CN115490822A - Anionic condensation polymer and preparation method and application thereof - Google Patents
Anionic condensation polymer and preparation method and application thereof Download PDFInfo
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- CN115490822A CN115490822A CN202211009534.1A CN202211009534A CN115490822A CN 115490822 A CN115490822 A CN 115490822A CN 202211009534 A CN202211009534 A CN 202211009534A CN 115490822 A CN115490822 A CN 115490822A
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- phenyl ether
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- 125000000129 anionic group Chemical group 0.000 title claims abstract description 34
- 238000009833 condensation Methods 0.000 title claims abstract description 16
- 230000005494 condensation Effects 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 42
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 42
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 90
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 40
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000003250 coal slurry Substances 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229940099596 manganese sulfate Drugs 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 229920002675 Polyoxyl Polymers 0.000 claims 1
- 239000003245 coal Substances 0.000 abstract description 60
- 239000002002 slurry Substances 0.000 abstract description 42
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 150000001450 anions Chemical class 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 3
- 125000003827 glycol group Chemical group 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229960003742 phenol Drugs 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 230000000740 bleeding effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002817 coal dust Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- -1 polyoxyethylenephenylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
- C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Combustion & Propulsion (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of clean energy, and particularly relates to an anionic condensation polymer and a preparation method and application thereof. According to the anion condensation polymer provided by the invention, a polyethylene glycol side chain and active groups such as carboxyl, sulfonic group and hydroxyl are introduced into a main chain consisting of a benzene ring and methylene, the benzene ring in the main chain can be adsorbed on the surface of coal powder particles, and the side chain extends outwards, so that a water film can be formed on the surface of the coal powder particles, the wettability of the surface of the coal powder particles is improved, the steric hindrance can be provided, the dispersibility of coal powder is improved, the viscosity of coal water slurry is reduced, the stability of the coal water slurry is improved, the active groups such as carboxyl, sulfonic group and hydroxyl can also give negative charges to the coal powder particles, the coal powder particles are dispersed by using electrostatic repulsion, and the viscosity of the coal water slurry is reduced. The coal water slurry dispersing agent can obtain good dispersing effect only by a small mixing amount, so that the coal water slurry has good fluidity and stability.
Description
Technical Field
The invention belongs to the technical field of clean energy, and particularly relates to an anionic condensation polymer and a preparation method and application thereof.
Background
China is a typical country with more coal and less oil, oil resources are in short supply, and the coal reserves are as high as 1 trillion tons and third in the world. The traditional coal utilization mode has the problems of large dust, large pollution, difficult transportation, low utilization rate and the like, which is not in accordance with the concepts of 'green development' and 'energy conservation and emission reduction'. The coal water slurry technology can just solve the problem. The coal water slurry consists of coal 60-70 wt%, water 30-40 wt% and dispersant in small amount. The coal water slurry keeps the combustibility of coal, and has the characteristics of high utilization rate of liquid fuel and less pollution. In addition, the coal water slurry can be conveyed by a pump and a pipeline, so that the storage and transportation difficulty of coal is solved, and the method is an effective means for clean utilization of coal energy. The coal water slurry dispersing agent is an essential additive in the preparation process of the coal water slurry, and the coal is a hydrophobic substance and is difficult to wet by water, and the coal dust particles have high surface energy and are easy to adsorb into a mass to form a precipitate, so the coal water slurry dispersing agent is required to be added to improve the flowability and the stability of the coal water slurry.
At present, the main coal water slurry dispersing agent products in the market of China are lignosulfonate and naphthalene sulfonate dispersing agents which have the advantage of cheap raw materials, but have the defects of high mixing amount (generally 1 percent of the mass of coal powder) and poor slurry stability. The dispersant of polycarboxylic acid is still in the theoretical research stage, and the main problems are that carboxyl and coal powder cannot form good adsorption, and the slurry stability is not good. Therefore, the research and development of the novel dispersing agent are actively carried out, the problems of the fluidity and the stability of the coal water slurry are solved, and the energy status of the assisted coal water slurry for replacing crude oil in production and life has great significance for the economic and social development of China.
