CN1243055C - High water absorbing and retaining composite containing calcined kaolin and method for preparing the same - Google Patents
High water absorbing and retaining composite containing calcined kaolin and method for preparing the same Download PDFInfo
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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 calcined kaolin clay is characterized in that the composite material comprises the calcined kaolin clay, a water soluble unsaturated ethylene monomer, a water soluble initiator for free radical polymerization, a crosslinking agent, wherein the adding weight of the calcined kaolin clay 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 monomer. The preparation method is characterized in that the calcined kaolin clay is added to a solution of the water soluble unsaturated ethylene monomer, which the water soluble initiator for free radical polymerization and the 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; after a polymerized product is dried under the condition of 40 to 150 DEG C, granular finished products are obtained by mechanical pulverization. The present invention has the characteristics of low cost, high solution absorption rate of calcium and magnesium ionized water solutions, favorable slat resistance and adaptability to 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 water-soluble vinyl monomer series, cellulose graft water-soluble vinyl monomer 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, and what be applicable to agroforestry contains composite materials with high water absorbing and retaining performances of calcined kaolin 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 calcined kaolin, it is characterized in that: it comprises calcined kaolin, water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, the interpolation weight of calcined kaolin 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; The metakaolinite content of undefined structure is 50-98% in the described calcined kaolin, described water-soluble vinyl unsaturated monomer is ionic comonomer or nonionic monomers, ionic comonomer is methacrylic acid and alkali metal salts or ammonium salt thereof, and nonionic monomers is acrylamide and derivative thereof.
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 calcined kaolin, it is characterized in that: calcined kaolin 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 is after drying under the 40-150 ℃ of condition, and mechanical disintegration gets the particulate state finished product; The interpolation weight of calcined kaolin is the 2%-300% of water-soluble vinyl unsaturated monomer, the interpolation weight of water-soluble radical polymerization initiator is the 0.001%-1.0% of water-soluble vinyl unsaturated monomer, and the interpolation weight of linking agent is the 0-0.5% of water-soluble vinyl unsaturated monomer; The metakaolinite content of undefined structure is 50-98% in the described calcined kaolin, described water-soluble vinyl unsaturated monomer is ionic comonomer or nonionic monomers, ionic comonomer is methacrylic acid and alkali metal salts or ammonium salt thereof, and nonionic monomers is acrylamide and derivative thereof.
Introduce the present invention below in detail.
1. calcined kaolin
Calcined kaolin is not a kaolin.
Kaolin is 1: 1 type stratiform dioctahedron silicate minerals, and structural formula is AlSi
4O
10(OH)
8Hydroxyl in its crystalline structure is main functional group and active reaction point.Calcined kaolin no matter be not exclusively to calcine or complete calcined earth, has become the metakaolinite of undefined structure from the kaolin of laminate structure, very big variation has taken place both physico-chemical properties.Surface hydroxyl disappears, and becomes the powder of how bulk pore texture; Because sloughing of water, surface functional group and active site become Si-O and AI-O key from hydroxyl; Potential of hydrogen changes, and the kaolin pH value is between 6-7, and calcined earth is reduced between the 5.6-6.1.
Calcined kaolin has special propertys such as polymolecularity 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 calcined kaolin, also 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.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.This is because calcined kaolin can adsorb a certain amount of calcium ions and magnesium ions in water.So the high water absorbing and retaining agent of compound calcined kaolin has certain anti-ionomer.
The metakaolinite content of undefined structure is 50-98% in the calcined kaolin.
The addition of calcined kaolin is the 2%-300% of water-soluble vinyl unsaturated monomer, preferred 10%-200%.
2. water-soluble vinyl unsaturated monomer
Typical ionic water-soluble 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, during any mixing more than two kinds, and ionic comonomer: nonionic monomers=99: 1 or 1: 99 (weight).
The concentration of water-soluble vinyl unsaturated monomer in aqueous solution is 5% to saturation concentration, preferred 15-40%.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 0-1% (weight), preferred 0.005-0.2%.
