US3464840A - Cellulose-sulfur composition which resists chain shortening - Google Patents
Cellulose-sulfur composition which resists chain shortening Download PDFInfo
- Publication number
- US3464840A US3464840A US423317A US3464840DA US3464840A US 3464840 A US3464840 A US 3464840A US 423317 A US423317 A US 423317A US 3464840D A US3464840D A US 3464840DA US 3464840 A US3464840 A US 3464840A
- Authority
- US
- United States
- Prior art keywords
- cellulose
- sulfur
- pulp
- alkali
- caustic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
Definitions
- a stable composition comprising a cellulosic material, alkali, and sulfur in an amount of from about 0.1% to 2.0% by weight of the cellulosic material.
- This invention relates to the production of cellulose having greater average chain lengths. More particularly, it relates to a method of inhibiting the breaking down of cellulose chains during aging or other reactions.
- step (a) Purified cellulose, either wood pulp or cotton linters, in sheet form, is placed in strong (about 18%) sodium hydroxide solution. Subsequently, the sheet may be broken up by vigorous agitation (slurry process) or allowed to remain undisturbed in the caustic solution (sheet steeping process). After a predetermined time, varying from seconds to hours, the excess caustic is drained off and the cellulose mass pressed to remove further caustic. The pressed mass, now known as alkali cellulose, is shredded and broken up into small fragments or almost to individual fibers. This shredding step can also be carried out at the end of step (b) infra;
- the alkali cellulose is allowed to age for a predetermined time and at a predetermined temperature
- the aged alkali cellulose is treated with carbon disulfide (xanthated) and dissolved at the end of the reaction time in dilute caustic soda (sodium hydroxide solution).
- the solution is known as viscose.
- the alkali cellulose can be treated with ethylene oxide to produce hydroxyethyl cellulose, with chloroacetic acid to produce carboxymethyl cellulose, or in other manners known to those skilled in the art.
- Cellulose when treated with strong alkali, undergoes a complex reaction with atmospheric oxygen and with alkali.
- the main feature of this reaction is a shortening of the molecular chain length by breakage at random positions. This reaction continues in the above process until such time as the cellulose derivative is dissolved in water or in more dilute caustic soda, or is freed from strong caustic by any means.
- the extent of the chain shortening is governed by the time and temperature used in step (b). Even if step (b) is eliminated, chain shortening occurs at all times in steps (a) and (c) when the cellulose is in contact with strong caustic.
- alkali metal sulfites US. Patent No. 1,857,948, to R. Dosne, dated May 10, 1932
- certain heavy metal salts Entwistle, Cole and Wooding, Text. Res. 1., 19,609-624 (1949)
- sodium borohydride Swedish Patent 162,095 to I. lullander dated Feb. 11, 1958
- polyhydric phenols German patent application No. ST 3147 filed Mar. 12, 1951 by Dr. Hermann Staudinger
- sodium trithiocarbonate US. Patent 2,473,954 dated June 21, 1949 to G. M. A. Kayser
- gluconic or mucic acids can inhibit chain shortening in the aging reaction.
- sulfur can be added to cotton linters or wood pulp before either is subjected to sheet or floc formation and that the sulfur is retained by the pulp.
- the sulfur is not soluble in a steeping lye and there is accordingly no contamination problem. Moreover, it does not cause difficulties in filtration of solutions of cellulose xanthate and has no detectable harmful elfect on the color or strengthvof the final product.
- the sulfur can also be added to caustic prior to bringing the caustic into contact with cellulose or to alkali cellulose prior to bringing the alkali caustic into contact with carbon disulfide in xanthation. But, for best results, it should be added as early as possible, preferably no later than at the start of the shredding operation, so as to assure even dispersal of the sulfur throughout the mass.
- Quantities of sulfur ranging from about 0.1 to 2.0% based on the weight of cellulose effectively inhibit aging.
- the preferred amount is 1% by weight.
- Example I A sulfite wood pulp of dissolving grade in sheet form (specifically, Tenacell grade pulp manufactured at the Kipawa Mill of Canadian International Paper Company) was treated with a solution of sulfur in carbon disulfide. The added weight of sulfur was 1% based on cellulose.
