CN103306136B - Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods - Google Patents
Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods Download PDFInfo
- Publication number
- CN103306136B CN103306136B CN201310261096.2A CN201310261096A CN103306136B CN 103306136 B CN103306136 B CN 103306136B CN 201310261096 A CN201310261096 A CN 201310261096A CN 103306136 B CN103306136 B CN 103306136B
- Authority
- CN
- China
- Prior art keywords
- solution
- cellulose fibre
- polyacid
- cross
- crosslinker composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of crosslinker composition, antigen fibrillation solution spins cellulose fibre and preparation method thereof.Wherein crosslinker composition comprises oligomeric polyacid and the C2 ~ C6 polyacid that molecular weight is 400 ~ 1000, and the weight ratio of oligomeric polyacid and C2 ~ C6 polyacid is 1:1 ~ 5.In the high-temperature heating process of cross-linking reaction, more easily formed between carboxyl functional group (-COOH) containing the strong multi-anhydride of acid anhydride in oligomeric polyacid included by crosslinker composition of the present invention and polyacid, thus be easy to react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to the anti-Fibrillation Properties improving fiber.
Description
Technical field
The present invention relates to 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, then is extruded in a kind of spinning coagulation bath by solution, now cellulose solidifies regeneration wherein, forms fiber after stretching.Said method is called " solution spins ", and gained fiber is that solution spins cellulose fibre.What known solution spun cellulose fibre is represented as viscose, but huge environmental pollution and energy consumption problem hinder it to expand the scale of production further.
In order to address this problem, being proposed in US Patent No. 4246221 and Chinese patent CN94190487.3 adopts novel dissolvent to prepare the method for cellulose fibre, by cellulose dissolution in the aqueous solution of organic solvent tertiary amino oxides, and solution obtains the technical scheme of fiber thus.Fiber prepared by this method is named as Lyocell fiber, and Chinese Lay match by name youngster, is commonly called as sky silk.
Lyocell fiber is mainly raw material with wood pulps, is solvent preparation with the mixture of tertiary amino oxides (NMMO) and water.The chemical constitution of Lyocell fiber is substantially identical with viscose, except the characteristic with natural fabric as hygroscopicity, gas permeability, comfortableness, glossiness, except dyeability and biodegradable, can also have the advantage of the high strength 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 21 century green fiber.
But, when Lyocell fiber is subject to mechanical stress effect under hygrometric state, easily there is fibrillation phenomenon in various degree.The phenomenon that so-called fibrillation phenomenon refers to " when fibre structure longitudinally ruptures, tiny fibril is just separated from fiber upper part ".The produced fiber that makes of this fibrillation phenomenon has crinosity shape appearance, affects the outward appearance of Lyocell fiber goods, dyeing uniformity and washability etc.
At present, the approach that solution Lyocell fiber is easy to fibrillation mainly carries out crosslinked post processing realization to fiber, and the industrialization that profit has realized the Lyocell fiber with anti-Fibrillation Properties in this way is produced.Wherein, invention number has three acrylamidos for patent reports of CN95192563.6, is preferably the crosslinking agent of 1,3,5-tri-acrylamido hexahydro-1,3,5-triazines, spins cellulose fibre react with moist state solution, reduces its fibrillation tendency.Invention number for CN98801507.2 patent reports the textile auxiliary with two reactive groups, be preferably 2,4-dichloro-6-hydroxy triazine sodium salts crosslinking agent reduce solution spin cellulose fibre fibrillation tendency method.But the crosslinking agent used in these techniques synthesis is loaded down with trivial details, expensive, and crosslinking agent not easily longer-term storage, be in use easily hydrolyzed, affect the efficiency 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, to solve the problem that solution spins cellulose fibre easily fibrillable.
To achieve these goals, according to an aspect of the present invention, provide a kind of crosslinker composition, comprise oligomeric polyacid and C2 ~ C6 polyacid that molecular weight is 400 ~ 1000, the weight ratio of oligomeric polyacid and C2 ~ C6 polyacid is 1:1 ~ 5.
Further, in above-mentioned crosslinker composition, the weight ratio of oligomeric polyacid and C2 ~ C6 polyacid is 1:2 ~ 3.
Further, in above-mentioned crosslinker composition, oligomeric polyacid is oligomaleic acid, oligomeric acrylic acid or acid-co-maleic acid.
Further, in above-mentioned crosslinker composition, polyacid is the polyacid at least containing two carboxyl functional groups, and/or at least contains the polyacid of two carboxyl functional groups and a hydroxy functional group,
Further, in above-mentioned crosslinker composition, polyacid is one or more in succinic acid, 1,2,3-the third three acid, citric acid, hydroxysuccinic acid and dyhydrobutanedioic acid.
Further, in above-mentioned crosslinker composition, crosslinker composition also comprises flexible linear polymer, and flexible linear polymerization is 1:2 ~ 10 with the weight ratio of oligomeric polyacid, the choosing of flexible linear polymer to be molecular weight be 200 ~ 800 polyethylene glycol.
