CN110655606B - Method for preparing cationic polyacrylamide by composite photo-initiation - Google Patents
Method for preparing cationic polyacrylamide by composite photo-initiation Download PDFInfo
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 63
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001723 curing Methods 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 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 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims 2
- UEZFTYYAPVKRKM-UHFFFAOYSA-N 1-[6-hydroxy-4-(2-hydroxyethoxy)-6-methylcyclohexa-2,4-dien-1-yl]propan-2-one Chemical compound OC1(C(C=CC(=C1)OCCO)CC(C)=O)C UEZFTYYAPVKRKM-UHFFFAOYSA-N 0.000 claims 1
- 150000001409 amidines Chemical class 0.000 claims 1
- -1 azo diisopropyl imidazoline hydrochloride Chemical compound 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 38
- 238000005189 flocculation Methods 0.000 abstract description 9
- 230000016615 flocculation Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 14
- 230000000977 initiatory effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
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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
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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Abstract
The invention relates to a method for preparing cationic polyacrylamide by composite photo-initiation, which comprises the steps of sequentially adding deionized water, an acrylamide monomer, a cationic monomer and a cosolvent into a reaction device until the deionized water, the acrylamide monomer, the cationic monomer and the cosolvent are completely dissolved, adjusting the pH value of the solution, filling high-purity nitrogen into the reaction device under the condition of keeping out of the sun while adding different photoinitiators, uniformly mixing, sealing and placing on a uniform-speed turntable, sequentially reacting under the conditions of main wavelength 254nm ultraviolet light and main wavelength 365nm ultraviolet light for a period of time, and then curing, washing, refining, drying and grinding the product to obtain a powder product. The method is characterized in that the photoinitiators with different decomposition wavelengths are coupled with the ultraviolet light with corresponding wavelengths, so that the advantages of the ultraviolet light with different wavelengths are fully exerted, the selectivity of the photoinitiators is strong, the polymerization reaction process is easy to control, the generation time period and the generation speed of free radicals can be controlled, and the CPAM with high cationic degree, good solubility and excellent flocculation performance can be prepared.
Description
Technical Field
The invention relates to a method for synthesizing an aqueous solution high-molecular polymer, in particular to a method for preparing cationic polyacrylamide by composite photo-initiation.
Background
Polyacrylamide (PAM) is a high molecular compound obtained by homopolymerization of an Acrylamide (AM) monomer, and broadly PAM also includes a copolymer obtained by copolymerization of AM and other monomers, and can be subdivided into: non-ionic polyacrylamide (NPAM), amphoteric polyacrylamide (zpram), Anionic Polyacrylamide (APAM) and Cationic Polyacrylamide (CPAM). Because the molecular chain of the CPAM has positive charge active groups and is a linear high molecular polymer, colloidal particles and suspended matters in water can be destabilized and flocculated to be removed through the actions of electrical neutralization, adsorption bridging and the like, and the CPAM has good functions of turbidity removal, decoloration and the like, and is widely applied to the fields of water treatment such as sludge conditioning, printing and dyeing wastewater and the like. The current main methods for preparing CPAM are copolymerization method and mannich method. Compared with the Mannich method, the CPAM prepared by the copolymerization method has higher cationic degree, and the cationic degree can be controlled by the using amount of the cationic monomer, so that the method is the most widely researched and applied method at present.
In the process of preparing cationic polyacrylamide by a copolymerization method, certain problems also exist, and common cationic monomers such as methacryloyloxyethyl trimethyl ammonium chloride (DMC), acryloyloxyethyl trimethyl ammonium chloride (DAC) or dimethyl diallyl ammonium chloride (DMDAAC) have large space resistance and low polymerization activity, so that the conversion rate of the cationic monomers is not high enough, the waste of raw materials is caused, the production and use cost of the flocculant is improved, the cationic degree of a product is not high enough usually, the electric neutralization performance of CPAM is influenced, and the flocculation performance of CPAM is further influenced. The invention patent with publication number CN 102206303A 'method for initiating dimethyl diallyl ammonium chloride and acrylamide copolymer by using composite initiator' discloses a CPAM preparation method, which is characterized in that the product has high relative molecular mass and high degree of cationization of the product, and the composite initiator is adopted, and three-step heating is carried out to initiate polymerization to generate a colloidal product.
