EP3701069A1 - Fibres ignifugées artificielles de cellulose - Google Patents

Fibres ignifugées artificielles de cellulose

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Publication number
EP3701069A1
EP3701069A1 EP18789171.8A EP18789171A EP3701069A1 EP 3701069 A1 EP3701069 A1 EP 3701069A1 EP 18789171 A EP18789171 A EP 18789171A EP 3701069 A1 EP3701069 A1 EP 3701069A1
Authority
EP
European Patent Office
Prior art keywords
precondensate
ammonia
reactor
compound
flame retardant
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.)
Pending
Application number
EP18789171.8A
Other languages
German (de)
English (en)
Inventor
Heinrich Firgo
Clemens Bisjak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of EP3701069A1 publication Critical patent/EP3701069A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/20—Jet mixers, i.e. mixers using high-speed fluid streams
    • B01F25/23—Mixing by intersecting jets
    • 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
    • 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
    • D06M13/322—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 nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2805—Mixing plastics, polymer material ingredients, monomers or oligomers
    • 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
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to a process for producing an oxidized polymer from a tetrakishydroxyalkylphosphonium compound having at least one nitrogen compound, comprising the steps of: reacting at least one tetrakishydroxyalkylphosphonium compound with at least one nitrogen compound to obtain a precondensate, wherein the molar ratio of the tetrakishydroxyalkylphosphonium compound to the nitrogen compound is in the range of 1: (0.05 to 2.0), preferably in the range of 1: (0.5 to 1, 5), more preferably in the range of 1: (0.65 to 1, 2); Cross-linking the previously obtained precondensate with ammonia to form a crosslinked polymer; and oxidizing the previously obtained crosslinked polymer by adding an oxidizing agent to the oxidized polymer.
  • the invention relates to a process for the preparation of flame-retarded cellulosic man-made products from a spinning mass, comprising the provision of a polymer of a Tetrakishydroxyalkylphosphonium für advant, and mixing with a dope based on cellulosic base.
  • the invention relates to flame-retarded cellulosic man-made products.
  • Regenerated cellulose fibers including the man-made fibers viscose, modal, cupro or lyocell, are sometimes provided with flame retardancy.
  • flame retardancy there are various known methods, on the one hand, according to the type of application of the flame retardancy - applying the flame retardant substance on the surface of the fiber or introducing the flame retardant compound into the fiber in the wet spinning process - and on the other hand distinguished by the responsible for the flame retardant compound.
  • Tris (2,3-bromopropyl) phosphate is proposed as flame retardant in US Pat. No. 3,266,918. Such fibers were industrially produced for some time, but production was stopped due to the toxicity of the flame retardant.
  • a substance class used as a flame retardant is that of the substituted phosphazenes.
  • a flame retardant viscose fiber was also industrially produced (US 3,455,713).
  • the flame retardant is liquid, can be spun into viscose fibers only at a low yield (about 75% by weight), and tends to migrate out of the fiber thereby imparting unwanted stickiness to the fiber.
  • WO 93/12173 describes phosphorus-containing triazine compounds as flame retardants for plastic materials, in particular polyurethane foam.
  • claim 18 is called cellulose, spun from a solution in a tertiary amine oxide, without giving an example of the actual suitability of the compounds as flame retardants for cellulose.
  • EP 0 836 634 describes the incorporation of phosphorus-containing compounds as flame retardants for regenerated cellulose fibers, in particular lyocell fibers.
  • phosphorus-containing compounds as flame retardants for regenerated cellulose fibers, in particular lyocell fibers.
  • 1, 4-diisobutyl-2,3,5,6-tetrahydroxy-1, 4-dioxophosphorinan is called.
  • the method has the disadvantage that the incorporation yield of the flame retardant is only 90% and therefore it is unsuitable for the lyocell process.
  • Lyocell fibers are treated with phosphoric acid and urea and kept at 150 ° C for 45 minutes. Fiber-level condensation reactions, however, dramatically affect fiber properties as they embrittle the fiber material.
  • WO 94/26962 describes the addition of a tetrakishydroxymethylphosphonium chloride (THPC) urea precondensate to the moist fiber before drying, ammonia treatment, condensation, oxidation and drying after repeated washing. The process described also severely impairs the mechanical properties of the fibers.
  • THPC tetrakishydroxymethylphosphonium chloride
  • AT 510 909 A1 cellulosic man-made fibers are described with permanent flame retardant properties, wherein the flame retardant property is achieved by adding to the dope an oxidized condensate of a salt of THP with an amino group or NH 3 .
