US2234861A

US2234861A - Treating cellulose derivative materials

Info

Publication number: US2234861A
Application number: US291395A
Authority: US
Inventors: Joseph B Dickey; James B Normington
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1939-08-22
Filing date: 1939-08-22
Publication date: 1941-03-11
Anticipated expiration: 1958-03-11

Description

atente Mar., l1, 194i NITE s PAT TRETIING @ELL sa nnniva'riva MATERIALS New nllersey No Drawing.

application August ft2, i939,

Serial No.. Ztllld il iClairns.

This invention relates to the conditioning oi textile yarns and more particularly to the conditioning of filaments and yarns composed oi organic derivatives of cellulose such as celluli lose acetate, cellulose proplonate, cellulose acetate proponate, and cellulose acetate butyrate, to render them more amenable to textile opera-tions such as knitting and the like. This invention also relates to compositions ot matter in which 10 cellulose derivatives `such as cellulose acetate, cellulose nitrate or cellulose ethers, are combined or mixed with other substances, such as a `compatible plasticzer, and a common solvent tor both, with or without other usetul addition J agents, so that the resulting product will have properties lsuch as will make the composition highly advantageous for use in the plastic and analogous arts, such i'or instance, as the manufacture of wrapping sheets, photographic film,

2O articial silk, varnishes or lacduers, and the like.

ns is well known in the manufacture oi yarns, particularly those composed oi or containing cellulose organic derivatives, it is necessary to treat -the yarn in order to reduce the tendency toward m breakage of the individual filaments or bers when they are subjected to various mechanical strains and to lubricate the yarn in order to tacilitate handling in such operations as spinning, twisting, winding and reeling. lit is also necesim .sary to treat yarn to adapt it for use as warp or nlling or tor the manufacture of various types ot knitted fabrics. In knitting, it is particularly impor-tant that the yarn be sott and pliable in i order that it may conform readily to the con- 3% tour of the needles and thus produce a closely knit fabric tree from such defects as stitch distortion, pin holes, laddering, and the like.

tiere'totore it has been proposed to employ softening agents such as polyhydrlc alcohols and similarl agents as ingredients of yarn conditioning or lubricating formulas, generally in connection with mineral, animal or vegetable oils. It has been found, however, that most of the known w softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is high vapor pressure, and

in some cases too drastic a solvent action on the yarn. Many of such agents possess slight or inno sumcient solvent power for the lubricants with which they are used, and it is accordingly necessary to employ blending agents or emulsifying agents in order to obtain operable yarn treating formulas. In addition, many of theA known l softening and lubricating agents are insufficiently soluble in water to permit satisfactory removal by aqueous scour baths.

While in the plastic and related arts cellulose acetates, nitrates and ethers have been lmown for decades, it has also been known that to utilize them, it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose or" reducing the iniiammability oi the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various ln'nds have been employed to increase flexibility,l transparency, toughness, and other properties which will enhance the value or the resulting product. Addition products tor the same or similar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquers, varnishes, artificial silk filaments, moulded compounds and the like. While the plas'ticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives have been put and the increasing number of desirable properties required of the cellulose derivative for most purposes has made the discovery of new and economical plasticizers or other addition agents a matter of considerable importance to the art.

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment oi yarns composed of or containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns more amenable to knitting and other textile operatlons. A further and specific object is to provide a class of conditioning agents which augment or assist the lubricating action of various lubricants when applied to such yarns.- A still further object is to provide yarn softening and lubricating formulas which can be readily removed from the yarns by the usual scour baths. A still further object is to provide an improved method for the conditioning of yarns, particularly those composed of or containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object is to provide an improved type of yarn which is especially amenable to textile operations including circular lil knitting, weaving, spinning and the like. Still another object of this invention is to produce a composition of matter which may be made into permanently transparent, strong and ivexible sheets or lms of desired thinness which are substantially waterproof, are unaiected by ordinary photographic fluids and possess the desired properties of a support for sensitive photographic coatings. Yet another object of our invention is to produce a composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such as in 'the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, and to produce a composition which will not injure, or be injured by, the substances o'r surfaces with which it is associated during manufacture. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that compounds prepared by the action of hydroxy acids, and esters on halogenated dioxanes, said compounds having the general formula:

