CN100393935C - High water-absorption fiber and its preparing method - Google Patents
High water-absorption fiber and its preparing method Download PDFInfo
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- CN100393935C CN100393935C CNB200510015297XA CN200510015297A CN100393935C CN 100393935 C CN100393935 C CN 100393935C CN B200510015297X A CNB200510015297X A CN B200510015297XA CN 200510015297 A CN200510015297 A CN 200510015297A CN 100393935 C CN100393935 C CN 100393935C
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Abstract
The present invention relates to a high water-absorption fiber and a making method thereof. The high water-absorption fiber is composed of 75 to 85% of polymer monomer and 15 to 25% of polymer blend; a potential crosslinking agent accounts for 0.1 to 15% of the total mass of the polymer monomer, and an initiating agent accounts for 0.1 to 1.0% of the total mass of the polymer monomer, wherein the polymer monomer is one or a plurality of acroleic acid, sodium acrylate and acrylamide; the polymer blend is polyvinyl alcohol; the potential crosslinking agent is one or a plurality of hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and N-hydroxymethyl acrylamide; the initiating agent is a persulfate oxidizing system or an oxidizing and deoxidizing system which is composed of persulfate and sulfite. According to the mass ratio formulation of the fiber, the making method of the fiber is completed by the following steps that (1) a polymer blend solution is directly prepared by a solution one-step polymerization method; (2) the product, namely the polymer blend solution, is directly used as a spinning solution for vacuum degassing; (3) the fiber is spun by solution dry spinning; (4) the high water-absorption fiber can be obtained after the obtained fiber is treated by hot crosslinking.
Description
Technical field
The present invention relates to a kind of functional fiber material and manufacture method thereof, be specially the high water-absorption fiber and the manufacture method technology thereof of a kind of dry spinning-back cross-linking type polyacrylic, international Patent classificating number intends being Int.Cl
7.D01D 5/34.
Background technology
Water-soluble acrylic polymers has a lot of characteristics, as thickening property, dispersion suspension, flocculability, caking property and film forming etc., be widely used in the industry such as coating, papermaking, weaving, oil recovery, mining, metallurgy, food, medicine, cosmetics, civil engineering and water treatment.Have extremely strong hydrophily through appropriately crosslinked acrylic polymer, become the important branch of high hydroscopic resin.High water-absorption fiber is another new functional macromolecule material that grows up after high hydroscopic resin, and its water absorbent rate is bigger tens times than conventional fibre, even higher.High water-absorption fiber has the physical-mechanical property similar to conventional fibre, can carry out pure spinning or blending and non-woven processing etc.Compare with high hydroscopic resin, high water-absorption fiber has that specific area is big, absorption speed is fast, plastic property and back good processability, and suction back gel do not flow, and can keep fibre morphology, advantages such as dehydration back is recycling have been widened the Application Areas of high-absorbent material greatly.
At present external preparation is synthetic to be that the industrial technology route of high water-absorption fiber mainly contains three kinds: the one, acrylic fiber is carried out chemical treatment, make the acrylic fiber surface-CN is hydrolyzed to-COOH or-COONa, and give its cross-linked structure, " Lanseal-F " fiber of producing as Japanese Exlan company, meet fibrocortex generation gelation behind the water, suction and water insoluble [A.Wada (day). high water-absorption fiber, fabrics for industrial use, 1993,11 (1): 34-37]; The 2nd, be spinning solution with the isobutene-copolymer-maleic anhydride aqueous solution that contains latent crosslinker, after dry spinning and heat cross-linking processing, make high water-absorption fiber, as " Fibersorb " fiber of No. 5026784 documents announcements of U.S. Pat P; The 3rd, be spinning solution with the aqueous solution of acrylic acid series copolymer, after dry spinning shaping and heat cross-linking processing, make high water-absorption fiber, as Britain Technical Absorbents company development and with " Bell Oasis " fiber that Japanese clock spins company's co-production is to be that raw material carries out aqueous solution polymerization with the vinyl unsaturated monomer, behind the neutralization part carboxyl, [the work of field, natural pond