Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
• • 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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes

Definitions

• Patented July 28, 1953 METHOD FOR MAKING READILY FILTERABLE VISCOSE Erich 'Iorke,. Hamburg, and Werner Matthaes,v Krefeld (Rhine), Germany; assignors to Phrix- Maschinene, A. G., Hamburg, Germany, a corpora tion of Germany No Drawing. Application December 2, 1950-, Serial No. 198,906. In Germany May 7, 1949 8 Claims. It;
• This invention relates to method for making readily filterable viscose.
• cellulose or linters are impregnated with about 10 times by weight of a 1:6 26-% sodium hydroxide solution, squeezed 01f to approximately 3v times the weight of the pulp used, and the fibers. disassociated.
• the alkali cellulose are then air-aged and placed in rotary drums or kneadingdevices for sulfiding.
• Sulfidin xanthating is carried out for about 90 minutes at 1'6-28 C., whereupon solvent lye or solvent water is added in portions during 3 hours in order to avoid the formation of lumps.
• the drum method as heretofore carried. out, has the disadvantage that: the dissolving of the xanthogenate must be eifected in a separate apparatus. This disadvantage can, be avoided by sulfi'din in the churn, but considerable power must be used for the churning of the mass which is initially crumbly and becomes rubberlike in the last stage of the sulfi'ding.
• the method according to the invention there is added to the alkali cellulose prior to or during the sulr'iding, at least to and preferably or more of the solvent lye and the solvent water, i. e., of the total diluent liquid.
• the alkali cellulose may be obtained in known manner by impregnating the pulp or lin-ters with 16-26% sodium hydroxide solution. The formation of rubberlike tough masses during the sulfiding is avoided in this way and at the same time the Xanthogenate obtained is entirely or partially dissolved in the course of the sulfiding reaction. In this connection, it is essential that the sulliding temperature beabove 20 C.
• the sulfiding is carried out at 26-30 C.
• the sulfiding is commenced at 20-23 C. and. the temperature at the end of the reaction is permitted to rise to 26-29 C.
• the alkali cellulose can be diluted prior to the commencing of the sulfiding by the addition of the corresponding quantity of solvent lye and solvent Water.
• the shortest manufacturing times are however had if the solvent lye and sol-vent water are continuously added at the very' start of the sulfiding.
• the alkalizing can also be effectedin such manner that only enough 16-26% mercerizing lye, is caused to act on the cellulose as to render a squeezing off of excess lye unnecessary.
• a wetting agent as for instance, sulfonated castor oil
• an organic liquid which is soluble in the lye and in carbon disulfide, such as, for example, methanol, glycol, orglycerine, in small quantities, for example, 1-10 cc. per kg. cellulose.
• the addition of the wetting agent and of the organic liquid can also be made to the carbon disulfide during the sulfiding.
• wetting agents and in particular abietic acid, also act to improve the degree of disassociation of the fibers. They can therefore also be added: during the disassociation process.
• a good disassociation of the alkali cellulose fibers is essential for the wet sulfidingmethod, particularly if the alkalizing is effected without excess lye.
• the alkali cellulose must be subjected to an ageing, which is preferably carried out at elevated temperatures, for example 35-80" C.
• an ageing which is preferably carried out at elevated temperatures, for example 35-80" C.
• suitable oxidizing or reducing agents it is advantageous to cause suitable oxidizing or reducing agents to act on the alkali cellulose at elevated temperatures, for example, 3050 C., in.
• oxidizing or reducing agents can be added to the alkalizing caustic or be permitted to trickle down in aqueous solution onto the alkali cellulose.
• Suitable oxidizing agents are persulfate, percarbonate and hydrogen peroxide.
• suitable reducing agents in accodance with the invention are sodium sulfide, sodium sulfite, sodium nitrite, hydroquinone or phenylhydrazine.
• the method can be carried out suitably in a conventional churn, or in simple agitator provided with a temperature jacket, although a temperature jacket is not necessary in all cases.
• the method can also be carried out in a rotating drum.
• a horizontal agitator is found to function particularly advantageously.
• the introduction of the pulp sheets, if the alkalizing is efiected without lye excess, can take place therein directly or after they have been subjected to a lye-trickling treatment.
• the lye-trickling treatment in this connection suitably takes place on a chute provided on the agitator, through which chute the pulp sheets are fed to the receptacle.
• the pulp can also be introduced dry and the agitator be filled with the lye.
• the disassociation of the fibers of the cellulose is effected by the agitator blades or the agitator arms which pass close to the wall of the vessel.
• An oxidizing or reducing ageing can be simultaneously connected with the alkalizing, the oxidizing or reducing agents being added to the trickling lye or the prior lye, or being permitted to trickle in aqueous solution down onto the alkali cellulose.
