CN1238418C - High water absorbing and retaining composite containing rectorite clay mineral and method for preparing the same - Google Patents
High water absorbing and retaining composite containing rectorite clay mineral and method for preparing the same Download PDFInfo
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- CN1238418C CN1238418C CN 200310111334 CN200310111334A CN1238418C CN 1238418 C CN1238418 C CN 1238418C CN 200310111334 CN200310111334 CN 200310111334 CN 200310111334 A CN200310111334 A CN 200310111334A CN 1238418 C CN1238418 C CN 1238418C
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- rectorite leng
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Abstract
The present invention relates to a high water absorbing and retaining agent with high water absorbing performance, and a preparation method thereof. A high water absorbing and retaining composite material containing rectorite clay minerals is characterized in that the high water absorbing and retaining composite material containing rectorite clay minerals comprises rectorite clay minerals, water soluble unsaturated ethylene monomers, and a water soluble initiator for free radical polymerization. The adding weight of the rectorite clay minerals is 2% to 300% of that of the water soluble unsaturated ethylene monomer, and the adding weight of the water soluble initiator for free radical polymerization is 0.001% to 1% of that of the water soluble unsaturated ethylene monomers. The preparation method is characterized in that the rectorite clay minerals are added to a solution of the water soluble unsaturated ethylene monomers, in which the soluble initiator for free radical polymerization or the soluble initiator for free radical polymerization and a crosslinking agent are dissolved, and the concentration of the solution of the water soluble unsaturated ethylene monomers is from 5% to 50%; the mixture is heated for 1 to 10 hours at 20 to 90 DEG C after dispersing treatment; granular finished products are obtained by mechanical pulverization after polymerized products are dried at 40 to 150 DEG C. The present invention has the characteristics of low cost, high solution absorption rate of absorbing water solution containing calcium and magnesium ions, favorable slat resistance and adaptability to agriculture and forestry.
Description
Technical field
The present invention relates to a kind of high water absorbing and retaining agent and preparation method thereof, especially for high water absorbing and retaining material of agroforestry and preparation method thereof.
Background technology
In recent years, the high water absorbing and retaining agent has been widely used as sanitary product, Industrial materials.In known high water absorbing and retaining agent, the kind of existing following several series: water-soluble vinyl monomer homopolymer, multipolymer, starch-grafted vinyl water-soluble mono series, cellulose graft vinyl water-soluble mono series, cross-linked carboxymethyl cellulose etc.Compound, super absorbent resin and organic compound that super absorbent resin and inorganics gel are arranged in compound series.More than in each series of products, the material cost that has is higher, the suction that has contains certain ionic concn, and particularly the liquid absorbency rate of the calcium ions and magnesium ions aqueous solution is not high, the salt tolerance that has is bad, the complex process that has, equipment requirements height.The water-absorbing-retaining material that is used for the agroforestry purpose, because material cost is higher, it is not high to inhale the liquid absorbency rate that contains the calcium ions and magnesium ions aqueous solution especially, salt resistance is poor, and its application is restricted.
Summary of the invention
The object of the present invention is to provide a kind of cost low, the liquid absorbency rate of the calcium ions and magnesium ions aqueous solution is higher, and salt resistance is better, is used for composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral of agroforestry and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: the composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral, it is characterized in that: it comprises rectorite leng clay mineral, water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, the interpolation weight of rectorite leng clay mineral is the 2%-300% of water-soluble vinyl unsaturated monomer, and the interpolation weight of water-soluble radical polymerization initiator is the 0.001%-1% of water-soluble vinyl unsaturated monomer; Described water-soluble vinyl unsaturated monomer is any one in acrylic or methacrylic acid and alkali metal salts or ammonium salt ionic comonomer, acrylamide and the derivative nonionic monomers thereof, and the rectorite leng chemical formula is Kx (H in the described rectorite leng clay mineral
2O)
4{ Al
2[AlxSi
4-xO
10] (OH)
2, rectorite leng content is 50-99%.
Also can add linking agent in the aforesaid component, the interpolation weight of linking agent is the 0-0.5% of the unsaturated water-soluble monomer of vinyl.
The preparation method who contains the composite materials with high water absorbing and retaining performances of rectorite leng clay mineral is: the rectorite leng clay mineral is joined in the water-soluble vinyl unsaturated monomer solution of the 5-50% concentration that is dissolved with water-soluble radical polymerization initiator (perhaps water-soluble radical polymerization initiator and linking agent), through after the dispersion treatment, in 20-90 ℃ of heating 1-10 hour, polymerisate is dried to water content less than 10% in 40-150 ℃ under vacuum (also can without vacuum) condition, after mechanical disintegration the particulate state finished product.
