CN101096395A - Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin - Google Patents
Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin Download PDFInfo
- Publication number
- CN101096395A CN101096395A CNA2007100525828A CN200710052582A CN101096395A CN 101096395 A CN101096395 A CN 101096395A CN A2007100525828 A CNA2007100525828 A CN A2007100525828A CN 200710052582 A CN200710052582 A CN 200710052582A CN 101096395 A CN101096395 A CN 101096395A
- Authority
- CN
- China
- Prior art keywords
- acid series
- persimmon tannin
- acrylic acid
- solution
- hydroscopic high
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for synthesizing persimmon tannic solution -acrylic acid series high polymer absorbent resin, which is characterized by the following: applying the reversed phase suspension polymerization method; putting skellysolve B in the autoclave with the jacket; adding the neutralized sodium acrylate solution, cross linker, initiating agent and persimmon tannic solution. The specific procedure comprises the following steps: weighing the material; synthesizing; discharging the reaction solution; separating the reaction solution with drier. The invention is provided with the simple technological process, which can control the synthesizing temperature effectively, accelerates the polymerization speed, doesn't pollute the environment, and has the high assurance coefficient and the low cost. The persimmon tannic solution -acrylic acid series high polymer absorbent resin is provided with the macromolecular weight, the high water absorption ratio, the wide usage on industry, agriculture, general goods, medical treatment or the like.
Description
Technical field
The present invention relates to the material field, the method for particularly a kind of synthetic persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin.
Background technology
In prior art, the synthetic method of acrylic acid series hydroscopic high-molecular resin mainly adopts methods such as solution polymerization, inverse suspension polymerization.Solution polymerization is simple to operate, non-environmental-pollution, shortcoming is that the heat that reaction is produced is difficult to distribute, the tensio-active agent that traditional inverse suspension polymerization method is used seldom, general as suspension agent, make synthetic hydroscopic high-molecular resin viscosity too high, suction back molecular chain can not disperse, be bulk congeries (see figure 1), the consequence of bringing thus is often to be difficult to carry out in common reactor, aftertreatment is difficulty very, and the molecular chain that does not reach hydroscopic high-molecular resin is nanometer degree dispersive particular requirement.
Summary of the invention
Technical problem to be solved by this invention is: at the defective of prior art existence, the method of a kind of maneuverable synthetic persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin is provided, this method synthetic product water-intake rate height, the homogeneously dispersed state that can in the aqueous solution, be nanoscale, therefore it is fit to do the energy storage solution material etc. that water-retaining agent, heavy metal chelating agent, deicing fluid subsidiary material, height solidify-dissolve latent heat, has the wide industrial purposes.
The present invention adopts the synthetic persimmon tannin solution of the method for following steps-acrylic acid series hydroscopic high-molecular resin, specifically:
(1) weighing:
By weight, the proportioning of each reactant is: 20～200 parts of normal hexanes, 1～12 part of persimmon tannin solution, 0.5～100 part of anion surfactant, N, 0.01～0.5 part of N '-methylene-bisacrylamide, 0.01～1 part of ammonium persulphate, 10～50 parts in vinylformic acid, 3～10 parts in sodium hydroxide, 8～20 parts in water;
(2) synthetic:
The reactant that takes by weighing is added in the reactor, feed nitrogen and stir under react, under normal pressure, make then progressively to be warmed up to 60～70 ℃ in the reactor and to react; The entire reaction time is 1～4 hour;
(3) after reaction finishes, make reactor reduce to room temperature, emit reaction soln again;
(4) with drier separating reaction solution: will be finished product after the reaction mass drying that dry, and isolated unreacted reactant uses after giving over to.
