CN1226343C - High water absorbing and retaining composite containing magnesian clay mineral and method for preparing the same - Google Patents
High water absorbing and retaining composite containing magnesian clay mineral and method for preparing the same Download PDFInfo
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- CN1226343C CN1226343C CN 200310111336 CN200310111336A CN1226343C CN 1226343 C CN1226343 C CN 1226343C CN 200310111336 CN200310111336 CN 200310111336 CN 200310111336 A CN200310111336 A CN 200310111336A CN 1226343 C CN1226343 C CN 1226343C
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Abstract
The present invention relates to a high water absorbing and retaining agent and a preparation method thereof. A high water absorbing and retaining composite material containing magnesium clay minerals is characterized in that the composite material comprises magnesium clay minerals, water soluble unsaturated ethylene monomers and a water soluble initiator for free radical polymerization. The adding weight of the magnesium clay minerals is 2% to 300% of that of the water soluble unsaturated ethylene monomers, and the adding weight of the water soluble initiator for free radical polymerization is 0.001% to 1.0% of that of the water soluble unsaturated ethylene monomers. The preparation method is characterized in that the magnesium clay minerals are added to a solution of the water soluble unsaturated ethylene monomers, which the water soluble initiator for free radical polymerization or the water soluble initiator for free radical polymerization and a crosslinking agent are dissolved in and has the concentration of 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 of 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: vinyl water-soluble 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, the liquid absorbency rate of inhaling the calcium ions and magnesium ions aqueous solution is not high 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 inhaling the calcium ions and magnesium ions aqueous solution is higher, and salt resistance is better, is applicable to composite materials with high water absorbing and retaining performances that contains the attaclay 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 attaclay mineral, it is characterized in that: it comprises the attaclay mineral, the water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, linking agent, the interpolation weight of attaclay mineral is the 2%-300% of water-soluble vinyl unsaturated monomer, the interpolation weight of water-soluble radical polymerization initiator is that the described water-soluble vinyl unsaturated monomer of the 0.001%-1% of the unsaturated water-soluble monomer of vinyl is acrylic or methacrylic acid and alkali metal salts or ammonium salt ionic comonomer thereof, in acrylamide and the derivative nonionic monomers thereof any one, described attaclay mineral are that the chemical formula of attaclay in the aqueous layer chain clay mineral is: Mg
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O or Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, attaclay 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 water-soluble vinyl unsaturated monomer.
The preparation method who contains the composite materials with high water absorbing and retaining performances of attaclay mineral, it is characterized in that: the attaclay mineral are 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. attaclay mineral
The attaclay mineral are aqueous layer chain clay minerals, and can be divided into two big classes: chemical formula is Mg
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O often has Al in the chemical constitution, Fe, and Ni, Cu is isomorphous replacement.This type of attaclay mineral color-variable, the tool satin luster has two kinds of forms of α and β, has bigger specific surface area and pore volume.Chemical formula is Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, its structure belongs to 2: 1 type clay minerals, and it is hair-like or fibrous that form is, and is generally woollen blanket shape or earthy aggregate.Layer chain clay mineral moiety content is 50-99%.
Main physical and chemical performance and processing performance have: have positively charged ion interchangeability, water-absorbent, swelling property, dispersiveness and adsorption bleaching in water, big specific surface area and colloid index and expansion capacity.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 attaclay 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 attaclay mineral have 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.
All attaclay mineral that meet above-mentioned feature all can be used for the present invention.
The addition of attaclay mineral is the 2%-300% of water-soluble vinyl unsaturated monomer, preferred 10%-200%.
2. water-soluble vinyl unsaturated monomer
Typical water-soluble ionic-type vinyl unsaturated monomer 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).
If during the acid of water-soluble vinyl unsaturated monomer acrylic or methacrylic, its degree of neutralization is 20-100%.
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 0-0.5% (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 attaclay mineral.The deep processing of attaclay mineral comprises: the attaclay mineral superfine powder is broken to 1250 orders or thinner, and the words that are necessary are carried out the chemical conversion treatment and the surface physics of attaclay mineral and are handled.Subordinate phase is the blending dispersion of attaclay mineral and water-soluble monomer.The blending dispersion of attaclay 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 20-4000W (watt), and frequency of ultrasonic is 10 kilo hertzs-300 megahertzes.Phase III is a polymerization stage.After 20-90 ℃ of preferred 40-70C heated 1-10 hour preferred 3-7 hour, elevated temperature 10-30 ℃ was reacted 1-3 hour mixture again, so that monomer conversion 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 attaclay 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 attaclay 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 480-650, and the multiplying power of inhaling tap water is 150-300, and the multiplying power of inhaling physiological saline is 40-80.