Disclosure of Invention
In view of the above, the primary object of the present invention is to provide a coal water slurry dispersant which can improve the stability and fluidity of coal water slurry with a small amount of addition.
The invention also aims to provide a preparation method and application of the coal water slurry dispersing agent which can improve the stability and the fluidity of the coal water slurry by only adding a small amount.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the present invention provides an anionic condensation polymer comprising structural units represented by formulae (II) to (V) in its molecular structure:
in the formula (II), m is an integer of 5-10, in the formula (IV), R is H, K or Na, and in the formula (V), R is H, K or Na.
In some embodiments of the invention, the anionic condensation polymer has a weight average molecular weight of 15000 to 25000.
In some embodiments of the present invention, the degree of polymerization x of the structural unit represented by formula (II) is an integer of 10 to 25, the degree of polymerization n of the structural unit represented by formula (III) is an integer of 10 to 60, the degree of polymerization y of the structural unit represented by formula (IV) is an integer of 0 to 50, the degree of polymerization z of the structural unit represented by formula (V) is an integer of 0 to 50, and the sum of y and z is 30 to 60.
Preferably, m is 7, x is 11, y is 22, z is 33, and n is 11; or
m is 7, x is 10, y is 30, z is 20, and n is 30; or alternatively
m is 7, x is 20, y is 10, z is 40, and n is 60; or alternatively
m is 7, x is 10, y is 10, z is 40, and n is 30; or
m is 7, x is 20, y is 0, z is 40, and n is 20.
In another aspect, the present invention provides a method for producing the above-mentioned anionic polycondensate, comprising the steps of:
under the action of a catalyst, carrying out polycondensation reaction on the polyethylene glycol phenyl ether, phenol and formaldehyde to obtain the anionic condensation polymer;
the polyethylene glycol phenyl ether has a structure shown in a formula (VI), wherein m is an integer of 5-10;
in some embodiments of the invention, the raw materials for the polycondensation reaction further comprise p-hydroxybenzoic acid and/or p-hydroxybenzoic acid, and the molar ratio of the polyglycol phenyl ether to the phenol, the p-hydroxybenzoic acid and the formaldehyde is 1-3.
Preferably, the ratio of the mole number of the polyethylene glycol phenyl ether to the sum of the mole numbers of the p-hydroxybenzene sulfonic acid and the p-hydroxybenzoic acid is 1.
As a preferred embodiment, the present invention provides a method for producing the above-mentioned anionic polycondensate, comprising the steps of:
dissolving the polyethylene glycol phenyl ether, the phenol, the p-hydroxybenzoic acid and the manganese sulfate in water to form a solution A, slowly dropwise adding concentrated sulfuric acid into the solution A, forming a solution B after the dropwise adding of the concentrated sulfuric acid is finished, slowly dropwise adding a formaldehyde aqueous solution into the solution B, controlling the reaction temperature to be 65-70 ℃ in the dropwise adding process, heating to 90-95 ℃ after the dropwise adding of the formaldehyde aqueous solution is finished, continuing to react for more than 2.5 hours, then adding alkali, and uniformly stirring to obtain the solution containing the anion condensation polymer.
Optionally, the dropping time of the concentrated sulfuric acid is 50-70 min.
Optionally, the dropping time of the formaldehyde aqueous solution is 50-70 min.
Optionally, the molar ratio of the manganese sulfate to the concentrated sulfuric acid is 0.8-1.2.
Optionally, the mass of the concentrated sulfuric acid is 15 to 20% of the mass of the formaldehyde.
Alternatively, the mass concentration of the anionic polycondensate in the finally obtained solution is 48 to 52%.
In some embodiments of the invention, the polyethylene glycol phenyl ether is obtained by reacting phenol and ethylene oxide in the presence of a base catalyst, wherein the molar ratio of the phenol to the ethylene oxide is 1.
Preferably, the polyethylene glycol phenyl ether has a weight average molecular weight of 350 to 500.
In a preferred embodiment, the polyethylene glycol phenyl ether is prepared by introducing ethylene oxide into the phenol and the alkali catalyst, and reacting the mixture at 145 to 155 ℃ and 0.13 to 0.5MPa for 6 hours or more.
