CN105525376A - Regenerated cellulose fiber and preparation method thereof - Google Patents
Regenerated cellulose fiber and preparation method thereof Download PDFInfo
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- CN105525376A CN105525376A CN201510848219.1A CN201510848219A CN105525376A CN 105525376 A CN105525376 A CN 105525376A CN 201510848219 A CN201510848219 A CN 201510848219A CN 105525376 A CN105525376 A CN 105525376A
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
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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
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Abstract
The invention provides a regenerated cellulose fiber and a preparation method thereof. The preparation method is characterized by comprising the following steps: dissolving corncob fiber pulp and a chelating agent with an NMMO solution so as to obtain a spinning stock solution; and preparing regenerated cellulose fiber from the spinning stock solution obtained in the previous step. According to the invention, the regenerated cellulose fiber is prepared by using a solvent method; corncob fiber is used as a raw material for Lyocell fiber, so the agricultural waste corncob is fully utilized and the problem of shortage of a raw material for the Lyocell fiber is effectively overcome; moreover, the corncob fiber pulp has short fiber length (in a range of 0 to 0.3 mm) and a uniform polymerization degree (in a range of 500 to 600) and can be rapidly and uniformly dispersed in a solvent system; and since a great number of holes are distributed in the surface of the corncob fiber pulp, strong capillarity is obtained, a solvent can be rapidly absorbed and the surface and interior of the pulp both participate in a reaction, and thus, reaction time is greatly reduced and reaction uniformity is improved.
Description
Technical field
The present invention relates to regenerated fiber technical field, particularly relate to a kind of regenerated celulose fibre and preparation method thereof.
Background technology
Regenerated celulose fibre refer to natural polymer be raw material, make through chemical method, substantially identical in chemical composition with original copolymer chemical fibre.Simultaneously again usable fibers element make for raw material, structure is the regenerated fiber of cellulose II.
In numerous regenerated celulose fibre, Lyocell fiber (meaning and disappearing fibre) is described as 21 century green fiber, and it is with N-methylmorpholine-N-oxide (NMMO) for solvent, for the regenerated celulose fibre of wet method spinning.Patent (US92179181) is just had to propose to produce with the direct dissolving cellulos of tertiary amine acid oxide new cellulosic-Lyocell fiber that performance is better than viscose as far back as the thirties in 20th century, its composition still belongs to cellulosic structure, product abandonment thing natural degradation, is considered to a kind of environmental protection fiber that combination property is good.It has the soft matter state of the comfortableness of cotton fiber, the intensity of polyester fiber, the drapability of viscose and silk, very popular.For this reason, from 20 century 70s so far, under the joint efforts of at home and abroad scientist, applied for or disclosed up to a hundred the patents about Lyocell fiber.
As patent " manufacture method of CN1472374A bamboo cellulose fibre by solvent " refer to a kind of manufacture method utilizing bamboo cellulose pulp to produce cellulose fiber by solvent method, its method is: be first the bamboo cellulose pulp small pieces cutting pulp grinder and be cut to specific standard of 400 ~ 1000 by the degree of polymerization, then carrying out dehydration makes moisture content reach 2 ~ 4%, then with concentrated after NMMO solvent, stirring, dissolve at being heated to 80 ~ 110 DEG C under vacuum, obtain spinning solution.Then this spinning solution is carried out the operation such as spinning, post processing and obtain the short silk of bamboo fibre or long filament.A kind of spinning of producing cellulose fiber by solvent method with Cotton Pulp or wood pulps is refer in patent " preparation technology of the spinning solution of CN1420214A cellulose fiber by solvent method ", equipment is simple, be applicable to small lot batch manufacture, but reaction need be completed in the dissolution kettle of transformation or polymeric kettle.
But relating to manufacture method in above-mentioned prior art, is all that the cellulose pulp made with cotton, wood or bamboo pulp is for raw material.But along with the high speed development of Lyocell fiber, forest cotton waits the day by day in short supply of agricultural resource, can not meet the demand trend of people to Lyocell fiber raw material.And, because adopted cellulose pulp is cotton, wooden or bamboo pulp, fibre length longer (length is generally greater than 0.5mm), the degree of polymerization is higher, conglomeration between fiber, bridging, the poly-effect of wadding obviously, are thus being dissolved in NMMO dissolving agent process, make NMMO solvent cannot fast, uniformly and pulp hybrid reaction, there is dissolution time length, affect the technical barriers such as follow-up ropiness energy, in actual production process, lack operability.
Therefore, how to find one to be more conducive to regenerated celulose fibre long-run development, and the preparation method of operability in actual production can be strengthened, become focus and the problem demanding prompt solution of institute of manufacturer extensive concern in industry.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of regenerated celulose fibre and preparation method thereof, the regenerated celulose fibre that theres is provided of the present invention and preparation method, take corncob as cellulose be raw material, regenerated celulose fibre is prepared through solvent method, effectively solve regenerated celulose fibre raw material in short supply, and the problem of poor operability in preparation process.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterized in that, comprise the steps:
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning solution in NMMO solution;
2) spinning solution above-mentioned steps obtained again carries out spinning, obtains regenerated celulose fibre.
Preferably, the degree of polymerization of described corn cob fiber pulp is 400 ~ 800.
Preferably, in described corn cob fiber pulp, first fibre is 80% ~ 95%, and whiteness is 70% ~ 90%, and ash content is 0 ~ 0.5%, and moisture is 5% ~ 50%.
Preferably, the quality of described corn cob fiber pulp accounts for 5% ~ 20% of spinning solution gross mass; The quality of described chelating agent is 0.1% ~ 0.5% of described corn cob fiber pulp quality.
Preferably, described chelating agent is one or more in carboxylic acids chelating agent, polycarboxylic acid chelating agent and organic multicomponent phosphonic acid type chelants;
Preferably, described carboxylic acids chelating agent is one or more of amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound and hydroxylamino carboxylic acids chelating agent;
Described amino carboxylic acid quasi-chelate compound comprises one or more in ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) and diethylene-triamine pentaacetic acid and salt thereof; Described hydroxylamino carboxylic acids chelating agent comprises one or more in hydroxyethylethylene diamine tri-acetic acid (HEDTA) and bicine N-(DEG); Described hydroxycarboxylic acid quasi-chelate compound comprises one or more in citric acid (CA), tartaric acid (TA) and gluconic acid (GA);
Described polycarboxylic acid chelating agent is one or more in polyacrylic acid and sodium salt thereof, polymethylacrylic acid, hydrolytic polymaleic anhydride, fumaric acid (fumaric acid)-propene sulfonic acid copolymer.
Preferably, described corn cob fiber pulp is through peracid treatment.
Preferably, described acid treatment is that described corn cob fiber pulp and the front acid solution of NMMO solution mixing process;
Or in described corn cob fiber pulp and NMMO solution mixed dissolution process, pass into sour gas and process.
The invention provides a kind of regenerated celulose fibre, it is characterized in that, obtained after preparation as fibrous raw material by corn cob fiber.
Present invention also offers a kind of article, it is characterized in that, containing regenerated celulose fibre prepared by the preparation method described in claim 1 ~ 7 any one, or the regenerated celulose fibre described in claim 8 ~ 9 any one;
Described article comprise civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterized in that, comprise the steps, first corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning solution in NMMO solution; Spinning solution above-mentioned steps obtained again carries out spinning, obtains regenerated celulose fibre.Compared with prior art, the present invention adopts solvent method to prepare regenerated celulose fibre, take corn cob fiber as the raw material of Lyocell fiber, make use of agricultural wastes corncob fully, not only effectively solve the yoke of Lyocell fiber shortage of raw materials, also for the comprehensive utilization of corncob provides brand-new approach; And corn cob fiber element pulp, fibre length short (length is between 0 ~ 0.3mm), the degree of polymerization evenly (between 500 ~ 600), in dicyandiamide solution can rapid dispersion even, and pulp surface distributed has a large amount of holes, there is stronger capillarity, can lyosoption fast, pulp surface is made all to participate in reacting with inside, greatly reduce the reaction time, improve the reaction uniformity, do not need the activation procedure through pulp, shorten production procedure, improve production efficiency.In addition, the present invention in the process preparing spinning solution, by add chelating agent, iron ion in corncob pulp was lost efficacy, thus avoid iron ion the spinning solution degree of polymerization is acutely declined, cause difficulty in spinning, easily break end, make into the negative effects such as a poor product quality, intensity is low.Experimental result shows, regenerated celulose fibre preparation method provided by the invention be uniformly dissolved stable, dissolution time is short, preparation method's dissolution time provided by the invention is 30 ~ 60min, compare wood pulp and shorten 20 ~ 70min, follow-up ropiness can be good, prepared regenerated celulose fibre elongation at break can reach 17.6%, and dry fracture strength can reach 4.5CN/dtex.
Accompanying drawing explanation
Fig. 1 is 500 times of SEM photos of corn cob fiber provided by the invention element pulp;
Fig. 2 is 5000 times of SEM photos of corn cob fiber provided by the invention element pulp;
Fig. 3 is 5000 times of SEM photos of the corn cob fiber element pulp in the embodiment of the present invention 1;
Fig. 4 is Lyocell fiber spinning technique general flow chart.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of the restriction to invention claim.
The all raw materials of the present invention, be not particularly limited its source, commercially buy or prepare according to conventional method well known to those skilled in the art.
The all raw materials of the present invention, are not particularly limited its purity, and the present invention preferably adopts analysis pure.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterized in that, comprise the steps:
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning solution in NMMO solution;
2) spinning solution above-mentioned steps obtained again carries out spinning, obtains regenerated celulose fibre.
First corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning solution by the present invention in NMMO solution; The degree of polymerization of described corn cob fiber pulp is preferably 400 ~ 800, is more preferably 400 ~ 750, is more preferably 400 ~ 700, be more preferably 400 ~ 650, and optimum is 400 ~ 600.In described corn cob fiber pulp, described first fibre is preferably 80% ~ 95%, is more preferably 83% ~ 92%, most preferably is 85% ~ 90%; Described whiteness is preferably 70% ~ 90%, is more preferably 75% ~ 85%, most preferably is 78% ~ 82%; Described ash content is preferably 0 ~ 0.5%, is more preferably 0.1% ~ 0.4%, most preferably is 0.2% ~ 0.3%.The present invention is not particularly limited described corncob, with corncob well known to those skilled in the art; The present invention's other conditions to described corn cob fiber pulp are not particularly limited, with the condition of corn cob fiber pulp well known to those skilled in the art; The present invention is not particularly limited described corn cob fiber pulp source, and with preparation method's preparation or commercially available well known to those skilled in the art, the present invention preferably can adopt following methods to be prepared,
Method one
(1) after corncob being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution be made up of formic acid and acetic acid is used to carry out boiling to corncob, control boiling temperature 120-155 DEG C, solid-liquid mass ratio is 1:5-1:15, reaction time 10-60min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid; In described organic acid solution, total acid is dense is 70-95wt%, and the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of corncob;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor be made up of formic acid, acetic acid is used to carry out pickling to described solid, control pickling temperature 30-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid; In described mix acid liquor, total acid is dense is 70-95wt%, and the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of corncob;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect described third time the solid that obtains of Separation of Solid and Liquid and screening obtain required screened stock cellulose, after bleaching, obtain corn cob fiber element pulp.
Method two
By in method one, the pickling of step (2) replaces with alkali cleaning, and actual conditions is 12% sodium hydroxide solution, carries out alkali cleaning, alkali cleaning temperature 30-100 DEG C to the solid of step (1), alkali cleaning time 10-30min.Other conditions are constant.
Method three
By in method one, the digestion process of step (1) replaces with: pulverized by corncob, carry out alkali lye boiling 0.5-1.2 hour, obtain corn cob fiber cellulose solution, then carry out Separation of Solid and Liquid.Other conditions are constant.
See 500 times of SEM photos that Fig. 1, Fig. 1 are corn cob fiber element pulp prepared by the present invention.See 5000 times of SEM photos that Fig. 2, Fig. 2 are corn cob fiber provided by the invention element pulp.
The quality optimization of corn cob fiber pulp of the present invention accounts for 5% ~ 20% of spinning solution gross mass, is more preferably 8% ~ 18%, most preferably is 10% ~ 15%; The quality optimization of described chelating agent is 0.1% ~ 0.5% of described corn cob fiber pulp quality, is more preferably 0.2% ~ 0.4%, most preferably is 0.25% ~ 0.35%; Chelating agent of the present invention is not particularly limited, with the chelating agent for removing iron ion well known to those skilled in the art, the present invention is for improving removal effect, be preferably one or more in carboxylic acids chelating agent, polycarboxylic acid chelating agent and organic multicomponent phosphonic acid type chelants, be more preferably carboxylic acids chelating agent, polycarboxylic acid chelating agent or organic multicomponent phosphonic acid type chelants, most preferably be carboxylic acids chelating agent or polycarboxylic acid chelating agent; Described carboxylic acids chelating agent is preferably one or more of amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound and hydroxylamino carboxylic acids chelating agent, is more preferably amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound or hydroxylamino carboxylic acids chelating agent; Described polycarboxylic acid chelating agent is preferably one or more in polyacrylic acid and sodium salt thereof, polymethylacrylic acid, hydrolytic polymaleic anhydride, fumaric acid (fumaric acid)-propene sulfonic acid copolymer, be more preferably polyacrylic acid and sodium salt, polymethylacrylic acid, hydrolytic polymaleic anhydride or fumaric acid (fumaric acid)-propene sulfonic acid copolymer, most preferably be polyacrylic acid and sodium salt, hydrolytic polymaleic anhydride or fumaric acid (fumaric acid)-propene sulfonic acid copolymer.
In described carboxylic acids chelating agent, described amino carboxylic acid quasi-chelate compound is specifically as follows one or more in ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) and diethylene-triamine pentaacetic acid and salt thereof, also can be ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) or diethylene-triamine pentaacetic acid and salt thereof; Described hydroxylamino carboxylic acids chelating agent is specifically as follows one or more in hydroxyethylethylene diamine tri-acetic acid (HEDTA) and bicine N-(DEG), also can be hydroxyethylethylene diamine tri-acetic acid (HEDTA) or bicine N-(DEG); Described hydroxycarboxylic acid quasi-chelate compound preferably includes one or more in citric acid (CA), tartaric acid (TA) and gluconic acid (GA), more preferably comprises citric acid (CA), tartaric acid (TA) or gluconic acid (GA).
The source of the present invention to described NMMO solution is not particularly limited, with method preparation or commercially available well known to those skilled in the art, the present invention obtains described NMMO solution after preferably adopting commercially available NMMO solvent (concentration is generally 50% or 60%) to be concentrated into moisture 10% ~ 30%.The present invention's other conditions to described NMMO solution are not particularly limited, with condition well known to those skilled in the art.
The concrete grammar of the present invention to described mixing is not particularly limited, and those skilled in the art can adjust according to actual conditions, product requirement and quality control, and the present invention is preferably Homogeneous phase mixing.The concrete grammar of the present invention to described dissolving is not particularly limited, and those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, and the dissolving of the preferred corn cob fiber pulp of the present invention can three kinds of modes be dissolved below:
Direct dissolution method: commercially available NMMO solvent concentration, adds corncob pulp, then heat up, and carries out dissolving cellulos.
Indirect dissolution method: commercially available NMMO solvent (mostly being 50% or 60%), first mix with corncob pulp, cellulose is swelling in a solvent, then through reducing pressure/vacuumizing removing excess water, dissolving cellulos.
Directly-dissolution method indirectly:
Commercially available NMMO solvent concentration, to moisture 10% ~ 30%, adds corncob pulp, then heats up, simultaneously through reducing pressure/vacuumizing removing excess water, dissolving cellulos.
The present invention improves the effect and the quality of subsequent product of dissolving, preferred sequestrant to add opportunity be the moisture of NMMO solution when being 10% ~ 30%, be more preferably 13% ~ 30%, be more preferably 15% ~ 30%, most preferably be 20% ~ 30%.
The concrete preparation process of the present invention to described spinning solution does not have other to limit especially, with the preparation method of spinning solution well known to those skilled in the art, those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, and the present invention is preferably:
Method one: get the NMMO aqueous solution, being concentrated into moisture is 10-30%, and by corn cob fiber element pulp, chelating agent and the mixing of the NMMO solution after concentrating, stir and heat up, dissolving cellulos, obtains spinning solution.
Method two: get the NMMO aqueous solution, by the mixing of corn cob fiber element pulp, chelating agent and NMMO solution, cellulose is swelling in a solvent, and then through reducing pressure/vacuumizing removing excess water, dissolving cellulos, obtains spinning solution.
Method three: get the NMMO aqueous solution, being concentrated into moisture is 10-30%, and by corn cob fiber element pulp, chelating agent and the mixing of the NMMO solution after concentrating, stir and heat up, simultaneously through reducing pressure/vacuumizing removing excess water, dissolving cellulos, obtains spinning solution.
The spinning solution that above-mentioned steps obtains by the present invention again carries out spinning, obtains regenerated celulose fibre.The detailed process of the present invention to described spinning is not particularly limited, the process of regenerated celulose fibre is prepared with spinning solution spinning well known to those skilled in the art, those skilled in the art can know and know, other filtration, spinning, wash, oil and drying etc. process, all be absolutely necessary conventional steps, and this is also known to those skilled in the art.Be Lyocell fiber spinning technique general flow chart see Fig. 4, Fig. 4.
The overall preparation method of the present invention to described regenerated celulose fibre does not have other to limit especially, with operating condition well known to those skilled in the art, those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, the present invention preferably adopts solvent method to prepare regenerated celulose fibre on the whole, is more preferably specially:
Method one: get the NMMO aqueous solution, being concentrated into moisture is 10-30%, and by corn cob fiber element pulp, chelating agent and the mixing of the NMMO solution after concentrating, stir and heat up, dissolving cellulos, obtains spinning solution.Then spinning solution is carried out filtering, obtaining regenerated celulose fibre through dry-jet wet spinning process, coagulating bath is NMMO dilute aqueous solution (concentration is 5 ~ 15%), and the tow after shaping can obtain corn cob fiber cellulose fiber through washing, cutting off, oil, after the postprocessing working procedures such as dry.
Method two: get the NMMO aqueous solution, by the mixing of corn cob fiber element pulp, chelating agent and NMMO solution, cellulose is swelling in a solvent, and then through reducing pressure/vacuumizing removing excess water, dissolving cellulos, obtains spinning solution.Then spinning solution is carried out filtering, obtaining regenerated celulose fibre through dry-jet wet spinning process, coagulating bath is NMMO dilute aqueous solution (concentration is 5 ~ 15%), and the tow after shaping can obtain corn cob fiber cellulose fiber through washing, cutting off, oil, after the postprocessing working procedures such as dry.
Method three: get the NMMO aqueous solution, being concentrated into moisture is 10-30%, and by corn cob fiber element pulp, chelating agent and the mixing of the NMMO solution after concentrating, stir and heat up, simultaneously through reducing pressure/vacuumizing removing excess water, dissolving cellulos, obtains spinning solution.Then spinning solution is carried out filtering, obtaining regenerated celulose fibre through dry-jet wet spinning process, coagulating bath is NMMO dilute aqueous solution (concentration is 5 ~ 15%), and the tow after shaping can obtain corn cob fiber cellulose fiber through washing, cutting off, oil, after the postprocessing working procedures such as dry.
The present invention improves the effect of overall preparation process and the quality of subsequent product, preferably also acid treatment step is comprised to described corn cob fiber pulp, the present invention is not particularly limited described acid treatment step, with acid treatment step well known to those skilled in the art, the present invention improves the chelate effect of iron ion and chelating agent, concrete steps are more preferably, and described corn cob fiber pulp and the front acid solution of NMMO solution mixing process; Or in described corn cob fiber pulp and NMMO solution mixed dissolution process, pass into sour gas and process.The present invention is not particularly limited the acid source in described acid solution, those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, and the present invention is preferably nonmetal strong acid weak base salt, weak acid (such as formic acid, acetic acid); The mode of the present invention to described acid solution process is not particularly limited, those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, and the present invention is preferably floods and/or drying in an acidic solution by corn cob fiber pulp.The present invention is not particularly limited described sour gas, and those skilled in the art can carry out adjusting and selecting according to actual conditions, product requirement and quality control, and the present invention is preferably carbon dioxide; The present invention is the carbon dioxide that passes into of preferred above-mentioned steps also, removes in the de-bubble step before follow-up spinning simultaneously.
The present invention has prepared regenerated celulose fibre through above-mentioned steps, i.e. the corn cob fiber regenerated celulose fibre of a kind of corn cob fiber element pulp production.The present invention effectively utilizes fibre length short (length is between 0 ~ 0.3mm) in corn cob fiber element pulp, the degree of polymerization evenly (between 500 ~ 600), in dicyandiamide solution can rapid dispersion even, and pulp surface distributed has a large amount of holes, there is stronger capillarity, can lyosoption fast, pulp surface is made all to participate in reacting with inside, greatly reduce the reaction time, improve the reaction uniformity, do not need the activation procedure through pulp, shorten production procedure, improve production efficiency.
In addition, the present invention is aided with the content that chelating agent reduces iron ion in preparation process, effectively overcome iron ion, on the one hand the spinning solution degree of polymerization obtained acutely is declined, cause difficulty in spinning, easily break end, make into the problems such as a poor product quality, intensity are low, the existence of iron ion can cause the decomposition of cellulose and solvent NMMO on the other hand, produce explosive intermediate product, there is the problem of major safety risks.
The invention provides a kind of regenerated celulose fibre, it is characterized in that, obtained after preparation as fibrous raw material by corn cob fiber.
Regenerated celulose fibre provided by the invention is using corn cob fiber as raw material, fruit axle-corncob after the present invention utilizes corn ear to slough seed, effectively solve the bottleneck that Lyocell fiber raw material limits its fast development, the existing annual output corn of China is about 1.5 hundred million tons simultaneously, the output of corresponding corncob is estimated also at about 4,000 ten thousand tons, so a large amount of corncobs, except industrial part is used as the product such as furfural, xylitol, major part goes out of use.Thus, the corncob not only comparatively cheap wide material sources of price that the present invention adopts, can also solve corncob and directly burn process as agricultural wastes, cause the problem such as the wasting of resources and environmental pollution after large-area applications.Compare other raw materials, the regenerated celulose fibre of preparation has better intensity, controls especially to the content of iron ion, effectively overcomes the defect that corn cob fiber exists as raw material.
