CN113698530B - High-steric-hindrance series cationic solid polyacrylamide and preparation method thereof - Google Patents
High-steric-hindrance series cationic solid polyacrylamide and preparation method thereof Download PDFInfo
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 57
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 40
- 239000007787 solid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 109
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 230000000977 initiatory effect Effects 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000084 colloidal system Substances 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 238000005286 illumination Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 33
- 230000000694 effects Effects 0.000 abstract description 5
- 229920006322 acrylamide copolymer Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 80
- 239000000047 product Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- -1 2,4, 6-trimethyl benzoyl ethyl Chemical group 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 150000001409 amidines Chemical class 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KVFFVDVAFFSIIL-UHFFFAOYSA-M dimethyl-(3-methyl-2-oxobut-3-enyl)-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CC(=O)C(C)=C KVFFVDVAFFSIIL-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 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 description 2
- 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 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OIFLLGNCLZLPAF-UHFFFAOYSA-M trimethyl-(5-methyl-4-oxohex-5-enyl)azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)CCC[N+](C)(C)C OIFLLGNCLZLPAF-UHFFFAOYSA-M 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/56—Polymerisation initiated by wave energy or particle radiation by ultrasonic vibrations
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of high steric hindrance series cationic solid polyacrylamide, belonging to the field of high molecular polymerization. The method comprises the following steps: preparing a raw material cationic monomer into a first polymerization solution; preparing a second polymerization solution from raw material acrylamide; preparing azo initiator solution from the azo initiator; adjusting the temperature and the pH value of the three solutions, and deoxidizing; pre-initiating the deoxidized first polymerization solution by ultrasonic radiation until the equilibrium viscosity of the first polymerization solution reaches 30-200 cps; then adding the second polymerization solution and the azo initiator solution into the first polymerization solution for further polymerization and curing; after the colloid is cured, a cationic solid polyacrylamide product is prepared. The invention initiates the allyl cationic monomer with high steric hindrance and low activity in advance by ultrasonic waves, can effectively improve the proportion of the acrylamide copolymer, increases the molecular weight of the polymer and reduces the content of residual monomers.
Description
Technical Field
The invention belongs to the field of high-molecular polymerization, and particularly relates to high-steric-hindrance series cationic solid polyacrylamide and a preparation method thereof.
Background
Cationic Polyacrylamide (CPAM) is a linear high molecular compound which has a plurality of active groups and can form hydrogen bonds by affinity and adsorption with a plurality of substances. The method is widely applicable to the treatment of wastewater with high organic colloid content in the industries of dyeing, paper making, food, construction, metallurgy, mineral separation, coal dust, oil fields, aquatic product processing, fermentation and the like, and is particularly applicable to the dehydration treatment of municipal sewage, municipal sludge, paper sludge and other industrial sludge. The solid powder type polymer can not only effectively avoid the problems of mildew, pH change, product layering and the like in the storage process of aqueous solution and emulsion polymer products; the method has the advantages of high content of effective substances, low transportation cost and the like, and is always a hotspot and a key point of research in the field.
In the process of synthesizing the high steric hindrance series cationic solid powder polyacrylamide, as methacryloxypropyltrimethylammonium chloride, dimethyldiallylammonium chloride, methacryloxyethyltrimethylammonium chloride and acryloyloxyethyltrimethylammonium chloride belong to allyl monomers, compared with acrylamide, the high steric hindrance cationic solid powder polyacrylamide has the advantages of large steric hindrance, low reactivity ratio and self-inhibition effect, thus the chain initiation and chain growth rate are reduced, the apparent activation energy required by polymerization reaction is high, the homopolymerization tendency of acrylamide is greater than copolymerization tendency during the reaction with the acrylamide, the synthesized product has low molecular weight and high residual monomer content.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a preparation method of high steric hindrance series cationic solid polyacrylamide, which aims to solve the problems related to the background technology.
