CN106674519A - Preparation method of special polyaspartic acid for agriculture - Google Patents
Preparation method of special polyaspartic acid for agriculture Download PDFInfo
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- CN106674519A CN106674519A CN201510756296.4A CN201510756296A CN106674519A CN 106674519 A CN106674519 A CN 106674519A CN 201510756296 A CN201510756296 A CN 201510756296A CN 106674519 A CN106674519 A CN 106674519A
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- phosphoric acid
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Abstract
The invention discloses a preparation method of special polyaspartic acid for agriculture, which comprises the steps of placing aspartic acid in a polymerization reactor, directly stirring at normal pressure for polymerizing the aspartic acid, and leading the constant temperature for polymerization to be 160-270 DEG C and leading the thermal insulation time to be 0.5-5 hours; then adopting the way of one-time feeding or slow adding for adding a catalyst of phosphoric acid in materials, carrying out continuous polymerization in the polymerization reactor at the normal pressure, leading the constant temperature for the polymerization to be 160-230 DEG C and leading the thermal insulation time to be 0.5-5 hours; and finally adding alkali for hydrolysis.; The ratio of the aspartic acid to the catalyst of the phosphoric acid by parts by weight is 100:1-35, and the content of the phosphoric acid is 85%. The method can ensure the fluidity of the materials, avoid the lumping problem of the materials and realize the large-scale production. Phosphate ions in the catalyst are taken as nutritional elements required by growth of crops, and the catalyst does not need to be separated, thereby eliminating water washing and other processes, simplifying production process and reducing manufacturing cost.
Description
Technical field
The present invention relates to a kind of preparation method of polymeric amino acid, refers in particular to prepare a kind of method for being suitable for agricultural is applied, molecular weight in the poly-aspartate of 5000-50000.
Background technology
Proved according to scientific worker's years of researches, reasonable economic fertilization, be one of important measures that crop yield increases matter, therefore fertilising is the material base of high yield and high quality.But, utilization rate of fertilizer is low to annoying always numerous agriculturists.
Poly-aspartate is a kind of polymer of amino acid, and in addition to the property with water-soluble polymeric carboxylic acid, the characteristic also easily degraded is a kind of extremely wide, nontoxic, pollution-free, the degradable environmentally friendly chemicals of purposes for it.The poly-aspartate of different molecular weight can be widely applied to the fields such as water process, fertilizer synergist, washing assisant, cosmetics, hydrogel.Poly-aspartate gradually obtains the accreditation of people as a kind of fertilizer synergist, its excellent performance.
United States Patent (USP) US 5593947 discloses a kind of method (Method for more efficient uptake of of more effective promotion plant growth Nutrient Absorption
Plant growth nutrients), it is 3000-100000 to disclose as the most suitable molecular weight ranges of fertilizer synergist.It is more preferable in the poly-aspartate effect of 5000-50000 as fertilizer synergist molecular weight according to our research.
Liu Jianliang et al. is in Zhongkai University of Agriculture And Technology (21 (2)：52-56,2008) once reported in " synthesizing and its in application agriculturally for the poly-aspartic-acid " text delivered, with ASPARTIC ACID (ASP) as primary raw material, the molecular weight 1000-5000 of the poly-aspartate produced by direct thermal condensation；PSI is generated by raw material oligomerisation or copolymerization of maleic acid, maleic anhydride, fumaric acid etc., the poly-aspartate molecular weight that further hydrolysis is generated is also than relatively low.The molecular weight of the poly-aspartate that both the above method is produced does not reach the requirement of fertilizer synergist (molecular weight 5000-50000).
Chinese patent application 200610085649.3 discloses a kind of preparation method of high molecular weight polyasparagic acid, it is characterized in that processing step point, raw material proportioning：With aspartic acid as raw material, catalyst mixing is added；2nd, polycondensation reaction：Temperature 160-240 DEG C, vacuum 0.08-0.09Mpa, time 1-2 hour；3rd, pulverize, cross 100 mesh sieves；4th, repeat step two, three；5th, it is washed to neutrality；6th, 80 DEG C of constant pressure and dries 2 hours, the weight average molecular weight of gained poly-aspartate is in 20000-200000.Above method is only realized in the lab, effect polymerisation in industrial processes due to catalyst is quickly carried out, granular aspartic acid becomes tacky, caking during polymerization dehydration, hinders the normal operation of system, it is difficult to realize in large-scale industry reactor.
Chinese patent 01141663.7 discloses a kind of synthetic method of poly-aspartic-acid, it is with asparatate as raw material, in the presence of acidic, under nitrogen, normal pressure or vacuum condition are passed through in biaxial kneader, in the range of 150～350 DEG C, constant temperature prepared powder Jing washings in 0.5～6 hour, dry prepared polysuccinimide, then Jing are hydrolyzed, precipitate, filter, are dried to obtain poly-aspartic-acid.The problem run well because of reaction caking obstruction system in course of reaction is overcome, molecular weight product is up to 1000-180000, and product colour is shallow, and quality is high.The poly-aspartate molecular weight of the method production has reached the requirement of fertilizer synergist, but this method is the stirring intensity by increasing equipment, material agglomeration problems in reaction are solved, big to the having high demands of equipment, equipment investment in production operation, operating cost is high；In addition, the removal of catalyst further increases production cost.