The ultraviolet light initiation is an initiation mode with high reaction rate, low energy consumption and simple operation, and is a new CPAM initiation method. According to the wavelength difference of the ultraviolet light, the ultraviolet light can be divided into long-wave ultraviolet light (UVA band, wavelength is 320-420nm), medium-wave ultraviolet light (UVB band, wavelength is 275-320nm), short-wave ultraviolet light (UVC band, wavelength is 200-275nm) and vacuum ultraviolet light (UVD band, wavelength is 100-200 nm). The photon energy of the ultraviolet light is inversely proportional to the wavelength, i.e., the shorter the wavelength, the higher the photon energy, and the short-wave ultraviolet light is usually generated by a low-pressure ultraviolet lamp, and has the disadvantages of low light intensity and low energy output efficiency. In contrast, long wavelength ultraviolet light has relatively little photon energy, but is typically produced by high pressure ultraviolet lamps, which have high light intensity and high energy output efficiency. In the polymerization reaction for initiating and preparing CPAM, the photon energy of short-wave ultraviolet light is high, which is easy to initiate the polymerization reaction, but the ultraviolet lamp adopted by the short-wave ultraviolet light has small power, slow reaction rate and slow heat release speed, the product is not easy to generate the problem of crosslinking, and the solubility is good, but the molecular weight of the CPAM prepared usually is not high enough. The opposite is true of long-wave ultraviolet light initiation, the reaction rate is high, the heat release rate is high, and implosion can be caused if the control is improper, so that the prepared product is difficult to dissolve in water. Different photoinitiators have different decomposition wavelengths, can be decomposed to generate free radicals only within a specific wavelength range to initiate polymerization, have strong selectivity, and can control whether the corresponding photoinitiators generate the free radicals or not by controlling the wavelengths. Therefore, the invention aims to couple the photoinitiators with different decomposition wavelengths with ultraviolet light with corresponding wavelengths, fully exert the advantages of the photoinitiators and the ultraviolet light, control the polymerization reaction process by controlling the generation time period and the generation speed of free radicals, is favorable for overcoming the space resistance of cationic monomers, ensures that the cationic monomers in a reaction system fully participate in the reaction, can prepare CPAM with high cationic degree, high relative molecular weight and excellent flocculation performance, has the advantages of low production energy consumption, high production efficiency, simple operation, easy control and the like in an ultraviolet light initiation mode, and has good market application prospect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to: the method for preparing the cationic polyacrylamide has the advantages of few types of added auxiliaries, low dosage, good CPAM (cationic polyacrylamide) solubility, good flocculation property, low production energy consumption, high production efficiency, simple operation and easy control.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing cationic polyacrylamide by a novel photoinitiation system comprises the following specific steps:
firstly, sequentially adding deionized water, an acrylamide monomer, a cationic monomer and a cosolvent urea into a reaction device, stirring and dissolving uniformly, and then adjusting the pH value of the solution to 2.5-10; counting a cationic monomer and an acrylamide monomer as total monomers, wherein the mass fraction of the total monomers in a reaction system is 15-60%, the acrylamide monomer accounts for 10-90% of the total monomers, and the cationic monomer accounts for 10-90% of the total monomers; cosolvent urea accounts for 0.2-5 per mill of the total monomer mass;
secondly, under the condition of keeping out of the sun, filling high-purity nitrogen into the reaction device to remove air in the reaction device, sequentially adding 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone (Irgacure2959) powder accounting for 1-5 per mill of the total monomer mass, and azodiisobutyramidine hydrochloride (V50) or azodiisopropyl imidazoline hydrochloride (V044) solution accounting for 0.02-1.00 per mill of the total monomer mass into the solution, uniformly stirring, sealing the reaction device after air in the reaction device is completely removed, and placing the reaction device in an ultrasonic instrument to vibrate for 2-10min after sealing;
the two photoinitiators adopted by the invention can react to generate free radicals to initiate polymerization reaction only under ultraviolet light with corresponding wavelength, namely Irgacure2959 can decompose to generate free radicals only under ultraviolet light with wavelength of 254nm, and V50 or V044 can decompose to generate free radicals only under ultraviolet light with wavelength of 254nm, and the two photoinitiators have good selectivity and are beneficial to control of the polymerization reaction process.