Introduce the present invention below in detail.
1. rectorite leng clay mineral
Rectorite leng is earthy shred shape more, and quality is loose, water-swellable.The rectorite leng clay mineral has polymolecularity and good special propertys such as ion exchangeable in water, they can with multiple polymer mutually compound make various excellent performances, cheap, some also brings the macromolecular material of specific function.In view of the special construction and the character of rectorite leng clay mineral, they can be prepared composite materials with high water absorbing and retaining performances with water-soluble vinyl unsaturated monomer blending dispersion in the aqueous solution.The rectorite leng clay mineral has positively charged ion interchangeability, water-absorbent, swelling property, dispersiveness in water, can adsorb a certain amount of calcium ions and magnesium ions.By the level difference analysis of orthogonal experiment, determined that the mineral content in the matrix material has considerable influence to the liquid absorbency rate that contains ionized water.So the high water absorbing and retaining agent of compound attaclay mineral has certain anti-ionomer and salt tolerance.
Rectorite leng clay mineral chemistry is composed as follows: Kx (H
2O)
4{ Al
2[AlxSi
4-xO
10] (OH)
2, content is 50-99%.
The addition of rectorite leng clay mineral is the 2%-300% of water-soluble vinyl unsaturated monomer, preferred 10%-200%.
2. water-soluble vinyl unsaturated monomer
The typical water-soluble water-soluble vinyl unsaturated monomer of ionic is: acrylic or methacrylic acid and alkali metal salts or ammonium salt thereof; Typical nonionic monomers is: acrylamide and derivative thereof.Wherein preferably vinylformic acid and sodium salt thereof or ammonium salt and acrylamide.These water-soluble vinyl unsaturated monomers can be used alone, but also also mix together.
The concentration of water-soluble vinyl unsaturated monomer in aqueous solution is 5% to saturation concentration, preferred 15-50%.Vinylformic acid can be partly or wholly to use with basic metal or ammonium compound neutral form.Degree of neutralization is 20-100% (mole).
3. water-soluble radical polymerization initiator
Being fit to this type of polymeric water-soluble radical polymerization initiator is persulphate, also redox initiation system.As: Potassium Persulphate, Sodium Persulfate, ammonium persulphate.These water soluble starters can mix use, also can fit in redox system with reducing substances such as ferrous ion, sodium bisulfite, S-WAT etc. and use.Each proportioning components is determined by the quantitative relation of chemical equation when being used.
Initiator or initiator mixture are 0.001-1.0% with respect to the consumption of water-soluble vinyl unsaturated monomer, preferred 0.05%-0.5% (weight).
4. linking agent
The linking agent that uses among the present invention contains at least two polymerisable groups.Typical linking agent has: it is crosslinked or lightly crosslinked to improve the gel-strength of high water absorbing and retaining agent that bisacrylamide such as N, N '-methylene-bisacrylamide, this type of linking agent make the high water absorbing and retaining agent form mutually at body.
With respect to the water-soluble vinyl unsaturated monomer, the consumption of linking agent is 0-1% (weight), preferred 0.005-0.2%
5. preparation method and polymeric reaction condition
Its preparation is divided into four-stage: the fs is the deep processing of rectorite leng clay mineral.The deep processing of rectorite leng clay mineral comprises: the gravity treatment of rectorite leng clay mineral, and superfine grinding, removal of impurities (as sulphur etc.), the words that are necessary are carried out the chemical conversion treatment and the surface physics of rectorite leng clay mineral and are handled.Subordinate phase is the blending dispersion of rectorite leng clay mineral and water-soluble monomer.The blending dispersion of rectorite leng clay mineral and water-soluble monomer can adopt homogenizer to carry out dispersed with stirring, disperse, also can adopt ultrasonic wave to carry out ultra-sonic dispersion with colloidal mill.If adopt ultrasonic dispersion, the power of ultrasonic generator is the 20-4000 watt, and frequency of ultrasonic is 10 kilo hertzs-300 megahertzes.Phase III is a polymerization stage.After 20-90 ℃ (preferred 50-70 ℃) heated 1-10 hour (preferred 3-7 hour), elevated temperature 10-30 ℃ was reacted 1-3 hour mixture again, so that transformation efficiency reaches greater than 98% in reactor.To be gel polymerisation product that the phase III is generated under vacuum (also can without vacuum) condition be dried to water content less than 10% in 40-150 ℃ to the quadravalence section, makes it be crushed to 0.1-5.0mm with mechanical method, obtains granular the finished product.
