US2336087A - Textile oil - Google Patents

Description

Patented Dec. 7, 1943 UNITED STATES PATENT OFFICE 'rsxmn om Alfred C. Goodings and Harry B. Marshall, To

ronto, Ontario, Canada, assignors to Ontario Research Foundation, Toronto, Ontario, Canada.

No Drawing. Application July 11, 1942, Serial No. 450,631

V 9 Claims. (01. ass-8.6)

tex-

conform to certain definite requirements and therefore must possess'certain definite properties. For example, it must not oxidise readily nor develop rancidity; it must not attack the card wires or other metal parts of the machines; it must have adequate lubricating properties, be completely liquid at ordinary working temperatures and of suitable viscosity; it must be readily removed from the textile material by simple scouring procedures. The oils which have been favoured for use in textile operation as conforming. most closely to all requirements have been certain triglyceride oils of which olive oil has been regarded as the best. Mineral oils on the other hand have not been found satisfactory for textile use chiefly because 'of the difliculty or impossibility of removing them from wool by conventional scouring methods.

Mineral oils do, however, possess many properties which conform in a highly desirable manner to the requirements of an ideal textile oil, and, in addition, their availability and low cost relative to olive oil render very attractive any possibility of using them for textile purposes. Indeed the one bad feature associated with refined mineral oil (poorly refined oils have other disadvantages) .is the serious difliculty experienced in its removal by scouring from th wool cloth made from yarns to which it has been applied. That this difflculty is a very real one can be readily illustrated by the results of experiments in which two samples of wool cloth were oiled with 10% by weight of olive oil in one case and 10% by weight of a mineral oil in the other and subjected to identical scouring procedures. The oil remaining in the fabrics after the scouring was subsequently determined and the following figures show this residual oil content as a percentage of the weight of oil originally present on the cloth before the scouring operation.

Mineral oil 35:0

' The problem of overcoming the difllculty encountered in the removal of mineral oil from wool and the rendering of such oil satisfactory for use in textile operations has been the subject 1 of investigation, and as a result it has been found that the addition of small percentages of certain partially esterified polyhydroxy compounds could completely modify the scouring properties of mineral oil and render it the equivalent of olive oil in this regard. The partially esteriiied polyhydroxy compounds which were of particular interest were the monoglycerides and di-- glycerides. Although a number of thes compounds had the desired influence in rendering mineral oil removable by scouring, from a practical point of view only those are of value which combine this emciency with an ability to stay completely blended with the mineral oil. In other words, most otherwise suitable monoand diglyceride compounds segregate and separate out in greater or less degree from the mineral oil on standing, particularly at low temperatures. It was necessary therefore to develop liquid compounds which would remain properly blended under all conditions to be met in transportation, storage and normal-use. This was achieved through the preparation of diglycerides having on of the acid chains consist of a short, rather than a long, aliphatic acid. A typical suitable diglyceride was found to be coconut-acetic diglyceride. The use of such compounds containing a short aliphatic acid chain along with a longer aliphatic acid in the diglyceride is described in United States Patent No. 2,238,882, April 22, 1941.

Since the outbreak of the present hostilities and particularly during the past six months, a serious shortage of the compound necessary to the preparation of the diglycerides of the type described in United States Patent 2,238,882 has arisen. The object of th present invention, therefore, is to produce compound having characteristics similar to those described in the above mentioned patent which can be made from available materials.

This object has been attained by the use of naphthenic acid either to replace the short-chain aliphatic acids described in the above patent, or by the use of naphthenic mono-ester 0r di-ester of a polyhydric. alcohol instead of the di-esters I described in said patent.

We have found that the monoglyceride and diglyceride of naphthenic acid when mixed with mineral oil not only render the mineral oil removable by scouring, but also remain blended with the 011 without undesirable separation. The naphthenic monoand dlglycerides may be prepared in a known manner by reacting naphthenic acid with glycerol. Instead of glycerol other polyhydric alcohols such as erythritol or mannitol may be partially esterified with naphthenic acid to form naphthenic mono-esters and di-esters. The naphthenic mono-ester of glycol may also be used.

We have also found that a satisfactoryscouring compound may be produced by reacting naphthenic acid with the mono-ester of longgchain aliphatic acids such as the constituent acids of coconut oil; lard oil,'neatsfoot oil or oleic acid. For example lard oil may be changed from a triglyceride to a monoglyceride by reacting with glycerol, and the monoglyceride subsequently reacted upon with the appropriate quantity of naphthenic acid to give a di-glyceride of lard oil and naphthenic acid.

Partial esters of polyhydric alcohols can be prepared using naphthenic acids, the following being an illustration of a suitable method in which the polyhydric alcohol is glycerol.

(1) Preparation of the naphthenic mono-ester of glycerol 92 parts of glycerol and 250 parts by weight of the naphthenic acids are heated together with vigorous stirring in an atmosphere of nitrogen. The use of an atmosphere of nitrogen is to obviate the presence of oxygen and so prevent'oxi-' .dation and an undue darkening in the colour (2) Preparation of the naphthenic di-ester of glycerol 92 parts of glycerol and 500 parts by weight of the naphthenic acids are heated together with vigorous stirring in an atmosphere of nitrogen. The water produced by the reaction is kept distilling oil at a fairly uniform rate by slowly raising the temperature from about 180 C. to 230 C. throughout the four hours required to carry out the completed preparation. Subsequent treatment of the product with 2-3% charcoal at 100 C. is an advantage to remove objectionable odours associated with crude naphthenic acids as well as toimprove the colour of the product.