Thirdly, placing the reaction device vibrated in the second step on a rotating disc rotating at a constant speed at room temperature, firstly irradiating and reacting for 10-70 min under the ultraviolet light with the main wavelength of 254nm, then irradiating for 30-110min under the ultraviolet light with the main wavelength of 365nm, standing and curing for 10-180min to obtain colloidal cationic polyacrylamide;
the photoinitiator can be decomposed only in the corresponding wavelength range to generate free radicals to initiate polymerization reaction, and the invention adopts two photoinitiators with different decomposition wavelengths to be coupled with ultraviolet light with corresponding wavelengths, so that the polymerization reaction process can be better controlled, and the specific principle is as follows. In the initial stage of reaction, under the condition of low-pressure ultraviolet irradiation with wavelength of 254nm, only Irgacure2959 can be reacted in the reactor to produce free radical to initiate polymerization reaction. When the reaction is carried out to a certain degree, a low-pressure ultraviolet lamp with the wavelength of 254nm is closed, and a high-pressure ultraviolet lamp with the wavelength of 365nm is opened, only V50 or V044 can react to generate free radicals to initiate polymerization reaction at the moment, but part of monomers in a polymerization reaction system are converted into polymers at the moment, the monomer content is reduced, the possibility of implosion is greatly reduced, chain growth can be still uniformly and orderly carried out, the linearity of a polymerization product can be ensured to be good, and the solubility of the product can be ensured; and because the long wave ultraviolet light penetration ability is strong, the reaction rate of the high pressure ultraviolet light is fast, the output efficiency of energy is improved in the later stage of the reaction, the initiator is promoted to initiate in an accelerated way, the space resistance of the cationic monomer is favorably overcome, the cationic monomer in the reaction system is completely reacted, the intrinsic viscosity and the cationic degree of the product are favorably improved, the residual monomer in the product can be reduced, the product conversion rate is improved, the utilization efficiency of the monomer is improved, and the production cost is reduced. If the polymerization reaction only adopts a low-pressure ultraviolet lamp with the wavelength of 254nm, although the solubility of the product can be ensured, the monomer can not fully participate in the reaction, the intrinsic viscosity of the product is not high enough, and the adsorption and bridging performance of the flocculant is not ideal in the flocculation process; if only a high-pressure ultraviolet lamp with the wavelength of 365nm is adopted in the polymerization reaction, the polymerization speed in the early stage of the polymerization reaction is not easy to control, and the solubility of the prepared product is difficult to ensure; if the redox-azo initiator is coupled with the light intensity increased in gradient, the selectivity of the initiator is poor, the redox initiator and part of the azo initiator can react to generate free radicals to initiate polymerization reaction in the early stage of the polymerization reaction, the control effect of the reaction speed is poor, and the solubility of the product can not be effectively ensured. The initiator with different initiation wavelengths is coupled with the ultraviolet light with corresponding wavelengths, so that the photoinitiator is good in selection, the polymerization reaction process is good in control effect, the advantages of low-pressure ultraviolet light (lambda-254 nm) and high-pressure ultraviolet light (lambda-365 nm) can be fully exerted, and the defects of the low-pressure ultraviolet light and the high-pressure ultraviolet light are effectively avoided, so that the prepared product is high in cationic degree, good in solubility and excellent in flocculation performance.