In still another aspect, the invention also provides the use of the above-mentioned anionic polycondensate or the anionic polycondensate obtained by the above-mentioned method for preparing an anionic polycondensate as a dispersant for coal water slurry.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. according to the anion condensation polymer provided by the invention, a molecular design concept is adopted, a polyethylene glycol side chain and active groups such as carboxyl, sulfonic group and hydroxyl are introduced into a main chain consisting of a benzene ring and methylene, the benzene ring in the main chain can be adsorbed on the surface of coal dust particles, and the side chain extends outwards, so that a water film can be formed on the surface of the coal dust particles to improve the wettability of the surfaces of the coal dust particles, a steric hindrance can be provided, the dispersibility of coal dust is improved, the viscosity of coal water slurry is reduced, and the stability of the coal water slurry is improved.
The anionic polycondensate is used as a water-coal-slurry dispersing agent, and the water-coal-slurry with the coal content of 60% can be prepared only by adding 0.3-0.5%, wherein the apparent viscosity of the prepared water-coal-slurry is 640mPa & s, the bleeding rate of 24h is 1.2%, and the bleeding rate of 48h is 1.5%. Therefore, the coal water slurry dispersing agent disclosed by the invention is low in mixing amount and good in dispersing effect, so that the coal water slurry has good fluidity and stability.
2. The preparation method of the anion condensation polymer provided by the invention has the advantages of less side reaction and high yield, and is suitable for industrial large-scale production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a chart of an infrared spectrum of a polyethylene glycol phenyl ether obtained in example 1.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The invention provides an anionic condensation polymer, which comprises structural units shown in formulas (II) to (V) in the molecular structure:
the molar ratio of the structural unit represented by the formula (II), the structural unit represented by the formula (III), the structural unit represented by the formula (IV) and the structural unit represented by the formula (V) is 1-3.
In some embodiments of the invention, the anionic condensation polymer has a weight average molecular weight of 15000 to 25000.
In some embodiments of the present invention, the degree of polymerization x of the structural unit represented by formula (II) is an integer of 10 to 25, the degree of polymerization n of the structural unit represented by formula (III) is an integer of 10 to 60, the degree of polymerization y of the structural unit represented by formula (IV) is an integer of 0 to 50, the degree of polymerization z of the structural unit represented by formula (V) is an integer of 0 to 50, and the sum of y and z is 30 to 60.
Preferably, m is 7, x is 11, y is 22, z is 33, and n is 11; or
m is 7, x is 10, y is 30, z is 20, and n is 30; or
m is 7, x is 20, y is 10, z is 40, and n is 60; or
m is 7, x is 10, y is 10, z is 40, and n is 30; or
m is 7, x is 20, y is 0, z is 40, and n is 20.
In another aspect, the present invention provides a method for producing the above-mentioned anionic polycondensate, comprising the steps of:
under the action of a catalyst, carrying out polycondensation reaction on polyethylene glycol phenyl ether with the molar ratio of 1-3; and the ratio of the mole number of the polyethylene glycol phenyl ether to the sum of the mole numbers of the p-hydroxybenzene sulfonic acid and the p-hydroxybenzoic acid is 1.5-5, the polyethylene glycol phenyl ether has a structure shown in formula (VI), wherein m is an integer of 5-10;
in some embodiments of the present invention, the present invention provides a method for preparing the above-described anionic condensation polymer, comprising the steps of:
dissolving the polyethylene glycol phenyl ether, the phenol, the p-hydroxybenzoic acid and the manganese sulfate in water to form a solution A, slowly dripping concentrated sulfuric acid into the solution A for 50-70 min to form a solution B after the concentrated sulfuric acid is dripped, slowly dripping a formaldehyde aqueous solution into the solution B, controlling the reaction temperature to be 65-70 ℃ in the dripping process, dripping the formaldehyde aqueous solution for 50-70 min, heating to 90-95 ℃ after the formaldehyde aqueous solution is dripped, continuously reacting for more than 2.5h, then adding alkali, and uniformly stirring to obtain a solution containing the anion condensation polymer with the mass concentration of 48-52%. Wherein the molar ratio of the manganese sulfate to the concentrated sulfuric acid is 0.8-1.2.
