CN102382262B - One-step continuous granulation preparation method for water absorbent granule - Google Patents
One-step continuous granulation preparation method for water absorbent granule Download PDFInfo
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- CN102382262B CN102382262B CN 201110231840 CN201110231840A CN102382262B CN 102382262 B CN102382262 B CN 102382262B CN 201110231840 CN201110231840 CN 201110231840 CN 201110231840 A CN201110231840 A CN 201110231840A CN 102382262 B CN102382262 B CN 102382262B
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Abstract
The invention discloses a one-step continuous granulation preparation method for a water absorbent granule, and the water absorbent granule consists of polysaccharide, monomer, initiator and cross-linking agents according to a certain proportion by weight. The method includes the following steps: (A) the polysaccharide and the primary cross-linking agent are added into a reactor and uniformly mixed under the condition of nitrogen protection until dissolution, the initiator and the monomer partially neutralized neutralizing alkali are added, and the temperature is controlled to initiate graft copolymerization reaction; (B) the secondary cross-linking agent is added, and after the reaction solution is uniformly mixed, granulation is fulfilled; (C) dispersion medium is filtered, the granules are transferred into washing reagent, and the residual dispersion medium on the surfaces of the granules is washed off with the washing reagent; (D) the washing reagent is filtered, and a heating fan is used for removing the residual washing reagent on the surfaces of the granules; (E) the water absorbent granules are obtained. The method is easy, and is simple and convenient to operate. The water absorbent granules cannot be easily caked under the high-humidity condition, and the invention solves the problems that: in the conventional aqueous solution method for preparation, the granules are mostly powdery, the grain size is ununiform, and the drying time is overlong. The one-step continuous granulation preparation method is suitable for mass production.
Description
Technical field
The present invention relates to a kind of preparation method of water absorbent granule one-step continuous granulation.This particle can be widely used in sanitary material, food, moistureproof, the afforestation of product.
Background technology
At present, the synthesizing super-strong water absorbing agent particle mainly contains two kinds of methods; The one, inverse suspension polymerization, the 2nd, it is again crosslinked synthetic to pulverize drying behind the aqueous solution polymerization.What suspension polymerization was synthetic is by the materials such as monomer, dispersion agent are distributed to it in disperse phase by the mode that stirs high speed shear, add the copolyreaction of initiator initiation grafting, increase progressively by synthetic particle reaction that sedimentation obtains water absorbent granule.This method advantage is that particle shape is better, and size distribution is comparatively concentrated, and shortcoming is to exist organic solvent residual, and difficulty is removed, and particle diameter is generally less than normal, and rotating speed needs strict control, amplifies building-up process and has certain difficulty.Water solution polymerization process is the main method of suitability for industrialized production particulate water absorbing agent.This method is main by the materials such as monomer are mixed, and with the copolyreaction of initiator initiation grafting, casting film-forming is finished reaction and dry on flat board.And by scraper plate absorbent membrane is scraped, with pulverizer film is ground into particle.The advantage of this method is that production technique is comparatively ripe, and shortcoming is that its drying process is longer, and particle shape is irregular after pulverizing, and mostly is Powdered, and size distribution is wider, and crushing process has certain impact to the product gel-strength.
Summary of the invention
The present invention seeks to be to provide a kind of preparation method of water absorbent granule one-step continuous granulation, it is easy to implement the method, and is easy and simple to handle.It is larger that this preparation method prepares grain diameter, the size distribution homogeneous, prevented from caking under super-humid conditions has solved that particle mostly is Powdered among traditional aqua-solution method preparation method, particle diameter heterogeneity, time of drying long problem.Simultaneously, this method is applicable to large-scale production.
In order to achieve the above object, the present invention adopts following technical measures:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide 1%-20%
Monomer 53%-98.92%
Initiator 0.05%-2%;
Linking agent primary cross-linking agent 0.01%-5%,
Secondary crosslinking agent 0.02%-20%.
