BE414712A - - Google Patents

Description

       

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  PATENT OF INVENTION "Manufacture of cellulose derivatives and of artificial filaments, films and other structures will conform using these derivatives".



   In Belgian Patents Nos. 368.617, 368.618, 378.205, 382.218, 407.052, 378. 200, 389. 619 and in British Patent No. 367.920, in the name of the Applicant, procedures have been described for the production of xanthates of various cellulose derivatives in which at least one hydroxyl hydrogen atom of the cellulose molecule n (C6HI005) is replaced by a radical is organic, particularly an alcohol radical, and in which at least one hydroxyl group is released and can bind to it - even as a chain to a CSS group, processes which consist in treating these cellulose derivatives, in the presence of alkali, with carbon disulphide.



   In these processes, the Applicant has used proportions of carbon disulfide which are commonly employed in the visoose industry, for example amounts of carbon disulfide ranging from 20 to 25 to 60 parts per 100 parts.

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 cellulose derivatives of the same nature.



   Now, the Applicant has discovered that it is possible, by using proportions of carbon disulfide which are lower than 20 parts of carbon disulfide per 100 parts of the cellulose derivative of the same nature, to produce xantha- These are the above-mentioned cellulosic derivatives which can be processed flawlessly into useful conformal structures.



   This finding is all the more surprising since it is well known that viscose solutions made from cellulose xanthates which are prepared using small proportions of carbon disulfide contain appreciable amounts of non-constituents. dissolved which make filtering difficult and which, moreover, by reason of their viscous nature, are liable to pass through the filter material and thus render the viscose unsuitable for the production of shaped structures, such as films, artificial threads and others using this viscose, or less well suited to the production of said structures.



   In addition, viscoses produced using amounts of carbon disulfide lower than 25 parts or 20 parts per 100 parts of cellulose have a higher viscosity of water than viscoses prepared from al-. cali-cellulose of the same degree of ripeness using quantities of caroone disulfide exceeding 20 or 25 parts per 100 parts of cellulose. is
It is further surprising that according to the present invention it is possible, by using in the xanthation amounts of carbon disulfide which are less than 10 parts, for example 5 to 8 parts of carbon disulfide per 100 parts of the carbon dioxide. .

   cellulosic derivative of the same nature, to produce very useful xanthates of cellulosic derivatives which have excellent properties and can be processed

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 in conformal structures with remarkable properties.



   The solutions of the xanthates produced according to the present invention are less colored than ordinary viscose; they can be easily filtered, and when filtered they have no pronounced tendency to clog or obstruct the spinning lines.



   Another technical progress achieved by the present invention is that, despite the small amounts of carbon disulfide used for their production, many of the xanthates of the cellulose derivatives produced according to the invention can be transformed into structures. conformed, such as threads, pellets, etc.

   possessing dynamometric properties which are not inferior or not appreciably inferior to the dynamometric properties of shaped structures which are prepared from xanthates of the same cellulose derivatives, but which are made with the usual amounts of carbon disulfide from 20 parts of disulfide increasing, ie with amounts of carbon disulphide specified in the processes described in the aforementioned patents and certificates of addition.



   In addition, said invention presents a considerable economic progress over the methods known hitherto.



   Although many cellulosic derivatives in which at least one hydroxyl hydrogen atom of the cellulose molecule n (C6H10O5) is replaced by an organic radical and in which at least one hydroxyl group is released and can bind itself chain to a CSS group, are materials of the same nature suitable with regard to the present process, according to the present state of knowledge of the Applicant, he prefers to use cellulose ethers of low degree of etherification.

   Because they can be transformed in a wide variety of ways into their xanthates, the aloali soluble cellulosic ethers (e.g. derivatives

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 cellulosic alkyls, or aralkyls, or hydroxyalooyls, or hydroxy acids which are at least partially soluble in a solution of caustic alkali at or below room temperature, or which can be made soluble in this solution by cooling their suspensions or incomplete solutions in a caustic alkali solution to a temperature between plus 5 C and minus 10 C or lower and bringing them back to the temperature of the chamber or to a temperature between 0 C and the room temperature)

   play a particularly important role in the present invention.



   These alkali-soluble ethers and the prooédés for their production are for the first time described in British Patents Nos. 177,810, 203,346, 203,347, 200,834, 200,816, 21,810 and in Belgian Patents Nos. 406. 905, 407.262, 407.768, 407.706 and 407.734 and dissolving or completely dissolving those members of those groups of cellulose ethers which do not dissolve or dissolve only incompletely in a solution of caustic alkali at room temperature is first described in UK Patent No. 212. 864 (see eg page 3, lines 62-71), in the name of the Applicant.



   Since alpha-soluble cellulose ethers are employed in the present invention as a material of the same nature, it should be understood that in the present invention, cellulose-soluble cellulose ethers can be employed. alkali which are produced by any process, for example by any of the processes described in UK Patents Nos. 177,810,203,346,205,347,200,834,200,816 in Belgian Goldens Nos. 407,262 and 407,706 and in patent applications. English Patents Nos. 9,762/35, g. 764/35, 9,765/35;

   9. 766/35, 9. 767/35, 9770/35, 9.771 / 35, 9. 772/35, 9.773 / 35 and 9. 774/35, or according to any other process suitable for the preparation of ethers cellulosics which are completely or almost completely soluble in a solution of alkali caus-

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 tick at room temperature and at a lower temperature, for example at a temperature between the room temperature and 0 C.

   or lower, or cellulose ethers which are insoluble or incompletely soluble
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 in an oaustic alkali solution at chamber temperature, but which may be made soluble or not fully soluble in this solution at chamber temperature.
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 chamber by cooling their suspensions or incomplete solutions in a solution of aloali oaustic to a temperature
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 between the room temperature and 0 C., or at 0 * C. or below 0 C., for example at minus 5 C., or at minus 10 * 0., or lower, and then allowing the temperature to rise to 0 C., or above 0 C ., or cellulose ethers which are insoluble or incompletely soluble in
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 a solution of oaustic alkali at the temperature of the oham:

  '"bre, or at a temperature between the temperature of the chamber and 0 * C., or even at 0 * C., but which can be made partially or completely soluble in this solution at the temperature of the chamber and (or ) at a temperature
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 taken between the temperature of the chamber and 0 ° C., or at 0 C., by cooling their suspensions u incomplete solutions to a temperature below 0 C., for example, unless
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 5 C., or minus 10 C., or lower, and then allowing the temperature to rise to 0 C., or above 0 C.



   In other words, in the present invention, it is possible to employ not only the cellulose ethers soluble in aloali which can be prepared by the methods and procedures described in the specifications mentioned in the preceding paragraph, but also the organic ethers. - losiques' soluble in aloali which are prepared by any other process suitable for the preparation of cellulose ethers which are at least partially soluble in a solution of oaustic aloali, or which can be made soluble in the latter by application of low temperatures, for example

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 by the method described in UK Patent No. 212. 864.



   It should be further understood that in the present invention, single or mixed cellulose ethers can be employed. As mixed ethers, the following can be given by way of example:
Cellulose derivatives containing in their molecule two different aloyl groups, cellulose derivatives containing in their molecule two different hydroxyalooyl groups, cellulose derivatives containing in their molecule an alkyl group and a hydroxyalooyl group, cellulose derivatives containing in their molecule two residues different hydroxy acids, cellulose derivatives containing in their molecule an alkyl group and a hydroxyacid residue,

     cellulosic derivatives containing in their molecule a hydroxyalooyl group and a hydroxyoid residue, and so on.



   The process can be carried out in various ways, the most important methods being described in the following lines by way of examples to which the present invention is however not limited. Since, in many cases, the combination of the preparation of the cellulose derivatives of the same nature, particularly of xanthater ethers, with the xanthation carried out in a continuous operation, or in a continuation of operations, has certain advantages Some examples for the preparation of the starting cellulose derivatives, particularly ethers, are also included in the description given below of the practice of the present invention.



   FIRST METHOD;
A cellulose derivative in which at least one γ-hydroxyl atom of the cellulose molecule n (C6HI005) is replaced by an organic radiol, particularly by an unsubstituted or substituted alcoholic radioal, and in which at least a hydroxyl group is released and can serially chain

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 to a CSS group, is, according to known methods for the production of aloali-cellulose in the viscose industry, transformed into an aloalin composa, and this is treated at room temperature, or at a temperature exceeding the temperature of the chamber, for example at 30 to 50 C., or at a temperature between the temperature of the chamber and 0 C., or at 0 C.,

   or below 0 C., for example at minus 5 to minus 10 C., or lower, or partly at the temperature of the room and partly at a temperature lower than the temperature of the field, for example between room temperature and 0 C., or below 0 C., for example at minus 5 C., or minus 10 C., or lower, with less carbon disulphide than 20 parts preferably less than 15 to 10 parts, per 100 parts of the oellulosic derivative, and the xanthate thus obtained is dissolved in water or in a solution of caustic aloali, the dissolution being carried out at the temperature of the chamber, or at a temperature between the chamber temperature and 0 C.

   , or at 0 C., or below 0 C., for example at minus 5 to minus 10 C., or lower, or partly at chamber temperature and partly below temperature of the chamber, for example between the temperature of the chamber and 0 C., or below 0 C., for example at minus 5 C., or at minus 10 * C., or lower.



     SFCONDR METHODF.



   An oellulose derivative in which at least one hydrogen atom #y droxyl of the cellulose moléoule n (C6H10O5) is replaced by an organic radical, particularly by an unsubstituted or substituted alooolic radical, and in which at least one group hydroxyl is liberated and may bind enphalne to a CSS group, is suspended or is dissolved in a caustic alkali solution (depending on its solubility ratios either at chamber temperature or

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 at a temperature between the chamber temperature and 0 C.

   , or at 0 C., or below 0 C., for example at minus 5 to minus 10 C., or lower, or partly at chamber temperature and partly below temperature of the chamber, for example between the temperature of the chamber and 0 C., or below 0 C., for example at minus 5 C., or at minus 10 C., or lower), after which an amount of carbon disulphide which is less than 20 parts, preferably less than 15 or 10 parts, per 100 parts of the cellulose derivative, is incorporated into the suspension, or complete or incomplete solution thus obtained, and the mixture is treated with carbon disulphide, preferably by stirring, shaking or otherwise.

   The treatment with the carbon disulfide can be carried out at the temperature of the chamber, or at a temperature between the temperature of the chamber and 0 C., or at 0 C., or below 0 C, by example at minus 5 C., or minus 10 C., or lower, or partly at the temperature of the chamber and partly at a temperature below the temperature of the chamber, for example ent: be the temperature of the chamber room and 0 C., or below 0 C., for example at minus 5 C., or at minus 10 C., or lower.



   THIRD METHOD
The cellulose in the presence of an aloali, for example in the form of alkali-cellulose, is acted on using a reagent capable of replacing one or more hydroxyl hydrogen atoms of the cellulose molecule by a organic radical, particularly with an unsubstituted or substituted alcohol radical, after which the mass resulting from the reaction is washed and is then treated with aloali-oaustic under the:

  the form of a solution of aloali-oaustic, or of solid caustic aloali, or of a mixture of a solution of alkali-caus- tic and solid-alkali-caustic, and by less disulphide of carbon than 20 parts, preferably less than 15 or 10

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 parts, per 100 parts of the cellulose derivative, the carbon disulfide being added either simultaneously with the oaus- tic aloali or after a more or less long period of time calculated from the contact of the oellulose derivative
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 with aloali-oa-ustic.