In some embodiments of the present invention, the polyethylene glycol phenyl ether is obtained by reacting phenol with ethylene oxide under the action of a base catalyst, specifically: introducing ethylene oxide into the phenol and the alkali catalyst, and reacting for more than 6h at 145-155 ℃ and 0.13-0.5 MPa to prepare the polyethylene glycol phenyl ether with the weight-average molecular weight of 350-500, wherein the molar ratio of the phenol to the ethylene oxide is 1.
Specific anionic polycondensates, and methods of preparation and use thereof, will be described in detail below by way of example.
Example 1
The preparation method of the cement grinding aid provided by the embodiment comprises the following steps:
s1, introducing nitrogen into the reaction kettle, and drying moisture in the reaction kettle. Adding 232.56kg of phenol and 0.99kg of sodium hydroxide, introducing nitrogen for protection, heating and stirring, controlling the temperature of the materials at 100 +/-5 ℃, then introducing 767.44kg of ethylene oxide, pressurizing the reaction kettle to 0.2MPa, heating to 150 ℃, reacting for 6 hours to obtain the polyethylene glycol phenyl ether, and directly using the polyethylene glycol phenyl ether in the next step without purification treatment.
S2, adding 268.17kg of the polyethylene glycol phenyl ether prepared in the step S1, 62.47kg of phenol, 183.37kg of p-hydroxybenzoic acid, 346.84kg of p-hydroxybenzoic acid, 10.57kg of manganese sulfate and 100kg of deionized water into another reaction kettle, heating to 65 ℃, and stirring for dissolving. And pumping 70kg of concentrated sulfuric acid into a concentrated sulfuric acid dropping tank, and slowly dropping the concentrated sulfuric acid into the reaction kettle at a dropping speed for 70min. 376.04kg of formaldehyde aqueous solution (with the mass concentration of 37%) is pumped into a formaldehyde dropping tank, and the formaldehyde aqueous solution is dropped after the concentrated sulfuric acid is dropped, wherein the reaction temperature is controlled to be 65-70 ℃ in the dropping process, and the dropping time is 70min. After the dropwise addition, the temperature is raised to 90-95 ℃, and the reaction is continued for 2.5h. Then 26.4kg of sodium hydroxide and 663kg of deionized water are added and stirred evenly to prepare the solution containing the polycondensate, which does not need purification treatment and can be directly used as a water-coal-slurry dispersant without generating three wastes.
Through measurement, the water-coal-slurry dispersing agent prepared in the embodiment contains a polycondensate with a mass concentration of 50%, the yield is 98%, the weight average molecular weight of the polycondensate is 16500, and in the structure, the polymerization degree x of the structural unit shown in the formula (II) is 11, the polymerization degree n of the structural unit shown in the formula (III) is 11, the polymerization degree y of the structural unit shown in the formula (IV) is 22, and the polymerization degree z of the structural unit shown in the formula (V) is 33.
FIG. 1 is an infrared spectrum of a polyethylene glycol phenylene ether monomer prepared in this example, 1598.53cm in FIG. 1 -1 And 1458.06cm -1 And a small peak sandwiched between the two, the three are characteristic absorption peaks of benzene ring, 1112.06cm -1 The characteristic absorption peak of C-O-C stretching vibration in polyethylene glycol is 950.45cm -1 The absorption peak is the characteristic absorption peak of stretching vibration of ether bond connected with benzene ring, 2866.26cm -1 Characteristic absorption peak of methylene at 3495.69cm -1 The characteristic absorption peak of O-H is shown. As can be seen in FIG. 1, the polyoxyethylenephenylene ether conforms to the structure shown in formula VI.
The polyethylene glycol phenyl ether prepared in this example had a weight average molecular weight of 400, and the polymerization degree m of the ethoxy structural unit was 7.