5. preparation method and polymeric reaction condition
Its preparation is divided into five stages: the fs is the deep processing of calcined kaolin.The calcined kaolin deep processing comprises: with calcined kaolin superfine grinding to 1250 order or thinner, the words that are necessary are carried out the chemical conversion treatment and the surface physics of calcined kaolin and are handled.Subordinate phase is for to join calcined kaolin 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.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 ℃ (preferred 40-70 ℃) 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.The quadravalence section is that the phase III polymerisate is dried to water content less than 10% under 40-150 ℃ of condition, 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 calcined kaolin and water-soluble vinyl unsaturated monomer elder generation blending dispersion repolymerization compound operational path, obtaining thus can be fully compound, material cost is lower, inhale contain certain ionic concn particularly the liquid absorbency rate of the calcium ions and magnesium ions aqueous solution big, stronger imbibition ability is arranged, stronger salt tolerance is arranged, better simply manufacturing process is arranged, be applicable to the composite materials with high water absorbing and retaining performances that contains calcined kaolin of agroforestry purpose.
The composite materials with high water absorbing and retaining performances that contains calcined kaolin 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 480-1000, and the multiplying power of inhaling tap water is 150-500, 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 0.0022 gram, Potassium Persulphate 0.0225 gram, dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein ultra-sonic dispersion 10 minutes 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 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 and add N down, N '-methylene-bisacrylamide 0.022 gram, Potassium Persulphate 0.425 gram, dissolving, calcined kaolin (content is greater than 90%) 50 grams with superfine grinding 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 150 ℃ of dryings 2 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, calcined kaolin (content is greater than 60%) 30 grams with superfine grinding add wherein again, 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 125 ℃ of dryings 4 hours 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 0.0022 gram, Potassium Persulphate 0.0225 gram, dissolving, calcined kaolin (content is greater than 50%) 60 grams with superfine grinding 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 105 ℃ of dryings 4 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 0.019 gram, ammonium persulphate 0.420 gram, dissolving, calcined kaolin (content is greater than 90%) 50 grams with superfine grinding 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 140 ℃ of dryings 3 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 0.051 gram, ammonium persulphate 0.229 gram, sodium bisulfite 0.230 gram, dissolving, calcined kaolin (content is greater than 60%) 50 grams with superfine grinding add wherein ultra-sonic dispersion 20 minutes 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 105 ℃ of dryings 4 hours then.
Embodiment 7:
In concentration is that 15% degree of neutralization is in 100% acrylic acid solution, 300 grams, stir to add Sodium Persulfate 0.0225 gram down, and dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein ultra-sonic dispersion 10 minutes again.In 50 ℃ of heating after 4 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 115 ℃ of dryings 3 hours then.
Embodiment 8:
In concentration is in 45% acrylamide soln, 300 grams, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, Sodium Persulfate 0.0119 and ammonium persulphate 0.0111 gram, dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein ultra-sonic dispersion 10 minutes 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 105 ℃ of dryings 4 hours then.
Embodiment 9:
In concentration is that 25% degree of neutralization is to add acrylamide 20 grams in 90% acrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, Potassium Persulphate 0.0125 and ammonium persulphate 0.0120 gram, dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein ultra-sonic dispersion 10 minutes again.In 40 ℃ of heating after 4 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 150 ℃ of dryings 1 hour then.
Embodiment 10:
In concentration is that 5% degree of neutralization is to add acrylamide 40 grams in 90% acrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, ammonium persulphate 0.041 gram, dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein again, and high-speed stirring was disperseed 30 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 105 ℃ of dryings 4 hours then.
Embodiment 11:
In concentration is that 40% degree of neutralization is to add acrylamide 40 grams in 90% methacrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, ammonium persulphate 0.0013 gram, dissolving, calcined kaolin (content is greater than 50%) 10 grams with superfine grinding add wherein again, and colloidal mill disperses.In 70 ℃ of heating after 1 hour, the reaction of 10 ℃ 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 140 ℃ of dryings 1 hour then.
Embodiment 12:
In concentration is that 40% degree of neutralization is to add acrylamide 40 grams in 90% methacrylic acid solution, 200 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.0025 gram, Sodium Persulfate 0.0116 and ammonium persulphate 0.0116 gram, dissolving, calcined kaolin (content is greater than 50%) 2.4 grams with superfine grinding add wherein again, and high-speed stirring was disperseed 10 minutes.In 70 ℃ of heating after 1 hour, the reaction of 20 ℃ 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 140 ℃ of dryings 1 hour then.
