CN1228360C - One-step synthesis process of producing biodegradable high-hydroscopicity resin directly with corn powder - Google Patents
One-step synthesis process of producing biodegradable high-hydroscopicity resin directly with corn powder Download PDFInfo
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Abstract
The present invention relates to a one-step synthesis method for directly producing the biodegradable resin with high water absorption through corn flour, which belongs to a chemical synthesis method for a high molecular material, particularly to a production method for synthetic resin. The one-step synthesis method is a combined method of natural high molecular artificial polymerization and high molecular graft copolymerization. The resin with high water absorption produced by traditional starch is changed into the resin with high water absorption directly produced by corn flour; and therefore, a two-step process from corn to starch to the resin with high water absorption is changed into a one-step process from corn flour to the resin with high water absorption. Peat is added in a reaction raw material to improve the performance. A heat crosslinked technique is carried out through an exothermic reaction, and the temperature is easily controlled. A product is not gelatinized by starch, not filtered, not washed or not protected by nitrogen, and the technology is simple. Raw materials are all generated to products, and the yield is high. By-products and waste materials do not exist in a reaction. The one-step synthesis method has the advantages of no pollution and low cost, and can realize mass production. The water absorption ratio of the product averagely reaches 800 to 1000 times, and the product can be degraded by organisms to solve the problem of the water shortage of farm crops. Simultaneously, the one-step synthesis method also has wide application prospect in the aspect of water saving materials.
Description
Technical field
The chemical industry synthetic method that the invention belongs to macromolecular material specially refers to the production method of synthetic resins.Super absorbent resin is to have the low crosslinking degree of many hydrophilic radicals or the high molecular polymer of partially crystalline, so it has the characteristic of general macromolecular compound, as: macromolecule, complicated structure etc.Also have the water retaining function that the gentle slow release of quick suction is put simultaneously, the chemical reaction of synthesizing high-hydroscopicity resin and reaction mechanism and rule, basic and general polymer chemistry reacting phase is together.
Background technology
Water resources problems is the major issue of puzzlement countries in the world survival and development.Especially in recent years, along with the development of industrial and agricultural production, the lack of water phenomenon is more and more serious, and countries in the world take different modes to solve " water shortage " one after another.China is one of serious water shortage country in the world, and arid and semi-arid area area reaches 565.86 ten thousand square kilometres, accounts for 58.6% of area.Water saving improves the utility value of existing water resources and has mentioned on the important schedule of national development.
Super absorbent resin is the new functional macromolecule material of exploitation in nearly more than 30 years, has excellent suction and water retention property.Traditional water-absorbent material such as paper, sponge and cotton etc. can only absorb the water of about several times to 20 times of own wts, and water retention capacity is very poor, and water will be extruded during pressurized.The super absorbent resin water-retaining capacity is strong especially, can absorb the own wt hundred times to several thousand times water, forms the gelinite of Peng Run after the water-swelling, and water retention capacity is extremely strong, and very also dehydration is seldom under the high pressure.It possesses the advantage of functional high molecule material again simultaneously, be widely used in every field such as agricultural, gardening, medicine, medical treatment, physiological hygiene, oil, chemical industry, building materials, environmental protection, food, artificial intelligence material, sensitive material, biochemical technology, papermaking, weaving, daily, makeup, become indispensable material in people's daily life and the national economy.The agricultural aspect contains a large amount of hydrophilic groups and has the three-dimensional space network structure owing to super absorbent resin, so its energy water-absorbing-retaining, reaches saving water, resisting drought and protects entropy, reduces the volatilization and the loss of agricultural chemicals and chemical fertilizer, strengthens fertilizer efficiency and drug effect.Strengthen soil water permeability and ventilation property simultaneously, form the bank of water and air naturally, the soil day and night temperature is dwindled in plant roots.Created good microbial environment for plant seed germination, growth.Aspect health, super absorbent resin also is applied to baby's paper nappy, personal hygiene article etc., and the super water-retaining capacity of super absorbent resin and water retention capacity make the lighting of physiological hygiene product, miniaturization.