The invention provides a preparation method of high steric hindrance series cationic solid polyacrylamide, which comprises the following steps:
dissolving raw material cationic monomers, a complexing agent, a solubilizer, a chain transfer agent, a chain extender and a photoinitiator in deionized water, and uniformly stirring to prepare a first polymerization solution; dissolving acrylamide as a raw material in deionized water, and uniformly stirring to prepare a second polymerization solution; preparing azo initiator solution from the azo initiator;
adjusting the temperatures of the first polymerization solution, the second polymerization solution and the azo initiator solution, and the pH values of the first polymerization solution and the second polymerization solution; deoxidizing the first polymerization solution, the second polymerization solution and the azo initiator solution through a deoxidizing device respectively;
conveying the deoxygenated first polymerization solution to an inert gas protection device, and pre-initiating by ultrasonic radiation until the equilibrium viscosity of the first polymerization solution reaches 30-200 cps; then adding the second polymerization solution and the azo initiator solution into the first polymerization solution, and after ultrasonic mixing for a certain time, entering an ultraviolet light region with a certain wavelength and different light intensities for further polymerization and curing;
and step four, after the colloid is cured, preparing a cationic solid polyacrylamide product through pre-grinding, granulating, drying and grinding.
Preferably or alternatively, the cationic monomer is selected from one or more of the quaternary ammonium salts of the compounds represented by the following general structural formulae (i), (ii), (iii):
wherein: r1Represents H or CH3；R2Represents CH2CH2，CH2CH2CH2Or
；R3，R4Respectively represent H, CH3，CH2CH3，
；
Wherein: r5Represents H or CH3，R6，R8， R9Represents H, CH3，CH2CH3Or
R7Represents CH2CH，CH2CH2CH；
Wherein: r10Represents H, CH3，CH2CH3Or
。
Preferably or optionally, adjusting the temperature of the first polymerization solution, the second polymerization solution and the azo initiator solution to-5-20 ℃;
adjusting the pH values of the first polymerization solution and the second polymerization solution to 3.0-7.0; and deoxidizing the first polymerization solution, the second polymerization solution and the azo initiator solution until the dissolved oxygen in a liquid phase is lower than 0.01 ppm.
Preferably or optionally, the ultrasonic power of the ultrasonic radiation pre-initiation is 50-7200W, and the ultrasonic time of the ultrasonic radiation pre-initiation is not more than 15 min;
adding the second polymerization solution and the azo initiator solution into the first polymerization solution, and then, controlling the ultrasonic power to be 50-200W; and continuously carrying out ultrasonic mixing for 0.5-10 min.
Preferably or alternatively, the equilibrium viscosity of the first polymerization solution is measured by an in-line viscometer.
Preferably or optionally, the ultraviolet light region comprises a first ultraviolet light region, a second ultraviolet light region, and a third ultraviolet light region; wherein the wavelengths of the ultraviolet light in the first ultraviolet light region, the second ultraviolet light region and the third ultraviolet light region are all 200-400 nm,
in the first ultraviolet region, the light intensity of the ultraviolet light is 1000-4000 μ w/cm2The illumination time is 10-30 min;
in the second ultraviolet light region, the light intensity of the ultraviolet light is 4000-8000 μ w/cm2Illumination time 20E50min；
In the third ultraviolet region, the light intensity of the ultraviolet light is 8000-12000 μ w/cm2And the illumination time is 0-30 min.
Preferably or optionally, the photoinitiator is a compound of 2,4, 6-trimethyl benzoyl phosphonic acid ethyl ester and 2-hydroxy-2-methyl-1-phenyl-1-acetone, and the mass ratio of the two is 30-70%.
Preferably or optionally, the chain extender is one or two of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol.
Preferably or alternatively, in the first polymerization solution, the mass concentration of each component is respectively as follows:
the cationic monomer accounts for at least 30wt%, the photoinitiator accounts for 10-500 ppm, the complexing agent accounts for 15-500 ppm, the chain transfer agent accounts for 15-300 ppm, the solubilizer accounts for 0.05-5 wt%, and the chain extender accounts for 50-1000 ppm;
in the azo initiator solution, the mass concentration of the azo initiator is 10-300 ppm.
