CN109023583A - A kind of preparation method of Sodium Polyacrylate water-absorption fiber - Google Patents
A kind of preparation method of Sodium Polyacrylate water-absorption fiber Download PDFInfo
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- CN109023583A CN109023583A CN201810671141.4A CN201810671141A CN109023583A CN 109023583 A CN109023583 A CN 109023583A CN 201810671141 A CN201810671141 A CN 201810671141A CN 109023583 A CN109023583 A CN 109023583A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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Abstract
The present invention relates to synthesis of polymer material fields, disclose a kind of preparation method of Sodium Polyacrylate water-absorption fiber, step are as follows: A) organic modification vermiculite power preparation: by lactose and dodecyl benzyl dimethyl ammonium chloride be added in water heat react, product is cleaned after vacuum distillation, dries and modified lactose is made；Vermiculite is calcined and is milled；It is formulated as suspension, is heated, modified lactose is added, stirs insulation reaction, be then centrifuged for, filter, dry；B it) neutralizes: acrylic acid and acrylamide is added in water, then neutralized with sodium hydroxide until pH is 5-5.5；C) it polymerize: first adds organise PERFORMANCE OF MODIFIED VERMICULITE and bacteria cellulose, then add triallylammonium chloride and initiator, reacts, obtain viscous liquid；D Sodium Polyacrylate fiber is made in) wet spinning；The present invention is compounded with organic modification vermiculite power in Sodium Polyacrylate fiber, can effectively promote the intensity and resistance to ag(e)ing of high microsteping.
Description
Technical field
The present invention relates to synthesis of polymer material field more particularly to a kind of preparation sides of Sodium Polyacrylate water-absorption fiber
Method.
Background technique
Sodium Polyacrylate is a kind of hydrophilic high molecular material, and solid product is that white (or light yellow) blocky or powder,
Liquid form product is colourless (or faint yellow) thick liquid.It is dissolved in the media such as cold water, warm water, glycerol, propylene glycol.
According to the component size of Sodium Polyacrylate, can be applied in different fields, for molecular weight in 1000-
Low molecular weight sodium polyacrylate in 5000 ranges, mainly as dispersing agent, for molecular weight within the scope of 1W-100W in
Equimolecular quantity Sodium Polyacrylate, mainly as thickener, for molecular weight 100W or more high molecular weight sodium polyacrylate,
It is practically insoluble in water, can only be swollen in water, mainly as flocculant and water-absorbent material,
Patent CN201610448522.7 discloses a kind of preparation method of water-absorbing resin high molecular weight sodium polyacrylate,
Include the following steps: that (1) prepares aqueous sodium acrylate solution；(2) it emulsifies；(3) polymerization reaction；(4) it purifies.The invention provides one
The preparation method of kind water-absorbing resin high molecular weight sodium polyacrylate, the outer moderate molecular weight distribution of resulting polyacrylic resin,
The energy-absorbing that absorbs water is excellent.
Although the Sodium Polyacrylate water imbibition of super high molecular weight is extremely strong, when it is as water-absorbent material, there is also one
A little insufficient: the intensity of such as Sodium Polyacrylate itself is not ideal enough, and dislikes when being chronically at high temperature, intense light irradiation, high saliferous etc.
When under bad environment, strand is easy to happen fracture, and molecular weight reduces, causes its intensity further to decline, finally influence product
The effect of.It is therefore desirable to develop the Sodium Polyacrylate water-absorbent material that a intensity is high, resistance to ag(e)ing is good.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation methods of Sodium Polyacrylate water-absorption fiber.This
Invention is compounded with organic modification vermiculite power when preparing Sodium Polyacrylate water-absorption fiber, can effectively promote high water-absorption fiber
Intensity and resistance to ag(e)ing.
The specific technical proposal of the invention is: a kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A) the preparation of organic modification vermiculite power: by 8-12 parts of lactose and 8-12 parts of dodecyl benzyl dimethyl ammonium chlorides
It is added in 90-110 parts of water, is heated to 60-70 DEG C of reaction 4-6h, cleans product with ethyl alcohol after vacuum distillation, drying is made
Modified lactose, it is spare；Vermiculite is calcined, vermiculite power is then ground into；90-110 parts of vermiculite powers are formulated as 3- with water
The suspension of 5wt%, is heated to 55-65 DEG C, and 40-60 parts of modified lactose are added into suspension, stirs insulation reaction 10-16h,
Then organic modification vermiculite power is made after centrifugation, filtering, drying.