The present invention compared with prior art has following major advantage:
Synthesis technique flow process of the present invention is simple, can effectively control synthesis temperature, not only polymerization velocity is fast, do not cause environmental pollution, production safety coefficient height, production cost is low, and increasing after the amount of surfactant of using institute's synthetic persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin in synthetic, to have a molecular weight big, owing to contain a large amount of tensio-active agents, tensio-active agent becomes inierpeneirating network structure with the molecular chain of described hydroscopic high-molecular resin, the molecular chain of macromolecular chain and tensio-active agent interacts after the resin suction, the molecular resin chain is disperseed, rapidly in the aqueous solution under the effect of stirring tool, can be in the aqueous solution homodisperse, the length of molecular chain is the number nanometer, thereby has improved water-intake rate, and water-intake rate is for absorbing more than 800 times of own wt.
Synthetic persimmon tannin solution of the present invention-acrylic acid series hydroscopic high-molecular resin, can be used as at aspects such as industry, agricultural, daily necessities, health cares and have extensive use, be particularly suitable for doing the uses such as energy storage solution material that water-retaining agent, heavy metal chelating agent, deicing fluid subsidiary material, height solidify-dissolve latent heat.
Description of drawings
Fig. 1 is the transmission electron microscope photo after traditional inverse suspension polymerization method synthetic polymer water-absorbent absorbs water.
Fig. 2 is the transmission electron microscope photo after the synthetic polymer water-absorbent suction of the present invention.
Embodiment
The present invention on the basis of traditional inverse suspension polymerization method, adopt increase substantially tensio-active agent synthesize persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin with metering method.Specifically: put into normal hexane in the reactor of strap clamp cover, and then add the neutral sodium acrylate aqueous solution, linking agent, initiator, persimmon tannin solution participate in reaction.Realize by following steps:
(1) weighing:
By weight, the proportioning of each reactant is: by weight, the proportioning of each reactant is: 20～200 parts of normal hexanes, 1～12 part of persimmon tannin solution, 0.5～100 part of anion surfactant, N, 0.01～0.5 part of N '-methylene-bisacrylamide, 0.01～1 part of ammonium persulphate, 10～50 parts in vinylformic acid, 3～10 parts in sodium hydroxide, 8～20 parts in water;
(2) synthetic:
The reactant that takes by weighing is added in the reactor, feed nitrogen and stir under react, under normal pressure, make then progressively to be warmed up to 60～70 ℃ in the reactor and to react; The entire reaction time is 1～4 hour;
(3) after reaction finishes, make and lead to cooling water temperature in the reacting kettle jacketing, emit reaction soln again to room temperature;
(4) with drier separating reaction solution: use drier that unreacted reactants such as normal hexane are isolated, reusable.After the reaction mass drying with drier, be persimmon tannin solution of the present invention-acrylic acid series hydroscopic high-molecular resin finished product, this resin is brown gelatinoid material, its water-intake rate can reach 800～1000 times that absorb own wt, when in the aqueous solution, disperseing, the length of the molecular chain of this resin is number nanometer (see figure 2), for example 1～9 nanometer.
In the described building-up process of above-mentioned steps (2), its method can be: earlier with normal hexane, persimmon tannin solution, the sulfuric acid ester type tensio-active agent, N, N ' methylene-bisacrylamide and ammonium persulphate add in the reactor, make these materials in reactor, feed nitrogen 15～30 minutes and start stirrer and remain on 450 rev/mins and reacted 10～30 minutes, add then by vinylformic acid, the sodium acrylate aqueous solution that sodium hydroxide and water constitute, and keep 400 rev/mins at stirrer, reactor is warmed up to 60 ℃ and kept 0.15 hour and be warmed up to 70 ℃ to keep reacting in 1 hour.
Above-mentioned anion surfactant can be selected fat polyoxyethylenated alcohol sulfuric acid for use, and (be called for short AES, molecular formula is R-O (CH
2CH
2O) nSO
3Na); Can also select other similar tensio-active agent for use, a kind of as in alkylbenzene sulfonate (LAS), alkylsulfonate (SAS), α-Xi Jihuangsuanyan (AOS), the fatty alcohol sulfate salt, or the mixture of its any proportioning.
