CN113512143A - Preparation method of temperature-sensitive response type hyperbranched flocculant - Google Patents
Preparation method of temperature-sensitive response type hyperbranched flocculant Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000004044 response Effects 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 17
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002091 cationic group Chemical group 0.000 claims abstract description 3
- -1 acryloyloxyethyl trimethylene Ammonium chloride Chemical compound 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000005189 flocculation Methods 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052753 mercury Inorganic materials 0.000 abstract description 8
- 239000006085 branching agent Substances 0.000 abstract description 6
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- VYBHLZOLHCQLHT-UHFFFAOYSA-N 1-(2-methylpropyl)-4,5-dihydroimidazole hydrochloride Chemical compound Cl.C(C(C)C)N1C=NCC1 VYBHLZOLHCQLHT-UHFFFAOYSA-N 0.000 abstract 2
- 238000007086 side reaction Methods 0.000 abstract 1
- 239000008394 flocculating agent Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000016615 flocculation Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229920001661 Chitosan Polymers 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
本发明公开了一种为温敏响应型超支化絮凝剂的制备方法。在该方法中以季戊四醇为支化剂，温敏单体N‑异丙基丙烯酰胺（PNIPAM）、阳离子单体丙烯酰氧乙基三甲基氯化铵（DAC）为原料；为别将PNIPAM、DAC分别加入反应器中，并加入适当的蒸馏水、季戊四醇和正硅酸乙酯，在快速搅拌条件下，充分混匀并完全溶解；将反应器通入氮气除氧；加入光引发剂偶氮二异丁咪唑啉盐酸盐（VA‑044）；最后将反应器置于低压紫外汞灯照射下反应1~3h。反应完毕经熟化后对产物进行提取和纯化，即得温敏响应型超支化絮凝剂。本发明反应稳定、易于控制，副反应少，所得温敏响应型超支化絮凝剂溶解性好、产物纯净，由于温敏材料的引入，絮凝过程中絮体的沉降速度加快，是一种高效的水处理絮凝剂。The invention discloses a preparation method of a thermoresponsive hyperbranched flocculant. In this method, pentaerythritol is used as branching agent, temperature-sensitive monomer N-isopropylacrylamide (PNIPAM) and cationic monomer acryloyloxyethyltrimethylammonium chloride (DAC) are used as raw materials; DAC and DAC were respectively added to the reactor, and appropriate distilled water, pentaerythritol and ethyl orthosilicate were added, and under the condition of rapid stirring, they were fully mixed and completely dissolved; nitrogen was introduced into the reactor to remove oxygen; Isobutylimidazoline hydrochloride (VA‑044); finally, the reactor was placed under the irradiation of a low pressure ultraviolet mercury lamp to react for 1 to 3 hours. After the reaction is completed, the product is extracted and purified to obtain a thermoresponsive hyperbranched flocculant. The invention has stable reaction, easy control, few side reactions, and the obtained temperature-responsive hyperbranched flocculant has good solubility and pure product. Due to the introduction of temperature-sensitive materials, the settling speed of flocs during the flocculation process is accelerated, which is an efficient and effective method. Water treatment flocculant.
Description
Technical Field
The invention relates to the technical field of flocculants, in particular to a preparation method of a temperature-sensitive response type hyperbranched flocculant.
Background
With the rapid growth of population and the development of industrial economy, the problems of water resource shortage and water pollution caused by the rapid growth of population are generally concerned by society. China pays high attention to environmental protection and treatment, insists on prevention as the main and comprehensive treatment, and puts forward the prevention and treatment of water pollution. In the water treatment process, suspended colloidal particles in a water body are mainly removed by coagulation. The flocculating agent is used as the key of the coagulation method, and the quality of the coagulation performance determines the water treatment effect. The flocculant method for treating sewage is one of the main ways for solving the problem of sewage at present and is also the key point of green chemical research. Compared with the traditional sewage treatment method, the flocculant technology has the advantages of high efficiency, environmental protection, energy conservation, easy operation and the like. The natural organic polymer flocculant is favored because of the advantages of low price, no secondary pollution, environmental friendliness, high selectivity, reproducibility and the like, and the conventional and literature-reported natural organic polymer flocculants mainly comprise chitosan-based flocculants, cellulose-based flocculants, starch-based flocculants and the like. The most important influencing factor of the treatment effect of the flocculation method is the performance of the flocculant, the research on the flocculant plays a crucial role in water pollution control, and the selection of a proper flocculant is the core of the flocculation method, so that the improvement of the performance of the flocculant is always a hotspot of research.