The invention also provides polyacrylamide obtained by the preparation method based on the high steric hindrance series cationic solid polyacrylamide.
The invention relates to a high steric hindrance series cationic solid polyacrylamide and a preparation method thereof, compared with the prior art, the high steric hindrance series cationic solid polyacrylamide has the following beneficial effects:
(1) the invention introduces ultrasonic waves as a pre-initiation means of the allyl high steric hindrance cationic monomer, the ultrasonic waves can enable the first polymerization solution to generate cavitation, the cavitation breaks the monomer to form free radicals, and then the free radicals initiate polymerization reaction, and the method has the advantages of no temperature limit on initiation, high conversion rate, high relative molecular quality of products, narrow particle size distribution, no need of additional initiator and the like; meanwhile, the ultrasonic waves can smash gas dissolved in the polymerization liquid during deoxygenation, so that the gas is prevented from being locked in the colloid during polymerization, and bubbles are formed along with the rise of polymerization temperature, thereby affecting the light transmittance of the colloid.
(2) The invention adopts allyl high steric hindrance cationic monomer for pre-initiation, and then high activity monomer acrylamide is added in sections, so that high activity acrylamide can be prevented from being initiated in advance, the content of acrylamide copolymer is effectively improved, the tendency of acrylamide to generate homopolymer is reduced, and the conversion rate of all monomers is improved. The prepared cationic solid polyacrylamide has high molecular weight, high dissolution speed and less residual monomers.
(3) The mode of ultrasonic pre-initiation and ultraviolet initiation is adopted, so that the simultaneous addition of acrylamide and high-steric-hindrance allyl cationic monomers can be effectively avoided, the acrylamide is initiated to generate a homopolymer in advance, and the ultraviolet initiation is carried out later, and the occurrence of side reactions such as polymer chain breakage, crosslinking and the like caused by overhigh temperature and pressure of local polymer during the ultrasonic treatment for a very long time can also be avoided.
(4) The invention adopts two photoinitiators for compounding, can effectively improve the photoinitiation efficiency, does not use an oxidative and reductive initiator, and avoids the polymer chain fracture caused by the initiator residue in the storage and application of a cationic polyacrylamide product.
(5) The method adopts a mode of pre-initiating allyl high-steric-hindrance cationic monomer by ultrasonic waves and initiating by ultraviolet light, so that the ultraviolet light with long wavelength has better light transmittance and more thorough initiation, the thickness of the belt-type polymerized colloid can be improved, and the production efficiency of the product can be improved; the ultrasonic time is not more than 15min, the breaking of polymer chains caused by long-time initiation of single ultrasonic wave can be avoided, the required equipment is simple to operate, the investment is low, and the method is favorable for industrial production.
(6) According to the invention, allyl cationic monomers are pre-initiated by ultrasound, acrylamide is mixed, and then the mixture is polymerized and cured by ultraviolet light with 365nm wavelength from low to high light intensity, so that a proper amount of free radicals are provided for a reaction system, the polymer can be ensured to be in linear structure extension, the polymerization process is carried out stably, the residual monomers of the synthesized product are low, and the solubility is good.
