CN103306136A - Cross-linking agent composition, antigen fibrillating solution spinning cellulose fiber, and preparation methods thereof - Google Patents
Cross-linking agent composition, antigen fibrillating solution spinning cellulose fiber, and preparation methods thereof Download PDFInfo
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Abstract
The invention discloses a cross-linking agent composition, an antigen fibrillating solution spinning cellulose fiber, and preparation methods thereof. The cross-linking agent composition comprises low poly polybasic acid of which the molecular weight is 400-1000, and C2-C6 polyatomic acid; the weight ratio of the low poly polybasic acid to the C2-C6 polyatomic acid is 1:(1-5). The multi-anhydride containing an anhydride bond is easily formed between the low poly polybasic acid and a carboxyl functional group (-COOH) in polybasic acid in a high-temperature heating process of crosslinking reaction. Thus, reaction with hydroxyl of the cellulose is easily carried out, and more crosslinking structures are formed. The crosslinking agent composition has a prominent role in improvement of the antigen fibrillating performance of the fiber.
Description
Technical field
The present invention relates to the fiber process field, spin cellulose fibre and their preparation methods in particular to a kind of crosslinker composition, antigen fibrillation solution.
Background technology
Cellulose dissolution is formed cellulose solution in appropriate solvent, solution is extruded in a kind of spinning coagulation bath again, this moment, cellulose solidified regeneration therein, formed fiber after stretching.Said method is called " solution spins ", and the gained fiber is that solution spins cellulose fibre.Known solution spins the viscose that is represented as of cellulose fibre, further expands the scale of production but huge environmental pollution and energy consumption problem hinder it.
In order to address this problem, all proposed to adopt novel dissolvent to prepare the method for cellulose fibre in US Patent No. 4246221 and Chinese patent CN94190487.3, be about to cellulose dissolution in the aqueous solution of organic solvent tertiary amino oxides, and solution makes the technical scheme of fiber thus.Be named as the Lyocell fiber by the prepared fiber of this method, Chinese Lay match by name youngster is commonly called as a day silk.
The Lyocell fiber is mainly take wood pulps as raw material, take the mixture of tertiary amino oxides (NMMO) and water as the solvent preparation.Chemical constitution and the viscose of Lyocell fiber are basic identical, but except characteristic such as hygroscopicity, gas permeability, comfortableness, glossiness dyeability and biodegradable with natural fabric, also have the high-intensity advantage of synthetic fiber.Compare other solution and spin cellulose fibre, the advantages such as production procedure is short, energy consumption is low, environmental pollution is little, the recyclable recycling of solvent that it has, it is expected to replace traditional viscose, is called as the 21 century green fiber.
Yet the Lyocell fiber is subject to mechanical stress and does the time spent under hygrometric state, and fibrillation phenomenon in various degree easily occurs.So-called fibrillation phenomenon refer to " when fibre structure at vertical fracture, tiny fibril just from the fiber part separate " phenomenon.The generation of this fibrillation phenomenon affects outward appearance, dyeing uniformity and the washability etc. of Lyocell fibre so that the fiber of producing has crinosity shape appearance.
At present, solving the approach that the Lyocell fiber is easy to fibrillation mainly is fiber to be carried out crosslinked post processing realize, utilizes this method to realize having the industrialization production of the Lyocell fiber of antigen fibrillation performance.Wherein, invention number for the patent report of CN95192563.6 have three acrylamidos, be preferably 1,3, the crosslinking agent of 5-three acrylamido hexahydro-1,3,5-triazines spins the cellulose fibre reaction with moist attitude solution, reduces its fibrillation tendency.Invention number for the patent report of CN98801507.2 have the textile auxiliary of two reactive groups, be preferably 2, the crosslinking agent of 4-dichloro-6-hydroxy triazine sodium salt reduces the method that solution spins the fibrillation tendency of cellulose fibre.But the crosslinking agent that uses in these techniques is synthetic loaded down with trivial details, expensive, and crosslinking agent is difficult for longer-term storage, in use easily is hydrolyzed, and affects the efficient of cross-linking reaction and the effect of resistant fiber Fibrillation Properties.
Summary of the invention
The present invention aims to provide a kind of crosslinker composition, antigen fibrillation solution spins cellulose fibre and preparation method thereof, spins the problem of cellulose fibre easily fibrillable to solve solution.
To achieve these goals, according to an aspect of the present invention, provide a kind of crosslinker composition, comprised that molecular weight is 400～1000 oligomeric polyacid and C2～C6 polyacid, the weight ratio of oligomeric polyacid and C2～C6 polyacid is 1:1～5.