  • the obtained fiber has a maximum tensile strength in the conditioned state of more than 18 cN / tex and incorporation yields of more than 99% are achieved.
  • the production process according to AT 510 909 A1 comprises a three-stage process to produce the oxidized condensate from a salt of THP having an amino group or NH 3 : First, a tetrakishydroxyalkylphosphonium compound is reacted with the nitrogen compound and a precondensate is obtained.
  • the flame retardant initially forms in coarse particle form.
  • the polymer In order to achieve a particle size which can be introduced into the spinning process for fiber production, the polymer must be wet-grounded. In general, particle sizes of about 2 ⁇ (d 99 ) are necessary to guarantee a stable spinning process and to obtain from it a textile fiber with acceptable mechanical properties. Due to the softness of the polymer, this wet milling step is very time and energy consuming and therefore uneconomical. Ultimately, the costs of grinding exceed raw material costs. For this reason, a successful commercialization of incorporating this flame retardant inherently flame-retardant lyocell fiber has been prevented to date.
  • the costs for the production of textile fibers with wet-ground flame retardant according to AT 510 909 A1 are very high and yet the mechanical properties of these fibers are not optimal.
  • the object of the present invention is therefore to provide an oxidized condensate of THP with a compound comprising an NH 2 radical or NH radicals or with NH 3 , which is less expensive to produce the desired particle size and provides fibers with better mechanical properties.
  • step (c) oxidizing the crosslinked polymer obtained in step (b) by adding an oxidizing agent to obtain the flame retardant characterized by
  • step (b) the precondensate from step (a) and the ammonia are each injected by means of a nozzle into a reactor space enclosed by a reactor housing to a common point of collision.
  • step (b) the precondensate from step (a) and the ammonia are injected in each case by means of a nozzle in a reactor chamber enclosed by a reactor chamber reactor space to a common collision point, the resulting products through an opening (2). be removed from the reactor housing by negative pressure on the product and gas outlet side.
  • step (b) the precondensate from step (a) and the ammonia are injected in each case by means of a nozzle in a reactor space enclosed by a reactor chamber to a common collision point, via an opening in the reactor space a Gas, an evaporating liquid, a cooling liquid or a cooling gas to maintain the gas atmosphere inside the reactor, in particular at the collision point of the liquid jets, or for cooling the resulting products is introduced, the resulting products and excess gas through another opening from the reactor housing be removed by overpressure on the gas inlet side or by negative pressure on the product and gas outlet side (see also Fig. 1).
  • the hydroxyalkyl groups of the tetrakishydroxyalkylphosphonium compounds are preferably hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl groups, so that in this case the alkyl radical of the tetrakishydroxyalkylphosphonium compound is selected from the group of methyl, ethyl, propyl or butyl. Furthermore, the tetrakishydroxyalkylphosphonium compounds are preferably salts.
  • the at least one tetrakishydroxyalkylphosphonium compound is particularly preferably a tetrakishydroxymethylphosphonium compound (THP) having the general formula (P + (CH 2 OH) 4) t X " , or else mixtures of such compounds, where X "is an anion and t is the valency of this anion, where t can be an integer from 1 to 3.
  • Suitable anions X " are, for example, sulfate, hydrogen sulfate, phosphate, mono- or dihydrogen phosphate, acetate or halogen anions such as fluoride, chloride and bromide.
  • the at least one nitrogen compound which is reacted with the tetrakishydroxyalkylphosphonium compound in process steps (a) and (b) is generally one compound, two compounds, three compounds or several compounds selected from the group ammonia, urea, thiourea, biuret, Melamine, ethyleneurea, guanidine and dicyandiamide.
  • the nitrogen compound is urea.
  • At least one nitrogen compound selected from the group consisting of urea, thiourea, biuret, melamine, ethyleneurea, guanidine and dicyandiamide is reacted and crosslinked in the subsequent process step (b) with ammonia.
  • the reaction in process step (a) is carried out in a solvent according to a preferred embodiment of the invention.
  • the preferred solvent used is water.
  • the content of the compounds to be reacted in process step (a) can vary over wide ranges and is generally from 10% by weight to 90% by weight, preferably from 20% by weight to 40% by weight, based on the total mass of the process step (A) used reaction mixture containing at least the two compounds to be reacted and the solvent.