(7) The method comprises the steps of introducing an online viscometer to monitor the initiation progress of the allylic high-steric-hindrance cationic monomer, when the online viscometer shows that the equilibrium viscosity of the polymerization liquid reaches 30-200 cps, the equilibrium viscosity of the polymerization liquid is larger than 30cps, so that the allylic high-steric-hindrance cationic monomer is initiated, adding monomer acrylamide, mixing, then further polymerizing and curing in a light initiation area, and when the polymerization liquid is further larger than 200cps and a second polymerization liquid and an azo initiator solution are added, the ultrasonic mixing time is increased by two times, which is not beneficial to improving the molecular weight of the product.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
1400kg of cationic monomer methacryloyloxyethyl trimethyl ammonium chloride (80%) and 5600kg of deionized water are added into a batching kettle, then 0.8kg of ethyl 2,4, 6-trimethylbenzoylphosphonate, 1.5kg of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2.3kg of ammonium formate, 2.1kg of disodium ethylenediamine tetraacetate, 1.1kg of diethylene glycol and 200kg of urea are added into the batching kettle to be uniformly mixed and stirred to obtain a polymer solution I, 2800kg of industrial acrylamide (40%) is added into the batching kettle 2 to serve as the polymer solution II, the pH values of the polymer solution I and amidine are respectively adjusted to 4.2 by adopting acrylic acid (30%), the polymer solution I and amidine are cooled to 2 ℃, 0.5kg of azobisisobutyrate hydrochloride is dissolved into 50kg of deionized water, the polymer solution I is deaerated by a feeding pump after being deoxidized, and is pumped into a polymerization belt with an ultrasonic device and carbon dioxide protection, adding the deoxidized polymer when the on-line viscometer shows that the equilibrium viscosity of the polymer solution is 105cpsUltrasonically mixing the polymerization solution and azodiisobutyramidine hydrochloride solution for 5min, and irradiating in ultraviolet region for polymerization and curing to obtain the product with light intensity of 2800 μ w/cm2Light irradiation for 28min polymerization, light intensity of 6500 μ w/cm2Illuminating for 25min, and then using light intensity of 8500 mu w/cm2Curing for 20min by illumination, then cutting gel, granulating, drying and grinding to obtain a cationic polyacrylamide product with the molecular weight of 1042 ten thousand, the dissolving time of 25min and the residual monomer of 75 ppm.
Example 2
1050kg of cationic monomer acryloyloxyethyl trimethyl ammonium chloride (80%) and 5775kg of deionized water are added into a batching kettle, then 0.6kg of auxiliary materials 2,4, 6-trimethyl benzoyl ethyl phosphonate, 1.6kg of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2.0kg of ammonium formate, 2.1kg of ethylene diamine tetraacetic acid, 1.2kg of diethylene glycol and 200kg of urea are added into the batching kettle to be uniformly mixed and stirred to obtain a polymer solution I, 2975kg of industrial acrylamide (40%) is added into the batching kettle 2 to obtain the polymer solution II, the pH values of the polymer solution I and the polymer solution II are respectively adjusted to 4.2 by adopting acrylic acid (30%), the polymer solution I and the polymer solution II are cooled to 2 ℃, 0.2kg of azodiisobutylamine hydrochloride is dissolved in 50kg of deionized water, the polymer solution I is deaerated by a feeding pump, and is pumped into a polymerization belt with an ultrasonic device and carbon dioxide protection after the polymer solution I is deaerated by the device, when the equilibrium viscosity of the polymerization solution is 85cps as shown by an on-line viscometer, adding deoxygenated polymerization solution and azodiisobutyramidine hydrochloride solution, ultrasonically mixing for 5min, irradiating in an ultraviolet region for polymerization and curing, wherein the light intensity is 2500 μ w/cm2Light intensity is 5500 mu w/cm for polymerization in 30min2Polymerizing and curing under illumination for 25min, and then using light intensity of 8000 μ w/cm2Curing for 20min by illumination, cutting into gel, granulating, drying and grinding to obtain a cationic polyacrylamide product with the molecular weight of 1210 ten thousand, the dissolving time of 30min and the residual monomer of 123 ppm.
