CN107475794A - A kind of fire-retardant koplon of silicon nitrogen system and preparation method thereof - Google Patents

A kind of fire-retardant koplon of silicon nitrogen system and preparation method thereof Download PDF

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Publication number
CN107475794A
CN107475794A CN201710709544.9A CN201710709544A CN107475794A CN 107475794 A CN107475794 A CN 107475794A CN 201710709544 A CN201710709544 A CN 201710709544A CN 107475794 A CN107475794 A CN 107475794A
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retardant
fire
preparation
spinning
koplon
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CN107475794B (en
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徐元斌
邱纯利
马峰刚
郭伟才
吴梅彬
徐导三
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SHANDONG YINYING CHEMICAL FIBRE CO Ltd
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SHANDONG YINYING CHEMICAL FIBRE CO Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—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
    • 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
    • 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
    • D01F1/10—Other agents for modifying properties

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of fire-retardant koplon of silicon nitrogen system, and the fiber does fracture strength >=2.6CN/dtex, wet breaking strength >=1.5CN/dtex, limited oxygen index >=30%, wet rupture modulus >=0.35CN/dtex.The present invention also provides a kind of preparation method of the fire-retardant koplon of silicon nitrogen system, and methods described includes：Prepare cellulose sulfonate step；Prepare spinning solution step；Injecting step before two spinnings；It is described to prepare cellulose sulfonate step：The degree of polymerization is subjected to yellow reaction in 800~1400 cotton and/or wood pulps, generates cellulose xanthate；It is described to prepare spinning solution step：Cellulose xanthate is dissolved in aqueous slkali, addition denaturant obtains spinning solution, and spinning solution is then made；High wet modulus FRC prepared by the present invention, the characteristics of having had physical and mechanical properties and high wet modulus concurrently, it can be applied to that there is the fields such as the high-grade textile garment fabric of fire-retardant needs.

Description

A kind of fire-retardant koplon of silicon nitrogen system and preparation method thereof
Technical field
The present invention relates to a kind of koplon and preparation method thereof, particularly a kind of fire-retardant high humidity mould of silicon nitrogen system Viscose rayon and preparation method thereof is measured, belongs to the production preparation field of textile raw material.
Background technology
With the rapid development in nearly more than 40 year of reforming and opening up to the outside world, the level of consumption of compatriots steadily improves, to fiber and its system The demand of product is also growing day by day.However, largely consume fibre in people, enjoy it bring people it is warm, comfortable, While beautiful, fire also has become one of disaster of modern society caused by fibre burns.To by fire The result that caused death by accident is investigated shows that the fire as caused by upholstery and textile holds pride of place, simultaneously It was found that the pernicious gas discharged during flammable textile combustion substantially exceeds flame retardant textiles to the extent of injury of human body.Cause This, prevents fire, reduces fire damage, the fire resistance fibre of Development and Production high-quality is increasingly valued by people.
Abroad, for the U.S., continuously fire is brought safety committee of the United States Federal to the life security of people Grave danger, made on the basis of original California, USA TB603 standards and required more strict 1633 bills, and On July 1st, 2007, beginning enforced in 50 states in the U.S., and the bill is primarily directed to bedding product fire resistance.
In this context, the FR of Austrian Lenzin, composite flame retardant fiber-VISIL of Finland Saden profit, Japan is big and spin, Permanent day sea otter, Jilin chemical fibre, Beijing Sail Lan Deng companies constantly release the FRC product of oneself, to meet society Need.The FR fibre properties of Lenzin are good, price is high, it is difficult into common people family.It is Japanese to be hindered with spinning, the silicon systems of permanent day sea otter greatly Fire fiber strength is low, feel it is crisp it is puckery, fault is high, be simply possible to use in the making of non-woven cloth, mattress etc., it is impossible to used in spinning, weave cotton cloth Deng place.The phosphorous flame-retardant fiber and textile of Jilin chemical fibre can produce a large amount of high toxicity flue gases with fire and fiber wastes can be dirty Contaminate water body and environment.