Present invention also offers a kind of article, it is characterized in that, containing regenerated celulose fibre prepared by the preparation method described in above-mentioned any one technical scheme, or the regenerated celulose fibre described in above-mentioned any one technical scheme;
Described article preferably include civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
The invention provides a kind of regenerated celulose fibre and its preparation method and application, solvent method is adopted to prepare regenerated celulose fibre, take corn cob fiber as the raw material of Lyocell fiber, make use of agricultural wastes corncob fully, not only effectively solve the yoke of Lyocell fiber shortage of raw materials, also for the comprehensive utilization of corncob provides brand-new approach; And corn cob fiber element pulp, fibre length short (length is between 0 ~ 0.3mm), the degree of polymerization evenly (between 500 ~ 600), in dicyandiamide solution can rapid dispersion even, and pulp surface distributed has a large amount of holes, there is stronger capillarity, can lyosoption fast, pulp surface is made all to participate in reacting with inside, greatly reduce the reaction time, improve the reaction uniformity, do not need the activation procedure through pulp, shorten production procedure, improve production efficiency.In addition, the present invention in the process preparing spinning solution, by add chelating agent, iron ion in corncob pulp was lost efficacy, thus avoid iron ion the spinning solution degree of polymerization is acutely declined, cause difficulty in spinning, easily break end, make into the negative effects such as a poor product quality, intensity is low.Experimental result shows, regenerated celulose fibre preparation method provided by the invention be uniformly dissolved stable, dissolution time is short, preparation method's dissolution time provided by the invention is 30 ~ 60min, compare wood pulp and shorten 20 ~ 70min, follow-up ropiness can be good, prepared regenerated celulose fibre elongation at break can reach 17.6%, and dry fracture strength can reach 4.5CN/dtex.
In order to further illustrate the present invention, be described in detail to regenerated celulose fibre provided by the invention and its preparation method and application below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Containing corn cob fiber pulp in the embodiment of the present invention and comparative example, the specific requirement in described corn cob fiber pulp, all selects in following scope, and first fibre is 80 ~ 95%, and whiteness is 70 ~ 90%, and ash content is 0 ~ 0.5%, and moisture is 5 ~ 50%.
Embodiment 1
With NMMO solubilize corn cob fiber pulp and chelating agent, obtain spinning solution, prepare regenerated celulose fibre with this spinning solution.
Wherein, corncob pulp accounts for 12% of total weight of material.Chelating agent (ethylenediamine tetra-acetic acid) addition is 0.1% of cellulose pulp.
See 5000 times of SEM photos that Fig. 3, Fig. 3 are the corn cob fiber element pulp in the embodiment of the present invention 1.
Embodiment 2 ~ 15
Embodiment 2-13, with embodiment 1, is only limitted to the change of corncob pulp content and the change of chelating agent, and the corncob pulp of embodiment 14 floods with acetic acid before mixing with NMMO, then dry, then is added in NMMO solution.In embodiment 15, after corncob pulp and the mixing of NMMO solution, in mixed serum, pass into carbon dioxide.The carbon dioxide now passed into, removes in the de-bubble step before spinning simultaneously.
In embodiment 1 ~ 15, when the moisture that the interpolation of chelating agent is NMMO opportunity is 10% ~ 30%, the character of the corn cob fiber pulp that embodiment 1-15 and documents 1 are selected: in corn cob fiber pulp, first fibre is 80 ~ 95%, whiteness is 70 ~ 90%, ash content is 0 ~ 0.5%, and moisture is 5 ~ 50%.
The preparation method of this corn cob fiber pulp is:
Method one
(1) after corncob being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution be made up of formic acid and acetic acid is used to carry out boiling to corncob, control boiling temperature 120-155 DEG C, solid-liquid mass ratio is 1:5-1:15, reaction time 10-60min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid; In described organic acid solution, total acid is dense is 70-95wt%, and the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of corncob;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor be made up of formic acid, acetic acid is used to carry out pickling to described solid, control pickling temperature 30-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid; In described mix acid liquor, total acid is dense is 70-95wt%, and the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of corncob;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect described third time the solid that obtains of Separation of Solid and Liquid and screening obtain required screened stock cellulose, after bleaching, obtain corn cob fiber element pulp.
Method two
By in method one, the pickling of step (2) replaces with alkali cleaning, and actual conditions is 12% sodium hydroxide solution, carries out alkali cleaning, alkali cleaning temperature 30-100 DEG C to the solid of step (1), alkali cleaning time 10-30min.Other conditions are constant.
Method three
By in method one, the digestion process of step (1) replaces with: pulverized by corncob, carry out alkali lye boiling 0.5-1.2 hour, obtain corn cob fiber cellulose solution, then carry out Separation of Solid and Liquid.Other conditions are constant.
The character of the corn cob fiber element pulp that comparative example 2 is selected: in corn cob fiber pulp, first fibre is 83%, and whiteness is 65%, and ash content is 1.2%, and moisture is 8%.
Corn cob fiber element pulp is replaced with the wood pulps that the degree of polymerization is 700 by comparative example 3-4.
Corn cob fiber element pulp is replaced with the Cotton Pulp that the degree of polymerization is 700 by comparative example 5-6.
Carry out Performance Detection to the regenerated celulose fibre prepared by above-described embodiment and comparative example, testing result specifically sees the following form 1, and table 1 is condition and the performance data of embodiment 1 ~ 15 and comparative example.
