CN102443868B - Method for manufacturing regenerated cellulose fibers - Google Patents
Method for manufacturing regenerated cellulose fibers Download PDFInfo
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Abstract
The invention discloses a method for manufacturing regenerated cellulose fibers, comprising the following steps of: using an alkali metal hydroxide/urea/water system, an alkali metal hydroxide/thiourea/water system or an alkali metal hydroxide/urea/thiourea/water system as a solvent, mixing with cellulose materials in a continuous dissolving-defoaming device to prepare spinning solution, and manufacturing the high-strength regenerated cellulose fibers in a dry-jet wet-spinning technology. The method has low cost, environment protection and high fiber property as well as continuous production and short period, and is applicable to the large-scale industrial production.
Description
Technical field
The present invention relates to material field of textiles, in particular to a kind of method of manufacturing regenerated celulose fibre.
Background technology
Cellulose fibre has good hygroscopicity, the advantage such as comfortable and easy to wear, is the important textile fabric of extensive use.Cotton fiber crops wait native cellulose fibre because restrictions such as being subject to soil, weather, water resource can not roll up, and the raw material-native cellulose of regenerated celulose fibre almost can obtain from all straws, is inexhaustible, nexhaustible.Therefore, make full use of native cellulose development regenerated celulose fibre, the environmental pollution that not only can avoid take nondegradation synthetic fiber that oil is main raw material to cause, and can save limited non-renewable petroleum resources.
The method of traditional mode of production regenerated celulose fibre is mainly viscose process and cuprammonium process, but these two kinds of methods all exist the serious problem of environmental pollution.Direct solvent legal system successfully solves the problem of environmental pollution in preparation process for regenerated celulose fibre, in nearly 30 years, although it is found that a variety of solvents that can dissolving cellulos, for example: methyl-sulfoxide/nitrogen oxide, paraformaldehyde/methyl-sulfoxide, lithium chloride/dimethylacetylamide, ammonia/ammonium thiocyanate aqueous solution, calcium thiocyanate/sodium thiocyanate water solution, solder(ing)acid, sodium hydrate aqueous solution etc., but adopt these solvent methods to manufacture regenerated celulose fibre and still exist various shortcoming, contaminated environment as easy in solvent, price is high, solvability is low, course of dissolution is numerous and diverse, manufacture process has accessory substance, or the problem such as the fibre strength making is very low, be difficult to realize industrialization.
It is worth noting, disclosed in recent years take alkali metal hydroxide (NaOH or lithium hydroxide)/urea or (with) thiocarbamide/water prepares the method for regenerated celulose fibre as solvent, as disclosed the mixed aqueous solution with 5～12wt% NaOH and 8～20wt% urea in CN 1482159A, the direct dissolving cellulos of rapid stirring after cooling; In CN 1702201A, the mixed aqueous solution of solvent 6～8wt% NaOH and 10～20wt% urea is chilled to-8～-15 ℃ in advance, then at room temperature high-speed stirred is directly dissolved viscosity average molecular weigh lower than 1.5 * 10
5cellulose make the cellulosic cellulose solution of 3～6wt%, through the standing vacuum defoamation of pot type, obtain spinning solution, by spinning machine wet spinning and two step coagulating bath methods, solidify regeneration and make regenerated celulose fibre.
CN 1544515A adopts NaOH/thiocarbamide/aqueous systems dissolving cellulos, and exploratory the regenerated celulose fibre that made; In WO 2007/121609A1, with pilot-scale, prepare regenerated celulose fibre, the mixed aqueous solution that is about to 8.1-12wt% NaOH and 3-6wt% thiocarbamide is chilled to-10～5 ℃ in advance, then in agitator tank, under room temperature (0～25 ℃), add cellulose high-speed stirred to dissolve and make the cellulosic solution of 4-10wt%, through the standing vacuum defoamation of pot type, make spinning solution, by spinning machine wet spinning and two step coagulating bath methods, solidify regeneration and obtain fiber.
CN 1699442A be take the mixed aqueous solution of 6～12wt% NaOH/3～8wt% thiocarbamide/1～15wt% urea and is prepared regenerated celulose fibre as solvent; CN101429682A is by being 7～10% NaOH by cellulose dissolution at the percentage by weight that contains that is chilled in advance-12 ℃～-8 ℃, 4.5～7% thiocarbamide, 1～10% urea, in the mixed solution of 73%～87.5% water and after filtration, to make concentration be 2～12% cellulose solution in deaeration, through two coagulating bath wet spinnings, makes regenerated celulose fibre.
Take alkali (NaOH or lithium hydroxide)/urea or (with) thiocarbamide/water prepares regenerated celulose fibre as solvent, there is solvent cheap and easy to get, nontoxic, cellulose dissolution is fast, course of dissolution turns to direct dissolving without deriving, dissolve, spinning temperature is low, with short production cycle, technological process is simple, the easy recycling use of solvent is free from environmental pollution, regenerated celulose fibre not sulfur-bearing (viscose sulfur content 10g/kg) is the very high advantages such as fibrous material of security, therefore has the development prospect of low cost, greenization.
Yet the Patents technology of above-mentioned this solvent method has the following disadvantages:
(1) adopt wet spinning, the regenerated celulose fibre making shows lower fibre strength, is difficult to obtain intensity higher than the fiber of 2.0cN/dtex, not as good as conventional viscose (2.0～2.5cN/dtex).Architectural characteristic due to cellulose macromolecule, when stoste spray silk enters coagulating bath, there is the desolvation effect of cellulosic molecule and be reconfigured to intermolecular and intramolecular hydrogen bond network, causing between macromolecular chain, to be difficult to slippage, to spin the can stretch orientation degree low of fiber in journey.Although adopt twice coagulating bath method can make fiber solidify, relax and fully, be beneficial to the uniformity of fibre structure and spin the multistage stretching in journey, one coagulating bath method can improve fibre strength, but still is difficult to obtain high strength fibre.For the processing that improves that if intensity is drawn by raising or the operation such as drawing-off forces to improve degree of molecular orientation, the elongate fiber rate that makes to make is too low.
(2) adopt the standing vacuum defoamation method of tank (or still) formula, the deaeration time is long.When scale is amplified the deaeration time longer, deaeration effect is also poor, affects stoste spinnability.Because the deaeration time is long, for making cellulose solution keep stable solution state, need under low temperature (as 5 ℃), carry out deaeration, this further reduces deaeration efficiency, and evacuation and centrifugal degassing method is unsuitable for scale.