• the carbon disulfide is emulsified in the pasty alkali cellulose. If the temperature increases substantially above 28, the vapor pressure of the carbon disulfide, which has a boiling point of 46 C., increases too rapidly and the carbon disulfide passes to a considerable extent out of the emulsion. At a lower sulfiding temperature of less than the sulfiding velocity of the alkali cellulose is too low and the carbon disulfide passes mainly into the side reactions. However, with the high reaction velocity of the pasty alkali cellulose, the sulfiding temperature can be increased to 3540 C.
• the carbon disulfide may be added to the alkali cellulose when the cellulose temperature is 16 to 20 C. and the temperature may then be increased to about 24 C. for the rapid initiation of the sulfiding reaction.
• sulfiding temperature can be controlled by suitably controlling the temperature of the solvent lye and solvent water added, as is also true of the temperature of the alkali cellulose subjected to the sulfiding.
• the shortest sulfiding and dissolving times are obtained if the sulfiding temperature does not drop below 26 C. during the course of the sulfiding.
• the temperature of the alkali cellulose, the speed of addition and temperatures of the solvent water and solvent lye are so regulated that the sulfiding reaction takes place at a temperature between 26 and 30 C. With this manner of operation, sulfiding and dissolving times of 20 to minutes can be obtained.
• the addition of the solvent lye water may take place during the first 20 to 60 minutes after the commencement of the sulfiding. As already mentioned, the addition of the solvent lye water may also be commenced before the beginning of iii the sulfiding.
• the alkali cellulose used according to the invention may be obtained in the customary manner by alkalizing with excess lye and squeezing off the excess lye, alkali cellulose so obtained must of course be subjected to an air ageing.
• the sulfiding can be commenced directly after the degradation has taken place without cooling the alkali cellulose, the temperature of the solvent lye and of the solvent water being chosen accordingly.
• the temperature of the solvent lye is, for instance, adjusted to 35 C., as is the temperature of the solvent water.
• Example 1 4000 grams of an alkali cellulose which were obtained from a spruce sulfite pulp by alkalizing with 18% NaOH in excess with a liquor ratio of 1/ 10, the excess lye being pressed off, are sulfided in an agitating vessel after 17 hours ageing at 34 C.
• the alkali cellulose has an alpha content of 25.1% and 17.2% NaOH.
• the viscose has a viscosity of 39 seconds and a filtration constant of 174.
• the filtration capacity is 460 liters per minute.
• the viscose is spun at an ammonium chloride number of 11 and gives a fiber having a breaking load of grams per denier and 23% elongation.
• the degree of polymerization of the fiber is 280.
• Example 2 75 kilos of a rayon-sulfite-spruce-pulp (alpha content 88.5%, polymerization degree 800) are churned at 20 C. with 260 liters of a sodium hydroxide solution to which 400 cc. of Monopol Brillant Oil (sulfonated castor oil or some other suitable wetting agent in the required amount) have been added and which contains 240 grams per liter NaOH, for two hours and then aged for 1'7 hours at 34 C. mixed in a churn or agitating vessel with 248 liters of water with the simultaneous addition of 16 liters CS2 and thereupon sulfided for 70 minutes at 20 to 28 C'.
• Monopol Brillant Oil sulfonated castor oil or some other suitable wetting agent in the required amount
• Example 3 700 grams of a synthetic fiber-spruce-sulfitepulp of a polymerization degree of 750 are coarsely comminuted in a xanthogenate churn. Over this there is poured a mixture of 2300 cc. lye (240 r ms NaOH per liter) and 2000 cc. water, heated to 80 C. in which 5 cc. of the wetting agent known under the trade name of Monopol Brillant Oil or some other wetting agent has been poured, and churning is efiected for one hour. After cooling to C. sulfiding is effected for 90 minutes with 260 grams of carbon disulfide. Thereupon a further 3000 cc.
• a viscose containing 8% cellulose, 7% NaOH and carbon disulfide (referred to alpha cellulose).
• the viscose does not have any swollen fibers.
• the viscosity is 89 seconds, the filtration constant 127 (KW) and the filter capacity 260 liters per minute.
• Example 4 The manner of operation is the same as the one indicated in Example 3, with the only difference that 75 grams NazS (referred to anhydrous sodium sulfide) are added to the 80 lye. In this way, a strong decrease in the viscosity is obtained.
• the viscosity of of the viscose obtained is 39 seconds with a cellulose content of 8% in addition to 7% NaOH; KW 198, filtration capacity 304 liters per minute.
• the viscose is spun in the customary manner in a Muller bath and gives a fiber of a dry strength of 160 grams per denier and 20% dry elongation.