B it) neutralizes: 85-95 parts of acrylic acid and 5-15 parts of acrylamides being added in 150-250 parts of water, hydrogen-oxygen is then used
Change sodium water solution neutralize until system pH is 5-5.5.
C) it polymerize: first adds 1-5 parts of organic modification vermiculites and 1-2 parts of bacteria celluloses under 25-35 DEG C, nitrogen protection
Add to step B) in acquired solution, successively 0.2-0.4 parts of triallylammonium chlorides are added again after being uniformly dispersed and 0.3-0.5 parts are drawn
Agent is sent out, break nitrogen after addition, reacts 8-10h at 60-70 DEG C, obtains viscous liquid.
D) wet spinning: by viscous liquid be diluted with water to concentration be 1-3wt% and simultaneously in real time adjust keep pH be
5-5.5 obtains colloidal sol spinning solution, and colloidal sol spinning solution is added in syringe, and colloidal sol spinning solution is sprayed from spinneret orifice at room temperature
Thread is formed out, and finally solidification forms Sodium Polyacrylate fiber in coagulating bath.
Above-mentioned each substance number is parts by weight.
Technical solution of the present invention has following technical effect that
1) vermiculite is a kind of natural silicate in layer structure.It, can after water suction with outstanding water absorbing properties
It expands, while it also has outstanding resistance to ag(e)ing as inorganic matter.The present invention exactly utilizes its above-mentioned two feature, will
It is compound in Sodium Polyacrylate of the invention, can not only effectively promote the heat-resisting quantity, light resistance and intensity of fiber, and
The high-hydroscopicity of fiber can also farthest be retained.
But as described above, common vermiculite is layer structure, and interlayer contains mass crystallization water.The disadvantage is that with poly-
Sodium acrylate compound tense causes it to be easy to reunite in the base, dispersibility is poor since layer structure is unable to fully remove.For
This, the present invention has carried out a series of improvement: first calcining vermiculite, as far as possible the removal interlayer crystallization water.Then with by ten
The modified lactic acid of dialkyl dimethyl benzyl ammonium chloride is modified it, since dodecyl benzyl dimethyl ammonium chloride is season
Ammonium salt can carry out cation with vermiculite and exchange, therefore with vermiculite intercalation can occur for modified lactic acid, so that modified lactic acid
It is sandwiched between lamella, increases piece interlamellar spacing, improve the extent of exfoliation of vermiculite, so that vermiculite power can be well-dispersed in
In Sodium Polyacrylate matrix.And hydroxyl rich in lactic acid molecules can generate a large amount of with the hydroxyl of vermiculite interlayer
Hydrogen bond, to improve modified lactic acid in the stability of vermiculite in flake interlayer.In addition, hydroxyl on lactic acid can also on Sodium Polyacrylate
Carboxyl react and generate chemical bonding, further increase the combination between organic modification vermiculite and Sodium Polyacrylate
Degree, not easily runs off it.In the prior art, also there is through addition inorganic filler the technical side for improving Sodium Polyacrylate intensity
Case, but inorganic material and Sodium Polyacrylate belong to inorganic material and organic material, limited compatibility, if excessive addition after all
Inorganic material also will affect the spinnability of Sodium Polyacrylate spinning solution.For this purpose, being only added in the present invention a small amount of inorganic
Material.
2) present invention is directed to the disadvantage of polyacrylic acid intensity deficiency, and some acrylamide is doped in acrylic monomers,
Bacteria cellulose is also successively added in polymerization and as the triallylammonium chloride of crosslinking agent, can effectively improve fiber
Intensity.Wherein, hydroxyl rich on bacteria cellulose, and the much extra general fibre element of the branch quantity on its main chain,
In flakes.Therefore bacteria cellulose can sufficiently be crosslinked with Sodium Polyacrylate in polymerization reaction, to form interpenetrating
Three-dimensional net structure, to improve the intensity of fiber.And bacteria cellulose equally has outstanding water-retaining property, will not influence
The water absorbing properties of Sodium Polyacrylate fiber.Triallylammonium chloride and traditional crosslinking agent N, N- methylene-bisacrylamide (are handed over
Connection key is amido bond) it compares, cross-bond less facile hydrolysis.