Example 2
The preparation method of the cement grinding aid provided by the embodiment comprises the following steps:
s1, introducing nitrogen into the reaction kettle, and drying moisture in the reaction kettle. Adding 232.56kg of phenol and 0.99kg of sodium hydroxide, introducing nitrogen for protection, heating and stirring, controlling the temperature of the materials at 100 +/-5 ℃, then introducing 767.44kg of ethylene oxide, pressurizing the reaction kettle to 0.3MPa, heating to 145 ℃, reacting for 6 hours to obtain the polyethylene glycol phenyl ether, and directly using the polyethylene glycol phenyl ether in the next step without purification treatment.
S2, adding 230.23kg of the polyethylene glycol phenyl ether prepared in the step S1, 160.89kg of phenol, 157.43kg of p-hydroxybenzoic acid, 297.76kg of p-hydroxybenzoic acid, 11.67kg of manganese sulfate and 100kg of deionized water into another reaction kettle, heating to 70 ℃, and stirring for dissolving. 77.32kg of concentrated sulfuric acid is pumped into a concentrated sulfuric acid dropping tank, and the concentrated sulfuric acid is slowly dropped into the reaction kettle at a controlled dropping speed for 60min. And (3) 415.35kg of formaldehyde aqueous solution (with the mass concentration of 37%) is pumped into the formaldehyde dropping tank, and after the concentrated sulfuric acid is dropped, the formaldehyde aqueous solution is dropped, wherein the reaction temperature is controlled to be 65-70 ℃ in the dropping process, and the dropping time is 60min. After the dropwise addition, the temperature is raised to 90-95 ℃, and the reaction is continued for 2.5h. Then 22.8kg of sodium hydroxide and 638.33kg of deionized water are added and stirred uniformly to prepare the solution containing the polycondensate, which can be directly used as a water-coal-slurry dispersant without purification treatment and three wastes.
Through measurement, the water-coal-slurry dispersing agent prepared in the embodiment contains a polycondensate with a mass concentration of 50%, the yield is 98.5%, the weight-average molecular weight of the polycondensate is 17540, and in the structure, the polymerization degree x of the structural unit shown in the formula (II) is 10, the polymerization degree n of the structural unit shown in the formula (III) is 30, the polymerization degree of the structural unit shown in the formula (IV) is 30, and the polymerization degree z of the structural unit shown in the formula (V) is 20.
The polyethylene glycol phenyl ether prepared in this example had a weight average molecular weight of 400, and the polymerization degree m of the ethoxy structural unit was 7.
Example 3
The preparation method of the cement grinding aid provided by the embodiment comprises the following steps:
s1, introducing nitrogen into the reaction kettle, and drying moisture in the reaction kettle. Adding 232.56kg of phenol and 0.99kg of sodium hydroxide, introducing nitrogen for protection, heating and stirring, controlling the temperature of the materials at 100 +/-5 ℃, then introducing 767.44kg of ethylene oxide, pressurizing the reaction kettle to 0.4MPa, heating to 155 ℃, reacting for 6 hours to obtain the polyethylene glycol phenyl ether, and directly using the polyethylene glycol phenyl ether in the next step without purification treatment.
S2, adding 324.92kg of the polyethylene glycol phenyl ether prepared in the step S1, 227.07kg of phenol, 222.19kg of p-hydroxybenzoic acid, 70.04kg of p-hydroxybenzene sulfonic acid, 11.83kg of manganese sulfate and 100kg of deionized water into another reaction kettle, heating to 60 ℃, and stirring for dissolving. And pumping 78.37kg of concentrated sulfuric acid into a concentrated sulfuric acid dropping tank, and slowly dropping the concentrated sulfuric acid into the reaction kettle at a dropping speed for 50min. 421.03kg of formaldehyde aqueous solution (with the mass concentration of 37%) is pumped into a formaldehyde dropping tank, and the formaldehyde aqueous solution is dropped after the concentrated sulfuric acid is dropped, wherein the reaction temperature is controlled to be 65-70 ℃ in the dropping process, and the dropping time is 60min. After the dropwise addition, the temperature is raised to 90-95 ℃, and the reaction is continued for 2.5h. Then 20kg of sodium hydroxide and 634.75kg of deionized water are added and stirred uniformly to prepare the solution containing the polycondensate, which can be directly used as a water-coal-slurry dispersant without purification treatment and three wastes.