And fourthly, washing and refining the prepared colloidal polyacrylamide by acetone and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃ or below, and grinding to obtain the cationic polyacrylamide powder product.
Furthermore, the reaction device is made of quartz, the quartz light transmittance is high, and the utilization rate of ultraviolet light and the initiator is improved, so that the addition amount of the initiator can be reduced on the premise of ensuring the polymerization degree, the crosslinking of molecular chains in the polymerization process is reduced, and the conversion rate and the molecular weight of CPAM are improved.
Further, the cosolvent urea is added in the form of solution, and the concentration range is 1.0 multiplied by 10-3g/ml-5×10- 2g/ml, which can help urea to be fully mixed in the reaction solution and ensure that the urea can fully play a role.
Further, the V50 or V044 initiator solution concentration ranges 1X 10-3g/ml-8.0×10-3g/ml, which can help the initiator and the monomer to be mixed well and participate in the polymerization reaction well.
Further, the cationic monomer is one of methacryloyloxyethyl trimethyl ammonium chloride (DMC), acryloyloxyethyl trimethyl ammonium chloride (DAC) or dimethyldiallylammonium chloride (DMDAAC).
Furthermore, in the second step, the power of the ultrasonic instrument is 480W, the frequency of generating ultrasonic waves is 40kHz, and various substances in the reaction system are fully and uniformly mixed through the oscillation of the ultrasonic waves, so that the uniform and orderly progress of the polymerization reaction is promoted.
Furthermore, in the third step, the rotating speed of the uniform rotating disc is 10-60s/r, which can help the reaction system to be uniformly illuminated, and the reaction speeds at different positions basically tend to be consistent.
Further, the light intensity of the ultraviolet lamp with the wavelength of 254nm is 0.1-1mW/cm2In the short wave ultraviolet light initiated polymerization reaction period, the initiator Irgacure2959 is decomposed to generate free radicals to initiate polymerization reaction, the amount of residual monomers in the reaction system is higher, but the reaction period is weaker in light intensity, the polymerization reaction temperature is maintained at a lower level, the reaction is smoother, and the chain growth can be uniformly and orderly carried out.
Furthermore, the light intensity of the 365nm ultraviolet light is 3-22mW/cm2In the long-wave ultraviolet light initiated polymerization reaction time period, the azo initiator is decomposed to generate free radicals to initiate polymerization reaction, the light intensity in the reaction time period is higher, as the polymerization reaction is carried out to a certain degree, the concentration of unreacted monomers in the reaction system is lower, the penetrability of the long-wave ultraviolet light is strong, the initiator is promoted to be initiated at an accelerated speed, the space resistance of cationic monomers is favorably overcome, the cationic monomers in the reaction system are enabled to react completely, the intrinsic viscosity and the cationic degree of products are favorably improved, residual monomers in the products can be reduced, the product conversion rate is improved, the utilization efficiency of the monomers is improved, and the production cost is reduced. And because the concentration of the unreacted monomer is lower, the polymerization reaction can be still uniformly and orderly carried out, the condition of molecular chain crosslinking is difficult to occur, the product has good linearity, good solubility and good flocculation performance.
Compared with the prior art, the invention has at least the following advantages:
1. the photoinitiator has strong selectivity, can be decomposed to generate free radicals only in the range of ultraviolet light with corresponding wavelength to initiate polymerization reaction, couples the photoinitiators with different decomposition wavelengths with the ultraviolet light with corresponding wavelength to fully play the advantages of the short-wave ultraviolet light and the long-wave ultraviolet light, and the initiation system adopted by the invention can keep the free radicals with certain concentration in the reaction system, thereby not only ensuring the uniform and orderly chain growth, but also ensuring the good linearity and the good solubility of the product; and AM monomer and cationic monomer can fully participate in polymerization reaction, the cationic degree and molecular weight of the product are improved on the premise of ensuring the monomer conversion rate, the product electric neutralization function and the adsorption bridging function are improved, and the aim of improving the flocculation performance of the product is fulfilled.