Further, step D) in, the coagulating bath is the ethanol water of 75-85wt%.
Further, step D) in, the speed that colloidal sol spinning solution is sprayed from spinneret orifice is 3-7mL/min.
Further, step A) in, the calcination condition of vermiculite is to calcine 2-4h at 500-600 DEG C.
Further, step B) in, the concentration of the sodium hydrate aqueous solution is 5-10wt%.
Further, step C) in, the initiator is potassium peroxydisulfate or ammonium persulfate.
Further, the molecular weight ranges of obtained Sodium Polyacrylate fiber are 500W-1500W.
Further, step C) in, the part initiator is carried on Leu-Glu-glycine copolymer pellet
On.
When Sodium Polyacrylate is in high temperature, illumination, high saline environment for a long time, molecular weight can occur a degree of
Degradation, long chain are cracked into multistage small molecule chain.In order to improve the intensity and resistance to ag(e)ing of fiber, it will usually increase and cause
Agent, crosslinking agent dosage, to improve Sodium Polyacrylate molecular weight or the degree of cross linking, but team of the present invention finds, molecular weight is also simultaneously
Non- to be the bigger the better, excessively high molecular weight and excessive crosslinking can make the viscosity of Sodium Polyacrylate excessively high instead, and spinnability is serious
Decline, is unfavorable for spinning.
For this purpose, the present invention solves above-mentioned technical problem from another angle.In the present invention, part initiator is carried on
In Leu-Glu-glycine copolymer pellet, the present invention uses special Leu-Glu-glycine copolymer
Grain loads initiator.Leu-Glu-glycine copolymer is triblock polymer, according to leucine, glutamic acid, sweet
The property of three kinds of propylhomoserin specific collocation amino acid, the polymer have characteristics that the polymerization when environment pH is lower than 3.5 or less
Three blocks of object are all positively charged, and due to the principle that identical charges repel each other, strand is in extended state；When environment pH is in 3.5-
When 5.5, the leucine segment and glycine segment positioned at strand both ends are negatively charged, and are located at the glutamic acid still band of interlude
Positive charge, therefore the block at both ends is close to interlude under electrostatic interaction, strand is " rolling up " state at this time；When environment is
When neutral or alkalinity (pH is greater than 7), the block at both ends is still negatively charged, and glutamic acid section also transitions into neutrality (pH 7 at this time
Left and right) or it is negatively charged (alkalinity), and both ends block repels each other at this time, and whole strand is in extended state.The present invention exactly utilizes should
The above-mentioned characteristic of polymer after loading initiator, is added, due to Sodium Polyacrylate of the invention in polyacrylic acid sodium polymerization
It is weakly acidic (pH is about 5-5.5) to polymerize environment, polymer molecular chain is in " rolling up " shape at this time, and strand tightly wraps initiator
It covers, initiator is difficult to participate in reaction (unsupported initiator participates in reaction) under its barrier, therefore can be avoided initiator and mention
Preceding whole runs out.After being prepared as water-absorption fiber, water-absorption fiber is in highly acid (pH is less than 3.5) or neutral or alkaline environment
Under the common environment of Sodium Polyacrylate (above-mentioned environment be), polymer molecule chain-unfolding, initiator is released, high for a long time
Initiator is able to carry out reaction and reconnects the Sodium Polyacrylate molecule segment of cracking under the conditions of temperature or solarization, plays ageing-resistant
Effect.
To sum up, the present invention passes through the molecular weight for reducing Sodium Polyacrylate to obtain the water-absorption fiber of ideal viscosity, and leads to
Cross later-stage utilization initiator and improve the strand of fracture again indirect mode the intensity and resistance to ag(e)ing of water-absorption fiber.
The present invention selects above-mentioned specific amino acid copolymer as carrier, close with Sodium Polyacrylate property, compatible
Property is good.
Further, load have initiator Leu-Glu-glycine copolymer pellet the preparation method comprises the following steps:
1) L-Leu-N- carboxyl-ring inner-acid anhydride, nickel chelate catalyst 100:2-4 in mass ratio are added to N, N-
In dimethylformamide, 10-12h is stirred to react at nitrogen protection, 30-35 DEG C；It is subsequently added into Pidolidone-N- carboxyl-ring
Inner-acid anhydride continues insulated and stirred and reacts 14-18h；Then L- glycine-N- carboxyl-ring inner-acid anhydride is added, it is anti-to continue insulated and stirred
Answer 10-12h；It is most precipitated afterwards through n-hexane and passes through dialysis and Leu-Glu-glycine copolymer pellet is made.