Further, the weight ratio of oligomeric polyacid and C2～C6 polyacid is 1:2～3 in the above-mentioned crosslinker composition.
Further, oligomeric polyacid is low poly, oligomeric acrylic acid or acrylic acid-maleic acid in the above-mentioned crosslinker composition.
Further, polyacid is to contain at least the polyacid of two carboxyl functional groups in the above-mentioned crosslinker composition, and/or contains at least the polyacid of two carboxyl functional groups and a hydroxy functional group,
Further, polyacid is succinic acid, 1,2 in the above-mentioned crosslinker composition, one or more in 3-the third three acid, citric acid, hydroxysuccinic acid and the dyhydrobutanedioic acid.
Further, crosslinker composition also comprises flexible linear polymer in the above-mentioned crosslinker composition, and the weight ratio of flexible linear polymerization and oligomeric polyacid is 1:2～10, and flexible linear polymer choosing is that molecular weight is 200～800 polyethylene glycol.
Another aspect of the present invention provides a kind of antigen fibrillation solution to spin cellulose fibre, spins cellulose fibre by solution and gets through above-mentioned crosslinker composition crosslinking Treatment.
Another aspect of the present invention, provide a kind of solution to spin the crosslinked post-processing approach of cellulose fibre, may further comprise the steps: above-mentioned crosslinker composition is dissolved in the solution, the cross-linking agent solution that to form oligomeric polyacid content be 5～60g/L, the cross-linking agent solution that to be preferably oligomeric polyacid content be 20～40g/L; Solution is spun cellulose fibre be immersed in the cross-linking agent solution, obtain blended fiber; Cross-linking reaction is carried out in the blended fiber heating, obtain antigen fibrillation solution and spin cellulose fibre.
Further, above-mentioned crosslinked post-processing approach also comprises the step of blended fiber being carried out preheating before cross-linking reaction is carried out in the blended fiber heating, and the temperature of preheating step is 70～100 ℃, and the time is 10～60min.
Further, cross-linking agent solution also comprises catalyst in the above-mentioned crosslinked post-processing approach, and C2 in catalyst and the crosslinker composition～C6 polyacid weight ratio is 1～3:5, is preferably 2～3:5.
Further, catalyst is preferably inorganic phosphate in the above-mentioned crosslinked post-processing approach, and catalyst is the mixture of one or more in sodium phosphate, sodium hydrogen phosphate, the inferior sodium phosphate more preferably.
Further, above-mentioned crosslinked post-processing approach forms in the process of blended fiber, and solution spins cellulose fibre and is immersed in 10-30min in the cross-linking agent solution, and heating-up temperature is 160～190 ℃ in the cross-linking reaction process, and the time is 2-10min.
Further, the antigen fibrillation solution that above-mentioned crosslinked post-processing approach forms spins in the cellulose fibre, and the weight that the relatively described solution of weight that antigen fibrillation solution spins cellulose fibre spins cellulose fibre increases by 0.3～3%.
Further, above-mentioned crosslinked post-processing approach solution spins the hygrometric state fiber that cellulose fibre is the undried processing.
Again one side of the present invention, provide a kind of antigen fibrillation solution to spin the preparation method of cellulose fibre, comprise that preparation solution spins the step of cellulose fibre and solution is spun the step that cellulose fibre carries out crosslinked post processing, solution is spun the above-mentioned crosslinked post-processing approach of step employing that cellulose fibre carries out crosslinked post processing.
In the high-temperature heating process of cross-linking reaction, carboxyl functional group in oligomeric polyacid in the crosslinker composition provided by the invention and the polyacid (is easy to COOH) form and contains the strong multi-anhydride of acid anhydride, thereby be easy to react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to the antigen fibrillation performance that improves fiber.Be 400～1000 oligomeric polyacid and little molecule C2～C6 polyacid by using molecular weight in the present invention, so that each raw molecule chain is relatively short in the crosslinking agent, the carboxyl functional group that can participate in reacting (COOH) more, and then can produce more cross-linked structure, to realize improving the effect of resistant fiber Fibrillation Properties
The specific embodiment
Need to prove, in the situation that do not conflict, embodiment and the feature among the embodiment among the present invention can make up mutually.Describe the present invention in detail below in conjunction with embodiment.