A kind of water absorbent granule, it forms (preferable range) by the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide 2%-15%
Monomer 58%-92%
Initiator 0.1%-1.5%;
Linking agent primary cross-linking agent 0.05%-4%,
Secondary crosslinking agent 0.1%-15%.
Described monomer is the monomer that partly neutralizes through neutralization bases, and it is comprised of 0-70mol% monomer acids and 100-30mol% monomer hydrochlorate (total is no more than 100mol%).Need to prove that degree of neutralization refers to the one-tenth salinity of monomer, the one-tenth salinity that the present invention is suitable for is 100-30mol%.
Described polysaccharide and monomer are carrying out graft copolymerization, it is transferred to allow its particle dehydration forming in the dispersion medium and continue to finish graft copolymerization, its mode is by once crosslinked control viscosity rise dispersion granulation, improves degree of crosslinking by secondary crosslinking and finishes reaction;
Described polysaccharide is a kind of or 2-7 kind arbitrary combination in starch, Rhizoma amorphophalli glucomannan, Mierocrystalline cellulose, chitosan, carrageenin, xanthan gum, the seaweed gel;
The composition of described monomer is vinylformic acid and/or its esters and other monomers: vinyl sulfonic acid, toxilic acid, styrene sulfonic acid, acrylamide etc. and/or its esters a kind of or 2-4 kind arbitrary combination wherein;
Described neutralization bases adopts a kind of or 2-3 kind arbitrary combination wherein such as sodium hydroxide, potassium hydroxide, ammoniacal liquor;
Described initiator is wherein a kind of of persulphate, Sodium Persulfate, Potassium Persulphate or ammonium persulphate, hydrogen peroxide thermolysis type initiator or azo-compound type initiator: azo-bis-isobutyrate hydrochloride; Initiator uses separately or arbitrary combination is used, and when using superoxide, carries out reductionoxidation polymerization with sulphite, hydrosulphite reductive agent;
Described linking agent is alkaline earth metal compound: such as aluminide, calcified material etc.; Amides: N,N methylene bis acrylamide, acrylamide-METHYLENE CHLORIDE ethernamine, epoxy compounds: such as wherein a kind of of epoxy chloropropane, polyvalent alcohol; Linking agent uses separately or arbitrary combination is used;
Described dispersion medium is alcohols: wherein a kind of of ethanol, polyoxyethylene glycol, ethylene glycol, glycerine, Polyglycerine and whiteruss; Dispersion medium uses separately or arbitrary combination is used;
Described washing reagent is the mixture of wherein a kind of of methyl alcohol, ethanol, acetone, ether or two to four kinds.
A kind of preparation method of water absorbent granule one-step continuous granulation the steps include:
(1), in reactor, add polysaccharide, primary cross-linking agent, add water under stirring and evenly mixing nitrogen protection condition, 10-90 ℃ of dissolving.The passing ratio pump adds initiator, through the monomer that neutralization bases partly neutralizes, temperature is controlled at the copolymerization of 20-90 ℃ of temperature initiation grafting, reaction times 30-180 minute.
(2), add the secondary crosslinking agent, after reaction solution mixed, by extrude, spray, shear, throw away, array modes a kind of or two kinds to five kinds in the mechanical dispersion mode such as emulsification are distributed to reaction solution and finish granulation in the 20-90 ℃ of dispersion medium, the moulding in dispersion medium of the particle of preparation is dewatered and is continued to finish graft copolymerization, the residence time 10-80 in disperse phase minute.
(3), filter dispersion medium, with transfer of granules to washing reagent, with the residual dispersion medium of washing reagent wash-out particle surface.
(4), filtration washing reagent, with the washing reagent of heating (40-250 ℃) air-blast device eliminating particle remained on surface.
(5), obtain the water absorbent granule of one-step continuous granulation.