2) initiator is dissolved in aqueous solution of the pH less than 3 and is stirred evenly, then adding quality is 6-10 times of initiator
Simultaneously ultrasonic disperse is uniform for Leu-Glu-glycine copolymer, and after standing adsorption 1-2h, regulation system pH is 4-5, finally
Leu-Glu-glycine copolymer pellet that load has initiator is obtained after dialysing.
Amino acid classes in above-mentioned amino acid copolymer of the invention are that Sodium Polyacrylate polymerize environment according to the present invention
And product use environment and targetedly strictly screen, the property of different aminoacids is different, not the amino of any combination
Acid copolymer can play previously described technical effect (may be completely opposite).Correspondingly, load initiator in step 2)
PH control is also that the characteristic of amino acid copolymer designs according to the present invention completely.Only just it is able to achieve within the scope of above-mentioned pH
The payload of initiator.
Further, the L-Leu-N- carboxyl-ring inner-acid anhydride, Pidolidone-N- carboxyl-ring inner-acid anhydride and L- are sweet
Propylhomoserin-N- carboxyl-ring inner-acid anhydride molar ratio is 0.6-0.8:0.9-1.2:0.6-0.8.
When preparing amino acid copolymer, the ratio between each block of strict control is needed, in the intermediate longer situation of segment,
Load factor can be effectively improved.
Further, the Leu-Glu-glycine copolymer pellet partial size is 100-500 nanometers.
Further, Leu-Glu-glycine copolymer pellet dosage that load has initiator is 0.1-0.2
Part.
It is compared with the prior art, the beneficial effects of the present invention are:
1, the method for the present invention adds organise PERFORMANCE OF MODIFIED VERMICULITE powder, bacteria cellulose in Sodium Polyacrylate, can effectively mention
The intensity and resistance to ag(e)ing of water-absorption fiber, and good dispersion of the vermiculite power in water-absorption fiber are risen, it is not easy to reunite.
It 2, can be by the poly- of cracking containing the initiator by amino acid copolymer cladding in Sodium Polyacrylate of the invention
Sodium acrylate strand rebuilds connection, to improve the intensity and resistance to ag(e)ing of Sodium Polyacrylate water-absorption fiber.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
A kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A) the preparation of organic modification vermiculite power:
10 parts of lactose and 10 parts of dodecyl benzyl dimethyl ammonium chlorides are added in 100 parts of water, are heated to 65 DEG C instead
5h is answered, cleans product with ethyl alcohol after vacuum distillation, dries and modified lactose is made, it is spare.
Vermiculite is calcined into 3h at 550 DEG C, is then ground into vermiculite power；100 parts of vermiculite powers are formulated as 4wt%'s with water
Suspension is heated to 60 DEG C, and 50 parts of modified lactose are added into suspension, stirs insulation reaction 14h, then by centrifugation, mistake
Organic modification vermiculite power is made after filter, drying.
B it) neutralizes: 90 parts of acrylic acid and 10 parts of acrylamides being added in 200 parts of water, are then 8wt%'s with concentration
Sodium hydrate aqueous solution neutralize until system pH is 5.2.
C) it polymerize: is first added to 3 parts of organic modification vermiculites and 1.5 parts of bacteria celluloses under 30 DEG C, nitrogen protection
Step B) in acquired solution, 0.3 part of triallylammonium chloride and 0.3 part of potassium peroxydisulfate, addition are successively added after being uniformly dispersed again
After break nitrogen, react 9h at 65 DEG C, obtain viscous liquid.
D) wet spinning: by viscous liquid be diluted with water to concentration be 2wt% and simultaneously in real time adjust keep pH be
5.2, obtain colloidal sol spinning solution, colloidal sol spinning solution be added in syringe, at room temperature colloidal sol spinning solution from spinneret orifice with
The flow of 5mL/min sprays to form thread, and finally solidification forms polyacrylic acid in coagulating bath (ethanol water of 80wt%)
Sodium fiber.