Mixed di-esters of glycerol can also be prepared using naphthenic acids in conjunction with long chain fatty acids such as are contained in lard oil. The following is a description of a diester of glycerol made from lard oil, glycerine and naphthenic acids.

(3) Preparation of a mixed di-ester of glycerol (lard oil-naphthenic diglyceride) atmosphere of nitrogen. No water is evolved in this reaction.

(11) The lard oil monoglyceride formed in (a) is allowed to react with naphthenic acids in the proportion of 351 parts by weight of the monoglyceride to 250 parts of the naphthenic acids. The materials are heated together with rapid stirring in a current of nitrogen, and the water evolved in the reaction is carried oil. The temperature is gradually raised throughout the reaction from about 200 C. to 230 C. to keep the water distilling over at a steady rate. A point is finally reached at which no further Water is formed, after which the reaction is complete. The time required to complete the reaction is about four hours. Subsequent treatment of the product with 2-3% charcoal is an advantage to remove objectionable odours associated with crude naphthenic acids and also for purposes of improving the colour of the product.

The quantity of these various compounds which is to be added to mineral oil to render it desirable for textile use is between 5% and 20%, a preferred quantity being 10% to 15%. The effectiveness of their addition to mineral oil on its ease of removal by scouring can be illustrated by the following table of results. In all cases wool fabric was oiled with 10% of its'weight of oil. The fabric was then scoured under controlled conditions identical for each oil tested, and the oil left in the'fabric subsequently determined This residual oil is expressed as a percentage of the original weight of oil present on the wool before scouring. For comparison, results using olive oil, and mineral oil without any addition agent are included. The scouring was carried out in an aqueous solution of soap and soda-ash.

Residual oil left in 4 the cloth, per cent Olive oil 7.6 100% mineral oil 85.0 mineral oil+10% lard oil-naphthenic Suitable mineral oils for use in the present invention are preferably of the following general characteristics, these being given for example only and without intending to preclude reasonable variation.

Table I General Preferred range range Gravity, A. P. I 23-36 25-32 I Viscosity (Saybolt Universal at F.) 50-250 -175 Pour point F.- 0-50 25-35 Naphthenic acid is a product obtained in the refining of petroleum. More strictly, commercial naphthem'c acid obtained in the course of petroleum refining is not a single chemical compound ,but a mixture of acids. For industrial uses it is customary to use this mixture of crude acids or separate fractions of the same. It is this commercial form of naphthenic acids, which is comparatively cheap and plentiful, which we employ in the formation of partially esterified glycerides containing naphthenic acid.

Although naphthenic acids are very complex in their nature and scientific knowledge on the subject is limited, refined naphthenic acids are believed to consist of both monoand bi-cyclic compounds built from a -membered ring, that is they are carboxylic acid derivatives of cyclopentane. A formula of one of the simplest naphthenic acids is as follows:

CH: /CHa of a mineral base oil having a viscosity within the approximate range of 50 and. 250 seconds Saybol Universal at 100 F. and containing as a scouring agent about 5% to 20% of,a di-ester The naphthenic glycerides may be used in comof a mineral base oil having a viscosity within the I approximate range of and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of a partial ester of a naphthenic acid and a polyhydric alcohol.

2. A textile oil comprising about to of a mineral base oil having a viscosity within the approximate range of 50 .and 250 seconds Saybolt Universal at F. and containing as a scouring agent about 5% to 20% of the monoester of polyhydric alcohol and naphthenic acid.

3. A textile oil comprising about 80% to 95% oi a mineral base oil having a viscosity within the approximate range of 50 and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of the di-ester of polyhydric alcohol and naphthenic acid.

4. A textile oil comprising about 80% to 95% of a polyhydric alcohol of at least three hydroxy groups with a long chain fatty acid and naphthenic acid.

5. A textile oil comprising about 80% to 95% of a mineral base oil having a viscosity within the approximate range of 50 and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of naphthenic monoglyceride. i

6. A textile oil comprising about 80% to 95% of a mineral baseoil having a viscosity Within the approximate range of 50 and 250 seconds Saybol Universal at 100 F. and containing as a scouring agent about 5% to 20% of naphthenic acid diglyceride. i

7. A textile oil comprising about 80% to 95% of a mineral base oil having a viscosity within the approximate range of 50 and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of the di-ester of glycerol with a long chain fatty acid and naphthenic acid.

8. A textile oil comprising about 80% to 957 of a mineral base oil having a viscosity within the approximate range of 50 and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of lard oilnaphthenic diglyceride.

9. A textile oil comprising about 80% to 95% of a mineral base oil having a viscosity within the approximate range of 50 and 250 seconds Saybolt Universal at 100 F. and containing as a scouring agent about 5% to 20% of oleic naphthenic diglyceride.

ALFRED C. GOODINGS. HARRY B. MARSHALL.