Described polysaccharide and monomer carry out graft copolymerization for some time (30-180 ℃) in certain temperature (20-90 ℃), it are transferred to allow its particle dehydration forming in the dispersion medium and continue to finish graft copolymerization.Its mode is to be convenient to disperse granulation by crosslinked control viscosity rise once, improves degree of crosslinking by secondary crosslinking and finishes reaction.
Described granulation dispersing method includes but not limited to extrude, emulsification, a kind of in throwing away, spray, shearing and their arbitrary combination.
Described polysaccharide is a kind of or 2-7 kind arbitrary combination in starch, Rhizoma amorphophalli glucomannan, Mierocrystalline cellulose, chitosan, carrageenin, xanthan gum, the seaweed gel.
The composition of described monomer is vinylformic acid and/or its esters and other monomers (such as vinyl sulfonic acid, toxilic acid, styrene sulfonic acid, acrylamide etc.) and/or its esters a kind of or 2-4 kind arbitrary combination wherein.
Described neutralization bases can adopt a kind of or 2-3 kind arbitrary combination wherein such as sodium hydroxide, potassium hydroxide, ammoniacal liquor.
Described initiator is wherein a kind of of persulphate, Sodium Persulfate, Potassium Persulphate or ammonium persulphate, hydrogen peroxide thermolysis type initiator or azo-compound type initiator (such as azo-bis-isobutyrate hydrochloride).These initiators can use separately also and can arbitrary combination use.And when using superoxide, can carry out reductionoxidation polymerization with reductive agents such as sulphite, hydrosulphite.
Described linking agent is that alkaline earth metal compound (such as aluminide, calcified material etc.), amides are (such as N, N-methylene-bisacrylamide, acrylamide-METHYLENE CHLORIDE ethernamine etc.), wherein a kind of of epoxy compounds (such as epoxy chloropropane etc.), polyvalent alcohol.These linking agents can use separately also and can arbitrary combination use.
Described dispersion medium is wherein a kind of of alcohols (such as ethanol, polyoxyethylene glycol, ethylene glycol, glycerine, Polyglycerine etc.) and higher alkane class (whiteruss etc.).These dispersion medium can use separately also and can arbitrary combination use.
Described washing reagent is the mixture of wherein a kind of of methyl alcohol, ethanol, acetone, ether or two to four kinds.
The method that drying and dehydrating is pulverized again behind the water absorbent granule one-step continuous granulation method that relates among the present invention and the existing aqueous solution polymerization is compared, and its distinguishing feature is that particle surface is comparatively smooth, and size distribution is homogeneous comparatively.From the scanning electron microscope picture, can see, the visible shape (Fig. 2) of significantly shearing of the synthetic particle surface of aqueous solution polymerization, the present invention synthesizes its surface of particle comparatively smooth (Fig. 3).The synthetic particle of aqueous solution polymerization mostly is Powdered, and its particle diameter mostly is micron order, and the synthetic particle of the present invention is naked eyes visible particle shape, and its particle diameter can reach grade.With the synthetic Particle Phase ratio of inverse suspension method method, the present invention prepares grain diameter and enlarges markedly, and it is comparatively easy that particle agglomeration resistance ability has remarkable lifting and preparation method of the present invention to operate, and is convenient to technique and amplifies.Carry out moisture absorption test in high, medium and low wet condition, the particle that the present invention synthesizes is without caking phenomenon, and rate of moisture absorption is significantly higher than the synthetic particle of drying and dehydrating behind the aqueous solution polymerization.This product can be widely used in the fields such as sanitary product, product protection against the tide, coping with agriculture drought water conservation.
Description of drawings
Fig. 1 is a kind of preparation method's block diagram of water absorbent granule one-step continuous granulation.
Wherein: moulding in polysaccharide 1, primary cross-linking agent 2, stirring and dissolving 3, proportioning pump 4, monomer 5, initiator 6, initiation grafting copolymerization 7, secondary crosslinking agent 8, diverting device 9, the disperse phase, reaction, dry 10, liquid-solid separation 11, washing reagent are removed the residual dispersion medium 12 of particle surface, filtration washing reagent 13, forced air drying and are removed the residual washing reagent of particle surface 14, granular disintegration 15.