The research on the flocculating agent has been developed for a long time, and a relatively comprehensive and perfect system is formed. The flocculating agent is divided into four types of inorganic flocculating agent, organic flocculating agent, composite flocculating agent and biological flocculating agent, wherein the inorganic flocculating agent is most widely applied at present due to low price and high quality, the organic flocculating agent has the best water treatment effect, but the practical application of the organic flocculating agent is hindered due to high cost, and the biological flocculating agent is still in the experimental research stage at present. In general, the flocculation mode of the high molecular polymer flocculant mainly takes adsorption bridging and net trapping sweeping, and the generated floc has large particle size but low compactness; the inorganic micromolecule flocculant mainly takes a charge neutralization mode as a main mode, and the characteristics of the generated flocs are just opposite. The development of a novel efficient, safe and economic flocculating agent is the main trend of the development of flocculating agents in the future.
At present, the temperature-sensitive response type hyperbranched flocculant is less researched.
Chinese patent application No. CN201710506710.5, entitled "preparation method of chitosan/poly (N-isopropyl acrylamide) graft copolymerization temperature-sensitive type polymeric flocculant", discloses a method for synthesizing dendritic macromolecules with four amino groups as end groups by using ethylenediamine and methyl acrylate as raw materials, taking 2-mercaptopropionic acid as a chain transfer agent, participating in the polymerization reaction of N-isopropyl acrylamide to prepare poly N-isopropyl acrylamide carboxylic acid derivatives, and reacting terminal carboxylic acid groups of the poly N-isopropyl acrylamide carboxylic acid derivatives with the amino groups of chitosan and dendritic macromolecules under the action of a dehydrating agent to obtain the temperature-sensitive type polymeric flocculant. The surface of the flocculant material contains a large number of active amino groups and imino groups, protonation or deprotonation can be carried out so as to change the positive charge density of the surface of the flocculant material, adsorption on negative charge pollutants is realized, and efficient flocculation is realized, but the preparation process is complex, stirring and mixing reaction at 70-80 ℃ is required in the preparation process, and high temperature can possibly influence the structure and performance of the chitosan flocculant.
Chinese patent application No. CN201610404239.4 entitled "a temperature sensitive chitosan flocculant and a preparation method and application thereof", the invention polymerizes temperature sensitive monomers and then introduces chitosan molecules to obtain the temperature sensitive chitosan flocculant, and a temperature switch is at about 25 ℃; the method of first polymerization and then graft modification not only improves the number and molecular weight of functional groups and strengthens the bridging flocculation, but also can meet the flocculation removal requirement of pollutants in a polluted water body at the temperature of about 25 ℃, and because the poly-n-propyl acrylamide grafted chain can generate hydrophilicity or hydrophobicity along with the temperature change, the poly-n-propyl acrylamide grafted chain has excellent flocculation capability particularly for pollutants of which the hydrophilicity/hydrophobicity is easy to convert in the water body. However, the resulting flocculant has a relatively slow settling rate, resulting in a less than optimal treatment.
Disclosure of Invention
Aiming at the defects in the prior art, a preparation method of the temperature-sensitive responsive hyperbranched flocculant, which has the advantages of simple reaction condition, short reaction time, excellent product performance, high sedimentation rate and good effect, is developed.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in the method, pentaerythritol is taken as a branching agent, and a temperature-sensitive monomer N-isopropyl acrylamide (PNIPAM) and a cationic monomer acryloyloxyethyl trimethyl ammonium chloride (DAC) are taken as raw materials; respectively adding APNIPAM and DAC into a reactor, adding proper distilled water, pentaerythritol and ethyl orthosilicate, and fully mixing and dissolving under the condition of rapid stirring; the mass fraction of PNIPAM and DAC total monomers is 20-30%; introducing nitrogen into the reactor to remove oxygen; adding a photoinitiator azobisisobutyrimidazoline hydrochloride (VA-044) with the mass fraction of 0.2-0.4% of the total monomer mass, and uniformly stirring; and then placing the reactor beside an ultraviolet lamp, and irradiating for 1-3 hours by the ultraviolet lamp. And after the reaction is finished, curing, extracting and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant. The method specifically comprises the following steps:
1) the method comprises the following steps of (1) mixing DAC and PNIPAM monomers in a mass ratio of 3-4: 1, adding the mixture into distilled water, and continuously stirring until the mixture is completely dissolved, wherein the total mass fraction of the DAC and the PNIPAM in the distilled water is controlled to be 20-30%.
2) The mass fraction of the added ethyl orthosilicate is 2.0-4.0%.
3) The mass fraction of the added pentaerythritol is 0.02-0.05%.
4) And adding 0.2-0.4% of a photoinitiator VA-044 in the process of introducing nitrogen and removing oxygen.
