CN101219355A - Synthesis and application of environmental friendly humic acid surfactant - Google Patents
Synthesis and application of environmental friendly humic acid surfactant Download PDFInfo
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- CN101219355A CN101219355A CNA2007100633146A CN200710063314A CN101219355A CN 101219355 A CN101219355 A CN 101219355A CN A2007100633146 A CNA2007100633146 A CN A2007100633146A CN 200710063314 A CN200710063314 A CN 200710063314A CN 101219355 A CN101219355 A CN 101219355A
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- surfactant
- humic acid
- fulvic acid
- quaternary ammonium
- ammonium salt
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Abstract
The invention designs and synthesizes an environmental-friendly multi-functional humic acid surfactant, mainly characterized in that: (1) the humic acid surfactant is generated through the ion reaction between yellow humic acid sodium salt and quaternary ammonium; (2) the humic acid surfactant is characterized in that: a. the surfactant contains quaternary ammonium group; b, the surfactant is a complex macromolecule which takes the yellow humic acid as the main body , has no fixed compounds and can be degraded in nature. The humic acid surfactant is a multi-functional surfactant with the characterizics of general macromolecule surfactant and the special functions of the humic acid. Employed as organic pesticide penetrating agents and wetting agents, the surfactant can improve the wettability and the penetrability of the organic pesticide on the surface of the plants and the pests.
Description
Technical field
The present invention relates to a kind of environmentally friendly high molecular surfactant.
Background technology
High molecular surfactant be often referred to molecular weight greater than 1000, have surface-active functional polymer compound, its molecular structure is made up of hydrophilic chain and hydrophobic chain two parts.High molecular surfactant by sources can be divided into synthetic high polymer surfactant and natural polymeric surface active agent.The synthetic high polymer surfactant is meant the macromolecule that obtains with the polymerization of petrochemical industry derivatives monomer, as polyacrylamide derivative, polyacrylic acid etc.In a broad sense, natural polymeric surface active agent comprises the material (comprising natural gum, starch, humic-acid-type substances, microbial fermentation polysaccharide etc.) of pure natural and is primary raw material with the natural materials, handles the compound with surface active function (comprising modified starch, cellulose, humic acid, protein, shitosan etc.) that obtains through processing.
In recent years, numerous researchers were more and more to the research of natural polymeric surface active agent, because most of natural polymeric surface active agent is environmentally friendly surfactant, low toxicity own has favorable biological degradability, and were also gentle to human body.
Humic acid extensively is present in nature, is a kind of rich natural resource, soil, lake, river, and marine environment in distribution is all arranged, mainly be distributed in soil, peat, coal, the weathered coal.The resource of humic acid of China is particularly abundant.The molecular weight of humic acid is very big, usually 10
3～10
7Between.Have various active functional group in the humic acid molecule, make it have acidity, hydrophily, interfacial activity, cation exchange capacity (CEC), complexing power and absorption dispersibility etc.Humic acid has many specific functions to the growth of crops, itself is exactly green fertilizer.
Fulvic acid is as a water-soluble part preferably in the humic acid, and itself just has surface-active, and just surface-active is lower.The present invention is directed to not high this shortcoming of the surface-active of fulvic acid own, it has been carried out chemical modification, design and synthesize out the higher environmental friendly humic acid surfactant of a kind of activity.The hydrophilic radical of this surfactant is the humic acid anion, has higher molecular weight, contains various active functional group, and itself goes back biologically active.Its hydrophobic grouping is the quaternary ammonium salt of a series of different carbon chain lengths.
Summary of the invention
The high molecular surfactant that the purpose of this invention is to provide a kind of environment amenable efficient, multifunction.
Another object of the present invention is a kind of wetting agent of preparation and bleeding agent, can be used in the organic agricultural chemicals, improves the drug effect and the utilization rate of organic agricultural chemicals.
Main advantage of the present invention is:
(1) the humic acid surfactant hydrophilic radical that designs and synthesizes of the present invention is the fulvic acid sodium salt structure with ultrahigh molecular weight, and hydrophobic grouping is the quaternary ammonium salt structure with a series of different carbon chain lengths, its surface-active height.
(2) humic acid surfactant that the present invention synthesized itself has biological degradability, and low toxicity has synergistic effect to organic agricultural chemicals.
(3) humic acid surfactant that the present invention synthesized is the Mobyneb surfactant.It not only has the characteristic of general high molecular surfactant, but also has the specific function of humic acid.
(4) the designed synthetic humic acid surfactant preparation technology of the present invention is simple, and raw material sources are wide, and are cheap, environmentally friendly.
The designed synthetic humic acid surfactant preparation method uniqueness of the present invention, simple: under alkali condition, the quaternary ammonium cation of humic acid anion and different carbon chain lengths forms by the ion pair suction-operated.Its building-up process is as follows:
(1) a certain amount of fulvic acid salt is put into the there-necked flask of 250ml, and is added a certain amount of deionized water, the pH value is transferred to certain value after, under suitable mixing speed, stir certain hour.
