Researches on Cellulose Part 2

A. FRAENKEL and P. FRIEDLAENDER (Mitt. k.-k. Techn. Gew. Mus., Wien, 1898, 326).

The authors, after investigation, are inclined to attribute the l.u.s.tre of mercerised cotton to the absence of the cuticle, which is destroyed and removed in the process, partly by the chemical action of the alkali, and partly by the stretching at one or other stage of the process. The authors have investigated the action of alcoholic solutions of soda also. The l.u.s.tre effects are not obtained unless the action of water is a.s.sociated.

In conclusion, the authors give the following particulars of breaking strains and elasticity:--

-------------------------------------------------------------------------- Treatment Experiments Breaking strain Elasticity -------------------------------------------------------------------------- Elongation Grammes in mm.

Cotton unmercerised. 1 360 20 2 356 20 3 360 22 Mercerised with Soda 35B. 1 530 44 2 570 40 3 559 35 Alcoholic soda 10 p.ct. 1 645 24 cold 2 600 27 3 610 33 Alcoholic soda 10 p.ct. 5 740 33 hot 2 730 38 3 690 30 --------------------------------------------------------------------------

FOOTNOTES:

[2] This and other similar references are to the matter of the original volume (1895).

SECTION II. SYNTHETICAL DERIVATIVES--SULPHOCARBONATES AND ESTERS

(p. 25) ~Cellulose sulphocarbonate.~--Further investigations of the reaction of formation as well as the various reactions of decomposition of the compound, have not contributed any essential modification or development of the subject as originally described in the author's first communications. A large amount of experimental matter has been acc.u.mulated in view of the ultimate contribution of the results to the general theory of colloidal solutions. But viscose is a complex product and essentially variable, through its p.r.o.nounced tendency to progressive decomposition with reversion of the cellulose to its insoluble and uncombined condition. The solution for this reason does not lend itself to exact measurement of its physical constants such as might elucidate in some measure the progressive molecular aggregation of the cellulose in a.s.suming spontaneously the solid (hydrate) form. Reserving the discussion of these points, therefore, we confine ourselves to recording results which further elucidate special points.

_Normal and other celluloses._--We may certainly use the sulphocarbonate reaction as a means of defining a normal cellulose. As already pointed out, cotton cellulose pa.s.ses quant.i.tatively through the cycle of treatments involved in solution as sulphocarbonate and decomposition of the solution with regeneration as structureless or amorphous cellulose (hydrate).

a.n.a.lysis of this cellulose shows a fall of carbon percentage from 44.4 to 43.3, corresponding with a change in composition from C_{6}H_{10}O_{5} to 4C_{6}H_{10}O_{5}.H_{2}O. The partial hydrolysis affects the whole molecule, and is limited to this effect, whereas, in the case of celluloses of other types, there is a fractionation of the ma.s.s, a portion undergoing a further hydrolysis to compounds of lower molecular weight and permanently soluble. Thus in the case of the wood celluloses the percentage recovered from solution as viscose is from 93 to 95 p.ct. It is evident that these celluloses are not h.o.m.ogeneous. A similar conclusion results from the presence of furfural-yielding compounds with the observation that the hydrolysis to soluble derivatives mainly affects these derivatives. In the empirical characterisation of a normal cellulose, therefore, we may include the property of quant.i.tative regeneration or recovery from its solution as sulphocarbonate.

In the use of the word 'normal' as applied to a 'bleached' cotton, we have further to show in what respects the sulphocarbonate reaction differentiates the bleached or purified cotton cellulose from the raw product. The following experiments may be cited: Specimens of American and Egyptian cottons in the raw state, freed from mechanical, i.e.

non-fibrous, impurities, were treated with a mercerising alkali, and the alkali-cotton subsequently exposed to carbon disulphide. The product of reaction was further treated as in the preparation of the ordinary solution; but in place of the usual solution, structureless and h.o.m.ogeneous, it was observed to retain a fibrous character, and the fibres, though enormously swollen, were not broken down by continued vigorous stirring. After large dilution the solutions were filtered, and the fibres then formed a gelatinous ma.s.s on the filters. After purification, the residue was dried and weighed. The American cotton yielded 90.0 p.ct., and the Egyptian 92.0 p.ct. of its substance in the form of this peculiar modification. The experiment was repeated, allowing an interval of 24 hours to elapse between the conversion into alkali-cotton and exposure of this to the carbon disulphide. The quant.i.tative results were identical.