Patent CN102352539B describes one kind and adds fire retardant in rear dissolution phase to prepare silicon nitrogen system fire resistance fibre New method, there is moderate, environment-protecting and non-poisonous, the preferable advantage of relative indicatrix, solve well drawbacks described above with deficiency. Improvement is optimized in patent CN106012074A on the basis of above-mentioned patent, and resistance is separately added into using injection technique before spinning twice Auxiliary agent and fire retardant are fired, a rate is changed so as to greatly reduce the turnover rate of fire retardant and spinning, improves spinnability, improves Flame retardant effect, beneficial to continual and steady production, but from the point of view of the information of Market Feedback, during the client's use of downstream, spinning quality It is not stable, spinning burr generation is more, and the loss of Weaving device is larger.
FRC product continue to optimize improved maximum technology barrier be exactly product fire resistance raising with The raising of fibrous physics mechanical performance is conflict, and fire retardant in increased fiber is had only in order to improve the flame retardant effect of product Content and this will certainly reduce the physical and mechanical properties of product.This is also the meaning not to the greatest extent of above-mentioned two patent, i.e. both technologies Although the silicon nitrogen system fire resistance fibre flame retardant effect of production is excellent, strength still show slightly it is relatively low, to the follow-up link such as spin cotton and weave cloth For it is barely satisfactory.Fiber wet modulus is poor, deforms larger after fabric washing, greatly hinders it to high technology content, height The development of the high grade cotton yarn, high-grade fabric direction of added value.
The content of the invention
The invention provides a kind of method of silicon nitrogen system FRC production, i.e., by the slurry with higher degrees of polymerization Blending adds denaturant in spinning solution prepared by the dregs of rice, and injection technique adds fire-retardant in spinning solution before then being spun again using substep Auxiliary agent and fire retardant, flame retardant are carried out mixing pre-reaction in advance with viscose glue, and raising viscose glue is combined active and steady with fire retardant Qualitative, then viscose glue carries out graft polymerization reaction with fire retardant again, is matched somebody with somebody using low sour, low sodium, high zinc coagulating bath during spinning moulding Crosslinking curing processing is carried out again so as to complete high wet modulus silicon nitrogen than, the spinning technique of high magnification echelon drawing-off, during post processing It is the preparation of fire resistance fibre.Fire retardant was both preferably resolved with this technique to be combined slowly with fiber, with reference to rear stability difference Problem, and improve the physical and mechanical properties of fire resistance fibre well, the characteristics of assigning fire resistance fibre high wet modulus.
The present invention be directed to existing silicon nitrogen system fire resistance fibre dry and wet state strength and the relatively low applied defect of wet modulus, one It is to provide a kind of high wet modulus fire resistance fibre, two are to provide the preparation method of this high wet modulus fire resistance fibre.
The preparation method of high wet modulus fire resistance fibre, carry out in accordance with the following steps：
A, cellulose sulfonate is prepared：By the degree of polymerization 800~1400, the cotton of content of alphacellulose >=95% and/or wood pulps It is sufficiently mixed with steeping liquor, alkali cellulose is made after dipping alkalizes；Alkali cellulose is by squeezing, crushing, experienced processing Afterwards, then with CS2Mixing carries out yellow reaction, generates cellulose xanthate；
B, spinning solution is prepared：Cellulose xanthate is dissolved in dilute alkaline soln, and addition is to first fibre 2.5 in rear dissolving alkali lye ~4.5% denaturant obtains spinning solution, dissolving, three filterings, deaeration, maturation after spinning solution is carried out successively, spinning is made Liquid；
C, two preceding inject is spun：By heat exchanger by the temperature control of spinning solution at 15-35 DEG C, then by being injected before spinning together System injects the flame retardant for 20~50wt% to fire retardant in spinning solution, after static mixer mixing pre-reaction, Injecting systems inject the fire retardant for 20~50wt% to the fine amount of first in spinning solution before being spun again by two, mixed by dynamic, static state Mixed after clutch into viscose glue blender, carry out going to spin after 10~180min graft polymerization reaction in a mixer Silk；
D, spinning：Wet spinning is carried out in spinning-drawing machine, after the spinning solution that with the addition of fire retardant and auxiliary agent is extruded by shower nozzle Reacted with spinning bath, as-spun fibre tow is obtained using the moulding process releived；
E, drawing-off and post processing：Nascent fibre bundle through shower nozzle, spin disk, the drawing-off of plasticizing-bath three-level gradient, plasticizing sizing after again Cut off and post-processed, wherein aftertreatment technology includes removing pickling, crosslinking curing, washing, oil；Then after being dried i.e. Obtain high wet modulus fire resistance fibre.