Synthetic loaded down with trivial details in order to solve existing crosslinking agent, expensive, and crosslinking agent is difficult for longer-term storage, the problem of hydrolysis in use easily occurs, the invention provides a kind of crosslinker composition, it comprises that molecular weight is 400～1000 oligomeric polyacid and C2～C6 polyacid, and the weight ratio of oligomeric polyacid and C2～C6 polyacid is 1:1～5.
Crosslinker composition provided by the invention carboxyl functional group in oligomeric polyacid and the polyacid in the high-temperature heating process of cross-linking reaction (is easy to COOH) form and contains the strong multi-anhydride of acid anhydride, thereby be easy to react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to the antigen fibrillation performance that improves fiber.The present invention is 400～1000 oligomeric polyacid and little molecule C2～C6 polyacid by the use molecular weight, so that each raw molecule chain is relatively short in the crosslinking agent, the carboxyl functional group that can participate in reacting (COOH) more, and then can produce more cross-linked structure, to realize improving the effect of resistant fiber Fibrillation Properties.
Simultaneously, the mixing polyacid crosslinking agent stability of the oligomeric polyacid that adopts in the crosslinker composition of the present invention and C2～C6 polyacid is better, not facile hydrolysis, and basis is as chemicals commonly used, and raw material is sufficient, price is low, do not need complicated building-up process, the crosslinking Treatment technique that is used for cellulose fibre is comparatively simple, and crosslinked cost is low, the physical property impact of solution being spun cellulose fibre is less, and can obviously improve the antigen fibrillation performance that solution spins cellulose fibre.
In addition, the content of polyacid can be identical with oligomeric polyacid in crosslinker composition of the present invention, also can be higher than oligomeric polyacid, and this is being useful aspect cost control of crosslinking agent.The weight ratio of oligomeric polyacid and C2～C6 polyacid is 1:1～1:5 in the preferred crosslinker composition, is preferably 1:2～1:3.
Oligomeric polyacid can any molecular weight be 400～1000 oligomeric polyacids in crosslinker composition of the present invention, preferably includes but is not limited to low poly (Polymaleic Acid, PMA), oligomeric acrylic acid or acrylic acid-maleic acid.
Polyacid can be the polyacid that contains at least two carboxyl functional groups in crosslinker composition of the present invention, also can be the polyacid that contains at least two carboxyl functional groups and a hydroxy functional group, or the combination of above-mentioned two kinds of polyacids.Wherein preferred employing contains the polyacid of two carboxyl functional groups and a hydroxy functional group at least, perhaps itself and the combination that contains at least the polyacid of two carboxyl functional groups.
Adopting when containing at least the polyacid of two carboxyl functional groups and a hydroxy functional group, the hydroxy functional group in the polyacid (OH) can with oligomeric polyacid-esterification occurs in COOH, thereby the more oligomeric polyacid mixture of formation-COOH content.This-more oligomeric polyacid mixture of COOH content-form that to contain the strong multi-anhydride of acid anhydride and the cellulosic hydroxyl formed cross-linked structure that reacts more stable between the COOH, can more obviously improve the antigen fibrillation performance that solution spins cellulose fibre.
The C2 that in crosslinker composition of the present invention, uses～C6 polyacid, can be in solution being spun the process that cellulose fibre carries out crosslinking Treatment, the physical property of avoiding solution being spun cellulose fibre causes obvious impact, and then the acquisition physical property is good and the well behaved antigen fibrillation of antigen fibrillation solution spins cellulose fibre.Wherein this polyacid includes but not limited to succinic acid, 1,2, one or more in 3-the third three acid, citric acid, hydroxysuccinic acid and the dyhydrobutanedioic acid.Preferably, this polyacid reaches the citric acid (CA) of three-COOH for containing one-OH.
In a kind of preferred embodiment of the present invention, also comprise flexible linear polymer in this crosslinker composition, flexible linear polymer content and oligomeric polyacid weight ratio are 1:2～10.Being added with of flexible linear polymer is beneficial to softening and spins cellulose fibre by the crosslinked prepared solution of this crosslinker composition in crosslinker composition of the present invention, avoid because of the adhesion amount of crosslinker composition of the present invention too high, the solution that causes spins the dry embrittlement phenomenon of cellulose fibre, reduce operation easier, strengthen the practicality of this crosslinker composition.This flexibility linear polymer can be any cross-linking reaction and solution to be spun any flexible linear polymer that the cellulose fibre physical property has no significant effect, wherein preferably adopting molecular weight is 200～800 flexible linear polymer, more preferred molecular weight is 400～600 flexible linear polymer, particularly preferably adopts end group to contain the polyethylene glycol of hydroxyl as flexible linear polymer.
Also provide in the present invention a kind of antigen fibrillation solution to spin cellulose fibre, it is to spin cellulose fibre by solution to get through above-mentioned crosslinker composition crosslinking Treatment that this antigen fibrillation solution spins cellulose fibre, it has preferably antigen fibrillation performance, thereby has preferably surface flatness, dyeing uniformity and washability.
Also provide in the present invention a kind of solution to spin the crosslinked post-processing approach of cellulose fibre, may further comprise the steps: above-mentioned crosslinker composition is dissolved in the solution, forms cross-linking agent solution, the concentration of this cross-linking agent solution does not have specific (special) requirements.The cross-linking agent solution that to be preferably oligomeric polyacid content be 5～60g/L, the more preferably oligomeric polyacid content cross-linking agent solution that is 20～40g/L; Solution is spun cellulose fibre be immersed in the cross-linking agent solution, obtain blended fiber; Cross-linking reaction is carried out in the blended fiber heating, obtain antigen fibrillation solution and spin cellulose fibre.
This solution provided by the present invention spins the crosslinked post-processing approach of cellulose fibre, by adopting above-mentioned crosslinker composition, simply crosslinker composition and solution is spun cellulose fibre and mixes crosslinked getting final product, and step is simple, but large-scale industrialized production.The method not only is applicable to spin the step of directly carrying out crosslinked post processing in the cellulose fibre preparation process at solution, is fit to also that simultaneously the solution of finishing production stage is spun cellulose fibre and reprocesses.This is the antigen fibrillation better performances that obtainable solution spins cellulose fibre by simple production technology, can improve the quality that solution spins cellulose fibre, and then more meet consumer's requirement.
Spin in the crosslinked post-processing approach of cellulose fibre at solution of the present invention, before cross-linking reaction is carried out in the blended fiber heating, preferably include the step of blended fiber being carried out preheating.Spin the step that increases preheating in the crosslinked post-processing approach of cellulose fibre at this solution, can improve crosslinker composition and solution and spin cellulosic activity in the cellulose fibre, and solution is spun cellulose fibre play dry effect, this process can improve cross-linking reaction efficient.The preferred temperature requirement of this pre-heat treatment is controlled at 70～100 ℃, and the time is 10～60min, and more preferred preheat temperature is 70～80 ℃, and be 30～60min preheating time.
Spin in the crosslinked post-processing approach of cellulose fibre at solution of the present invention, can also add the catalyst that promotes cross-linking reaction in the cross-linking agent solution, the inventory of this crosslinking agent does not have specific (special) requirements.Preferably, the weight ratio of C2 in this catalyst and the crosslinker composition～C6 polyacid is preferably 1～3:5, more preferably 2～3:5.Those skilled in the art have the ability to select suitable catalyst, in the present invention preferred adopt be not limited to inorganic phosphate, comprise one or more the mixture in sodium phosphate, sodium hydrogen phosphate, the inferior sodium phosphate.For example the mixture of inferior sodium phosphate and dibastic sodium phosphate wherein particularly preferably uses separately inferior sodium phosphate (SHP).
Spin the crosslinked post-processing approach of cellulose fibre at solution of the present invention and form in the process of blended fiber, the time of dipping and temperature do not have special requirement, preferably solution are spun cellulose fibre and are immersed in 10～30min in the cross-linking agent solution.In this scope, can in the control time cost, make crosslinker composition be impregnated into solution more fully, equably and spin in the cellulose fibre
Spin in the crosslinked post-processing approach of cellulose fibre at solution of the present invention, acid extraction does not have special requirement, but spin the antigen fibrillation performance of cellulose fibre in order to improve better solution, preferred control heating-up temperature is 160～190 ℃, be preferably 170～180 ℃, be 2～10min heat time heating time.In this acid extraction scope, polyacid is difficult for autohemagglutination occurs in the crosslinker composition raw material, and then can safeguard better the self structure of fiber, improves fiber physical property.
Spin in the crosslinked post-processing approach of cellulose fibre at solution of the present invention, through cross-linking reaction, antigen fibrillation solution spins existing crosslinker composition in the cellulose fibre and does not have special requirement through the fixed amount that cross-linking reaction changes the compound that forms (following general designation chemical reagent), preferred prepared antigen fibrillation solution spins in the cellulose fibre, the fixed amount of chemical reagent is 0.3～3%(weight), being equivalent to the weight that the relative solution of weight that antigen fibrillation solution spins cellulose fibre spins cellulose fibre increases by 0.3～3%.The chemical reagent fixed amount is controlled in this scope, is conducive to guarantee cross-linking effect, improve the antigen fibrillation performance that solution spins cellulose fibre, avoid excessive because of the chemical reagent fixed amount, reduce the possibility that solution spins the cellulose fibre physical property.