It was determined that the dispersant for coal-water slurry obtained in this example contained a polycondensate at a concentration of 50% by mass, with a yield of 99%, and the polycondensate had a weight average molecular weight of 25000 and a structure in which the degree of polymerization x of the structural unit represented by formula (II) was 20, the degree of polymerization n of the structural unit represented by formula (III) was 60, the degree of polymerization y of the structural unit represented by formula (IV) was 10, and the degree of polymerization z of the structural unit represented by formula (V) was 40.
The polyethylene glycol phenyl ether prepared in this example had a weight average molecular weight of 400, and the polymerization degree m of the ethoxy structural unit was 7.
Example 4
The preparation method of the cement grinding aid provided by the embodiment comprises the following steps of:
s1, introducing nitrogen into the reaction kettle, and drying moisture in the reaction kettle. Adding 232.56kg of phenol and 0.99kg of sodium hydroxide, introducing nitrogen for protection, heating and stirring, controlling the temperature of the materials at 100 +/-5 ℃, then introducing 767.44kg of ethylene oxide, pressurizing the reaction kettle to 0.5MPa, heating to 150 ℃, reacting for 6 hours to prepare the polyethylene glycol phenyl ether, and directly using in the next step without purification treatment.
S2, adding 240.43kg of the polyethylene glycol phenyl ether prepared in the step S1, 168.02kg of phenol, 328.82kg of p-hydroxybenzoic acid, 103.65kg of p-hydroxybenzoic acid, 12.08kg of manganese sulfate and 100kg of deionized water into another reaction kettle, heating to 65 ℃, and stirring for dissolving. And pumping 80.02kg of concentrated sulfuric acid into a concentrated sulfuric acid dropping tank, and slowly dropping the concentrated sulfuric acid into the reaction kettle at a dropping speed for 60min. And (3) 429.89kg of formaldehyde aqueous solution (mass concentration of 37%) is pumped into the formaldehyde dropping tank, and after the concentrated sulfuric acid is dropped, the formaldehyde aqueous solution is dropped, wherein the reaction temperature is controlled to be 65-70 ℃ in the dropping process, and the dropping time is 50min. After the dropwise addition, the temperature is raised to 90-95 ℃, and the reaction is continued for 2.5h. Then 24kg of sodium hydroxide and 629.17kg of deionized water are added and stirred uniformly to prepare a solution containing the polycondensate, which does not need purification treatment, can be directly used as a water-coal-slurry dispersant and does not generate three wastes.
Through measurement, the water-coal-slurry dispersing agent prepared in the embodiment contains a polycondensate with a mass concentration of 50%, the yield is 99.0%, the weight-average molecular weight of the polycondensate is 16948, and in the structure, the polymerization degree x of the structural unit shown in the formula (II) is 10, the polymerization degree n of the structural unit shown in the formula (III) is 30, the polymerization degree y of the structural unit shown in the formula (IV) is 10, and the polymerization degree z of the structural unit shown in the formula (V) is 40.
The polyethylene glycol phenyl ether prepared in the embodiment has the weight average molecular weight of 400, and the polymerization degree m of the ethoxy structural unit is 7.
Example 5
The preparation method of the cement grinding aid provided by the embodiment comprises the following steps of:
s1, introducing nitrogen into the reaction kettle, and blowing water in the reaction kettle to dry. Adding 232.56kg of phenol and 0.99kg of sodium hydroxide, introducing nitrogen for protection, heating and stirring, controlling the temperature of the materials at 100 +/-5 ℃, then introducing 767.44kg of ethylene oxide, pressurizing the reaction kettle to 0.3MPa, heating to 150 ℃, reacting for 6 hours to prepare the polyethylene glycol phenyl ether, and directly using in the next step without purification treatment.