There are many observations incidental to chemical treatments of cotton fabrics which tend to show that the bleaching process produces other effects than the mere removal of mechanical impurities. In the sulphocarbonate reaction the raw cotton, in fact, behaves exactly as a compound cellulose. Whether the const.i.tutional difference between raw and bleached cotton, thus emphasised, is due to the group of components of the raw cotton, which are removed in the bleaching process, or to internal const.i.tutional changes determined by the bleaching treatments, is a question which future investigation must decide.

_The normal sulphocarbonate (viscose)._--In the industrial applications of viscose it is important to maintain a certain standard of composition as of the essential physical properties of the solution, notably viscosity. It may be noted first that, with the above-mentioned exception, the various fibrous celluloses show but slight differences in regard to all the essential features of the reactions involved. In the mercerising reaction, or alkali-cellulose stage, it is true the differences are considerable. With celluloses of the wood and straw cla.s.ses there is a considerable conversion into soluble alkali-celluloses. If treated with water these are dissolved, and on weighing back the cellulose, after thorough washing, treatment with acid, and finally washing and drying, it will be found to have lost from 15 to 20 p.ct. in weight. The lower grade of celluloses thus dissolved are only in part precipitated in acidifying the alkaline solution. On the other hand, after conversion into viscose, the cellulose when regenerated re-aggregates a large proportion of these lower grade celluloses, and the final loss is as stated above, from 5 to 7 p.ct.

only.

Secondly, it is found that all the conditions obtaining in the alkali-cellulose stage affect the subsequent viscose reaction and the properties of the final solution. The most important are obviously the proportion of alkali to cellulose and the length of time they are in contact before being treated with carbon disulphide. An excess of alkali beyond the 'normal' proportion--viz. 2NaOH per 1 mol.

C_{6}H_{10}O_{5}--has little influence upon the viscose reaction, but lowers the viscosity of the solution of the sulphocarbonate prepared from it. But this effect equally follows from addition of alkali to the viscose itself. The alkali-cellulose changes with age; there is a gradual alteration of the molecular structure of the cellulose, of which the properties of the viscose when prepared are the best indication.

There is a progressive loss of viscosity of the solution, and a corresponding deterioration in the structural properties of the cellulose when regenerated from it--especially marked in the film form.

In regard to viscosity the following observations are typical:--

(a) A viscose of 1.8 p.ct. cellulose prepared from an alkali-cellulose (cotton) fourteen days old.

(b) Viscose of 1.8 p.ct. cellulose from an alkali-cellulose (cotton) three days old.

(c) Glycerin diluted with 1/3 vol. water.

a b b c Diluted with equal vol.

water Times of flow of equal volumes from 112 321 103 170 narrow orifice in seconds

Similarly the cellulose in reverting to the solid form from these 'degraded' solutions presents a proportionate loss of cohesion and aggregating power expressed by the inferior strength and elasticity of the products. Hence, in the practical applications of the product where the latter properties are of first importance, it is necessary to adopt normal standards, such as above indicated, and to carefully regulate all the conditions of treatment in each of the two main stages of reaction, so that a product of any desired character may be invariably obtained.

Incidentally to these investigations a number of observations have been made on the alkali-cellulose (cotton) after prolonged storage in closed vessels. It is well known that starch undergoes hydrolysis in contact with aqueous alkalis of a similar character to that determined by acids [Bechamp, Annalen, 100, 365]. The recent researches of Lobry de Bruyn [Rec. Trav. Chim. 14, 156] upon the action of alkaline hydrates in aqueous solution on the hexoses have established the important fact of the resulting mobility of the CO group, and the interchangeable relationships of typical aldoses and ketoses. It was, therefore, not improbable that profound hydrolytic changes should occur in the cellulose molecule when kept for prolonged periods as alkali-cellulose.

We may cite an extreme case. A series of products were examined after 12-18 months' storage. They were found to contain only 3-5 p.ct.