(3) adopt tank (or still) formula stirring and dissolving cellulose, mass-and heat-transfer weak effect easily causes solution uneven, and easily produces gel particles piece when dissolving is amplified in scale, and impact is filtered and spinning.Because solvent is cooling in advance, when adopting large tank (or still) to dissolve, being difficult for regulation and control quickly, to required solution temperature, affects solute effect and extends dissolution time.
(4) adopting tank (or still) formula to dissolve and deaeration, is batch process, can not realize the preparation of serialization spinning solution, inapplicable suitability for industrialized production.
As can be seen here, urgently develop a kind of serialization preparation that realizes, the regenerated celulose fibre intensity preparing is higher, and is suitable for the regenerated celulose fibre preparation method of suitability for industrialized production.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of regenerated celulose fibre, comprise the following steps: cellulosic material mixes in continuous-dissolution-defoaming device with cellulose solvent, continuous production spinning solution, wherein, above-mentioned cellulose solvent is alkali metal hydroxide/urea/aqueous systems, alkali metal hydroxide/thiocarbamide/aqueous systems or alkali metal hydroxide/urea/sulphur urea/aqueous systems; After the spinning solution making is filtered, adopt dry-jet wet spinning process to make regenerated celulose fibre.
According to preparation method provided by the invention, continuous-dissolution-the defoaming device adopting is the full hybrid propulsion formula of single screw extrusion machine, double screw extruder, the continous vacuum LIST mixing-dissolving machine that has exhaust to arrange, or the pusher Film Fractionation machine of continous vacuum film.
According to preparation method provided by the invention, the air section length in dry-jet wet spinning process is 1～15cm, preferably 2～10cm, more preferably 2～7cm.
According to preparation method provided by the invention, the jet stretch ratio in dry-jet wet spinning process is 1.5～12 times, preferably 3～10 times, and more preferably 5～8 times.
According to preparation method provided by the invention, in above-mentioned air section, implement air gap blowing.
According to preparation method provided by the invention, the coagulating bath in dry-jet wet spinning process can be one coagulating bath, or twice coagulating bath.Coagulating bath can be the aqueous coagulation bath that forms of sulfuric acid and sodium sulphate, the hot-water coagulating bath that contains solvent composition, here the hot-water coagulating bath of indication refer to a kind of composition between hot water and alkali/urea or (and) coagulating bath of thiocarbamide/aqueous solvent between forming.
In a specific embodiment provided by the invention, above-mentioned preparation method comprises the cellulose solvent of cellulosic material and precooling in 3～14.9: 100 ratio is injected continuous-dissolution-defoaming device simultaneously, makes continuously spinning solution under the vacuum condition of normal temperature and 1000pa～9000pa; Then, after the spinning solution making being filtered, adopt dry-jet wet spinning process to make regenerated celulose fibre.
As a kind of alternative way of above-mentioned preparation method, in another specific embodiment provided by the invention, before the cellulose solvent of above-mentioned cellulosic material and precooling injects continuous-dissolution-defoaming device, the two mixes in advance in continuous mixer.
In another specific embodiment provided by the invention, cellulose solvent is by alkali hydroxide soln, and aqueous solution of urea and/or thiourea solution form.In the preparation process of regenerated celulose fibre, first the alkali hydroxide soln of cellulosic material and precooling is injected to continuous mixer simultaneously and mix, make mixed material; Then, mixed material is delivered to continuous-dissolution-defoaming device, and inject aqueous solution of urea and/or thiourea solution, the mass ratio of final above-mentioned cellulosic material and cellulose solvent is 3～14.9: 100, alkali hydroxide soln is 12～20wt% alkali metal hydroxide aqueous solution and 2～40wt% aqueous solution of urea, makes continuously described spinning solution under the vacuum condition of normal temperature and 1000pa～9000pa; Then, after the spinning solution making being filtered, adopt dry-jet wet spinning process to make regenerated celulose fibre.As a kind of alternative way of above-mentioned preparation method, in another specific embodiment provided by the invention, after making mixed material, directly aqueous solution of urea and/or thiourea solution are injected to continuous mixer, uniform stirring; Then gained mixed material is delivered to continuous-dissolution-defoaming device, under the vacuum condition of normal temperature and 1000pa～9000pa, makes continuously described spinning solution; Then, after the spinning solution making being filtered, adopt dry-jet wet spinning process to make regenerated celulose fibre.
In a specific embodiment provided by the invention, cellulose and be chilled in advance the 12wt% NaOH of-8 ℃ and 8wt% urea mixed aqueous solution injects single screw extrusion machine, continuous production spinning solution under the vacuum condition of normal temperature and 1000pa～9000pa with the mass ratio of 3.1: 100 simultaneously; Spinning solution, after prefilter filters, is sent into spinning machine spinning pack through measuring pump and is carried out dry-jet wet spinning process, and jet stretch ratio is 2 times, and air section length is 2cm, and implements air gap blowing at described air section, and blowing temperature is 80 ℃, wind speed 2 meter per seconds; Then described spinning is immersed in coagulating bath, the body lotion of coagulating bath is 10wt% sulfuric acid and 15wt% ammonium sulfate mixed aqueous solution, and bathing temperature is 20 ℃, and in process, wet goods lower procedure makes regenerated celulose fibre.
In a specific embodiment provided by the invention, the consumption mass ratio of described cellulose, 14wt% sodium hydrate aqueous solution and 20wt% aqueous solution of urea of take is metering in 5.3: 50: 50, by cellulose be chilled in advance the described sodium hydrate aqueous solution of 0 ℃ and be injected in mixer simultaneously; Then in mixer, add the 20wt% aqueous solution of urea of 5 ℃ and mix, then the mass transport that this is mixed is to Film Fractionation machine, continuous production spinning solution under room temperature and vacuum condition; From the spinning solution of Film Fractionation machine output, after prefilter filters, send into spinning machine spinning pack carry out dry-jet wet-spinning through measuring pump, described jet stretch ratio is 5 times, air section length is 5cm, and implement air gap blowing at described air section, blowing temperature is 65 ℃, wind speed 6 meter per seconds; The first coagulating bath body lotion of described coagulating bath is comprised of 10wt% sulfuric acid and 15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 12 ℃; Second coagulating bath body lotion is 5wt% aqueous sulfuric acid, and bathing temperature is 12 ℃, and in process, wet goods lower procedure makes regenerated celulose fibre.