Spin in the crosslinked post-processing approach of cellulose fibre at solution of the present invention, it can be the dry state fiber of processing through super-dry that solution spins cellulose fibre, also can be the hygrometric state fiber that undried is processed.Wherein be preferably the hygrometric state fiber.This dry hygrometric state fiber itself possesses swellability, and the reactant liquors such as crosslinking agent, catalyst more easily enter fibrous inside, and the efficient that reacts is higher, and fiber surface swells, and more abundant with the reaction of crosslinking agent, the cross-linked structure of formation is more.If the dry state fiber of having processed through super-dry, at least 15min preferably at room temperature is soaked in water the dry state fiber first before carrying out the crosslinked post processing of the present invention.
In a kind of preferred embodiment of the present invention, provide a kind of antigen fibrillation solution to spin the preparation method of cellulose fibre, it comprises that preparation solution spins the step of cellulose fibre and solution is spun the step that cellulose fibre carries out crosslinked post processing, and this spins the above-mentioned crosslinked post-processing approach of step employing that cellulose fibre carries out crosslinked post processing to solution.
This method not only is applicable to spin on the industrial production line of cellulose fibre at production solution, through coagulating bath shaping after washing, cut-out, carries out this crosslinked post-processing approach again; Also be fit to simultaneously carry out crosslinking Treatment behind the fiber washing under extended state, washing is dried again, all can obtain possessing the Lyocell fiber of antigen fibrillation performance.
To spin cellulose fibre can be that any existing solution spins cellulose fibre on the market to described solution in the present invention, preferably take wood pulp, cotton pulp or bamboo pulp as raw material, take the aqueous solution of N-methylmorpholine-N-oxide (NMMO) as solvent, the solution that makes by the method for doing spray-wet spinning spins cellulose fibre.
Further specify beneficial effect of the present invention below with reference to specific embodiment 1-7.
The test raw material: in following embodiment, it is to adopt following method to be prepared from that solution spins cellulose fibre:
(1) cellulose pulp is dissolved in the NMMO/ aqueous solvent forms cellulose solution;
(2) cellulose solution is extruded by spinnerets, and through the air-gap cooling, formed strand;
(3) with strand by solidification forming in the coagulating bath, and again by water-bath eccysis NMMO, obtain cellulose fibre;
(4) fiber extrusion is removed excessive moisture, the acquisition moisture content is that the solution of 80-120% spins cellulose fibre.
Antigen fibrillation performance test method: the wet friction value, fracture strength and the elongation at break that comprise the antigen fibrillation performance that represents fiber.
The method of testing of wet friction value: experimental provision is for to adhere well to smooth roller surface with wetting cotton, then be to contact with the grinding roller that rotates under the applied load effect of 12g in weight with fibre bundle, roller speed is 12m/min, and drips with per two seconds one speed above fiber.Measure grinding roller and begin to turn to the fibre bundle required time that ruptures fully, be the wet friction value, this value is larger, and the antigen fibrillation performance of fiber is stronger.
The fiber physical property test: with reference to GB GB/T14337-2008, the man-made staple fibres Wella is stretched method for testing performance and is tested.
Embodiment 1
Under the normal temperature be 600 PMA, CA, SHP with molecular weight according to weight ratio be that 2:5:3 is dissolved in and obtains cross-linking agent solution in the distilled water, the content of PMA is that the content of 40g/L, CA is that the content of 100g/L, SHP is 60g/L in this cross-linking agent solution.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, the dipping 10min get blended fiber, with the blended fiber the pre-heat treatment, preheat temperature is controlled to be respectively 70,80,90 ℃, again with blended fiber in 170 ℃ of high-temperature heating 8min, the washing, drying.Gained fiber wet friction value and mechanical property are listed in table 1.
Table 1
By content in the table 1 as can be known, use crosslinker composition provided by the invention that cellulose fibre is carried out crosslinked post processing, antigen fibrillation performance that can the Effective Raise fiber.Particularly in manufacturing process, the antigen fibrillation performance of fiber has obtained obvious lifting after the step of increase the pre-heat treatment.Preheat temperature is higher, and the time is longer, and fiber wet friction value is higher, and antigen fibrillation performance is stronger, but too high preheat temperature and long time caused the decline of fibre strength and elongation, fiber physical property is impacted larger.Preferably preheat temperature is controlled at 70-80 ℃ in the present invention, preheating 10-60min is controlled at 30-60min more preferred preheating time.
