CN1502638A - Agricultural moisture-retaining material made of stalk protofibril graft acrylate derivative and mfg method - Google Patents
Agricultural moisture-retaining material made of stalk protofibril graft acrylate derivative and mfg method Download PDFInfo
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- CN1502638A CN1502638A CNA021532044A CN02153204A CN1502638A CN 1502638 A CN1502638 A CN 1502638A CN A021532044 A CNA021532044 A CN A021532044A CN 02153204 A CN02153204 A CN 02153204A CN 1502638 A CN1502638 A CN 1502638A
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Abstract
The present invention relates to a water-retaining material obtained by copolymerizing straw raw fibre and acrylic acid derivative and its preparation process. Said process includes the following steps: adding cross-linking agent and initiator in acrylic acid derivative monomer, then adding modified straw powder and initiation adjuvant, in the solution, uniformly stirring them, drying and pulverizing so as to obtain the invented water-absorbing resin.
Description
Technical field
The present invention relates to a kind of agricultural water-keeping material, relate in particular to the copolymerization water-keeping material that a kind of stalk protofibril graft acrylic acid (salt) class obtains, and the manufacture craft of this water-keeping material.
Background technology
Water-keeping material has very high water-retaining capacity, has been used as water-holding agent, sanitary material, spices sustained release dosage of agricultural, forestry etc.Except that the requirement of water-retaining capacity, general also the requirement has higher water retention capacity, and for the water-holding agent that is used in farming, woods crop in a large number, also edatope etc. is easily degraded, do not destroyed to special requirement.
Present industrial production strong water absorbent mainly contains two big classes, and synthetic is that water-absorbing resin and grafting are water-absorbing resin.Synthetic is that water-absorbing resin is to use maximum super absorbent resins in the present industry, wherein has the electrolytical polymer of ionic, particularly has the crosslinked body of polymer of carboxyl, and water-absorbent is strong especially, thereby vinylformic acid has obtained maximum application in the SAP field.At present, world SAP mostly is sodium polyacrylate greatly.Form the water-retaining agent that obtains by olefinic monomer polymerization or multiple monomer copolymerization, its water-intake rate has reached 500-900, and at the aqueous phase polymeric acrylic acid, water-intake rate reaches 850g/g as people's (openly speciallyying permit communique, clear 57-40749) such as wooden paddy Mays.Upright people's (openly speciallyying permit communique, clear 55-58205) such as adopted will with vinylformic acid and polyethyleneglycol diacrylate in the aqueous phase copolymerization, obtain the water-retaining agent of 1189g/g.But this synthetic resins cost of material cost height based on vinylformic acid is difficult to big area popularization on agricultural.
Grafting is that water-absorbing resin mainly is with natural polysaccharide compounds grafting olefinic monomer.The grafting raw material mainly is starch, Mierocrystalline cellulose, also has protein, pectin, chitosan etc.Grafted monomer can be one or more, and its water-intake rate is satisfactory, have up to more than the 1000g/g.Adopt antiphase emulsifiable method as Zou Xinxi, with starch and water in 1: the ratio of 4-10 adds reactor, be heated to 80-95 ℃, make it gelatinization, be cooled to room temperature, add dispersion medium normal hexane (being the twice of water), emulsifier tween (1-2%), vinylformic acid (2-3 of starch doubly), adding Potassium Persulphate again with the neutralization of 40% sodium hydroxide again--ferrous sulfate causes, and logical nitrogen stirs, and is heated to 40-50 ℃, reacted 2-4 hour, and obtained the water-retaining agent of water-intake rate 1000-1400g/g after product filtration, washing, the drying.This method has partly been alleviated environmental stress, also reduced cost, but its raw material still uses highly purified starch and Mierocrystalline cellulose, reversed-phase polymerization uses a large amount of expensive organic solvents---normal hexane, the production cost height, can not be in agricultural large-scale application, this grafting is that water-absorbing resin does not also have industrialized prospect.And because starch-grafted polymerization or cellulose graft aggretion type SAP are in a disadvantageous position than polyacrylic acid (salt) at aspects such as industrialization aftertreatment and storings.
Summary of the invention
The purpose of this invention is to provide a kind of water-intake rate height, water regain is big, and is with low cost, and the grafting that is easy to prepare is a water-absorbing resin, and this resin is suitable for large-scale promotion use on agricultural.
