CN108623837B - Polyurethane hydrophilic modification method based on polystyrene diazonium salt - Google Patents
Polyurethane hydrophilic modification method based on polystyrene diazonium salt Download PDFInfo
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- CN108623837B CN108623837B CN201710154493.8A CN201710154493A CN108623837B CN 108623837 B CN108623837 B CN 108623837B CN 201710154493 A CN201710154493 A CN 201710154493A CN 108623837 B CN108623837 B CN 108623837B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/02—Aerobic processes
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention relates to a polyurethane hydrophilic modification method based on polystyrene diazonium salt. The invention relates to a polyurethane hydrophilic modification method based on polystyrene diazonium salt, which comprises the following steps: step 1: weighing a proper amount of polystyrene diazonium salt solution, and soaking a polyurethane carrier in the polystyrene diazonium salt solution for a certain time under a certain temperature condition; step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing with cold air for a certain time, soaking the polyurethane carrier in a solution of anionic polyelectrolyte, adsorbing and soaking for a certain time under the condition of a certain temperature, taking out and drying, and thus completing the hydrophilic modification process of the polyurethane carrier. The invention utilizes the property of polyfunctional group and high reaction activity of the polystyrene diazonium salt to fix the anionic polyelectrolyte on the surface of the polyurethane to realize hydrophilic modification of the polyurethane.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for hydrophilic modification of the surface of a polyurethane carrier based on polystyrene diazonium salt.
Background
The chemical industry is the traditional prop industry in China, and the produced chemical raw materials and products are widely applied to various fields and make great contribution to national economy. The chemical industry is a highly polluted industry, the produced sewage contains high-concentration organic pollutants, and the common biochemical and physicochemical treatment methods have poor treatment effect on a plurality of chemical wastewater and are difficult to realize standard discharge.
In the biochemical treatment of chemical sewage, the filler is added to immobilize the microorganism, so that the removal rate of pollutants can be obviously improved, the impact resistance of the biochemical treatment is improved, and the yield of biochemical sludge is reduced, thereby receiving wide attention of people. The difficulty of the immobilized microorganism technology lies in the research and development of carriers, polyurethane is a polymer prepared from polyisocyanate, polyol, polyamine and other chain extenders or cross-linking agents, the polyurethane carrier has the characteristics of large specific surface area, more foam pores, strong supporting capacity, stable property and the like, and the connectivity of the space structure of the polyurethane carrier provides environments such as oxygen and oxygen deficiency for the growth of microorganisms, so that the immobilized microorganism technology has wide application in the field of immobilized microorganisms. However, the common polyurethane filler has the problems of slow film formation, small microbial adhesion and easy shedding in the sewage treatment process due to hydrophobic surface, and the problems can be obviously improved by carrying out hydrophilic modification on the surface of the common polyurethane filler.
The diazonium salt is a salt containing diazonium group, and is a simple, rapid and effective method for the surface chemical modification of materials due to the strong electron-withdrawing effect and high reactivity. Zhang Jing et al, in the journal of macromolecules 2002,2:180-185, describe a method for synthesizing a polystyrene diazonium salt, which has potential applications in many fields due to its long-chain structure and multi-functional property.
The patent "a preparation method of hydrophilic polymer modified polyurethane foam plastic carrier" (application No. 201210306198.7) introduces a method for hydrophilic modification of polyurethane surface, which is characterized in that polyurethane foam is immersed in starch aqueous solution, sodium carboxymethylcellulose aqueous solution and N, N-dimethylformamide solution of polysuccinimide, then transferred to cross-linking agent aqueous solution, and heated to obtain hydrophilic modified polyurethane foam. The patent "a method for hydrophilic modification of polyurethane based on hyperbranched diazonium salt" introduces a method for hydrophilic modification of polyurethane surface by dilution-grafting-modification using hyperbranched diazonium salt.