The persimmon tannin solution that the present invention adopts, its characteristic is: persimmon fruit juice forms (seeing trecento publication " farming and sericulture basic necessities of life summary ") by fermentation, and special odor is arranged, contain persimmon tannin (amount: 3～5%), with after the air contact, become dark brownly, form epithelium easily.The effect that waterproof, insect protected, sanitas are arranged.Sorrel liquid, 100 ℃ of boiling points, vapour pressure and water are same, and melting point is-2 ℃.Soluble in water and ethanol etc.
The invention will be further described below in conjunction with specific embodiment, but do not limit the present invention.
Embodiment 1
In small-sized glass-lined kettle, add 2.6 liter normal hexanes, persimmon tannin solution 5kg, sulfuric acid ester type tensio-active agent 0.5 liter, N, N methylene-bisacrylamide 20g, ammonium persulphate 37g, in reactor, fed the nitrogen aeration time 15～30 minutes, start stirrer remain on 450 rev/mins 10～30 minutes, add the sodium acrylate aqueous solution (vinylformic acid 13kg, sodium hydroxide 5kg, water 15kg) remains on 400 rev/mins then, be warmed up to 60 ℃ and kept 1 hour, be warmed up to 70 ℃ and kept 3 hours, after reaction finishes.Logical cooling water temperature is emitted reaction mass to room temperature in the reacting kettle jacketing.Use drier that unreacted reactants such as normal hexane are isolated, its isolate is reusable.To be finished product after the reaction mass drying that dry, the goods that obtain are brown gelatinoid material, and its water-intake rate can reach and absorb more than 900 times of own wt.
Embodiment 2
In small-sized glass-lined kettle, add 3.2 liter normal hexanes, persimmon tannin solution 10kg, sulfuric acid ester type tensio-active agent 1.25 liters, N, N methylene-bisacrylamide 40g, ammonium persulphate 26g, in reactor, fed the nitrogen aeration time 15～30 minutes, start stirrer remain on 450 rev/mins 10～30 minutes, add the sodium acrylate aqueous solution (vinylformic acid 13kg, sodium hydroxide 5kg, water 15kg) remains on 400 rev/mins then, be warmed up to 60 ℃ and kept 0.15 hour, be warmed up to 70 ℃ and kept 1 hour, after reaction finishes.Logical cooling water temperature is emitted reaction mass to room temperature in the reacting kettle jacketing.Use drier that unreacted reactants such as normal hexane are isolated, its isolate is reusable.To be finished product after the reaction mass drying that dry, the goods that obtain are brown gelatinoid material, and its water-intake rate can reach and absorb more than 850 times of own wt.
Embodiment 3
In small-sized glass-lined kettle, add 3.8 liter normal hexanes, persimmon tannin solution 11kg, sulfuric acid ester type tensio-active agent 1.5 liters, N, N methylene-bisacrylamide 7g, ammonium persulphate 26g, in reactor, fed the nitrogen aeration time 15～30 minutes, start stirrer remain on 450 rev/mins 10～30 minutes, add the sodium acrylate aqueous solution (vinylformic acid 13kg, sodium hydroxide 5kg, water 15kg) remains on 400 rev/mins then, be warmed up to 60 ℃ and kept 0.15 hour, be warmed up to 70 ℃ and kept 1 hour, after reaction finishes.Logical cooling water temperature is emitted reaction mass to room temperature in the reacting kettle jacketing.Use drier that unreacted reactants such as normal hexane are isolated, its isolate is reusable.To be finished product after the reaction mass drying that dry, the goods that obtain are newborn brown gelatinoid material, and its water-intake rate can reach and absorb more than 800 times of own wt.
Claims (5)
1. the method for synthetic persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin is characterized in that adopting the method for following steps to synthesize persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin, specifically:
(1) weighing:
By weight, the proportioning of each reactant is: 20～200 parts of normal hexanes, 1～12 part of persimmon tannin solution, 0.5～100 part of anion surfactant, N, 0.01～0.5 part of N '-methylene-bisacrylamide, 0.01～1 part of ammonium persulphate, 10～50 parts in vinylformic acid, 3～10 parts in sodium hydroxide, 8～20 parts in water;
(2) synthetic:
The reactant that takes by weighing is added in the reactor, feed nitrogen and stir under react, under normal pressure, make then progressively to be warmed up to 60～70 ℃ in the reactor and to react; The entire reaction time is 1～4 hour;
(3) after reaction finishes, make reactor reduce to room temperature, emit reaction soln again;
(4) with drier separating reaction solution: will be finished product after the reaction mass drying that dry, and isolated unreacted reactant uses after giving over to.