- This pulp was dried until no trace of carbon disulfide remained and was subsequently converted to alkali cellulose by sheet steeping in 18% sodium hydroxide solution. After draining and pressing, the alkali cellulose contained 32% cellulose. A sheet of this alkali cellulose was torn into small pieces and thoroughly dispersed in an about 5% aqueous acetic acid solution (this step causes cellulose to be reformed from the alkali cellulose). The D.P. of the cellulose after thorough washing was determined from its viscosity in cuprammonium hydroxide solution.
- the bulk of the alkali cellulose was shredded for 60 minutes and a second sample of cellulose was regenerated for D.P. determination.
- a third sample was regenerated after aging for 24 hours, after which time the remaining alkali cellulose was treated with carbon disulfide (about 33% CS and converted to cellulose xanthate.
- the cellulose xanthate was dissolved in an aqueous alkali solution to yield a viscose containing 5% cellulose and 6% sodium hydroxide. The ball fall viscosity in seconds of this viscose was determined after ripening for 48 hours.
- Example V Aging was inhibited when a prehydrolyzed sulfate pulp (specifically Tyrecell grade pulp manufactured at the Natchez Mill of International Paper Company) and cotton linters pulp were used as cellulosic raw materials. All conditions in the following runs, including method of TABLE I.-EFFEOT OF 1% SULFUR ON THE AGING REACTION Reduction of chain shortening with sulfur is indicated, as is the advantage of early addition of the sulfur.
- sulfate pulp specifically Tyrecell grade pulp manufactured at the Natchez Mill of International Paper Company
- cotton linters pulp were used as cellulosic raw materials. All conditions in the following runs, including method of TABLE I.-EFFEOT OF 1% SULFUR ON THE AGING REACTION Reduction of chain shortening with sulfur is indicated, as is the advantage of early addition of the sulfur.
- Example II Example VI
- the sulfur used in Example I was an unpurified grade such as is commonly used in the preparation of wood pulp. Two purer grades have also been tried at the 1% level while in CS solution in an experiment using the techniques given in Example I.
- Example II The purified sulfite pulp of Example I in sheet form was soaked in water overnight. Each soaked sheet was then slurried in water by 5 seconds stirring with a high speed mixer of the Osterizer type. Sulfur (1%) was added in dry form to the pulp slurry which was stirred a. Further TABLE II.-RESULTS USING PURIFIED SULFUR Table II shows that the degree of inhibition effected by these purer grades of sulfur is of the same order as found in Example I.
- Example III Using the pulp and procedures of Example I, the effect of the addition of different amounts of U.S.P. grade sulfur to pulp was studied.
- the slurry which contained 0.3% cellulose, was diluted with ten volumes of water using hand or mild mechanical stirring for 30 seconds.
- the diluted pulp slurry was poured onto a screen, and excess Water allowed to drain. Drained water was used in the preparation of the next sheet. Make up water only was added.
- the wet sheet on the screen was pressed and 6 passed through a set of wringers of the type used in home dissolved in caustic to give viscoses containing 7% celwashing machines to remove all loosely retained water. lulose and 6% NaOH. The viscoses had ball fall viscosi-
- the new pulp sheets were dried, conditioned, and procties of 38 seconds.
- pubhshlflg f wsheet steeping properties (such as floating, cracking, and Caustlc dralned and expressed from the above Sheets processing absorption-all well known to those learned during alkali cellulose pressing was retained and reused i th rt of cellulose sheet steeping) were all identical in steeping a second batch of the original sheets of the between the samples.
- the two viscoses filtered with equal same pulp.
- E l VII Percent viscose viscosity increase It is shown by Example IV that sulfur inhibits alkali 100 (Viscose Viscosity, inhibitOrviscose viscosity, control) cellulose aging but does not influence the catalytic effect Viscose viscosity, control of heavy metal impurities in caustic or pulp. This was illustrated further when a purer caustic is used in steep- All processing parameters were as given in Example I ing. This caustic contained 0.7 ppm. iron rather than and viscosities of control batches varied by not more the 5 ppm. present in the caustic used in all other than i4.0 seconds. exampes' 5O estes-estates re reates?
- the sulfite dissolving grade wood pulp was treated with jzAs lolyllnflnqpliglflN OH 1 K li lf in causltic, Shredded As'iii vi n iii i ireh Uis. Pat. No; 1,689,958 to Moro.