   Treatment with ala.aalioauâtiquer or carbon disulphide, or both, and dissolution of the xanthatic cellulose derivative can be carried out at room temperature, or at a temperature between
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 room temperature and 0 C., or at 0 C., or below 0 * C., for example at minus 5 C., or minus 10 * C.% or lower, or above the temperature of the chamber, for example at 30 to 50 ° C., or partly at the temperature of the chamber and partly at a temperature lower than the temperature of the chamber, eg between the temperature of the chamber and 0 C. , or below 0 * C. , for example at minus 5 C., or minus 10 ° C., or lower, or above the temperature of the chamber for example at 30 to 50 C.,
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 QUA TRIEME r: lF TI-tODF.



  The cellulose is acted on, in the presence of an aloali, for example in the form of thaloali-cellulose, using a reagent capable of replacing one or more hydroxyl hydrogen ator.ies of the molecule of oellulose by an organic radical, particularly by an unsubstituted or substituted alooolic radical, the mass resulting from the reaction, without being washed, is subjected to the addition of a new quantity of aloe-
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 li-oaustic, in the form of a solution of solid aloali-caustic or aloali-caustic or a mixture of a solution of aloa.li-aaustic and solid aloali-oustic, ot it is finally contacted with less carbon disulphide than 20 parts, preferably less than 15 or 10 parts per 100 parts of the cellulose derivative.

   Treatment with aloe vera
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 the causative agent or the carbon disulfide, or both, and the dissolution of the xanthate of the oellulosic derivative May be

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 conducted at the temperature of the chambra or, at a temperature
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 between the temperature of the canker and 0 'G. , or at 0 C., or below 0 C., eg minus 5 * 0. , or less 10C. , or lower, or above the temperature of the room, for example 30 to 50 C., or partly at the temperature of the chamber and partly at a temperature below the temperature of the chamber, for example between the temperature of the
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 room and 0 Cr;

   or below 0 ° C., for example at minus 5 ° C., or minus 10 "cc, or lower, or above the temperature of the chamber, for example at 30 to 50 C.
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 FIFTH METHOD
The cellulose is acted upon in the presence of an alkali, for example in the form of alkali-cellulose using a reagent capable of replacing one or more hydroxyl hydrogen atoms of the cellulose molecule by a radical
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 orgmi-read, particularly with an unsubstituted or substituted alcoholic radical and the mass resulting from the reaction without being washed and without incorporating a new quantity of al-
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 oali-oaustiqie is treated with less carbon disulphide than 20 parts, preferably less than 15 or 10 parts,

   per 100 parts of the oellulosic derivative. The treatment with carbon disulphide and dissolving the xanthate of the olulosic derivative can be carried out at the temperature of the chamber or at a temperature between the temperature of the chamber.
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 bre and 0 C., or at onc., or below onc., for example at minus 5 ° C., or minus 10 ° C. , or lower or above the temperature of the chamber, for example at 30 to 50 ° C. , or partly at the temperature of the Qhambra and partly at a temperature below the temperature of the chamber, for example between the
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 canker temperature and 0 ° C., or below 0 ° C., for example at minus 5 ° C., or minus 10'G. , or lower, or above the temperature of the haliber, for example 30 to 50 ° C.

   

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 SIXTH Ml! 'THODF
A reagent capable of replacing one or more hydroxyl hydrogen atoms of the cellulose molecule by an organic radical, particularly by an unsubstituted or substituted alcohol radical, and less carbon disulfide than 20 parts, preferably less than 15 or 10 parts, per 100 parts of the cellulose derivative, are added to
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 aloalioellulose sirr.7.tan6ment, or (in one order or the other) consecutively at an interval, which, in the case of adding the arbene disulphide before the detl-, 4rifying agent may be so Therefore, a complete transformation of the alkali - cellulose into a xanthate does not occur.

   The xanthate thus othenu is then dissolved in water or in an aloali-oaustic solution, the dissolution being carried out at temperature.
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 temperature of the chamber, or at a temperature between the temperature of the chamber and 0C. , or at 0'C. , or below 0 * 0., for example at minus 5 'to minus 10'C. , or lower, or partly at the temperature of the chamber, and partly at a temperature lower than the temperature of the chamber, for example between the temperature of the chamber and 0 ° C., or below 0 * C. , for example at minus 5 * C., or minus 10 * C., or lower.



     SFPTIFMF METHOD
The oellulose is acted on in the presence of an alkali, for example in the form of aloali-oallalose, using a reagent capable of replacing one or more hydroxyl hydrogen atoms of the hydrogen molecule. cellulose with an organic radical, particularly with an unsubstituted or substituted alcoholic radical, after which the resulting mass is washed and (if desired after being Beaked) brought to the oontaot with an aloali-oaustic solution of a degree of concentration such that the quantity added to the washed product of the reaction as well as the water, if any, contained in this solution, deter-

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 will undermine the proportion of water, caustic aloali and organic substitute derivative,

    particularly cellulose ether, which is desired to have in the final solution or paste. Then, the solution or paste or suspension (the nature and appearance of the product, during this phase of the process depends on the nature, the solubility in a solution of caustic alkali and the proportion of the substitute organic derivative, soluble cellulose present) may or may not be cooled to a temperature below the temperature of the chamber, or to 0 C., or below 0 C., after which it is subjected to the addition of a quantity of carbon disulphide less than 20 parts, preferably less than 15 or 10 parts per 100 parts of the cellulose derivative at the temperature of the chamber,

     or above this temperature, for example at 30 to 50 C., or at a temperature between the temperature of the chamber and 0 C., or at 0 C., or below 0 C., for example at minus 5 C., or minus 10 C., or lower, or partly at the temperature of the chamber and partly at a temperature below the temperature of the chancre, for example entered the temperature of the chamber and 0 C., or below 0 C., for example minus 5 C., or minus 10 C., or lower.



   EIGHTH METHOD.



     Same way of operating as in the seventh method, but with the difference that, before being put in oontaot with the caustic alkali solution, the mass subjected to the reaction is not washed. It goes without saying that, in this case, account must be taken of the caustic alkali (if any) contained in said mass when determining the degree of oonoentra- tion of the solution of caustic alkali.



   The above methods are applicable to substituted organic cellulose derivatives which are soluble or insoluble in caustic alkali solution, while the following method is only suitable for organic derivatives.

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 Cellulose substitutes which are soluble in a caustic alkali solution.



   NINTH METHOD.



   The cellulose is acted upon, in the presence of an alkali, for example in the form of alkali-cellulose, using a reagent capable of replacing one or more atoms of hydrogen hydroxyl. of the cellulose molecule by an organic radical, particularly by an unsubstituted or substituted alcoholic radical, and the reaction product is isolated from the mixture subjected to the reaction by dissolving it, if desired after washing in a solution dilute of causative alkali (the dissolution being carried out at the temperature of the chamber or between the temperature of the chamber and 0 C., where at 0 C., or below 0 C.

   , or partly at the temperature of the chamber and partly at a temperature lower than the temperature of the chamber, for example between the temperature of the chamber and 0 C., or below 0 C., for example at minus 5 C., or minus 10 C., or lower), if necessary by removing undissolved particles from the solution thus obtained by filtering, centrifugation, settling and decantation, or the like, and precipitating the derivative substituted organic cellulose substitute, using an acidic substance or a salt, or a dehydrating agent, such as alcohol, or any other suitable precipitating agent.

   The cellulose substitute thus isolated is (if desired after) having been washed and, if desired, dried) then redissolved in a solution of caustic alkali at or below chamber temperature. this temperature, or at 0 ° C., or below 0 ° C., and exposed to the action of an amount of carbon disulfide less than 20 parts, preferably less than 15 or 10 parts, per 100 parts of the cellulose derivative at the temperature of the chamber or above this temperature, for example at 30 to 50 C., or at a temperature between the temperature of the chamber and 0 C., or at 0 C,

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 or below 0 C., for example at minus 5 C., or minus 10 C., or lower,

   or partly at the temperature of the chancre and partly at a lower temperature of the chamber, for example between the latter temperature and 0 C., or below 0 C., for example at minus 5 C., or less 10 C., or lower.



   Since the foregoing description is far from exhausting all the possible methods of carrying out the invention, it must be expressly stated that it is not desired to limit the invention to the preceding embodiments, and further, that the alkali soluble or insoluble substitution derivatives, particularly ethers or cellulose ethers-like compounds, can be prepared by any method useful for this purpose, i.e. the methods and methods described herein, or according to the methods described in the patents specified in the first paragraph and the eleventh paragraph of this specification, or by any other method or method.



   After treatment with carbon disulfide, the end products can be purified or isolated from the masses resulting from the reaction, for example (optionally after neutralizing them with a weak acid, for example acetic acid) by precipitating them with an alcohol such as methyl or ethyl alcohol, or a solution of a salt, such as sodium chloride, or an ammonium salt, or the like, or carbon dioxide, or sulfurous acid or sodium bisulfite. Xanthate can also be purified by dialysis.



   However, in many cases purification or isolation is unnecessary, since the crude mass subjected to the reaction are readily soluble in a caustic alkali solution and give solutions which contain little or no acid. undissolved particles.



   Despite the fact that the xanthates of the present invention

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 tion are produced using small proportions of carbon disulphide, they are easily soluble in caustic aloali and in water. On being acidified, they give coagulated products or precipitates which are insoluble in water. With salts of heavy metals, for example zino or drunk, they give salts of these metals.



   It is furthermore remarkable that, unlike the cellulose itself, the reaction of xanthate easily takes place in the presence of dilute solutions of aloali.



   The transformation of the xanthatic cellulose derivatives prepared according to the present invention into shaped structures, for example threads, films, coatings of any kind or other, is carried out, for example, by giving a solution of a cellulose derivative obtained according to l The invention forms it as desired and by acting on the solution thus formed with the aid of a coagulating agent, for example one of the coagulating agents known in the viscose industry.



   The xanthatic cellulose derivatives produced according to the present invention can also be made into shaped structures, such that their shaped solutions are contacted with one or more agents which have or have an ooagulating effect on the shaped solution and a plasticizing effect. on freshly coagulated material.

   As coagulating and plasticizing agents, baths containing at least 25% sulfuric acid monohydrate (eg 25 to about 70% sulfuric acid monohydrate), or a proportion of another strong inorganic acid which will produce, in the manufacture of shaped structures, an effect analogous to that given by sulfuric acid containing at least 25% sulfuric acid, has given satisfactory results.

   Coagulation and plasticization of the shaped solutim can also occur in two phases by acting on the shaped solution first with one or more agents which have a coagulating effect on the conforming solution. mée, and then by means of one or more agents (for example

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 strong mineral acids, particularly strong sulfuric acid) which have a plasticizing effect on freshly coagulated material.



   With regard to artificial structures without support, such as artificial threads, artificial horsehair, artificial straw, films, bands or the like, conformation and coagulation can be effected by spinning the xanthate solutions. of cellulose derivatives, through openings oonvenaolement formed in a coagulation bath.