Another aspect of the present invention, provides a kind of antigen fibrillation solution and spins cellulose fibre, spin cellulose fibre obtain through above-mentioned crosslinker composition crosslinking Treatment by solution.
Another aspect of the present invention, provide a kind of solution to spin cellulose fibre and be cross-linked post-processing approach, comprise the following steps: above-mentioned crosslinker composition is dissolved in solution, forming oligomeric polyacid content is the cross-linking agent solution of 5 ~ 60g/L, and being preferably oligomeric polyacid content is the cross-linking agent solution of 20 ~ 40g/L; Solution being spun cellulose fibre is immersed in cross-linking agent solution, obtains blended fiber; Cross-linking reaction is carried out in blended fiber heating, obtains 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 blended fiber heating, and the temperature of preheating step is 70 ~ 100 DEG C, and the time is 10 ~ 60min.
Further, in above-mentioned crosslinked post-processing approach, cross-linking agent solution also comprises catalyst, and in catalyst and crosslinker composition, C2 ~ C6 polyacid weight ratio is 1 ~ 3:5, is preferably 2 ~ 3:5.
Further, in above-mentioned crosslinked post-processing approach, catalyst is preferably inorganic phosphate, and catalyst is more preferably one or more the mixture in sodium phosphate, sodium hydrogen phosphate, inferior sodium phosphate.
Further, above-mentioned crosslinked post-processing approach is formed in the process of blended fiber, and solution spins cellulose fibre and is immersed in 10-30min in cross-linking agent solution, and in cross-linking reaction process, heating-up temperature is 160 ~ 190 DEG C, and the time is 2-10min.
Further, the antigen fibrillation solution that above-mentioned crosslinked post-processing approach is formed spins in 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 undried process.
Another aspect of the invention, provide the preparation method that a kind of antigen fibrillation solution spins cellulose fibre, comprise and prepare solution and spin the step of cellulose fibre and the step that cellulose fibre carries out crosslinked post processing is spun to solution, the step that cellulose fibre carries out crosslinked post processing is spun to solution and adopts above-mentioned crosslinked post-processing approach.
In the high-temperature heating process of cross-linking reaction, be easy between carboxyl functional group (-COOH) in oligomeric polyacid in crosslinker composition provided by the invention and polyacid be formed containing the strong multi-anhydride of acid anhydride, thus be easy to react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to the anti-Fibrillation Properties improving fiber.Be oligomeric polyacid and Small molecular C2 ~ C6 polyacid of 400 ~ 1000 in the present invention by use molecular weight, make each raw molecule chain in crosslinking agent relatively short, the more of the carboxyl functional group (-COOH) reacted can be participated in, and then more cross-linked structure can be produced, to realize the effect improving resistant fiber Fibrillation Properties
Detailed description of the invention
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
Loaded down with trivial details in order to solve the synthesis of existing crosslinking agent, expensive, and crosslinking agent not easily longer-term storage, in use easily there is the problem of hydrolysis, the invention provides a kind of crosslinker composition, it comprises oligomeric polyacid and C2 ~ C6 polyacid that molecular weight is 400 ~ 1000, and the weight ratio of oligomeric polyacid and C2 ~ C6 polyacid is 1:1 ~ 5.
Crosslinker composition provided by the invention is easy between carboxyl functional group (-COOH) in oligomeric polyacid and polyacid be formed containing the strong multi-anhydride of acid anhydride in the high-temperature heating process of cross-linking reaction, thus be easy to react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to the anti-Fibrillation Properties improving fiber.The present invention is oligomeric polyacid and Small molecular C2 ~ C6 polyacid of 400 ~ 1000 by use molecular weight, make each raw molecule chain in crosslinking agent relatively short, the more of the carboxyl functional group (-COOH) reacted can be participated in, and then more cross-linked structure can be produced, to realize the effect improving resistant fiber Fibrillation Properties.
Simultaneously, the mixing polyacid crosslinking agents stability of the oligomeric polyacid adopted in crosslinker composition of the present invention and C2 ~ C6 polyacid is better, not facile hydrolysis, and this is as conventional chemicals, raw material is sufficient, price is low, do not need complicated building-up process, the crosslinking Treatment technique for cellulose fibre is comparatively simple, and crosslinked cost is low, physical property impact solution being spun to cellulose fibre is less, and obviously can improve the anti-Fibrillation Properties that solution spins cellulose fibre.
In addition, in crosslinker composition of the present invention, the content of polyacid can be identical with oligomeric polyacid, also can higher than oligomeric polyacid, and this is useful in the cost control of crosslinking agent.In preferred crosslinker composition, the weight ratio of oligomeric polyacid and C2 ~ C6 polyacid is 1:1 ~ 1:5, is preferably 1:2 ~ 1:3.