length that is shaped, makes after crosslinked through dry spinning, Chen Longyun translates, high suction water absorbent fiber BELL OASIS, external textile technology, 2002,4:7～9].The suction area of high water-absorption fiber is big, and the rate of water absorption height is of many uses, promise well, and many companies and scientific research institution participate in its research and development one after another, and pertinent literature has been reported many new methods.For example, as disclosing the blend aqueous solution that adopts polyacrylic acid and polyvinyl alcohol in the Japanese patent laid-open 4-73208 document, split through curing, heat cross-linking, film that to make hydroscopicity be 51% film-fibre; Y.J.Kim etc. are that coagulating agent carries out wet spinning with glutaraldehyde as cross linker, aqueous hydrochloric acid solution, sodium alginate is spun into high water-absorption fiber [Y.J.Kim, K.J.Yoon, S.W.Ko. the preparation of glutaraldehyde cross-linking sodium alginate high water-absorption fiber and performance study .Journal of Applied Polymer Science thereof, 2000,78:1797-1804]; Lim etc. add high water-absorbent starch graft copolymers (particle diameter is less than 100 μ m) in the Lyocell spinning solution, adopt dry-wet spinning, spin out novel Lyocell fiber, its water absorbing properties can improve 7～8 times of [K.Y.Lim than fibrillation, K.J.Yoon, B.C.Kim. cellulose/hydrolyzed polyacrylonitrile graft starch blend NMMO solution spinning height absorbs lyocell fiber .EuropeanPolymer Journal, 2003,39 (11): 2115-2120].
Domestic development to high water-absorption fiber is later relatively, the Sun Yushan of China Textile Academy etc. are comonomer with acrylic acid, sodium acrylate, acrylamide, hydroxy propyl methacrylate, potassium peroxydisulfate is an initator, adopt water solution polymerization process to obtain aqueous copolymers solution, behind polyvinyl alcohol blending, through wet spinning shaping, heat cross-linking, obtain high water-absorption fiber [Sun Yushan, Xu Jigang, Luo Qiang. the research of superabsorbent fiber polymerization technique and polymerization stoste spinnability. synthetic fiber, 2000,29 (6): 23-25; Sun Yushan, Xu Jigang, Luo Qiang. the super research that absorbs water into fine copolymerized blend. Tianjin University of Technology's journal, 2001,20 (9): 18-20]; Chinese patent CN1407147A document discloses the super suction of acrylic acid series copolymer and polyvinyl alcohol blending fibre-forming polymer and has extruded continuously through double screw extruder and spin sheath-core type composite high-water uptake fiber.
But the preparation process more complicated in the said method easily loses fibre morphology after the suction of gained high water-absorption fiber becomes gel, and the physical-mechanical property of forfeiture fiber is difficult to be effective as fibrous material and uses, and it is applied be subjected to very big restriction.
Summary of the invention
At the deficiencies in the prior art, technical problem to be solved by this invention is to design a kind of high water-absorption fiber and manufacture method thereof.This high water-absorption fiber is the high water-absorption fiber of the back cross-linking type polyacrylic of a kind of dry spinning preparation, and it not only has good water imbibition, and suction have under long-lasting, the high temperature can guarantor's type, have the better physical mechanical performance.High water-absorption fiber manufacture method of the present invention, adopted polymerization single polymerization monomer fed batch, sectional temperature-controlled one-step polymerization method to prepare spinning solution, can obtain high water-absorption fiber of the present invention through the solution dry spinning shaping, process is simple, do not need special equipment, constant product quality is suitable for the commercial scale Application and Development.
The technical scheme that the present invention solves described high water-absorption fiber technical problem is, designs a kind of high water-absorption fiber, and its mass ratio prescription is:
Polymer monomer 75～85%;
Polymer blend 15～25%;
Latent crosslinker accounts for 0.1～15% of polymer monomer gross mass;
Initator accounts for 0.1～1.0% of polymer monomer gross mass;
Wherein, polymer monomer is one or more of acrylic acid, sodium acrylate and acrylamide; Polymer blend is a polyvinyl alcohol; Latent crosslinker is one or more in hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methylacrylate and the N hydroxymethyl acrylamide; Initator is the persulfate oxidation system, perhaps is the oxidation-reduction system that persulfate and sulphite constitute.