In this invention, adopt following method to measure and calculate the liquid absorbency rate of inhaling distilled water, tap water and physiological saline:
The powder material that takes by weighing after the 0.5-1.0g drying treatment places the 500-1000ml beaker, powder material after adding 450-900ml distilled water or tap water or taking by weighing the 0.5-1.0g drying treatment places the 150ml beaker to add 100ml0.9%NaCl solution, after leaving standstill 24 hours, with 30 order mesh screens with the gravity water elimination, weigh up gel quality affects, be calculated as follows water absorbent rate:
Liquid absorbency rate=(gel quality affects-dry powder material quality)/dry powder material quality
The present invention is by adopting cheap rectorite leng clay mineral and water-soluble vinyl unsaturated monomer elder generation blending dispersion repolymerization recombining process route, the liquid absorbency rate that obtaining thus can be fully compound, material cost is lower, inhale the calcium ions and magnesium ions aqueous solution is higher, stronger salt tolerance is arranged, better simply manufacturing process is arranged, and is applicable to the composite materials with high water absorbing and retaining performances that contains the attaclay mineral of agroforestry purpose.
The composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral that the present invention makes, material cost is than the sodium polyacrylate 20-50% that descends.The scope that orthogonal experiment records the liquid absorbency rate of this serial high water absorbing and retaining agent is: the multiplying power of inhaling distilled water is 480-800, and the multiplying power of inhaling tap water is 150-300, and the multiplying power of inhaling physiological saline is 50-80.
Embodiment
Embodiment 1:
In concentration is that 15% degree of neutralization is in 100% acrylic acid solution, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.0032 gram, Potassium Persulphate 0.0382 gram, dissolving, rectorite leng clay mineral (content is greater than 50%) 10 grams with deep processing add wherein ultra-sonic dispersion 15 minutes again.In 40 ℃ of heating after 7 hours, the reaction of 30 ℃ of elevated temperatures is 2 hours again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in following 60 ℃ of dryings of vacuum condition 4 hours then.
Embodiment 2:
In concentration is that 30% degree of neutralization is in 80% acrylic acid solution, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.020 gram, ammonium persulphate 0.491 gram, dissolving, rectorite leng clay mineral (content is greater than 90%) 50 grams with deep processing add wherein ultra-sonic dispersion 20 minutes again.In 70 ℃ of heating after 2 hours, the reaction of 10 ℃ of elevated temperatures is 2 hours again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 110 ℃ of dryings 5 hours then.
Embodiment 3:
In concentration is that 45% degree of neutralization is in 20% acrylic acid solution, 200 grams, stir and add N down, N '-methylene-bisacrylamide 0.005 gram, Potassium Persulphate 0.050 gram, dissolving, rectorite leng clay mineral (content is greater than 60%) 30 grams with deep processing add wherein again, and colloidal mill disperses.In 60 ℃ of heating after 3 hours, the reaction of 20 ℃ of elevated temperatures is 3 hours again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 150 ℃ of dryings 1 hour then.
Embodiment 4:
In concentration is that 15% degree of neutralization is in 50% acrylic acid solution, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.0019 gram, Potassium Persulphate 0.225 gram, dissolving, rectorite leng clay mineral (content is greater than 50%) 40 grams with deep processing add wherein again, and high-speed stirring was disperseed 30 minutes.In 65 ℃ of heating after 3 hours, the reaction of 25 ℃ of elevated temperatures is 1 hour again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 90 ℃ of dryings 7 hours then.
Embodiment 5:
With concentration is that 30% degree of neutralization is in 100% acrylic acid solution, 280 grams, stir and add acrylamide 20 grams down, N, N '-methylene-bisacrylamide 0.029 gram, ammonium persulphate 0.425 gram, dissolving, rectorite leng clay mineral (content is greater than 90%) 50 grams with deep processing add wherein ultra-sonic dispersion 20 minutes again.In 70 ℃ of heating after 3 hours, the reaction of 10 ℃ of elevated temperatures is 2 hours again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 90 ℃ of dryings 7 hours then.
Embodiment 6:
With concentration is that 30% degree of neutralization is in 40% acrylic acid solution, 280 grams, stir and add acrylamide 40 grams down, N, N '-methylene-bisacrylamide 0.05 gram, ammonium persulphate 0.225 gram, sodium bisulfite 0.260 gram, dissolving adds wherein ultra-sonic dispersion 20 minutes with 50 grams of the rectorite leng clay mineral (content is greater than 60%) after superfine grinding, the removal of impurities again.In 60 ℃ of heating after 3 hours, the reaction of 20 ℃ of elevated temperatures is 2 hours again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 140 ℃ of dryings 2 hours then.