Embodiment 2
Under the normal temperature be 600 PMA, CA, SHP with molecular weight according to weight ratio be that 2:5:3 is dissolved in and obtains cross-linking agent solution in the distilled water, the content of PMA is that the content of 40g/L, CA is that the content of 100g/L, SHP is 60g/L in this cross-linking agent solution.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, the dipping 10min, then with fiber at 80 ℃ of lower the pre-heat treatment 60min, more respectively with fiber at 160 ℃, 170 ℃, 180 ℃, 190 ℃ lower high-temperature heating certain hours, the washing, drying.Gained fibre bundle wet friction value and mechanical property are listed in table 2.
Table 2
By content in the table 2 as can be known, in the situation that other conditions are determined, use crosslinker composition provided by the invention cellulose fibre to be carried out the increase of heat time heating time and temperature in the crosslinked post processing, all be conducive to improve the wet friction value of fiber, the raising of temperature is larger to fiber antigen fibrillation performance impact, but too high heating-up temperature and the long decline that has caused fibre strength and elongation heat time heating time, larger on the fiber physical property impact, preferably controlling in the present invention heating-up temperature is 170-180 ℃, and the time is 2-10min.
Comparative Examples 1
Repeat among the embodiment 2 institute in steps, difference is that with cellulose fibre at 150 ℃ of high-temperature heating 10min, the wet friction value of gained fibre bundle is 0.73.This shows, when heating-up temperature is lower than 170 ℃, adopt the application's crosslinker composition still to have the effect that improves the resistant fiber Fibrillation Properties, very little but the resistant fiber Fibrillation Properties that obtains improves.Same, when temperature is higher than 180 ℃, as more than 190 ℃, adopt the application's crosslinker composition also still to have the effect that improves the resistant fiber Fibrillation Properties, but the fiber physical property to prepared fiber has larger adverse effect, therefore preferably controlling in the present invention heating-up temperature is 170-180 ℃, and the time is 2-10min.
Embodiment 3
Under the normal temperature be that 600 oligomeric polyacid, CA and SHP are dissolved in and obtain cross-linking agent solution in the distilled water with molecular weight, the content of oligomeric polyacid is that the content of 5～60g/L, CA is that the content of 100g/L, SHP is 60g/L in the described cross-linking agent solution.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, and dipping 10min obtains blended fiber, then with blended fiber at 80 ℃ of lower the pre-heat treatment 60min, again with fiber in 170 ℃ of high-temperature heating 8min, washing, drying.The fixed amount of chemical reagent is listed in table 3 on gained fiber wet friction value, mechanical property and the fiber.
Table 3
By content in the table 3 as can be known, in the crosslinker composition of the present invention, the content of PMA has a significant effect to the resistant fiber Fibrillation Properties.The content of PMA is higher, and fiber wet friction value is higher, and antigen fibrillation performance is stronger.And several oligomeric polyacids can both play the effect that raising solution spins cellulose fibre antigen fibrillation performance, wherein use PMA more obvious to the antigen fibrillation performance improvement that solution spins cellulose fibre.
Simultaneously, oligomeric polyacid is relevant with the content of C2～C6 polyacid in the fixed amount of chemical reagent and the crosslinker composition of the present invention.Content at PMA is in 5～60g/L scope, and oligomeric polyacid content is more, and the fixed amount of chemical reagent is more.But higher PMA content causes the cross-linking reaction aggravation, makes fiber physical property be subject to obvious impact.
Embodiment 4
Under the normal temperature be that 600 PMA, CA, catalyst obtain cross-linking agent solution according to being dissolved in the distilled water with molecular weight, the content of PMA is that the content of 40g/L, CA is that the content of 100g/L, SHP is as shown in table 4 in the described cross-linking agent solution.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, the dipping 10min obtain blended fiber, then with blended fiber at 80 ℃ of lower the pre-heat treatment 60min, again with it at 180 ℃ of lower high-temperature heating 3～9min, the washing, drying.Wet friction value and the mechanical property of gained fibre bundle are listed in table 4.
Table 4
By content in the table 4 as can be known, in the situation that other conditions are constant, add catalyst, the resistant fiber Fibrillation Properties improves more obvious, and catalyst concn and heat time heating time are obvious on resistant fiber originality voltinism energy and physical property impact, but use inferior sodium phosphate as catalyst, and the impact effect that solution is spun cellulose fibre antigen fibrillation performance is maximum, the concentration of preferred catalyst is 20-60g/l in the present invention, and the weight ratio of catalyst and polyacid is 1～3:5.