Embodiment 2
A kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A) the preparation of organic modification vermiculite power:
10 parts of lactose and 10 parts of dodecyl benzyl dimethyl ammonium chlorides are added in 100 parts of water, are heated to 65 DEG C instead
5h is answered, cleans product with ethyl alcohol after vacuum distillation, dries and modified lactose is made, it is spare.
Vermiculite is calcined into 3h at 550 DEG C, is then ground into vermiculite power；100 parts of vermiculite powers are formulated as 4wt%'s with water
Suspension is heated to 60 DEG C, and 50 parts of modified lactose are added into suspension, stirs insulation reaction 14h, then by centrifugation, mistake
Organic modification vermiculite power is made after filter, drying.
B it) neutralizes: 90 parts of acrylic acid and 10 parts of acrylamides being added in 200 parts of water, are then 8wt%'s with concentration
Sodium hydrate aqueous solution neutralize until system pH is 5.2.
C) it polymerize: is first added to 3 parts of organic modification vermiculites and 1.5 parts of bacteria celluloses under 30 DEG C, nitrogen protection
Step B) in acquired solution, 0.3 part of triallylammonium chloride, 0.3 part of potassium peroxydisulfate and 0.15 are successively added after being uniformly dispersed again
Part load has Leu-Glu-glycine copolymer pellet of potassium peroxydisulfate, and break nitrogen after addition, reacts at 65 DEG C
9h obtains viscous liquid.
D) wet spinning: by viscous liquid be diluted with water to concentration be 2wt% and simultaneously in real time adjust keep pH be
5.2, obtain colloidal sol spinning solution, colloidal sol spinning solution be added in syringe, at room temperature colloidal sol spinning solution from spinneret orifice with
The flow of 5mL/min sprays to form thread, and finally solidification forms polyacrylic acid in coagulating bath (ethanol water of 80wt%)
Sodium fiber.
Wherein, load have initiator Leu-Glu-glycine copolymer pellet the preparation method comprises the following steps:
1) L-Leu-N- carboxyl-ring inner-acid anhydride, nickel chelate catalyst 100:3 in mass ratio are added to N, N- bis-
In methylformamide, 11h is stirred to react at nitrogen protection, 32 DEG C；It is subsequently added into Pidolidone-N- carboxyl-ring inner-acid anhydride, after
Continuation of insurance temperature is stirred to react 16h；Then L- glycine-N- carboxyl-ring inner-acid anhydride is added, continues insulated and stirred and reacts 11h；Most pass through afterwards
N-hexane, which precipitates and passes through dialysis, is made Leu-Glu-glycine copolymer pellet, wherein L-Leu-N- carboxyl-ring
Inner-acid anhydride, Pidolidone-N- carboxyl-ring inner-acid anhydride and L- glycine-N- carboxyl-ring inner-acid anhydride molar ratio are 0.7:1:0.8.
2) initiator is dissolved in the aqueous solution that pH is 2 and is stirred evenly, then add the bright ammonia that quality is 8 times of initiator
Simultaneously ultrasonic disperse is uniform for acid-glutamic-glycine copolymer, and after standing adsorption 1.5h, regulation system pH is 4.5, most afterwards through saturating
Leu-Glu-glycine copolymer pellet that the load that partial size is 100-500 nanometers has initiator is obtained after analysis.
Embodiment 3
A kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A) the preparation of organic modification vermiculite power: by 8- parts of lactose and 8 parts of dodecyl benzyl dimethyl ammonium chloride additions
Into 90 parts of water, 60 DEG C of reaction 6h are heated to, clean product with ethyl alcohol after vacuum distillation, dried and modified lactose is made, it is spare.
Vermiculite is calcined into 4h at 500 DEG C, is then ground into vermiculite power；90 parts of vermiculite powers are formulated as 3wt%'s with water
Suspension is heated to 55 DEG C, and 40 parts of modified lactose are added into suspension, stirs insulation reaction 10h, then by centrifugation, mistake
Organic modification vermiculite power is made after filter, drying.
B it) neutralizes: 85 parts of acrylic acid and 15 parts of acrylamides being added in 150 parts of water, are then 5wt%'s with concentration
Sodium hydrate aqueous solution neutralize until system pH is 5.