5) Placing the reactor in an ultraviolet lamp with the light intensity range of 0.06-0.34 mW/cm2And (3) reacting for 1-3 h under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12h, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
Wherein: and (2) adding the PNIPAM after the DAC is uniformly dispersed in the step (1), otherwise, adding a small amount of DAC which cannot be dissolved, wherein the mass ratio of the DAC to the PNIPAM is 3-4: 1. The total mass fraction of AM and PNIPAM is 20-25%. When the monomer concentration is low, the monomer contact probability is low, the relative molecular mass of the polymer is low due to the slow polymerization reaction rate, when the monomer concentration is continuously increased, the reaction monomer contact probability is greatly increased, the synthesis reaction speed is accelerated, and the apparent viscosity and yield of the solution are increased; when the total monomer concentration exceeds 25%, the heat of polymerization hardly evolves to the detriment of the progress of polymerization, resulting in a decrease in the apparent viscosity and yield of the polymer solution.
The mass fraction of the tetraethoxysilane added in the step (2) is 2.0-4.0%. When the mass fraction of the tetraethoxysilane is less than 2.0%, the characteristic viscosity number is reduced after being increased along with the increase of the mass fraction of the tetraethoxysilane. This is because the reaction between the monomers is incomplete at the initial stage of the reaction, resulting in crosslinkingThe degree is lower, and the characteristic viscosity is reduced; after reacting for a period of time, adding an ethyl orthosilicate monomer for reaction, and increasing the characteristic viscosity of the flocculant, wherein the degree of crosslinking is higher than that of complete reaction; when the added tetraethoxysilane is more than 4.0 percent, the tetraethoxysilane is hydrolyzed to generate nano Si O2The alcohol and water are generated at the same time, so that the concentration of the whole system monomer is reduced, the collision probability of the residual monomer is reduced, the further polymerization reaction speed of the monomer is influenced, the chain termination probability is increased, the chain growth rate is slowed down, and the characteristic viscosity of the product is reduced.
The mass fraction of the branching agent pentaerythritol added in the step (3) is 0.02-0.05%. In the polymerization process, when the amount of the branching agent is too small, the probability of generating branched chains of the polymer is reduced, the number of branched chains of the polymer is increased along with the increase of the amount of the branching agent, the space structure is regular, and when the amount of the branching agent is too high, self-crosslinking reaction is generated, so that the solubility of the polymer is reduced.
And (4) adding a photoinitiator with the mass fraction of 0.2-0.4% of the total monomer mass in the process of introducing nitrogen and removing oxygen. If the amount of the initiator is small, the amount of the generated active radicals is reduced, so that the chain growth becomes slow, the polymerization reaction is difficult to initiate or the reaction time is long, the radical polymerization reaction cannot be normally performed, and if the amount of the initiator is large, the amount of the generated active radicals is increased, so that the reaction rate is increased, a large amount of heat generation is caused, the molecular chain is easily broken, and both of these two cases result in the reduction of the relative molecular mass of the product.
In the step (5), the ultraviolet illumination time is 1-3 h, and the light intensity range is 0.06-0.34 mW/cm2When the illumination intensity is too low, enough free radicals cannot be generated to excite chain initiation, and the polymerization reaction is difficult to initiate or the reaction time is long, so that the reaction efficiency is reduced; when the illumination intensity is too high, the polymerization reaction rate is too high, so that the heating rate is too high, the chain termination rate is also accelerated, and the polymer has a short molecular chain, low relative molecular mass and low intrinsic viscosity. The initiator can be decomposed by ultraviolet irradiation, free radicals are further generated for polymerization reaction, and when the irradiation time is less than 1h, the reaction is not completed; when the reaction time is higher than 3h, the transparent solution becomesThe gel state affects the transmission of ultraviolet light, so that the reaction efficiency is reduced.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the invention has the advantages of simplicity, less energy consumption, short reaction time, excellent product performance, faster sedimentation rate, good stability of the obtained organic polymeric flocculant, concentrated molecular weight, easy dissolution and better economic and social benefits.
2. The temperature-sensitive responsive hyperbranched flocculant prepared by the method has the flocculation effect of the conventional flocculant, can exert a better flocculation effect at a specific temperature due to the specific temperature sensitivity, and has a high sedimentation rate. Therefore, the temperature-sensitive responsive hyperbranched flocculant has good social benefit and economic benefit in practical application.
Detailed Description
The present invention will be described in further detail with reference to specific examples, wherein the raw materials used are common commercial products unless otherwise specified.
Example 1:
1) mixing DAC and PNIPAM monomers in a mass ratio of 3: 1 is added into distilled water and stirred continuously until the two are dissolved completely, and the total mass fraction of DAC and PNIPAM in the distilled water is controlled to be 20 percent.
2) The mass fraction of the added tetraethoxysilane is 2.0 percent.
3) The mass fraction of the added pentaerythritol was 0.01%.