2. The invention has the advantages of ultraviolet light initiation mode, namely, the photoinitiation is easier to control than thermal initiation, the regulation of ultraviolet light wavelength is easier to realize than thermal initiation, the energy propagation speed is high, the propagation is uniform, the polymerization reaction is more favorably carried out, the simplicity and the energy saving are realized, and the preparation process is easy to control. Meanwhile, the method also has the advantages of high reaction speed and low reaction energy consumption.
3. According to the quartz reaction device, the ultrasonic oscillation and uniform speed turntable and other methods provided by the invention, various additives (especially initiators) can be fully utilized, so that the addition amount is extremely low, and the occurrence of side reactions can be effectively avoided while production materials are saved; and the polymerization reaction is uniform and thorough, and the flocculation performance of the product can be improved.
The raw materials selected by the method are all commercial materials, are low in price and convenient to select, and can be directly purchased, so that the synthetic method provided by the invention is low in production cost and easy to realize marketization.
Drawings
FIG. 1 shows the reaction equation of AM with DMDAAC, DMC, DAC
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples, HCl solutions with different concentrations are used as inorganic acids, NaOH solutions with different concentrations are used as inorganic bases to adjust the pH, and in specific implementation, other inorganic acids and inorganic bases that do not affect the polymerization reaction in the prior art may be used to adjust the pH. The limit viscosity and the dissolution time of the prepared CPAM are measured by referring to GB/T31246-2014 water treatment agent cationic polyacrylamide technical conditions and test methods, and the conversion rate of the CPAM is measured by a gravimetric method. Specific sludge resistance and water content of sludge cake were measured in reference paper (Zheng H, Sun Y, Zhu C, et al. UV-initiated polymerization of hydrolytic analytical locations: Synthesis, chromatography, and dewatering properties [ J ]. Chemical Engineering Journal,2013,234: 318-.
Example 1: a preparation method of CPAM flocculant comprises the following specific steps:
firstly, sequentially adding deionized water, an acrylamide monomer, a cationic monomer DAC and a cosolvent urea into a reaction device, stirring and dissolving uniformly, and then adjusting the pH value of the solution to 2.5; the DAC monomer and the AM monomer are counted as total monomers, the mass fraction of the total monomers in a reaction system is 60%, the acrylamide monomer accounts for 10% of the mass of the total monomers, and the cationic monomer accounts for 90% of the mass of the total monomers; cosolvent urea accounts for 5 per mill of the total monomer mass (added in the form of solution, the concentration of the solution is 5.0 multiplied by 10)-2g/ml)；
Secondly, under the condition of keeping out of the sun, the reaction device is filled with high-purity nitrogen to remove the air in the reaction device, and the Irgacure2959 powder accounting for 5 per mill of the total monomer mass and the V50 solution (with the concentration of 1 multiplied by 10 and 0.02 per mill of the total monomer mass) are sequentially added into the solution-3g/ml), stirring uniformly, sealing the reaction device after air in the reaction device is completely removed, and placing the reaction device in an ultrasonic instrument to vibrate for 2min after sealing (the power of the ultrasonic instrument is 480W, and the frequency of generating ultrasonic waves is 40 kHz).
Thirdly, under the condition of room temperature, on a uniform rotating disc with the rotating speed of 10s/r of the reaction device after the oscillation in the second step, firstly, the dominant wavelength is 254nm, and the light intensity is 1mW/cm2Irradiating under ultraviolet light for 70min, and then irradiating with light with dominant wavelength of 365nm and light intensity of 22mW/cm2Irradiating for 30min under ultraviolet light, standing and curing for 180min to obtain colloidal cationic polyacrylamide.
And fourthly, washing and refining the prepared colloidal polyacrylamide by acetone and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃, and grinding to obtain the cationic polyacrylamide powder product.