Further, the experienced temperature of a steps is 20~30 DEG C, and ageing time is 1~4h, experienced rear alkali cellulose copper Ammonia viscosity is 70~90mPa.S.
Further, CS in a steps yellow process2Addition be that the weight ratio fine to first is 35~45%.
Further, the b step denaturant is from polyethenoxy alkylphenols, polyoxyethylene alkyl amine, polyoxy second Alkene, polyoxygenated alkene ethylene glycol, polyethylene glycol, aromatic alcohol, polyalcohol, diethylamine, dimethylamine, cyclohexylamine, the poly- second two of alkylamine The one or more of alcohol, preferably two or more above-mentioned denaturants are used as combined degeneration agent use.
Further, the b step spinning solution index：First fibre weight ratio：6.5~10.0%, weight containing alkali than 6.0~ 10.0%, 35~100S of viscosity, degree of ripeness 5-20ml.
Further, described flame retardant is silane coupling agent and/or polyalcohols crosslinking agent.The silanes is even The chemical formula of connection agent is RSiX3, and R represents amino, vinyl, epoxy radicals in formula, and these groups and different matrix resins have There is stronger respond, X represents the alkoxy that can be hydrolyzed, such as methoxyl group, ethyoxyl.The polyalcohols crosslinking agent, Such as polyethylene glycol, polyglycerol, trimethylolpropane.
Further, described fire retardant is that organosilan hydrolyzes dispersion liquid.Its chemical formula is [MexOy· nSiO2]+[- CONH], wherein Me represents metal ion, metal ion Ti4+、Ca2+、Li+、K+、Na+In it is several, metal ion is incorporated in In cellulosic backbone, spacial framework is formed.
Further, described spinning bath composition：60~90g/L of sulfuric acid, 40~80g/L of zinc sulfate, sodium sulphate 100~ 160g/L, 30~50 DEG C of temperature.
Further, come into being in the step e strand by shower nozzle bear drawing-off be -50~60%, spinning disk drawing-off be 36~ 6%th, plasticizing-bath drawing-off is 6~18%.
Further, the crosslinking curing technique：85-99 DEG C of solidification temperature, 10 ± 5 minutes hardening times, fixation bath group Into：Soft water：T-4=10-80%：80-20%, T-4 are the novel flame-retardant crosslinking and curing agent that new chief of township expands Chemical Co., Ltd.'s production, The characteristics of effect is lasting, nontoxic pollution-free, can further improve the bond strength of fire retardant and fiber, system is greatly improved The washing-resistant effect of standby viscose rayon, after repeatedly washing use, still with good flame retardant effect.
By adopting the above-described technical solution, the present invention reach have the technical effect that：
1st, the high wet modulus silicon nitrogen system FRC dry and wet strength prepared using the present invention is high, has good spinnability, The physical and mechanical properties of fiber is excellent, does fracture strength >=2.6CN/dtex, dry elongation at break 13~16%, wet breaking strength ≥1.5CN/dtex。
2nd, high wet modulus silicon nitrogen system FRC limited oxygen index >=30% prepared using the present invention, wet fracture mould 0.35~0.55CN/dtex is measured, can be applied to that there is the fields such as the high-grade textile garment fabric of fire-retardant needs.
3rd, in preparation process of the present invention, first flame retardant is first carried out with viscose glue to mix pre-reaction, improves viscose glue and resistance Fire activity and stability that agent combines.
4th, after flame retardant and viscose glue carry out pre-reaction in preparation process of the present invention, then viscose glue and fire retardant are connect Branch polymerisation, matched using low sour, low sodium, high zinc coagulating bath during spinning moulding, the spinning technique of high magnification echelon drawing-off, after Crosslinking curing processing is carried out during processing again so as to completing the preparation of high wet modulus silicon nitrogen system fire resistance fibre, improve fire retardant with The joint efficiency of viscose glue, the flame retardant effect of fiber is further increased, extend the duration of fire resistance of fiber.
5th, FRC prepared by the present invention, has had the physical and mechanical properties of fire resistance fibre and the spy of high wet modulus concurrently Point.
6th, blending, which adds, in preparation process of the present invention, in the spinning solution prepared by the pulp with higher degrees of polymerization is denatured Agent, injection technique adds flame retardant and fire retardant, denaturant and flame retardant in spinning solution before then being spun again using substep It is used in combination, during making fire-retardant high-wet-modulus fibre downstream client's use of preparation, spinning quality is more stable, reduces spinning The generation of yarn hair thorn, reduces the loss to equipment.
7th, flame retardant and viscose glue carry out pre-reaction and graft polymerization reaction in preparation process of the present invention, avoid due to resistance Agent and the phenomenon of flame-retardant fiber effect difference caused by viscose glue are fired, the phenomenon of " with batch different effects " is avoided, improves the fire-retardant of preparation The mass uniformity of viscose rayon.
8th, because the cross-linking and curing reaction of post processing, the bond strength of fire retardant and fiber is further increased, significantly The washing-resistant effect of the viscose rayon of preparation is improved, after repeatedly washing use, still with good flame retardant effect.
Embodiment
Embodiment 1
1st, spinning solution is prepared：
By the degree of polymerization 830 or so, five batch cottons, wood pulps of content of alphacellulose >=95% mixed with arbitrary proportion after with Steeping liquor is sufficiently mixed, and is squeezed after 238 ± 1g/L, 50 DEG C of sodium hydroxide aqueous slkali 60min dippings and alkali cellulose is made； Alkali cellulose is by crushing, experienced processing, experienced temperature：22 DEG C, ageing time 1h；Again with CS2Mixing carries out yellow reaction, yellow Change 18 DEG C of temperature, yellow time 60min, carbon disulfide generates cellulose xanthate to first fibre addition 34% during yellow；Fiber Plain xanthate acid carries out obtaining spinning solution after just dissolving in dilute alkaline soln, upon dissolution denaturation of the phase addition to first fibre 4.5% Agent, consisting of 3% PEG and 1.5% ethylol amine；Dissolving, three filterings, deaeration, maturation after spinning solution is carried out successively, Spinning solution is made.Spinning solution index：First is fine：8.58wt%, containing alkali 6.2%, esterification degree 57, viscosity 82S.
2nd, injected before twice are spun：
Via heat exchanger by spinning solution temperature adjustment to 25 DEG C, injected via injecting systems before spinning together in spinning solution to fire retardant For 25% epoxy silane coupling, injecting systems are noted before being spun by static mixer mixing pre-reaction and then by two Enter the fire retardant for 48wt% to the fine amount of first.Contain titanium oxide, calcium oxide, silica and acid amides wherein in fire retardant.By dynamic Mixed into viscose glue blender after state, static mixer, in a mixer the graft polymerization reaction of progress 30 minutes it After go spinning.
3rd, spinning：
Spinning solution is reacted by shower nozzle extrusion with coagulating bath in spinning-drawing machine, obtains as-spun fibre tow；Coagulating bath component sulfuric acid 86 ± 1g/L, 58 ± 0.5g/L of zinc sulfate, 125 ± 10g/L of sodium sulphate, reaction temperature：38 ± 1 DEG C, strand length of immersion： 800mm；Ring combined spinning nozzle diameter 0.055mm；Two 96 ± 2 DEG C of bath temperatures；Two 30 ± 5g/L of bath sulfuric acid concentration.
4th, drawing-off and post processing：
Spinning disk drawing-off, 8% plasticizing-bath drawing-off and -1% retraction drawing-off of the nascent fibre bundle through 47.5% shower nozzle drawing-off, 38% Cut off and post-processed again after this level Four gradient drawing-off, plasticizing sizing, wherein aftertreatment technology includes going pickling, solidification to hand over Join, wash, oil；Then high wet modulus fire resistance fibre is obtained after being dried.
Washing：PH value 8.5,60~80 DEG C of temperature.
Crosslinking curing：88 ± 1 DEG C of temperature, 8 minutes hardening times, fixation bath composition：Soft water：T-4=60%：40%
Oil bath：PH value 5~6,65 DEG C of temperature, concentration 6g/L.
By high-strength regenerated celulose fibre finished product index made from above-mentioned technique：Nominal fiber number 1.67dtex, do strong 2.67CN/dtex, dry elongation at break 13.5%, wet breaking strength 1.71CN/dtex, wet rupture modulus 0.45CN/dtex, pole Limited oxygen index 31%.
Embodiment 2
1st, spinning solution is prepared：
By the degree of polymerization 1000 or so, five batch cottons, wood pulps of content of alphacellulose >=95% mixed with arbitrary proportion after with Steeping liquor is sufficiently mixed, and is squeezed after dipping and alkali cellulose is made；Alkali cellulose is by crushing, experienced processing, experienced temperature 26 DEG C of degree, ageing time 120min；Again with CS2Mixing carries out yellow reaction, 19 DEG C of yellow temperature, yellow time 65min, yellow When carbon disulfide to first fibre addition 36%, generate cellulose xanthate；Cellulose xanthate carries out just dissolving in dilute alkaline soln After obtain spinning solution, upon dissolution the phase add to the denaturant of first fibre 3%, consisting of 2% polyethenoxy alkylphenols With 1% cyclohexylamine；Dissolving, three filterings, deaeration, maturation after spinning solution is carried out successively, spinning solution is made.Spinning solution Index：First is fine：9.1wt%, containing alkali 7.5%, esterification degree 62, viscosity 90S.
2nd, injected before twice are spun：
Via heat exchanger by spinning solution temperature adjustment to 20 DEG C, injected via injecting systems before spinning together in spinning solution to fire retardant For 35% trimethylolpropane, injecting systems injection pair before being spun by static mixer mixing pre-reaction and then by two The fire retardant that the fine amount of first is 40wt%.Contain titanium oxide, calcium oxide, silica and acid amides wherein in fire retardant.By dynamic, Mixed after static mixer into viscose glue blender, in a mixer after the graft polymerization reaction of progress 100 minutes Go spinning.
3rd, spinning：
Spinning solution is reacted by shower nozzle extrusion with coagulating bath in spinning-drawing machine, obtains as-spun fibre tow；Coagulating bath component sulfuric acid 75 ± 1g/L, 65 ± 1g/L of zinc sulfate, 146 ± 10g/L of sodium sulphate, reaction temperature：42±1℃.Remaining spinning condition is with implementing Example 1 is identical.
4th, drawing-off and post processing：
Spinning disk drawing-off, 12% plasticizing-bath drawing-off and -0.5% retraction of the nascent fibre bundle through 40.4% shower nozzle drawing-off, 45% Cut off and post-processed again after drawing-off this level Four gradient drawing-off, plasticizing sizing, wherein aftertreatment technology includes going pickling, solidification It is crosslinked, wash, oils；Then high wet modulus fire resistance fibre is obtained after being dried.
Crosslinking curing：95 ± 2 DEG C of temperature, 10 minutes hardening times, fixation bath composition：Soft water：T-4=50%：50%；
By high-strength regenerated celulose fibre finished product index made from above-mentioned technique：Do strong 2.83CN/dtex, dry elongation at break 14.2%, wet breaking strength 1.74CN/dtex, wet rupture modulus 0.49CN/dtex, limited oxygen index 32%.
Embodiment 3
1st, spinning solution is prepared：
By the degree of polymerization 1380 or so, five batch cottons, wood pulps of content of alphacellulose >=95% mixed with arbitrary proportion after with Steeping liquor is sufficiently mixed, and is squeezed after 70min impregnates and alkali cellulose is made；Alkali cellulose is by crushing, experienced processing, always Into temperature：29 DEG C, ageing time 210min；Again with CS2Mixing carries out yellow reaction, and carbon disulfide is to first fibre addition during yellow 40%, generate cellulose xanthate；Cellulose xanthate carries out obtaining spinning solution after just dissolving in dilute alkaline soln, is dissolving Later stage adds the denaturant to first fibre 2.5%, consisting of 1.5% polyoxygenated alkene ethylene glycol and 1.0% diethylamine；Spinning Dissolving, three filterings, deaeration, maturation after stoste is carried out successively, spinning solution is made.Spinning solution index：First is fine：9.8wt%, Containing alkali 8.9%, esterification degree 68, viscosity 85S.
2nd, injected before twice are spun：
Via heat exchanger by spinning solution temperature adjustment to 25 DEG C, injected via injecting systems before spinning together in spinning solution to fire retardant For 40% epoxy silane coupling, injecting systems are noted before being spun by static mixer mixing pre-reaction and then by two Enter the fire retardant for 38wt% to the fine amount of first.Contain titanium oxide, calcium oxide, silica and acid amides wherein in fire retardant.By dynamic Mixed into viscose glue blender after state, static mixer, in a mixer the graft polymerization reaction of progress 160 minutes it After go spinning.
3rd, spinning：
Spinning solution is reacted by shower nozzle extrusion with coagulating bath in spinning-drawing machine, obtains as-spun fibre tow；Coagulating bath component sulfuric acid 64g/L, 75 ± 1g/L of zinc sulfate, 155 ± 10g/L of sodium sulphate, reaction temperature：47±1℃.Remaining spinning condition and embodiment 1 It is identical.
4th, drawing-off and post processing：
Nascent fibre bundle is led through 27.2% shower nozzle drawing-off, 52% drawing-off of spinning disk, 16% plasticizing-bath drawing-off and -1% retraction Cut off and post-processed again after stretching this level Four gradient drawing-off, plasticizing sizing, wherein aftertreatment technology includes going pickling, solidification to hand over Join, wash, oil；Then high wet modulus fire resistance fibre is obtained after being dried.
Crosslinking curing：98 ± 1 DEG C of temperature, 14 minutes hardening times, fixation bath composition：Soft water：T-4=40%：60%；
By high-strength regenerated celulose fibre finished product index made from above-mentioned technique：Do strong 2.89CN/dtex, dry elongation at break 15.6%, wet breaking strength 1.80CN/dtex, wet rupture modulus 0.52CN/dtex, limited oxygen index 33%.
The fire-retardant koplon prepared from embodiment 1-3, the fire-retardant high humidity of silicon nitrogen system prepared by embodiment 3 Modulus viscose rayon physical synthesis index is the most outstanding.
Comparative example 4
In order to further verify influence of the related process to the fiber of preparation in preparation process of the present invention, using the system of embodiment 3 Preparation Method, the crosslinking curing technique in drawing-off and post-processing step is omitted, be specially：
1st, spinning solution is prepared：
By the degree of polymerization 1380 or so, five batch cottons, wood pulps of content of alphacellulose >=95% mixed with arbitrary proportion after with Steeping liquor is sufficiently mixed, and is squeezed after 70min impregnates and alkali cellulose is made；Alkali cellulose is by crushing, experienced processing, always Into temperature：29 DEG C, ageing time 210min；Again with CS2Mixing carries out yellow reaction, and carbon disulfide is to first fibre addition during yellow 40%, generate cellulose xanthate；Cellulose xanthate carries out obtaining spinning solution after just dissolving in dilute alkaline soln, is dissolving Later stage adds the denaturant to first fibre 2.5%, consisting of 1.5% polyoxygenated alkene ethylene glycol and 1.0% diethylamine；Spinning Dissolving, three filterings, deaeration, maturation after stoste is carried out successively, spinning solution is made.Spinning solution index：First is fine：9.8wt%, Containing alkali 8.9%, esterification degree 68, viscosity 85S.
2nd, injected before twice are spun：
Via heat exchanger by spinning solution temperature adjustment to 25 DEG C, injected via injecting systems before spinning together in spinning solution to fire retardant For 40% epoxy silane coupling, injecting systems are noted before being spun by static mixer mixing pre-reaction and then by two Enter the fire retardant for 38wt% to the fine amount of first.Contain titanium oxide, calcium oxide, silica and acid amides wherein in fire retardant.By dynamic Mixed into viscose glue blender after state, static mixer, in a mixer the graft polymerization reaction of progress 160 minutes it After go spinning.
3rd, spinning：
Spinning solution is reacted by shower nozzle extrusion with coagulating bath in spinning-drawing machine, obtains as-spun fibre tow；Coagulating bath component sulfuric acid （64±1）G/L, zinc sulfate（75±1）G/L, sodium sulphate（155±10）G/L, reaction temperature：(47±1)℃.Remaining spinning bar Part is same as Example 1.
4th, drawing-off and post processing：
Nascent fibre bundle is led through 27.2% shower nozzle drawing-off, 52% drawing-off of spinning disk, 16% plasticizing-bath drawing-off and -1% retraction Stretch this level Four gradient drawing-off, plasticizing sizing after cut off and post-processed again, wherein aftertreatment technology include go pickling, washing, Oil；Then high wet modulus fire resistance fibre is obtained after being dried.
By fire-retardant high-strength regenerated celulose fibre finished product index made from above-mentioned technique：Strong 2.35CN/dtex is done, is done disconnected Split elongation 13.8%, wet breaking strength 1.60CN/dtex, wet rupture modulus 0.49CN/dtex, limited oxygen index 31%.
In the implementation process of comparative example 4, the crosslinking curing technique in drawing-off and post-processing step is omitted, therefore made The physical index of standby fire-retardant high-strength regenerated celulose fibre is fine compared with fire-retardant high-strength regenerated cellulose prepared by the embodiment of the present invention 3 The physical index of dimension declines substantially, and particularly dry fracture strength decreases drastically, and illustrates that crosslinking curing technique can be notable The raising fire resistance fibre particularly fire-retardant high-wet-modulus fibre of silicon nitrogen system dry fracture strength.
The fire-retardant koplon of the present invention prepare and use during it was found that crosslinking curing technique not only The dry fracture strength of the fire-retardant koplon of silicon nitrogen system can be improved, while silicon nitrogenated flame retardant can also be improved to fibre The adhesive force of dimension, allow the fiber of preparation after washing repeatedly, still with good fire resistance, in order to further verify So as to find out optimal production technology, We conducted the experiment of herein below：
Content of the test：It is residual that its calcination detects after being washed to the fire-retardant koplon of silicon nitrogen system of preparation in our company Stay；
Preparation of samples：Viscose rayon prepared by the embodiment of the present invention 1,2,3 and comparative example 4 is prepared into 50 equal portions respectively, it is standby；
Test method：
Non-phosphide detergent：Fiber=0.25:100, water covers fiber, and hand rubbing washing, each 15min, dehydration are carried out to fiber 3min, last time equivalent clear water is then added, hand rubbing washing, 3min is washed, is dehydrated 3min, is dried after the completion of dehydration, drying temperature 120 DEG C, drying time 2h of degree, weigh sample quality；
Calcination remains：Fiber after drying is subjected to calcination in high temperature furnace, 780-800 DEG C of calcination, calcination 2.5h, weighs calcination Residual mass；
Using above washing methods, to sample（Embodiment 1,2,3 and comparative example 4）Persistently wash 50 times, after every 10 times are entered washing Calcination residue detection of row, specific testing result are shown in Table 1
Table 1
As can be seen from Table 1, the fire-retardant koplon of silicon nitrogen system that prepared by 1-3 of the embodiment of the present invention, it is solid using crosslinking Chemical industry skill, residue on ignition is higher after fiber calcination, that is, proves after repeatedly washing, the fire-retardant active ingredient stream of fibrous inside Lose it is less, therefore the flame retardant effect duration grow.
And FRC prepared by comparative example 4, due to eliminating the crosslinking curing work in drawing-off and post-processing step Skill, its residue on ignition is relatively low, that is, proves after repeatedly washing, and the fire-retardant active ingredient loss of fibrous inside is larger, therefore The FRC flame retardant effect duration prepared by comparative example 4 is short, and anti-washability is poor.
In conventional production process, we, which use, adds flame retardant and fire retardant, flame retardant and viscose glue in spinning solution Mixing pre-reaction is carried out in advance, improves activity and stability that viscose glue is combined with fire retardant, and then viscose glue is carried out with fire retardant again Graft polymerization reaction, although so improving in the reserved downstream spinning process of fire retardant in the fibre, often produce Spin burr, adds the loss and abrasion of equipment, and in preparation process of the present invention, prepared by the pulp with higher degrees of polymerization Spinning solution in blending add denaturant, then again using substep spin before injection technique is added in spinning solution flame retardant with Fire retardant, denaturant and flame retardant are used in combination, and during making fire-retardant high-wet-modulus fibre downstream client's use of preparation, spin Yarn quality is more stable, reduces the generation of spinning burr, reduces loss of the spinning process to equipment, improve the matter of product Amount.