According to the invention, polyurethane is used as a carrier, and the anionic polyelectrolyte is fixed on the surface of the polyurethane by utilizing the multifunctional group property and high reaction activity of the polystyrene diazonium salt, so that hydrophilic modification of the polyurethane is realized.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polyurethane hydrophilic modification method based on polystyrene diazonium salt, which utilizes the multifunctional group property and high reaction activity of the polystyrene diazonium salt to ensure that the polyurethane surface has certain reaction activity, and then fixes anionic polyelectrolyte on the polyurethane surface.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a hydrophilic modification method of polyurethane based on polystyrene diazonium salt comprises the following steps:
step 1: weighing a proper amount of polystyrene diazonium salt solution, and soaking a polyurethane carrier in the polystyrene diazonium salt solution for a certain time under a certain temperature condition;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing with cold air for a certain time, soaking the polyurethane carrier in a solution of anionic polyelectrolyte, adsorbing and soaking for a certain time under the condition of a certain temperature, taking out and drying, and thus completing the hydrophilic modification process of the polyurethane carrier.
On the basis of the technical scheme, the molecular structural formula of the polystyrene diazonium salt in the step 1 is shown as
Wherein n is the number of repetitions of the chemical group in parentheses in the molecular structural formula.
On the basis of the technical scheme, the polyurethane carrier used in the step 1 is prepared by foaming in a laboratory, and the shape of the polyurethane carrier is a cube with the side length of 10-20 mm.
On the basis of the technical scheme, the certain temperature in the step 1 is 2-4 ℃.
On the basis of the technical scheme, the certain time in the step 1 is 0.5-3 hours.
On the basis of the technical scheme, the cold air is blown for 1-5 min in the step 2.
On the basis of the technical scheme, the certain temperature in the step 2 is 2-4 ℃.
On the basis of the technical scheme, the adsorption soaking in the step 2 is carried out for 2-10 hours.
On the basis of the technical scheme, the anionic polyelectrolyte in the step 2 is sodium polystyrene sulfonate, sodium polyacrylate or sodium polymethacrylate.
The synthetic method of the polystyrene diazonium salt adopts a route designed by Zhang Jing et al in the high molecular science report 2002,2: 180-185.
The invention has the characteristics and beneficial effects that:
1) the method utilizes the polystyrene diazonium salt to carry out hydrophilic modification on the polyurethane carrier, has the characteristics of simple steps, easy operation and the like, and is beneficial to realizing industrialization;
2) the hydrophilic modification of the polyurethane carrier by utilizing the polystyrene diazonium salt has no special requirements on the used anionic polyelectrolyte, and the application range is wide;
3) the diazo group contained in the polystyrene diazonium salt used in the method has high reaction activity, high adsorption efficiency and stable adsorption effect;
4) the method has high universality and can be applied to carriers made of various different materials;
5) compared with hyperbranched diazonium salt, polystyrene has more adsorbed anionic polyelectrolyte due to the linear structure and diazonium salt groups with higher density, and has firmer adsorption on the surface of the carrier and better hydrophilic modification effect.
Drawings
The invention has the following drawings:
fig. 1 shows the contact angle before modification of the polyurethane film (contact angle 92 °).
Fig. 2 is a schematic view of the contact angle of the surface of the polyurethane film after modification (the contact angle is 50 °).
Detailed Description
The present invention is described in further detail below with reference to FIGS. 1-2.
The polystyrene diazonium salt used in the invention is independently developed and synthesized in a laboratory, the diazonium group contained in the polystyrene diazonium salt has strong reaction activity, and the anionic polyelectrolyte can be simply and effectively fixed on the carrier, compared with the patent 'preparation method of hydrophilic polymer modified polyurethane foam plastic carrier' (application No. 201210306198.7), the polystyrene diazonium salt has the characteristics of simple operation, wide adaptability and the like, and the polystyrene diazonium salt is realized by the following steps:
step 1: weighing a proper amount of polystyrene diazonium salt solution, and soaking a polyurethane carrier in the polystyrene diazonium salt solution for a certain time under a certain temperature condition;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing with cold air for a certain time, soaking the polyurethane carrier in a solution of anionic polyelectrolyte, adsorbing and soaking for a certain time under the condition of a certain temperature, taking out and drying, and thus completing the hydrophilic modification process of the polyurethane carrier.