Fig. 2 is the synthetic particle surface synoptic diagram of a kind of aqueous solution polymerization.
Fig. 3 is the comparatively smooth synoptic diagram in its surface of a kind of synthetic particle.
Embodiment
Example 1:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide konjaku glucomannan 0.9%
Xanthan gum 0.1%
Monomer vinylformic acid 98.14%
Initiator potassium persulfate 0.1%
Linking agent primary cross-linking agent aluminum oxide 0.6%
Secondary crosslinking agent N,N methylene bis acrylamide 0.16%
Annotate: monomer is that its degree of neutralization is 80mol% (being that sodium acrylate in the monomer, acrylic acid mol ratio are 80: 20) through the monomeric compound (sodium acrylate) of neutralization bases (sodium hydroxide) part neutralization;
Obtain as particle diameter is the 2.5mm granular disintegration, product is 1000 times to the water absorbent rate of pure water, 90 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation the steps include:
(1), in reactor, add 1 part of polysaccharide 1 (formed by 0.9 part of Rhizoma amorphophalli glucomannan and 0.1 part of xanthan gum, mass fraction, lower with), 0.6 part of primary cross-linking agent 2 (aluminum oxide), 100 parts of pure water.Under stirring and dissolving mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 98.14 parts of monomers 5 (vinylformic acid) 0.1 part of initiator 6 (Potassium Persulphate), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 0.16 part of secondary crosslinking agent 8 (N, the N-methylene-bisacrylamide), reaction solution is distributed to reaction solution in 20 or 34 or 45 or 56 or 64 or 76 or 84 or 90 ℃ of dispersion medium (polyoxyethylene glycol) by diverting device 9 (pressure extrusion device) after mixing, treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (polyoxyethylene glycol), with transfer of granules to washing reagent (ethanol), the dispersion medium 12 (polyoxyethylene glycol) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (ethanol), with the washing reagent (ethanol) 14 of heat blowing device eliminating particle remained on surface.Obtain as particle diameter is 2.5mm granular disintegration 15, product is 1000 times to the water absorbent rate of pure water, 90 times in physiological saline.
Example 2:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide starch 2%
Monomer vinylformic acid 95.8%
Initiator ammonium persulfate 0.15%
Linking agent primary cross-linking agent N,N methylene bis acrylamide 0.05%
Secondary crosslinking agent epoxy chloropropane 2%
Annotate: monomer is that its degree of neutralization is 50mol% (being that potassium acrylate in the monomer, acrylic acid mol ratio are 50: 50) through the monomeric compound (potassium acrylate) of neutralization bases (potassium hydroxide) part neutralization;
Acquisition is the 1.5mm granular disintegration for particle diameter.Product is 400 times to the water absorbent rate of pure water, 50 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation, it may further comprise the steps:
(1), in reactor, adds 2 parts of polysaccharide 1 (starch), 0.05 part of linking agent 2 (N,N methylene bis acrylamide), 100 parts of pure water.Under stirring and dissolving mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 95.8 parts of monomers 5 (vinylformic acid), 0.15 part of initiator 6 (Ammonium Persulfate 98.5), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 2 parts of secondary crosslinking agent 8 (epoxy chloropropane), reaction solution is distributed to reaction solution in 20 or 34 or 45 or 56 or 64 or 76 or 84 or 90 ℃ of dispersion medium (Polyglycerine) by diverting device 9 (emulsifier unit) after mixing, treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (Polyglycerine), with transfer of granules to washing reagent (methyl alcohol), the dispersion medium 12 (Polyglycerine) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (methyl alcohol), with the washing reagent 14 (methyl alcohol) of heat blowing device eliminating particle remained on surface.Acquisition is 1.5mm granular disintegration 15 for particle diameter.Product is 400 times to the water absorbent rate of pure water, 50 times in physiological saline.