4) 0.02 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.08W/cm2And (3) reacting for 1h under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature for 12h after the reaction is finished, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
Example 2:
1) mixing DAC and PNIPAM monomers in a mass ratio of 3.5: adding the mixture into distilled water according to the proportion of 1, and continuously stirring until the mixture is completely dissolved, wherein the total mass fraction of DAC and PNIPAM in the distilled water is controlled to be 25%.
2) The mass fraction of the added tetraethoxysilane is 2.5 percent.
3) The mass fraction of the added pentaerythritol was 0.02%.
4) 0.03 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.12W/cm2And (3) reacting for 12 hours under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12 hours, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
Example 3:
1) mixing DAC and PNIPAM monomers in a mass ratio of 4:1 is added into distilled water and stirred continuously until the two are dissolved completely, and the total mass fraction of the DAC and the PNIPAM in the distilled water is controlled to be 30 percent.
2) The mass fraction of the added tetraethoxysilane is 3.0 percent.
3) The mass fraction of the added pentaerythritol was 0.03%.
4) 0.04 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.15W/cm2And (3) reacting for 2 hours under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12 hours, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
Example 4:
1) mixing DAC and PNIPAM monomers in a mass ratio of 4:1 is added into distilled water and stirred continuously until the two are dissolved completely, and the total mass fraction of DAC and PNIPAM in the distilled water is controlled to be 20 percent.
2) The mass fraction of the added tetraethoxysilane is 3.0 percent.
3) The mass fraction of the added pentaerythritol was 0.03%.
4) 0.04 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.24W/cm2Reacting for 1h under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12h, and purifying the product to obtain the productA sensitive response type hyperbranched flocculant.
Example 5:
1) mixing DAC and PNIPAM monomers in a mass ratio of 3: adding the mixture into distilled water according to the proportion of 1, and continuously stirring until the mixture is completely dissolved, wherein the total mass fraction of DAC and PNIPAM in the distilled water is controlled to be 25%.
2) The mass fraction of the added tetraethoxysilane is 3.5%.
3) The mass fraction of the added pentaerythritol was 0.04%.
4) 0.03 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.26W/cm2And (3) reacting for 2 hours under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12 hours, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
Example 6:
1) mixing DAC and PNIPAM monomers in a mass ratio of 3.5: 1 is added into distilled water and stirred continuously until the two are dissolved completely, and the total mass fraction of the DAC and the PNIPAM in the distilled water is controlled to be 30 percent.
2) The mass fraction of the added tetraethoxysilane is 4.0%.
3) The mass fraction of the added pentaerythritol was 0.05%.
4) 0.02 percent of photoinitiator VA-044 is added in the process of introducing nitrogen and removing oxygen.
5) Finally, the reactor is placed in an ultraviolet lamp with the light intensity range of 0.28W/cm2And (3) reacting for 3 hours under the irradiation of a low-pressure ultraviolet mercury lamp, curing at room temperature after the reaction is finished for 12 hours, and purifying the product to obtain the temperature-sensitive response type hyperbranched flocculant.
The intrinsic viscosity and the removal rate of kaolin wastewater of the temperature-sensitive responsive hyperbranched flocculants prepared in examples 1 to 6 were measured, and the data are detailed in table 1.
TABLE 1 Performance parameters of organic polymeric flocculants
| Product performance | Intrinsic viscosity (dL/g) | Kaolin wastewater removal (%) |
| Example 1 | 11.9 | 95.4 |
| Example 2 | 11.1 | 94.9 |
| Example 3 | 12.2 | 96.9 |
| Example 4 | 11.8 | 97.8 |
| Example 5 | 11.2 | 96.9 |
| Example 6 | 11.6 | 96.7 |
As can be seen from the above table 1, the product prepared by the preparation method of the temperature-sensitive responsive hyperbranched flocculant of the present invention has excellent and stable performance, the intrinsic viscosity is in a good range, and the kaolin wastewater treatment effect is good. The method is a feasible and excellent preparation method of the temperature-sensitive responsive hyperbranched flocculant.
Finally, it should be noted that the above-mentioned examples of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. All obvious changes and modifications of the present invention are within the scope of the present invention.
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| CN114685738A (en) * | 2022-05-06 | 2022-07-01 | 重庆工商大学 | Preparation method of temperature-responsive hyperbranched segmented flocculant |
| CN115043975A (en) * | 2022-07-04 | 2022-09-13 | 重庆工商大学 | Preparation method of temperature-sensitive magnetic organic polymeric flocculant |
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| CN114685738A (en) * | 2022-05-06 | 2022-07-01 | 重庆工商大学 | Preparation method of temperature-responsive hyperbranched segmented flocculant |
| CN115043975A (en) * | 2022-07-04 | 2022-09-13 | 重庆工商大学 | Preparation method of temperature-sensitive magnetic organic polymeric flocculant |
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