'soluble carbohydrates'; these were precipitated by Fehling's solution but without reduction on boiling. They were, therefore, of the cellulose type. On acidifying with sulphuric acid and distilling, traces only of volatile acid were produced. It is clear, therefore, that the change of molecular weight of the cellulose, the disaggregation of the undoubtedly large molecule of the original 'normal' cellulose--which effects are immediately recognised in the viscose reactions of such products--are of such otherwise limited character that they do not affect the const.i.tution of the unit groups. We should also conclude that the cellulose type of const.i.tution covers a very wide range of minor variations of molecular weight or aggregation.

The resistance of the normal cellulose to the action of alkalis under these hydrolysing conditions should be mentioned in conjunction with the observations of Lange, and the results of the later investigations of Tollens, on its resistance to 'fusion' with alkaline hydrates at high temperatures (180). The degree of resistance has been established only on the empirical basis of weighing the product recovered from such treatment. The product must be investigated by conversion into typical cellulose derivatives before we can p.r.o.nounce upon the const.i.tutional changes which certainly occur in the process. But for the purpose of this discussion it is sufficient to emphasise the extraordinary resistance of the normal cellulose to the action of alkalis, and to another of the more significant points of differentiation from starch.

_Chemical constants of cellulose sulphocarbonate (solution)._--In investigations of the solutions we make use of various a.n.a.lytical methods, which may be briefly described, noting any results bearing upon special points.

_Total alkali._--This constant is determined by t.i.tration in the usual way. The cellulose ratio, C_{6}H_{10}O_{5} : 2NaOH, is within the ordinary error of observation, 2 : 1 by weight. A determination of alkali therefore determines the percentage of cellulose.

_Cellulose_ may be regenerated in various ways--viz. by the action of heat, of acids, of various oxidising compounds. It is purified for weighing by boiling in neutral sulphite of soda (2 p.ct. solution) to remove sulphur, and in very dilute acids (0.33 p.ct. HCl) to decompose residues of 'organic' sulphur compounds. It may also be treated with dilute oxidants. After weighing it may be ignited to determine residual inorganic compounds.

_Sulphur._--It has been proved by Lindemann and Motten [Bull. Acad. R.

Belg. (3), 23, 827] that the sulphur of sulphocarbonates (as well as of sulphocyanides) is fully oxidised (to SO_{3}) by the hypochlorites (solutions at ordinary temperatures). The method may be adapted as required for any form of the products or by-products of the viscose reaction to be a.n.a.lysed for _total sulphur_.

The sulphur present in the form of dithiocarbonates, including the typical cellulose xanthogenic acid, is approximately isolated and determined as CS_{2} by adding a zinc salt in excess, and distilling off the carbon disulphide from a water bath. From freshly prepared solutions a large proportion of the disulphide originally interacting with the alkali and cellulose is recovered, the result establishing the general conformity of the reaction to that typical of the alcohols. On keeping the solutions there is a progressive interaction of the bisulphide and alkali, with formation of trithiocarbonates and various sulphides. In decomposing these products by acid reagents hydrogen sulphide and free sulphur are formed, the estimation of which presents no special difficulties.

In the spontaneous decomposition of the solution a large proportion of the sulphur resumes the form of the volatile disulphide. This is approximately measured by the loss in total sulphur in the following series of determinations, in which a viscose of 8.5 p.ct. strength (cellulose) was dried down as a thin film upon gla.s.s plates, and afterwards a.n.a.lysed:

(a) Proportion of sulphur to cellulose (100 pts.) in original.

(b) After spontaneous drying at ordinary temperature.

(c) After drying at 40C.

(d) As in (c), followed, by 2 hours' heating at 98.

(e) As in (c), followed by 5 hours' heating at 98.

a b c d e Total sulphur 40.0 25.0 31.0 23.7 10.4

The dried product in (b) and (c) was entirely resoluble in water; in (d) and (e), on the other hand, the cellulose was fully regenerated, and obtained as a transparent film.