Example 3
Adding 3360kg of cationic monomer dimethyl diallyl ammonium chloride (65%) and 4900kg of deionized water into a blending kettle, and adding 1.1kg of auxiliary materials of 2,4, 6-trimethyl benzoyl ethyl phosphonate and 2-hydroxy-2-methyl1.7kg of 1-phenyl-1-acetone, 2.2kg of ammonium formate, 2.1kg of ethylene diamine tetraacetic acid disodium, 1.2kg of diethylene glycol and 200kg of urea are added into a batching kettle and uniformly mixed to obtain a polymerization solution I, 1540kg of industrial acrylamide (40%) is added into the batching kettle 2 to obtain the polymerization solution II, the pH values of the polymerization solution I and II are respectively adjusted to 4.0 by adopting acrylic acid (30%), the polymerization solution I and II are cooled to 2 ℃, 0.35kg of azobisisobutyramidine hydrochloride is dissolved in 50kg of deionized water, the polymerization solution is deaerated by a deaerator and pumped into a polymerization belt with an ultrasonic device and carbon dioxide protection by a feeding pump, when the equilibrium viscosity of the polymerization solution I is 152cps by an on-line viscometer, the deaerated polymerization solution amidine and the solution of azobisisobutyramidine hydrochloride are added, the mixture is subjected to ultrasonic mixing for 6min and enters an ultraviolet region for illumination polymerization, the light intensity is 3000 mu w/cm2Light intensity of 7500 mu w/cm after 28min of polymerization2Polymerizing and curing under illumination for 30min, and then curing with light intensity of 8500 μ w/cm2Curing for 15min by illumination, cutting into gel, granulating, drying and grinding to obtain the cationic polyacrylamide product with the molecular weight of 1453 ten thousand, the dissolving time of 29min and the residual monomer of 254 ppm.
Example 4
Adding 4200kg of cationic monomer methacryl propyl trimethyl ammonium chloride (50%) and 3850kg of deionized water into a batching kettle, then adding 1.4kg of ethyl 2,4, 6-trimethyl benzoyl phosphonate, 1.8kg of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2.0kg of ammonium formate, 2.1kg of ethylene diamine tetraacetic acid, 1.3kg of diethylene glycol and 200kg of urea into the batching kettle, uniformly mixing and stirring to obtain a polymer solution I, adding 1750kg of industrial grade acrylamide (40%) into the batching kettle 2 to obtain the polymer solution II, respectively adjusting the pH values of the polymer solution I and the polymer solution II to 4.0 by adopting acrylic acid (30%), cooling the polymer solution I and the polymer solution II to 2 ℃, dissolving 0.4kg of azodiisobutylamine hydrochloride into 50kg of deionized water, deoxidizing the polymer solution I through a feeding pump, pumping the polymer solution I into a polymerization belt with an ultrasonic device and carbon dioxide protection, the power of ultrasonic equipment is 180w, the time of ultrasonic initiation is 2.5min, when the equilibrium viscosity of the polymerization solution is 145cps as shown by an online viscometer, the polymerization solution (II) and the polymer (III) which are deoxidized are addedUltrasonically mixing nitrogen diisobutyl amidine hydrochloride solution for 6min, and irradiating in ultraviolet region for polymerization and curing to obtain final product with light intensity of 3500 μ w/cm2Light irradiation for 30min polymerization, light intensity of 7800 mu w/cm2Polymerizing and curing for 45min by illumination, and then using light intensity of 8600 mu w/cm2Curing by illumination for 20min, cutting, granulating, drying and grinding to obtain a cationic polyacrylamide product with the molecular weight of 1365 ten thousand, the dissolving time of 29min and the residual monomer of 72 ppm.
Comparative example 1
1750kg of industrial acrylamide (40%), 4200kg of cationic monomer methacryloyl propyl trimethyl ammonium chloride (50%) and 3850kg of deionized water are added into a batching kettle, then 1.4kg of ethyl 2,4, 6-trimethyl benzoyl phosphonate, 1.8kg of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2.0kg of ammonium formate, 2.1kg of disodium ethylene diamine tetraacetate, 1.3kg of diethylene glycol, 0.4kg of azodiisobutylamine hydrochloride and 200kg of urea are added into the batching kettle to be mixed and stirred uniformly to obtain a polymerization liquid, the pH value of the polymerization liquid is adjusted to 4.0 by acrylic acid (30%), the polymerization liquid is cooled to 2 ℃, after deoxidization is carried out by a deaerating device, the polymerization liquid is pumped onto a polymerization belt with an ultrasonic device and carbon dioxide protection by a feeding pump, the polymerization liquid is initiated to 2.5min by the ultrasonic power of 180w, and then the polymerization liquid is irradiated and cured in an ultraviolet region, the light intensity is 3500 mu w/cm2Light irradiation for 30min polymerization, light intensity of 7800 mu w/cm2Polymerizing and curing for 45min by illumination, and then using light intensity of 8600 mu w/cm2Curing by illumination for 20min, cutting, granulating, drying and grinding to obtain a cationic polyacrylamide product with the molecular weight of 756 ten thousand, the dissolving time of 33min and the residual monomer of 2271 ppm.