  • the molar ratio of the tetrakishroxyalkyl phosphonium compound to the nitrogen compound may vary widely and is generally in the range of 1: (0.05 to 2.0), preferably 1: (0.5 to 1.5), more preferably 1: ( 0.65 to 1, 2). The targeted selection of this molar ratio ensures that the flame retardant prepared according to the invention does not dissolve or only to a small extent in the solvents used in the production of flame-retardant cellulose fibers.
  • Process step (a) is generally carried out at a temperature in the range of 40 to 120 ° C, preferably at a temperature in the range of 80 to 100 ° C over a period of 1 to 10 hours, preferably over a period of 2 to 6 hours.
  • one or more dispersing agents are added to the polymer after carrying out process step (a) and before carrying out process step (b), and thus before carrying out the crosslinking by means of ammonia.
  • These dispersants are preferably selected from the group polyvinylpyrrolidone, Ci4-Ci 7 alkyl sulfonates, hydroxypropyl cellulose (HPC), polyethylene glycol (PEG), modified polycarboxylates such.
  • polycarboxylate As etherified or esterified polycarboxylates, in particular polycarboxylate (PCE).
  • PCE polycarboxylate
  • the dispersant serves to stabilize the constituents of the composition and prevents agglomeration of the precipitating polymers in the subsequent cross-linking reaction, in process step (b). Furthermore, the addition of very finely divided solids such as nanocrystalline cellulose or nanoparticulate barium sulfate as an agglomeration inhibitor is possible.
  • the dispersant or the spacer in a concentration in the range of 0.01 wt .-% to 3 wt .-%, for example in the range of 1 wt .-% to 2 wt .-%, based on the reaction mixture used.
  • z As polycarboxylate in a smaller amount is sufficient than z. For example, polyvinylpyrrolidone.
  • the cross-linking of the precondensate obtained in step (b) with ammonia to give a crosslinked polymer takes place in such a way that the precondensate (precondensate stream) and ammonia (ammonia stream) are provided as liquid media and sprayed onto the collision point (Fig. 1).
  • the liquid medium is preferably an aqueous solution of the precondensate.
  • a suspension or a colloid may also be present.
  • the preferred solvent for ammonia is water.
  • the content of precondensate in the precondensate stream in process step (b) can vary over a wide range and is generally from 5% by weight to 50% by weight, preferably from 8% by weight to 30% by weight, particularly preferably 9% by weight. % to 20 wt .-% based on the total mass of the aqueous solution.
  • the ratio of ammonia flow: precondensate flow is controlled so that ammonia in a molar ratio to the tetrakishydroxymethylphosphonium compound in the range of (1, 0 to 4.0): 1, preferably in the range of (1, 2 to 3.5): 1, particularly preferably in the range of (2 to 2.5): 1 is metered.
  • ammonia is metered in such a way that the resulting dispersion in the outlet has a pH in the range from 7 to 10, preferably in the range from 8 to 9.
  • the precondensate and the ammonia in step (b) can be injected into the reactor space under a pressure of 10 bar or above, for example more than 50 bar, but in any event not more than 4,000 bar.
  • Step (c) may be carried out either in the reaction space of step (b) or in a separate reactor space. It is preferably provided that the oxidation of the cross-linked polymer obtained in step (b) takes place outside the reaction space of step (b).
  • the reaction can be carried out in a conventional reactor with the aid of an oxidizing agent.
  • the oxidation in the reaction space of step (b) can take place.
  • the oxidation in process step (c) can be carried out with the aid of the usual oxidizing agents such as hydrogen peroxide, ammonium peroxodisulfate, oxygen, air (oxygen) or perchloric acid.
  • the molar ratio between the precursor of the flame retardant and the oxidizing agent is generally about 1: 1 to 1: 1.2.
  • a process step (d) may be provided, according to which after the oxidation according to step (c) soluble reaction products are separated.
  • the flame retardant can be separated from dissolved impurities via the permeate stream by means of methods known to those skilled in the art, for example by means of filtration, preferably by tangential flow filtration (cross-flow filtration) or diafiltration, and concentrated via the retentate stream (FIG. 2).
  • an additional acid may be used to more selectively remove unwanted by-products such as oligomers and basic compounds.
  • the acid used is generally selected from the group HCl, H2SO4, H3PO4 and acetic acid.
  • the acid is generally diluted in a concentration of about 1 to 75%, preferably in a concentration of about 1 to 20%, more preferably in a concentration of about 1 to 9% in a solvent selected from the group of water, methanol, ethanol or other, known in the art solvents, or a mixture of these, used.
  • the solvent preferably used for diluting the acid is water.