In crosslinker composition of the present invention, oligomeric polyacid can any molecular weight be 400 ~ 1000 oligomeric polyacids, preferably includes but is not limited to oligomaleic acid (PolymaleicAcid, PMA), oligomeric acrylic acid or acid-co-maleic acid.
In crosslinker composition of the present invention, polyacid can be the polyacid at least containing two carboxyl functional groups, also can be the polyacid at least containing two carboxyl functional groups and a hydroxy functional group, or the combination of above-mentioned two kinds of polyacids.Wherein preferably adopt the polyacid at least containing two carboxyl functional groups and a hydroxy functional group, or itself and the combination of polyacid at least containing two carboxyl functional groups.
When adopting the polyacid at least containing two carboxyl functional groups and a hydroxy functional group, can there is esterification with the-COOH of oligomeric polyacid in the hydroxy functional group (-OH) in polyacid, thus form the more oligomeric polyacid mixture of-COOH content.Form the multi-anhydride of being good for containing acid anhydride and cellulosic hydroxyl the formed cross-linked structure that reacts between-the COOH of the more oligomeric polyacid mixture of this-COOH content more stable, more obviously can improve the anti-Fibrillation Properties that solution spins cellulose fibre.
C2 ~ C6 the polyacid used in crosslinker composition of the present invention, can carry out in the process of crosslinking Treatment spinning solution cellulose fibre, avoid physical property solution being spun to cellulose fibre to cause obvious impact, and then it is good and the antigen fibrillation solution that anti-Fibrillation Properties is good spins cellulose fibre to obtain physical property.Wherein this polyacid includes but not limited to one or more in succinic acid, 1,2,3-the third three acid, citric acid, hydroxysuccinic acid and dyhydrobutanedioic acid.Preferably, this polyacid is for containing-an OH, and the citric acid of three-COOH (CA).
In the 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.In crosslinker composition of the present invention, being added with of flexible linear polymer is beneficial to softening and is cross-linked prepared solution by this crosslinker composition and spins cellulose fibre, avoid the adhesion amount because of crosslinker composition of the present invention too high, the solution caused spins the dry embrittlement phenomenon of cellulose fibre, reduce operation easier, strengthen the practicality of this crosslinker composition.This flexible linear polymer can be anyly spin to cross-linking reaction and solution any flexible linear polymer that cellulose fibre physical property has no significant effect, wherein preferably employing molecular weight is the flexible linear polymer of 200 ~ 800, more preferred molecular weight is the flexible linear polymer of 400 ~ 600, particularly preferably adopts end group to contain the polyethylene glycol of hydroxyl as flexible linear polymer.
Additionally provide a kind of antigen fibrillation solution in the present invention and spin cellulose fibre, it is spin cellulose fibre by solution to obtain through above-mentioned crosslinker composition crosslinking Treatment that this antigen fibrillation solution spins cellulose fibre, it has good anti-Fibrillation Properties, thus there is good surface flatness, dyeing uniformity and washability.
Additionally provide a kind of solution in the present invention to spin cellulose fibre and be cross-linked post-processing approach, comprise the following steps: be dissolved in solution by above-mentioned crosslinker composition, form cross-linking agent solution, the concentration of this cross-linking agent solution does not have particular/special requirement.Being preferably oligomeric polyacid content is the cross-linking agent solution of 5 ~ 60g/L, and being more preferably oligomeric polyacid content is the cross-linking agent solution of 20 ~ 40g/L; Solution being spun cellulose fibre is immersed in cross-linking agent solution, obtains blended fiber; Cross-linking reaction is carried out in blended fiber heating, obtains antigen fibrillation solution and spin cellulose fibre.
This solution provided by the present invention spins cellulose fibre and is cross-linked post-processing approach, and by adopting above-mentioned crosslinker composition, simply crosslinker composition and solution are spun cellulose fibre and mix crosslinked, step is simple, can large-scale industrialized production.The method is not only applicable to spin the step of directly carrying out crosslinked post processing in cellulose fibre preparation process at solution, is also applicable to spinning cellulose fibre to the solution completing production stage simultaneously and reprocesses.This to spin the anti-Fibrillation Properties of cellulose fibre by simple production technology and obtainable solution better, can improve the quality that solution spins cellulose fibre, and then more meet consumer's requirement.
Spinning cellulose fibre at solution of the present invention is cross-linked in post-processing approach, before cross-linking reaction is carried out in blended fiber heating, preferably include the step of blended fiber being carried out preheating.Spin cellulose fibre at this solution and be cross-linked in post-processing approach the step increasing preheating, crosslinker composition can be improved and solution spins cellulosic activity in cellulose fibre, and the effect that cellulose fibre plays drying is spun to solution, this process can improve cross-linking reaction efficiency.The preferable temperature of this pre-heat treatment requires to control at 70 ~ 100 DEG C, and the time is 10 ~ 60min, and more preferred preheat temperature is 70 ~ 80 DEG C, and preheating time is 30 ~ 60min.