C) it polymerize: 1 part of organic modification vermiculite and 2 parts of bacteria celluloses is first added to step under 25 DEG C, nitrogen protection
Rapid B) in acquired solution, 0.2 part of triallylammonium chloride, 0.4 part of ammonium persulfate are successively added after being uniformly dispersed again, addition finishes
Break nitrogen afterwards, reacts 8h at 60 DEG C, obtains viscous liquid.
D) wet spinning: being diluted with water to concentration for viscous liquid and be 1wt% and adjust holding pH in real time simultaneously to be 5,
Colloidal sol spinning solution is obtained, colloidal sol spinning solution is added in syringe, colloidal sol spinning solution is from spinneret orifice with 3mL/min at room temperature
Flow spray to form thread, finally solidification forms Sodium Polyacrylate fiber in the coagulating bath (ethanol water of 75wt%).
Embodiment 4
A kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A) the preparation of organic modification vermiculite power: by 12 parts of lactose and 12 parts of dodecyl benzyl dimethyl ammonium chloride additions
Into 10 parts of water, 70 DEG C of reaction 4h are heated to, clean product with ethyl alcohol after vacuum distillation, dried and modified lactose is made, it is spare.
Vermiculite is calcined into 2h at 600 DEG C, is then ground into vermiculite power；110 parts of vermiculite powers are formulated as 5wt%'s with water
Suspension is heated to 65 DEG C, and 60 parts of modified lactose are added into suspension, stirs insulation reaction 16h, then by centrifugation, mistake
Organic modification vermiculite power is made after filter, drying.
B it) neutralizes: 95 parts of acrylic acid and 5 parts of acrylamides being added in 250 parts of water, are then 10wt%'s with concentration
Sodium hydrate aqueous solution neutralize until system pH is 5.5.
C) it polymerize: 5 parts of organic modification vermiculites and 1 part of bacteria cellulose is first added to step under 35 DEG C, nitrogen protection
Rapid B) successively to add 0.4 part of triallylammonium chloride, 0.4 part of ammonium persulfate and 0.1 part in acquired solution, after being uniformly dispersed again negative
It is loaded with Leu-Glu-glycine copolymer pellet of ammonium persulfate, break nitrogen after addition, 10h is reacted at 70 DEG C,
Obtain viscous liquid.
D) wet spinning: by viscous liquid be diluted with water to concentration be 3wt% and simultaneously in real time adjust keep pH be
5.5, obtain colloidal sol spinning solution, colloidal sol spinning solution be added in syringe, at room temperature colloidal sol spinning solution from spinneret orifice with
The flow of 7mL/min sprays to form thread, and finally solidification forms polyacrylic acid in coagulating bath (ethanol water of 85wt%)
Sodium fiber.
Wherein, load have initiator Leu-Glu-glycine copolymer pellet the preparation method comprises the following steps:
1) L-Leu-N- carboxyl-ring inner-acid anhydride, nickel chelate catalyst 100:4 in mass ratio are added to N, N- bis-
In methylformamide, 10h is stirred to react at nitrogen protection, 35 DEG C；It is subsequently added into Pidolidone-N- carboxyl-ring inner-acid anhydride, after
Continuation of insurance temperature is stirred to react 14h；Then L- glycine-N- carboxyl-ring inner-acid anhydride is added, continues insulated and stirred and reacts 10h；Most pass through afterwards
N-hexane, which precipitates and passes through dialysis, is made Leu-Glu-glycine copolymer pellet, wherein L-Leu-N- carboxyl-ring
Inner-acid anhydride, Pidolidone-N- carboxyl-ring inner-acid anhydride and L- glycine-N- carboxyl-ring inner-acid anhydride molar ratio are 0.6:0.9:
0.6。
2) initiator is dissolved in the aqueous solution that pH is 2.5 and is stirred evenly, then adding quality is 10 times of initiator bright
Simultaneously ultrasonic disperse is uniform for propylhomoserin-glutamic-glycine copolymer, and after standing adsorption 2h, regulation system pH is 4, most afterwards through dialysing
Leu-Glu-glycine copolymer pellet that the load that partial size is 100-500 nanometers has initiator is obtained afterwards.
Comparative example 1
A kind of preparation method of Sodium Polyacrylate water-absorption fiber, steps are as follows:
A it) neutralizes: 90 parts of acrylic acid and 10 parts of acrylamides being added in 200 parts of water, are then 8wt%'s with concentration
Sodium hydrate aqueous solution neutralize until system pH is 5.2.