Embodiment 13:
In concentration is that 10% degree of neutralization is to add acrylamide 40 grams in 90% acrylic acid solution, 400 grams, dissolving, stir and add N down, N '-methylene-bisacrylamide 0.0022 gram, Sodium Persulfate 0.0115 and ammonium persulphate 0.0110 gram, dissolving, calcined kaolin (content is greater than 50%) 240 grams with superfine grinding add wherein again, and colloidal mill disperses.In 70 ℃ of heating after 1 hour, the reaction of 10 ℃ 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 140 ℃ of dryings 1 hour then.
Claims (6)
1. the composite materials with high water absorbing and retaining performances that contains calcined kaolin, it is characterized in that: it comprises calcined kaolin, water-soluble vinyl unsaturated monomer, water-soluble radical polymerization initiator, the interpolation weight of calcined kaolin 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; The metakaolinite content of undefined structure is 50-98% in the described calcined kaolin, described water-soluble vinyl unsaturated monomer is ionic comonomer or nonionic monomers, ionic comonomer is methacrylic acid and alkali metal salts or ammonium salt thereof, and nonionic monomers is acrylamide and derivative thereof.
2. the composite materials with high water absorbing and retaining performances that contains calcined kaolin 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 calcined kaolin according to claim 1, it is characterized in that: the each component proportioning is: the interpolation weight of calcined kaolin is 10%-200% times 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 calcined kaolin 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 calcined kaolin, it is characterized in that: calcined kaolin 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 is after drying under the 40-150 ℃ of condition, and mechanical disintegration gets the particulate state finished product; The interpolation weight of calcined kaolin is the 2%-300% of water-soluble vinyl unsaturated monomer, the interpolation weight of water-soluble radical polymerization initiator is the 0.001%-1.0% of water-soluble vinyl unsaturated monomer, and the interpolation weight of linking agent is the 0-0.5% of water-soluble vinyl unsaturated monomer; The metakaolinite content of undefined structure is 50-98% in the described calcined kaolin, described water-soluble vinyl unsaturated monomer is ionic comonomer or nonionic monomers, ionic comonomer is methacrylic acid and alkali metal salts or ammonium salt thereof, and nonionic monomers is acrylamide and derivative thereof.
6. the preparation method who contains the composite materials with high water absorbing and retaining performances of calcined kaolin according to claim 5 is characterized in that: concrete steps are: 1). the deep processing of calcined kaolin: with calcined kaolin superfine grinding to 1250 order or thinner; 2). the calcined kaolin of superfine grinding is 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). the phase III polymerisate is dried to water content less than 10% under 40-150 ℃ of condition, makes it be crushed to 0.1-5.0mm, obtain granular the finished product with mechanical method.
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| CN 200310111335 CN1243055C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing calcined kaolin and method for preparing the same |
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| CN 200310111335 CN1243055C (en) | 2003-11-05 | 2003-11-05 | High water absorbing and retaining composite containing calcined kaolin and method for preparing the same |
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| CN1243055C true CN1243055C (en) | 2006-02-22 |
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Families Citing this family (6)
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| CN100419027C (en) * | 2006-03-23 | 2008-09-17 | 中国地质大学（武汉） | Method for preparing high water absorption and water retention composite materials containing layer silicate mineral |
| CN103980420A (en) * | 2014-05-27 | 2014-08-13 | 河南工业大学 | Preparation method of kaolin-based water-absorbing and water-retaining material |
| CN109336717A (en) * | 2018-11-16 | 2019-02-15 | 西北师范大学 | A kind of preparation method of multi-functional concave convex rod ground mass wisdom ceramsite material |
| CN111363284B (en) * | 2020-03-23 | 2022-03-08 | 温州大学 | Shell-core structure super absorbent resin/kaolin composite ball moisture absorption material and preparation method thereof |
| CN112876624B (en) * | 2021-03-03 | 2022-03-11 | 中国科学院兰州化学物理研究所 | Preparation method of organic/inorganic composite polymer water-retaining material |
| CN113416071A (en) * | 2021-06-24 | 2021-09-21 | 嘉兴学院 | Raw material and additive manufacturing method of colorful multi-transparency dental prosthesis |
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