Example 3:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Monomer methacrylic acid 77.5%
Styrene sulfonic acid 8.75%
Initiator Sodium Persulfate 0.15%
Linking agent primary cross-linking agent epoxy chloropropane 0.1%
Secondary crosslinking agent aluminum oxide 4.5%
Annotate: monomer is the monomeric compound (ammonium methacrylate, styrene sulfonic acid ammonium) of neutralization bases (ammoniacal liquor) part neutralization, its degree of neutralization is 70mol% (mol ratio that is ammonium methacrylate in the monomer, methacrylic acid is 70: 30, and the mol ratio of styrene sulfonic acid ammonium, styrene sulfonic acid is 70: 30);
Acquisition is the 3mm granular disintegration for particle diameter.Product is 600 times to the water absorbent rate of pure water, 70 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation, it may further comprise the steps:
(1), in reactor, adds 9 parts of polysaccharide 1 (seaweed gel), 0.1 part of primary cross-linking agent 2 (epoxy chloropropane), 110 parts of water.Under stirring and dissolving mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 86.25 parts of monomer 5 (methacrylic acid and styrene sulfonic acid) 0.15 part of initiators 6 (Sodium Persulfate), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 4.5 parts of secondary crosslinking agent 8 (aluminum oxide), reaction solution is distributed to reaction solution in 20 or 34 or 45 or 56 or 64 or 76 or 84 or 90 ℃ of dispersion medium (ethylene glycol) by diverting device 9 (centrifugal pan) after mixing, treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (ethylene glycol), with transfer of granules to washing reagent (acetone), the dispersion medium 12 (ethylene glycol) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (acetone), with the washing reagent 14 (acetone) of heat blowing device eliminating particle remained on surface.
Acquisition is 3mm granular disintegration 15 for particle diameter.Product is 600 times to the water absorbent rate of pure water, 70 times in physiological saline.
Example 4:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide carboxymethyl cellulose 7%
Monomer vinylformic acid 64%
Vinyl sulfonic acid 14.9%;
Linking agent primary cross-linking agent BDO 4%,
Secondary crosslinking agent aluminum oxide 10%;
Annotate: monomer is the monomeric compound (ammonium acrylate, vinyl sulfonic acid ammonium) of neutralization bases (ammoniacal liquor) part neutralization, its degree of neutralization is 70mol% (be that ammonium acrylate in the monomer, acrylic acid mol ratio are 80: 20, the mol ratio of vinyl sulfonic acid ammonium, vinyl sulfonic acid is 80: 20);
Acquisition is the 2mm granular disintegration for particle diameter.Product is 600 times to the water absorbent rate of pure water, 80 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation, it may further comprise the steps:
(1), in reactor, adds 7 parts of polysaccharide 1 (carboxymethyl cellulose), 4 parts of primary cross-linking agent 2 (BDO), 120 parts of water.Under stirring and dissolving mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 78.9 parts of monomers 5 (vinylformic acid and vinyl sulfonic acid), 0.1 part of initiator 6 (hydrogen peroxide), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 10 parts of secondary crosslinking agent 8 (aluminum oxide), reaction solution is distributed to reaction solution in 20 or 34 or 45 or 56 or 64 or 76 or 84 or 90 ℃ of dispersion medium (whiteruss) by diverting device 9 (spraying plant) after mixing, treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (paraffin), with transfer of granules to washing reagent (ether), the dispersion medium 12 (whiteruss) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (ether), with the washing reagent 14 (ether) of heat blowing device eliminating particle remained on surface.
Acquisition is 2mm granular disintegration 15 for particle diameter.Product is 600 times to the water absorbent rate of pure water, 80 times in physiological saline.