B) it polymerize: successively adds 0.3 part of triallylammonium chloride and 0.3 part of potassium peroxydisulfate under 30 DEG C, nitrogen protection, add
Break nitrogen after adding, and reacts 9h at 65 DEG C, obtains viscous liquid.
C) wet spinning: by viscous liquid be diluted with water to concentration be 2wt% and simultaneously in real time adjust keep pH be
5.2, obtain colloidal sol spinning solution, colloidal sol spinning solution be added in syringe, at room temperature colloidal sol spinning solution from spinneret orifice with
The flow of 5mL/min sprays to form thread, and finally solidification forms polyacrylic acid in coagulating bath (ethanol water of 80wt%)
Sodium fiber.
Performance test
One, water absorption rate test: each 5 groups of water-absorption fiber 0.1g of embodiment 1-2 and comparative example 1 are weighed, 500mL is added to
Distilled water in, stand 1.5h at 25 DEG C, filter off residual moisture and measure the volume X of residual moisture, calculate water absorption rate: water absorption rate
(ml/g)=(500-X) mL/0.1g, as a result as follows:
1 mean water absorption rate of embodiment is about 1731mL/g, and 2 mean water absorption rate of embodiment is about 1718mL/g, and comparative example 1 is flat
Equal water absorption rate is about 1739mL/g.
Two, heat-resisting quantity is tested: the water-absorption fiber of embodiment 1-2 and comparative example 1 are placed in 98 ± 2 DEG C of distillation water ring
It is impregnated 10 days, 20 days and 30 days in border, detects its water absorption rate, as a result as follows:
10 days: 1 mean water absorption rate of embodiment was about 1789mL/g, and 2 mean water absorption rate of embodiment is about 1779mL/g, comparison
1 mean water absorption rate of example is about 1785mL/g.
20 days: 1 mean water absorption rate of embodiment was about 1666mL/g, and 2 mean water absorption rate of embodiment is about 1681mL/g, comparison
1 mean water absorption rate of example is about 1569mL/g.
30 days: 1 mean water absorption rate of embodiment was about 1518mL/g, and 2 mean water absorption rate of embodiment is about 1611mL/g, comparison
1 mean water absorption rate of example is about 1327mL/g.
From the foregoing, it will be observed that the water absorption rate of water-absorption fiber had a degree of raising at 10 days, reason may be the leaching of its long-time
It ducks in drink abundant swelling, volume becomes larger, and water absorption rate is reinforced.At 20 days, water-absorption fiber occurred a degree of at high temperature
Aging, therefore water absorption rate is gradually reduced, after 30 days, water absorption rate further declines.And by correlation data it is found that embodiment 1
Water absorption rate fall off rate with 2 will obviously delay in comparative example 1.Therefore the heat-resisting quantity of the water-absorption fiber of embodiment 1-2 wants stronger.
Three, light resistance is tested: the water-absorption fiber of embodiment 1-2 and comparative example 1 being placed in 25 DEG C of distillation water environment
(in ultraviolet light and aging case, ultraviolet wavelength 340nm, sample and fluorescent tube distance 50mm) impregnates 15 days, 30 days and 45 days, detects it
Water absorption rate, as a result as follows:
15 days: 1 mean water absorption rate of embodiment was about 1538mL/g, and 2 mean water absorption rate of embodiment is about 1571mL/g, comparison
1 mean water absorption rate of example is about 1489mL/g.
30 days: 1 mean water absorption rate of embodiment was about 1321mL/g, and 2 mean water absorption rate of embodiment is about 1423mL/g, comparison
1 mean water absorption rate of example is about 1212mL/g.
45 days: 1 mean water absorption rate of embodiment was about 985mL/g, and 2 mean water absorption rate of embodiment is about 1141mL/g, comparison
1 mean water absorption rate of example is about 813mL/g.