Further aim of the present invention provides the making method that this grafting is a water-absorbing resin.
Grafting of the present invention is that water-absorbing resin is the polymkeric substance of agricultural crop straw and acrylate derivative, stalk accounts for 16%-55% (W/W) in this polymkeric substance, acrylate derivative accounts for 45-84% (W/W), phosphoric acid salt accounts for 0.1-5.0% (W/W), the content of urea accounts for 0.8-5.0% (W/W), and wherein carboxylic acrylic monomer accounts for the 10-50% of total monomer weight in the acrylate derivative monomer.
Described grafting is that the preparation method of water-absorbing resin comprises the steps:
A) straw powder is broken into the powder of 20-200 order granularity;
B) with adding the solution that phosphoric acid salt and urea are made into, soak straw powder and make its swelling; Wherein the consumption of urea accounts for the 5-10% of straw powder quality in this solution, the phosphoric acid salt consumption accounts for the 1-10% of stalk quality, then at 40 ℃--and insulation is 2-24 hour in 60 ℃ the baking oven, is warmed up to 80-160 ℃ at last, be incubated 2-5 hour, obtain the modified stalk powder after the water evaporates;
C) under the room temperature acrylate derivative monomer is made the aqueous solution, during preparation acrylate derivative monomer solution, the water yield of adding is controlled at 2-4 times of raw material gross weight (comprising monomer and stalk); Add linking agent and initiator then, stir, the consumption of linking agent accounts for the 0.01-2% of raw material (comprising monomer and stalk) gross weight, and the consumption of initiator is the 0.01-2% of monomer total amount; Wherein carboxylic acrylic monomer accounts for the 10-50% of monomer total amount in the acrylate derivative monomer;
D) with b) step the modified stalk powder and c that obtain) in solution mix, the mass ratio of modified stalk powder and polymerization single polymerization monomer is at 0.2-1: between 1, stir, stir fast after adding aided initiating, the consumption of aided initiating is the 0.01-2% of monomer total amount;
E) stir pre-polymerization 2-6 hour down at 60-80 ℃, reheat was by 90-120 ℃ of polymerization 2-6 hour, and oven dry is pulverized then.
In the described step a), crushed stalk is to the above better effects if of 60 orders, the more little polyreaction that helps more of the particle of pulverizing.Used stalk can be wheat stalk, broomcorn straw and rape stalk.
Phosphoric acid salt in the step b) preferably can be from being sodium phosphate (potassium), SODIUM PHOSPHATE, MONOBASIC (potassium), Sodium phosphate dibasic (potassium), tripoly phosphate sodium STPP (potassium) etc.
Step is from c) the consumption of linking agent to account for the consumption of 0.2-0.5% of raw material (comprising monomer and stalk) gross weight more suitable.The concentration of the acrylic acid derivative aqueous solution is an important factor, and concentration is too big, is difficult to evenly the product performance instability when mixing with modified stalk powder, linking agent and initiator; Polymerization difficulty when the water yield is excessive.
The quality optimization ratio of straw powder and polymerization single polymerization monomer is 0.4-0.7 in the step d): between 1.
The used acrylate derivative monomer of the present invention is selected from following several monomer, and wherein first kind contains carboxylic monomer and be essential thing, and preferred proportion is the 15-30% that accounts for acrylate derivative monomer total amount.
Specifically comprise:
1) contains carboxylic monomer, be acrylic or methacrylic acid or the mixture of the two.
2) carboxylic acid group's salt monomer, carboxylic acid group and 1) identical, its salt has sylvite, sodium salt, ammonium salt, amine salt etc.As sodium acrylate, sodium methacrylate, vinylformic acid trolamine, methacrylic acid trolamine etc.,
3) ester or ether monomer such as Jia Jibingxisuanyizhi, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate, methacrylic acid second triethyleneglycol ester, vinylformic acid second triethyleneglycol ester etc.;
4) amide-containing monomer:
1. acrylamide, Methacrylamide etc.
2. the N-alkyl acrylamide wherein alkyl be the straight or branched alkyl of C1 to C6, as N methacrylamide, N-hexyl acrylamide etc.
4. N-hydroxyalkyl acrylamide, wherein alkyl is the alkyl of C1 to C3, as N-hydroxyethyl acrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-hydroxypropylmethyl acrylamide etc.
