Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
• • 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
  • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/12—Stretch-spinning methods
  • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
• • 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
  • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
  • D01F13/02—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of cellulose, cellulose derivatives or proteins
• • 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
  • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
  • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
  • F16D27/00—Magnetically- or electrically- actuated clutches; Control or electric circuits therefor
  • F16D27/02—Magnetically- or electrically- actuated clutches; Control or electric circuits therefor with electromagnets incorporated in the clutch, i.e. with collecting rings
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
  • F16D27/00—Magnetically- or electrically- actuated clutches; Control or electric circuits therefor
  • F16D2027/002—Electric or electronic circuits relating to actuation of electromagnetic clutches
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
  • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
  • Y10S264/47—Processes of splitting film, webs or sheets

Definitions

• Articles made of acetylated cotton or acetylated regenerated cellulose have long been known. They are obtained by acetylating cotton or regenerated cellulose without passing through the solution stage by causing acetic anhydride to react on the cellulose fibres in the presence of a catalyst and of a diluent which is miscible in any proportion and at any temperature with the anhydride, especially benzene, toluene, xylene and amyl acetate. This method of acetylation is usually designated heterogeneous acetylation.
• acetylated cottons have a reduced dyeing affinity, and the acetylated regenerated celluloses so far known do not have a fibrillar structure.
• the present invention provides new textile articles of an acetylated regenerated cellulose having a fibrillar structure.
• the fibrillar microstructure of the new cellulose acetate fibres can be shown by proceeding as follows:
• the cellulose acetate fibres having all these characteristics can be obtained, by processes which are also novel and which are hereinafter described, especially but by no means exclusively from regenerated cellulose fibres known as Polynosic fibres characterized by an oriented fibrillated microstructure, a minimum wet strength in the order of 2.2 grams per denier and a wet elongation of less than 3.5% at a stress of 0.5 gram per denier.
• Polynosic fibres characterized by an oriented fibrillated microstructure, a minimum wet strength in the order of 2.2 grams per denier and a wet elongation of less than 3.5% at a stress of 0.5 gram per denier.
• Ac cording to Tachikawa the degree of polymerization of these fibers ranges from about 350 to upwards of 750.
• Patent 2,732,279 and Kenyon et al. US. Patent 3,124,860 They form new articles of great techni cal interest, in that they are highly resistant to wear, their total strength is as good as before acetylation, and the elongation at break is even improved, which is quite unexpected. They are easily dyed in a very homogeneous manner throughout the thickness of the strands.
• one part of regenerated cellulose is acetylated in at least parts of a bath containing 50100% of acetic anhydride and 50- 0% of an inert organic liquid diluent, using as catalyst an acetate of an alkali metal in a quantity such that when 3,215,490 Patented Nov. 2, 1965 the acetylation is completed the bath does not contain more than 2% by weight of free acetic acid.
• acetylation catalyst sodium acetate, potassium acetate or lithium acetate is preferably used. It has been found that by carefully regulating firstly the quantity of acetylation bath in relation to the regenerated cellulose and-secondly the quantity of catalyst, it is possible to keep to a very small percentage the quantity of free acetic acid in the acetylation bath, this making it possible to preserve particularly the strength and the structure of the original cellulose.
• the catalyst can be added directly to the acetylation bath or can be incorporated into the regenerated cellulose prior to the acetylation.
• inert diluent there may be used for example benzene, toluene, xylene, carbon tetrachloride, tetrachlorethylene, perchlorethylene or amyl acetate.
• the quantity of diluent can be considerably below 50% of the bath and it can even be omitted entirely.
• the acetylation bath is a mixture of acetic anhydride with a diluent which is immiscible with it at ambient temperature but becomes miscible at higher temperatures, and the acetylation is effected at a temperature at which the anhydride and the diluent are miscible.
• diluents will hereinafter be referred to as diluents with potential miscibility.
• heterogeneous acetylation had only been achieved by causing acetic anhydride to react on the cellulose in the presence of a catalyst and a diluent miscible in all proportions and at ambient temperature with this anhydride, such as benzene, toluene, xylene, amyl acetate, carbon tetrachloride, trichlorethylene and perchlorethylene.
• acetic anhydride such as benzene, toluene, xylene, amyl acetate, carbon tetrachloride, trichlorethylene and perchlorethylene.
• an alkali metal acetate especially the acetate of sodium, potassium or lithium can be used as catalyst as already known.
• the catalyst is preferably incorporated into the cellulose prior to the acetylation.
• diluents with potential miscibility with acetic anhydride there are preferably employed organic liquids which become miscible with the anhydride at a temperature higher than 50 C.
• Particularly useful diluents include decahydronaphthalene, whose miscibility point is in the region of C., and white spirit, whose miscibility point is in the region of 70 C.
• Carbon disulphide and cyclohexane can also be used.
• weight of acetylation bath weight of cellulose be at least 10: 1; the ratio:
• weight of diluent weight of anhydride can advantageously be between 3:7 and 8:2, the most advantageous ratios being between 2:3 and 3:2.
• Cooling of the bath to below the miscibility point of the diluent after completing the acetylation causes a separation into two layers, one of which contains practically all the diluent and the other practically all the anhydride which has not reacted and the acetic acid which has formed during the reaction.
• This possibility of separating the constituents of the acetylation bath greatly facilitates subsequent operations.
• the recovery and the separation of the excess anhydride and the acetic acid produced in the reaction can be carried out much more easily than in the conventional processes, which require a complete rectification of a homogeneous mixture.
• distillation temperatures of the diluents referred to above are widely spaced from the boiling points of the acetic acid and anhydride. It is known that the distillation temperature of decahydronaphthalene is in the region of 193 C. and that of white spirit is between 150 and 210 C. (Chemical Dictionary of Clement Duval, Paris, 1959), as compared with 118 C. for acetic acid and 140 C. for acetic anhydride.
• the heterogeneous acetylation can be effected at any desired stage, continuously or discontinuously, either on threads with continuous filaments, or on fibres in the form of tows, slivers, rovings or the like, or on spun yarns, or on woven or knitted fabrics or made-up articles.
• the acetylation can also be carried out on articles containing a certain percentage of another fibre, which is capable of resisting the acetylation treatment.
• Cloths and fabrics prepared from the acetylated threads or fibres of the invention are very resistant to creasing. They can be very easily washed and their afiinity for dyeing with plasto-soluble dyes is excellent.
• the form of the transverse section of the acetylated fibres is similar to that of the fibres before acetylation.
• Example I 100 parts of continuous Polynosic regenerated cellulose threads were acetylated for 2% hours at 50 C. in a bath consisting of Parts Acetic anhydride 2000 Perchlorethylene 1000 Sodium acetate 150 After the acetylation, the content of free acetic acid in the bath was 0.1%.
• the combined acetic acid content of the acetylated threads was 50% and their transverse section was circular.
• the threads had a fibrillar microstructure and excellent resistance to wear, and were dyed with plasto-soluble dyes throughout their thickness.
• Example 11 180 parts of Polynosic regenerated cellulose staple fibre impregnated with 80 parts of potassium acetate were acetylated for 2 hours at 98 in the following mixture:
• Acetic anhydride 2000 Perchlorethylene 1500 100 parts of a 3000 denier tow of continuous Polynosic regenerated cellulose filaments having a degree of polymerisation of 520 were treated for 1 hour in an aqueous solution of potassium acetate of 500 g./l. After being centrifuged and dried, the filaments contained 78% of potassium acetate.
• the filaments were acetylated in 2500 parts of acetic anhydride at C. without any other addition. At the end of the acetylation, the bath contained only 1.2% of free acetic acid.
• Acetylation time 2 hours 5 hours material Denier (total count) 4, 300 4, 550 3, 000 Total dry strength in g 10, 700 11, 000 10, 700 Elongation, percent 10. 6 13.6 7. 4 Content of combined acetic a cent 50 51 0
• the filaments obtained had an excellent resistance to wear and a fibrillar structure, and their transverse section was circular. Furthermore, as shown in the table, their total strength was maintained and their elongation at break was greater than that of the un-acetylated filaments.
• Example IV 100 parts of continuous Polynosic regenerated cellulose filaments were treated for 1 hour at 30 C. in an aqueous solution containing 550 g. of potassium acetate per litre. After centrifuging and drying at 60 C., the filaments contained of potassium acetate. They were then acetylated for 2 hours at C. in a mixture of 1500 parts of acetic anhydride and 1500 parts of toluene. After the acetylation, the bath contained only 0.9% of free acetic acid.
• the filaments were completely insoluble in acetone. Their resistance to flexion was 10 times better than that of ordinary cellulose acetate filaments and they had a marked fibrillar structure.
• Example V 220 parts of discontinuous Polynosic regenerated cellulose fibres containing parts of potassium acetate were acetylated for 2 hours at 100 C. in a mixture of 3000 parts of acetic anhydride and 1000 parts of xylene. After the acetylation the bath contained only 0.3% of free acetic acid.
• the resulting acetylated fibres had a fibrillar structure and a combined acetic acid content of 53%; their resistance to wear was excellent.
• Example VI The bath remaining after the acetylation was cooled to 50 C., whereupon it separated clearly into two layers having respectively the following compositions:
• the upper layer could be used again directly.
• the lower layer B was used, after rendering it substantially free from acetic acid by distilling 011 30% of its weight.
• Example VII A flock or wad of Polynosic regenerated cellulose fibre containing 65% of potassium acetate was acetylatedfor 2% hours at 95 C. in a bath composed of 45% of acetic anhydride and 55% of white spirit.
• the acetylated flock was thoroughly washed and dried. Its content of combined acetic acid was 57.4%. The mean breaking load of the treated fibres was substantially equal to that of the initial fibres.
• Example VIII 100 parts of continuous filaments of regenerated cellulose of the ordinary viscose type were treated for 1 hour in a solution containing 500 g. of potassium acetate per litre. After centrifuging and drying, the filaments, which now contained 60% of this salt, were acetylated for 1% hours at 100 C. in the following mixture:
• the resulting filaments had a combined acetic acid content of 54%, and their transverse section was serrated; they had a total strength of 300 g., as compared with 306 g. before acetylation, and a dry elongation of 24%.
• Example IX 100 parts of cellulose fibres of the same type were acetylated for 2 hours at 95 C. in a bath formed of:
• the combined acetic acid content of the acetylated fibres was 45 and their transverse section was serrated. They dyed very satisfactorily with plasto-soluble dyes.
• Example X One part of spun staple fibre regenerated cellulose yarn of normal structure and containing 70% of potassium acetate was acetylated in parts of a mixture consisting of 50% of acetic anhydride and 50% of decahydronaphthalene. The acetylation was carried out at 80 C. for
• Process for the production of textile articles which comprises acetylating an article comprising fibres of regenerated cellulose having an oriented fibrillar microstructure, a minimum wet strength in the order of 2.2 grams per denier and a wet elongation of less than 3.5% at a stress of 0.5 gram per denier in an acetylating bath containing acetic anhydride and an inert liquid organic diluent which is a non-solvent for cellulose acetate of the combined acetic acid content being produced and which is completely miscible with acetic anhydride to form a homogeneous mixture only at temperatures above 50 C., the acetylation being effected at a temperature above 5 0 C.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Electromagnetism (AREA)
• Materials Engineering (AREA)
• Biochemistry (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Artificial Filaments (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compounds Of Unknown Constitution (AREA)

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Citations (10)

• 0
  • NL NL256447D patent/NL256447A/xx unknown
  • BE BE595632D patent/BE595632A/xx unknown
  • NL NL129911D patent/NL129911C/xx active
• 1959
  • 1959-10-02 FR FR806620A patent/FR1247962A/fr not_active Expired
  • 1959-10-12 FR FR807235A patent/FR1247965A/fr not_active Expired
• 1960
  • 1960-06-10 FR FR829632A patent/FR1267309A/fr not_active Expired
  • 1960-09-20 ES ES0261369A patent/ES261369A1/es not_active Expired
  • 1960-09-26 US US58312A patent/US3215490A/en not_active Expired - Lifetime
  • 1960-09-26 GB GB33049/60A patent/GB919053A/en not_active Expired
  • 1960-09-29 CH CH1095760A patent/CH371086A/fr unknown
  • 1960-09-30 DE DE19601419513 patent/DE1419513A1/de active Pending

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