Above-mentioned technology is all just to add catalyst at the initial stage of reaction and make polymerisation accelerate, moisture can be deviate from when being polymerized due to aspartic acid, plus the moisture that catalyst is brought into, these moisture can all enter material, so as to cause the tacky caking of material, and make material gradually be hardened as moisture is steamed from material, therefore, it is difficult to realizing large-scale industrial production.
The content of the invention
The technical problem to be solved in the invention there is provided a kind of economical and efficient, be suitable for the poly-aspartate preparation method of agricultural application, and prepared poly-aspartate molecular weight is in 5000-50000.
To solve above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of agriculture special poly-aspartate, it is raw materials used for asparatate, comprise the steps
The first step, preliminary polymerization
Asparatate is placed in polymer reactor, directly stirring makes asparatate be polymerized under normal pressure, between 160-270 DEG C, temperature retention time is 0.5-5 hours to the thermostat temperature of polymerization；
Second step, catalytic polymerization
Add catalyst phosphoric acid in the material of Jing first steps reaction, polymerization is continued in polymer reactor under normal pressure, between 160-230 DEG C, temperature retention time is 0.5-5 hours to the thermostat temperature of polymerization；
3rd step, alkaline hydrolysis obtains agriculture special poly-aspartate, and its molecular weight is between 5000-50000.
The present invention further concrete scheme be：The quality parts ratio of the asparatate and catalyst phosphoric acid is：100∶1-35.That is the addition of phosphoric acid is rested between the mass fraction 1～35% of asparagine acid starting material.
The present invention further concrete scheme be：The catalyst phosphoric acid is food-grade that content is 85% or PHOSPHORIC ACID TECH.GRADE.
The present invention further concrete scheme be：The addition manner of catalyst phosphoric acid is by the way of once adding or as reaction is slowly added to.
As a result of above-mentioned technical proposal, the technological progress that the present invention is obtained is：
The technical scheme is that first make asparatate without direct polymerization in the case of catalyst to a certain extent after, add catalyst phosphoric acid, make polymerisation proceed that poly-aspartate is obtained.The major advantage of the method is：Through the polymerization of the first step, most of material has been dehydrated, then through 160-270 DEG C of high temperature evaporation, the water of major part abjection is steamed from material；Now add catalyst to continue to be polymerized, be now polymerized produced by the water yield substantially reduce, so as to ensure that the mobility of material, it is to avoid material agglomeration problems.Solve the rapid dehydration that occurs because the initial stage in polymerisation just adds catalyst to carry out fast reaction in prior art and when material the drawbacks of become sticky, lump, it is possible to achieve large-scale production.
The advantage for making catalyst from phosphoric acid is：First, phosphoric acid is as catalyst from the food-grade or PHOSPHORIC ACID TECH.GRADE that content is 85%, not only raw material is easy to get, phosphoric acid is finally in the form of phosphate anion in product, and phosphate anion is exactly the nutrient required for plant growth, so not needing separating catalyst, the processes such as washing are eliminated, production procedure is simplified, manufacturing cost is reduced.In addition, using phosphoric acid does catalyst, be not only able to accelerate reaction speed, and the molecular weight ranges of obtained poly-aspartate are big, and its molecular weight is just being suitable in the range of the 5000-50000 that crops use.The addition of catalyst phosphoric acid is conducive to reaction to carry out for the 1～35% of asparatate mass fraction, and is suitable for the ratio for agriculturally using.
Because poly-aspartate agriculturally using when be all by the way of the aqueous solution, it is also to be added to by the way of the aqueous solution in chemical fertilizer when remanufacturing chemical fertilizer, and technical scheme is directly obtained final products --- the aqueous solution of poly-aspartate after catalytic polymerization by the way of hydrolysis, agricultural production is can be directly used for.Therefore dry process is eliminated, further shorten flow process, reduce production cost.
Technological progress acquired by above, in guarantee product on the premise of agriculturally using effect, reduces conjunction
Into requirement of the process to equipment, equipment investment is reduced, shorten production procedure, improve yield, reduce cost, be a kind of poly-aspartate preparation method of economical and efficient.Being slowly added to of catalyst phosphoric acid is conducive to that what is reacted to be smoothed out.
Specific embodiment
The present invention is described in further details with reference to specific embodiment：
Embodiment 1
Under condition of normal pressure, by 50.0KgL- asparatates, in adding kneader, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 10 minutes, temperature of charge reaches 180 DEG C in chamber, constant temperature 30 minutes at 180 DEG C, evaporates part moisture.Then phosphoric acid (technical grade) 0.5Kg was slowly added in 60 minutes, is continued constant temperature and is stopped heating after 30 minutes, polymerization terminates.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 5000.The detection of molecular weight product in example, entrusts the Hebei Academy of Sciences energy to be detected, similarly hereinafter.