Example 5:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide chitosan 4%
Monomer vinylformic acid 60%,
Acrylamide 25.6%
Initiator Sodium Persulfate 0.16%
S-WAT 0.04%
Linking agent primary cross-linking agent calcium oxide 0.2%,
Secondary crosslinking agent BDO 10%;
Annotate: monomer is the monomeric compound (ammonium acrylate, acrylamide) of neutralization bases (ammoniacal liquor) part neutralization, and its degree of neutralization is 100mol% (being that ammonium acrylate in the monomer, acrylic acid mol ratio are 100: 0);
Acquisition is the 1mm granular disintegration for particle diameter.Product is 800 times to the water absorbent rate of pure water, 100 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation, it may further comprise the steps:
(1), in reactor, adds 4 parts of polysaccharide 1 (chitosan), 0.2 part of primary cross-linking agent 2 (calcium oxide), 100 parts water (containing 0.1ml/L acetic acid).Under stirring and dissolving mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 85.6 parts of monomers 6 (vinylformic acid, acrylamide), 0.2 part of initiator 5 (Sodium Persulfate and S-WAT), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 10 parts of secondary crosslinking agent 8 (1, the 4-butyleneglycol), reaction solution is distributed to reaction solution in 20 or 34 or 45 or 56 or 64 or 76 or 84 or 90 ℃ of dispersion medium (glycerine) by diverting device 9 (centrifugal pan and emulsifier unit) after mixing, treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 80 or 70 or 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (glycerine), with transfer of granules to washing reagent (ethanol and methyl alcohol, volume ratio are 8: 2), the dispersion medium 12 (glycerine) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (ethanol and methyl alcohol), with the washing reagent 14 (ethanol and methyl alcohol) of heat blowing device eliminating particle remained on surface.
Acquisition is 1mm granular disintegration 15 for particle diameter.Product is 800 times to the water absorbent rate of pure water, 100 times in physiological saline.
Example 6:
A kind of water absorbent granule, it is comprised of the raw material of following quality proportioning:
Raw materials quality compares %
Polysaccharide carrageenin 1.5%
Monomer methacrylic acid 77.5%
Acrylamide 19.32%
Initiator azo-bis-isobutyrate hydrochloride 0.18%
Linking agent primary cross-linking agent epoxy chloropropane 0.5%,
Secondary crosslinking agent N,N methylene bis acrylamide 1%
Annotate: monomer is the monomeric compound (methacrylic acid potassium, acrylamide) of neutralization bases (potassium hydroxide) part neutralization, and its degree of neutralization is 90mol% (mol ratio that is methacrylic acid potassium, methacrylic acid in the monomer is 90: 10);
Acquisition is the 2.5mm granular disintegration for particle diameter.Product is 800 times to the water absorbent rate of pure water, 140 times in physiological saline.
A kind of preparation method of water absorbent granule one-step continuous granulation, it may further comprise the steps:
(1), in reactor, adds 1.5 parts of polysaccharide 1 (carrageenin), 0.5 part of primary cross-linking agent 2 (epoxy chloropropane), 100 parts of water.Under stirring and evenly mixing nitrogen protection condition 3,10 or 20 or 30 or 40 or 50 or 60 or 70 or 80 or 90 ℃ of dissolvings.Passing ratio pump 4 adds 96.82 parts of monomers 5 (methacrylic acid, acrylamide), 0.18 part of initiator 6 (azo-bis-isobutyrate hydrochloride), 20 or 35 or 45 or 55 or 65 or 75 or 85 or 90 ℃ of initiation grafting copolymerization 7, reaction times 180 or 170 or 150 or 130 or 110 or 90 or 70 or 50 or 30 minutes.
(2), add 1 part of secondary crosslinking agent 8 (N, the N-methylene-bisacrylamide), by diverting device 9 (shear) reaction solution being distributed to 20 or 34 or 45 or 56 or 64 or 70 after reaction solution mixed spends in the dispersion medium (ethanol), treat its moulding dehydration and continue to finish graft copolymerization 10, reaction times 60 or 50 or 40 or 30 or 20 or 10 minutes.