   In the case of shaped structures which are formed with a rigid or foldable support, such as coatings, layers and impregnations of all kinds, fabric finishes, printing on fabrics, cloth for bookbinding, tracing cloth, in- bonding of threads and paper, paper-like coatings, etc.

   shaping and coagulation can be effected by coating, impregnating, imprinting or otherwise covering, in whole or in part, or by soaking with the solution of cellulose derivative xanthate a rigid or pliable support and with or without intermediate drying and treatment of the material by an ooagulation bath, by introducing the material into a coagulation bath or by leading this material through vapors of the ooagulation bath, and by any another method of applying a liquid to a rigid or pliable support.



   The xanthatic cellulose derivatives prepared according to the present invention can be made into artificial materials, for example threads, or films, or coatings or layers of any kind, or impregnations of any kind, alone in combination with other colloids, such as than cellulose xanthate.

   This combination with cellulose xanthate can be carried out by mixing a solution of a xanthate of a cellulose derivative prepared according to the invention with viscose, or by dissolving cellulose xanthate (from

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 sulphurized alkaline cellulose) in a solution of a xanthatic cellulosic derivative, or by dissolving a xanthatic cellulose derivative in visoose, or by carrying out the present process so that the arbone disulphide can act in the presence of caustic alkali, on a mixture of a substitute organic derivative of cellulose of the types previously mentioned, particularly an ether of cellulose, or an oellulosic compound analogous to ether, and of cellulose,

   for example by treating the aloali-cellulose with a reagent capable of replacing one or more hydroxyl hydrogen atoms of the cellulose mold with an organic radical, particularly with an unsubstituted or substituted alcohol radical, under conditions such that only part of the cellulose contained in the alkali cellulose is converted into a corresponding olulosic derivative, and then, by treatment with carbon disulphide, converting the mass thus obtained as a mixture of a xanthate of the corresponding oellulose derivative with cellulose xanthate. In addition, other cellulose derivatives soluble in aloali, or cellulose hydrates soluble in aloali, or proteins ,

   or gelatin can be used for mixing with the xanthatated cellulose derivatives prepared according to the present invention.



   Any suitable softening agents, '' such as glycerin, or a glyool, or a sugar, such as gluoose, or a soap, or Turkish red oil, or a drying oil or not siccative, or a halogen derivative of a di- or poly- valent alcohol, particularly a halohydrin, such as a diohydrin or a monochlorohydrin of glyoerol, or of ethylene hydrochloride, can be added to the solutions of xanthatic cellulose derivatives prepared according to the present invention.



   It is impossible to state every condition for success in every particular case, and it is understood that preliminary experiments cannot be avoided to find out what are the necessary conditions for success when employing a

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 special kind of cellulose, a. derivative organizes from partial substitution of cellulose, a particular proportion of carbon disulphide, and a partial process of xanthation.



   In order to explain the nature of the present invention, the following specific examples are given. It is understood that the invention is not limited to oes examples, to the precise proportions of the ingredients, to the times and to the temperatures and to the order of the operations mentioned; parts are by weight.



   EXAMPLE I - A to G.



   A. 1000 parts of air-dry cotton lintar, or oois paste, are soaked in 10,000 to 20,000 parts of an 18% caustic soda solution at 15 to 20 C., and allowed to stand. the mixture at 15 to 20 C., for 1 to 24 hours.



  The resulting bundle is then squeezed to give 3,000 to 3,500 parts and is reduced to small fragments at 10 to 20 C., for 2 to 3 hours, in a Werner-Pfleiderer dehickener, or other suitable fragmenting machine, or in a Werner-Pfleiderer xanthater machine, the blades of which can be toothed.

   Then 100 to 200 parts of ethylene hydrochloride, or 100 to 280 parts of glycerol-alpha-mono-hydrochloride, or 100 to 300 parts of dimethyl sulfate, or diethyl sulfate, or acid monoohloraoetic (for example in the form of a concentrated aqueous solution of sodium mono-chloracetate), or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glycoid, are added in one or more portions, and the mass resulting from the reaction is shredded for about 3 hours at 18-21 C.



   Immediately after, or after, the quantity of oustic soda consumed in the reaction (quantity which was determined by titration of the gross mass subjected to the reaction) has been replaced (replacement which is preferably carried out using a strong caustic soda solution, for example at 50%),

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 140 to 160 parts of carbon bisulfate are added, and allowed to act, preferably while kneading, kneading, stirring or otherwise stirring the mixture for 2 to 10 hours.

   The xanthatic mass is dissolved in a quantity of water and of caustic soda sufficient to give a solution containing about 6 to 9% of the cellulose of the same nature which was used for the preparation of the oellulose derivative now xanthatic and 6 to 9 % NaOH.



   Before adding carbon disulphide, the reaction mass, optionally after strengthening the sodium hydroxide solution, can stand at room temperature for 12 to 96 hours.



   After being aged at 15 to 18 ° C. for 12 to 36 or 48 hours, during which time it has been filtered two or three times, the solution can be made into shaped structures of various kinds and also be used for priming, or coating, or impregnating, or printing fabrics, or gluing yarns, the production of some shaped structures being indicated in the following examples to which the invention is not limited, since they are far from encompassing all types of Shaped structures or other useful articles which can be produced from the solutions of the products of the present invention.



   1). Cellulose ether xanthate solution (to which can be added a softening agent, such as oxy-trimethylene sulfide, or glycerin, or turo red oil, or a other sulfonated oil, or a sugar), is spun, through a suitable die or slot, in a suitable precipitation or coagulation bath, for example any coagulation bath known in the viscose industry, such as 10 to 20% sulfuric acid, or a bath containing 10 to 16% sulfuric acid and 20 to 25% sodium sulphate or a bath containing 10 to 16% sodium sulphate,
 EMI19.1
 or 00;

   'thread; 1 n' 1ontemmt 10 to 16% M sulfata do oodiUE.1, 14 to 30%

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 of magnesium sulphate and 2 to 16% sulfuric acid, etc.



   To all the above baths, a certain quantity of an organic substance can be added, for example. 5-10% glyoose or glycerin, and also some (eg 1-2%) zinc sulfate.



   Solutions of the cellulose ether xanthate can also be spun into a solution of a salt, for example a 25% solution of ammonium sulphate, and then be washed from this solution of the salt into an acid bath, for example any of the said baths specified above by way of example.



   The coagulation bath can be used at or below the temperature of the chair, for example at 4 to 8 ° C., or at a higher temperature, for example at 35 to 45 ° C. or more.



   The solidified film is washed with water and, optionally after contacting with a dilute solution of a substance having an alkaline reaction, such as a dilute solution of ammonia, or a dilute solution. of Na2CO3 or NaHCO3, or the like and washed again, it is dried in the usual manner.



   Film spinning, or film drying (or both) can be carried out without additional tension, or with more or less additional tension.



   The film can be treated, before or after drying, with an aqueous solution of glyoterol (for example from 4 to 10%) or of glyool in order to increase its flexibility.



   It goes without saying that the film can also be treated with any of the known agents or compositions for waterproofing against moisture or water.



   The film can be treated, either during its manufacture or in the finished state, with a curing agent, such as formaldehyde, or the like.

  <Desc / Clms Page number 21>

 



   The manufacture of narrow strips or artificial straw follows automatically from the preceding example.



   2) The cellulose ether xanthate solution is, in the known manner, spun through one or more dies, in any coagulation or precipitation bath known in the visoose silk industry, for example in one of the precipitation or coagulation baths, or combination of two baths, mentioned in paragraph (1).



   The spinning operation can be carried out with or without additional tension which can be carried out, for example by placing in the path that the thread follows from the spinneret to the devices which collect it, such as a spool or oentrifuge apparatus, a or several interrupting members, such as buckets, or rollers or glass or metal rods arranged angularly with respect to one another, or other sensitive elements. Additional tension can also be given to the yarn by a high spinning speed, for example a speed of 80 to 100 meters, or more, per minute.



   Artificial yarns can be treated, either during their manufacture or in the finished state, with a curing agent, such as formaldehyde, or the like.



   3). A mixture of 50 parts of viscose (prepared in the usual manner and containing 6 to 10% by weight of cellulose) and 50 parts of cellulose ether anthate, is fil-, in the form of a film or strands. artificial, as in subsection (1) or (2).



   4). The process is carried out as in 1 or 2 or 3, but with the difference that a bath is employed which has a plasticizing effect on the freshly coagulated material, for example 25-70% sulfuric acid or another. mineral acid, such as hydrochloric acid, or phosphoric acid, or nitric acid having a degree of concentration which exerts a plasticizing effect on the film or freshly ooa- wire

  <Desc / Clms Page number 22>

 gule equivalent to the plasticizing action of 25 to 70% sulfuric acid, or a strong solution of zinc chloride free of hydrochloric acid or containing a little thereof, or one of the plasticizing baths mentioned in British Patent No. 393,392, or other.



   The plasticization can be carried out using one or two baths. In other words, the solution can be spun directly into a bath which has a coagulating effect pure the conformed solution and a plasticizing effect on the freshly coagulated film or yarn (eg one of the plasticizing baths specified above), eu it can be spun in a bath which has little or no plasticizing effect on the formed solution (for example one of the baths specified in 1 or 2) and it can be run from there in a plasticizing bath (for example one of the baths specified in 1 or 2). plasticizers specified above).



   It goes without saying that films or threads which have a shiny fault or which are completely dull can also be produced from the xanthate solution by any process available in the artificial silk industry.



  The same is true of the wires in which empty spaces or gas bubbles are distributed.



   The manufacture of fibers in strands follows automatically from the above.



   5). A woven fabric, such as a cotton fabric, is coated using a suitable machine, such as a plating or plating or spreading machine, with one or more layers of the solution. cellulose ether xanthate, a solution to which a filler can be added such as talc, or porcelain earth, or zinc white, or a dye, or pigment, such as a lacquer , or carbon black, or mica, or a softening agent (or both) for example an oxy-trimethylene sulfide (see British Patent No. 25246/1911 or a soap, or oil for turkish red, or a sio-

  <Desc / Clms Page number 23>

 oative or not siooative, eto. eto ..

   The coated, or impregnated, or filled material is then introduced directly, or after intermediate drying or steaming, or both, into a precipitation bath as mentioned in 1 or 4, and is then washed and dried.



   The textile material can be treated, before or after drying, with a softening agent, such as soap, or Turkish red oil, or glyoerol, or the like.



   6). The procedure is the same as in 5, except that the cellulose ether xanthate solution is mixed with a solution of starch, or dextrin, or any other oil known in the finishing industry. .



   7). The process is carried out as in 5 or 6, except measures are taken to incorporate into the final material deposited in or on the fibers of the fabric, gas bubbles or empty spaces. This can be done in any known manner, either by dispersing or otherwise distributing a gas, such as air, or hydrogen, or nitrogen, or the like, in the solution, or by introducing into the solution. the latter a substance (eg sodium carbonate or sodium sulphide) which, during the subsequent coagulation or precipitation operation, will give off a gas.



   8). The process is carried out as in 5 to 7, but with the difference that, before being applied to the fabric, the solution is transformed into a foam according to the process described in Belgian patent no. 389,620.



   Examples for the sizing of yarns follow automatically from Examples 5 to 8.