Spinning cellulose fibre at solution of the present invention is cross-linked in post-processing approach, and can also add the catalyst promoting cross-linking reaction in cross-linking agent solution, the inventory of this crosslinking agent does not have particular/special requirement.Preferably, in this catalyst and crosslinker composition, the weight ratio of C2 ~ C6 polyacid is preferably 1 ~ 3:5, is more preferably 2 ~ 3:5.Those skilled in the art have the ability to select suitable catalyst, and what preferably adopt in the present invention is not limited to inorganic phosphate, comprises one or more the mixture in sodium phosphate, sodium hydrogen phosphate, inferior sodium phosphate.The mixture of such as inferior sodium phosphate and dibastic sodium phosphate, is wherein particularly preferably used alone inferior sodium phosphate (SHP).
Spinning cellulose fibre at solution of the present invention is cross-linked in the process of post-processing approach formation blended fiber, and the time of dipping and temperature special requirement, preferably solution are spun cellulose fibre and are immersed in 10 ~ 30min in cross-linking agent solution.Within the scope of this, while control time cost, crosslinker composition can be made to be impregnated into solution more fully, equably and to spin in cellulose fibre
Spinning cellulose fibre at solution of the present invention is cross-linked in post-processing approach, the requirement that acid extraction is not special, but the anti-Fibrillation Properties of cellulose fibre is spun in order to improve solution better, preferred control heating-up temperature is 160 ~ 190 DEG C, be preferably 170 ~ 180 DEG C, heat time heating time is 2 ~ 10min.Within the scope of this acid extraction, in crosslinker combination raw material not easily there is autohemagglutination in polyacid, and then can safeguard the self structure of fiber better, improves fiber physical property.
Spinning cellulose fibre at solution of the present invention is cross-linked in post-processing approach, through cross-linking reaction, antigen fibrillation solution to spin in cellulose fibre existing crosslinker composition and special requirement through the fixed amount that cross-linking reaction change institute forms compound (being referred to as chemical reagent below), preferably prepared antigen fibrillation solution spins in cellulose fibre, the fixed amount of chemical reagent is 0.3 ~ 3%(weight), being equivalent to the weight that weight relative solution that antigen fibrillation solution spins cellulose fibre spins cellulose fibre increases by 0.3 ~ 3%.Chemical reagent fixed amount is controlled within the scope of this, is conducive to ensureing cross-linking effect, improve the anti-Fibrillation Properties that solution spins cellulose fibre, avoid because chemical reagent fixed amount is excessive, reduce the possibility that solution spins cellulose fibre physical property.
Spinning cellulose fibre at solution of the present invention is cross-linked in post-processing approach, and it can be through the dry state fiber of super-dry process that solution spins cellulose fibre, also can be the hygrometric state fiber of undried process.Wherein be preferably hygrometric state fiber.This not dry hygrometric state fiber itself possesses swellability, and the reactant liquor such as crosslinking agent, catalyst more easily enters fibrous inside, and the efficiency reacted is higher, and fiber surface swells, and more abundant with the reaction of crosslinking agent, the cross-linked structure of formation is more.If through the dry state fiber of super-dry process, be preferably first at room temperature soaked in water dry state fiber at least 15min before carrying out the present invention and being cross-linked post processing.
In the preferred embodiment of the present invention, provide the preparation method that a kind of antigen fibrillation solution spins cellulose fibre, it comprises prepares solution and spins the step of cellulose fibre and spin to solution the step that cellulose fibre carries out crosslinked post processing, and this spins to solution the step that cellulose fibre carries out crosslinked post processing and adopts above-mentioned crosslinked post-processing approach.
This method is not only applicable to spin on the industrial production line of cellulose fibre at production solution, through coagulating bath shaping after washing, cut-out, then carries out this crosslinked post-processing approach; In a stretched state carry out crosslinking Treatment after being also applicable to fiber washing simultaneously, then wash oven dry, all can obtain the Lyocell fiber possessing anti-Fibrillation Properties.
It can be that the existing solution of any one spins cellulose fibre on the market that solution described in the present invention spins cellulose fibre, preferably with wood pulp, cotton pulp or bamboo pulp for raw material, with the aqueous solution of N-methylmorpholine-N-oxide (NMMO) for solvent, the solution obtained by the method for dry spray-wet spinning spins cellulose fibre.
Beneficial effect of the present invention is further illustrated below with reference to specific embodiment 1-7.
Test raw material: in the following example, it is adopt to be prepared from the following method that solution spins cellulose fibre:
(1) cellulose pulp is dissolved in NMMO/ aqueous solvent forms cellulose solution;
(2) cellulose solution is extruded by spinnerets, and through air-gap cooling, form strand;
(3) strand is passed through solidification forming in coagulating bath, and again by water-bath eccysis NMMO, obtain cellulose fibre;
(4) fiber extrusion is removed excessive moisture, acquisition moisture content is that the solution of 80-120% spins cellulose fibre.