(3), filter dispersion medium 11 (ethanol), with transfer of granules to washing reagent (methyl alcohol), the dispersion medium 12 (ethanol) that the wash-out particle surface is residual.
(4), filtration washing reagent 13 (methyl alcohol), with the washing reagent 14 (methyl alcohol) of heat blowing device eliminating particle remained on surface.Acquisition is 2.5mm granular disintegration 15 for particle diameter.Product is 800 times to the water absorbent rate of pure water, 140 times in physiological saline.
Claims (2)
1. water absorbent granule, it is comprised of the raw material of following quality proportioning:
Described monomer is the monomer that partly neutralizes through neutralization bases, and it is comprised of 0-70mol% monomer acids and 100-30mol% monomer hydrochlorate, adds up to be no more than 100mol%;
Described polysaccharide and monomer are carrying out graft copolymerization, it is transferred to allow its particle dehydration forming in the dispersion medium and continue to finish graft copolymerization, its mode is by once crosslinked control viscosity rise dispersion granulation, improves degree of crosslinking by secondary crosslinking and finishes reaction;
Described polysaccharide is a kind of or 2-7 kind arbitrary combination in starch, Rhizoma amorphophalli glucomannan, Mierocrystalline cellulose, chitosan, carrageenin, xanthan gum, the seaweed gel;
The composition of described monomer is vinylformic acid and/or its esters and other monomers: vinyl sulfonic acid, toxilic acid, styrene sulfonic acid, acrylamide and/or its esters a kind of or 2-4 kind arbitrary combination wherein;
Described neutralization bases adopts sodium hydroxide, potassium hydroxide, ammoniacal liquor a kind of or 2-3 kind arbitrary combination wherein;
Described initiator is wherein a kind of of Sodium Persulfate, Potassium Persulphate or ammonium persulphate, hydrogen peroxide thermolysis type initiator or azo-compound type initiator: azo-bis-isobutyrate hydrochloride; Initiator uses separately or arbitrary combination is used, and when using superoxide, carries out reductionoxidation polymerization with sulphite, hydrosulphite reductive agent;
Described linking agent is alkaline earth metal compound: aluminide, calcified material; Amides: N,N methylene bis acrylamide, acrylamide METHYLENE CHLORIDE ethernamine, epoxy compounds: wherein a kind of of epoxy chloropropane, polyvalent alcohol; Linking agent uses separately or arbitrary combination is used;
Described dispersion medium is alcohols: wherein a kind of of ethanol, polyoxyethylene glycol, ethylene glycol, glycerine, Polyglycerine and whiteruss; Dispersion medium uses separately or arbitrary combination is used.
2. the preparation method of a kind of water absorbent granule one-step continuous granulation claimed in claim 1 the steps include:
A, in reactor, add polysaccharide, primary cross-linking agent, add water under stirring and evenly mixing nitrogen protection condition, 10-90 ℃ of dissolving, the monomer that the passing ratio pump adds initiator, partly neutralizes through neutralization bases, temperature is controlled at the copolymerization of 20-90 ℃ of temperature initiation grafting, reaction times 30-180 minute;
B, the agent of adding secondary crosslinking, after reaction solution mixed, by extrude, spray, shear, throw away, array modes a kind of or two to five kinds in the emulsification machinery dispersing mode are distributed to reaction solution in the 20-90 ℃ of dispersion medium and finish granulation, the moulding in dispersion medium of the particle of preparation is dewatered and is continued to finish graft copolymerization, the residence time 10-80 in disperse phase minute;
C, filtration dispersion medium to washing reagent, are used the residual dispersion medium of washing reagent wash-out particle surface with transfer of granules;
D, filtration washing reagent are with the washing reagent of 40-250 ℃ of air-blast device eliminating particle remained on surface of heating;
The water absorbent granule of E, acquisition one-step continuous granulation;
Described washing reagent is the mixture of wherein a kind of of methyl alcohol, ethanol, acetone, ether or two to four kinds.
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