_Iodine reaction._--Fresh solutions of the sulphocarbonate show a fairly constant reaction with normal iodine solution. At the first point, where the excess of iodine visibly persists, there is complete precipitation of the cellulose as the bixanthic sulphide; and this occurs when the proportion of iodine added reaches 3I_{2} : 4Na_{2}O, calculated to the total alkali.

_Other decompositions._--The most interesting is the interaction which occurs between the cellulose xanthogenate and salts of ammonia, which is taken advantage of by C. H. Stearn in his patent process of spinning artificial threads from viscose. The insoluble product which is formed in excess of the solution of ammonia salt is free from soda, and contains 9-10 p.ct. total sulphur. The product retains its solubility in water for a short period. The solution may be regarded as containing the ammonium cellulose xanthate. This rapidly decomposes with liberation of ammonia and carbon disulphide, and separation of cellulose (hydrate). As precipitated by ammonium-chloride solution the gelatinous thread contains 15 p.ct. of cellulose, with a sp.gr. 1.1. The process of 'fixing'--i.e. decomposing the xanthic residue--consists in a short exposure to the boiling saline solution. The further dehydration, with increase of gravity and cellulose content, is not considerable. The thread in its final air-dry state has a sp.gr. 1.48.

~Cellulose Benzoates.~--These derivatives have been further studied by the authors. The conditions for the formation of the mon.o.benzoate [C_{6}H_{9}O_{4}.O.CO.Ph] are very similar to those required for the sulphocarbonate reaction. The fibrous cellulose (cotton), treated with a 10 p.ct. solution NaOH, and subsequently with benzoyl chloride, gives about 50 p.ct. of the theoretical yield of mon.o.benzoate. Converted by 20 p.ct. solution NaOH into alkali-cellulose, and with molecular proportions as below, the following yields were obtained:--

Calc. for Mon.o.benzoate (a) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : C_{6}H_{5}.COCl-- 150.8} }164.0 (b) C_{6}H_{10}O_{5} : 2.0-2.5 NaOH : 1.5 mol. C_{6}H_{5}COCl 159.0}

An examination of (a) showed that some dibenzoate (about 7 p.ct.) had been formed. The product () was exhaustively treated with cuprammonium solution, to which it yielded about 20 p.ct. of its weight, which was therefore unattacked cellulose.

Under conditions as above, but with 2.5 mol. C_{6}H_{5}COCl, a careful comparison was made of the behaviour of the three varieties of cotton, which were taken in the unspun condition and previously fully bleached and purified.

___________________________________________________________________ Sea Island Egyptian American ________________________________ ____________ __________ __________ Aggregate yield of benzoate 153 148 152 Moisture in air dry state 5.28 5.35 5.15 Proportion of dibenzoate p.ct. 8.30 13.70 9.4 Yield of cellulose by 58.0 54.0 58.3 saponification ________________________________ ____________ __________ __________

It appears from these results that the benzoate reaction may proceed to a higher limit (dibenzoate) in the case of Egyptian cotton. This would necessarily imply a higher limit of 'mercerisation,' under equal conditions of treatment with the alkaline hydrate. It must be noted that in the conversion of the fibrous cellulose into these (still) fibrous mon.o.benzoates, there are certain mechanical conditions imported by the structural features of the ultimate fibres. For the elimination of the influence of this factor a large number of quant.i.tative comparisons will be necessary. The above results are therefore only cited as typical of a method of comparative investigation, more especially of the still open questions of the cause of the superior effects in mercerisation of certain cottons (see p. 23). It is quite probable that chemical as well as structural factors co-operate in further differentiating the cottons.

Further investigation of the influence upon the benzoate reaction, of increase of concentration of the soda lye, used in the preliminary alkali cellulose reaction, from 20 to 33 p.ct. NaOH, established (1) that there is no corresponding increase in the benzoylation, and (2) that this ester reaction and the sulphocarbonate reaction are closely parallel, in that the degree and limit of reaction are predetermined by the conditions of formation of the alkali cellulose.

_Mon.o.benzoate_ prepared as above described is resistant to all solvents of cellulose and of the cellulose esters, and is therefore freed from cellulose by treatment with the former, and from the higher benzoate by treatment with the latter. Several of these, notably pyridine, phenol and nitrobenzene, cause considerable swelling and gelatinisation of the fibres, but without solution.