The technical scheme that the present invention solves described high water-absorption fiber manufacture method technical problem is, design a kind of manufacture method of high water-absorption fiber, mass ratio prescription according to high water-absorption fiber of the present invention, finish by following step: 1. adopt the directly described polymer monomer of preparation of solution one-step polymerization method, polymer blend, the polymer blend solution of latent crosslinker and initator, when described preparation product polymer solution, after described latent crosslinker and polymer monomer mix, to together join in the polymer blend polyvinyl alcohol water solution, under nitrogen protection, fully stir, and the aqueous phase solution polymerization is carried out in intensification; Polymerization temperature is 55～85 ℃, and polymerization time is 6～8h, and the mass concentration that reaction finishes the afterproduct polymer solution is controlled at 17～25%; During described polymerization technique, adopt enamel polymerization still, circulation water bath with thermostatic control heating, and adopt the fed batch technology progressively drip comonomer cold burden and initator cold burden and the chain of polymerization cause and two strict control of stage of chain growth temperature at 60～65 ℃, after the automatic hastening phenomenon disappearance in the polymerization process, be warmed up to the polymerization process of 80～90 ℃ sectional temperature-controlled technology to system; 2. with described product polymer solution directly as spinning solution, vacuum defoamation 1-3h; 3. adopt the solution dry spinning spinning fibre; 4. the gained fiber is carried out heat cross-linking and handle, the temperature that heat cross-linking is handled is 120～180 ℃, and the processing time is 3～30min, promptly can be made into described high water-absorption fiber after the processing.
The unrighted acid that the present invention is monomer with the acrylic compounds, contain active reactive group is that the oxidation-reduction system that latent crosslinker, polymer blend, water-soluble persulfate oxidation system or persulfate and sulphite constitute is an initator, the fibre-forming polymer spinning solution is made in the aqueous phase solution polymerization, after deaeration, adopt solution dry spinning, crosslinked or heat cross-linking is handled after suitable again, promptly can be made into the high water-absorption fiber of back of the present invention cross-linking type polyacrylic.Compared with prior art, high water-absorption fiber of the present invention not only has good water imbibition, and water absorption rate can reach 400gg-1, and suction has under long-lasting, the high temperature and can keep prototype, and has the better physical mechanical performance.The characteristics of manufacture method of the present invention are to adopt polymerization single polymerization monomer fed batch, sectional temperature-controlled one-step polymerization method to prepare spinning solution, through solution dry spinning be shaped and after after the crosslinking Treatment, can obtain high water-absorption fiber of the present invention, process is simple, do not need special installation, constant product quality is convenient to commercial scale and is developed and apply.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment:
A kind of high water-absorption fiber of the present invention's design, its mass ratio prescription is:
Polymer monomer 75-85%;
Polymer blend 15-25%;
Latent crosslinker accounts for the 0.1-10% of polymer monomer gross mass;
Initator accounts for 0.1～1.0% of polymer monomer gross mass;
Wherein, polymer monomer is one or more of acrylic acid, sodium acrylate and acrylamide; Polymer blend is a polyvinyl alcohol; Latent crosslinker is one or more in hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methylacrylate and the N hydroxymethyl acrylamide; Initator can be the oxidation-reduction system that persulfate oxidation system or persulfate and sulphite constitute.
In the mass ratio prescription of high water-absorption fiber of the present invention, the preferred N hydroxymethyl acrylamide of described latent crosslinker, it accounts for the ratio preferred 10% of copolymerized polymer monomer gross mass; The preferred azodiisobutyronitrile of described initator, it accounts for the ratio preferred 0.5% of copolymerized polymer monomer gross mass.
The manufacture method of high water-absorption fiber of the present invention, it is mass ratio prescription according to high water-absorption fiber of the present invention, finish by following step: 1. adopt the directly polymer blend solution of the described polymer monomer of preparation, polymer blend, latent crosslinker and initator of solution one-step polymerization method, polymerization temperature is 55～85 ℃, polymerization time is 6～8h, and the mass concentration that reaction finishes the afterproduct polymer solution is controlled at 17～25%; 2. with described product polymer solution directly as spinning solution, vacuum defoamation 1-3h; 3. adopt the solution dry spinning spinning fibre; 4. the gained fiber is carried out heat cross-linking and handle, the temperature that heat cross-linking is handled is 120～180 ℃, and the processing time is 3～30min, promptly can be made into described high water-absorption fiber after the processing.Embodiment is a kind of high water-absorption fiber of back cross-linking type polyacrylic of dry spinning preparation.
In the manufacture method of high water-absorption fiber of the present invention; when described preparation product polymer solution; after described latent crosslinker and polymer monomer mix; to together join in the polymer blend polyvinyl alcohol water solution; under nitrogen protection; fully stir, and the aqueous phase solution polymerization is carried out in intensification.This design can make latent crosslinker with active reactive group be combined in on the fine polyacrylic acid macromolecular chain by the two bonds of himself in polymerization process, becomes the part of fibre-forming polymer, helps the stable of its structure.The ratio of described latent crosslinker should be no more than 10% of polymer monomer gross mass.
The purpose that adds polymer blend in the manufacture method of the present invention is to improve the spinnability of fibre-forming polymer solution dry spinning technology.But its additional proportion should be no more than 25% of polymer monomer gross mass.
In the manufacture method of the present invention, when described acrylic monomer aqueous phase solution polymerization, be easy to generate seriously gathering of heat of polymerization, can bring following problem thus:
1. the implode phenomenon appears easily.This is because monomer polymerization when entering automatic acceleration mode, in the polymerization system the instantaneous increase of viscosity very big, the heat of polymerization that is produced seriously gathers and is caused;
2. the copolymerized blend unstable properties of each batch polymerization gained;
3. the polymer mean molecule quantity in the spinning solution is on the low side, and molecular weight distribution is wider.This may be because monomer to stainless corrosion, produces the small amounts of iron ion, and its inhibition makes the mean molecule quantity of polymer reduce.
For addressing the above problem, manufacture method of the present invention has been done research and has been improved: aspect production equipment, replace the stainless steel polymeric kettle with enamel polymerization still, to reduce the influence of iron ion to radical polymerization; Replace electrical heating with circulation water bath with thermostatic control heating, to improve the heat transfer system of polymeric kettle; Fed batch technology and sectional temperature-controlled technology aspect polymerization technique, have been adopted.So-called fed batch technology progressively drips the polymerization process of comonomer cold burden and initator cold burden when being meant polymerization, to slow down seriously gathering of heat of polymerization; So-called sectional temperature-controlled technology is meant in the chain initiation of polymerization and two stage strictnesses of chain growth controls temperature at 60～65 ℃, after disappearing, the automatic hastening phenomenon in the polymerization process begins to be warmed up to 80～90 ℃ polymerization process to system, to improve the mean molecule quantity and the monomer conversion of product.The low-temperature zone polymerization combines with the dropping cold burden and makes the accumulation phenomena of heat of polymerization reduce significantly, and helps improving the monomer conversion of polymerization system in the high temperature section polymerization.
In the manufacture method of high water-absorption fiber of the present invention, the heat cross-linking treatment process process of described fiber is carried out in nitrogen protection or vacuum protection.Design can be avoided side reaction such as fiber generation thermal degradation in the heat cross-linking process and influence the mechanical property and the water absorbing properties of fiber like this.
In the manufacture method of high water-absorption fiber of the present invention, when its further feature was described solution dry spinning, selecting diameter for use was that 0.4m, length are the dry spinning path of 9m.This mainly is to consider in the manufacture method of described high water-absorption fiber, and the spin solvent of described high water-absorption fiber is a water, and its gasification latent heat is very high, obtains intensive drying for making the strand of extruding, and decision is increased to 9 meters with dry method path length.The employing diameter is that 0.4m, length are the dry spinning path of 9m, and this is that a kind of of embodiment selects for use, and the embodiment that does not mean that manufacture method of the present invention cannot carry out other and selects for use.After dry method path length is increased to 9 meters, long because of the path, temperature is higher, and the strand intensity of just having extruded is very low, general reverse-flowly gives air-dry dry mode effect undesirable, manufacture method of the present invention has adopted the mode of time exhausting to carry out drying, promptly is similar to following current and carries out drying for the mode of wind.
The concrete parameter of the described solution dry spinning technology of manufacture method of the present invention is as follows:
Spinning solution concentration 20-35%
Spinning temperature 70-90 ℃
Spinning pressure 0.4-0.8MPa
80-100 ℃ of pipeline temperature
Measuring pump rotating speed 15-35rpm
Spin manifold temperature 80-100 ℃
Spinnerets Φ (0.15-0.3) * (12-36) hole
Temperature 120-220 ℃ in I district, path
Temperature 150-220 ℃ in II district, path
Temperature 150-220 ℃ in III district, path
Temperature 100-220 ℃ in IV district, path
Winding speed 60-100m/min,
Can make as-spun fibre, again with as-spun fibre at 130-160 ℃ of following heat cross-linking 10-20min, promptly make the high water-absorption fiber of polyacrylic of the present invention.
To the test shows of prepared high water-absorption fiber, it is respectively 100-420gg-1 and 40-60gg-1 to the water absorption rate of distilled water with to the water absorption rate of 0.9 sodium-chloride water solution.The method of testing of described water absorption rate to distilled water (or absorption salt ratio) is: certain mass is tested fiber place distilled water (or 0.9% sodium-chloride water solution) to soak 5min, take out, room temperature is dripped behind the 10min, calculates described water absorption rate or absorption salt ratio according to the mass change of sample before and after the suction.
Provide specific embodiments of the invention below:
Embodiment 1
Acrylic acid, acrylamide, NaOH, polyvinyl alcohol, distilled water are added in the reactor by 48/12/16/15/225 mass ratio, with the potassium peroxide is initator (accounting for polymer monomer gross mass 0.5%), with the acrylic acid hydroxy propyl ester is latent crosslinker (accounting for polymer monomer gross mass 1%), mix the back and react 7h down in 60 ℃, obtain product polymer quality concentration and be 25% fibre-forming polymer solution, vacuum defoamation 2h, adopt following technological parameter dry spinning to make as-spun fibre:
Spinning shaft length 9m
Spinning shaft diameter 0.4m
85 ℃ of spinning temperatures
Spinning pressure 0.6MPa
80 ℃ of pipeline temperature
Measuring pump rotating speed 30rpm
80 ℃ of spin manifold temperatures
Spinnerets Φ 0.18mm * 36 holes
180 ℃ of I district, path temperature
210 ℃ of II district, path temperature
190 ℃ of III district, path temperature
120 ℃ of IV district, path temperature
Winding speed 80m/min,
Can make as-spun fibre,, promptly can be made into the high water-absorption fiber of polyacrylic of the present invention again with as-spun fibre heating, the crosslinked 9min of nitrogen protection under 140 ℃.
Test shows, the suction distilled water rate of gained high water-absorption fiber is 416gg
-1, be 50gg to the water absorption rate of 0.9% sodium-chloride water solution
-1
Embodiment 2
Acrylic acid, acrylamide, NaOH, polyvinyl alcohol, distilled water are added in the reactor by 48/12/16/15/266 mass ratio, with the potassium peroxide is initator (accounting for polymer monomer gross mass 0.8%), with N '-n-methylolacrylamide is latent crosslinker (accounting for polymer monomer gross mass 0.5%), mix the back and react 6h down in 70 ℃, obtain product polymer quality concentration and be 22% fibre-forming polymer solution, vacuum defoamation 3h, the dry spinning condition is equal to embodiment 1, makes as-spun fibre; Again with as-spun fibre at 130 ℃ of heating, the crosslinked 15min of nitrogen protection, promptly can be made into the high water-absorption fiber of polyacrylic of the present invention.
Test shows, the water absorption rate of the distilled water of gained high water-absorption fiber are 378gg
-1, be 45gg to the water absorption rate of 0.9% sodium-chloride water solution
-1
Embodiment 3
Fibre-forming polymer is formed, polymerizing condition is equal to embodiment 1, and the dry-spinning process parameter is:
Spinning shaft length 9m
Spinning shaft diameter 0.4m
Spinning solution concentration 20%
90 ℃ of spinning temperatures
Spinning pressure 0.4MPa
80 ℃ of pipeline temperature
Measuring pump rotating speed 15rpm
80 ℃ of spin manifold temperatures
Spinnerets Φ (0.3) * (12) hole
120 ℃ of I district, path temperature
190 ℃ of II district, path temperature
150 ℃ of III district, path temperature
100 ℃ of IV district, path temperature
Winding speed 60m/min,
Can make as-spun fibre, with as-spun fibre heating, the crosslinked 20min of vacuum protection under 130 ℃, promptly can be made into high water-absorption fiber of the present invention again.
To the test shows of prepared high water-absorption fiber, it is respectively 100 (gg-1) and 40 (gg-1) to the water absorption rate of distilled water with to 0.9 sodium-chloride water solution.
Embodiment 4
Press embodiment 1 method, after hydroxypropyl acrylate content is, makes as-spun fibre, make high water-absorption fiber at 140 ℃ of heat cross-linking 9min, 12min, 15min, 18min and 21min respectively at 1% o'clock.
Its dry-spinning process parameter is:
Spinning solution concentration 35%
90 ℃ of spinning temperatures
Spinning pressure 0.8MPa
100 ℃ of pipeline temperature
Measuring pump rotating speed 35rpm
100 ℃ of spin manifold temperatures
Spinnerets Φ (0.15) * (24) hole
220 ℃ of I district, path temperature
220 ℃ of II district, path temperature
220 ℃ of path III temperature
220 ℃ of IV district, path temperature
Winding speed 100m/min,
To the test shows of prepared high water-absorption fiber, its water absorption rate to distilled water is respectively 416,235,120,112 and 73 (gg-1).
Embodiment 5
Press embodiment 1 method, after hydroxypropyl acrylate content is, makes as-spun fibre, make high water-absorption fiber at 1% o'clock respectively at 130 ℃, 140 ℃ and 150 ℃ of heating, the crosslinked 15min of nitrogen protection.
Test shows, the high water-absorption fiber of making is respectively 402,120 and 58 (gg to the water absorption rate of distilled water
-1).
Embodiment 6
Press embodiment 1 method, the mass ratio of acrylic acid/NaOH is respectively 1/0,18/5,3/1,18/7,9/4 and 9/5 o'clock, make as-spun fibre after, make high water-absorption fiber through 140 ℃ of heat cross-linking 9min again.Test shows, the high water-absorption fiber of making is respectively 56,270,416,350,320 and 78 (gg to the water absorption rate of distilled water
-1).
Embodiment 7
Press embodiment 1 method, mass ratio at acrylic acid/NaOH is 3/1, the mass ratio of acrylic acid is respectively 50/50,60/40,70/30,80/20 and at 90/10 o'clock, make as-spun fibre after, make high water-absorption fiber through 140 ℃ of heat cross-linking 9min.
Test shows, the high water-absorption fiber of making is respectively 152,178,263,416 and 403 (gg to the water absorption rate of distilled water
-1); Water absorption rate to 0.9% sodium-chloride water solution is respectively 55,53,46,50 and 28 (gg
-1).
Embodiment 8
Press embodiment 1 method, mass ratio at acrylic acid/NaOH is 3/1, and the mass ratio of acrylic acid is 80/20, and the mass ratio of monomer and polyvinyl alcohol is respectively 85/15,80/20 and at 75/25 o'clock, after making as-spun fibre, make high water-absorption fiber through 140 ℃ of heat cross-linking 9min again.
Test shows, the high water-absorption fiber of making is respectively 422,416 and 220 (gg to the water absorption rate of distilled water
-1).
Embodiment 9
Press embodiment 1 method, mass ratio at acrylic acid/NaOH is 3/1, the mass ratio of acrylic acid is 80/20, the mass ratio of monomer and polyvinyl alcohol is 80/20, the as-spun fibre of latent crosslinker hydroxypropyl acrylate 1%, and crosslinking process is 140 ℃ of crosslinked 9min, being dipped in reaches capacity in the distilled water absorb after, taking-up is with fiber drying, then be dipped in once more and survey its water absorption rate in the distilled water, 3 times so repeatedly, investigate water-absorption fiber and use its changes of properties of back repeatedly.
Check the test shows of long-acting performance, the high water-absorption fiber of making is respectively 416,385 and 357 (gg to 3 water absorption rates of distilled water
-1), illustrate that high water-absorption fiber of the present invention can use repeatedly, has long-lasting in practical operation.
Embodiment 10
1g is pressed three kinds of different high water-absorption fibers of the embodiment 8 prepared polyvinyl alcohol contents of prescription, put into the distilled water 20min that temperature is respectively 25 ℃, 80 ℃, 90 ℃ and 100 ℃, investigate the heat-resistant stability of fiber.The check heat-resistant stability can test shows, the time that the high water-absorption fiber of making reaches embodiment 8 described water absorption rates is respectively 15,3,2 and 3min, and can keep original shape of fiber and basic physical mechanical index.