   9) The cellulose ether xanthate solution is mixed with a colorant, or pigment, such as lacquer or smoky black, or zinc blano or finely divided mica, and it is then printed in a roller printing machine where it is stenciled onto a cotton fabric.

  <Desc / Clms Page number 24>

 



   After having and.? printed, the cotton fabric is, if desired after being dried, introduced into one of the non-plasticizing or plasticizing baths or combinations of baths indicated in 1 and 4 and, after having passed through the bath (s), the said fabric is washed and dried.



   10). The cellulose ether xanthate solution can also be used to peel together two or more sheets of paper or board, or cotton fabrics, the materials then being glued together, if desired after intermediate drying. , introduced into one of the non-plasticizing or plasticizing baths, or combination of baths specified above in 1 and 4.



     He). Thick plates can be made accordingly by conforming concentrated solutions or pastes of the cellulose ether xanthate and, optionally after intermediate drying, treating them with one of the precipitation aains or combinations of precipitation baths specified herein. above in 1 and 4.



   B. The process is carried out as in A. but with the difference that, before being dissolved, or during any other phase of the xanthation operation, the mass subjected to the reaction is cooled to a temperature. temperature between the temperature of the chamber and 0 C., or at 0 C., or at minus 5 C., or rapins 10 C., and Maintained at this temperature by stirring it, or by kneading it, or by the stirring otherwise for 20 minutes to 2 hours or longer.



   C. Same way of operating as in A. or B. except that the dissolution of the xanthatic mass in a caustic soda solution is carried out in such a way that, during any phase of the operation of dissolution, for example, at the end of this operation, the complete or incomplete solution is -cooled, by rerauating it, or by kneading it, or by stirring it in some other way, at a temperature between the temperature of the chamber and 0 C., or at 0 C., or below

  <Desc / Clms Page number 25>

 from 0 C., for example to minus 5 C., or minus 10 C.

   , and that it is then brought back, if desired, to the temperature of / the chamber, or to any other desired temperature between 0 ° C., and the temperature of the chamber, or higher.



   D. Same procedure as in any of Examples A to C except that the reaction of the alkali cellulose with the etherifying agent (s) is carried out at 5 to 10 C.



   A. Same procedure as in any of Examples A to C, except that the reaction of the aloali-cellulose with the etherifying agent is carried out at 50 C.



   F. The process is carried out as any of Examples A to E. but with the difference that the alkalellulose is subjected to ripening for 12 to 96 hours, or longer, at 10 to 25 C.



   G. The procedure is carried out as in any of Examples A. to F. except that after having stirred, kneaded, or shredded the mass resulting from the reaction for 3 hours, as provided in A This mass is allowed to stand at chamber temperature for 20 to 96 hours or longer.



     EXAMPLE II A to G.



   The process is carried out as in any of Examples IA to G, except that instead of 140 to 160 parts, 70 to 100 parts of carbon disulfide are added, the age of the xanthate solution at the time of mixing. transform into a conformal structure being 8-24 or 36-48 hours.



   EXAMPLE IIIA to G.



   The process is carried out as in any of Examples IA to G. except that instead of 140 to 160 parts, 40 to 65 parts of carbon disulfide are added, the age of the xanthate solution at the time of mixing. transform into a conformal structure being 8 to 24 or 36 hours.



   EXAMPLES IV A to G.



   A. 1000 parts of air-dried cotton linters, or

  <Desc / Clms Page number 26>

 of wood pulp are soaked in 10,000 to 20,000 parts of an 18% solution of 15 to 20% caustic soda. , and the mixture is allowed to stand at 15 to 20 ° C. for 1 to 24 hours. The resulting mass is then squeezed to give 3000 to 3500 parts and is reduced to small fragments at 10-20 ° C., for 2-3 hours, in a Werner-Pfleiderer shredder, or other suitable shredder. , or in a Werner-Pfleiderer xanthater machine, the blades of which can be sharpened.

   Then 100 to 200 parts of ethylene ohlorohydrin: or 100 to 280 parts of glyceromealpha-monochlorohydrin, or 100 to 300 parts of dimethyl sultate, or of ethyl sulfate, or of monochloroacetic acid (for example under the form of a concentrated aqueous solution of sodium monochloroacetate), or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glyoid, are added in one or more portions, and the resulting reaction mass is stirred for about 3 hours at 18-21 C.



   Immediately thereafter, the crude reaction product as it is, or after having been neutralized or acidified, is washed with water and is then preferably pressed, after which the washed and pressed product is thoroughly mixed in a machine. suitable, for example in a Werner-Pfleiderer xanthater machine the blades of which may be toothed, or in a kneading or kneading machine, or in a shredding machine, or in a rotating drum or the like, at 15 at 18 C. with a quantity of caustic soda and water which together with the quantity of water present in the mass will form 10,000 to 20,000 parts of an 18% solution of caustic soda.



   After having rested at the temperature of the chancre, or at about that temperature for 1 to 3 hours, the mass is pressed to form 3,400 to 4,200 parts and it is then reduced into small fragments in a shredding machine, or in another suitable chopping machine, for 2 to

  <Desc / Clms Page number 27>

 3 hours, at 11 to 15 C. After shredding, and optionally maturing at 10 to 25 C., for 12 to 96 hours, 140 to 160 parts of carbon disulfide are added, and the reacted mass is processed. by this carbon disulfide while kneading it, or shredding it, or stirring it, or stirring it in some other way (eg in a rotating drum) for 3 to 10 hours.

   The xanthatic mass is dissolved in the desired quantity of water and caustic soda to give a solution containing about 6 to 8% of the cellulose of the same nature which was used for the preparation of the cellulose derivative now xanthatated, and 6 to 9% NaOH.



   After being aged at 15-18 ° C. for 12-36 hours, during which time it has been filtered two to three times, the cellulose ether xanthate solution can be made into shaped structures according to any one. methods described by way of example in paragraphs 1 to 11.



   B. The process is carried out sum in A, but with the difference that, before being dissolved, or during any other phase of the xanthation operation, the mass subjected to the reaction is cooled to a temperature between between the temperature of the free ha. and 0 C., or at 0 C., or at minus 5 C., or at minus 10 C., and it is kept at that temperature while stirring it, or kneading it or stirring in another way for 20 minutes to 2 hours, or longer.



   C. Same way of operating as in A or B, except that the dissolution of the xanthatic mass in a solution of oaustic alkali is carried out in such a way that, during any phase of l 'dissolving operation, for example at the end of this operation, the complete or incomplete solution is cooled, while stirring it, or by kneading it, or by stirring it in another way, at a temperature comprised between-

  <Desc / Clms Page number 28>

 be the temperature of the chamber and 0 C., or at 0 C., or below 0 C.

   , for example minus 5 C., or at minus 10 C., and that then, if desired, it is brought back to the temperature of the room, or to any other desired temperature between 0 C., and the temperature from the bedroom, or higher.



   D. Same procedure as in any of Examples A to C except that the reaction of the alkali cellulose with the etherifying agent (s) is carried out at 5 to 10 C.



   E. Same procedure as in any of Examples A. to C. except that the reaction of the alkali-cellulose with the etherifying agent is carried out at 50 C.



   F. The process is carried out as in any of Examples A through E with the differentiation that the alkali-aellulose is cured for 12 to 96 hours, or longer at 10 to 25 hours. vs.



   G. The process is carried out as in any of Examples A through F, except that after stirring, kneading, or shredding the mass subjected to the reaction for 3 hours, as provided in A, this mass is allowed to stand at chamber temperature for 20 to 96 hours.



   EXAMPLE V A to G.



   The process is carried out as in any of Examples IV to to G, except that instead of 140 to 160 parts 70 to 100 parts of carbon disulfide are added, the age of the xanthate solution at the time of mixing. transform into a conformal structure being 8 to 24 or 36 to 48 hours.



     EXAMPLE VI A to G
The process is carried out as in any of Examples IV to G, but with the difference that instead of 140 to 160 parts, 40 to 65 parts of carbon disulfide are added, the age of the xanthate solution is added. at the time of conversion to a shaped structure being 8 to 24 or 36 hours.

  <Desc / Clms Page number 29>

 



   EXAMPLE VI I A to G.



   The procedure is carried out in any of Examples IV to to G, to VI A to G, united with the difference that,
 EMI29.1
 instead of being aloa1inis4 with a salt of a sodium hydroxide solution and then freed of the excess of the caustic soda solution by pressure, the washed and pressed product resulting from the treatment of the alkali cellulose by ohlorhy-
 EMI29.2
 ethylene drine, or ethylene monochlorohydrin, or dimethyl sulfate, or diethyl sulfate, or monoohloroacetic acid (for example in the form of sodium monochlorohydrin), or oxide of 'ethylene, or propylene oxide
 EMI29.3
 or glyoid ,, is mixed, in any suitable apparatus for example in a) 1j, ohine to xanthater Wel'l1el '' 'PfleiderGJ.,

   or in a naohine at d 30hi'J.uete r Werner-Pi'leiderer, or in a kneading machine 9th mr;: c -Pî le.derer, with the desired amount of a caustic soda solution of one degree of appropriate concentration to give a mixture containing 1000 parts of the
 EMI29.4
 sid of the dry washed and pressed product of the etherification operation, and 1000 to 2400 parts of an 18% caustic soda solution, the xanthation of the product thus maintained and its dissolution being carried out as in n ' any of Examples IV A to G to VI A to G.



   EXAMPLE VIII A to G.



   The process is carried out as in any of Examples IV A to G, to VI A to G, but with the difference that, instead of being aloalinated with an excess of an oaustic sodium hydroxide solution and then freed from of the excess of the caustic soda solution by pressure, the washed and pressed product resulting from the treatment of the alkali-cellulose with ohlorhy-
 EMI29.5
 ethylene dtJhne, or la, monoohlo rl1;

  ) rdrin of ethylene, or of dimethyl sulfate, or of diethyl sulfate, or of chloroacetic acid (for example in the form of sodium monochloroacetate), or of ethylene oxide, or of propylene oxide
 EMI29.6
 or glycide, is mixed, 3, in any suitable apparatus., pa, r 1

  <Desc / Clms Page number 30>

   example in a Werner-Pfleiderer xanthater machine, or in a Werner-Pfleiderer shredding machine, or in a Werner-Pfleiderer kneading machine, with the desired amount of a caustic soda solution of an appropriate degree of concentration to give a mixture containing a sufficient quantity of the dry residue of the pressed and washed product from the etherification operation and of an 18% caustic alkali solution so that,

   after xanthation (which is carried out as described in any of Examples IV A to G to VI A to G) and addition of an appropriate amount of water, a solution is obtained containing about 6 to 9% of the dry residue of the washed and squeezed reaction product in 6-9% caustic soda solution.



   EXAMPLE IX A to G.



   The process is carried out as in any of Examples IV A to G to VIII A to G, except that the mass resulting from the treatment of the alkali-cellulose with ohlorohydrin or ethylene monochlorohydrin, or sulfate dimethyl or diethyl sulfate, or monchloroacetic acid for example in the form of sodium monaohloraoetate) or ethylene oxide, or propylene oxide, or glyoid, is, without being washed , alkalized, with 6,600 to 13,600 parts of an 18% caustic soda solution at 15 ° C. and is then, by pressure, shredding and sulphurization, made into a final man- thate as described in any which of Examples IV A to G to VIII A to G.

   the latter xanthate being transformed into any of the conformal structures specified above in paragraphs 1 to 11.