S2, adding 452.41kg of the polyethylene glycol phenyl ether prepared in the step S1, 105.39kg of phenol, 309.36kg of p-hydroxybenzoic acid, 10.08kg of manganese sulfate and 100kg of deionized water into another reaction kettle, heating to 65 ℃, and stirring for dissolving. And pumping 66.82kg of concentrated sulfuric acid into a concentrated sulfuric acid dropping tank, and slowly dropping the concentrated sulfuric acid into the reaction kettle at a dropping speed for 60min. 359kg of formaldehyde aqueous solution (the mass concentration is 37%) is pumped into the formaldehyde dropping tank, and after the concentrated sulfuric acid is dropped, the formaldehyde aqueous solution is dropped, wherein the reaction temperature is controlled to be 65-70 ℃ in the dropping process, and the dropping time is 60min. After the dropwise addition, the temperature is raised to 90-95 ℃, and the reaction is continued for 2.5h. Then adding 17.92kg of sodium hydroxide and 673.82kg of deionized water, and uniformly stirring to obtain a solution containing the polycondensate, wherein the solution is not required to be purified and can be directly used as a coal water slurry dispersant without generating three wastes.
The dispersant for coal water slurry prepared in this example was found to contain a polycondensate at a concentration of 50% by mass in a yield of 99.3%, and the polycondensate had a weight average molecular weight of 17873 and a structure in which the degree of polymerization x of the structural unit represented by formula (II) was 20, the degree of polymerization n of the structural unit represented by formula (III) was 20, the degree of polymerization y of the structural unit represented by formula (IV) was 0, and the degree of polymerization z of the structural unit represented by formula (V) was 40.
The polyethylene glycol phenyl ether prepared in this example had a weight average molecular weight of 400, and the polymerization degree m of the ethoxy structural unit was 7.
Test examples
The coal water slurry dispersant prepared in the embodiments 1 to 4 of the invention and the dispersant sold in the market are respectively added into coal dust to prepare the coal water slurry, and the apparent viscosity, the fluidity, the bleeding rate of 24h and the bleeding rate of 48h of the coal water slurry are measured.
The measurement method is as follows:
1. preparation of coal water slurry
The coal water slurry is stirred by a planetary ball mill, the coal powder is formed by mixing inner Mongolia coal with two particle sizes of 100 meshes and 300 meshes according to a mass ratio of 1. 200g of coal powder, 133.33g of water and a designed amount of coal water slurry dispersing agent are weighed and added into a grinding tank, and 200g of grinding balls are added. And covering a cover, and slightly shaking the grinding tank to preliminarily mix the pulverized coal, the water and the grinding balls. And fixing the grinding tank on a ball mill, setting the rotating speed to be 500r/min, and grinding for 30min. Filtering the grinding balls to obtain the coal water slurry.
2. Apparent viscosity measurement
The apparent viscosity test was performed using a rotational viscometer. Stirring the coal water slurry until no precipitate exists, pouring the mixture into a measuring container, and placing the measuring container into a constant-temperature water bath at 20 ℃ for 5min at constant temperature. Selecting a proper rotor and a proper rotating speed, starting a rotary viscometer, timing, recording the instrument reading every 1min from the 5 th min, recording for 5 times in total, and taking an average value.
3. Fluidity measurement
The fluidity is measured by adopting a metal cone test mold with an upper caliber of 36mm, a lower caliber of 60mm, a height of 60mm and a smooth and non-spliced inner wall. And placing the test mold in the center of the wet and waterless glass plate, pouring the stirred water-coal-slurry into the test mold, and scraping by using a scraper. And vertically lifting the test mold upwards to allow the coal water slurry to flow freely until the coal water slurry does not flow. The maximum diameter of the flowing portion and the diameter perpendicular thereto were measured, and the average of the two was taken.
4.24h of bleeding rate and 48h of bleeding rate
The stirred water-coal-slurry was poured into a 100mL stoppered graduated cylinder until just 100mL. Plugging the plug and standing. And (5) after standing for 24 hours, observing the volume of the upper clear water, wherein the ratio of the clear water volume to the water-coal-slurry volume is the bleeding rate of 24 hours. And (5) after standing for 48 hours, observing the volume of the upper layer clear water, wherein the ratio of the clear water volume to the water-coal-slurry volume is the bleeding rate of 48 hours.
The measurement results are shown in table 1.