The kind of super absorbent resin is a lot, and multiple sorting technique is arranged.Common method is the method by the raw material sources classification that Wen Pinqian two proposes.Can be divided into 6 big series, i.e. starch system, cellulose-based, synthesized polymer system, protein system, blend and compound system and other natural goodses and the system of deriving thereof.
1961, the USDA north C.R.Russell of institute etc. developed starch-grafted acrylonitrile copolymer first, and its water-retaining capacity is 300-1000 a times of own wt.Thereafter the U.S., Japan have carried out a large amount of research to the synthetic and application of super absorbent resin.The kind of super absorbent resin is on the increase in recent years, and range of application constantly enlarges, and production quantity improves year by year.China is the research that begins this respect from the eighties, synthetic at first sodium polyacrylate super absorbent resin in the chemical the country one belongs in nineteen eighty-two Chinese Academy of Sciences Beijing, water-retaining capacity is 400 times of own wt, and patent and the bibliographical information about super absorbent resin increases gradually afterwards.Beginning in 1988 has patent, successively there be more than 40 unit to be engaged in the research of this respect, for example, units such as Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences, Beijing chemistry institute of the Chinese Academy of Sciences, Xinjiang chemistry institute, Hubei chemistry institute, Guangzhou chemistry institute conduct a research the earliest, Chinese Academy of Sciences Changchun should be changed many units such as institute, Beijing University of Chemical Technology, Jilin Petroleum chemical research institute, Wuhan University, University Of Tianjin, Chengdu Univ. of Science ﹠ Technology and also carry out the research of High hydrophilous resin afterwards, thereby makes super absorbent resin form fast-developing situation.
The synthetic method of starch-grafted propenyl monomer class super absorbent resin is a lot, the principal reaction process is that starch is under action of evocating, form elementary starch free radical, elementary free radical generates the free radical monomer with monomer reaction again, further obtain the monomer-polymer chain that is connected on the starch molecule, i.e. a graftomer after the chainpropagation again.Multipolymer is undertaken crosslinked by thermopositive reaction, but free radical can form on monomer sometimes, obtains not amyloid monomer-polymer, i.e. homopolymer.In fact, the starch graft copolymer product is the mixture of graftomer and homopolymer.
The technological process of prior synthesizing method is as follows:
Earlier starch and water are mixed, starch under agitation is dispersed in the water uniformly, be heated to 50-95 ℃, reaction was carried out 0.5-2 hour.Gelatinization point and time, and different, the mass ratio of water and starch was generally 4-20: 1 with the starch kind.Continue after the gelatinization to stir to be cooled to normal temperature, so that carry out graft copolymerization.
Remove oxygen in the reactive system to the logical nitrogen of cooled reaction solution then, add initiator, monomer and linking agent again, constantly stir, at a certain temperature, reacted 2-5 hour.Polyreaction major control ratio of components, temperature of reaction and reaction times.They have difference with the requirement of response situation and water-absorbing material, and in general, starch is 2.0-0.5 with the monomer mass ratio: 1; Initiator is monomeric 0.1-1%, and is relevant with initiator type; Temperature of reaction is 25-80 ℃.
In reaction solution, add alkali again and be neutralized to the pH value for 6-8.The used alkali that neutralizes is sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide etc.Mixed solution after the neutralization filters and washs through whizzer (or strainer).Water, methyl alcohol, ethanol, acetone etc. are adopted in washing.Product after filtering and washing, because the size of particle is uneven, what have sticks together, and need pulverize with pulverizer, is screened into qualified product." the super water-retaining agent research of starch graft copolymer acrylamide manufacturing " (Huaqiao University's journal (natural science edition) the 20th is rolled up in October, 1999 the 4th phase).