where R. is alkyl, and R is a substituent selected from the group consisting of hydrogen, alkyl, alkoxylalkyl and heterocy'clic groups, may be used as yarn conditioning agents .and particularly as sof-teningl agents, with -or without the addition of anm-al, mineral, or vegetable oils, in the treat- CH-o-R-C o o R' CH-o-R-C o o R' ment of yarns composed of or containing organic derivatives of cellulose. Among such alkyl and alkoxyalkyl groups may be mentioned methyl, ethyl, propyl, amyl, ethoxyethyl, hydroxyethyl, phenoxyethyl, allyl, etc., While among the heterocyclic substituents may be mentioned furan, tetrahydrof-uran and thienyl. We have found that these compounds when 'employed as described in the detailed examples set fonth below have a slight solvent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at the same time having too drastic an action thereon. These compounds, which are dioxane ethers corresponding to the respective acids or esters employed in the etheiification reaction, may be prepared in a manner similar to that described for lthe preparation of ethers of p-dioxane as described in the co-pending application of J. G. McNally and J. B. Dickey, Serial No. 176,693, filed November 26, 1937. i yOur invention also comprises the discovery that valuable properties may be induced in and/oir contributed -to compositions containing cellulose derivatives such as cellulose acetate, by adding rthereto as plasticizing agenlts fthe above-mentioned compounds. This class of compounds is compatible with cellulose derivatives and particularly compatible with cellulose acetate in `the percentages hereinafter given.

PREPARATION or COMPOUNDS Di-a-carbutomy ethyl-2,3-dioxane ether 15 gm. of 2,3-dichloro-p-dioxane'and 31 gm. butyl lactate are heated on the steam bath until the evolution of HCl ceases. The dissolved gas is then blown out of the solution with air and the rproduct distilled. The fraction (80% of the distillate) boiling at 80/0.1 mm. is taken as the desired product. 'Ihe product is di-a-,carbutoxy ethyl-2,3-dioxane ether having the structural formula.:

H CHI H-O-(Il--C O-0C4H9 O CH:

Di-a-carbethoy--ethoxy ethyl-2,3-dioane ether 15 gm. dioxane dichloride and 35 gm. ethoxyethyl lactate are heated on the steam bath for 20 hr., Iwhen the evolution of HC1 has practically ceased. The product is Worked up as in the preceding paragraph. It lboils 200/0.1 mm. The product is di-a-carbethoxy--ethoxy ethyl-2,3- diox-ane ether having the structural formula:

Di-a-carbethoxy methyZ-Z-dioxane diether 62 gm. of dichlorodioxane and 40 gm. glycollic acid are heated on the steam bath, While passing dry air through .the solution, until nb more HC1 is given ofi. The acid obtained is a dark red oil and may be decolorized by treatment With Norite in boiling acetone. The product that remains after removal of the acetone is not :further puried but is immediately esteritled by dissolving it in 200 cc. absolute ethanol containing 40 gm. dry HC1. The solution is then allowed to stand for two days at room temperature and is then rectified by distillation. The product which is di-acarbethoxy methyl-2,3-dioxane diether boils at 95-105/0.1 mm., and has the following structural formula: 1

In a similar manner we may prepare the ethoxyethyl ester, B. P. 140-150/0.1 mm., the tetrahydrofurfuryl ester, B. P. 200-220/0.1 mm., and ethoxyethoxyethyl ester, B. P. 190-210/0.1

Instead of glycollic acid we may use other oxy acids such as lactic, a-hydroxy-isobutyric, and then esteri-fy Ithe products in the usual way.

D-a-carbethozy ethyl-2,3-dioane diether 0 CH: l H CH-O-CH-COOCzHf H| CH-O-CH-COOCZER \0/ CHI lll analisti znwcurlnttory isopropyl-2,3-dioxdne diether d'7 gm. dichlorodioxane and lllll gm. butyl ohydroay-isoloutyrate are dissolved in lllll cc. toluene and .the solution reiiuxed until the evolution oi l-iCl ceases. The removal oi the last traces oi i-lCl is accomplished by washing with cold dilute NaliCOa solution The toluene layer is then iractionally distilled to give a product boiling at ll530/ll.l mm. The product is di-a-carbutoiry isopropyl-Z-dioirane diether, having the structural formula:

o om

cu2 oir-of-o-ooocim o Cin CH3 Di-acarbietrahydroyurfurylory ethyl-2,3-dzoo3- une ether lll gin. dichlorodioxane and 85 gm. tetrahydroiuriuryl lactate are dissolved in 100 cc. dry .toluene. The solution is stirred under reflux with i5 gni. anhydrous sodium bicarbonate for Ll hr. The salt is ithen ltered out Iand the :nitrate iractionally distilled to give a product of B. P. 220- 3i/ll.ll mm. The product is di-o-carbtetrahydroiurfuryloiry ethyl-2,3-dioxane ether, having the structural formula:

CH3 CH2- CH2 TREATMENT or TEXTILE YARNS In accordance with the invention these compounds may be applied directly to the yarn during or atter spinning, or may -be added to the spinning solution itself. We have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and anim-a1 oils and accordingly they may be, and preferably are, employed as ingredients oi vyarn conditioning or lubricating formulas in 'conjunction with agents which function wholly or partially as lubricants.

in the following exam-ples and description we have set forth several of the preferred embodirnents of our invention, but they are included merely for purposes `of illustration and not as a limitation thereof.