TABLE 1
As can be seen from Table 1, the coal water slurry dispersant of the invention can obtain good dispersion effect only by a small amount of addition, so that the prepared coal water slurry has good fluidity and stability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An anionic polycondensate characterized in that it contains structural units represented by the formulae (II) to (V):
in the formula (II), m is an integer of 5-10, in the formula (IV), R is H, K or Na, and in the formula (V), R is H, K or Na.
2. The anionic polycondensate according to claim 1 wherein the anionic polycondensate has a weight average molecular weight of from 15000 to 25000.
3. The anionic polycondensate according to claim 1 or 2, wherein the degree of polymerization x of the structural unit represented by formula (II) is an integer of 10 to 25, the degree of polymerization n of the structural unit represented by formula (III) is an integer of 10 to 60, the degree of polymerization y of the structural unit represented by formula (IV) is an integer of 0 to 50, the degree of polymerization z of the structural unit represented by formula (V) is an integer of 0 to 50, and the sum of y and z is 30 to 60.
4. The anionic polycondensate of claim 3 wherein m is 7, x is 11, y is 22, z is 33, and n is 11; or alternatively
m is 7, x is 10, y is 30, z is 20, and n is 30; or
m is 7, x is 20, y is 10, z is 40, and n is 60; or
m is 7, x is 10, y is 10, z is 40, and n is 30; or
m is 7, x is 20, y is 0, z is 40, and n is 20.
5. A method for producing the anionic polycondensate according to any one of claims 1 to 4, which comprises the steps of:
under the action of a catalyst, carrying out polycondensation reaction on the polyethylene glycol phenyl ether, phenol and formaldehyde to obtain the anionic condensation polymer;
the polyethylene glycol phenyl ether has a structure shown in a formula (VI), wherein m is an integer of 5-10;
6. the method for producing an anionic polycondensate according to claim 5, wherein the raw materials for the polycondensation reaction further comprise p-hydroxybenzoic acid and/or p-hydroxybenzoic acid, and the molar ratio of the polyoxyl phenyl ether to the phenol, the p-hydroxybenzoic acid and the formaldehyde is 1 to 3;
preferably, the ratio of the number of moles of the polyethylene glycol phenyl ether to the sum of the number of moles of the p-hydroxybenzoic acid and the p-hydroxybenzenesulfonic acid is 1.
7. The method for producing an anionic polycondensate according to claim 6, wherein the polyethylene glycol phenyl ether, the phenol, the p-hydroxybenzoic acid and the manganese sulfate are dissolved in water to form a solution A, concentrated sulfuric acid is slowly dripped into the solution A to form a solution B after the dripping of the concentrated sulfuric acid is finished, a formaldehyde aqueous solution is slowly dripped into the solution B, the reaction temperature is controlled to be 65-70 ℃ during the dripping process, the temperature is raised to 90-95 ℃ after the dripping of the formaldehyde aqueous solution is finished, the reaction is continued for more than 2.5 hours, and then alkali is added and the mixture is uniformly stirred;
preferably, the dropping time of the concentrated sulfuric acid is 50-70 min;
preferably, the dropping time of the formaldehyde aqueous solution is 50-70 min;
preferably, the molar ratio of the manganese sulfate to the concentrated sulfuric acid is 0.8-1.2;
preferably, the mass of the concentrated sulfuric acid is 15-20% of the mass of the formaldehyde;
preferably, the mass concentration of the finally obtained anionic polycondensate is 48 to 52%.
8. The method for producing an anionic polycondensate according to any one of claims 5 to 7, wherein the polyethylene glycol phenyl ether is obtained by reacting phenol with ethylene oxide in a molar ratio of 1 to 10, under the action of a basic catalyst;
preferably, the polyethylene glycol phenyl ether has a weight average molecular weight of 350 to 500.
9. The method of producing an anionic polycondensate according to claim 8, wherein the ethylene oxide is introduced into the phenol and the basic catalyst and reacted at 145 to 155 ℃ and 0.13 to 0.5MPa for 6 hours or more.
10. Use of the anionic polycondensate according to any one of claims 1 to 4 or the anionic polycondensate obtained by the method for producing an anionic polycondensate according to any one of claims 5 to 9 as a dispersant for a water-coal-slurry.
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