- Example X same conditions. No samples were taken for D.P. determination.
- a sample of sulfite dissolving pulp, specifically Filmcell The sulfur-containing pulp was aged for three days at H, manufactured at the Hawkesbury mill of the Cana- 28 C. and the sulfur-free pulp was aged for three days dian International Paper Company, was treated with a at 23 C.
- the aged alkali celluloses were xanthated and solution of sulfur in carbon disulfide. The added weight of sulfur was 1% based on cellulose.
- This pulp was dried until no trace of carbon disulfide remained and was then converted to alkali cellulose by slurry steeping in 18% sodium hydroxide. After draining and pressing the alkali cellulose, containing 34% cellulose, was shredded and aged for three days at 25 C. After this time, the alkali cellulose was reacted with ethylene oxide gas (11% based on cellulose) simply by rotating the glass storage vessel at room temperature while connected to another vessel containing the required amount of liquid ethylene oxide. The ethylene oxide vaporized and was completely absorbed into, and reacted with, the alkali cellulose after two hours.
- ethylene oxide gas (11% based on cellulose
- the hydroxyethyl cellulose was dissolved in dilute caustic soda to give a solution containing 8% hydroxyethyl cellulose and 7% NaOH. The solution was frozen overnight, thawed, and allowed to come to 20 C. before the viscosity was determined.
- a control batch of the same pulp was converted to alkali cellulose, then to hydroxyethyl cellulose, and dissolved simultaneously and using identical procedures to those used for the sulfur-containing pulp.
- the hydroxyethyl cellulose solution prepared using the pulp containing 1% sulfur had a viscosity of 52.6 secs. while the control batch containing no sulfur had a viscosity of 12.2 secs.
- a stable composition comprising a cellulosic material, alkali, and sulfur in an amount of from about 0.1% to 2.0% by weight of the cellulosic material.
- composition as in claim 1 wherein the cellulosic material is selected from the group consisting of cotton linters, wood pulp and alkali cellulose.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US42331765A | 1965-01-04 | 1965-01-04 |
Publications (1)
Publication Number | Publication Date |
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US3464840A true US3464840A (en) | 1969-09-02 |
Family
ID=23678442
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US423317A Expired - Lifetime US3464840A (en) | 1965-01-04 | 1965-01-04 | Cellulose-sulfur composition which resists chain shortening |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1857948A (en) * | 1929-04-12 | 1932-05-10 | Int Paper Canada | Process of preparing cellulose xanthate |
US2473954A (en) * | 1942-11-11 | 1949-06-21 | American Enka Corp | Treatment of alkali cellulose |
-
1965
- 1965-01-04 US US423317A patent/US3464840A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1857948A (en) * | 1929-04-12 | 1932-05-10 | Int Paper Canada | Process of preparing cellulose xanthate |
US2473954A (en) * | 1942-11-11 | 1949-06-21 | American Enka Corp | Treatment of alkali cellulose |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CIP INC. Free format text: MERGER;ASSIGNORS:CANADIAN INTERNATIONAL PAPER COMPANY;PORTEMIAC PAPER CORPORATION;INTERNATIONAL PAPER SALES COMPANY INC.;AND OTHERS;REEL/FRAME:003933/0966 Effective date: 19811001 |
|
AS | Assignment |
Owner name: CIP INC. (FORMERLY KNOWN AS CIP FOREST PRODUCTS IN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE DATE 07/26/85;ASSIGNOR:TALBERT INC.;REEL/FRAME:004606/0152 Effective date: 19860616 Owner name: CIP INC. (FORMERLY KNOWN AS CIP FOREST PRODUCTS IN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TALBERT INC.;REEL/FRAME:004606/0152 Effective date: 19860616 Owner name: CIP INC. Free format text: CHANGE OF NAME;ASSIGNOR:CIP FOREST PRODUCTS INC./PRODUITS FORESTIERS CIP INC.;REEL/FRAME:004592/0491 Effective date: 19850729 |
|
AS | Assignment |
Owner name: TABERT INC Free format text: CHANGE OF NAME;ASSIGNOR:CIP INC;REEL/FRAME:004697/0506 Effective date: 19861126 |