parts which have not yet been in contact with Neradol D appear pure white; the results of this reaction are therefore opposite to those obtained by the use of indigotine.

8. Combination Tannages with Neradol D