  • the amount of acid used to purify the flame retardant obtained in step (c) may vary over a wide range.
  • a volume fraction of flame retardant with a volume fraction of acid used is used.
  • the flame retardant obtained according to process step (d) can subsequently be washed once or several times with a solvent, wherein for washing the simple to double volume of solvent, based on the volume of the flame retardant is used to wash acid-free. This is done by placing the flame retardant obtained after process step (d) with a solvent and then carrying out a tangential flow filtration (cross-flow filtration) or diafiltration.
  • water is preferably used.
  • it is washed with water to pH 7 at the beginning and washed at the end with N-methylmorpholine-N-oxide.
  • a thickening step may be carried out by mechanical means known to those skilled in the art (e.g., centrifugation) or thermal processes (e.g., evaporation).
  • the invention also relates to a process for the preparation of flame-retarded cellulosic man-made fibers from a dope, comprising providing a polymer of a Tetrakishydroxyalkylphosphoniumtagen prepared in the aforementioned manner and mixing with a cellulose-based spinning mass, wherein the polymer of a TetrakishydroxyalkylphosphoniumENS in Form of an aqueous dispersion in an amount of 5 wt .-% to 50 wt% based on the cellulose,
  • the filaments can be endless multifilaments or staple fibers.
  • staple fibers after the precipitation of the filaments, a step of cutting the filaments into staple fibers is provided.
  • One aspect of the invention further relates to cellulosic man-made products, comprising a flame retardant comprising an oxidized polymer of a Tetrakishydroxyalkylphosphoniumharm with at least one nitrogen compound comprising at least one NH 2 or at least two NH groups, or NH 3 having a particle size d 99 of ⁇ 1 , 8, preferably ⁇ 1, 7, more preferably ⁇ 1 ⁇ . Particle sizes d 99 to 0.9 ⁇ are conceivable.
  • the cellulosic man-made product may be, for example, a foil, powder, nonwoven or fibrid.
  • the nonwovens may, for example, be meltblown nonwovens according to the Lyocell or Cupro process.
  • a particle size d 99 of ⁇ 1, 8, preferably ⁇ 1, 7, more preferably ⁇ 1 ⁇ can be achieved.
  • the limit is at d 99 of 2 ⁇ or more.
  • the dope is a solution of cellulose in an aqueous tertiary amine oxide.
  • step (b) is carried out in a microjet reactor by reacting the precondensate with ammonia to form a crosslinked polymer.
  • ammonia and the precondensate are each sprayed separately from each other in aqueous solution into a reactor chamber enclosed by a reactor chamber to a common collision point by means of a nozzle.
  • a cooling gas for maintaining the gas atmosphere in the interior of the reactor is introduced via an opening in the reactor space.
  • the resulting products and excess gas are removed through a further opening from the reactor housing by overpressure on the gas inlet side or by negative pressure on the gas outlet side.
  • the alternative embodiment provides that in the reactor space no cooling gas is introduced and resulting products are removed through an opening in the reactor housing by negative pressure on the gas outlet side.
  • step (c) takes place outside the microjet reactor, H2O2 being added as the oxidizing agent to the oxidized polymer.
  • Fig. 1 shows schematically step (b) of the process in a reactor.
  • Fig. 2 shows schematically step (d) of the method.
  • a reactor housing is shown with a reactor space, wherein the precondensate R1 from step (a) is introduced laterally into the reactor space.
  • Ammonia R2 is also introduced into the reactor space, wherein the precondensate R1 and the ammonia R2 on hit a collision point.
  • a gas can be introduced via an opening 1, which exits at the gas outlet side 2 with the reaction product. It has also been shown that precondensate R1 and the ammonia R2 are brought to a collision point without a carrier gas being introduced via the opening 1.
  • the reactor housing with reactor space and closed opening 1 can be operated for gas. By means of negative pressure via the gas outlet side 2, the reaction product can then be removed.
  • Fig. 2 shows the purification step (d), wherein first the reaction product from step (c) is introduced as a feed 1 1 in a master container 12. Via the pump 16, this is passed over a membrane 14, e.g. cleaned by tangential flow filtration. The retentate 13 is fed back into the original container 12. The permeate 15 is derived.
  • Example 1 Preparation of a Flame Retardant Dispersion by Use of a Microjet Reactor (MJR) and subsequent Spinning of Flame Retardant Fibers After the Viscose Process
  • TPC Tetrakishydroxymethylphosphoniumchlorid
  • the crosslinking of the resulting precondensate with ammonia is subsequently carried out in a microjet reactor.