     EXFMPLF, X A to F.



   A. 1000 parts of air-dry cotton linters, or wood pulp, are soaked in 10,000 to 20,000 parts of an 18% caustic soda solution at 15 to 20 C. and the mixture is allowed to stand at 15 to 20 C., for 1 to 24 hours. The resulting mass is then squeezed to give 3000 to 3500 parts and is reduced to small fragments at 10 to 20 C. during

  <Desc / Clms Page number 31>

 2 to 3 hours, in a Werner-Pfleiderer shredder, or other suitable shredder, or in a Wemer-Pfleiderer xanthater machine whose blades can be toothed.

   then 100 to 200 parts of ethylene ohlohydrin, or 100 to 280 parts of glycerol-alpha-monophlorohydrin, or 100 to 300 parts of dimethyl sulfate, or of diethyl sulfate, or of monoohloraoetic acid (for example under in the form of an oono-entered aqueous solution of sodium menochloroacetate) or, 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glycol are added in one or more portions, and the mass resulting from the reaction is shredded for about 3 hours at 18-21.

   Then, the mass subjected to the reaction is, in the crude state or in the washed and pressed state, mixed with the desired quantity of a caustic soda solution of an appropriate degree of concentration to give a mixture of 1000 parts of the cellulose derivative ocontained in the crude mass subjected to the reaction or of the seo residue of the washed and dried product of the reaction and 11,100 to 19,000 parts of a 6 to 9% solution of caustic soda.

   The mixture is now stirred in a Werner-Pfleiderer xanthater machine, or in another suitable machine, at chamber temperature, or at any temperature between chamber temperature and 0 ° C., or at 0 C. ., or at 0 ° C., for example at minus 2 or minus 5, or minus 10 ° C., for 20 minutes to 2 hours, after which 140 to 160 parts of carbon disulfide are added, and the mixture is maintained. the mixture while stirring it, or shaking it, or stirring it for 2-10 hours, at room temperature or 10C.



   After being aged at 15 to 18 ° C. for 12 to 36 or 48 hours and after (during aging) having been filtered two to three times, the xanthate solution thus obtained is transformed into any of the conforming structures. specified above in the conforms specified above in paragraphs 1 to 11.

  <Desc / Clms Page number 32>

 



   B. The procedure is carried out as in A, but with the difference that, after being treated with carbon bisulphide at room temperature, or at 10 ° C., for 2 to 10 hours, the mass resulting from the reaction is cooled to a temperature between the temperature of the chamber and 0 C., or to 0 C., or below 0 C., for example to minus 5 to minus 10 C., it is maintained at this temperature for 20 to 30 minutes, or even for 1 to 2 hours, while stirring it, kneading it, or stirring it in some other way, it is then brought back to the temperature of the chamber .



   VS,. Same procedure as in A or B, except that the reaction of the alkali-celialose with the etherifying agent (s) is carried out at 5 to 10 C.



   D. same procedure as in any of Examples A or B except that the reaction of the alkali-cellulose with the etherifying agent is carried out at 50 C.



   E. The process is carried out as in any of Examples A to C, but with the difference that the alkali cellulose is matured at 10 to 25 C., for 12 to 96 hours, or more. long time.



   F. The process is carried out as in any of Examples A through E, except that after being stirred, kneaded, or shredded for 3 hours, as provided in A, the mass resulting from the Reaction stand at room temperature for 20 to 96 hours, or longer.



   EXAMPLE XI A to F.



   The process is carried out as in any of Examples XA to F, except that instead of 140 to 160 parts, 70 to 100 parts of carbon disulfide are added, the age of the xanthate solution at the time of mixing. transform into a conformal structure being 8 to 24, or 36 to 48 hours.



     EXAMPLE XII A to F.



   The process is carried out as in any of Examples X A to F, but with the difference that, instead of

  <Desc / Clms Page number 33>

 140 to 160 parts, 40 to 65 parts of carbon disulfide are added) the age of the xanthate solution at the time of transformation into a shaped structure being 8 to 24 or 36 hours.



     EXAMPLE XIII
The process is carried out as in any of the
 EMI33.1
 Examples IA to 0 to TX A to .G, or XA to F to XII A to F, but with the difference that, instead of 100 to 200 parts of ethylene hydrochloride, or 100 to 280 parts of glycerol. alpha - mono-
 EMI33.2
 ohlorohydrin, or 100 to 300 parts of dimethyl sulfate, or of diethyl sulfate, or of monoohloraoetic acid (for example as a concentrated aqueous solution of mono-
 EMI33.3
 sodium chloraoetate), or 55 to 120 parts of ethylene oxide or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glycide, for the preparation of cellulose ether 200 to 400 parts of ethylene hydrochloride or 150
 EMI33.4
 to 600 parts of alpha-nonoahlorohydrin glyoerol;

   or 00 to 500 parts of dimethyl sulfate, or of diethyl sulfate, or of monoohloroacetic acid (eg as a concentrated aqueous solution of sodium monoohloroetate), or 120 to 240 parts of ethylene oxide , or 150 to 300 parts of propylene oxide, or 180 to 360 parts of glyoid
EXAMPLE XIV
The procedure is carried out as in any of Examples I A to G to IX A to G, or XII A to F but with the difference that instead of 100 to 200 parts of e- phlorohydrin
 EMI33.5
 thylene, or 100 to 280 parts of glyoerol-alpha-111onoohlorhydride, or 100 to 300 parts of dimethyl sulfate, or of diethyl sulfate,

   or monoh10raoetic acid (eg as a concentrated aqueous solution of sodium monohloroetate), or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of ethylene oxide. propylene, or 90 to 180 parts of glyoid, uses it for the preparation of ether
 EMI33.6
 of cellulose one Iné1anr, e from 100 to 200 parts of ohlorohydrin

  <Desc / Clms Page number 34>

 
 EMI34.1
 of ethylene, or from 100 to 200 parts of glyoero1-alpha-loono-ohlorhydrin or from 55 to 120 parts of ethylene oxide, or from 75 to 150 parts of propylene oxide, or from 90 to 180 parts of parts of glyoid, and 100 to 200 parts of diethyl sulfate, or of dimethyl sulfate, or a mixture of 100 to 200 parts of dimethyl sulfate and 100 to 200 parts of diethyl sulfate,

   or a mixture of 100 to 200 parts of ethylene ohlorhydrin, or of 100 to 200 parts of monoohlorohydrin, or of 100 to 200 parts of dimethyl sulfate, or of sulfate
 EMI34.2
 of diethyl, or from 55 to 120 parts of ethylene oxide, or from 75 to 150 parts of propylene oxide, or from 90 to 180 parts of glyoid and 100 to 300 parts of monoohloraoàtiqae acid (for example under the form of sodium inonoohloraoetate).



   EXAMPLE XV
The process is carried out as in Examples IA to G to IX A to G, or X A to F, to XII A to F.



   A. 1000 parts of air-dry cotton linters, or wood pulp, are soaked in 10,000 to 20,000 parts
 EMI34.3
 of a caustic soda solution at 18 leo L 15 at 20 ° C. , and the mixture is allowed to stand at 15 to 20 ° C. for 1 to 24 hours. The resulting mass is then squeezed to give 3000 to 3500 parts and is reduced to small fragments at 10 to 20 C., for 2 to 3 hours, in a Werner-Pfleiderer shredder or other suitable shredder, or in a Werner-Pfleiderer xanthater machine, the blades of which can be toothed.

   Then 100 to 200 parts of
 EMI34.4
 ethylene ohlorohydrin, or 100 to 280 parts of glyoerol-alpha-monoahlorohydrin, or 100 to 300 parts of dimethyl sulfate, or of diethyl sulfate or monochloroetic acid (for example in the form of an aqueous solution (sodium monoohloroetate) or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glyoid, are added in one or more

  <Desc / Clms Page number 35>

 several portions, and the mass resulting from the reaction is shredded for about 3 hours at 18-21 C.

   In the preparation of cellulose ether, a mixture of 50 parts of ethylene hydrochloride or of 70 parts of monoohlorohydrin, or 30 to 40 parts of ethylene oxide, or 70 to 80 parts of oxide is used. of propylene, or from 80 to 120 parts of glyoid and 100 to 200 parts of diethyl sulfate, or of dimethyl sulfate
 EMI35.1
 or 100 to 300 parts of monoohloraoetic acid (for example in the form of sodium inonochlorine), or a mixture of 50 to 100 parts of dimethyl sulfate and 100 to 200 parts of diethyl sulfate, or 100 to 300 parts of monochlor-
 EMI35.2
 alcohol (for example in the form of sodium inonoohloroacetate), or a mixture of 50 to 100 parts of diethyl sulfate,

   or dimethyl sulfate and 100 to 300 parts of monoohlorao1tic acid (eg in the form of sodium monoohloroetate).



   EXAMPLE XVI
The process is carried out as in Examples I A to G to IX A to G, or X A to F to XII A to F,
A. 1000 parts of air-dry cotton linters, or
 EMI35.3
 wood pulp, are tz er.lp3eâ in 10,000 to 20,000 parts of an 18% caustic soda solution at 15 to 20 C., and the mixture is allowed to stand at 15 to 20 C. for 1 to 24 hours. The resulting mass is then squeezed to give 3,000 to 3,500 parts and is reduced to small fragments at 10 to 20 ° C. for 2 to 3 hours, in a Werner-de-hooking machine.
 EMI35.4
 Pfleiderer, or other suitable fraGG1enter machine, or in a Werner-rfleiderer xanthater machine, the blades of which can be toothed.

   Then 100 to 200 parts of ethyl hydrochloride
 EMI35.5
 lene, or 100 to 280 parts of glycol-alpha-monoohlorhydrin, or 100 to 300 parts of dimethyl sulphate, or of diethyl sulphate, or of monoohlorohydrin (for example in the form of an aqueous solution monoohlorac3tate concentrate

  <Desc / Clms Page number 36>

 sodium) or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide, or 90 to 180 parts of glyoid, are added in one or more portions, and the resulting mass
 EMI36.1
 both of the reauti-on. is shredded for about 3 hours at 18-21 C.

   In the preparation of cellulose ether, a mixture of 25 to 50 parts of ethylene hydrochloride or
 EMI36.2
 from 30 to 60 parts of monohlorohydrin, or from 20 to 30 parts of ethylene oxide and 50 parts of diethyl sulphate, or of dnethyl sulphate, or 50 parts of monouhloroacetic acid (for example in the form of sodium mono-ohloroetate) or a mixture of 25 to 50 parts of dimethyl sulfate and
 EMI36.3
 50 parts of diethyl sulphate, or of monoohloraoetic acid (for example under the melting of sodium monachloroetate) or a mixture of 25 to 50 parts of diethyl sulphate, or of dim: thyl sulphate, and 50 parts monoohloraoetic acid (for example in the form of sodium imnachloroacetate).



     EXAMPLE XVII
The process is carried out as in Examples I A to G to IX A to G, or X A to F to XII A to F.