Comparative example 2
Adding 4200kg of cationic monomer methacrylpropyltrimethylammonium chloride (50%) and 3850kg of deionized water into a batching kettle, then adding 1.4kg of auxiliary materials of 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester, 1.8kg of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2.0kg of ammonium formate, 2.1kg of ethylene diamine tetraacetic acid disodium, 1.3kg of diethylene glycol and 200kg of urea into the batching kettle, mixing and stirring uniformly to obtain a polymer solution I, adding 1750kg of industrial acrylamide (40%) into the batching kettle, and adding the polymer solution I into the batching kettleA kettle 2 is a polymerization solution II, the pH values of polymerization solutions I and II are respectively adjusted to 4.0 by adopting acrylic acid (30%), the polymerization solutions I and II are cooled to 2 ℃, 0.4kg of azodiisobutyramidine hydrochloride is dissolved in 50kg of deionized water, the polymerization solution I is deoxidized by an deoxidizing device, pumped on a polymerization belt protected by carbon dioxide by a feeding pump and enters an ultraviolet light region for illumination polymerization curing, the light intensity is 3500 mu w/cm2, the polymerization is performed by illumination, when the viscosity of the polymerization solution is 145cps as shown by an on-line viscometer, the deoxidized polymerization solution II and the azodiisobutyramidine hydrochloride solution are added, and after the ultrasonic mixing is performed for 6min, the polymerization solution is continuously mixed by using the light intensity of 3500 mu w/cm2Light irradiation for 30min polymerization, light intensity of 7800 mu w/cm2Polymerizing and curing for 45min by illumination, and then using light intensity of 8600 mu w/cm2The mixture is cured by illumination for 20min, and then is cut into glue, granulated, dried and ground to obtain a cationic polyacrylamide product with the molecular weight of 653 ten thousand, the dissolution time of 34min and 6507ppm of residual monomers.
The differences and related test preparations of the preparation methods of the cationic polyacrylamides of comparative examples 1-2 and example 4 are summarized in table 1.
TABLE 1 detection data of cationic polyacrylamides in comparative examples 1-2 and example 4
Discussion of the related Art
As is apparent from the differences listed in Table 1, in comparative example 1, the monomer is fed once, and the mode of ultrasonic pre-initiation and photoinitiation is adopted in the preparation of the cationic polyacrylamide; in the comparative example 2, monomer sectional feeding is adopted in the preparation of the cationic polyacrylamide, and all the monomer sectional feeding modes are photoinitiated; in example 4, after the allyl high steric hindrance cationic monomer is preferentially pre-initiated by ultrasound, acrylamide and an azo initiator are added, and then a photo-initiation mode is adopted, so that the cationic polyacrylamide with the molecular weight of 1365 ten thousand, the dissolution time of 29min and the residual monomer of 72ppm are synthesized, and the effect of example 4 cannot be achieved by adopting a single technical means, or by adopting the ultrasonic pre-initiation mode only during one-time feeding or by adopting the pure photo-initiation mode only in a segmented feeding manner.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (10)
1. A preparation method of high steric hindrance series cationic solid polyacrylamide is characterized by comprising the following steps:
dissolving raw material cationic monomers, a complexing agent, a solubilizer, a chain transfer agent, a chain extender and a photoinitiator in deionized water, and uniformly stirring to prepare a first polymerization solution; dissolving acrylamide as a raw material in deionized water, and uniformly stirring to prepare a second polymerization solution; preparing azo initiator solution from the azo initiator;
adjusting the temperatures of the first polymerization solution, the second polymerization solution and the azo initiator solution, and the pH values of the first polymerization solution and the second polymerization solution; deoxidizing the first polymerization solution, the second polymerization solution and the azo initiator solution through a deoxidizing device respectively;
conveying the deoxygenated first polymerization solution to an inert gas protection device, and pre-initiating by ultrasonic radiation until the equilibrium viscosity of the first polymerization solution reaches 30-200 cps; then adding the second polymerization solution and the azo initiator solution into the first polymerization solution, and after ultrasonic mixing for a certain time, entering an ultraviolet light region with a certain wavelength and different light intensities for further polymerization and curing;
and step four, after the colloid is cured, preparing a cationic solid polyacrylamide product through pre-grinding, granulating, drying and grinding.