Embodiment 2
Under condition of normal pressure, by 50.0KgL- asparatates, in adding pan dryer, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 10 minutes, temperature of charge reaches 200 DEG C in chamber, constant temperature 90 minutes at 200 DEG C.It is disposable to add phosphoric acid (technical grade) 5Kg, continue constant temperature and stop heating after 120 minutes, polymerization terminates.By the product cooling, add water and sodium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 18000.
Embodiment 3
Under condition of normal pressure, by 50.0KgL- asparatates, in adding kneader, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 15 minutes, temperature of charge reaches 270 DEG C in chamber, constant temperature 60 minutes at 270 DEG C.Then 160 DEG C were reduced the temperature in 39 minutes, phosphoric acid (technical grade) 2Kg is now disposably added, after continuing constant temperature 180 minutes at 160 DEG C heating is stopped, polymerization terminates.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 10800.
Embodiment 4
Under condition of normal pressure, by 50.0KgL- asparatates, in adding pan dryer, rotating speed is 20 turns/
Minute, heat up simultaneously in whipping process, after 10 minutes, temperature of charge reaches 220 DEG C in chamber, at 220 DEG C
Constant temperature 120 minutes.Then phosphoric acid (technical grade) 5Kg is disposably added, is continued constant temperature and is stopped heating after 60 minutes, polymerization terminates.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 12800.
Embodiment 5
Under condition of normal pressure, by 50.0KgL- asparatates, in adding kneader, rotating speed is 10 revs/min, is heated up simultaneously in whipping process, and after 13 minutes, temperature of charge reaches 230 DEG C in chamber, constant temperature 90 minutes at 230 DEG C.Then phosphoric acid (technical grade) 1Kg is disposably added, is continued constant temperature and is stopped heating after 30 minutes, polymerization terminates.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 15300.
Embodiment 6
Under condition of normal pressure, by 50.0KgL- asparatates, in adding pan dryer, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 10 minutes, temperature of charge reaches 200 DEG C in chamber, constant temperature 180 minutes at 200 DEG C.Then phosphoric acid (technical grade) 17.5Kg was slowly added in 60 minutes, is continued constant temperature and is stopped heating after 120 minutes.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 48000.
Embodiment 7
Under condition of normal pressure, by 50.0Kg asparatates, in adding pan dryer, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 10 minutes, temperature of charge reaches 160 DEG C in chamber, constant temperature 300 minutes at 160 DEG C.Then phosphoric acid (technical grade) 17.5Kg was slowly added in 60 minutes, is continued constant temperature and is stopped heating after 300 minutes.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 50000.
Embodiment 8
Under condition of normal pressure, by 50.0KgL- asparatates, in adding pan dryer, rotating speed is 20 revs/min, is heated up simultaneously in whipping process, and after 10 minutes, cavity temperature reaches 210 DEG C, constant temperature 90 minutes at 210 DEG C.Then phosphoric acid (technical grade) 10Kg was slowly added in 60 minutes, is continued constant temperature and is stopped heating after 120 minutes.By the product cooling, add water and potassium hydroxide hydrolysis, obtain solid content for 40% poly-aspartate solution.
After testing the molecular weight of poly-aspartate is 35000.
The preferred embodiment for the present invention is the foregoing described, the present invention is not limited to.Those skilled in the art can carry out the improvement and change without departing from scope and spirit to embodiment disclosed herein.Therefore the modification without departing substantially from essence of the invention is fallen within the scope of the invention.
Claims (3)
1. a kind of preparation method of agriculture special poly-aspartate, raw materials used for asparatate, it is characterised in that：Comprise the steps
The first step, preliminary polymerization
Asparatate is placed in polymer reactor, directly stirring makes asparatate be polymerized under normal pressure, between 160-270 DEG C, temperature retention time is 0.5-5 hours to the thermostat temperature of polymerization；
Second step, catalytic polymerization
To in the material of Jing first steps reaction plus the quality parts ratio of catalyst phosphoric acid, the asparatate and catalyst phosphoric acid is：100: 1-35, continue polymerization in polymer reactor under normal pressure, between 160-230 DEG C, temperature retention time is 0.5-5 hours to the thermostat temperature of polymerization；
3rd step, alkaline hydrolysis obtains agriculture special poly-aspartate.
2. the preparation method of a kind of agriculture special poly-aspartate according to claim 1, it is characterised in that the catalyst phosphoric acid is food-grade that content is 85% or PHOSPHORIC ACID TECH.GRADE.
3. the preparation method of a kind of agriculture special poly-aspartate according to claim 1, it is characterised in that the addition manner of the catalyst phosphoric acid is by the way of once adding or as reaction is slowly added to.
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| CN201510756296.4A CN106674519A (en) | 2015-11-10 | 2015-11-10 | Preparation method of special polyaspartic acid for agriculture |
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| CN201510756296.4A CN106674519A (en) | 2015-11-10 | 2015-11-10 | Preparation method of special polyaspartic acid for agriculture |
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Application publication date: 20170517 |