2. the method for synthetic persimmon tannin solution according to claim 1-acrylic acid series hydroscopic high-molecular resin, it is characterized in that in building-up process, earlier with normal hexane, persimmon tannin solution, anion surfactant, N, N ' methylene-bisacrylamide and ammonium persulphate add in the reactor, make these materials in reactor, feed nitrogen 15～30 minutes and start stirrer and remain on 450 rev/mins and reacted 10～30 minutes, add then by vinylformic acid, the sodium acrylate aqueous solution that sodium hydroxide and water constitute, and keep 400 rev/mins at stirrer, reactor is warmed up to 60 ℃ and kept 0.15 hour and be warmed up to 70 ℃ to keep reacting in 1 hour.
3. the method for synthetic persimmon tannin solution according to claim 1-acrylic acid series hydroscopic high-molecular resin is characterized in that anion surfactant selects polyoxyethylene alkyl ether sulfate salt, alkylbenzene sulfonate, alkylsulfonate, α-Xi Jihuangsuanyan, fatty alcohol sulfate salt for use.
4. the method for synthetic persimmon tannin solution according to claim 1-acrylic acid series hydroscopic high-molecular resin, it is characterized in that the persimmon tannin solution-acrylic acid series hydroscopic high-molecular resin that obtains is brown gelatinoid material, its water-intake rate is at least and absorbs self 800 times weight.
5. the method for synthetic persimmon tannin solution according to claim 1-acrylic acid series hydroscopic high-molecular resin is characterized in that persimmon tannin solution-when the acrylic acid series hydroscopic high-molecular resin disperseed, the length of the molecular chain of this resin was 1～9 nanometer in the aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100525828A CN100482702C (en) | 2007-06-28 | 2007-06-28 | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100525828A CN100482702C (en) | 2007-06-28 | 2007-06-28 | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101096395A true CN101096395A (en) | 2008-01-02 |
| CN100482702C CN100482702C (en) | 2009-04-29 |
Family
ID=39010498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100525828A Expired - Fee Related CN100482702C (en) | 2007-06-28 | 2007-06-28 | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100482702C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967210A (en) * | 2010-10-29 | 2011-02-09 | 武汉理工大学 | Method for synthesizing gallnut tannic acid-acrylic acid series high polymer absorbent resin |
| CN102060366A (en) * | 2010-11-26 | 2011-05-18 | 武汉理工大学 | Composite for treating waste water containing cadmium compound and preparation method thereof |
| CN102205232A (en) * | 2011-03-25 | 2011-10-05 | 东北林业大学 | Development of larch tannin metal ion absorbing agent |
| CN102408807A (en) * | 2011-09-14 | 2012-04-11 | 武汉理工大学 | High performance bionic antifouling composite paint and synthetic method thereof |
| CN102614834A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering heavy metals of lead and copper by persimmon tannin-containing metal adsorbent |
| CN102614837A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal gold by persimmon tannin-containing metal adsorbent |
| CN102614836A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal palladium by persimmon tannin-containing metal adsorbent |
| CN112473627A (en) * | 2020-10-19 | 2021-03-12 | 西北农林科技大学 | Tannin composite adsorbent and preparation method thereof |
-
2007
- 2007-06-28 CN CNB2007100525828A patent/CN100482702C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967210A (en) * | 2010-10-29 | 2011-02-09 | 武汉理工大学 | Method for synthesizing gallnut tannic acid-acrylic acid series high polymer absorbent resin |
| CN102060366B (en) * | 2010-11-26 | 2012-06-27 | 武汉理工大学 | Composite for treating waste water containing cadmium compound and preparation method thereof |
| CN102060366A (en) * | 2010-11-26 | 2011-05-18 | 武汉理工大学 | Composite for treating waste water containing cadmium compound and preparation method thereof |