And by correlation data it is found that the water absorption rate fall off rate of Examples 1 and 2 will obviously delay in comparative example 1.Therefore real
The light resistance for applying the water-absorption fiber of a 1-2 wants stronger.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (10)
1. a kind of preparation method of Sodium Polyacrylate water-absorption fiber, it is characterised in that steps are as follows:
A) the preparation of organic modification vermiculite power: by 8-12 parts of lactose and 8-12 parts of dodecyl benzyl dimethyl ammonium chloride additions
Into 90-110 parts of water, it is heated to 60-70 DEG C of reaction 4-6h, cleans product with ethyl alcohol after vacuum distillation, dried and modification is made
Lactose, it is spare；Vermiculite is calcined, vermiculite power is then ground into；90-110 parts of vermiculite powers are formulated as 3-5wt%'s with water
Suspension is heated to 55-65 DEG C, and 40-60 parts of modified lactose are added into suspension, stirs insulation reaction 10-16h, then passes through
Organic modification vermiculite power is made after crossing centrifugation, filtering, drying；
B it) neutralizes: 85-95 parts of acrylic acid and 5-15 parts of acrylamides being added in 150-250 parts of water, sodium hydroxide is then used
Aqueous solution neutralize until system pH is 5-5.5；
C) it polymerize: is first added to 1-5 parts of organic modification vermiculites and 1-2 parts of bacteria celluloses under 25-35 DEG C, nitrogen protection
Step B) in acquired solution, 0.2-0.4 part triallylammonium chlorides are successively added again after being uniformly dispersed and 0.3-0.5 parts are caused
Agent, break nitrogen after addition, reacts 8-10h at 60-70 DEG C, obtains viscous liquid；
D) wet spinning: viscous liquid is diluted with water to concentration and is 1-3wt% and adjusts holding pH in real time simultaneously to be 5-
5.5, colloidal sol spinning solution is obtained, colloidal sol spinning solution is added in syringe, colloidal sol spinning solution is sprayed from spinneret orifice at room temperature
Thread is formed, finally solidification forms Sodium Polyacrylate fiber in coagulating bath；
Above-mentioned each substance number is parts by weight.
2. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as described in claim 1, which is characterized in that step D) in,
The coagulating bath is the ethanol water of 75-85wt%.
3. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as claimed in claim 1 or 2, which is characterized in that step D)
In, the speed that colloidal sol spinning solution is sprayed from spinneret orifice is 3-7mL/min.
4. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as described in claim 1, which is characterized in that step A) in,
The calcination condition of vermiculite is to calcine 2-4h at 500-600 DEG C.
5. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as described in claim 1, which is characterized in that obtained is poly-
The molecular weight ranges of sodium acrylate fiber are 500W-1000W.
6. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as described in claim 1, which is characterized in that step C) in,
The part initiator is carried on Leu-Glu-glycine copolymer pellet.
7. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as claimed in claim 6, which is characterized in that load has initiation
The Leu-Glu of agent-glycine copolymer pellet the preparation method comprises the following steps:
1) L-Leu-N- carboxyl-ring inner-acid anhydride, nickel chelate catalyst 100:2-4 in mass ratio are added to N, N- diformazan
In base formamide, 10-12h is stirred to react at nitrogen protection, 30-35 DEG C；It is subsequently added into Pidolidone-N- carboxyl-ring sour
Acid anhydride continues insulated and stirred and reacts 14-18h；Then L- glycine-N- carboxyl-ring inner-acid anhydride is added, continues insulated and stirred reaction
10-12h；It is most precipitated afterwards through n-hexane and passes through dialysis and Leu-Glu-glycine copolymer pellet is made；
2) initiator is dissolved in aqueous solution of the pH less than 3 and is stirred evenly, then add the bright ammonia that quality is 6-10 times of initiator
Simultaneously ultrasonic disperse is uniform for acid-glutamic-glycine copolymer, and after standing adsorption 1-2h, regulation system pH is 4-5, most afterwards through saturating
Leu-Glu-glycine copolymer pellet that load has initiator is obtained after analysis.
8. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as claimed in claim 7, which is characterized in that the bright ammonia of L-
Acid-N- carboxyl-ring inner-acid anhydride, Pidolidone-N- carboxyl-ring inner-acid anhydride and L- glycine-N- carboxyl-ring inner-acid anhydride molar ratio
For 0.6-0.8:0.9-1.2:0.6-0.8.
9. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as claimed in claim 6, which is characterized in that the bright ammonia
Acid-glutamic-glycine copolymer pellet partial size is 100-500 nanometers.
10. a kind of preparation method of Sodium Polyacrylate water-absorption fiber as claimed in claim 6, which is characterized in that load, which has, draws
Leu-Glu-glycine copolymer pellet the dosage for sending out agent is 0.1-0.2 parts.
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