The method of testing of anti-Fibrillation Properties: comprise the wet friction value of the anti-Fibrillation Properties representing fiber, fracture strength and elongation at break.
The method of testing of wet friction value: experimental provision is that wetting cotton is adhere well to smooth roller surface, then with the contact roll rotated under applied load effect fibre bundle being 12g in weight, roller speed is 12m/min, and drips with the every two seconds speed of one above fiber.Measure grinding roller to start to turn to fibre bundle and to rupture completely required time, be wet friction value, this value is larger, and the anti-Fibrillation Properties of fiber is stronger.
Fiber physical property is tested: with reference to GB GB/T14337-2008, man-made staple fibres Wella is stretched method for testing performance and tested.
Embodiment 1
Under normal temperature by molecular weight be 600 PMA, CA, SHP be that 2:5:3 is dissolved in distilled water and obtains cross-linking agent solution according to weight ratio, in this cross-linking agent solution, the content of the content of PMA to be the content of 40g/L, CA be 100g/L, SHP is 60g/L.Be impregnated into by cellulose fibre in above-mentioned cross-linking agent solution, dipping 10min obtains blended fiber, and by blended fiber the pre-heat treatment, preheat temperature is controlled as 70,80,90 DEG C, then by blended fiber in 170 DEG C of high-temperature heating 8min, washing, dry.Gained fiber wet friction value and mechanical property list in table 1.
Table 1
From content in table 1, use crosslinker composition provided by the invention to carry out crosslinked post processing to cellulose fibre, effectively can improve the anti-Fibrillation Properties of fiber.Particularly in manufacturing process, after increasing the step of the pre-heat treatment, the anti-Fibrillation Properties of fiber obtains obvious lifting.Preheat temperature is higher, and the time is longer, and fiber wet friction value is higher, and anti-Fibrillation Properties is stronger, but too high preheat temperature and longer time cause the decline of fibre strength and elongation, impact larger to fiber physical property.Preferably in the present invention control at 70-80 DEG C by preheat temperature, preheating 10-60min, more preferred preheating time controls at 30-60min.
Embodiment 2
Under normal temperature by molecular weight be 600 PMA, CA, SHP be that 2:5:3 is dissolved in distilled water and obtains cross-linking agent solution according to weight ratio, in this cross-linking agent solution, the content of the content of PMA to be the content of 40g/L, CA be 100g/L, SHP is 60g/L.Cellulose fibre is impregnated in above-mentioned cross-linking agent solution, dipping 10min, then by fiber the pre-heat treatment 60min at 80 DEG C, more respectively by fiber high-temperature heating certain hour at 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, washing, dry.Gained fibre bundle wet friction value and mechanical property list in table 2.
Table 2
From content in table 2, when other conditions are determined, crosslinker composition provided by the invention is used to carry out the increase of heat time heating time and temperature in crosslinked post processing to cellulose fibre, all be conducive to the wet friction value improving fiber, the raising of temperature is larger on the impact of resistant fiber Fibrillation Properties, but too high heating-up temperature and cause the decline of fibre strength and elongation longer heat time heating time, larger on fiber physical property impact, preferably controlling heating-up temperature is in the present invention 170-180 DEG C, and the time is 2-10min.
Comparative example 1
In steps, difference is by cellulose fibre at 150 DEG C of high-temperature heating 10min, and the wet friction value of gained fibre bundle is 0.73 in institute in repetition embodiment 2.As can be seen here, when heating-up temperature is lower than 170 DEG C, adopt the application's crosslinker composition still to have the effect improving resistant fiber Fibrillation Properties, but the resistant fiber Fibrillation Properties obtained improve very little.Same, when temperature is higher than 180 DEG C, as more than 190 DEG C, the application's crosslinker composition is adopted also still to have the effect improving resistant fiber Fibrillation Properties, but there is larger adverse effect to the fiber physical property of prepared fiber, therefore preferably controlling heating-up temperature is in the present invention 170-180 DEG C, and the time is 2-10min.
Embodiment 3
Under normal temperature by molecular weight be 600 oligomeric polyacid, CA and SHP be dissolved in distilled water and obtain cross-linking agent solution, in described cross-linking agent solution, the content of oligomeric polyacid is 5 ~ 60g/L, the content of CA be the content of 100g/L, SHP is 60g/L.Be impregnated into by cellulose fibre in above-mentioned cross-linking agent solution, dipping 10min obtains blended fiber, then by blended fiber the pre-heat treatment 60min at 80 DEG C, then by fiber in 170 DEG C of high-temperature heating 8min, and washing, dry.On gained fiber wet friction value, mechanical property and fiber, the fixed amount of chemical reagent lists in table 3.