On the basis of the technical scheme, the molecular structural formula of the polystyrene diazonium salt in the step 1 is shown as
Wherein n is the number of repetitions of the chemical group in parentheses in the molecular structural formula.
On the basis of the technical scheme, the polyurethane carrier used in the step 1 is prepared by foaming in a laboratory, and the shape of the polyurethane carrier is a cube with the side length of 10-20 mm.
On the basis of the technical scheme, the certain temperature in the step 1 is 2-4 ℃.
On the basis of the technical scheme, the certain time in the step 1 is 0.5-3 hours.
On the basis of the technical scheme, the cold air is blown for 1-5 min in the step 2.
On the basis of the technical scheme, the certain temperature in the step 2 is 2-4 ℃.
On the basis of the technical scheme, the adsorption soaking in the step 2 is carried out for 2-10 hours.
On the basis of the technical scheme, the anionic polyelectrolyte in the step 2 is sodium polystyrene sulfonate, sodium polyacrylate or sodium polymethacrylate.
The synthetic method of the polystyrene diazonium salt adopts a route designed by Zhang Jing et al in the high molecular science report 2002,2: 180-185.
The specific embodiment is as follows:
example 1:
step 1: weighing the synthesized polystyrene diazonium salt solution, and soaking a polyurethane carrier with the side length of 10mm in the diluted solution for 0.5h at the temperature of 2 ℃;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing cold air for 1min, soaking the polyurethane carrier in a solution of sodium polystyrene sulfonate, adsorbing and soaking for 2h at the temperature of 2 ℃, taking out and drying to finish the hydrophilic modification of the polyurethane carrier.
And measuring the contact angle of the polyurethane film after hydrophilic modification, wherein the contact angle of the body film is 92 degrees, the contact angle of the polyurethane surface after modification is 50 degrees, and the hydrophilic modification effect is obvious.
The polyurethane carrier modified by the hyperbranched diazonium salt and the polystyrene diazonium salt under the same condition is respectively placed in an acidic aqueous solution with the pH value of 1, the contact angle of the polyurethane carrier modified by the hyperbranched diazonium salt is increased after the polyurethane carrier is placed for one month, the hydrophilicity is poor, and the hydrophilicity of the polyurethane carrier modified by the polystyrene diazonium salt is not obviously changed after the polyurethane carrier is placed for more than 3 months, so that the polyurethane carrier modified by the polystyrene diazonium salt in a hydrophilic mode has better stability.
Example 2:
step 1: weighing the synthesized polystyrene diazonium salt solution, and soaking a polyurethane carrier with the side length of 15mm in the diluted solution for 3 hours at the temperature of 4 ℃;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing cold air for 5min, soaking the polyurethane carrier in a sodium polyacrylate solution, adsorbing and soaking for 10h at 4 ℃, taking out and drying, and thus finishing the hydrophilic modification of the polyurethane carrier.
And measuring the contact angle of the polyurethane film after hydrophilic modification, wherein the contact angle of the body film is 92 degrees, the contact angle of the polyurethane surface after modification is 53 degrees, and the hydrophilic modification effect is obvious.
Example 3:
step 1: weighing the synthesized polystyrene diazonium salt solution, and soaking a polyurethane carrier with the side length of 20mm in the diluted solution for 1h at the temperature of 3 ℃;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing cold air for 2min, soaking the polyurethane carrier in a solution of sodium polymethacrylate, adsorbing and soaking for 6h at the temperature of 3 ℃, taking out and drying to finish the hydrophilic modification of the polyurethane carrier.
And measuring the contact angle of the polyurethane film after hydrophilic modification, wherein the contact angle of the body film is 92 degrees, the contact angle of the polyurethane surface after modification is 48 degrees, and the hydrophilic modification effect is obvious.
Example 4:
step 1: weighing the synthesized polystyrene diazonium salt solution, and soaking a polyurethane carrier with the side length of 10mm in the diluted solution for 2.5 hours at the temperature of 4 ℃;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing cold air for 3min, soaking the polyurethane carrier in a solution of sodium polymethacrylate, adsorbing and soaking for 8h at the temperature of 3 ℃, taking out and drying to finish the hydrophilic modification of the polyurethane carrier.