5. N, N-dihydroxyalkyl acrylamide, wherein alkyl is alkyl such as the N of C1 to C3, N-dihydroxy ethyl Methacrylamide, N, N-dihydroxypropyl acrylamide.
The linking agent that the present invention uses can be selected for use from following several classes:
1) polyvalent alcohol: ethylene glycol, glycerol, polyoxyethylene glycol, polyglycerol etc.
2) bisacrylamide, two Methacrylamide: as N, N-methylene bis acrylamide, N, N '-methylene-bisacrylamide.
3) can form the polyvalent metal compounds of ion-exchange, comprising having:
1. alkaline earth metal compound: as magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium acetate, magnesium acetate etc.
2. Zinc compounds: as zinc oxide, zinc hydroxide, zinc acetate etc.
The linking agent that the present invention uses must be water miscible, can use the mixture of one or more 2-3 kinds.
The oxidation-reduction trigger system that uses among the present invention can be selected for use from following several classes: hydrogen peroxide-ferrous sulfate, ammonium persulfate-sodium bisulfite, Potassium Persulphate-ferrous sulfate, Potassium Persulphate-Sulfothiorine or hydrogen peroxide-L-xitix.
The invention has the advantages that, greatly reduce raw materials cost with the stalk for the grafting raw material, both utilized the effective constituent in the stalk, realize straw-returning, turn waste into wealth, create certain economic benefits, product of the present invention with compare in the product that 30: 100 ratio grafting goes out with paper pulp and vinylformic acid, cost has reduced 15-20%.On the other hand, the water-keeping material that makes of the present invention overcomes the shortcoming that simple polyacrylic acid water-holding agent is difficult for degraded.Utilize degradable polyose natural component in the stalk, it is grafted on the olefinic monomer.Owing to cellulosic degraded, original macromolecules degradation is that small molecules is degraded or the part degraded, alleviates the destroyed degree of soil after water-holding agent has been brought into play water retention.In addition, the invention provides, mild condition simple than the organic phase converging operation, technology aqueous polymerization production method with low cost, whole process need not expensive raw material, three-waste free discharge, thus realize friendly process.
Embodiment 1
A) straw powder is broken into the powder of 40-60 order granularity; B) take by weighing 100 and restrain the wheat stalk powder that has crushed, put into 1 gram SODIUM PHOSPHATE, MONOBASIC, 5 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 10 hours, took out in 3 hours 140--160 ℃ of insulation then, obtain the modified stalk powder.C) at room temperature, vinylformic acid 50 grams, sodium acrylate 225 grams and acrylamide 225 grams are added beaker together, be made into the aqueous solution of 1500 grams; In solution, add 0.7 gram polyoxyethylene glycol (400), 1.2 gram ammonium persulphate, stir, d) modified stalk of handling well is added in the aqueous solution, back adding 0.6 gram sodium bisulfite stirs, continue to be stirred to temperature and no longer raise, e) place 60 ℃ of baking oven insulations 2 hours, be incubated 3 hours in the steam oven about 120 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 182 times of water-intake rates.
Each main ingredient content of product: stalk 16.34%, vinylformic acid 8.4%, sodium acrylate and acrylamide 74.3%, phosphoric acid salt 0.16%, urea 0.8%
Embodiment 2
A) straw powder is broken into the powder of 30-50 order granularity; B) take by weighing the wheat stalk powder that 100 grams have crushed, put into 10 gram SODIUM PHOSPHATE, MONOBASIC, 10 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 10 hours, took out in 3 hours 140--160 ℃ of insulation then, obtain the modified stalk powder.C) at room temperature, 50 gram methacrylic acids, 50 gram sodium acrylate preparations are added beaker, be mixed with the aqueous solution of 1200 grams; In solution, add 0.24 gram N,N methylene bis acrylamide, 0.4 gram magnesium hydroxide, 1.2 gram ammonium persulphates stir; D) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram sodium bisulfite, continues to be stirred to temperature and no longer raises.E) place 60 ℃ of baking oven insulations 2 hours, be incubated 3 hours in the steam oven about 120 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 123 times of water-intake rates.