Example 1 Silk, wool, xcellulose acetate, cotton, viscose, etc., yarn is treated byapplying thereto by means of a wick, roller, spray, pad, etc., to facilitate knitting, weaving, spinning and the like, a yarn treating liquid composition having the following composition:I

Di-o-carbutoxy methyl-2,3-dioxane diether,

having the formula li the yarn is intended primarily for knitting the amount of conditioning liquid applied may vary trom 5-20% by weight of the yarn, and if the yarn is intended for weaving, the amount of liquid applied may vary between l--5% by weight of the yarn.

Example 2 lDi-a-carbutoxy ethyl-2,3-dioirane ether lm CH2 orr-oncrpoo-ocun Parts 80-90 CH2 oH--o-(|iH-Co-oo..m

CH3 l Blown olive oil lll-2O is applied to teictile materials such as silk, wool, cotton, viscose, cellulose acetate, etc., las described in :Example l. li the yarn is intended primarily for knitting, the amount oi conditioning liquid applied may vary from 5-2l)% by weight oi the yarn, and if the yarn is intended for Weaving, .the amount oi liquid :applied may vary between l5% Iby weight of the yarn. Cellulose-acetate filaments or iiloers treated as described are quite soft and pliable and -give improved results in various textile operations, such as Weaving, knitting, etc.

Another example of yarn conditioning composition which rnay be applied .to vario-us types of yarns, particularly those composed |oi or containing .cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and similar cellulose organic acid esters in accordance with our invention and which renders such yarns soft and pliable land especially well Iadapted for vari ous textile operations, particularly knitting, is as follows:

Erample 3 Di-o-carbethoxy-ethoxy ethyl-2,3-dioxanc ether Any ofthe above compositions may be applied -to the yarn intended for use in circular knitting as an ingredient of the spinning dope from which the laments are formed the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative used in making the yarn, the solvent or solvent ccmbination used in making up the spinning solution, and the degree of softness of pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith, or the liquid may be applied toy immersion, spray, or otherwise. The particu-` lar point at which the liquid is applied may vary. It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and Igodet roll, between the godet or other roll or guide and the point of winding and/or twisting. -In some cases, 'the liquid may even be applied to the yarn after winding onto cones, spools, bobbins, or the like or by the so-called bobbin to bobbin method. In the case of staple ber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specic nature of -the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For exam-ple, in a given case Where a cellulose organic acid esteryarn such as a yarn composed of cellulose acetate, is intended for knit/ting, about 5-20% or more by weight, based on the weight of the dry yarn, may be satisfactory, While if the yarn is intended for weaving, Ithe amount may vary between about 1 and 5%.

Although in the above examples we have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifying agents, blending agents and the like, may be added within the scope lof our invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or iugitively tint or dye the material undergoing treatment.

Although we hafve found it convenient to illustrate our invention by reference to compositions containing speciiic percentages of the various ingredients, these Ipercentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired to control the solvent or softening action of the conditioning agent, the amount ofthe agent may be adjusted as, for example, by reducing the amount of the agent and correspondingly increasing the amount of oil or other ingredient. i While We have described our invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate profpiionaite,` cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, Wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be vunderstood as including a single lament, a rplurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture onf natural and artificial filaments or a composite thread `formed by twisting together individual strands of natural or artificial materials, as well as cut staple bers produced from natural and/or artificial iilamenfts or threads and spun yarn produced from such staple iibers.

As indicated above, the yarn conditioning agents of our invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, newts foot, sperm and otherioils. 'Ihis enables them-to be used with any oi such oilsin making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and comxpositions of our invention possess many outstanding advantages. 'Ihe fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetate and render them soft and pliable and amenable to `various textile operations, especially operations such as those involved in Weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Anotheroutstanding characteristic of these compounds is their excepitional solvent power for a Wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubility in walter, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in vthe manufacture of yarns and woven fabrics and especially the production from rthese yarns of closely knit fabrics free from defects such as `pin holes, stitch distortion, laddering and the like.

Use 0F COMPOUNDS As PLAsTIcIzEns The following examples illustrate preferred compositions in which the above-mentioned compounds are employed in accordance with our invention:

Example 4 A Iplastic composition suitable for use in laminated glass may be made up as follows:

This is then coated out inthe usual manner to y give a thin, clear,A elastic sheet.