  • the resulting precondensate as a 10 wt .-% solution, after addition of 12 wt .-% polyvinylpyrrolidone (Duralkan INK 30) based on precondensate, as a precondensate continuously metered to position R1 of the MJR with a pressure of 1 1 bar.
  • a 1 .5 wt .-% strength ammonia solution is metered at position R2 at a pressure of 1 1 bar continuously.
  • the emerging at the product or gas outlet side 2 reaction product is collected, mixed with H 2 0 2 and stirred for 30 min at a temperature not higher than 40 ° C, wherein the molar ratio between the precursor of the flame retardant (precondensate) and the oxidizing agent 1: 1.
  • a suspension having a solid content of oxidized, crosslinked precondensate of 4.9% is obtained.
  • the particle size d 99 is 1, 79 ⁇ .
  • the oxidized, cross-linked precondensate is subsequently purified by tangential flow filtration (FIG. 2) and concentrated.
  • the suspension produced is particularly suitable for the production of flame-retardant cellulosic moldings.
  • the proportion of the flame retardant in the cellulosic man-made fiber, in the form of a viscose or lyocell fiber can be between 5% by weight and 50% by weight, preferably between 10% by weight and 30% by weight. , more preferably between 15 wt .-% and 25 wt .-% based on the fiber. If it is too low, the flame-retardant effect is insufficient, and if it exceeds the recommended limit, the mechanical properties of the fiber are excessively deteriorated. With these proportions, it is possible to obtain a man-made flame retardant cellulosic fiber characterized in that the strength in the conditioned state is from 18 cN / tex to 50 cN / tex.
  • a viscose of the composition 6.0% cellulose / 6.5% NaOH was prepared using 40% CS2.
  • the viscose with a Spinngamma value of 62 and a viscosity of 120 falling ball seconds was added a modifier (2% dimethylamine and 1% polyethylene glycol 2000, each based on cellulose) and 22% based on cellulose of the flame retardant in the form of 14.7% dispersion.
  • the mixed viscose was spun with 60 ⁇ nozzles in a spin bath composition 72 g / l sulfuric acid, 120 g / l sodium sulfate and 60 g / l zinc sulfate at a temperature of 38 ° C, in a second bath (water at 95 ° C) to 120 % stretched, and subtracted at 42 m / min.
  • the aftertreatment hot diluted H 2 SO 4 / water / desulfurization / water / bleach / water / softening
  • a fiber was obtained with a titer of 2.19 dtex, a strength (conditioned) of 21, 2 cN / tex and a maximum tensile elongation (conditioned) of 12.4%.
  • Example 2 Preparation of a Flame Retardant Dispersion by Use of a Microjet Reactor (MJR) and subsequent Spinning of Flame Retardant Fibers After the Lyocell Process
  • TPC Tetrakishydroxymethylphosphoniumchlorid
  • the crosslinking of the resulting precondensate with ammonia is subsequently carried out in a microjet reactor.
  • the resulting precondensate as 10 wt .-% solution, after addition of 5 wt .-% of an esterified polycarboxylate (Viscocrete P-510) based on precondensate, as a precondensate continuously to position R1 of the MJR with a pressure of 1 1 bar dosed.
  • a 1 .5 wt .-% strength ammonia solution is metered at position R2 at a pressure of 1 1 bar continuously.
  • the emerging at the product or gas outlet side 2 reaction product is collected, mixed with H 2 0 2 and stirred for 30 min at a temperature not higher than 40 ° C, wherein the molar ratio between the precursor of the flame retardant (precondensate) and the oxidizing agent 1: 1.
  • a suspension having a solids content of oxidized, crosslinked precondensate of 5.3% is obtained.
  • the particle size d 99 is 1.71 ⁇ .
  • the oxidized, cross-linked precondensate is subsequently purified by tangential flow filtration (FIG. 2) and concentrated.
  • FOG. 2 tangential flow filtration
  • 12.3 kg of suspension are filled into the receiver and processed via a polyethersulfone membrane (150 kDa and 0.6 m 2 filter area) at a pressure of 2 bar for 4 cycles. After cycles 1 to 3, deionized water is diluted so that the starting weight in the feed tank is 12.3 kg. After 4 cycles over a total of 2.5 hours, 4.3 kg of suspension having a solids content of 16% are obtained.
  • the suspension produced is particularly suitable for the production of flame-retardant cellulosic moldings.