The condition of table 1 embodiment 1 ~ 15 and comparative example and performance data
Applicant states, the present invention illustrates process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not namely mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for regenerated celulose fibre, is characterized in that, comprises the steps:
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning solution in NMMO solution;
2) spinning solution above-mentioned steps obtained again carries out spinning, obtains regenerated celulose fibre.
2. preparation method according to claim 1, is characterized in that, the degree of polymerization of described corn cob fiber pulp is 400 ~ 800.
3. preparation method according to claim 1, is characterized in that, in described corn cob fiber pulp, first fibre is 80% ~ 95%, and whiteness is 70% ~ 90%, and ash content is 0 ~ 0.5%, and moisture is 5% ~ 50%.
4. preparation method according to claim 1, is characterized in that, the quality of described corn cob fiber pulp accounts for 5% ~ 20% of spinning solution gross mass; The quality of described chelating agent is 0.1% ~ 0.5% of described corn cob fiber pulp quality.
5. preparation method according to claim 1, is characterized in that, described chelating agent is one or more in carboxylic acids chelating agent, polycarboxylic acid chelating agent and organic multicomponent phosphonic acid type chelants.
6. preparation method according to claim 5, is characterized in that, described carboxylic acids chelating agent is one or more of amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound and hydroxylamino carboxylic acids chelating agent;
Described amino carboxylic acid quasi-chelate compound comprises one or more in ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) and diethylene-triamine pentaacetic acid and salt thereof; Described hydroxylamino carboxylic acids chelating agent comprises one or more in hydroxyethylethylene diamine tri-acetic acid (HEDTA) and bicine N-(DEG); Described hydroxycarboxylic acid quasi-chelate compound comprises one or more in citric acid (CA), tartaric acid (TA) and gluconic acid (GA);
Described polycarboxylic acid chelating agent is one or more in polyacrylic acid and sodium salt thereof, polymethylacrylic acid, hydrolytic polymaleic anhydride, fumaric acid (fumaric acid)-propene sulfonic acid copolymer.
7. preparation method according to claim 1, is characterized in that, described corn cob fiber pulp is through peracid treatment.
8. preparation method according to claim 7, is characterized in that, described acid treatment is that described corn cob fiber pulp and the front acid solution of NMMO solution mixing process;
Or in described corn cob fiber pulp and NMMO solution mixed dissolution process, pass into sour gas and process.
9. a regenerated celulose fibre, is characterized in that, is obtained as fibrous raw material by corn cob fiber after preparation.
10. article, is characterized in that, containing regenerated celulose fibre prepared by the preparation method described in claim 1 ~ 7 any one, or the regenerated celulose fibre described in claim 8 ~ 9 any one;
Described article comprise civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
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| CN201510848219.1A CN105525376B (en) | 2015-11-27 | 2015-11-27 | A kind of regenerated celulose fibre and preparation method thereof |
| PCT/CN2016/107317 WO2017088826A1 (en) | 2015-11-27 | 2016-11-25 | Regenerated cellulose fiber and method preparing the same and article manufactured from the same |
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| CN201510848219.1A CN105525376B (en) | 2015-11-27 | 2015-11-27 | A kind of regenerated celulose fibre and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757464A (en) * | 2016-11-15 | 2017-05-31 | 天津捷盛东辉保鲜科技有限公司 | Food oxydating resistance cellulose acetate nanofiber preservative film |
| WO2017088826A1 (en) * | 2015-11-27 | 2017-06-01 | 济南圣泉集团股份有限公司 | Regenerated cellulose fiber and method preparing the same and article manufactured from the same |
| KR101904771B1 (en) * | 2017-09-22 | 2018-10-05 | 오영세 | The lyocell fibers and The method for produce it |
| WO2018191980A1 (en) * | 2017-04-21 | 2018-10-25 | 中国农业大学 | Preparation of oxidized cellulose, and application of oxidized cellulose in washing and drug loading |
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| CN114892296A (en) * | 2022-05-23 | 2022-08-12 | 东华大学 | Method for compounding and spinning high-performance Lyocell fiber by using waste cotton regenerated pulp |
| CN116356441A (en) * | 2023-03-02 | 2023-06-30 | 东华大学 | Preparation method of regenerated cellulose fiber based on corncob |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383965A (en) * | 2001-04-30 | 2002-12-11 | 许炯 | Process for production of LYOCELL fiber with bamboo material |