| CN102614837B (en) * | 2011-01-28 | 2013-09-25 | 华中农业大学 | Method for adsorbing and recovering precious metal gold by persimmon tannin-containing metal adsorbent |
| CN102614834A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering heavy metals of lead and copper by persimmon tannin-containing metal adsorbent |
| CN102614837A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal gold by persimmon tannin-containing metal adsorbent |
| CN102614836A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal palladium by persimmon tannin-containing metal adsorbent |
| CN102614836B (en) * | 2011-01-28 | 2013-09-25 | 华中农业大学 | Method for adsorbing and recovering precious metal palladium by persimmon tannin-containing metal adsorbent |
| CN102614834B (en) * | 2011-01-28 | 2014-01-15 | 华中农业大学 | Method for adsorbing and recovering heavy metals of lead and copper by persimmon tannin-containing metal adsorbent |
| CN102205232A (en) * | 2011-03-25 | 2011-10-05 | 东北林业大学 | Development of larch tannin metal ion absorbing agent |
| CN102408807A (en) * | 2011-09-14 | 2012-04-11 | 武汉理工大学 | High performance bionic antifouling composite paint and synthetic method thereof |
| CN102408807B (en) * | 2011-09-14 | 2013-07-17 | 武汉理工大学 | High performance bionic antifouling composite paint and synthetic method thereof |
| CN112473627A (en) * | 2020-10-19 | 2021-03-12 | 西北农林科技大学 | Tannin composite adsorbent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100482702C (en) | 2009-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100482702C (en) | Method for synthesizing persimmon tannin-crylic acid series macromolecule bibulous resin | |
| EP3078650B1 (en) | Seed product comprising seed coated with polyanionic polymer | |
| CN1319999C (en) | Method of preventing coloration of water-absorbing resin | |
| US10737988B2 (en) | Polymer-boric acid compositions | |
| EA023402B1 (en) | Fatty amines, amidoamines, and their derivatives from natural oil metathesis | |
| ES2603610T3 (en) | Polyisobutene emulsions, substance and procedure | |
| EP0482687A1 (en) | Concentrated, liquid, pourable composition | |
| CN102936348A (en) | Crylic acid water-absorbent resin with excellent water-retaining property and yellowing resistance and preparation method thereof | |
| CN1970584B (en) | Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood and containing low content soluble substance | |
| CN101045789B (en) | Manufacturing method of high whiteness water absorption resin | |
| JP2021507076A (en) | Aromatic polyetheramine alkoxylate | |
| US5446188A (en) | Process for the production of highly concentrated fatty alcohol sulfate pastes | |
| CN103172788A (en) | Preparation method of dispersing agent | |
| DE3900207A1 (en) | USE OF COPOLYMERISES FROM 1,2-DI-ALKOXYETHYLENES AND MONOETHYLENICALLY UNSATURATED DICARBONE ACID ANHYDRIDES IN DETERGENTS AND DETERGENTS CONTAINING SUCH COPOLYMERISES | |
| MXPA06014512A (en) | Method for producing granulated or powdery detergent compounds. | |
| CN100558761C (en) | Production method of high-performance super absorbent | |
| CN100503663C (en) | Preparation method of powdery, water-insoluble high hydroscopicity resin capable of adsorbing water, urine or blood | |
| CN101143912B (en) | Method for producing high-performance high water absorption resin | |
| JP2527459B2 (en) | Water absorbent resin composition | |
| CN101967210B (en) | Method for synthesizing gallnut tannic acid-acrylic acid series high polymer absorbent resin | |
| CN1132863C (en) | Process without drying step for preparing resin with high absorption of water | |
| CN112225842A (en) | Polyacrylic acid emulsion thickener and preparation method and application thereof | |
| CN100564406C (en) | Production method of high-performance super absorbent | |
| CN101967261B (en) | Method for preparing super absorbent resin containing plant nutrients and auxin | |
| JPH07303825A (en) | Nonionic surfactant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090429 Termination date: 20130628 |