  • the proportion of the flame retardant in the cellulosic man-made fiber, in the form of a viscose or lyocell fiber can be between 5% by weight and 50% by weight, preferably between 10% by weight and 30% by weight. , more preferably between 15 wt .-% and 25 wt .-% based on the fiber. If it is too low, the flame-retardant effect is insufficient, and if it exceeds the recommended limit, the mechanical properties of the fiber are excessively deteriorated. With these proportions, it is possible to obtain a man-made flame retardant cellulosic fiber characterized in that the strength in the conditioned state is from 18 cN / tex to 50 cN / tex.
  • the spinning mass was spun by the known wet-dry spinning process at a spinning temperature of 1 10 ° C using a 100 ⁇ nozzle in a spin bath containing 25% NMMO at a temperature of 20 ° C to 2.2 dtex fibers. Fibers with a strength (conditioned) of 35.0 cN / tex and a maximum tensile elongation (conditioned) of 13.3% were obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un procédé pour la préparation d'un polymère oxydé à partir d'un composé de type tétrakishydroxyalkylphosphonium avec du NH3 ou au moins un composé azoté, comprenant au moins un groupe NH2 ou au moins deux groupes NH, ou du NH3, comprenant les étapes consistant à (a) transformer au moins un composé de type tétrakishydroxyalkylphosphonium avec du NH3 ou au moins un composé azoté pour obtenir un produit de précondensation, le rapport molaire du composé de type tétrakishydroxyalkylphosphonium au composé azoté se situant dans la plage de 1:(0,05 à 2,0), de préférence dans la plage de 1:(0,5 à 1,5), de manière particulièrement préférée dans la plage de 1:(0,65 à 1,2), (b) réticuler le produit de précondensation obtenu dans l'étape de procédé (a) à l'aide d'ammoniaque en un polymère réticulé, (c) oxyder le polymère réticulé obtenu dans l'étape (b) par addition d'un agent d'oxydation en polymère oxydé, le produit de précondensation de l'étape (a) et l'ammoniaque étant chacun injectés, dans l'étape (b), au moyen d'une buse dans une chambre de réacteur entourée par une cuve de réacteur sur un point de collision commun.
EP18789171.8A 2017-10-27 2018-10-25 Fibres ignifugées artificielles de cellulose Pending EP3701069A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17198949.4A EP3476985A1 (fr) 2017-10-27 2017-10-27 Fibres synthétiques cellulosiques ignifugées
PCT/EP2018/079227 WO2019081617A1 (fr) 2017-10-27 2018-10-25 Fibres ignifugées artificielles de cellulose

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EP3701069A1 true EP3701069A1 (fr) 2020-09-02

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EP17198949.4A Withdrawn EP3476985A1 (fr) 2017-10-27 2017-10-27 Fibres synthétiques cellulosiques ignifugées
EP18789171.8A Pending EP3701069A1 (fr) 2017-10-27 2018-10-25 Fibres ignifugées artificielles de cellulose

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EP17198949.4A Withdrawn EP3476985A1 (fr) 2017-10-27 2017-10-27 Fibres synthétiques cellulosiques ignifugées

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US (1) US12116701B2 (fr)
EP (2) EP3476985A1 (fr)
JP (1) JP7433221B2 (fr)
KR (1) KR20200074943A (fr)
CN (1) CN111315924B (fr)
AU (1) AU2018356458B2 (fr)
BR (2) BR112020006196B1 (fr)
CA (1) CA3079878A1 (fr)
TW (1) TWI790303B (fr)
WO (1) WO2019081617A1 (fr)

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CN113563486B (zh) * 2021-07-01 2022-07-05 杭州志合新材料有限公司 一种含磷腈基团的阻燃纳米纤维素、制备方法及其阻燃聚乳酸

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TW201925267A (zh) 2019-07-01
WO2019081617A1 (fr) 2019-05-02
JP2021500451A (ja) 2021-01-07
AU2018356458B2 (en) 2023-03-09
JP7433221B2 (ja) 2024-02-19
US12116701B2 (en) 2024-10-15
CN111315924A (zh) 2020-06-19
CN111315924B (zh) 2022-07-29
BR112020006196B1 (pt) 2024-02-06
KR20200074943A (ko) 2020-06-25
US20200340143A1 (en) 2020-10-29
AU2018356458A1 (en) 2020-04-16
EP3476985A1 (fr) 2019-05-01
TWI790303B (zh) 2023-01-21
BR122023020724A2 (pt) 2023-12-12
BR112020006196A2 (pt) 2020-10-13
CA3079878A1 (fr) 2019-05-02

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