   A. 1000 parts of air-dry cotton linters, or wood pulp, are soaked in 10,000 to 20,000 parts
 EMI36.4
 an 18% oaustic soda solution at 15 to 20'G. , and envm leaves the mixture to stand at 15 to 20 C. for 1 to 24 hours.



  The resulting mass is then squeezed to give 3,000 to 3,500 parts and is reduced to small fragments at 10 to 20 C., for 2 to 3 hours, in a Werner-Pfleiderer shredder, or other suitable shredder, or in
 EMI36.5
 a Werner-Pfleiderer xanthater machine, the blades of which can be toothed.

   Then 100 to 200 parts of ethylene chlorohydrin, or 100 to 280 parts of alpha-glycerol monocshlorhydrin, or 100 to 300 parts of dimethyl sulphate, or of diethyl sulphate or nnnoohioraoeal aid (for example under the form of a concentrated aqueous solution of sodium monochlorinated acetate), or 55 to 120 parts of ethylene oxide,

  <Desc / Clms Page number 37>

 or 75 to 150 parts of propylene oxide or 90 to 180 parts of glyoid, are added in one or more parts, and the mass resulting from the reaction is shredded for about 3 hours at 18 to 21 C. Add 300 to 1200 parts of chlorine-ethyl-diethylamine hydrochloride.



   EXAMPLE XVIII
The process is carried out as in the Fxeinples I A to G to IX A to G, or X A to F to XII A to F,
A. 1000 parts of air-dry cotton linters, or wood pulp, are soaked in 10,000 to 20,000 parts of an 18% caustic soda solution at 15 to 20 ° C., and left rest the mixture at 15 to 20 C., for 1 to 24 hours.



  The resulting mass is then squeezed to give 3000 to 3500 parts and is reduced to small fragments at 10 to 20 C., for 2 to 3 hours, in a Werner-rfleiderer shredder, or other suitable shredder, or in a Werner-Pfleiderer xanthater machine, the blades of which can be toothed.

   Then 100 to 200 parts of ethylene ohlorohydrin, or 100 to 280 parts of glycerol-alpha-monochlorhydrin, or 100 to 300 parts of dimethyl sulfate, or diethyl sulfate, or monochloraoetic acid (for example in the form of a concentrated aqueous solution of sodium monochloroetate), or 55 to 120 parts of ethylene oxide, or 75 to 150 parts of propylene oxide or 90 to 180 parts of glyoid, are added in one or more portions, and the mass resulting from the reaction is shredded for about 3 hours at 18-21 C. 100 to 500 parts of the product of Example 1 of Belgian Patent No. 389,569, purified according to the first or the second method, are used. given in this Example.



   EXAMPLE XIX
The process is carried out as in any of the preceding Examples, but with the difference that the cellulose ethers employed in these Examples are in the form of

  <Desc / Clms Page number 38>

 crude masses subjected to the reaction, (when retested with the addition of a small amount of a concentrated oaustic alkali solution in replacement or in excess of the causal alkali consumed in the reaction.), or in the isolated form, that is to say in the form of the lava and optionally dry mixtures subjected to the reaction, or in the purified form, treated, in the presence of alkali,

     (preferably in an amount less than the weight of the water present), by 50 to 200 parts of ethyl chloride, or by 70 to 150 parts of propyl chloride, or by 100 to 600 parts of benzyl chloride , or by 50 to 200 parts of ethyl chloride at 50 to 120 ° C., or by 40 to 180 parts of methyl chloride at 50 to 110 ° C., and then xanthatated and dissolved as described in any which of the preceding Examples, and the solution thus obtained can be transformed into the shaped structures oomne described in Example I in paragraphs 1 to 11.



   EXAMPLE XX
The process is carried out as in any of the preceding Examples, except that instead of being pressed to form 3000 to 3500 parts, the alkali cellulose used in the preparation of the cellulose ether is pressed to form. form 2000 parties.



     EXAMPLE XXI
The process is carried out as in any of Examples I to XIX, except that, instead of being pressed to form 3000 to 3500 parts, the alkali cellulose used in the preparation of the cellulose ether is pressed. to form 1300 to 1600 parts.



   EXAMPLE XXII A to H.



   A. 1000 parts of air-dry cotton linters, or wood pulp, are soaked in 10,000 to 20,000 parts of an 18% caustic soda solution at 15 to 20 C., and the mixture is allowed to stand. mix at 15 to 20 C., for 1 to 24 hours.



  The resulting mass is then pressed to form 3000 to 3500

  <Desc / Clms Page number 39>

 parts and is reduced to small fragments at 10 to 18 ° C., for 2 to 3) ripe, in a Werner-Pfleiderer shredder, or other suitable shredder.



  Then the alkali-cellulose is placed in a retatative autoclave, or in an autoclave provided with a stirrer device, 200 parts of pre-cooled ethyl chloride are added, and the material is heated to 60 to 80 C. , and maintained at this temperature, for 12 to 24 hours.



   The reaction product is xanthated and dissolved as defined in any of the preceding Examples, and the solution can be made into artificial structures as described in Example I under paragraphs 1 to 11.



   B. Lerooédé is carried out as in Example A, but with the difference that, instead of 200 parts, 300 to 1500 parts of ethyl chloride are used in the preparation of the cellulose ether.



   C. The process is carried out in Example A except that instead of 200 parts, 75 to 100 parts of ethyl chloride are used in the preparation of the cellulose ether.



   D. The process is carried out as in Example A, except that instead of 200 parts of ethyl chloride, a mixture of 50 parts of ethyl chloride and 50 to 200 parts of hydrochloride is used. ethylene, or 25 to 140 parts of ethylene oxide, or 100 to 200 parts of dimethyl sulfate, or 100 to 200 parts of methyl chloride, or 100 to 300 parts of benzyl chloride, or nonochlorac acid ethical (eg in the form of sodium monochloroacetate).



   F. The process is carried out as in any of Examples A to D, but with the difference that the etherification operation is carried out at 50 C.



   F. The process is carried out as in any of Examples A to D, but with the difference that the etherification operation is carried out at 95 C.

  <Desc / Clms Page number 40>

 
 EMI40.1
 



  G. The is carried out in which of Examples A to F, except that in the etherification operation the time of heating is only 3 to 6 hours.



  H. The process is carried out as in which of Examples A to. G, but with the difference that the alkali-cellulose is subjected to maturation for 12 to 96 hours, or longer.



   If there is no excess of ethnic chloride compared to the proportion calculated on the proportion of NaOH contained
 EMI40.2
 in alkali-cellulose, here the etherification reaction can be carried out at a% * i12é; atu #; J.Ópu-a3a, t 100 C. eg 110 to 130 C. or more.
 EMI40.3
 



  FXFUPLF XXIII A 5 H.



  The proood'3 is carried out OClrJià6 in which of Examples XXII A to II, with the difference that, instead of being pressed to iber 3000 to 3500 parts, the alkali-cellulose used in the pr, -> p - ratior, cellulose ether is press3el- to form 2000 parts.



     EXAMPLE XXIV A to H.
 EMI40.4
 



  The process is carried out in any of Examples XXII A to H, except that instead of being pressed to form 3000 to 3500 parts, the alkali cellulose used in the preparation of the cellulose ether is pressed to melt. 1350 to 1600 parities.



   EXAMPLE XXV
Any of the ethyl-cellulose obtained in
 EMI40.5
 Sxeinples XXII A to C and E to H, or XXIII A to C and E to H, or XXIV A to C and E to H, can be hydroxyalooylated as follows:
The NaOH content of the crude mixture resulting from the operation
 EMI40.6
 tion of ethylation in any of Fxeinples XXII A to C and E to H, XXIII A to C and E to H, or XXIV A to C and E to H, is determined by analysis, after which, optionally after com

  <Desc / Clms Page number 41>

 thinking of the quantity of NaOH consumed in the alkylation reaction by supplying the mixture subjected to the reaction with the equivalent quantity of NaOH in the form of powder, or of a strong solution, for example at 30 to 50%,

   said mixture is treated with 50 to 150 parts of ethylene chlorohydrin, or with 0 to 210 parts of glycerol-alpha-monophlorohydrin, or with 25 to 75 parts of ethylene oxide, or with 32 to 100 parts of propylene oxide, as described in any of Examples I to XVI for alkali cellulose.



   The ethyl-hydroxy-ethyl-cellulose thus obtained, or ethyl-1: 2-dihydroxypropyl-cellulose, or propyl-cellulose, is kanthatated and dissolved as described in any of the preceding Examples and the solution thus obtained can be transformed into shaped structures, as described in Example I under paragraphs 1 to 11.



   EXAMPLE XXVI
The process is carried out as in Example XXV, except that not the crude product, but the washed, and optionally dried, product of the reaction of any of Examples XXII A to C and E to H, or XXIII A to C and E to H, or XXIV A to C and E to H, is hydroxyalkyl.



   For this purpose, washed 1-ethyl cellulose resulting from any of the Examples specified in the preceding paragraph and which, if desired can be dried, is soaked in an excess of sodium hydroxide solution. caustic of a degree of concentration such that together with the water (if any) adhering to the ethyl cellulose, an 18% solution of caustic soda is obtained, and the product thus obtained is pressed to form 3000 to 4000 parts. The pressed wafer is then shredded in the usual manner, and then hydroxyalkylated and worked and processed as described in Example XXV.



   Instead of being made by soaking ethyl cellulose in an excess of caustic soda solution and removing it. excess by pressure, the alkali-ethyl-cellulose can be removed

  <Desc / Clms Page number 42>

 trimmed by mixing washed ethyl cellulose, or washed and dried in a mixing apparatus, for example in a Werner-Pfleiderer xanthater machine, or in a shredding machine, with the desired amount of soda solution Caustic acid of an appropriate degree of concentration to give, together with the water (if any) adhering to the ethyl cellulose, 200 to 3000 parts of an 18% caustic soda solution.



   EXAMPLE XXVII
The process is carried out as in any of Examples IA to G to IX A to G, or XA to F to XII A to F or XIII to XXVI, but with the difference, that instead of the caustic soda solution in 18%, uses a 12% sodium hydroxide solution for the preparation of the alkali-cellulose.



    EXAMPLE XXVIII
The process is carried out as in any of Examples IA to G to IX A to G, or XA to F, to XII A to F, or XIII to XXVI, but with the difference that, instead of the sodium hydroxide solution 18% caustic, a 9% caustic soda solution is used for the preparation of the alkali-cellulose.



   EXAMPLE XXIX
The process is carried out as in any of Examples I A to G to IX A to G ,. or XA to F to XII A to F or XIII to XXVI, but with the difference that, instead of the 18% caustic soda solution, om uses a 10% caustic soda solution for the preparation of the alkali. cellulose.



     EXAMPLE XXX
The process is carried out as in any of Examples IA to G to IX A to G, or XA to F, aXII A to F, or XIII to XXVI, but with the difference that, instead of the caustic soda solution at 18%, a 5% solution of caustic soda is used for the preparation of the alkali-cellulose.



   EXAMPLE XXXI
The process is carried out as in any of Examples IA to G to IX A to G, or XA to F to XII A to F or XIII to XXVI, but with the difference that, apart from the caustic soda solution to 18%, a caustic soda solution is used.

  <Desc / Clms Page number 43>

 that from 5 to 12% for the preparation of the alkali cellulose, and that instead of being pressed to form 2000 or 3000 to 3400 parts, the alkali cellulose is pressed to form 1300 to 1500 parts.