Claims (4)
1. the preparation method of a high water-absorption fiber, this method be according to the mass ratio prescription of following high water-absorption fiber, and finish by following step: described prescription is:
Polymer monomer 75～85%;
Polymer blend 15～25%;
Latent crosslinker accounts for 0.1～15% of polymer monomer gross mass;
Initator accounts for 0.1～1.0% of polymer monomer gross mass;
Wherein, polymer monomer is one or more of acrylic acid, sodium acrylate and acrylamide; Polymer blend is a polyvinyl alcohol; Latent crosslinker is one or more in hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methylacrylate and the N hydroxymethyl acrylamide; Initator is the persulfate oxidation system, perhaps is the oxidation-reduction system that persulfate and sulphite constitute;
Described step is: 1. adopt the directly polymer blend solution of the described polymer monomer of preparation, polymer blend, latent crosslinker and initator of solution one-step polymerization method, when described preparation product polymer solution, after described latent crosslinker and polymer monomer mix, to together join in the polymer blend polyvinyl alcohol water solution, under nitrogen protection, fully stir, and the aqueous phase solution polymerization is carried out in intensification; Polymerization temperature is 55～85 ℃, and polymerization time is 6～8h, and the mass concentration that reaction finishes the afterproduct polymer solution is controlled at 17～25%; During described polymerization technique, adopt enamel polymerization still, circulation water bath with thermostatic control heating, and adopt the fed batch technology progressively drip comonomer cold burden and initator cold burden and the chain of polymerization cause and two strict control of stage of chain growth temperature at 60～65 ℃, after the automatic hastening phenomenon disappearance in the polymerization process, be warmed up to the polymerization process of 80～90 ℃ sectional temperature-controlled technology to system; 2. with described product polymer solution directly as spinning solution, vacuum defoamation 1-3h; 3. adopt the solution dry spinning spinning fibre; 4. the gained fiber is carried out heat cross-linking and handle, the temperature that heat cross-linking is handled is 120～180 ℃, and the processing time is 3～30min, promptly can be made into described high water-absorption fiber after the processing.
2. according to the preparation method of the described high water-absorption fiber of claim 1, it is characterized in that described latent crosslinker is a N hydroxymethyl acrylamide, it accounts for 10% of polymer monomer gross mass; Described initator is an azodiisobutyronitrile, and it accounts for 0.5% of polymer monomer gross mass.
3. according to the preparation method of the described high water-absorption fiber of claim 1, it is characterized in that the technological parameter of described solution dry spinning is:
Spinning solution concentration 20-35%
Spinning temperature 70-90 ℃
Spinning pressure 0.4-0.8MPa
80-100 ℃ of pipeline temperature
Measuring pump rotating speed 15-35rpm
Spin manifold temperature 80-100
Spinnerets Ф (0.15-0.3) * (12-36) hole
Temperature 120-220 ℃ in I district, path
II district, path temperature 150-220
III district, path temperature 150-220
Temperature 100-220 ℃ in IV district, path
Winding speed 60-100m/min,
Can make as-spun fibre, again with as-spun fibre at the 130-160 ℃ of crosslinked 10-20min of following heating, nitrogen or vacuum protection, promptly can be made into described high water-absorption fiber.
4. according to the preparation method of the described high water-absorption fiber of claim 3, when it is characterized in that described solution dry spinning, selecting diameter for use is that 0.4m, length are the dry spinning path of 9m, and adopts the mode drying of exhausting down.
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| CN1407147A (en) * | 2001-09-03 | 2003-04-02 | 中国纺织科学研究院 | Manufacture of water super-absorbing fiber and fiber thereby |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1407147A (en) * | 2001-09-03 | 2003-04-02 | 中国纺织科学研究院 | Manufacture of water super-absorbing fiber and fiber thereby |
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| 超吸水成纤共聚共混物和研究. 孙玉山等.天津工业大学学报，第20卷第1期. 2001 |
| 超吸水成纤共聚共混物和研究. 孙玉山等.天津工业大学学报，第20卷第1期. 2001 * |
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