EP1260632B1 - Antiknitterausrüstung von Leinenfasern und Garnen - Google Patents

Antiknitterausrüstung von Leinenfasern und Garnen Download PDF

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Publication number
EP1260632B1
EP1260632B1 EP20010130848 EP01130848A EP1260632B1 EP 1260632 B1 EP1260632 B1 EP 1260632B1 EP 20010130848 EP20010130848 EP 20010130848 EP 01130848 A EP01130848 A EP 01130848A EP 1260632 B1 EP1260632 B1 EP 1260632B1
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EP
European Patent Office
Prior art keywords
linen
yarns
cellulose
cross
slivers
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Expired - Lifetime
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EP20010130848
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English (en)
French (fr)
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EP1260632A1 (de
Inventor
Maura Comoli
Rocco Di Modugno
Giangiacomo Torri
Elena Vismara
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Linificio e Canapificio Nazionale SpA
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Linificio e Canapificio Nazionale SpA
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Priority claimed from EP01830331A external-priority patent/EP1260522B1/de
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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
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease

Definitions

  • the present invention relates to modified linen fibers, in particular modified linen slivers and yarns, having an allomorph I content of at least 40% and a solubility in cuproethylendiamine (Cued) 0.5 M lower than 1.4 g/l, as well as to a process for their preparation.
  • Cued cuproethylendiamine
  • cellulose is a beta-1,4-linked polymer of D-glucopyranose and it occurs in several distinct crystalline forms known as allomorphs, such as for instance cellulose I, II, III and IV [see A. Sarko in New developments of industrial polysaccharides, page 87, Ed. V. Crescenzi, I.C.M.].
  • Cellulose allomorphs can be identified by a variety of analytical techniques, such as spectroscopic (IR, Raman or solid state 13 C-NMR spectroscopy) and diffractional (electron, neutron or x-ray diffraction) techniques.
  • Cellulose I and cellulose II are the commercially dominant allomorphs of cellulose.
  • Cellulose I (“native cellulose”) is the naturally occurring form in nearly all plants while cellulose II, also known as “hydrate” cellulose, is mainly produced by treatment of cellulose I with strong basic agents such as concentrated aqueous potassium or sodium hydroxides. Such a treatment, known as mercerization, is commonly used for removing the non-cellulosic components, such as lignin and hemicelluloses, from raw materials containing cellulose. It causes the irreversible transition of cellulose I to the thermodynamically more stable cellulose II.
  • Fibers made of cellulose I are characterized, in the dry state, by a greater breaking load resistance and, most of all, by a typical brightness and luster that are particularly appreciated in the textile field.
  • linen fabrics do not spontaneously recover the initial arrangement after washing and drying and, unavoidably, an additional ironing step is required in order to return to the original shape.
  • some cross-linking processes are performed on natural fibers, in particular etherification reactions.
  • the known processes for preparing cellulose ethers are generally carried out in two stages, with the preparation of the "alkali cellulose" taking place first followed by its etherification.
  • Alkali cellulose is, in turn, prepared by mixing cellulose, as homogeneously as possible, with water and alkali metal hydroxides in suitable industrial units.
  • the etherification stage is usually carried out by reacting the alkali cellulose produced in the first stage together with an etherifying agent (United States patent n. 5,493,013 - Hoechst Aktiengesellschaft).
  • Etherification cross-linking processes by linking together hydroxyl groups of different cellulose chains with strong covalent bonds instead of weak hydrogen bonds, can improve several properties of the final products, such as wet strength or crease resistance. Nevertheless, the rather drastic aqueous alkaline conditions can irreversibly alter the appearance and the crystalline structure of cellulosic materials and, therefore, not always, they applies to textiles.
  • cross-linking reagents for cellulose textiles have been investigated but they generally require high temperatures or aqueous basic conditions that can damage the native structure of cellulose [see, as an example, the cross-linking process claimed in US 6,036,731 in the name of Ciba SC Holding AG].
  • US 3,567,362 discloses a process by which conditioned and wet crease recovery can be imparted to cotton fabrics. Fabrics are treated with aqueous soda and then with butadienediepoxide in carbon tetrachloride solution, obtaining crosslinking of the fabric fibers. When using low amounts of soda solution, cotton maintains the allomorph I configuration.
  • the cross-linked linen slivers and yarns according to the invention have an allomorph I content measured by solid state 13 C NMR of at least 40%, preferably at least 45%, and a solubility in cuproethylendiamine (Cued) 0.5 M lower than 1.4 g/l.
  • the low solubility in Cued indicates the presence of cross-linking between cellulose chains which is stable to the strong basic conditions of Cued.
  • Untreated linen slivers and yarns have a solubility in Cued 0.5 M much higher than 1.4 g/l, since Cued is able to destroy the chain to chain interactions present in linen fibers.
  • the cross-linking is obtained by formation of an ester bond, the cross-linked cellulose is also dissolved in Cued because of the hydrolysis of the ester bonds under these conditions.
  • basic conditions are also applied in standard laundry washings. This is why fibers cross-linked by formation of ester bonds loose their crease-resistance properties in time.
  • the low solubility of the products according to the invention proves that they do not hydrolyze in the presence of bases and, consequently, are likely to have increased crease resistance even after repeated washes.
  • Another object of the present invention is a process for preparing modified linen slivers and yarns, by reacting linen slivers and yarns with a cross-linking agent in the presence of a base in a non-aqueous medium
  • the cross-linking reaction is performed by formation of an ether bond between the hydroxyls of cellulose chains.
  • the number of hydroxyls per glucose unit of cellulose that can be cross-linked ranges from 0.0001 to 3, more preferably from 0.001 to 1; most preferably, from 0.005 to 0.15.
  • the present cross-linking reaction is an heterogeneous reaction
  • the final distribution of cross-linking can be irregular.
  • the extent of cross-linking could be higher on the surface of the fiber and negligible inside.
  • any composition comprising modified linen slivers and yarns, having allomorph I content of at least 40% and a solubility in cuproethylendiamine (Cued) 0.5 M lower than 1.4 g/l, optionally together with not modified linen slivers and yarns.
  • Preferred cross-linking reagents suited for the present process include compounds of formula X-A-X' (I) wherein X and X' are reactive groups, i.e. moieties capable of reacting with hydroxyl groups of cellulose, rather than undergoing self-polymerization.
  • Such reactive groups include, for example, detachable groups, activated unsaturated groups, formyl, aziridino and epoxy groups.
  • detachable groups also known as leaving groups
  • leaving groups are halogens, cyano, triflate, mesylate, tosylate, trifluoroacetate, ammonium, sulphate, p-nitrobenzoate, phosphato, acetoxy, propionyloxy and the like.
  • Halogens are preferred leaving groups. Chloro is particularly preferred.
  • Activated unsaturated groups are for example vinyl, halovinyl, styryl, acryloyl or methacryloyl groups.
  • Further reactive groups according to the present invention are formyl, comprising masked formyls, aziridino and epoxy groups, such as for instance ethylene or propylene oxides, and the like.
  • Preferred cross-linking reagents contain glycidyl residues.
  • A is a bivalent bridging radical comprising from 1 to 100 carbon atoms and, optionally, from 1 to 50 heteroatoms selected among halogens, oxygen, nitrogen, sulfur, boron, phosphorus and silicon.
  • a bivalent bridging radical A an aliphatic, aromatic or heteroaromatic radical linking X and X' is intended.
  • the bivalent radical A includes linear, branched or cyclic aliphatic radicals such as methylene, ethylidene, propylidene, isopropylidene, butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene, decylidene, dodecylidene, tetradecylidene, hexadecylidene, heptadecylidene, octadecylidene, cyclohexylidene and the like.
  • Preferred bivalent aliphatic radicals A are C 1 -C 18 aliphatic linear radicals.
  • Radical A may optionally include double or triple bonds and from 1 to 50 heteroatoms selected from halogens, oxygen, nitrogen, sulphur, boron, phosphorus and silicon. These heteroatoms can alternate with carbon atoms along the bridging chain or can represent side functional groups linked to the bridging chain. Examples of heterogroups linked to the bridging chain are halogens, amino or hydroxyl groups.
  • heteroatom-containing radicals A are poly(oxyethylene), poly(oxypropylene), poly(vinylchloride), poly(ethyleneimine), poly(propyleneimine), optionally substituted by one or more hydroxyl groups.
  • Bivalent radicals A comprising aromatic systems, such as benzene, naphthalene, anthracene, phenantrene, fluorene and the like, or heterocyclic rings such as furan, pyrrole, thiophene, pyrazole, imidazole, triazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, tetrahydrofuran, dioxane, tetrahydropyran, piperidine, dihydropyran, dihydropyridine, optionally benzo-condensed, and the like are also included in the present invention.
  • aromatic systems such as benzene, naphthalene, anthracene, phenantrene, fluorene and the like
  • heterocyclic rings such as furan, pyrrole, thiophene,
  • a preferred group of cross-linking reagents comprises compounds in which A is selected among poly(oxyethylene), poly(oxypropylene), poly(ethyleneimine) or poly(propyleneimine).
  • X and X' are identical, they are preferably selected from 1,2-epoxyethyl, vinyl and chloro.
  • a preferred group of cross-linking reagents according to the present invention is represented by diglycidyl reagents.
  • a particularly preferred reagent is poly(propylene glycol)diglycidyl ether.
  • cross-linking reagents have X different from X', in particular X is a halogen and X' is 1,2-epoxyethyl.
  • epichlorohydrin is particularly preferred.
  • the obtained cross-linked linen fibers have the following formula (II): wherein n is an integer from 100 to 100,000 R is a hydrogen, a group of formula AR" in which A is a bivalent bridging radical comprising from 1 to 100 carbon atoms and, optionally, from 1 to 50 heteroatoms selected from halogens, oxygen, nitrogen, sulphur, boron, phosphorus and silicon, and R" is an O-cellulose I radical derived from formula II; provided that AR" groups are present in a AR"/n ratio from 0.0001 to 3.
  • the present process is particularly mild and a relevant advantage is that it does not significantly alter the appearance, the strength and the allomorph I content of starting linen slivers and yarns.
  • the linen slivers and yarns, starting materials used in the present invention contain an average content of water of about 14% and according to the present process, linen slivers and yarns do not generally need any previous dehydrating step, but can be used as such.
  • the application of the cross-linking reagent generally comprises the imbibition of the linen slivers and yarns, with the commercial grade reagent, and the removal of the exceeding reagent by centrifugation or squeeze.
  • the cross-linking reagent can be used as such or can be previously dissolved in a suitable solvent.
  • step a) of the present process is generally performed at a mild temperature and for the time needed to saturate the starting material.
  • Step b) of the process comprises the treatment of linen slivers and yarns, previously processed according to step a), with a base in a non-aqueous medium.
  • bases any basic reagent which is able to activate the hydroxyl groups of cellulose towards cross-linking etherification is meant.
  • Suitable bases are both organic and inorganic bases.
  • organic base are nitrogen-containing compounds such as amines, pyridines and the like.
  • inorganic bases are alkaline hydroxides and ammonia.
  • suitable basic reagents are, for instance, quaternary ammonium hydroxides, alkaline alcoholates or carbanions. They are commercially available or can be prepared by known methods.
  • Preferred bases for the process of the present invention are alkaline hydroxides and alcoholates. Among them sodium and potassium hydroxide, sodium methoxide and ethoxide are the most preferred.
  • step b) of the process comprises the treatment of linen slivers and yarns previously processed according to step a), with a base in a non-aqueous medium.
  • non aqueous medium a polar solvent with a low content of water is intended.
  • the absence of water is important for the present process, however commercially available "pure grade” solvents can successfully be used without any further dehydrating treatment.
  • Polar solvents suitable for the present process are able to dissolve or to suspend the base without giving side reactions or irreversibly altering the cellulose crystalline structure.
  • a suitable dissolving agent in order to dissolve the selected base, such as for instance a phase transfer catalyst and the like.
  • Solvents particularly suited for the present purpose are, for instance, alcohols, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, ter-butanol and the like.
  • Methanol, ethanol and i-propanol are preferred.
  • I-propanol is particularly preferred from an industrial point of view.
  • the base is usually dissolved in the selected solvent and then the resultant solution is used in step b).
  • concentration of non-aqueous basic solutions used in step b) of the present invention can vary. Suitable values of concentration are those sufficient to activate hydroxyl groups of cellulose towards cross-linking etherification. Examples of usable ranges of concentration are 1-30% (w/v) for alkaline hydroxides and 0.01-5M for alcoholates.
  • the linen slivers and yarns processed according to step a) are dipped into the non-aqueous basic solution above described, at a temperature and for a time needed to complete the reaction.
  • the linen slivers and yarns are repeatedly washed, at first with the same solvent selected for step b) and then with water up to neutral pH.
  • the process comprises a step b) of the process, according to the present invention, followed by a step a) of the process, according to the present invention.
  • modified linen slivers and yarns of the present invention maintain the allomorph I content, the strength and the beautiful appearance of the natural fibers and increase the crease resistance.
  • a further advantage of the present process is that it can be performed as a continuous process.
  • the allomorph I content of the samples was evaluated by solid state 13 C-NMR spectroscopy (CP/MAS and MAS techniques).
  • Breaking-load test (g/tex) was performed according to ASTM D 1445/2524.
  • a linen sliver was dipped in the selected cross-linking reagent for a proper time (contact time) and at a suitable temperature. It was then centrifuged for about 10 minutes at 1000 r.p.m. The procedure can be repeated twice (double imbibition).
  • the sliver was then dipped into a non-aqueous basic solution, at the reported temperature, and left for the indicated contact time.
  • the final product was washed first with the same solvent used for the basic solution and then with water up to neutral pH.
  • Experiments 3-4 were carried out according to the general procedure 1. Epichlorohydrin (Aldrich) was used as cross-linking reagent. Step a) was performed at 50°C and for a contact time of 30 minutes while step b) at 50°C and for a contact time of 60 minutes.
  • Comparative experiment 1 represents the unmodified linen sliver.
  • Comparative experiment 2 is a cross-linking reaction according to general procedure 1 but performed in an aqueous base.
  • Table 1 Step B Exp. n. Base Solvent Conc. Solubility in Cued 0.5M (g/l) Resistance g/tex Allomorph I content (%) 1 (comp.) - - - ⁇ 1.4 29 58 2 (comp.) NaOH H 2 O 24% ⁇ 1.4 14 n. d. 3 CH 3 ONa CH 3 OH 0.2M ⁇ 1.4 28 57 4 CH 3 ONa CH 3 OH 1.0M ⁇ 1.4 29 56 n. d. not detectable
  • Comparative experiment 1 represents the unmodified linen sliver.
  • Comparative experiment 5 is a cross-linking reaction according to general procedure 1 but performed in an aqueous base.
  • Table 2 Step B Exp. n. Base Solvent Conc. Solubility in Cued 0.5M (g/l) Resistance g/tex Allomorph I content (%) 1(comp.) - - - ⁇ 1.4 29 58 5 (comp.) NaOH H 2 O 24% ⁇ 1.4 12 n. d. 6 CH 3 ONa CH 3 OH 0.2M ⁇ 1.4 26 57 7* CH 3 ONa CH 3 OH 0.2M ⁇ 1.4 25 62 8 CH 3 ONa CH 3 OH 1M ⁇ 1.4 29 57 * double imbibition n. d. not detectable
  • a linen sliver or yarn is dipped into a non-aqueous basic solution, at the reported temperature, and left for the indicated contact time.
  • the sliver or yarn is then dipped in the selected cross-linking reagent for a proper time (contact time) and at a suitable temperature.
  • the final product is washed first with the same solvent used for the basic solution and then with water up to neutral pH.
  • Step a) and step b) ware performed at 50°C and for a contact time of 15 minutes.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (10)

  1. Modifizierte Leinenfasern und Garne, die einen Allomorph I-Gehalt von mindestens 40% haben, der mit Festkörper-13C-NMR gemessen wurde, und die durch eine Löslichkeit von weniger als 1,4 g/l in 0,5 m Kupferethylendiamin (Cued) charakterisiert sind.
  2. Modifizierte Leinenfasern und Garne nach Anspruch 1, worin die Leinenfasern durch die Bildung einer Etherbindung zwischen den Hydroxylgruppen der Celluloseketten vernetzt sind.
  3. Modifizierte Leinenfasern und Garne nach Anspruch 1, worin der Allomorph I-Gehalt mindestens 45% beträgt.
  4. Modifizierte Leinenfasern und Garne nach den Ansprüchen 1 - 3, die die folgende Formel besitzen:
    Figure imgb0003
     worin
    n eine ganze Zahl von 100 bis 100.000 ist,
    R ein Wasserstoff oder eine Gruppe der Formel AR" ist, in der A ein zweiwertiges Brückenradikal ist, das 1 bis 100 Kohlenstoffatome und wahlweise 1 bis 50 Heteroatome, ausgewählt aus Halogenen, Sauerstoff, Stickstoff, Schwefel, Bor, Phosphor und Silizium, enthält, und R" ein O-Cellulose I-Radikal ist, das sich von der Formel I ableitet; vorausgesetzt, dass die AR"-Gruppen in einem AR"/n-Verhältnis von 0,0001 bis 3 vorliegen.
  5. Modifizierte Leinenfasern und Garne nach Anspruch 4, worin A ein lineares aliphatisches C1-C18-Radikal ist, das wahlweise durch eine oder mehrere Hydroxylgruppen substituiert ist.
  6. Modifizierte Leinenfasern und Garne nach Anspruch 4, worin A Polyoxyethylen, Polyoxypropylen, Polyethylenimin und Polypropylenimin ist, das wahlweise durch eine oder mehrere Hydroxylgruppen substituiert ist.
  7. Ein Verfahren zur Herstellung von modifizierten Leinenfasern und Garnen nach den Ansprüchen 1 - 6, enthaltend die Schritte:
    a) Anwendung eines Vemetzungsreagenzes auf die Leinenfasern und Garne und
    b) Behandlung mit einer Base in einem nichtwässrigen Medium.
  8. Ein Verfahren nach Anspruch 7, worin Schritt a) vor Schritt b) durchgeführt wird.
  9. Ein Verfahren nach Anspruch 7, worin Schritt b) vor Schritt a) durchgeführt wird.
  10. Ein Verfahren nach den Ansprüchen 7 - 9, worin das Vernetzungsreagenz eine Verbindung der Formel

            X'-A-X     (I)

    ist und X und X' reaktive Gruppen sind, z. B. Komponenten, die eher mit Hydroxylgruppen von Cellulose reagieren können als eine Selbstpolymerisation zu durchlaufen;
    A ein zweiwertiges Brückenradikal ist, das 1 bis 100 Kohlenstoffatome und wahlweise 1 bis 50 Heteroatome, ausgewählt aus Halogenen, Sauerstoff, Stickstoff, Schwefel, Bor, Phosphor und Silicium, enthält.
EP20010130848 2001-05-23 2001-12-27 Antiknitterausrüstung von Leinenfasern und Garnen Expired - Lifetime EP1260632B1 (de)

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Application Number Priority Date Filing Date Title
EP20010130848 EP1260632B1 (de) 2001-05-23 2001-12-27 Antiknitterausrüstung von Leinenfasern und Garnen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP01830331A EP1260522B1 (de) 2001-05-23 2001-05-23 Leinenfasern, die O-alkylierte Celluloseether enthalten, und Verfahren zu deren Herstellung
EP01830331 2001-05-23
EP20010130848 EP1260632B1 (de) 2001-05-23 2001-12-27 Antiknitterausrüstung von Leinenfasern und Garnen

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EP1260632B1 true EP1260632B1 (de) 2006-06-07

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1123769A (en) * 1961-02-17 1968-08-14 Calico Printers Ass Ltd Improvements in the treatment of cotton, linen and rayon fabrics
DE1936668A1 (de) * 1968-04-11 1971-02-04 Quehl & Co Gmbh Dr Verfahren zur Veredelung von ganz oder teilweise aus nativer oder regenerierter Cellulose bestehenden Textilien
US3567362A (en) * 1969-11-07 1971-03-02 Us Agriculture Erasure of configurational memory in crosslinked cotton
US3702754A (en) * 1971-01-26 1972-11-14 Us Agriculture Fibrous (carboxyalkylthio)- and (carboxyarylthio) chlorodeoxycelluloses and method of preparation
FR2224485B1 (de) * 1973-04-05 1977-12-30 Centre Tech Ind Papier
AU3539989A (en) * 1988-04-12 1989-11-03 Peter Grandics Novel crosslinked cellulose chromatography media

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