In a specific embodiment provided by the invention, by cellulose be chilled in advance the mixed solution being formed by 8wt% NaOH and 4.5wt% thiocarbamide mixed aqueous solution and 10wt% urea of-8 ℃, with the mass ratioes of 11.5: 100, inject continuous mixer simultaneously, then be delivered in Film Fractionation machine continuous production spinning solution under the vacuum condition of-8～0 ℃ and 1000pa～9000pa; The spinning solution of exporting from described film machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, jet stretch ratio is 10 times, air section is that 5cm solidifies under the effect of spinning funnel and implements jet stretch, and implement air gap blowing at air section, the wind speed of air gap blowing is 8m/s, and wind-warm syndrome is 80 ℃; Tow after described jet stretch and following current are solidified enters described bath from spinning funnel, and the temperature of described coagulating bath is 75 ℃, and body lotion is the solution that is equivalent to 2 times of dicyandiamide solution dilutions described in this, and in process, wet goods lower procedure makes regenerated celulose fibre.
According to regenerated celulose fibre preparation method provided by the invention, with alkali metal hydroxide/urea/aqueous systems, alkali metal hydroxide/thiocarbamide/aqueous systems or alkali metal hydroxide/urea/sulphur urea/water body, it is solvent, cellulosic material and above-mentioned solvent are mixed with to spinning solution in continuous-dissolution-defoaming device, utilize dry-jet wet-spinning spining technology to make high-intensity regenerated celulose fibre, realized the continuous production of regenerated fiber bundle fiber, do not need quiet tank deaeration step, be very suitable for suitability for industrialized production; And owing to having adopted dry-jet wet spinning process, the regenerated celulose fibre intensity making is higher.
The specific embodiment
To be described in further detail goal of the invention of the present invention, technical scheme and beneficial effect below.
Be noted that following detailed description is all exemplary, is intended for the requested to provide further explanation of the invention.Unless otherwise, all technology used herein and scientific terminology have the identical meanings of conventionally understanding with general technical staff of the technical field of the invention.
For solve in existing regenerated celulose fibre preparation technology, exist cannot suitability for industrialized production, the problem of the regenerated celulose fibre insufficient strength preparing, preparation method provided by the invention is: cellulosic material mixes in continuous-dissolution-defoaming device with cellulose solvent, continuous production spinning solution, after the spinning solution making is filtered, adopt dry-jet wet spinning process to make regenerated celulose fibre.Wherein, above-mentioned cellulose solvent is alkali metal hydroxide/urea/aqueous systems, alkali metal hydroxide/thiocarbamide/aqueous systems or alkali metal hydroxide/urea/sulphur urea/aqueous systems; The present invention adopts continuous-dissolution-defoaming device, has realized the abundant dissolving of cellulosic material and cellulose solvent, in course of dissolution, can not produce bubble, does not need deaeration to process, and has realized the continuous production of spinning solution; In addition, the present invention has adopted the preparation method of dry-jet wet-spinning, is different from original wet-spinning method, the regenerated celulose fibre good mechanical performance preparing, and its intensity level is more than or equal to 2.3cN/dtex.
Indication of the present invention " alkali metal hydroxide/urea/aqueous systems ", can be alkali metal hydroxide, and urea is dissolved in the solution forming in the aqueous solution jointly, can also refer to the dicyandiamide solution that alkali metal hydroxide aqueous solution and aqueous solution of urea form.
Indication of the present invention " alkali metal hydroxide/thiocarbamide/aqueous systems ", can be alkali metal hydroxide, and thiocarbamide is dissolved in the solution forming in the aqueous solution jointly, can also refer to the dicyandiamide solution that alkali metal hydroxide aqueous solution and thiourea solution form.
Indication of the present invention " alkali metal hydroxide/urea/sulphur urea/aqueous systems ", it can be alkali metal hydroxide, urea, thiocarbamide is dissolved in the solution forming in the aqueous solution jointly, can also refer to the dicyandiamide solution that alkali metal hydroxide aqueous solution, aqueous solution of urea and thiourea solution form.
Indication " dry-jet wet spinning process " is a kind of prior art spinning process that dry method and wet method combine.Spinning solution is extruded from spinning head, first, through one section of air section, then enter coagulating tank, from coagulating tank, derive as-spun fibre.It is direct solvent that existing dry-jet wet-spinning method adopts N-methyl-N-morpholine oxide (NMMO), this solvent is expensive, dissolution conditions is harsh, spinning temperature is higher, and the present invention adopts alkali metal hydroxide/urea/aqueous systems, alkali metal hydroxide/thiocarbamide/aqueous systems or alkali metal hydroxide/urea/sulphur urea/aqueous systems are as solvent, the spinning solution preparing is after prefilter filters, through measuring pump, send into the spinning pack of spinning machine, from the stoste thread of spinnerets ejection, air section is stretched, enter and in coagulating bath, solidify regeneration cellulose strand, cellulose strand is through drawing-off, washing, oil, after dry, by winder winding, be coiled into cylinder and make regenerated celulose fibre, complete whole dry-jet wet spinning process.
The cellulosic material that the present invention adopts can be cotton linter pulp, wood pulp, bagasse pulp, straw pulp etc. at interior various cellulose pastes, the cellulose paste that preferred degree of polymerization is 250～800.
Indication continuous-dissolution-defoaming device of the present invention can be: have the LIST mixing-dissolving machine of the full hybrid propulsion formula of single, double screw extruder, continous vacuum of steam vent, the Film Fractionation machine of continous vacuum film push type; be understandable that, this area is also included within the scope of the application's protection with other conventional continuous-dissolution-defoaming devices.
Indication alkali metal hydroxide of the present invention can be the compounds such as NaOH, lithium hydroxide.
According to preparation method provided by the invention, the air section length of dry-jet wet-spinning is 1～15cm, preferably 2～10cm, more preferably 2～7cm.
According to preparation method provided by the invention, wherein the jet stretch ratio of above-mentioned dry-jet wet-spinning is 1.5～12 times, preferably 3～10 times, and more preferably 5～8 times.
According to preparation method provided by the invention, in the spinning solution wherein making, cellulosic content is 3-13wt%.
In a kind of specific embodiment provided by the invention, be by dry cellulosic material and be chilled in advance the cellulose solvent of-15～5 ℃ and inject by a certain percentage list or double screw extruder or LIST mixing-dissolving machine simultaneously, vacuumize simultaneously, vacuum reaches 1000pa～9000pa, under normal temperature (0～25 ℃), carry out limit mixing, dissolving, propelling, limit deaeration, makes spinning solution continuously.In a specific embodiment provided by the invention, the ratio of cellulosic material and cellulose solvent is 3～14.9: 100; Wherein, described cellulose solvent is the cellulose solvent that alkali metal hydroxide, urea and/or thiocarbamide and water form.Wherein the concentration of alkali metal hydroxide is 4～12wt%, and the concentration of urea is 8～20wt%, and the concentration of thiocarbamide is 8～20wt%, and all the other are water.