Example 5 Parts Cellulose acetopropionate Di-a-carbutoxy isopropyl-2,3-dioxane diether /O\ C ga /C Hs (Ilm CH-0C -C O-o CH CH2 ca o-c-oo-ocln 50-100 O C Ha C H3 Acetone 50() Example 6 Parts Cellulose acetate (36-.42 acetyl) 100 Di-a-carbtetrahydrofurfuryloxy v ethyl-2,3-diaxane-ether C H3 C H2 C Hz i CH2 CH-O*CHC O-O--CHr-CH CH2 i \O l i 0 50-80 g2 H-o-oH-co'-o-CHZ-c/H \CH1 0 H CH ylit Acetone 2 500 CHi preparation of rods, sheets, tubes. etc., as illustrated by the following.

Example f Parts Cellulose acetobutyrate lil@ y are mixed and malaxated on hot rolls and then till tid

dit

pressed in hot molds to give a plastic with irnproved properties.

ilompositions of matter prepared as ahove de scribed may be deposited upon any suitable forming surface to form a hlm. or sheet, as is well known to those skilled in the art.. ,d hlm so produced has permanently lorilliant transparency and loW-indammahility, 1 f uit no more readily than ordinary newsprint. Such iilrn is exceedingly tough and herdole, as shown by the fact that it `will withstand many folds upon a modified @chopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for a considerable number of days to air maintained at a temperature of 65 C., the hlm still maintains hexibility (in contrast to almost complete lack of nexibility Where no plasticizer is used) demonstrating that the iilm will withstand ordinary usage satisfactorily for many years. The sum total of the above advantageous properties of a product produced from our new composition is considerably in excess of that of products produced with what have previously been regarded as the laetter plasticiaers.

Other similar solvents than those mentioned above which are compatible with cellulose acetate and our new plasticizers may also occur to those skilled in this art. In like manner our plasticizers may be compounded with other single or mixed organic esters of cellulose, such as cellulose aceto-stearato, aceto-malate, or cellulose nitro-acetate, the cellulose others, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being ernployed.

Uur novel plasticizers may be employed also with advantage in connection With a number of Vthe known lacquer and varnish formulas with which it may be found to be compatible. lin such cases the plasticizer is usually first put into solution with the cellulose derivative solution and, if non-solvents are added, only to such an extent as will not precipitate the derivative from solution. Also the plasticizer is usually employed in larger amounts', such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of our invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto. .Y

What we claim is:

1. The process of conditioning yarn to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component a dioxane ether having the general formula:

where R is alkyl, and R' is a substituent se-v lected from the group consisting of hydrogen, alkyl, allroxyallryl and heterocyclic groups.

2.. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubri-Il cating and softening composition containing as its essential lubricating and softening compo-I nent a dioxane ether having the general formula:

where R is alkyl, and it is a substituent selected from the group consisting of hydrogen, alkyl, alkoxyaliryl and heterocyclic groups.

3. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, vvea ving spinning,r and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component a dioxane ether having the general formula:

om oH--o-R-ooon' on, on-onz--ooon' `iyhere R is alkyl, and R is a substituent selected from the group consisting of hydrogen, alkyl, alkoxyallryl and heterocyclic groups. f

d. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning .and the like, which comprises applying thereto a lubricating and softening composition containing as its essentialV lubricating and softening component a dioxane ether having the general formula:

C Hz

wnere R. is alkyl, and R. is a substituent selected from the group consisting of hydrogen, alkyl, alkoxyalkyl and heterocyclic groups.

i CH-O-R-C O O R lll dit

6. A conditioning agent for rendering textile yarns composed of or containing organic derivatives of cellulose more amenable to textile operations including knitting, weaving, spinning and the like which comprises a dioxane ether having the general formula:

en: CH-o-R-C 0 0 R' CH, CH-o-R-C o o R' Where R is alkyl, and R is a substituent selected from the group consisting of hydrogen, alkyl, alkoxyalkyl and heterocyclic groups.

8. Textile yarns composed of or containing organic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a conditioning agent comprising a dioxane ether having the general formula:

where R. is alkyl, and R' is a substituent selected from the groupconsisting of hydrogen, alkyl, alkoxyalkyl and heterocyclic groups.

9. Textile yarns composed of or containing organic derivatives of Acellulose amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a conditioning' agent comprising a dioxane ether having the general formula.:

where R is alkyl, and R is a substituent selected from the group consisting of hydrogen, alkyl, alkoxyalkyl and heterocyclic groups, and a textile lubricant.

JOSEPH B. DICKEY.

JAMES B. NORMINGTON.