Each main ingredient content of product: stalk 45.6%, methacrylic acid 22.7%, sodium acrylate 22.7%, phosphoric acid salt 4.5%, urea 4.5%
Embodiment 3
A) straw powder is broken into the powder of 70-90 order granularity; B) take by weighing 100 and restrain the wheat stalk powder that has crushed, put into 8 gram sodium phosphates, 6 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 10 hours, took out in 6 hours 140-160 ℃ of insulation then, obtain the modified stalk powder.C) at room temperature prepare the 1100 gram aqueous solution, contain 80 gram vinylformic acid, contain 150 gram potassium acrylates, 56 gram methacrylic ethyl esters; In solution, add 0.24 gram N,N methylene bis acrylamide again, 0.15 gram polyglycerol, 0.08 gram magnesium acetate, 2 grams, 30% hydrogen peroxide stirs; D) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram L-xitix, continues to be stirred to temperature and no longer raises.E) place 80 ℃ of baking oven insulations 3 hours, be incubated 3 hours in the steam oven about 100 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 210 times of water-intake rates.
Each main ingredient content of product: stalk 25%, vinylformic acid 20%, potassium acrylate 37.5%, methacrylic ethyl ester 14.0%, phosphoric acid salt 2%, urea 1.5%
Embodiment 4
A) straw powder is broken into the powder of 40-60 order granularity.B) take by weighing 100 and restrain the broomcorn straw powder that has crushed, put into 8 gram Sodium phosphate dibasics, 8 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 10 hours, took out in 3 hours 140--160 ℃ of insulation then, obtain the modified stalk powder.C) at room temperature prepare the 1000 gram aqueous solution, wherein contain 45 gram vinylformic acid, contain 100 gram sodium acrylates and 39 gram N methacrylamides; Add 0.7 gram polyoxyethylene glycol (400) again in solution, 1.2 gram ammonium persulphates stir.D) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram Sulfothiorine, continues to be stirred to temperature and no longer raises.E) place 60 ℃ of baking oven insulations 2 hours, be incubated 6 hours in the steam oven about 90 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 232 times of water-intake rates.Each main ingredient content of product: stalk 33.3%, vinylformic acid 15.0%, sodium acrylate 33.3%N ,-Methacrylamide 13.0%, phosphoric acid salt 2.7%, urea 2.7%
Embodiment 5
A) straw powder is broken into the powder of 40-60 order granularity.B) take by weighing 100 and restrain the wheat stalk powder that has crushed, put into 10 gram SODIUM PHOSPHATE, MONOBASIC, 5 gram urea and 200 ml waters, fully stir, mix, place 40 ℃ baking oven to be incubated 10 hours, took out in 3 hours 80-100 ℃ of insulation then.C) at room temperature prepare the aqueous solution that 1100 grams contain the acrylamide of 63 gram vinylformic acid, 257 gram sodium acrylates and 50 grams.Add 0.7 polyoxyethylene glycol (400), 1.2 gram ammonium persulphates, d stirs) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram sodium bisulfite, continues to be stirred to temperature and no longer raises.E) place 70 ℃ of baking oven insulations 2 hours, be incubated 3 hours in the steam oven about 120 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 238 times of water-intake rates.Each main ingredient content of product: stalk 20.5.3%, vinylformic acid 12.9%, sodium acrylate 52.7%,, acrylamide 10.2%, phosphoric acid salt 2.0%, urea 1.0%
Embodiment 6
A) straw powder is broken into the powder of 40-60 order granularity.B) take by weighing 100 and restrain the rape straw that has crushed, put into 8 gram sodium phosphates, 6 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 20 hours, took out in 3 hours 140-160 ℃ of insulation then.C) at room temperature prepare the aqueous solution that 1100 grams contain 80 gram vinylformic acid, 150 gram ammonium acrylates and 56 gram Jia Jibingxisuanyizhis; In solution, add 0.24 gram N,N methylene bis acrylamide, 0.15 gram polyglycerol, 0.08 gram magnesium acetate, 1.2 gram ammonium persulphates stir.D) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram-L-xitix, continues to be stirred to temperature and no longer raises.E) place 60 ℃ of baking oven insulations 6 hours, be incubated 3 hours in the steam oven about 120 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 112 times of water-intake rates.Each main ingredient content of product: stalk 25%, vinylformic acid 20%, potassium acrylate 37.5%, methacrylic ethyl ester 14.0%, phosphoric acid salt 2%, urea 1.5%
Embodiment 7
A) straw powder is broken into the powder of 40-60 order granularity.B) take by weighing 100 and restrain the broomcorn straw powder that has crushed, put into 10 gram SODIUM PHOSPHATE, MONOBASIC, 8 gram urea and 200 ml waters, fully stir, mix, place 50 ℃ baking oven to be incubated 10 hours, took out in 3 hours 140--160 ℃ of insulation then.C) at room temperature prepare the 900 gram aqueous solution, wherein contain 30 gram methacrylic acids, 100 gram sodium acrylates and 228 gram N, N-dihydroxypropyl acrylamide; In solution, add 0.7 polyoxyethylene glycol (400), 1.2 gram ammonium persulphates, d stirs) modified stalk of handling well is added in the aqueous solution, the back that stirs adds 0.6 gram sodium bisulfite, continues to be stirred to temperature and no longer raises.E) place 60 ℃ of baking oven insulations 2 hours, be incubated 3 hours in the steam oven about 120 ℃ again.Discharging, below 120 ℃ the oven dry, pulverize product, 94 times of water-intake rates.Each main ingredient content of product: stalk 30%, vinylformic acid 10%, sodium acrylate 33.3%, N, N-dihydroxypropyl acrylamide 17.3%, phosphoric acid salt 3.3%, urea 2.7%.