Different from the above-mentioned specific embodiment is, preparing in spinning material process of the another kind of specific embodiment provided by the invention, first by above-mentioned cellulosic material be chilled in advance-15～5 ℃ of cellulose solvents and add mixer simultaneously, and then mixed material is delivered in continuous-dissolution-defoaming device, under above-mentioned normal temperature and vacuum condition, make continuously spinning solution.
Another specific embodiment provided by the invention, above-mentioned cellulose solvent can be the system that 12～20wt% alkali metal hydroxide aqueous solution and 2～40wt% aqueous solution of urea form, the system that 12～20wt% alkali metal hydroxide aqueous solution and 2～40wt% thiourea solution form, or 12～20wt% alkali metal hydroxide aqueous solution, the dicyandiamide solution that 2～40wt% aqueous solution of urea and 2～40wt% thiourea solution form.By cellulosic material be chilled in advance the above-mentioned alkali metal aqueous solution of-4～10 ℃ and inject continuous mixer and mix, then be delivered to list or double screw extruder or LIST mixing-dissolving machine, and inject above-mentioned aqueous solution of urea and/or the thiourea solution of-4～25 ℃ measuring in this equipment, under normal temperature and vacuum condition, (1000pa～9000pa) makes spinning solution continuously.The mass ratio of cellulosic material, alkali metal hydroxide aqueous solution, aqueous solution of urea and/or thiourea solution is 3.1～14.9: 50: 50.Different from this specific embodiment is, in the another kind of specific embodiment provided by the invention, by dry cellulosic material be chilled in advance the alkali metal hydroxide aqueous solution of-4～10 ℃ and inject and (or first inject alkali metal hydroxide aqueous solution simultaneously, and then inject cellulosic material) after mixer, to the above-mentioned aqueous solution of urea and/or the thiourea solution that directly add quantifier in mixer, again mixed material is delivered in continuous-dissolution-defoaming device, makes continuously spinning solution.
According to above-mentioned preparation method provided by the invention, in the described spinning solution making, cellulosic content is 3～13wt%.
According in preparation method provided by the invention, described coagulating bath can be the aqueous coagulation bath that sulfuric acid and sodium sulphate form, also hot-water coagulating bath, also can be form between water and alkali/urea or (and) between thiocarbamide/aqueous solvent forms, temperature coagulating bath of (as 40～100 ℃) more than gelling temperature.Preferably body lotion form between water and alkali/urea or (and) between thiocarbamide/aqueous solvent forms, temperature more than spinning solution gelling temperature (as 40～100 ℃, preferably 55～95 ℃, most preferably 65～85 ℃) coagulating bath, to reduce solvent recovery cost.The water temperature of the follow-up washing of cellulose strand is controlled at 40～100 ℃, and preferably 55～95 ℃, most preferably 65～85 ℃.Because coagulating bath can adopt body lotion to form similar dicyandiamide solution, form, temperature is higher than the coagulation bath of spinning solution gelling temperature, thereby solvent recovery cost is greatly reduced.One side has avoided any chemical reaction occurring in process of setting, alleviate on the other hand the concentrated load of solvent recovery, after coagulating bath is purified after filtration, adopted membrane technology or evaporation technique concentrated, after cooling, can directly as solvent, recycle, thereby greatly improve Technical Economy.
In dry-jet wet spinning process provided by the invention, adopt the method for implementing air gap blowing in air section.Weaving stoste completes dominant draft and macromolecular orientation in air gap, the temperature of blowing is determined according to stoste solution temperature and gelling temperature, for example, according to the concrete cellulose pulp degree of polymerization and concentration, between room temperature wind and warm braw, the speed of blowing is 1～12m/s, preferably 4～8m/s.
With specific embodiment, further set forth preparation method of the present invention below.
Comparative example
By dry wood pulps (degree of polymerization 400) be chilled in advance 5wt% NaOH/20wt% urea mixed aqueous solution of-15 ℃ and fully stir 30～60 minutes with the mass ratio of 3.5: 100, with vacuum under quiet de-tank is de-, within 25 hours, make it degassed, obtain spinning solution.Spinning solution is sent into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.08mm * 275, enter and first coagulating bath, be solidified into cellulose strand, body lotion consists of 10wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 10 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 5wt% aqueous sulfuric acid, and bathing temperature is 15 ℃.Cellulose strand after solidifying drawing-off through washing, oil, being dried, is finally coiled into cylinder by winder winding and makes regenerated celulose fibre again.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 1.35cN/dtex and 4.3%.
Embodiment 1
By dry bamboo pulp (degree of polymerization 500) be chilled in advance 5wt% NaOH/20wt% urea mixed aqueous solution of-15 ℃ and feed in double screw extruder with the mass ratio of 5: 100 simultaneously, and the material in extruder is vacuumized continuous production spinning solution at room temperature simultaneously.The spinning solution of exporting from extruder is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 1.5 times, from the long air section of 1cm, through following current, solidifying spinning funnel enters and first coagulating bath, is solidified into cellulose strand, 90 ℃ of air gap blowing temperature, wind speed 1 meter per second, body lotion consists of 10wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 10 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 5wt% aqueous sulfuric acid, and bathing temperature is 15 ℃.Cellulose strand after solidifying drawing-off fully washs, oils, is dried through 97 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.3cN/dtex and 7.7%.
Embodiment 2
By dry Cotton Pulp (degree of polymerization 800) be chilled in advance 12wt% NaOH/8wt% urea mixed aqueous solution of-8 ℃ and inject single screw extrusion machine, continuous production spinning solution under room temperature and vacuum condition with the mass ratio of 3.1: 100 simultaneously.The spinning solution of exporting from extruder is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 2 times, from the long air section of 2cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, 80 ℃ of air gap blowing temperature, wind speed 2 meter per seconds, body lotion consists of 10wt% sulfuric acid/15wt% ammonium sulfate mixed aqueous solution, and bathing temperature is 20 ℃.Cellulose strand after solidifying drawing-off fully washs, oils, is dried through 92 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.7cN/dtex and 11.6%.
Embodiment 3
By dry wood pulps (degree of polymerization 400) be chilled in advance 7wt% NaOH/12wt% urea mixed aqueous solution of-12 ℃ and feed LIST mixing-dissolving machine, continuous production spinning solution under room temperature and vacuum condition with the mass ratio of 8.7: 100 simultaneously.The spinning solution of making is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 3 times, from the long air section of 8cm, through following current, solidifying spinning funnel enters and first coagulating bath, is solidified into cellulose strand, air gap blowing temperature 70 C, wind speed 4 meter per seconds, body lotion consists of 5wt% sulfuric acid/20wt% sodium sulphate mixed aqueous solution, and bathing temperature is 5 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 10wt% aqueous sulfuric acid, and bathing temperature is 40 ℃.Cellulose strand after solidifying drawing-off fully washs, oils, is dried through 85 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.8cN/dtex and 6.9%.
Embodiment 4
By dry Cotton Pulp (degree of polymerization 600) be chilled in advance 7.5wt% NaOH/11wt% urea mixed aqueous solution of-12 ℃ and inject continuous mixer and mix with the mass ratio of 6.5: 100 simultaneously, then be delivered in Film Fractionation machine continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from Film Fractionation machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 5 times, from the long air section of 5cm, through following current, solidifying spinning funnel enters and first coagulating bath, is solidified into cellulose strand, air gap blowing temperature 60 C, wind speed 8 meter per seconds, body lotion consists of 5wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 20 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 10wt% aqueous sulfuric acid, and bathing temperature is 20 ℃.Cellulose strand after solidifying drawing-off fully washs, oils, is dried through 85 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.1cN/dtex and 12.1%.
Embodiment 5
The consumption mass ratio of cellulose, 14wt% sodium hydrate aqueous solution and 20wt% aqueous solution of urea of take is metering in 5.3: 50: 50, by dry Cotton Pulp (degree of polymerization 800) be chilled in advance the sodium hydrate aqueous solution of 0 ℃ and be injected in mixer and mix simultaneously, then in this mixer, add the aqueous solution of urea of 5 ℃ and mix, the mass transport again this being mixed to Film Fractionation machine, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from Film Fractionation machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 5 times, from the long air section of 5cm, through following current, solidifying spinning funnel enters and first coagulating bath, is solidified into cellulose strand, 65 ℃ of air gap blowing temperature, wind speed 6 meter per seconds, body lotion consists of 10wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 12 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 5wt% aqueous sulfuric acid, and bathing temperature is 12 ℃.Cellulose strand after solidifying drawing-off fully washs, oils, is dried through 80 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.2cN/dtex and 13.7%.
Embodiment 6
The consumption mass ratio of cellulose, 14wt% sodium hydrate aqueous solution and 20wt% aqueous solution of urea of take is metering in 5.8: 50: 50, by dry Cotton Pulp (degree of polymerization 620) be chilled in advance the sodium hydrate aqueous solution of 0 ℃ and be injected in mixer and mix simultaneously, then in this mixer, add the aqueous solution of urea of 5 ℃ and mix, the mass transport again this being mixed to LIST mixing-dissolving machine, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from LIST mixing-dissolving machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 5 times, from the long air section of 5cm, through following current, solidifying spinning funnel enters and first coagulating bath, is solidified into cellulose strand, 65 ℃ of air gap blowing temperature, wind speed 5 meter per seconds, body lotion consists of 10wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 12 ℃.Then cellulose strand enters in second coagulating bath and carries out fully solidifying regeneration, and body lotion consists of 5wt% aqueous sulfuric acid, and bathing temperature is 12 ℃.Cellulose strand after solidifying drawing-off again 65 ℃ of hot water fully washs, oils, is dried, and finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.0cN/dtex and 11.9%.
Embodiment 7
The consumption mass ratio of cellulose, 20wt% sodium hydrate aqueous solution and 24wt% aqueous solution of urea of take is metering in 8.7: 50: 50, by dry wood pulps (degree of polymerization 400) be chilled in advance the sodium hydrate aqueous solution of 0 ℃ and inject continuous mixer and mix simultaneously, then be delivered to double screw extruder, and the while is to the aqueous solution of urea of 15 ℃ of extruder injections, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of making is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 10 times, from the long air section of 10cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, air gap blowing temperature 50 C, wind speed 10 meter per seconds, body lotion consists of 10wt% sulfuric acid/15wt% sodium sulphate mixed aqueous solution, and bathing temperature is 10 ℃.Cellulose strand after solidifying drawing-off fully washs washing, oils, is dried through 70 ℃ of hot water again, finally by winder winding, is coiled into cylinder and makes regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.8cN/dtex and 5.2%.
Embodiment 8
The consumption mass ratio of cellulose, 20wt% sodium hydrate aqueous solution and 4wt% aqueous solution of urea of take is metering in 4.7: 50: 50, by dry wood pulps (degree of polymerization 500) be chilled in advance the sodium hydrate aqueous solution of 10 ℃ and inject continuous mixer and mix simultaneously, then be delivered to LIST mixing-dissolving machine, and the while is to the aqueous solution of urea of 10 ℃ of LIST mixing-dissolving machine injections, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of making is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 3 times, from the long air section of 5cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, 40 ℃ of air gap blowing temperature, wind speed 12 meter per seconds, body lotion consists of 10wt% aqueous sulfuric acid, and bathing temperature is 0 ℃.Cellulose strand after solidifying drawing-off again through 55 ℃ wash, oil, dry, finally by winder winding, be coiled into and tin make regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.5cN/dtex and 13.6%.
Embodiment 9
The consumption mass ratio of cellulose, 12wt% sodium hydrate aqueous solution and 40wt% aqueous solution of urea of take is metering in 4.7: 50: 50, by dry wood pulps (degree of polymerization 500) be chilled in advance the sodium hydrate aqueous solution of-4 ℃ and inject continuous mixer and mix simultaneously, then be delivered to single screw extrusion machine, and the while is to the aqueous solution of urea of 15 ℃ of single screw extrusion machine injections, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of making is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 2 times, from the long air section of 3cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, 30 ℃ of air gap blowing temperature, wind speed 12 meter per seconds, body lotion consists of 15wt% aqueous acetic acid, and bathing temperature is 10 ℃.Cellulose strand after solidifying drawing-off again through 40 ℃ fully wash, oil, dry, finally by winder winding, be coiled into cylinder and make regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.4cN/dtex and 13.7%.