Above-described embodiment only expresses the specific embodiment of the present invention, but therefore can not be interpreted as to the present invention The limitation of scope.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, Various modifications and improvements can be made, these belong to protection scope of the present invention.

Claims (10)

  1. A kind of 1. fire-retardant koplon of silicon nitrogen system, it is characterised in that：The fiber does fracture strength >=2.6CN/ Dtex, wet breaking strength >=1.5CN/dtex, limited oxygen index >=30%, wet rupture modulus >=0.35CN/dtex.
  2. A kind of 2. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 1, it is characterised in that： Methods described includes：Prepare cellulose sulfonate step；Prepare spinning solution step；Injecting step before two spinnings；
    It is described to prepare cellulose sulfonate step：The degree of polymerization is subjected to yellow reaction in 800~1400 cotton and/or wood pulps, Generate cellulose xanthate；
    It is described to prepare spinning solution step：The cellulose xanthate of preparation is dissolved in aqueous slkali, addition denaturant obtains spinning Stoste, spinning solution is then made；
    Injecting step before two spinning：Flame retardant is separately added into the spinning solution of preparation and fire retardant is mixed.
  3. A kind of 3. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, it is characterised in that： Methods described also includes drawing-off and post-processing step, and the aftertreatment technology includes cross-linking curing step；The crosslinking curing step Suddenly it is that cross-linking and curing reaction is carried out to the fiber after cut-out in fixation bath.
  4. A kind of 4. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 3, it is characterised in that： The curing schedule, solidification temperature：85-99 DEG C, hardening time：10 ± 5 minutes, the fixation bath composition was soft water：T-4= 10-80%：80-20%.
  5. A kind of 5. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 3, it is characterised in that： The drawing-off includes shower nozzle drawing-off, spins disk drawing-off and plasticizing-bath drawing-off, and the shower nozzle drawing-off is -50~60%, the spinning disk drawing-off It is 6~18% for 36~6%, the plasticizing-bath drawing-off.
  6. A kind of 6. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, it is characterised in that： Methods described also includes spinning process；Spinning bath in the spinning process, which forms, is：60~90g/L of sulfuric acid, zinc sulfate 40~ 80g/L, 100~160g/L of sodium sulphate, 30~50 DEG C of temperature.
  7. A kind of 7. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, it is characterised in that： The addition of the denaturant be 2.5~4.5%, the denaturant be polyethenoxy alkylphenols, polyoxyethylene alkyl amine, Polyoxyethylene, polyoxygenated alkene ethylene glycol, polyethylene glycol, aromatic alcohol, polyalcohol, diethylamine, dimethylamine, cyclohexylamine, alkylamine The one or more of polyethylene glycol.
  8. A kind of 8. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, it is characterised in that： The addition of the flame retardant is the 20-50wt% of fire retardant, and the addition of the fire retardant is first fibre content in spinning solution 20~50wt%, described flame retardant are silane coupling agent and/or polyalcohols crosslinking agent, and described fire retardant is organic Silane hydrolyzate dispersion liquid, the organosilan hydrolysis dispersion liquid chemical formula is [MexOy· nSiO2]+[- CONH], wherein Me generations Table metal ion, the metal ion are Ti4+、Ca2+、Li+、K+、Na+In one or more.
  9. A kind of 9. preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, it is characterised in that： The cellulose sulfonate step for preparing includes experienced step, and experienced temperature is 20~30 DEG C, and ageing time is 1~4h, experienced Alkali cellulose cuprammonium viscosity is 70~90mPa.S afterwards.
  10. 10. a kind of preparation method of fire-retardant koplon of silicon nitrogen system according to claim 2, its feature exist In：The spinning solution index is：First fibre weight ratio：6.5~10.0%, weight containing alkali is than 6.0~10.0%, 35~100S of viscosity, 5~20ml of degree of ripeness, CS in the yellow process2Addition be that the weight ratio fine to first is 35~45%.
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