• the polymerization degree of the fiber is 350.
• the alkali solubility corresponds to that of a viscose synthetic fiber spun in accordance with convention method.
• Ewamnle 5 1000 grams of a spruce-sulfite-pulp (alpha content 886%, degree of polymerization 600) are alkalized with 3.5 liters NaOI-I (240 grams NaOH per liter) containing 2 cc.
• Monopol Brillant Oil per liter at 20 C. for 2 hours in an agitating vessel and thereupon diluted to a NaOI-I content of about 11% by the addition of 3 liters of water.
• sulfiding is effected for 70 minutes at 20 to 28 C". with 350 cc. of CS2 and by the addition of the corresponding quantity of solvent water, there is obtained a viscose containing 7.5% alpha and 7.5% NaOI-I.
• the viscosity of the viscose is 940 seconds (measured at 18 according to the convention method with a steel ball of 3 mm. diameter and a distance of fall of 20 cm).
• the viscose is ripened to a salt point of 0.1% and after setting aside for three days at 20 C'., is spun under a pressure of 8.5 atmospheres guage according to the funnel spinning process through nozzles of a width of 0.8 mm., into water of a temperature of 20 C.
• the drawing-01f velocity is 80 meters.
• the thread which passes over a guide bar passes through a setting bath containing 3% H2804 and 5% N azSOe.
• the viscose feed is adjusted in such a manner that a fiber thickness of 3.6 denier is obtained.
• the strength of the spun fiber is 1.6 to 2 grams per denier and the elongation is between 12 and 18%.
• Eazample 6 kilos of alkali cellulose of an alpha cellulose content 01 25 to 29%, for example 25.6%,. and a caustic soda content of 16.5 to 17.5 for example 17.1%, produced from a rayonspruce-sulfitepulp of a polymerization degree of 750 (alpha cellulose content 88.5%) by steeping in a sodium hydroxide solution containing 240 grams caustic soda per liter in a liquor ratio of 1 to 10- with the squeezing 01f of the excess lye are introduced after 17 hours ageing at 34 C. into an xanthate churn. To the alkali cellulose cooled to 28, there are added 4.5 liters carbon disulfide.
• the viscose does not contain any swollen fiber, has a cellulose content of 8.3%, a caustic soda content of 6.4% and a viscosity of 20.
• the polymerization degree of the film precipitated from the viscose is 299.
• the total sulphur in the viscose corresponds to 32% carbon disulfide referred to alpha cellulose.
• Example 7 40 kilos of alkali cellulose of 29 C. produced in the same manner as indicated in Example 6, are mixed in the churn with 25 liters 9% solvent lye and 5 liters water, both of 29 0., and thereupon 3.5 liters of carbon disulfide are added. Sulfiding is effected for 20 minutes, the temperature rising to 31 C. Thereupon, the remaining50 liters of 15 C. solvent water are added over the course of 12 minutes, due to which any decrease in the temperature of the viscose obtained is obtained simultaneously with the dissolving. Dissolving is continued for 20 minutes after the addition of the rest of the solvent water. The viscose obtained has the same composition as the one according to Example 6 and has a filtration value KW of 83.
• Example 8 50 kilos of cellulose (alpha cellulose content 88.5%. polymerization degree 750) are brought by a chute into an agitating vessel in which there are contained liters of 19.5% sodium hydroxide solution in which 1.5 kilos of sodium sulfide (anhydrous NazS) are dissolved.
• the pulp sheets fill up with lye and are converted into a fiber paste by the passing of the agitator blades close by the vessel wall.
• Alkalizing is efiected for one hour at 40 C. Thereupon, 15 liters of carbon disulfide are added andat the same time or immediately after the. addition of. 270 liters of water of 20 C.
• 17.1% made from a rayon-spruce-sulfite-pulp of a polymerization degree of 750 (alpha content 88.5%) by steeping in a sodium hydroxide solution containing 240 grams NaOH per liter in a liquor ratio of 1 to 10 with the squeezing off of the excess lye, are diluted after 17 hours ageing at 34 C. in a xanthate churn by the addition of 4550 cc. of water to 8% NaOI-I.
• the alkali cellulose paste of a temperature of 23 to 24 C. is sulfided for 50 minutes with 360 grams carbon disulfide, the temperature rising to 28 C. By the addition of 2200 cc.
• viscose containing 6.6% NaOH and 8% cellulose.
• the viscose has a viscosity measured according to the convention method of 22 seconds, a filtration constant of 40, and a filtration capacity of 908 liters.
• the viscose can be readily filtered and spun and gives a thread of a dry strength of 145 grams per denier and elongation.