And measuring the contact angle of the polyurethane film after hydrophilic modification, wherein the contact angle of the body film is 92 degrees, the contact angle of the polyurethane surface after modification is 46 degrees, and the hydrophilic modification effect is obvious.
Example 5:
step 1: weighing the synthesized polystyrene diazonium salt solution, and soaking a polyurethane carrier with the side length of 20mm in the diluted solution for 1h at the temperature of 2 ℃;
step 2: and after soaking, taking out the polyurethane carrier, cleaning with water, blowing cold air for 5min, soaking the polyurethane carrier in a solution of sodium polystyrene sulfonate, adsorbing and soaking for 9h at 4 ℃, taking out and drying to finish the hydrophilic modification of the polyurethane carrier.
And measuring the contact angle of the polyurethane film after hydrophilic modification, wherein the contact angle of the body film is 92 degrees, the contact angle of the polyurethane surface after modification is 45 degrees, and the hydrophilic modification effect is obvious.
Those not described in detail in this specification are within the skill of the art.
Claims (6)
1. A polyurethane hydrophilic modification method based on polystyrene diazonium salt is characterized in that: the method comprises the following steps:
step 1: weighing a proper amount of polystyrene diazonium salt solution, and soaking a polyurethane carrier in the polystyrene diazonium salt solution for a certain time under a certain temperature condition;
step 2: after soaking, taking out the polyurethane carrier, cleaning with water, blowing with cold air for a certain time, soaking the polyurethane carrier in a solution of anionic polyelectrolyte, adsorbing and soaking for a certain time under a certain temperature condition, taking out and drying to finish the hydrophilic modification process of the polyurethane carrier;
the molecular structural formula of the polystyrene diazonium salt in the step 1 is shown in the specification
Wherein n is the number of repetitions of chemical groups in parentheses in the molecular structural formula;
in the step 2, the adsorption soaking is carried out for a certain time of 2-10 hours;
and in the step 2, the cold air is blown for 1-5 min.
2. The method for hydrophilic modification of polyurethane based on polystyrene diazonium salt according to claim 1, characterized in that: the shape of the polyurethane carrier in the step 1 is a cube with the side length of 10-20 mm.
3. The method for hydrophilic modification of polyurethane based on polystyrene diazonium salt according to claim 1, characterized in that: in the step 1, the certain temperature is 2-4 ℃.
4. The method for hydrophilic modification of polyurethane based on polystyrene diazonium salt according to claim 1, characterized in that: the certain time in the step 1 is 0.5-3 hours.
5. The method for hydrophilic modification of polyurethane based on polystyrene diazonium salt according to claim 1, characterized in that: in the step 2, the certain temperature is 2-4 ℃.
6. The method for hydrophilic modification of polyurethane based on polystyrene diazonium salt according to claim 1, characterized in that: in the step 2, the anionic polyelectrolyte is sodium polystyrene sulfonate, sodium polyacrylate or sodium polymethacrylate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900345A (en) * | 1997-10-06 | 1999-05-04 | Kodak Polychrome Graphics, Llc | Surfactant in precoat for lithographic plates |
| CN101735475A (en) * | 2009-12-10 | 2010-06-16 | 清华大学 | Preparation method of hydrophilic polyurethane porous support |
| CN106256848A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that polyurethane hydrophilic based on hyperbranched diazol is modified |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5900345A (en) * | 1997-10-06 | 1999-05-04 | Kodak Polychrome Graphics, Llc | Surfactant in precoat for lithographic plates |
| CN101735475A (en) * | 2009-12-10 | 2010-06-16 | 清华大学 | Preparation method of hydrophilic polyurethane porous support |
| CN106256848A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that polyurethane hydrophilic based on hyperbranched diazol is modified |
Non-Patent Citations (1)
| Title |
|---|
| "聚4-重氮基苯乙烯与聚苯乙烯磺酸钠的自组装";杨朝晖等;《高分子学报》;20030630(第3期);第442-444页 * |
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