Table 3
From content in table 3, in crosslinker composition of the present invention, the content of PMA has a significant effect to resistant fiber Fibrillation Properties.The content of PMA is higher, and fiber wet friction value is higher, and anti-Fibrillation Properties is stronger.And several oligomeric polyacid can play the effect that raising solution spins the anti-Fibrillation Properties of cellulose fibre, PMA is wherein used to improve more obvious to the anti-Fibrillation Properties that solution spins cellulose fibre.
Meanwhile, the fixed amount of chemical reagent is relevant with the content of C2 ~ C6 polyacid with oligomeric polyacid in crosslinker composition of the present invention.Be that oligomeric polyacid content is more, and the fixed amount of chemical reagent is more within the scope of 5 ~ 60g/L at the content of PMA.But higher PMA content causes cross-linking reaction to be aggravated, fiber physical property is made to be subject to obvious impact.
Embodiment 4
Under normal temperature by molecular weight be 600 PMA, CA, catalyst obtain cross-linking agent solution according to being dissolved in distilled water, in described cross-linking agent solution, the content of the content of PMA to be the content of 40g/L, CA be 100g/L, SHP is as shown in table 4.Be impregnated into by cellulose fibre in above-mentioned cross-linking agent solution, dipping 10min obtains blended fiber, then by blended fiber the pre-heat treatment 60min at 80 DEG C, then by its high-temperature heating 3 ~ 9min at 180 DEG C, and washing, dry.The wet friction value of gained fibre bundle and mechanical property list in table 4.
Table 4
From content in table 4, when other conditions are constant, add catalyst, resistant fiber Fibrillation Properties improves more obvious, and catalyst concn and heat time heating time affect obviously on resistant fiber originality voltinism energy and physical property, but use inferior sodium phosphate as catalyst, impact effect solution being spun to the anti-Fibrillation Properties of cellulose fibre 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 under normal temperature molecular weight be 600 PMA, CA and PMA, SHP obtain cross-linking agent solution according to being dissolved in distilled water, in described cross-linking agent solution, the content of PMA is the ratio content as shown in table 5, SHP of 40g/L, PMA:CA is 60g/L.Be impregnated into by cellulose fibre in above-mentioned cross-linking agent solution, dipping 10min obtains blended fiber, then by blended fiber the pre-heat treatment 60min at 80 DEG C, then by fiber high-temperature heating 7min at 180 DEG C, and washing, dry.The fixed amount of gained fiber wet friction value, mechanical property and chemical reagent lists in table 5.
Table 5
From content in table 5, when other condition is constant, when PMA and CA amount ratio is 1:2 ~ 3, fiber wet friction value improves obviously, and fibre strength declines little, when although PMA and CA amount ratio is 1:4 ~ 5, on fiber, the fixed amount of chemical reagent is comparatively large, and wet friction value also improves more, but fiber physical property is a greater impact, fibre strength declines more, so preferably PMA and CA amount ratio is 1:2 ~ 3.When the fixed amount of chemical reagent is 3.0% to the maximum, under this condition, the wet friction value of fiber is also maximum, so in conjunction with the embodiments 3, after in visible the present invention, crosslinker composition and solution spin cellulose fibre generation cross-linking reaction, the fixed amount scope that antigen fibrillation solution spins chemical reagent in cellulose fibre is 0.3 ~ 3%.
Embodiment 6
Be the PMA, 1 of 600 by molecular weight under normal temperature, 2, the polyethylene glycol (PEG) of 3-the third three acid, SHP, different molecular weight is dissolved in distilled water in proportion, the weight ratio of PMA, 1,2,3-the third three acid, SHP is 2:6:3, in described cross-linking agent solution, the content of PMA is 20g/L, 1, the content of 2,3-the third three acid is 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 above-mentioned cross-linking agent solution, dipping 10min, by fiber at 80 DEG C of the pre-heat treatment 60min, then by fiber in 170 DEG C of high-temperature heating 5min, washing, dry.Gained fiber wet friction value and mechanical property list in table 6.
Table 6
From content in table 6, when other conditions are constant, increase flexible linear polymer, can play and improve the effect that solution spins the anti-Fibrillation Properties of cellulose fibre, and the adding to also help and alleviate due to the crosslinked and phenomenon of the dry embrittlement of cellulose fibre that is that cause of flexible linear polymer, improve 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 preferably PEG molecular weight is 400 ~ 600.
Embodiment 7
The PMA of different molecular weight, polyacid, SHP are dissolved in distilled water obtain cross-linking agent solution by weight 4:6:3 under normal temperature, in described cross-linking agent solution, the content of PMA is 40g/L, the content of polyacid be the content of 60g/L, SHP is 30g/L.Be impregnated into by cellulose fibre in above-mentioned cross-linking agent solution, dipping 10min obtains blended fiber, by blended fiber at 80 DEG C of the pre-heat treatment 30min, then by it in 170 DEG C of high-temperature heating 7min, and washing, dry.Gained fiber wet friction value and mechanical property list in table 7.