• Example 10 An alkali cellulose produced and aged as indicated in Example 9 is diluted in a quantity of similarly 4000 grams by the addition of 2260 cc. Water and 1950 cc. solvent lye (100 grams NaOl-I per liter) to 10.5% NaOI-I and sulfided in an agitating vessel for 30 minutes at 20 to 28 C. By the addition of 3500 cc. water, there is obtained a viscose containing 8.4% cellulose in addition to 7.2% NaOH and 33.5% CS2, The addition of the water is effected within 5 minutes.
• Example 11 17 kilos of alkali cellulose prepared and aged in the manner indicated in Example 9, are
• churned in an agitator vessel provided with a pumping line for a few minutes with 6 liters of viscose is easily filterable and has a filtration value of 50.
• Example 12 kilos of alkali cellulose prepared in the manner indicated in Example '7 are introduced into a rotating drum (alpha content of the alkali cellulose 24.8%, NaOH content 17.1%, temperature 27). After the closing and evacuation of the drum, 31.5 liters CS2 are permitted to fiow in during rotation and thereupon 200 liters of solvent lye containing 100 grams NaOH per liter and 100 liters of water, both of 30 C., are added over the course of 10 minutes. sulfiding is continued for an additional 30 minutes without any addition, and thereupon a further amount of 250 liters of water are added over the course of 20 minutes.
• a viscose containing 8% cellulose and 7% NaOH and having a viscosity of 30 seconds there is obtained within 10 minutes, a viscose containing 8% cellulose and 7% NaOH and having a viscosity of 30 seconds. If necessary, the viscose can be further dissolved for a After the addition of 23.1 liters short period of time, for instance, one hour in a dissolver or high speed mixer, or can be worked on by a crushing pump for further homogenizing.
• the viscose is easily filterable and has a KW value of 115. It is advantageous to subject the alkali cellulose to a good shredding prior to the sulfiding.
• the viscosity of a spinning solution is defined in Goetze Kunststoffseide und Zellwolle, pages 262-263.
• the viscosity is equal to the time needed by a ball to fall through the spinning solution.
• a viscosity of 30 means that the time which the ball needs to fall through the solution is 30 seconds.
• a special ball of a diameter of 3.160 millimeters and a weight of 129-131 milligrams is used for this purpose. The ball has to fall through a height of 200 millimeters of solution at a temperature of 20 C.
• Liquor ratio means the quantity of liquid in liters which is used for solving one kilogram of solid matter.
• a liquor ratio of 3 means that one kilogram of cellulose pulp is alkalized with 3 liters of caustic soda solution.
• the polymerization degree is defined in Goetze (see above) pages 31-36.
• the polymerization degree is measured by means of a diluted ammonia solution of copper hydroxide.
• the polymerization degree will be arrived at by dividing the time which such a solution containing cellulose needs to pass a viscosity meter by the respective time needed by the pure copper hydroxide ammonia solution.
• the filter capacity KW is defined in the publication of Hermans and H. L. Bredes Rec. Trav. chim. 547-548, 680, 1935.
• the KW value is equal to the number of cubic centimeters of a spinning solution passing a standard filter in a fixed time.
• the salt point is a measure for the degree of ripeness of a spinning solution. It is defined in Goetze (see above) page 289. The method is based on the fact that the coagulation speed of a viscose increases with the degree of ripeness. To determine the salt point it is necessary to drop a solution of sodium chloride of decreasing concentrations into the spinning solution. The salt point is reached at that concentration of the sodium chloride solution at which the viscose no longer coagulates.
• said alkali cellulose is a pre-ripened alkali cellulose of a degree of polymerization corresponding to the degree of polymerization of an alkali cellulose prepared without pre-ripening from cellulose with a degree of polymerization of about 250 to 400.
• said alkali cellulose is a pre-ripened alkali cellulose having a polymerization degree corresponding to the polymerization degree of an alkali cellulose produced from a cellulose having a polymerization degree of about 250 to 400 without pro-ripening.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Artificial Filaments (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)
• Floor Finish (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (17)

• 0
  • BE BE496684D patent/BE496684A/xx unknown
  • NL NL76916D patent/NL76916C/xx active
• 1949
  • 1949-11-29 FR FR1000440D patent/FR1000440A/fr not_active Expired
• 1950
  • 1950-06-24 CH CH289684D patent/CH289684A/de unknown
  • 1950-12-02 US US198906A patent/US2647114A/en not_active Expired - Lifetime
• 1951
  • 1951-03-05 CH CH293441D patent/CH293441A/de unknown
  • 1951-03-21 FR FR1034237D patent/FR1034237A/fr not_active Expired

Patent Citations (17)

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