Embodiment
Embodiment 1:
In concentration is that 15% degree of neutralization is in 100% acrylic acid solution, 300 grams, stir to add N down, and N '-methylene-bisacrylamide 0.0022 gram, Potassium Persulphate 0.225 gram, dissolving again will (chemical formula be: Mg through the attaclay mineral of superfine grinding
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O, content is greater than 50%) 10 grams add 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 110 ℃ of dryings 5 hours then.
Embodiment 2:
In concentration is that 30% degree of neutralization is in 80% acrylic acid solution, 300 grams, stir to add N down, and N '-methylene-bisacrylamide 0.022 gram, Potassium Persulphate 0.225 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
5(H
2O)
4[Si
4O
10]
2(OH)
2, content is greater than 90%) and 50 grams add wherein ultra-sonic dispersion 20 minutes.In 70 ℃ 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 following 50 ℃ of dryings of vacuum condition 5 hours then.
Embodiment 3:
In concentration is that 45% degree of neutralization is in 20% acrylic acid solution, 300 grams, stir to add N down, and N '-methylene-bisacrylamide 0.4 gram, Potassium Persulphate 0.5 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
5(H
2O)
4[Si
4O
10]
2(OH)
2, content is greater than 60%) and 30 grams add wherein, and colloidal mill disperses.In 60 ℃ of heating after 4 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 to add N down, and N '-methylene-bisacrylamide 0.0022 gram, Sodium Persulfate 0.0045 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O, content is greater than 50%) 55 grams add wherein, 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 0.022 gram, ammonium persulphate 0.0425 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O, content is greater than 90%) 50 grams add wherein ultra-sonic dispersion 20 minutes.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, stirs to add acrylamide 8.4 grams, N down, N '-methylene-bisacrylamide 0.05 gram, ammonium persulphate 0.225 gram, sodium bisulfite 0.200 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
5(H
2O)
4[Si
4O
10]
2(OH)
2, content is greater than 60%) and 50 grams add wherein ultra-sonic dispersion 20 minutes.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, stir to add N down, and N '-methylene-bisacrylamide 0 gram, Sodium Persulfate 0.0225 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
5(H
2O)
4[Si
4O
10]
2(OH)
2, content is greater than 50%) and 10 grams add wherein ultra-sonic dispersion 10 minutes.In 50 ℃ of heating after 5 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.
Embodiment 8:
In concentration is that 15% degree of neutralization is in 100% acrylamide soln, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, Sodium Persulfate 0.0115 and ammonium persulphate 0.0110 gram, dissolving, (chemical formula is: Mg with the attaclay mineral of superfine grinding again
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O, content is greater than 50%) 10 grams add 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 following 50 ℃ of dryings of vacuum condition 5 hours then.
Claims (6)
1. the composite materials with high water absorbing and retaining performances that contains the attaclay mineral, it is characterized in that: it comprises attaclay mineral, water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, the interpolation weight of attaclay 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 described attaclay mineral are that the chemical formula of attaclay in the aqueous layer chain clay mineral is: Mg
8(H
2O)
4[Si
6O
15]
2(OH)
48H
2O or Mg
5(H
2O)
4[Si
4O
10]
2(OH)
2, attaclay content is 50-99%.
2. the composite materials with high water absorbing and retaining performances that contains the attaclay 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 water-soluble vinyl unsaturated monomer.
3. the composite materials with high water absorbing and retaining performances that contains the attaclay mineral according to claim 1, it is characterized in that: the each component proportioning is: the interpolation weight of attaclay 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 attaclay 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. as claim 1 or the 3 described preparation methods that contain the composite materials with high water absorbing and retaining performances of attaclay mineral, it is characterized in that: the attaclay mineral are 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 attaclay mineral according to claim 5 is characterized in that: concrete steps are: 1). the deep processing of attaclay mineral: the attaclay mineral superfine powder is broken to 1250 orders or thinner; 2). the attaclay mineral are joined in the water soluble ethylene 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, blending dispersion, 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 20-4000W, 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; 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 200310111336 CN1226343C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing magnesian clay mineral and method for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111336 CN1226343C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing magnesian clay mineral and method for preparing the same |
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| Publication Number | Publication Date |
|---|---|
| CN1542048A CN1542048A (en) | 2004-11-03 |
| CN1226343C true CN1226343C (en) | 2005-11-09 |
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| HU228872B1 (en) * | 2007-05-31 | 2013-06-28 | Univ Szegedi | Nanocomposites of synthetised hydrogeles prepared by polymerisation of n-isopropyl-acrylamide, acrylamide and acrylacid, process for preparation thereof and their use for preparation of osmotically active hydrogeles in tissue expanding expanders |
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2003
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