2. The method for preparing high steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the cationic monomer is selected from one or more of quaternary ammonium salts of compounds represented by the following general structural formulas (I), (II) and (III):
wherein: r1Represents H or CH3；R2Represents CH2CH2，CH2CH2CH2Or
；R3，R4Respectively represent H, CH3，CH2CH3，
；
Wherein: r5Represents H or CH3，R6，R8，R9Represents H, CH3，CH2CH3Or
；
R7Represents CH2CH，CH2CH2CH；
Wherein: r10Represents H, CH3，CH2CH3Or
。
3. The method for preparing the high steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the temperature of the first polymerization solution, the second polymerization solution and the azo initiator solution is adjusted to-5 to 20 ℃;
adjusting the pH values of the first polymerization solution and the second polymerization solution to 3.0-7.0; and deoxidizing the first polymerization solution, the second polymerization solution and the azo initiator solution until the dissolved oxygen in a liquid phase is lower than 0.01 ppm.
4. The preparation method of the high steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the ultrasonic power of the ultrasonic radiation pre-initiation is 50-7200W, and the ultrasonic time of the ultrasonic radiation pre-initiation is not more than 15 min;
adding the second polymerization solution and the azo initiator solution into the first polymerization solution, and then, controlling the ultrasonic power to be 50-200W; and continuously carrying out ultrasonic mixing for 0.5-10 min.
5. The method for preparing the high steric hindrance series cationic solid type polyacrylamide according to claim 1, wherein the equilibrium viscosity of the first polymerization solution is measured by an in-line viscometer.
6. The method for preparing high-steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the ultraviolet region includes a first ultraviolet region, a second ultraviolet region and a third ultraviolet region; wherein the wavelengths of the ultraviolet light in the first ultraviolet light region, the second ultraviolet light region and the third ultraviolet light region are all 200-400 nm,
in the first ultraviolet region, the light intensity of the ultraviolet light is 1000-4000 μ w/cm2The illumination time is 10-30 min;
in the second ultraviolet light region, the light intensity of the ultraviolet light is 4000-8000 μ w/cm2The illumination time is 20-50 min;
in the third ultraviolet region, the light intensity of the ultraviolet light is 8000-12000 μ w/cm2And the illumination time is 0-30 min.
7. The preparation method of the high-steric-hindrance series cationic solid polyacrylamide according to claim 1, wherein the photoinitiator is a compound of ethyl 2,4, 6-trimethylbenzoylphosphonate and 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the mass ratio of the ethyl 2,4, 6-trimethylbenzoylphosphonate to the 2-hydroxy-2-methyl-1-phenyl-1-propanone is 30-70%.
8. The method for preparing the high steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the chain extender is one or two of 1, 4-butanediol, ethylene glycol, propylene glycol, diethylene glycol and neopentyl glycol.
9. The method for preparing the high steric hindrance series cationic solid polyacrylamide according to claim 1, wherein the mass concentrations of the components in the first polymerization solution are as follows:
the cationic monomer accounts for at least 30wt%, the photoinitiator accounts for 10-500 ppm, the complexing agent accounts for 15-500 ppm, the chain transfer agent accounts for 15-300 ppm, the solubilizer accounts for 0.05-5 wt%, and the chain extender accounts for 50-1000 ppm;
in the azo initiator solution, the mass concentration of the azo initiator is 10-300 ppm.
10. A polyacrylamide obtained by the method for preparing a high steric hindrance series cationic solid type polyacrylamide according to any one of claims 1 to 9.
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