     EXAMPLE: XXXII
The process is carried out as in any of Examples I to XX, but with the difference that, before being etherlized, the alkali cellulose is dried, preferably in vacuum, or in a countercurrent. air at the temperature of the chamber, or at a higher temperature, for example at 40 to 60 C., and this completely, that is to say at a constant weight or at a weight between the original weight alkali cellulose and perfect dryness.



   Instead of being prepared by soaking the cellulose in an excess of an alkali-caustic solution and removing the excess by pressure, in any of the preceding Examples the alkali-cellulose can also be prepared. by mixing the cellulose in a suitable mixing apparatus, for example in a shredding or kneading machine, or a mill, or a disintegrating machine, or a grinding machine, or the like, with the amount of a caustic soda solution corresponding to the amount remaining after pressure in the alkali-cellulose used in the Examples.

   The mixing of the cellulose with the caustic alkali solution can be carried out at the temperature of the chamber, or at a temperature above the temperature of the chamber, for example at 24 to 30 ° C., or with cooling, by example at 15 or 10 C. or lower. The duration of the mixing operation can vary within wide limits, for example from 1 hour to 24 hours, or longer.



   In the foregoing Examples, any excess of the etching agents which have not been consumed in the reaction can be recovered by condensation or distillation.



   Instead of the cellulose ethers used in the foregoing Examples, other cellulose derivatives can be employed which are prepared by acting on cellulose in the presence of al-

  <Desc / Clms Page number 44>

 cali, by one or more reagents which tend to react with cellulose, so as to determine the introduction of an organic rad # - cal in place of hydrogen of hydroxy # e, for example compounds cellulosics which are xanthatated in the process described in Belgian Patents Nos. 382,218 and 389,619 and in British Pat. No. 367,920.



   In the above Examples, instead of cellulose, gold. can employ as a material of the same nature any cellulose transformation product which is insoluble or only barely soluble in a caustic alkali solution, for example a cellulose hydrate, or a hydrocellulose produced by chemical action on cellulose, such as mercerization with subsequent washing and, if desired, drying, or by ur treatment. strong inorganic or organic acid, or a mixture of the two, or by heating with a dilute solution of a mineral acid or by treatment with a zinc halide or by a mechanical process, such as grinding in the presence of water or the like liquid;

   or an oxycellulose, in short any body of the cellulose group which has been proposed for the manufacture of viscose, or of any other cellulose derivative or compound, or of cellulose with ammoniacal copper oxide.



   In the above examples, a small amount of a catalyst, for example a metal salt, such as a copper salt, a nickel salt, a silver salt, a zinc salt, an iron salt, or a peroxide, for example benzogl peroxide, or ammonia, or primary, secondary or tertiary organic bases, such as a mono-or - dialkoyl-aniline, or a mono-di-or-tri- alkylamine or an aralkyl amine, or an oxyalkylamine, or the like, can be added to the alkali cellulose or to the mixture subjected to the reaction.



   If possible or useful, in the foregoing Examples, instead of the halogenated etherifying agents used in these Examples, equivalent amounts of the corresponding brominated or iodinated reagents (eg, alkyl bromides, or alkyl iodides, or mono-bromhy-

  <Desc / Clms Page number 45>

 
 EMI45.1
 drine, or monohydrin, or ethyl brorihydrin; or ethylene tkitylaxial iodhydrin, or bromacetic acid, or iodacetic acid, etc.).



   If possible or useful, in the Examples which precede
 EMI45.2
 Instead of the alkylating and hydroxyalkylating agents used in these Examples, equivalent units of alkylated or hydroxyalkylated agents containing other alkyl or hydroxyalkyl groups may be employed, for example chlorinated ur. methyl, or propyl chloride, or a chloride
 EMI45.3
 anyl, or butyl chloride, or propylene ohlorohydrin or butylene hydrochloride.



  If it is possible or useful, instead of tY :: 1: oxide or of ropylene, other alkylene axides, such as butylene oxide, in summary, any suitable compounds which contain an ethylene oxide ring.



   If possible or useful, instead of alkyl halides or dialkyl sulfate, equimolecular amounts of their compounds may be employed in the foregoing Examples.
 EMI45.4
 substitution or addition derivatives, for example '3.P1irf; halogenated alkyls, such as the halogenated alkyl-alkyls, or their hydrochlorides.



  If possible or useful, in the Examples which precede
 EMI45.5
 give way and which are relative? hydroxy acid derivatives of cellulose, instead of chloroacetic acid, it is possible to use
 EMI45.6
 equimolecular amounts of an ester of chloracH acid, i.e.- as, for example methyl or ethyl chloracabate, or Hxmrl a halogen derivative of a homologue of acetic acid, for example acid alpha-chloroproprionic, or alpha-chloroisobutyric acid, or alpha-bromoisobutyric acid or alpha-bromoisobutyric acid, or other, cu d, -; ;:

   alkali salt or an ester thereof. '

  <Desc / Clms Page number 46>

 
If possible or useful, in the foregoing Examples, the coagulation or precipitation baths described in UK Patent Application Nos. 14242/35 or 21347/35 respectively, can be used for processing the products of the. invention, shaped structures or other useful articles.



   If desired, the extensibility of the conformal structures, such as threads, films, coatings, or the like, produced according to the invention) can be increased by treating them, either during their manufacture, by example after coagulation and washing, either in the wet or dry finished state, with shrinkage agents, for example some of the shrinkage agents mentioned in Belgian Patents Nos. 342,831, 335,400, 397,588, 361,532, 361,564 and 371,966.



   As an indication or guide as to whether or not the alkali-cellulose should be subjected to ripening prior to mixing with the etherifying agent (s), one may base this on: , inter alia, on the desired viscosity of the xanthate solution which is to be transformed into shaped structures, and, in combination with this viscosity, on the viscosity of the kind of cellulose envisaged.



  If it is desired to give the solution a determined viscosity, the allycellulose produced from the kind of cellulose contemplated is subjected to a ripening process if without ripening this kind of cellulose gives a higher viscosity. However, if the xanthate solution exhibits the desired degree of viscosity from the start, ie without maturation, maturation is superfluous.

   However, since the viscosities of 5 different types of cellulose on the market (linters and cois pulp) differ greatly from one another, the question of maturation depends, in most cases, on a on the one hand, the desired viscosity of the xanthate solution intended for the production of shaped structures and, on the other hand, the viscosity of the kind of cellulose being processed.

  <Desc / Clms Page number 47>

 



  Whenever the context permits, expressions
 EMI47.1
 Cellulose ether which is soluble or at least partially soluble in a solution of alkali soluble cellulose "and" cellulose ether which is at least partially soluble in a solution of alkali. caustic alkali ", are intended to include the ethers ce11.'J.2. '':

  2-1¯- simple and mixed which are completely or almost completely soluble in a solution of caustic alkali at the temperature of the chamber and%, a lower temperature, for example at a temperature between the temperature of the chamber.
 EMI47.2
 room and OÔC. , or lower, and ni'npie and mixed cellulose ethers which are insoluble or incompletely soluble in a solution of caustic alkali at the temperature of
 EMI47.3
 room, but which can be made soluble or co: plc. :: ¯:

   soluble in this solution at the temperature of the chamber without cooling their suspensions or incomplete solutions in a solution of caustic alkali to a temperature between-
 EMI47.4
 be the temperature of the chamber and 0 C. or at 0 C *, or a ..- rie:; - under 0 C. for example at less than 5 Cl or at minus 10 C., or lower, and leaving then the temperature rise to 0 C or above 0 C., and the single cellulose ethers or
 EMI47.5
 mixed which are insoluble or incÍ: Íibplèterüent soluble in; -i =;

  in caustic alkali solution at the temperature of the chamber or at a temperature between the temperature of the chair
 EMI47.6
 and OOC. or at 0 C., but which may be made part. l ert or completely soluble in this solution at room temperature, or at a temperature between the temperature of the chamber.
 EMI47.7
 temperature of the chamber and 0 ° C. or 0 C., cooling 121.11 "8 suspensions or incomplete solutions at an ilfer temperature. at 0 C., for example at minus 5 ° C., or minus 10 ° C. or lower, and then allowing the temperature to rise to 0 C., or
 EMI47.8
 above OOC.



   The term "cellulose" used in the description and the summary is, whenever the context permits, intended for
 EMI47.9
 understand cellulose, its transformation products! oi'L and

  <Desc / Clms Page number 48>

 
 EMI48.1
 oxidation, such as cellulose hydrate; hydrocellu-iloxyc2l '-alo.:3e, acid-cellulose, and the like, summarizes any cellulose group which has been proposed as a starting material for the preparation of derivatives or cellulosics of any kind.



   The term "alkali-cellulose" is intended to include
 EMI48.2
 whenever the context permits, alkali-elb l03 prepared in the usual manner, that is to say by soaking cellulose in an alkali-caustic solution and removing the excess of the latter by pressing, or by mixing cellulose with the amount of caustic alkali solution desired to be present in the final alkali cellulose.



   The expression "etherification" in the description and
 EMI48.3
 The summary includes the alkylation or ara1coylatiorJ., or the hy- Jrxjalcoy1ation, or the production of hjd! ox derivatives; acie8, the term "ether. It includes the ether- alcyl ethers 3,; le, s and hydroxyalkyls and hydrofluids, and the term "etherifying agents" includes alkyl: thy and aralkylants and .'- hydroValcylants and halogen fatty acids.



   In the description and summary, whenever the context permits, the term "cellulose ether" is intended to include aliphatic and cellulose ethers.
 EMI48.4
 single and mixed aromatics of any kind, that is to say any cellulose compound containing an alcoholic radical related in the manner of ethers of the cellulose molecule, whether the alcoholic radical is unsubstituted or substituted by any group or radical arganic or by a suitable inorganic element,
 EMI48.5
 such as nitrogen or sulfur, or a group containing an inorganic finite, such as a nitrogen-hydrogen group, or a hydrogen-sulfur group, in short any group or radical which is known to remain in radicals alcoholics.



  In the description and summary, whenever the con-

  <Desc / Clms Page number 49>

 As permitted, the expression "unsubstituted or substituted alcoholic radical" is intended to include unsubstituted or substituted alcoholic radicals of any kind, for example unsubstituted or substituted alkyl radicals; or unsubstituted or substituted hydroxyalkyl radicals? and unsubstituted or substituted hydroxyacid radicals.



   The term "halohydrin" employed in the specification and in the summary includes, whenever the context permits, compounds containing both at least one halogen and at least one hydroxyl group which may be considered to be derivative. a di-or-poly-hydroxy alcohol or by partial exchange of the hydroxyl groups for chlorine; bromine, or iodine (or of a mono- or polyhydroxy alcohol by the substitution of one or more hydrogen atoms in the alcohol radical) and derivatives (such as esters) or internal anhydrides (such as epichlorhydrin) of these halohydrins or substances or mixtures of substances which are capable of giving such halohydrins.



   The term "hydroxyalkyl" is intended to include halogenated or non-halogenated radicals of di-or-polyvalent alcohols in combination with one or more oxygen or hydroxyl.