| US20060070711A1 (en) * | 2004-09-30 | 2006-04-06 | Mengkui Luo | Low pH treatment of pulp in a bleach sequence to produce pulp having low D.P. and low copper number for use in lyocell manufacture |
| CN104004207A (en) * | 2014-05-21 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing corn cob cellulose material or blended fiber material by using ionic liquid |
| KR20160116195A (en) * | 2015-03-26 | 2016-10-07 | (주)세왕섬유 | Method of preparing knitted fabric comprising cellulose fiber |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3033698A (en) * | 1959-10-23 | 1962-05-08 | Eastman Kodak Co | Cellulose acetate spinning solutions and process of spinning fine denier filaments |
| ZA834139B (en) * | 1982-06-08 | 1984-03-28 | Courtaulds Plc | Polymer solutions |
| WO1997033018A1 (en) * | 1996-03-06 | 1997-09-12 | Mitsubishi Rayon Co., Ltd. | Fibril based fibers, method of manufacturing same, spinning nozzle used in same, and moldings obtained therefrom |
| DE10331342B4 (en) * | 2003-07-11 | 2009-03-12 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Thermostable molding or spinning mass |
| DE102004024029A1 (en) * | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell method and apparatus with metal ion content control |
| DE102006033591B4 (en) * | 2006-07-18 | 2008-10-16 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Process for stabilizing the spinning solution in the production of cellulosic composite moldings |
| CN103541022B (en) * | 2013-11-06 | 2016-04-20 | 济南圣泉集团股份有限公司 | Porous corn cob fiber and preparation method thereof |
| CN105525376B (en) * | 2015-11-27 | 2018-03-27 | 济南圣泉集团股份有限公司 | A kind of regenerated celulose fibre and preparation method thereof |
| CN105648561B (en) * | 2016-04-01 | 2018-05-18 | 山东嘉成赛尔新材料技术有限公司 | A kind of preparation method of solvent method corn cob fiber cellulose fiber |
-
2015
- 2015-11-27 CN CN201510848219.1A patent/CN105525376B/en active Active
-
2016
- 2016-11-25 WO PCT/CN2016/107317 patent/WO2017088826A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1383965A (en) * | 2001-04-30 | 2002-12-11 | 许炯 | Process for production of LYOCELL fiber with bamboo material |
| US20060070711A1 (en) * | 2004-09-30 | 2006-04-06 | Mengkui Luo | Low pH treatment of pulp in a bleach sequence to produce pulp having low D.P. and low copper number for use in lyocell manufacture |
| CN104004207A (en) * | 2014-05-21 | 2014-08-27 | 中国科学院过程工程研究所 | Method for preparing corn cob cellulose material or blended fiber material by using ionic liquid |
| KR20160116195A (en) * | 2015-03-26 | 2016-10-07 | (주)세왕섬유 | Method of preparing knitted fabric comprising cellulose fiber |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017088826A1 (en) * | 2015-11-27 | 2017-06-01 | 济南圣泉集团股份有限公司 | Regenerated cellulose fiber and method preparing the same and article manufactured from the same |
| CN106757464A (en) * | 2016-11-15 | 2017-05-31 | 天津捷盛东辉保鲜科技有限公司 | Food oxydating resistance cellulose acetate nanofiber preservative film |
| WO2018191980A1 (en) * | 2017-04-21 | 2018-10-25 | 中国农业大学 | Preparation of oxidized cellulose, and application of oxidized cellulose in washing and drug loading |
| KR101904771B1 (en) * | 2017-09-22 | 2018-10-05 | 오영세 | The lyocell fibers and The method for produce it |
| CN109610023A (en) * | 2017-09-22 | 2019-04-12 | 吴永世 | Lyocell fibers and its manufacturing method |
| US11987906B2 (en) | 2018-01-15 | 2024-05-21 | Lenzing Aktiengesellschaft | Method of reusing a mixed textile comprising cellulose and synthetic plastic |
| CN111630217A (en) * | 2018-01-15 | 2020-09-04 | 兰精股份公司 | Method for reusing mixed textile containing cellulose and synthetic plastics |
| CN113005533A (en) * | 2021-03-22 | 2021-06-22 | 太原理工大学 | Method for removing iron ions in seed hemp pulp |
| CN113005533B (en) * | 2021-03-22 | 2022-03-15 | 太原理工大学 | Method for removing iron ions in seed hemp pulp |
| TWI825401B (en) * | 2021-03-23 | 2023-12-11 | 聚隆纖維股份有限公司 | Lyocell fiber with recycled cellulose |
| CN114214784A (en) * | 2021-12-10 | 2022-03-22 | 湖南俏妃卫生用品有限公司 | Preparation method of bamboo fiber and corn fiber bi-component non-woven fabric |
| CN114892296A (en) * | 2022-05-23 | 2022-08-12 | 东华大学 | Method for compounding and spinning high-performance Lyocell fiber by using waste cotton regenerated pulp |
| CN116356441A (en) * | 2023-03-02 | 2023-06-30 | 东华大学 | Preparation method of regenerated cellulose fiber based on corncob |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017088826A1 (en) | 2017-06-01 |
| CN105525376B (en) | 2018-03-27 |
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