(2) at a certain temperature, slowly add certain density M liquid by separatory funnel in there-necked flask, control pH value of solution value is reacted synthetic certain hour within the specific limits.Wherein M represents 1831 (OTACs), 1231 (DTACs), D821 (two eight alkyl-dimethyl ammonium chlorides).
(3) purification products therefrom behind the dry at a certain temperature certain hour, obtains fulvic acid type surfactant.
The test of fulvic acid type surfactant emulsifiability:
Get deionized water and the 40ml atoleine of 40ml, join in the graduated cylinder of 100ml.The fulvic acid type surfactant of getting 0.4g adds in the graduated cylinder.Firmly fluctuate 30 times, make it become emulsion, static, the needed time of 10ml water is separated out in the record layering, and the time, the long more emulsifying capacity that shows was strong more.
Measurement result shows: the emulsifiability of humic acid type surfactant (HA-1831) is best, has reached 340 seconds, and 1831 be 135 seconds, and the humic acid that does not have modification was less than 100 seconds.The emulsifying capacity height of the emulsifying capacity of modified humic acid (HA-1831) than humic acid itself is described, can be used as emulsifying agent and use.
Fulvic acid type surfactant surface wettability test:
Get and be dried to block fulvic acid type surfactant 0.1g, add deionized water and be made into 1% aqueous surfactant solution, measure its contact angles on ptfe surface down at 20 ℃.
Measurement result shows: the contact angle of humic acid type surfactant (HA-1231) is minimum, is 70.0 degree.Illustrating that humic acid type surfactant (HA-1231) can be used as is that wetting agent uses.
The mensuration of fulvic acid type surfactant surface property:
In the 100mL volumetric flask, use deionized water testing sample to be made into the solution of the different quality concentration of scope between 0.1～10g/L.Utilize the bubble platen press to measure the equilibrium surface tension γ of serial solution, make γ-lgC curve with the logarithm of surface tension and solution concentration then.With the straight line portion extension of curve break both sides, the concentration of joining is critical micelle concentration CMC.
Measurement result shows: under same solution concentration, the surface tension of humic acid type surfactant (HA-D821), critical micelle concentration (CMC) and lowest surface tension are all lower, illustrate that its surface-active is higher.The critical micelle concentration CMC of humic acid type surfactant (HA-D821) is 3.16g/L, and the lowest surface tension value is 35.64mN/m;
The test of fulvic acid type surfactant foamability:
Get the 20ml deionized water, 0.2g has been dried to block fulvic acid type surfactant, joins in the graduated cylinder of 100ml.After fulvic acid type surfactant dissolves fully, graduated cylinder is firmly fluctuated 30 times record and measure the height of the foam in the certain hour.
Measurement result shows: the foamability of humic acid type surfactant (HA-D821) is relative better with steady bubble ability.Its foaming when beginning highly is 41 centimetres, and the steady bubble after 5 minutes highly is 23 centimetres, and the steady bubble after 10 minutes highly is 18 centimetres.
The specific embodiment
Embodiment 1
(1) fulvic acid salt of 2.5g is put into the there-necked flask of 250ml, and is added the deionized water of 10ml, the pH value is transferred to 9-11 after, vigorous stirring 30min.
(2) under 50 ℃, by separatory funnel slow 1831 liquid that add 3% (mass fraction) in there-necked flask, control pH value of solution value is in the 9-11 scope, and 3h is synthesized in reaction.
(3) with products therefrom at 50 ℃ down behind the dry 48h, obtain fulvic acid type surfactant (HA-1831).
Embodiment 2
(1) fulvic acid salt of 2.5g is put into the there-necked flask of 250ml, and is added the deionized water of 10ml, the pH value is transferred to 9-11 after, at vigorous stirring 30min.
(2) under 50 ℃, by separatory funnel slow 1231 liquid that add 3% (mass fraction) in there-necked flask, control pH value of solution value is reacted Synthetic 2 h in the 9-11 scope.
(3) with products therefrom 50 ℃ down behind the dry 48h at 50 ℃ down behind the dry 48h, obtain fulvic acid type surfactant (HA-1231).
Embodiment 3
(1) fulvic acid salt of 2.5g is put into the there-necked flask of 250ml, and is added the deionized water of 10ml, the pH value is transferred to 9-11 after, vigorous stirring 30min.
(2) under 50 ℃, by separatory funnel slow D821 liquid that adds 3% (mass fraction) in there-necked flask, control pH value of solution value is in the 9-11 scope, and 3h is synthesized in reaction.
(3) with products therefrom 50 ℃ down behind the dry 48h at 50 ℃ down behind the dry 48h, obtain fulvic acid type surfactant (HA-D821).
Three embodiment of the present invention have synthesized humic acid surfactant HA-1831, HA-1231, the HA-D821 with different carbon chain lengths respectively.The present invention is applied to these three kinds of humic acid surfactants in the organic agricultural chemicals (flolimat), has prepared the surfactant solution of different quality mark concentration, and is testing the wetability of organic agricultural chemicals on leaf (the leaves of purpurea) under 16 ℃ respectively.