Traditional synthetic method has several shortcomings: (1) starch needs gelatinization, needs heating, the waste resource.(2) because monomer concentration is lower, and rate of polymerization is slower, plant factor and throughput are lower.(3) because the existence of solvent must be adopted retrieving arrangement, the product needed that reaction obtains is filtered, washing, causes the loss of raw material, also produces the waste water, waste residue etc. that environment there are pollution in the reaction process.(4) equipment is many, complex process, and the productive rate of product is low.
" the super water-retaining agent research of starch graft copolymer acrylamide manufacturing " (Huaqiao University's journal (natural science edition) the 20th is rolled up in October, 1999 the 4th phase).
These shortcomings cause super absorbent resin to produce difficulty, and cost is too high, is unfavorable for environmental protection, makes big industrial production infeasible.Also make its application on agricultural can not get large-area popularization.
Summary of the invention
In order to solve the problem that the traditional synthetic method of super absorbent resin exists many shortcomings to cause its scale operation to be difficult to realize, in order to seek a kind of simple production method of super absorbent resin, reduce cost, be beneficial to environmental protection, special this invention of development of increasing economic efficiency.
Technological process of the present invention is as follows:
(1) configuration of neutralizer: the sodium hydrate solid of accurate weighing certain mass is mixed with certain density solution.The propenyl compound of weighing certain mass again under continuous stirring condition, joins sodium hydroxide solution and carries out neutralization reaction in the propenyl compound.After question response is complete, stops stirring neutralizer is cooled off gradually.
(2) graft copolymerization: in the same container, under continuous agitation condition, the Semen Maydis powder and the peat dust of certain mass successively joined in the neutralizer that is cooled to certain temperature.Steady temperature stirs 30min, and starch and peat dust are uniformly dispersed.Add a certain amount of initiator, linking agent more slowly.Constant temperature 1.5h.Question response liquid fades to translucent viscous fluid, adds certain amount of ammonia water, and the pH value of system is transferred to 5-9.Behind the static 15min, the system reaction is emitted gas to finishing.
(3) aftertreatment of product: product is processed into little bulk, is placed in the baking oven, be dried to constant weight at a certain temperature.Through broken, pulverizing, obtain particle or pulverous super water-absorbent composite.
Technology key of the present invention is raw-material selection, raw-material proportioning, and temperature controlling comprises the consumption of potential of hydrogen, Semen Maydis powder and the peat dust of neutralizer, the consumption of initiator.The temperature of reaction system is controlled in 20-40 ℃ the scope.Raw material is Semen Maydis powder, peat dust, propenyl monomer (vinylformic acid, vinyl cyanide etc.), sodium hydroxide, initiator, linking agent, ammoniacal liquor.Proportioning between them is: the ammoniacal liquor 10-20ml of Semen Maydis powder 3-20g, peat dust 1-5g, propenyl monomer 40-60g, sodium hydroxide 20-30g, initiator 0.35-1.6g, linking agent 0.1-0.8g and 25% (weight), reaction system cumulative volume 150-200ml.Scale operation can be amplified in proportion.
The present invention has following major advantage:
(1) direct method
We know, Maize Production goes out the starch 50-100% that can rise in value.But technological processs such as immersion, separation are arranged.Produce a large amount of waste water and smell.Starch based high-absorbent material research is both at home and abroad carried out graft copolymerization all from starch.And we from corn directly, the direct production High hydrophilous resin.It can become " corn-(starch)-super absorbent resin " step direct reaction to two steps of " corn-starch " and " starch-super absorbent resin ".Semen Maydis powder does not need gelatinization in our technology, and system does not just need too high temperature, has saved the energy.And the minimizing production process, reduce production costs, make production simpler; Simultaneously, got rid of and in the Starch Production the big water gaging that environment brought has been polluted, helped environment protection.Open up new road for China's corn deep processing, can make corn one step increment 10-15 doubly.
(2) make raw material with peat dust
The peat incomplete decomposing that is the marsh plant remains in crossing wet and anaerobic environment and the hover ground plastid that contains organic and humic acids that forms.We select peat do prepared using peat itself-a little characteristics, improve the part character of High hydrophilous resin.