Embodiment 7:
In concentration is that 15% degree of neutralization is in 100% acrylic acid solution, 300 grams, stirs to add Sodium Persulfate 0.0225 gram down, and dissolving adds wherein ultra-sonic dispersion 10 minutes with 10 grams of the rectorite leng clay mineral (content is greater than 50%) after superfine grinding, the removal of impurities again.In 50 ℃ of heating after 7 hours, the reaction of 30 ℃ of elevated temperatures is 1 hour again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in following 50 ℃ of dryings of vacuum condition 5 hours then.
Embodiment 8:
In concentration is in 15% acrylamide soln, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, Sodium Persulfate 0.0115 and ammonium persulphate 0.0160 gram, dissolving, again 10 grams of the rectorite leng clay mineral (content is greater than 50%) after superfine grinding, the removal of impurities are added wherein ultra-sonic dispersion 10 minutes.In 50 ℃ of heating after 7 hours, the reaction of 30 ℃ of elevated temperatures is 1 hour again in reactor for mixture, and the gel of generation makes its pulverizing obtain the finished product with mechanical method in 100 ℃ of dryings 4 hours then.
Claims (6)
1. the composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral, it is characterized in that: it comprises rectorite leng clay mineral, water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, the interpolation weight of rectorite leng clay mineral is the 2%-300% of water-soluble vinyl unsaturated monomer, and the interpolation weight of water-soluble radical polymerization initiator is the 0.001%-1.0% of water-soluble vinyl unsaturated monomer; Described water-soluble vinyl unsaturated monomer is any one in acrylic or methacrylic acid and alkali metal salts or ammonium salt ionic comonomer, acrylamide and the derivative nonionic monomers thereof, and the rectorite leng chemical formula is Kx (H in the described rectorite leng clay mineral
2O)
4{ Al
2[AlxSi
4-xO
10] (OH)
2, rectorite leng content is 50-99%.
2. the composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral according to claim 1 is characterized in that: also can add linking agent in the described component, the interpolation weight of linking agent is the 0-0.5% of the unsaturated water-soluble monomer of vinyl.
3. the composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral according to claim 1, it is characterized in that: the each component proportioning is: the interpolation weight of rectorite leng clay mineral is the 10%-200% of water-soluble vinyl unsaturated monomer, and the interpolation weight of water-soluble radical polymerization initiator is the 0.05-0.5% of water-soluble vinyl unsaturated monomer.
4. the composite materials with high water absorbing and retaining performances that contains the rectorite leng clay mineral according to claim 2 is characterized in that: the interpolation weight of described linking agent is the 0.005-0.2% of water-soluble vinyl unsaturated monomer.
5. the preparation method who contains the composite materials with high water absorbing and retaining performances of rectorite leng clay mineral as claimed in claim 1 or 2, it is characterized in that: the rectorite leng clay mineral is joined in the water-soluble vinyl unsaturated monomer solution of the 5-50% concentration that is dissolved with water-soluble radical polymerization initiator or water-soluble radical polymerization initiator and linking agent, through after the dispersion treatment, in 20-90 ℃ of heating 1-10 hour, polymerisate gets the particulate state finished product in 40-150 ℃ of drying after mechanical disintegration.
6. the preparation method who contains the composite materials with high water absorbing and retaining performances of rectorite leng clay mineral according to claim 5 is characterized in that: concrete steps are: 1). the deep processing of rectorite leng clay mineral: the gravity treatment of rectorite leng clay mineral, the removal of impurity; 2). blending dispersion: will contain in the water-soluble vinyl unsaturated monomer solution that the rectorite leng clay mineral joins the 5-50% concentration that is dissolved with water-soluble radical polymerization initiator or water-soluble radical polymerization initiator and linking agent, the employing homogenizer carries out dispersed with stirring or disperses with colloidal mill, or adopt ultrasonic wave to carry out ultra-sonic dispersion, if adopt ultrasonic dispersion, the power of ultrasonic generator is the 20-4000 watt, and frequency of ultrasonic is 10 kilo hertzs-300 megahertzes; 3). polyreaction: mixture in reactor in 20-90 ℃ the heating 1-10 hour after, again elevated temperature 10-30 ℃ the reaction 1-3 hour so that transformation efficiency reaches greater than 98%; 4) with the phase III polymerisate in vacuum or without being dried to water content less than 10% in 40-150 ℃ under the vacuum condition, make it be crushed to 0.1-5.0mm with the method for machinery, obtain granular the finished product.
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|---|---|---|---|
| CN 200310111334 CN1238418C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing rectorite clay mineral and method for preparing the same |
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|---|---|---|---|
| CN 200310111334 CN1238418C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing rectorite clay mineral and method for preparing the same |
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| CN1238418C true CN1238418C (en) | 2006-01-25 |
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