The result shows: humic acid type surfactant (HA-D821) is best to the wetability of organic agricultural chemicals, can reduce to 45 degree (this moment s: n: w=1: 500: 4500) to the contact angle of organic agricultural chemicals on leaf (the leaves of purpurea) by 69.5 degree (this moment s=w=0), minimum 40.5 degree (this moment s: n: w=1: 500: 500) that drop to. illustrated that humic acid surfactant of the present invention (HA-D821) can be applied in the organic agricultural chemicals (flolimat) as wetting agent, improved the wetability of organic agricultural chemicals.Wherein s is the quality of humic acid type surfactant, and n is the quality of organic agricultural chemicals (flolimat), and w is the quality of deionized water.
Claims (6)
1. the humic acid surfactant that designs and synthesizes out of the present invention is that quaternary ammonium salt by fulvic acid sodium salt and different carbon chain lengths obtains by ion-exchange.
2. according to the fulvic acid type surfactant of claim 1, wherein said fulvic acid sodium salt originates from Xinjiang two imperial humic acid company, its water-soluble 〉=85%.
3. according to the fulvic acid type surfactant of claim 1, the quaternary ammonium salt of wherein said different carbon chain lengths can be represented with following general formula:
4. according to the fulvic acid type surfactant of claim 3, wherein said quaternary ammonium salt general formula, R
1Be eight, 12 or 18 carbon saturated alkyls.
5. according to the fulvic acid type surfactant of claim 3, wherein said quaternary ammonium salt general formula, R
2, R
3And R
4Can be the same or different, be selected from the saturated alkyl of methyl or 7～10 carbon; X
-Be chlorion, bromide ion or iodide ion.
6. according to the fulvic acid type surfactant of claim 1, wherein said reactions steps is as follows:
(a) surpassing under 1000 rev/mins the stirring, sodium fulvic acid salt is scattered in the water, solid content is 10～25%, and control pH value of solution value is 9～11.
(b) under the normal temperature that quaternary ammonium salt is soluble in water, solid content is 2～5%, and the amount of the quaternary ammonium salt that is used to react is 0.024～1 times of fulvic acid sodium salt amount.
(c) under 40～80 ℃ and mixing speed are no more than 4000 rev/mins condition, dropwise add the quaternary ammonium salt solution for preparing by separatory funnel in the fulvic acid sodium salt solution, the pH that regulates mixed solution is 7～9.
(d) fully reacted 3～10 hours after, filter 50 ℃ of following vacuum drying.
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|---|---|---|---|
| CNA2007100633146A CN101219355A (en) | 2007-01-09 | 2007-01-09 | Synthesis and application of environmental friendly humic acid surfactant |
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| CNA2007100633146A CN101219355A (en) | 2007-01-09 | 2007-01-09 | Synthesis and application of environmental friendly humic acid surfactant |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012807A (en) * | 2012-12-21 | 2013-04-03 | 贵州大学 | Preparation method and application of modified humic acid quaternary ammonium salt |
| CN103788723A (en) * | 2014-02-27 | 2014-05-14 | 新疆大学 | Modified soapstone, quaternary ammonium polylactide/fulvate modified soapstone composite material and preparation methods and products thereof |
| CN104152150A (en) * | 2014-08-18 | 2014-11-19 | 四川国光农化股份有限公司 | Soil conditioning composition, its application, and soil conditioner |
| CN106587702A (en) * | 2016-11-10 | 2017-04-26 | 董晓 | Preparation method of stable-type odor-free low-density foam concrete foamer |
| CN110724535A (en) * | 2019-11-01 | 2020-01-24 | 河南城建学院 | Novel ecological garden greening soil remediation treatment agent and preparation method thereof |
-
2007
- 2007-01-09 CN CNA2007100633146A patent/CN101219355A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012807A (en) * | 2012-12-21 | 2013-04-03 | 贵州大学 | Preparation method and application of modified humic acid quaternary ammonium salt |
| CN103788723A (en) * | 2014-02-27 | 2014-05-14 | 新疆大学 | Modified soapstone, quaternary ammonium polylactide/fulvate modified soapstone composite material and preparation methods and products thereof |
| CN103788723B (en) * | 2014-02-27 | 2015-06-24 | 新疆大学 | Modified soapstone, quaternary ammonium polylactide/fulvate modified soapstone composite material and preparation methods and products thereof |
| CN104152150A (en) * | 2014-08-18 | 2014-11-19 | 四川国光农化股份有限公司 | Soil conditioning composition, its application, and soil conditioner |
| CN106587702A (en) * | 2016-11-10 | 2017-04-26 | 董晓 | Preparation method of stable-type odor-free low-density foam concrete foamer |
| CN106587702B (en) * | 2016-11-10 | 2018-10-12 | 厦门合智新材料科技有限公司 | A kind of preparation method of the odorless low density foam concrete foamer of stable type |
| CN110724535A (en) * | 2019-11-01 | 2020-01-24 | 河南城建学院 | Novel ecological garden greening soil remediation treatment agent and preparation method thereof |
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Open date: 20080716 |