The organic matter of peat, content of humic acid height, fibre content is abundant, and loose porous, ventilating permeable is good, and specific surface area is big, and the absorption sequestering power is strong, and stronger ion-exchange capacity and salt balance controllability are arranged.For super absorbent resin provides big molecular skeleton, the utilization ratio of super absorbent resin is improved.At the solid soil in agriculture hillside fields, prevent that sand ground from leaking on, very high use value is all arranged.
The free radical of peat humic acid belongs to the semiquinone structure, can be oxidized to quinone, can be reduced to phenol again, plays an important role in the redox of plant materials, has higher biological activity and physiological stimulation effect.More help the biological degradation of super absorbent resin.
Humic acid in peat has the effect of stronger suction drought resisting, disease-resistant, anti-low temperature, anti-salt marsh, has the comprehensive green effect that improves fertilizing soil, the volatilization of minimizing fertilizer, raising utilization rate of fertilizer and pesticide efficacy, the absorption of minimizing hazardous and noxious substances, enhancing plant stress-resistance ability, improves crop quality, increase crop yield.The High hydrophilous resin of making raw material with peat can reach very high multiple on water-retaining capacity, also improved many-sided performance of super absorbent resin simultaneously.
(3) one-step synthesis
Our invented technology is compared with traditional production method, does not need the nitrogen protection, and product is one-step synthesis in process of production, and without processes such as saponification, filtration, washings, equipment is simple, reaction is continuous, has improved usage ratio of equipment and throughput.The raw material that adds all generates product, does not have by product, and productive rate improves greatly.In reaction process, reduced the loss of raw material.The single stage method production process technology is simple, the production process normal temperature and pressure.In " one pot ", finish.Utilization is finished the heat cross-linking reaction from heat release, and technology advanced person is with short production cycle, the production efficiency height, and water-saving and electricity-saving is energy-conservation.Equipment and raw material domesticize fully, make that cost reduces, scale operation is easier, more feasible.
After this invention is promoted, there is not industrial waste to produce in process of production, three waste discharges such as no waste water, no waste gas, no waste residue, pollution-free, help the protection of environment.The product that obtains can not only water-absorbing-retaining, and water regain reaches 1000 times of own wt, and can inhale fertile protect fertile, inhale medicine and protect medicine, reach saving water, resisting drought, soil moisture conservation, reduce the loss and the volatilization of agricultural chemicals.It can make soil form crumb structure in soil, and soil water permeability and ventilation property are strengthened, and forms a water and air bank naturally in plant roots, reduces day and night temperature.It can not only the water conservation drought resisting like this, and the structure of improving the soil, and strengthens fertilizer efficiency, strengthens the anti-diseases prevention ability of crop, has created good micro-ecological environment for budding, growth, growth, promotes crop precocity, volume increase.Except being used for farm crop, also can be used for forestry, also can be used for multiple industries such as gardening, herbal medicine plantation, petrochemical complex, building, food, medicine, fishery, bright development prospect is arranged.To in the national economic development, make great contribution.
Description of drawings
Accompanying drawing is the process flow sheet of the one-step method for synthesizing of Semen Maydis powder direct production biodegradable super absorbent resin.
Embodiment
Optimum implementation of the present invention is: at normal temperatures, compound concentration is the sodium hydroxide solution 85ml of 26% (weight), slowly joins behind the cool to room temperature in the propenyl monomer of 60g, constantly stirs to make to react completely.Be cooled to 35 ℃.Successively add the peat dust of 11g Semen Maydis powder, 1g under continuous stirring condition, Semen Maydis powder, peat dust are uniformly dispersed, constant temperature stirs 30min.The initiator, the 0.2g linking agent that add 0.7g more slowly successively, constant temperature stirring reaction 2h.Add 17ml ammoniacal liquor, reaction system can react to finishing after leaving standstill 10min.120 ℃ of oven dry down, broken, pulverizing obtains flaxen powdery product the product that obtains, and is water absorbent rate and on average reaches 800-1000 the finished product doubly.