   Whenever the context permits, the terms "alkyl," alkyl "," alkylating agent "," alkylating ", si ,,! Intended to include unsubstituted or substituted alkyl groups (eg aralkyl groups), alkylated with alkylating agents which contain unsubstituted or substituted alkyl groups (eg aralkyl groups), alkylating agents which contain unsubstituted or substituted alkyl groups (eg aralkyl groups), alkylated with alkylating agents which contain alkyl groups, unsubstituted or substituted (eg aralkyl groups).



  The term "hydroxyalkylating agents" is intended

  <Desc / Clms Page number 50>

 include halogenated derivatives of di- or polyhydric alcohols, particularly halchhydrines, such as monohalohydrines and alkylene oxides.



   In the specification and in the summary, the term "halogenated fatty acid" or "monohalogenous fatty acid" includes, whenever the context permits, acids containing a single atom of chlorine, bromine, and iodine themselves. their derivatives (such as esters and their salts, as well as substances and mixtures of substances which give monohalogenic fatty acids or their derivatives.



     The term "artificial structures" or "shaped structures" used in the specification and in the summary is intended to include: artificial yarns, especially artificial silk and strand fibers, artificial horsehair, artificial straw , films, banners and plates of all kinds, plastic masses of any description, adhesives and cements, finishes, coatings and layers of all kinds, particularly those which are applicable in finishing, filling and sizing of textile fabrics, sizing of yarns, thickening or fixing agents for pigments in fabric printing and the like, paper-like coatings, paper sizing , in the manufacture of artificial leather or your binding,

   or tracing canvas, or transparent paper, or transparent canvas and the like.



   The term "artificial yarns" includes artificial yarns and spun articles of all kinds, for example artificial silk, artificial cotton, artificial wool, artificial horsehair, and artificial straw of all kinds. .



   CLAIMS.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

1. A process for the manufacture of xa nthates of cellulosic compounds, said process comprising treating, in the presence of an alkali, a cellulosic compound, in which at least one hydroxylated hydrogen atom of the cellulose molecule n <Desc / Clms Page number 51> 6 10 5 n (C H 0) is replaced by an organic radical which contains at least one free hydroxyl group capable of 2 binding of CS, by less than 20 percent carbon disulfide calculated on the weight of the cellulosic compound. 2. A process for the manufacture of xanthates of cellulosic compounds, said process comprising treating, in the presence of an alkali, a cellulosic compound, in which at: noins a hydroxyl hydrogen atom of the mol- 6 10 5 cellulose capsule n (C H 0) is replaced by an organic radical and which contains at least one free hydroxyl group 2 capable of binding CS, not less than 10% carbon disulfide calculated on the weight of the cellulosic compound. 3. A process for the manufacture of xanthates of cellulosic compounds, which process comprises treating, in the presence of an alkali, a cellulosic compound, wherein at least one hydroxylated hydrogen atom of the cell molecule. 6 10 5 lose n (C H O) is replaced by an organic radical and which contains at least one free hydroxyl group capable of binding 2 of the CS, not less than 7% carbon disulfide calculated on the weight of the cellulosic compound. 4. A process for the manufacture of xanthates of cellulose compounds, said process comprising treating, in the presence of an alkali, a cellulose ether containing at least one 2 free hydroxyl group capable of binding CS, by less than 20% carbon disulphide calculated on the weight of cellulose ethe #. 5. A process for the manufacture of cellulosic compound xanthates, this process consisting in treating, in the presence of an alkali, a cellulose ether containing at least one group. 2 pe free hydroxyl capable of binding CS, by less than 10% carbon disulphide calculated on the weight of the cellulose ether. 6. A process for the manufacture of cellulosic compound xanthate, this process consisting of processing, in the presence of <Desc / Clms Page number 52> of an alkali, a cellulose ether containing at least one free hydroxyl group capable of binding CS hal less than 7% of carbon disulphide calculated on the weight of the cellulose ether. 7. A method as claimed in claim 4, or. 5, or 6, in which the cellulose ether is an ether EMI52.1 a - oyl, or a hydroxyalkyl ether, or a hydroxyacid ether, or an alkylhydroxyalkyl ether, or a hydroxyalkyl ether, or a hydroxyalkyl ether-hydroxyacid of cellulose. 8. A process as claimed in any one of claims 4 to 7, wherein the cellulose ether is soluble or at least partially soluble in a solution of caustic alkali. 9. A process as claimed in any one of claims 4 to 8, wherein the cellulose ether contains substantially less than a non-alcoholic radical. 6 10 5 aubsituated or substituted for a molecular unit C H 0 of cellulose. 10. A process as claimed in any one of claims 4 to 9, wherein the cellulose ether contains no more than one unsubstituted alcohol radical. 6 10 5 or substituted for two C H 0 molecular units of cellulose. 11. A process as claimed in any one of claims 4 to 10, wherein the cellulose ether contains no more than one unsubstituted alcohol radical. 6 IO 5 or Substituted for four C H 0 molecular units of cellulose. 12. A process as claimed in any one of claims 4 to 11, wherein the single or mixed cellulose ether contains no more than one unsubstituted or substituted alcohol radical per six molecular units. 6 10 5 C H 0 of cellulose. <Desc / Clms Page number 53> 13. A proceeded as claimed in any EMI53.1 of <claims 4 to 9, wherein the cell ether "contains substantially less than an alkyl group, eu 4-dr ':) Y- 6 10 5 alkyl or hydroxy acid per one C H 0 molecular unit of cellulose. 14. A process as claimed in any one of claims 4 to 10 and 13, wherein the calcium ether EMI53.2 1? 1.o.s p does not contain more than one alkyl or hydroxyalkyl or hydroxyacid group per two 6 10 5 C H 0 molecular units of cellulose. 15. A process as claimed in any one of claims 4 to 11 and 13 and 14, wherein the cellulose ether contains not more than one alkyl group, or EMI53.3 h; rdroxJa1coyl, or hydroxy acid for four molecular units 6 10 5 C H 0 of cellulose. 16. A process as claimed in any one of claims 4 to 15, wherein the cellulose ether is not EMI53.4 contains no more than one alkyl or hydroxyalkyl group 0'1 h; y- 6 10 5 droxyacid per six molecular units C H 0 of this '' 1. '' ¯o:> c. 17. A manufacture of yarns, beads or other shapes in which the solution of a xanthati 4c cellulosic compound prepared according to any r: ': 8', processes claimed in any of the above, 7cwt: ns procedures, is given an appropriate form and is processed.: S ... "'" one or more coagulating agents. 18. A manufacture of yarns, films, or other shaped structures as claimed in claim 17, wherein any coagulation bath, or combination of two coagulation baths known in the screw industry is or are. used as a coagulating agent or agents. 19.A manufacture as claimed in claim 17 or 18 in which a solution of a xantha is introduced. EMI53.5 te of a cellulosic compound prepared according to the procedure 5. :: <i rS '! C! 1- specified in which of claims 1' 16, to EMI53.6 through at least one opening coi.vcnablenant f,) 1 ': -: 1:} -:' 0.:.--: un <Desc / Clms Page number 54> coagulation bath. 20. The manufacture of yarns, films, or other shaped structures, as claimed in any one of claims 17 to 19, wherein a solution of a xanthate of a cellulosic compound prepared according to the manufacture claimed in Any of claims 1 to 16 is given the form of a shaped structure by threading this solution through a shaped opening, directly into a coagulation bath, the shaped structure being pulled and pulled away in a manner. continues from said compliant opening. 21. The manufacture of shaped structures as claimed in claim 19 where. 20, wherein the shaped opening is such as to distribute a stream of the solution in the form of threads or films. 22. The manufacture of yarns, films, or other shaped structures as claimed in any one of claims 17 to 21, wherein the shaped sclutio of a xanthate of a cellulosic compound prepared according to any one. of the methods claimed in any one of claims 1 to 16 is treated with an agent or agents which have or have a coagulating effect on the shaped material and a plasticizing effect on the freshly coagulated material. 23. The manufacture of yarns, films or other shaped structures as claimed in claim. 22, in which the solution of a xanthate of a cellulosic compound prepared by any of the methods set forth in any one of claims 1 to 16 is treated with an agent which substantially contains no less than 25% and substantially not more than 70% sulfuric acid monohydrate. 24. The manufacture of yarns, films. other buddy conformal structures claimed in claim 22 <Desc / Clms Page number 55> or 23, wherein the conformal solution of a xanthate of a cellulosic compound prepared by any of the methods claimed in any of claims 1 to 16 is first treated with an agent (s) EMI55.1 which has or have a coagulating effect on the n9nforrrèc material; it then by one or more agents which have or have a plasticizing effect on the freshly coagulated material. EMI55.2 25. A process as claimed by d / -aris r, 'ia; orte lan..r 7.e of claims 17 to 24, wherein, during its journey EMI55.3 from the conformal opening -14th to the device which collects it, the conformal structure receives a tension er-) more than that which is necessary for the formation of 1.,. conformed structure. 26. A method as claimed in claim 35, wherein additional tension is applied to the shaped structures while they are in the tin, EMI55.4 or while they are between the bath and the ten g; 7i, - tif which collects them, or both while they are in the bath and between the latter and the device which collects them. EMI55.5 27. Xanthates of cellulosic compounds in 7¯esyu:.? ^ At least one hydroxyl hydrogen atom of the molecule ie 6 10 5 cellulose n (Ce 0) is replaced by an organic radical.) ', EMI55.6 xanthates which, when fresh, contain less than a high CSS group for two, preferably five molecular units 6 10 5 EMI55.7 C H 0 of cellulose, when made by n'il1j) '):; -' + :; 1s "any of the methods claimed in any one of claims 1 to 16, or any method which is an equivalent EMI55.8 obvious chemical slow of any of these: Jr <> c4 <àb, s. 28 * Xanthates of single or mixed ethers of cellulose, in which at least one hydroxylated hydrogen atom is replaced by an unsubstituted or substituted alcohol radical xanthates which, when fresh, contain less than one group EMI55.9 CSS for two, preferably for five units mo19cu'.a-: "': J <Desc / Clms Page number 56> EMI56.1 6 10 5 EMI56.2 C H 0 âe cellulose, when made by any of the relatives claimed in any, '= -1 ", claims 1 to 16, or by any process which is a 3i- EMI56.3 slow chemical evident from any of these proceeds. EMI56.4 29. Xanthates of alkyl ethers, or hydrofalcoles or hy drc., Acids or of aleoyy-hydroxy-alkyl ethers or of alkyl-hydroxy-acid ethers or of ethers of hydrcy.y- alcoarles-hàràroxj. Cellulose acids which co : t.errer.t. fresh state less than a CSS group for aer; ,, 1 #,:!: i. "'f'4re;.,'", EMI56.5 6 10 5 EMI56.6 for five edecular units C H 0 of cell '.: l,: vE, .g.:. What did they do? by KENasx any of the procedures claimed in any of the claims 1.j :: "s 1 16 or by any method which is a chiciqU2 '(: -: 1.-' er t of any of these processes. 30. Structured ccr.forms which can be performed:; "'. R includes which of the methods mentioned in does not include' '? .- y¯-'1 ze of claims 17 to 26, whenever they are EMI56.7 so done, or that they are made by any process which EMI56.8 is an obvious chemical equivalent of any ic EMI56.9 these processes.