Claims (7)
1, a kind of grafting is a water-absorbing resin, it is characterized in that: comprise agricultural crop straw and acrylate derivative polymeric polymer substance, wherein straw content is 16%-55% (W/W), acrylate derivative accounts for 45-84% (W/W), phosphoric acid salt accounts for 0.1-5.0% (W/W), and the content of urea is 0.8-5.0% (W/W); Wherein carboxylic acrylic monomer accounts for the 10-50% of total monomer weight in the acrylate derivative monomer.
2, a kind of described grafting of claim 1 is the preparation method of water-absorbing resin, comprises the steps:
A) straw powder is broken into the powder of 20-200 order granularity;
B) with adding the solution that phosphoric acid salt and urea are made into, soak straw powder and make its swelling; The consumption of urea accounts for the 5-10% of straw powder quality in this solution, and the phosphoric acid salt consumption accounts for the 1-10% of stalk quality, is incubated 2-24 hour then in 40 ℃-60 ℃ baking oven, is warmed up to 80-160 ℃ at last, is incubated 2-5 hour, obtains the modified stalk powder after the water evaporates;
C) under the room temperature acrylate derivative monomer is made the aqueous solution, in the acrylate derivative monomer solution of being prepared, the water yield of adding is controlled at 2-4 times of raw material gross weight; Add linking agent and initiator then, stir, the consumption of linking agent accounts for the 0.01-2% of raw material gross weight, and the consumption of initiator is the 0.01-2% of total monomer weight; Wherein carboxylic acrylic monomer accounts for the 10-50% of total monomer weight in the acrylate derivative monomer;
D) with b) step the modified stalk powder and c that obtain) in solution mix, the mass ratio of straw powder and polymerization single polymerization monomer is at 0.2-1: between 1, stir, stir fast after adding aided initiating, the consumption of aided initiating is the 0.01-2% of monomer total amount;
E) stir pre-polymerization 2-6 hour down at 60-80 ℃, reheat was by 90-120 ℃ of polymerization 2-6 hour, and oven dry is pulverized then.
3, grafting as claimed in claim 2 is the preparation method of water-absorbing resin, it is characterized in that crushed stalk is to more than 60 orders in the step a).
4, grafting as claimed in claim 2 is the preparation method of water-absorbing resin, it is characterized in that phosphoric acid salt is selected from sodium phosphate, potassiumphosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, tripoly phosphate sodium STPP and Potassium tripolyphosphate in the step b).
5, grafting as claimed in claim 2 is the preparation method of water-absorbing resin, it is characterized in that the consumption of linking agent in the step c) accounts for the 0.2-0.5% of raw material gross weight.
6, grafting as claimed in claim 2 is the preparation method of water-absorbing resin, it is characterized in that in the step c) that carboxylic acrylic monomer in the acrylate derivative monomer accounts for the 15-30% of total monomer weight.