Embodiment 5
Add molecular weight under the normal temperature and be 600 PMA, CA and PMA, SHP and obtain cross-linking agent solution in the distilled water according to being dissolved in, the content of PMA is 40g/L in the described cross-linking agent solution, and the ratio of PMA:CA is as shown in table 5, the content of SHP is 60g/L.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, and dipping 10min obtains blended fiber, then with blended fiber at 80 ℃ of lower the pre-heat treatment 60min, again with fiber at 180 ℃ of lower high-temperature heating 7min, washing, drying.The fixed amount of gained fiber wet friction value, mechanical property and chemical reagent is listed in table 5.
Table 5
By content in the table 5 as can be known, in the situation that other condition is constant, PMA and CA amount ratio are 1:2～3 o'clock, and fiber wet friction value improves obviously, and fibre strength descends little, although PMA and CA amount ratio are 1:4～5 o'clock, the fixed amount of chemical reagent is larger on the fiber, and the wet friction value also improves morely, but fiber physical property is a greater impact, fibre strength descends more, so preferred PMA and CA amount ratio are 1:2～3.When the fixed amount of chemical reagent is 3.0% to the maximum, the wet friction value of fiber is also maximum under this condition, so in conjunction with the embodiments 3, as seen after crosslinker composition and solution spun cellulose fibre generation cross-linking reaction among the present invention, the fixed amount scope that antigen fibrillation solution spins chemical reagent in the cellulose fibre was 0.3～3%.
Embodiment 6
Under the normal temperature be 600 PMA, 1 with molecular weight, 2, the polyethylene glycol (PEG) of 3-the third three acid, SHP, different molecular weight is dissolved in the distilled water in proportion, PMA, 1,2, the weight ratio of 3-the third three acid, SHP is 2:6:3, the content of PMA is 20g/L, 1 in the described cross-linking agent solution, the content of 2,3-, the third three acid is that the content of 60g/L, SHP is 30g/L, and molecular weight and the consumption of polyethylene glycol (PEG) are as shown in table 6.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, the dipping 10min,, with fiber at 80 ℃ of the pre-heat treatment 60min, again with fiber in 170 ℃ of high-temperature heating 5min, the washing, drying.Gained fiber wet friction value and mechanical property are listed in table 6.
Table 6
By content in the table 6 as can be known, in the situation that other conditions are constant, increase flexible linear polymer, can play and improve the effect that solution spins cellulose fibre antigen fibrillation performance, and the adding of flexible linear polymer also helps the phenomenon of alleviating owing to the crosslinked dry embrittlement of cellulose fibre that causes, improve the fiber compliance, strengthen the practicality of crosslinker composition.In the present invention, the weight ratio of flexible linear polymer P EG and PMA is 1:2～10, and preferred PEG molecular weight is 400～600.
Embodiment 7
Under the normal temperature PMA of different molecular weight, polyacid, SHP be dissolved in by weight 4:6:3 and obtain cross-linking agent solution in the distilled water, the content of PMA is that the content of 40g/L, polyacid is that the content of 60g/L, SHP is 30g/L in the described cross-linking agent solution.Cellulose fibre is impregnated in the above-mentioned cross-linking agent solution, the dipping 10min obtain blended fiber, with blended fiber at 80 ℃ of the pre-heat treatment 30min, again with it in 170 ℃ of high-temperature heating 7min, the washing, drying.Gained fiber wet friction value and mechanical property are listed in table 7.
Table 7
By content in the table 7 as can be known, in the crosslinker composition, when polyacid is CA solution is spun the antigen fibrillation performance impact of cellulose fibre the most obvious, and the PMA molecular weight is all influential to resistant fiber Fibrillation Properties and physical property, molecular weight is to have better effects at 600～800 o'clock.
As can be seen from the above-described embodiment, crosslinker composition of the present invention in the high-temperature heating process of cross-linking reaction in oligomeric polyacid and the polyacid carboxyl functional group (more easily form COOH) and contain the strong multi-anhydride of acid anhydride, thereby easier and cellulosic hydroxyl reacts, form more cross-linked structure, this cross-linked structure has obvious effect to playing the antigen fibrillation performance that improves fiber.Be 400～1000 oligomeric polyacid and little molecule C2～C6 polyacid by using molecular weight in the present invention, so that each raw molecule chain is relatively short in the crosslinking agent, the carboxyl functional group that can participate in reacting (COOH) more, and then can produce more cross-linked structure, to realize improving the effect of resistant fiber Fibrillation Properties.
The above is the preferred embodiments of the present invention only, 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., all should be included within protection scope of the present invention.
Claims (11)
1. a crosslinker composition is characterized in that, comprises that molecular weight is 400～1000 oligomeric polyacid and C2～C6 polyacid, and the weight ratio of described oligomeric polyacid and described C2～C6 polyacid is 1:1～5.
2. crosslinker composition according to claim 1 is characterized in that, the weight ratio of described oligomeric polyacid and described C2～C6 polyacid is 1:2～3; Preferably, described oligomeric polyacid is low poly, oligomeric acrylic acid or acrylic acid-maleic acid; Preferably, described polyacid is for containing at least the polyacid of two carboxyl functional groups, and/or contain at least the polyacid of two carboxyl functional groups and a hydroxy functional group, preferably, described polyacid is succinic acid, 1, in 2,3-, the third three acid, citric acid, hydroxysuccinic acid and the dyhydrobutanedioic acid one or more.
3. crosslinker composition according to claim 1 and 2, it is characterized in that, described crosslinker composition also comprises flexible linear polymer, the weight ratio of described flexible linear polymer and described oligomeric polyacid is 1:2～10, preferably, described flexible linear polymer is that molecular weight is 200～800 polyethylene glycol.
4. an antigen fibrillation solution spins cellulose fibre, it is characterized in that, spins cellulose fibre each described crosslinker composition crosslinking Treatment and getting in claims 1 to 3 by solution.
5. a solution spins the crosslinked post-processing approach of cellulose fibre, it is characterized in that, may further comprise the steps:
Each described crosslinker composition in the claims 1 to 3 is dissolved in the solution cross-linking agent solution that to form oligomeric polyacid content be 5～60g/L, the cross-linking agent solution that to be preferably oligomeric polyacid content be 20～40g/L;
Described solution is spun cellulose fibre be immersed in the described cross-linking agent solution, obtain blended fiber;
Cross-linking reaction is carried out in described blended fiber heating, obtain antigen fibrillation solution and spin cellulose fibre.
6. crosslinked post-processing approach according to claim 5, it is characterized in that, also comprise the step of described blended fiber being carried out preheating before cross-linking reaction is carried out in described blended fiber heating, the temperature of described preheating step is 70～100 ℃, and the time is 10～60min.
7. according to claim 5 or 6 described crosslinked post-processing approachs, it is characterized in that, also comprise catalyst in the described cross-linking agent solution, C2 in described catalyst and the described crosslinker composition～C6 polyacid weight ratio is 1～3:5, be preferably 2～3:5, preferably, described catalyst is inorganic phosphate, more preferably, described catalyst is one or more the mixture in sodium phosphate, sodium hydrogen phosphate, the inferior sodium phosphate.
8. each described crosslinked post-processing approach in 7 according to claim 5, it is characterized in that, form in the process of described blended fiber, described solution spins cellulose fibre and is immersed in 10～30min in the described cross-linking agent solution, heating-up temperature is 160～190 ℃ in the described cross-linking reaction process, and the time is 2-10min.
9. each described crosslinked post-processing approach in 8 according to claim 5 is characterized in that, the weight that the relatively described solution of weight that described antigen fibrillation solution spins cellulose fibre spins cellulose fibre increases by 0.3～3%.
10. each described crosslinked post-processing approach in 9 according to claim 5 is characterized in that, it is the hygrometric state fiber that undried is processed that described solution spins cellulose fibre.
11. an antigen fibrillation solution spins the preparation method of cellulose fibre, comprise that preparation solution spins the step of cellulose fibre and described solution is spun the step that cellulose fibre carries out crosslinked post processing, it is characterized in that, described solution is spun the step that cellulose fibre carries out crosslinked post processing adopt each described crosslinked post-processing approach in the claim 5 to 10.
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| CN112281483A (en) * | 2019-07-22 | 2021-01-29 | 中国纺织科学研究院有限公司 | Rapid crosslinking method of cellulose fibers and preparation method of anti-fibrillation cellulose fibers |
| CN112695399A (en) * | 2020-12-10 | 2021-04-23 | 中国纺织科学研究院有限公司 | Preparation method of high wet modulus viscose fiber and high wet modulus viscose fiber |
| US11155963B2 (en) | 2014-11-21 | 2021-10-26 | Rohm And Haas Company | Binder compositions for making crosslinked cellulose fiber |
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