The limiting viscosity was found to be 7.3dL/g, with a conversion of 97.6%.
Example 2: a preparation method of CPAM flocculant comprises the following specific steps:
firstly, sequentially adding deionized water, an AM monomer, a DMDAAC monomer and cosolvent urea into a reaction device, uniformly stirring and dissolving, and then adjusting the pH value of the solution to 9; counting a DMDAAC monomer and an AM monomer as total monomers, wherein the mass fraction of the total monomers in a reaction system is 15%, an acrylamide monomer accounts for 90% of the mass of the total monomers, and a cationic monomer accounts for 10% of the mass of the total monomers; cosolvent urea accounts for 0.2 per mill (1.0 multiplied by 10) of the total monomer mass-3g/ml)；
Secondly, under the condition of keeping out of the sun, the reaction device is filled with high-purity nitrogen to remove the air in the reaction device, and Irgacure2959 powder accounting for 0.1 per mill of the total monomer mass and V044 solution (with the concentration of 8.0 multiplied by 10 and the weight of 1.00 per mill of the total monomer mass) are sequentially added into the solution-3g/ml), stirring uniformly, sealing the reaction device after air in the reaction device is completely removed, and placing the reaction device in an ultrasonic instrument to vibrate for 10min after sealing (the power of the ultrasonic instrument is 480W, and the frequency of generating ultrasonic waves is 40 kHz).
Thirdly, under the condition of room temperature, the reaction device after the oscillation in the second step is placed on a turntable which rotates at a constant speed, and the light intensity is 0.1mW/cm firstly under the condition that the dominant wavelength is 254nm2+Is irradiated under ultraviolet light for 10min, and then the light intensity is 3mW/cm with the dominant wavelength of 365nm2Irradiating for 110min under ultraviolet light, standing and curing for 180min to obtain colloidal cationic polyacrylamide.
And fourthly, washing and refining the prepared colloidal polyacrylamide by acetone and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃, and grinding to obtain the cationic polyacrylamide powder product.
The limiting viscosity was found to be 18.2dL/g with a conversion of 99.2%.
Example 3: a preparation method of CPAM flocculant comprises the following specific steps:
firstly, sequentially adding deionized water, an AM monomer, a DMC monomer and a cosolvent urea into a reaction device, stirring and dissolving uniformly, and then adjusting the pH value of the solution to 4; calculating DMC monomer and AM monomer as total monomer, the mass fraction of the total monomer in the reaction system is 35The mass percent of the acrylamide monomer is 70 percent of the total mass of the monomers, and the mass percent of the cationic monomer is 30 percent of the total mass of the monomers; cosolvent urea accounts for 3 per mill of the total monomer mass (solution concentration is 3.6 multiplied by 10)-3g/ml)；
Secondly, under the condition of keeping out of the sun, the reaction device is filled with high-purity nitrogen to remove the air in the reaction device, and the Irgacure2959 powder accounting for 0.5 per mill of the total monomer mass and the V50 solution (with the concentration of 6.0 multiplied by 10 and 0.3 per mill of the total monomer mass) are sequentially added into the solution-3g/ml), stirring uniformly, sealing the reaction device after air in the reaction device is completely removed, and placing the reaction device in an ultrasonic instrument to vibrate for 5min after sealing (the power of the ultrasonic instrument is 480W, and the frequency of generating ultrasonic waves is 40 kHz).
Thirdly, under the condition of room temperature, the reaction device after the oscillation in the second step is placed on a turntable which rotates at a constant speed, and the light intensity is 1mW/cm firstly under the condition that the dominant wavelength is 254nm2Is irradiated under ultraviolet light for 30min, and then the light intensity is 20mW/cm with the dominant wavelength of 365nm2Irradiating for 50min under ultraviolet light, standing and aging for 120min to obtain colloidal cationic polyacrylamide.
And fourthly, washing and refining the prepared colloidal polyacrylamide by acetone and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃ or below, and grinding to obtain the cationic polyacrylamide powder product. The limiting viscosity was found to be 22.1dL/g with a conversion of 99.5%.
Examples 4-7 were the same procedure as for the cationic polyacrylamide powder product prepared in example 1, except for the selection of parameters, as detailed in table 1.
The ultimate viscosities and conversion of the cationic polyacrylamide powder products prepared in examples 4-7 are shown in Table 2.
TABLE 1
TABLE 2
TABLE 3. examples 3, 7 Performance and sludge with commercially available CPAM productsaComparison of dewatering Performance
Is the excess sludge of a certain sewage treatment plant of Nanjing Jiangning: the results of all indexes of the sludge sample are as follows: the water content is 98.91%, the density is 0.985kg/L, and the pH value is 7.3.
As can be seen from examples 1 to 7 and Table 2, the cationic polyacrylamide powder product prepared by the method of the present invention has CPAM with high cationicity and good solubility. As can be seen from Table 3, compared with the commercial CPAM product, the home-made product has higher limiting viscosity, shorter dissolving time, smaller dosage when sludge conditioning is carried out, and better sludge dewatering performance.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A method for preparing cationic polyacrylamide by composite photo-initiation is characterized by comprising the following specific steps:
firstly, sequentially adding deionized water, an acrylamide monomer, a cationic monomer and a cosolvent urea into a reaction device, stirring and dissolving uniformly, and then adjusting the pH value of the solution to 2.5-10; counting a cationic monomer and an acrylamide monomer as total monomers, wherein the mass fraction of the total monomers in a reaction system is 15-60%, the acrylamide monomer accounts for 60-90% of the mass of the total monomers, and the cationic monomer accounts for 10-40% of the mass of the total monomers; cosolvent urea accounts for 0.2-5 per mill of the total monomer mass;
the cationic monomer is one of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride or dimethyl diallyl ammonium chloride;
secondly, filling high-purity nitrogen into the reaction device to remove air in the reaction device under a dark condition, sequentially adding 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenylpropanone powder accounting for 0.1-5 per mill of the mass of the total monomers, azobisisobutyramidine hydrochloride or azobisisopropylimidazoline hydrochloride accounting for 0.02-1.00 per mill of the mass of the total monomers into the solution, uniformly stirring, sealing the reaction device after the air in the reaction device is completely removed, and placing the reaction device in an ultrasonic instrument to vibrate for 2-10min after sealing;
the concentration range of the azo diisobutyl amidine hydrochloride or the azo diisopropyl imidazoline hydrochloride initiator solution is 1 x 10- 3g/ml-8.0×10-3g/ml；
Thirdly, placing the reaction device vibrated in the second step on a rotating disc rotating at a constant speed at room temperature, firstly irradiating and reacting for 10-70 min under the ultraviolet light with the main wavelength of 254nm, then irradiating for 30-110min under the ultraviolet light with the main wavelength of 365nm, standing and curing for 10-180min to obtain colloidal cationic polyacrylamide;
and fourthly, washing and refining the prepared colloidal polyacrylamide by acetone and alcohol, drying in a vacuum drying oven at the temperature of 60 ℃ or below, and grinding to obtain the cationic polyacrylamide powder product.
2. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: the reaction device is made of quartz.
3. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: the cosolvent urea is added in the form of solution, and the concentration range is 1.0 multiplied by 10-3 g/ml-5×10 -2 g/ml。
4. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: in the second step, the power of the ultrasonic instrument is 480W, and the frequency of generating ultrasonic waves is 40 kHz.
5. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: the rotating speed of the rotating disc is 10-60 s/r.
6. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: the light intensity of an ultraviolet lamp with the wavelength of 254nm is 0.1-1mW/cm2 。
7. The method for preparing the cationic polyacrylamide by composite photo-initiation according to claim 1, wherein: the light intensity of the 365nm ultraviolet light is 3-22mW/cm2 。
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