Table 7
From content in table 7, in crosslinker composition, when polyacid is CA, the anti-Fibrillation Properties impact of cellulose fibre is spun the most obviously to solution, and PMA molecular weight there is impact to resistant fiber Fibrillation Properties and physical property, has better effects when molecular weight is 600 ~ 800.
As can be seen from the above-described embodiment, crosslinker composition of the present invention is more easily formed between carboxyl functional group (-COOH) containing the strong multi-anhydride of acid anhydride in oligomeric polyacid and polyacid in the high-temperature heating process of cross-linking reaction, thus more easily react with cellulosic hydroxyl, form more cross-linked structure, this cross-linked structure has obvious effect to playing the anti-Fibrillation Properties improving fiber.Be oligomeric polyacid and Small molecular C2 ~ C6 polyacid of 400 ~ 1000 in the present invention by use molecular weight, make each raw molecule chain in crosslinking agent relatively short, the more of the carboxyl functional group (-COOH) reacted can be participated in, and then more cross-linked structure can be produced, to realize the effect improving resistant fiber Fibrillation Properties.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, 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 amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a crosslinker composition, it is characterized in that, comprise oligomeric polyacid and C2 ~ C6 polyacid and flexible linear polymer that molecular weight is 400 ~ 1000, the weight ratio of described oligomeric polyacid and described C2 ~ C6 polyacid is 1:2 ~ 3, described polyacid is 1,2,3-the third three acid and/or hydroxysuccinic acid, the weight ratio of described flexible linear polymer and described oligomeric polyacid is 1:2 ~ 10.
2. crosslinker composition according to claim 1, is characterized in that, described oligomeric polyacid is oligomaleic acid, oligomeric acrylic acid or acid-co-maleic acid.
3. crosslinker composition according to claim 1, is characterized in that, described flexible linear polymer to be molecular weight be 200 ~ 800 polyethylene glycol.
4. antigen fibrillation solution spins a cellulose fibre, it is characterized in that, spins cellulose fibre obtain through the crosslinker composition crosslinking Treatment according to any one of claims 1 to 3 by solution.
5. solution spins cellulose fibre and is cross-linked a post-processing approach, it is characterized in that, comprises the following steps:
Be dissolved in solution by the crosslinker composition according to any one of claims 1 to 3, forming oligomeric polyacid content is the cross-linking agent solution of 5 ~ 60g/L;
Described solution is spun cellulose fibre be immersed in described cross-linking agent solution, obtain blended fiber;
Cross-linking reaction is carried out in described blended fiber heating, obtains antigen fibrillation solution and spin cellulose fibre.
6. the cellulose fibre that spins according to claim 5 is cross-linked post-processing approach, it is characterized in that, described oligomeric polyacid content is the cross-linking agent solution of 20 ~ 40g/L.
7. crosslinked post-processing approach according to claim 6, it is characterized in that, before cross-linking reaction is carried out in described blended fiber heating, also comprise the step of described blended fiber being carried out preheating, the temperature of described preheating step is 70 ~ 100 DEG C, and the time is 10 ~ 60min.
8. the crosslinked post-processing approach according to any one of claim 5 to 7, is characterized in that, also comprises catalyst in described cross-linking agent solution, and in described catalyst and described crosslinker composition, C2 ~ C6 polyacid weight ratio is 1 ~ 3:5.
9. crosslinked post-processing approach according to claim 8, in described catalyst and described crosslinker composition, C2 ~ C6 polyacid weight ratio is 2 ~ 3:5.
10. crosslinked post-processing approach according to claim 8, described catalyst is inorganic phosphate.
11. crosslinked post-processing approachs according to claim 10, described catalyst is one or more the mixture in sodium phosphate, sodium hydrogen phosphate, inferior sodium phosphate.
12. crosslinked post-processing approachs according to any one of claim 5 to 7, it is characterized in that, formed in the process of described blended fiber, described solution spins cellulose fibre and is immersed in 10 ~ 30min in described cross-linking agent solution, in described cross-linking reaction process, heating-up temperature is 160 ~ 190 DEG C, and the time is 2-10min.
13. crosslinked post-processing approachs according to any one of claim 5 to 7, 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%.
14. crosslinked post-processing approachs according to any one of claim 5 to 7, it is characterized in that, described solution spins the hygrometric state fiber that cellulose fibre is undried process.