Embodiment 10
The consumption mass ratio of cellulose, 12wt% sodium hydrate aqueous solution and 40wt% aqueous solution of urea of take is metering in 5.3: 50: 50, by dry Cotton Pulp (degree of polymerization 600) be chilled in advance the sodium hydrate aqueous solution of-4 ℃ and be injected in mixer and mix simultaneously, then in this mixer, add the aqueous solution of urea of 25 ℃ and mix, the mass transport again this being mixed to single screw extrusion machine, continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from single screw extrusion machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 3 times, from the long air section of 5cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, air gap blowing temperature 60 C, wind speed 8 meter per seconds, body lotion consists of 3wt% aqueous sulfuric acid, and bathing temperature is 40 ℃.Cellulose strand after solidifying drawing-off again through 75 ℃ wash, oil, dry, finally by winder winding, be coiled into and tin make regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.6cN/dtex and 12.9%.
Embodiment 11
By dry Cotton Pulp (degree of polymerization 620) be chilled in advance 9.5wt% NaOH/4.5wt% thiocarbamide mixed aqueous solution of-5 ℃ and inject continuous mixer and mix with the mass ratio of 5.3: 100 simultaneously, then be delivered in single screw extrusion machine continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from extruder is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275 through the long air section of 4cm, in following current, solidify under the effect of spinning funnel and implement jet stretch, the wind speed of air gap blowing is 6m/s, wind-warm syndrome is 65 ℃, and jet stretch ratio is 4 times.Tow after jet stretch and following current are solidified enters in first coagulating bath and solidifies from spinning funnel, and body lotion consists of 10wt% sulfuric acid/13wt% sodium sulphate mixed aqueous solution, and bathing temperature is 15 ℃.Then enter in second coagulating bath and carry out fully solidifying regeneration, body lotion consists of 5wt% aqueous sulfuric acid, and bathing temperature is 18 ℃.Go out cellulose tow after coagulating bath successively through 90 ℃ of hot water fully wash, oil, be dried, reeling obtains regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.9cN/dtex and 9.6%.
Embodiment 12
By dry wood pulps (degree of polymerization 450) be chilled in advance 9.5wt% NaOH/4.3wt% thiocarbamide mixed aqueous solution of 5 ℃ and inject continuous mixer and mix with the mass ratio of 5.2: 100 simultaneously, then be delivered in LIST mixing-dissolving machine continuous production spinning solution under-5 ℃ and vacuum condition.The spinning solution of exporting from LIST mixing-dissolving machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275, through the jet stretch of 2 times, from the long air section of 2cm, through following current, solidifying spinning funnel enters and coagulating bath, solidifies regeneration cellulose strand, the wind speed of air gap blowing is 5m/s, wind-warm syndrome is 60 ℃, body lotion consists of 15wt% aqueous ammonium chloride solution, and bathing temperature is 30 ℃.Cellulose strand after solidifying drawing-off again through 55 ℃ fully wash, oil, dry, finally by winder winding, be coiled into cylinder and make regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 2.4cN/dtex and 10.2%.
Embodiment 13
By dry wood pulps (degree of polymerization 400) be chilled in advance 9.5wt% NaOH/4.3wt% thiocarbamide mixed aqueous solution of-4.6 ℃ and inject continuous mixer and mix with the mass ratio of 8.7: 100 simultaneously, then be delivered in double screw extruder continuous production spinning solution under room temperature and vacuum condition.The spinning solution of exporting from extruder is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275 through the long air section of 5cm, in following current, solidify under the effect of spinning funnel and implement jet stretch, the wind speed of air gap blowing is 6m/s, wind-warm syndrome is 60 ℃, and jet stretch ratio is 6.5 times.Tow after jet stretch and following current are solidified enters coagulating bath from spinning funnel, and coagulation bath temperature is 99 ℃, and body lotion forms and is equivalent to 0.1 times of this dicyandiamide solution dilution aqueous solution of 8.64wt% NaOH, 3.91wt% thiocarbamide (containing).The cellulose tow going out after coagulating bath is fully washed through 99 ℃ of hot water, is dried to obtain regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.3cN/dtex and 14.0%.
Embodiment 14
The consumption mass ratio of cellulose, 14wt% sodium hydrate aqueous solution and 8wt% thiourea solution of take is metering in 8.7: 50: 50, by dry Cotton Pulp (degree of polymerization 400) be chilled in advance the sodium hydrate aqueous solution of 0 ℃ and be injected in mixer and mix simultaneously, then in this mixer, add the thiourea solution of 5 ℃ and mix, the mass transport again this being mixed to Film Fractionation machine, continuous production spinning solution under room temperature (25 ℃) and vacuum condition.The spinning solution of exporting from Film Fractionation machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste of the spinnerets ejection in hole, the 0.12mm * 275 long air section of 5cm of flowing through, in following current, solidify under the effect of spinning funnel and implement jet stretch, the wind speed of air gap blowing is 6m/s, wind-warm syndrome is 60 ℃, and jet stretch ratio is 6.5 times.Tow after jet stretch and following current are solidified enters coagulating bath from spinning funnel, and coagulation bath temperature is 99 ℃, and body lotion forms and is equivalent to 0.1 times of this dicyandiamide solution dilution aqueous solution of 6.36wt% NaOH, 3.64wt% thiocarbamide (containing).The cellulose tow going out after coagulating bath is fully washed through 99 ℃ of hot water, is dried to obtain regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.4cN/dtex and 14.6%.
Embodiment 15
Other conditions are with embodiment 14, difference be by the mass transport mixing in mixer to continuous production spinning solution in double screw extruder, the fracture strength of gained regenerated celulose fibre and elongation at break are respectively 3.4cN/dtex and 14.2%.
Embodiment 16
By dry Cotton Pulp (degree of polymerization 450) be chilled in advance 5wt% lithium hydroxide/5wt% thiocarbamide mixed aqueous solution of-8 ℃ and inject continuous mixer and mix with the mass ratio of 8: 100 simultaneously, then be delivered in Film Fractionation machine continuous production spinning solution under-8～0 ℃ and vacuum condition.The spinning solution of exporting from film machine is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275 through the long air section of 5cm, in following current, solidify under the effect of spinning funnel and implement jet stretch, the wind speed of air gap blowing is 6m/s, wind-warm syndrome is 60 ℃, and jet stretch ratio is 6.5 times.Tow after jet stretch and following current are solidified enters coagulating bath from spinning funnel, and coagulation bath temperature is 90 ℃, and body lotion forms and is equivalent to 0.5 times of this dicyandiamide solution dilution.The cellulose tow going out after coagulating bath is fully washed through 90 ℃ of hot water, is dried to obtain regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.4cN/dtex and 14.8%.
Embodiment 17
Other conditions are with embodiment 14, and the consumption mass ratio of different is cellulose, 10wt% lithium hydroxide aqueous solution and 8wt% thiourea solution is metering in 9.3: 50: 50; Adopt the Cotton Pulp that the degree of polymerization is 550; After the thiourea solution temperature that adds be 4 ℃; The wind speed of air gap blowing is 8m/s, and wind-warm syndrome is 80 ℃, and jet stretch ratio is 7.7 times; 85 ℃ of coagulation bath temperatures, body lotion forms and is equivalent to 1 times of this dicyandiamide solution dilution, and the strand going out after coagulating bath fully washs, is dried to obtain regenerated celulose fibre through 85 ℃ of hot water.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.7cN/dtex and 14.9%.
Embodiment 18
Other conditions are with embodiment 16, and the cellulosic degree of polymerization that different is is that the precooling temperature of 440,5wt% lithium hydroxide/10wt% urea mixed aqueous solution is-10 ℃, and jet stretch ratio is 6.6 times.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.4cN/dtex and 14.0%.
Embodiment 19
Other conditions are with embodiment 14, different is cellulose, 10wt% lithium hydroxide aqueous solution and 20wt% aqueous solution of urea consumption mass ratio be metering in 7.7: 50: 50; Adopt the Cotton Pulp that the degree of polymerization is 550; 90 ℃ of coagulation bath temperatures, body lotion forms and is equivalent to 0.5 times of this dicyandiamide solution dilution; The cellulose strand going out after coagulating bath fully washs, is dried to obtain regenerated celulose fibre through 90 ℃ of hot water.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.5cN/dtex and 14.5%.
Embodiment 20
Other conditions are with embodiment 16, and the mass ratio of different is cellulose and 8wt% NaOH/4.5wt% thiocarbamide/10wt% urea mixed aqueous solution is 11.5: 100; Cellulose used is the wood pulps of the degree of polymerization 550; The precooling temperature of 8wt% NaOH/4.5wt% thiocarbamide/10wt% urea mixed aqueous solution is-12 ℃; The temperature of continuous production spinning solution is 0 ℃; The wind speed of air gap blowing is 8m/s, and wind-warm syndrome is 80 ℃, 10 times of jet stretch ratios; Coagulation bath temperature is 75 ℃, and body lotion forms and is equivalent to 2 times of this dicyandiamide solution dilutions, and the strand going out after coagulating bath fully washs, is dried to obtain regenerated celulose fibre through 75 ℃ of hot water.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.9cN/dtex and 15.0%.
Embodiment 21
The consumption mass ratio of cellulose, 16wt% sodium hydrate aqueous solution and 13wt% thiocarbamide/16wt% urea mixed aqueous solution of take is metering in 11.5: 50: 50, by dry wood pulps (degree of polymerization 550) be chilled in advance the sodium hydrate aqueous solution of 0 ℃ and add in continuous mixer and mix simultaneously, then be delivered to LIST mixing-dissolving machine, and the while is to thiocarbamide/urea mixed aqueous solution of 5 ℃ of LIST mixing-dissolving machine injections, continuous production spinning solution under room temperature (25 ℃) and vacuum condition.The spinning solution of making is after prefilter filters, through measuring pump, send into spinning machine spinning pack and carry out dry-jet wet-spinning, from the stoste thread of the spinnerets ejection in hole, 0.12mm * 275 through the long air section of 15cm, in following current, solidify under the effect of spinning funnel and implement jet stretch, the wind speed of air gap blowing is 8m/s, wind-warm syndrome is 80 ℃, and jet stretch ratio is 10 times.Tow after jet stretch and following current are solidified enters coagulating bath from spinning funnel, and coagulation bath temperature is 75 ℃, and body lotion forms and is equivalent to 2 times of this dicyandiamide solution dilutions.The tow going out after coagulating bath fully washs through 75 ℃ of hot water, is dried to obtain regenerated celulose fibre.The fracture strength of this regenerated celulose fibre and elongation at break are respectively 3.9cN/dtex and 15.0%.
Embodiment 22
Other conditions are with embodiment 20, and the mass ratio of different is cellulose and 4.6wt% lithium hydroxide/4.5wt% thiocarbamide/10wt% urea mixed aqueous solution is 13.6: 100; Cellulosic degree of polymerization is 450; The temperature of continuous production spinning solution is-2 ℃; Jet stretch ratio is 11 times; Coagulation bath temperature is 45 ℃, consists of pure water.The fracture strength of gained regenerated celulose fibre and extension at break are respectively 4.0cN/dtex and 14.5%.
Embodiment 23
Other conditions are with embodiment 21, and the consumption mass ratio of different is cellulose, 9.6wt% lithium hydroxide aqueous solution and 9.2wt% thiocarbamide/19wt% urea mixed aqueous solution is 14.9: 50: 50; Cellulosic degree of polymerization is 450; With Film Fractionation machine continuous production spinning solution; Jet stretch ratio is 12 times; Coagulation bath temperature is 40 ℃, consists of pure water.The fracture strength of gained regenerated celulose fibre and extension at break are respectively 4.1cN/dtex and 14.7%.
Embodiment 24
Other conditions are with embodiment 21, different, at air section, do not implement space blowing, and the fracture strength of gained regenerated celulose fibre and extension at break are respectively 3.4cN/dtex and 11.5%.
Table 1 shows the performance of above-described embodiment gained regenerated celulose fibre
| Fracture strength (cN/dtex) | Extension at break (%) | |
| Comparative example 1 | 1.35 | 4.3 |
| Embodiment 1 | 2.7 | 7.7 |
| Embodiment 2 | 2.7 | 11.6 |
| Embodiment 3 | 2.8 | 6.9 |
| Embodiment 4 | 3.1 | 12.1 |
| Embodiment 5 | 3.2 | 13.7 |
| Embodiment 6 | 3.0 | 11.9 |
| Embodiment 7 | 2.8 | 5.2 |
| Embodiment 8 | 2.5 | 13.6 |
| Embodiment 9 | 2.4 | 13.7 |
| Embodiment 10 | 2.6 | 12.9 |
| Embodiment 11 | 2.9 | 9.6 |
| Embodiment 12 | 2.4 | 10.2 |
| Embodiment 13 | 3.3 | 14.0 |
| Embodiment 14 | 3.4 | 14.6 |
| Embodiment 15 | 3.4 | 14.2 |
| Embodiment 16 | 3.4 | 14.8 |
| Embodiment 17 | 3.7 | 14.9 |
| Embodiment 18 | 3.4 | 14.0 |
| Embodiment 19 | 3.5 | 14.5 |
| Embodiment 20 | 3.9 | 15.0 |
| Embodiment 21 | 3.9 | 15.0 |
| Embodiment 22 | 4.0 | 14.5 |
| Embodiment 23 | 4.1 | 14.7 |
| Embodiment 24 | 3.4 | 11.5 |
From above-mentioned data, can find out, compare with comparative example, embodiment 1-23 is all showing significant raising aspect fracture strength and elongation at break.According to the experimental data of embodiment 20-23, its solvent adopting is alkali metal hydroxide/thiocarbamide/aqueous solution of urea, and the fracture strength of the regenerated celulose fibre obtaining and the Performance Ratio of elongation at break are better.Embodiment 14 compares with embodiment 15, in the situation that other conditions are identical, difference be by the mass transport mixing in mixer to continuous production spinning solution in double screw extruder, gained regenerated celulose fibre performance is similar.Embodiment 21 compares with embodiment 24, and owing to not adopting space blowing, the performance of gained regenerated fiber fiber is obviously not as adopting the effective of space blowing, and visible void blowing has a certain impact to the performance tool of regenerated celulose fibre.
Compare with related art, the invention has the advantages that:
First, adopt dry-jet wet-spinning spinning process, make stoste thread from spinnerets ejection entering coagulating bath with regard to stretch orientation, because cellulosic molecule is now in solution state, intermolecular hydrogen bonding network is destroyed by solvent, between macromolecular chain, be easy to slippage, can stretch orientation degree far above solidifying state, thereby can make orientation, high strength regenerative cellulose fiber that degree of crystallinity is high.
The second, the continuous-dissolution adopting, defoaming device mass-and heat-transfer be effective, shear that the uniformity is high, automatically cleaning, non-blind area, thereby mix, dissolve Quick uniform; Meanwhile, material is wherein to push ahead continuously with membranaceous, is easy to vacuum defoamation, and deaeration efficiency greatly improves; And mixing, dissolving and deaeration three carry out simultaneously, residence time of material is short, can make fast high-quality spinning solution.
The 3rd, owing to being spinning solution continuous production-spinning, production is serialization, and with short production cycle; Do not exist solution to treat the long dwell period that deaeration and deaeration process and stoste are to be spun, avoided solution and stoste to pass in time the deterioration of spinnability etc., the possibility of gel even, thereby be applicable to extensive industrialization.
More than explanation is only the preferred embodiment of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a preparation method for regenerated celulose fibre, is characterized in that, described method comprises:
Cellulosic material mixes in continuous-dissolution-defoaming device with cellulose solvent, continuous production spinning solution, wherein, described cellulose solvent is alkali metal hydroxide/urea/aqueous systems, alkali metal hydroxide/thiocarbamide/aqueous systems or alkali metal hydroxide/urea/sulphur urea/aqueous systems
After described spinning solution is filtered, adopt dry-jet wet spinning process to make described regenerated celulose fibre, the coagulating bath in described dry-jet wet-spinning method is to contain solvent composition and temperature at the hot-water coagulating bath of 75～100 ℃.
2. method according to claim 1, it is characterized in that, the described cellulose solvent of described cellulosic material and precooling is injected to described continuous-dissolution-defoaming device by the mass ratio of 3～14.9:100, under the vacuum condition of normal temperature and 1000pa～9000pa, make continuously described spinning solution, wherein, the concentration of described alkali metal hydroxide is 4～12wt%, and the concentration of urea is 8～20wt%, and the concentration of thiocarbamide is 8～20wt%.
3. method according to claim 2, is characterized in that, before the described cellulose solvent of described cellulosic material and precooling injects described continuous-dissolution-defoaming device, mixes in advance in continuous mixer.
4. method according to claim 1, is characterized in that,
Described cellulose solvent is by alkali hydroxide soln, and aqueous solution of urea and/or thiourea solution form;
The described alkali hydroxide soln of described cellulosic material and precooling is injected to continuous mixer and mix, make mixed material;
Described mixed material is delivered to described continuous-dissolution-defoaming device, and injects described aqueous solution of urea and/or thiourea solution, under the vacuum condition of normal temperature and 1000pa～9000pa, make continuously described spinning solution.
5. method according to claim 4, is characterized in that,
Make after described mixed material, directly described aqueous solution of urea and/or thiourea solution are injected to described continuous mixer, uniform stirring;
Gained mixed material is delivered to described continuous-dissolution-defoaming device.
6. method according to claim 4, it is characterized in that, described alkali hydroxide soln is 12～20wt% alkali metal hydroxide aqueous solution and 2～40wt% aqueous solution of urea, and the mass ratio of above-mentioned cellulosic material and cellulose solvent is 3～14.9:100.
7. according to the method described in any one in claim 1-6, it is characterized in that, the air section length that described dry-jet wet spinning process relates to is 1～15cm, and jet stretch ratio is 1.5～12 times.
8. method according to claim 7, is characterized in that, at described air section, implements air gap blowing.
9. method according to claim 1, it is characterized in that, described continuous-dissolution-defoaming device is the full hybrid propulsion formula of single screw extrusion machine, double screw extruder, the continous vacuum LIST mixing-dissolving machine that has exhaust to arrange, or the pusher Film Fractionation machine of continous vacuum film.
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| CN105887226B (en) * | 2016-06-29 | 2019-06-25 | 中国纺织科学研究院有限公司 | Preparation facilities and preparation method, fibre bundle of cellulose fibre tow |
| CN106245131A (en) * | 2016-08-09 | 2016-12-21 | 东华大学 | A kind of precursor fiber preparation method of low-temperature alkaline urea method cellulose base carbon fiber |
| WO2018213117A1 (en) * | 2017-05-14 | 2018-11-22 | Washington State University | Environmentally friendly cellulose waste recycling |
| CN110057644B (en) * | 2019-05-13 | 2020-08-04 | 中国科学院山西煤炭化学研究所 | Method for measuring limiting oxygen index of spinning solution |
| CN111499883A (en) * | 2020-05-19 | 2020-08-07 | 武汉水木弘新材料有限公司 | Low-temperature dissolving method adopting cellulose combined raw materials and application thereof |
| CN115537954B (en) * | 2022-09-26 | 2023-09-22 | 新乡化纤股份有限公司 | Preparation method of cellulose spinning solution, and product prepared by preparation method and application of cellulose spinning solution |
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