7, grafting as claimed in claim 2 is the preparation method of water-absorbing resin, it is characterized in that initiator and aided initiating are selected from: hydrogen peroxide-ferrous sulfate, ammonium persulfate-sodium bisulfite, Potassium Persulphate-ferrous sulfate, Potassium Persulphate-Sulfothiorine or hydrogen peroxide-L-xitix.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02153204 CN1225490C (en) | 2002-11-26 | 2002-11-26 | Agricultural moisture-retaining material made of stalk protofibril graft acrylate derivative and mfg method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02153204 CN1225490C (en) | 2002-11-26 | 2002-11-26 | Agricultural moisture-retaining material made of stalk protofibril graft acrylate derivative and mfg method |
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| CN1225490C CN1225490C (en) | 2005-11-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101173157B (en) * | 2007-10-15 | 2010-06-02 | 东北林业大学 | Water-loss reducer using waste pouce or Chinese medicine slag and wastepaper as raw material, and production method thereof |
| CN101215359B (en) * | 2007-12-29 | 2010-08-11 | 大连海事大学 | Micro-flow column discharge method for grafting corn straw and methyl methacrylate |
| CN101838171A (en) * | 2010-05-21 | 2010-09-22 | 山东大学 | Straw-based amphoteric liquid manure controlled-release agent and application thereof |
| CN101735396B (en) * | 2009-12-31 | 2011-10-26 | 陕西科技大学 | Method for preparing super absorbent resin by using wheat straw |
| CN102604644A (en) * | 2012-02-27 | 2012-07-25 | 甘肃源岗农林开发有限公司 | Ecological water-retaining agent used for restoring saline lands, and preparation method thereof |
| CN102859064A (en) * | 2010-04-23 | 2013-01-02 | 吉姆诺布莱恩有限公司 | Method for producing functional polyester fiber, and polyester products using functional polyester fiber |
| CN104029268A (en) * | 2014-06-17 | 2014-09-10 | 镇江市高等专科学校 | Preparation method of crop bean straw fiber composite material |
| CN108753303A (en) * | 2018-06-29 | 2018-11-06 | 陕西省土地工程建设集团有限责任公司 | A kind of method that bio-waste prepares soil conditioner |
| CN109503778A (en) * | 2018-11-28 | 2019-03-22 | 河南农业大学 | A kind of preparation method of offal base composite hydrogel |
| CN115946200A (en) * | 2022-11-30 | 2023-04-11 | 优优新材料股份有限公司 | Method for treating straws for artificial boards by adopting iron ion compounds |
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2002
- 2002-11-26 CN CN 02153204 patent/CN1225490C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173157B (en) * | 2007-10-15 | 2010-06-02 | 东北林业大学 | Water-loss reducer using waste pouce or Chinese medicine slag and wastepaper as raw material, and production method thereof |
| CN101215359B (en) * | 2007-12-29 | 2010-08-11 | 大连海事大学 | Micro-flow column discharge method for grafting corn straw and methyl methacrylate |
| CN101735396B (en) * | 2009-12-31 | 2011-10-26 | 陕西科技大学 | Method for preparing super absorbent resin by using wheat straw |
| CN102859064A (en) * | 2010-04-23 | 2013-01-02 | 吉姆诺布莱恩有限公司 | Method for producing functional polyester fiber, and polyester products using functional polyester fiber |
| CN101838171A (en) * | 2010-05-21 | 2010-09-22 | 山东大学 | Straw-based amphoteric liquid manure controlled-release agent and application thereof |
| CN101838171B (en) * | 2010-05-21 | 2012-10-24 | 山东大学 | Straw-based amphoteric liquid manure controlled-release agent and application thereof |
| CN102604644A (en) * | 2012-02-27 | 2012-07-25 | 甘肃源岗农林开发有限公司 | Ecological water-retaining agent used for restoring saline lands, and preparation method thereof |
| CN102604644B (en) * | 2012-02-27 | 2015-03-11 | 甘肃源岗农林开发有限公司 | Ecological water-retaining agent used for restoring saline lands, and preparation method thereof |
| CN104029268A (en) * | 2014-06-17 | 2014-09-10 | 镇江市高等专科学校 | Preparation method of crop bean straw fiber composite material |
| CN108753303A (en) * | 2018-06-29 | 2018-11-06 | 陕西省土地工程建设集团有限责任公司 | A kind of method that bio-waste prepares soil conditioner |
| CN109503778A (en) * | 2018-11-28 | 2019-03-22 | 河南农业大学 | A kind of preparation method of offal base composite hydrogel |
| CN115946200A (en) * | 2022-11-30 | 2023-04-11 | 优优新材料股份有限公司 | Method for treating straws for artificial boards by adopting iron ion compounds |
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| CN1225490C (en) | 2005-11-02 |
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