Claims (2)
1; a kind of one-step method for synthesizing of producing the biodegradable super absorbent resin; it is characterized in that its technological process is as follows: the configuration of neutralizer: with sodium hydrate solid; be mixed with the solution that concentration is 26% (weight); under continuous stirring condition; sodium hydroxide solution joined carry out neutralization reaction in the propenyl compound; after question response is complete; stopping to stir cools off neutralizer gradually; graft copolymerization: in the same container; under continuous agitation condition; Semen Maydis powder and peat dust successively join in the neutralizer that is cooled to 20-24 ℃; steady temperature; stirred 30 minutes; starch and peat dust are uniformly dispersed; add initiator more slowly; linking agent; constant temperature 1.5 hours; question response liquid fades to translucent viscous fluid; add ammoniacal liquor; the pH value of system is transferred to 5-9; after static 15 minutes; the system reaction; emit gas to finishing; the aftertreatment of product: product is processed into little bulk; be placed in the baking oven; under 20-24 ℃ temperature, be dried to constant weight, through broken; pulverize, obtain particle or pulverous super water-absorbent composite; the raw material Semen Maydis powder; peat dust; the propenyl monomer; sodium hydroxide; initiator; linking agent; proportioning between the ammoniacal liquor is: Semen Maydis powder 3-20g; peat dust 1-5g; propenyl monomer 40-60g; sodium hydroxide 20-30g; initiator 0.35-1.6g; the ammoniacal liquor 10-20ml of linking agent 0.1-0.8g and 25% (weight), reaction system cumulative volume 150-200ml, scale operation can be amplified in proportion.
2, one-step method for synthesizing according to the described production biodegradable of claim 1 super absorbent resin, it is characterized in that: at normal temperatures, compound concentration is the sodium hydroxide solution 85ml of 26% (weight), slowly join behind the cool to room temperature in the propenyl monomer of 60g, constantly stir and make complete reaction, be cooled to 35 ℃, constantly successively adding the 11g Semen Maydis powder under the stirring condition, the peat dust of 1g, make Semen Maydis powder, peat dust is uniformly dispersed, constant temperature stirred 30 minutes, the initiator that adds 0.7g more slowly successively, 0.2g linking agent, constant temperature stirring reaction 2 hours adds 17ml ammoniacal liquor, reaction system can react after leaving standstill 10 minutes to finishing, the product that obtains is dried fragmentation down at 120 ℃, pulverize, obtain flaxen powdery product.
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| CN 03127061 CN1228360C (en) | 2003-06-06 | 2003-06-06 | One-step synthesis process of producing biodegradable high-hydroscopicity resin directly with corn powder |
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| CN 03127061 CN1228360C (en) | 2003-06-06 | 2003-06-06 | One-step synthesis process of producing biodegradable high-hydroscopicity resin directly with corn powder |
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| CN1228360C true CN1228360C (en) | 2005-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268994B (en) * | 2008-04-30 | 2010-10-13 | 东北师范大学 | Preparation of Chinese medicine health care pedicure mud and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100516097C (en) * | 2007-08-17 | 2009-07-22 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by solution polymerization process |
| CN100532411C (en) * | 2007-08-17 | 2009-08-26 | 广东工业大学 | Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization |
| CN103739784A (en) * | 2014-01-15 | 2014-04-23 | 东北师范大学 | Diatomite composite super-absorbent resin material and preparation method thereof |
| CN109853326B (en) * | 2019-03-18 | 2021-03-05 | 乐途景辰(浙江)体育有限公司 | Football court layer structure with natural lawn surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268994B (en) * | 2008-04-30 | 2010-10-13 | 东北师范大学 | Preparation of Chinese medicine health care pedicure mud and use method thereof |
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