15. 1 kinds of antigen fibrillation solution spin the preparation method of cellulose fibre, comprise and prepare solution and spin the step of cellulose fibre and the step that cellulose fibre carries out crosslinked post processing is spun to described solution, it is characterized in that, step that cellulose fibre carries out crosslinked post processing is spun to described solution and adopts crosslinked post-processing approach according to any one of claim 5 to 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310261096.2A CN103306136B (en) | 2013-06-26 | 2013-06-26 | Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310261096.2A CN103306136B (en) | 2013-06-26 | 2013-06-26 | Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103306136A CN103306136A (en) | 2013-09-18 |
| CN103306136B true CN103306136B (en) | 2016-03-30 |
Family
ID=49131826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310261096.2A Active CN103306136B (en) | 2013-06-26 | 2013-06-26 | Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103306136B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11155963B2 (en) | 2014-11-21 | 2021-10-26 | Rohm And Haas Company | Binder compositions for making crosslinked cellulose fiber |
| CN109402774B (en) * | 2018-11-02 | 2021-10-15 | 恒天海龙（潍坊）新材料有限责任公司 | Anti-fibrillation cellulose fiber and preparation method thereof |
| 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 |
| CN111893749B (en) * | 2020-08-14 | 2022-12-06 | 亚太森博（山东）浆纸有限公司 | Crosslinking agent and method for fibrillation-resistant treatment of lyocell fiber |
| CN112695399B (en) * | 2020-12-10 | 2022-09-23 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705475A (en) * | 1992-12-21 | 1998-01-06 | Ppg Industries, Inc. | Non-formaldehyde durable press finishing for cellulosic textiles with phosphonoalkylpolycarboxylic |
| JP3247386B2 (en) * | 1995-06-15 | 2002-01-15 | ザ、プロクター、エンド、ギャンブル、カンパニー | Method for producing individualized polycarboxylic acid crosslinked fibers with reduced odor, improved whiteness |
| JP2007527472A (en) * | 2003-10-02 | 2007-09-27 | レイヨニーア ティーアールエス ホールディングス インコーポレイテッド | Cross-linked cellulose fiber and method for producing the same |
| CN103132330A (en) * | 2011-11-25 | 2013-06-05 | 香港纺织及成衣研发中心有限公司 | Textile having shape memory interpenetrating polymer network |
-
2013
- 2013-06-26 CN CN201310261096.2A patent/CN103306136B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705475A (en) * | 1992-12-21 | 1998-01-06 | Ppg Industries, Inc. | Non-formaldehyde durable press finishing for cellulosic textiles with phosphonoalkylpolycarboxylic |
| JP3247386B2 (en) * | 1995-06-15 | 2002-01-15 | ザ、プロクター、エンド、ギャンブル、カンパニー | Method for producing individualized polycarboxylic acid crosslinked fibers with reduced odor, improved whiteness |
| JP2007527472A (en) * | 2003-10-02 | 2007-09-27 | レイヨニーア ティーアールエス ホールディングス インコーポレイテッド | Cross-linked cellulose fiber and method for producing the same |
| CN103132330A (en) * | 2011-11-25 | 2013-06-05 | 香港纺织及成衣研发中心有限公司 | Textile having shape memory interpenetrating polymer network |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103306136A (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103306136B (en) | Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods | |
| CN101195933B (en) | Method for producing Lyocell fibre for tire cord | |
| CN109023621B (en) | Flame-retardant antibacterial wool blended yarn | |
| CN101525786B (en) | Colored profiled polyester multifilament fiber with stable dimension and preparation method thereof | |
| CN107574507B (en) | Three-dimensional crimped elastic fiber and preparation method thereof | |
| CN103710782A (en) | High-moisture-absorption easy-dying cotton-imitating polyester short fiber and preparation method thereof | |
| TWI623659B (en) | Polyester fiber manufacturing method, polyester fiber, yarn, and fabric | |
| US11124900B2 (en) | Method for preparing flame-retardant cellulosic fibers | |
| CN109537088B (en) | Method for manufacturing different-shrinkage polyester low-stretch yarns | |
| WO2016127833A1 (en) | Acetic nitrile fibre and preparation method therefor | |
| CN101240468A (en) | Polyacrylonitrile-chitin composite fiber and its production process | |
| CN110172754A (en) | A kind of preparation method of antigen fibrillated fibers element fiber | |
| JP7053956B2 (en) | Wool-like polyester filament and its manufacturing method | |
| CN101255618A (en) | Method for preparing easily-soluble polyester fiber | |
| CN109402774B (en) | Anti-fibrillation cellulose fiber and preparation method thereof | |
| CN101942705A (en) | Preparation method of regenerated bacterial cellulose fiber | |
| CN107354531A (en) | A kind of modified PBT fiber spinning process | |
| CN104005225B (en) | A kind of method reducing lyocell fiber cellulose fiber fibrillation tendency | |
| CN107475794A (en) | A kind of fire-retardant koplon of silicon nitrogen system and preparation method thereof | |
| CN105755613B (en) | A kind of sun washs compound sea-island fibre and preparation method thereof | |
| CN101240466B (en) | Solvent method cellulose cotton and bamboo composite fiber and preparation method thereof | |
| CN113802232A (en) | Bamboo fiber and cotton fiber blended yarn and manufacturing process thereof | |
| CN110172741A (en) | A kind of preparation method of functional fiber element fiber | |
| CN111826763B (en) | Yarn or fabric with effect of graying and preparation method and application thereof | |
| CN110468460A (en) | A kind of preparation method and regeneration acrylic fibers product of regeneration acrylic fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |