CN111944101A - Preparation method of high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregate - Google Patents
Preparation method of high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention discloses a preparation method of a high-adaptability polycarboxylate water reducer suitable for low-quality aggregate, which is prepared by carrying out aqueous solution free radical polymerization on an unsaturated polyoxyethylene ether monomer a, an unsaturated carboxylic acid monomer b and an unsaturated phosphate ester monomer c according to the molar ratio of 1 (3.0-4.5) to (0.5-1.0) under the action of an oxidation-reduction initiator and a chain transfer agent, wherein the dosages of an oxidant, a reducing agent and the chain transfer agent are respectively 0.4-1.2%, 0.1-0.5% and 0.2-0.8% of the total dosage of the monomers. The preparation method has the advantages of simple process, easily controlled conditions, short reaction time, low energy consumption and the like, and the prepared high-adaptability polycarboxylate superplasticizer has extremely high adaptability to the application of the polycarboxylate superplasticizer to sand aggregate with poor quality, high mud content and machine-made sand concrete, and shows excellent dispersing performance and slump retaining capacity.
Description
Technical Field
The invention belongs to the technical field of building material concrete water reducing agents, and particularly relates to a preparation method of a high-adaptability polycarboxylate water reducing agent suitable for low-quality aggregates.
Background
The polycarboxylate superplasticizer is a new generation high-performance water reducing agent which is created after lignin sulfonate water reducing agents and naphthalene high-efficiency water reducing agents, and has the advantages of low mixing amount, high water reducing rate, high slump retaining property, adjustable molecular structure, environmental friendliness and the like, so that the polycarboxylate superplasticizer is widely applied to concrete. However, in recent years, the transportation, pumping and construction of concrete are seriously affected by the problems of great reduction of the workability of fresh concrete, rapid loss of slump and expansion degree, strength reduction and the like. Therefore, the development of the polycarboxylic acid water reducing agent with higher adaptability to low-quality aggregates is of great significance.
Patent CN104861127B discloses a preparation method and application of an anti-mud polycarboxylic acid water reducing agent. The copolymer is prepared by copolymerization of isobutylene alcohol polyoxyethylene ether, maleic anhydride-beta-cyclodextrin, acrylic acid and styryl formate in an aqueous solution. The method introduces beta-cyclodextrin into a polycarboxylic acid product, the molecular structure of the beta-cyclodextrin is a cup-shaped structure, the beta-cyclodextrin has good mud resistance and plastic retention performance over time, and the production process is green and environment-friendly. However, in the reaction, the synthesis conversion rate of the maleic anhydride-beta cyclodextrin monomer is low, the polymerization activity is poor, and the styryl formate monomer is difficult to dissolve into a water phase system, so that the polymerization controllability is poor and the precipitation is easy to occur.
Patent CN103803846B discloses a preparation method of a mud-resistant and salt-resistant polycarboxylate water reducer, which is obtained by copolymerization of unsaturated polyether, unsaturated acid, unsaturated anhydride and silane monomers, and the product can greatly improve the adaptability of cement in concrete, improve the effect of mud resistance and salt resistance, and has the advantages of low doping amount, high water reducing rate, low slump loss and the like. However, this method requires a large amount of expensive silane monomer as a raw material, and is costly and not suitable for industrial production.
At present, most of polycarboxylate water reducers designed for high-mud content natural sand and machine-made sand are synthesized by vinyl alcohol 4C (methyl allyl polyoxyethylene ether HPEG) and 5C (isopentenyl polyoxyethylene ether TPEG) macromonomers, and are influenced by low reaction activity of unsaturated double bonds of the monomers, polymerization reaction is generally carried out at high temperature, although normal-temperature polymerization is realized by an oxidation-reduction agent initiating system, the reaction time is 3-5h, the production period is long, the energy consumption is high, and the problem of poor workability of freshly mixed concrete of the machine-made sand by the polycarboxylate water reducers synthesized by the HPEG and the TPEG is still difficult to solve.
Disclosure of Invention
In order to solve the defects in the prior art, the invention uses macromonomer ethylene glycol monovinyl polyglycol ether (EPEG) with high reaction activity and unsaturated phosphate with adsorption effect on clay, and simultaneously provides a preparation method of polycarboxylic acid water reducing agent with short reaction time, low energy consumption and ultrahigh adaptability to low-quality aggregate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates comprises the following steps:
s1: configuration of the drip solution A, B: uniformly mixing an unsaturated carboxylic acid monomer b, an unsaturated phosphate ester c, a chain transfer agent and deionized water to obtain a dropping liquid A; uniformly mixing a reducing agent and deionized water to be used as a dropping liquid B for later use;
s2: adding deionized water and an unsaturated polyoxyethylene ether monomer a into a reaction kettle, stirring at normal temperature to fully dissolve the monomers, regulating the temperature to 10-30 ℃, adding a small amount of an unsaturated carboxylic acid monomer b with an acidity regulating effect, and uniformly stirring;
s3: sequentially adding 1% concentration iron catalyst and oxidant into the mixed solution obtained in step S2 at an initial reaction temperature of 10-30 ℃, stirring for 5min, then beginning to dropwise add solution A and solution B at a constant speed, wherein the dropwise adding time is 45-90min, the highest temperature of the reaction solution is controlled not to exceed 40 ℃, the solution B is 15min later than the solution A and completely dropwise added, and after the dropwise adding is finished, carrying out aging reaction for 30-60 min;
s4: and adding a proper amount of alkali liquor for neutralization, adjusting the pH to 5-6, and adding deionized water for dilution until the solid content is 40-50%, thus obtaining the high-adaptability polycarboxylate superplasticizer suitable for the low-quality aggregate.
As a preferred embodiment of the invention, the molar ratio of the unsaturated polyoxyethylene ether monomer a, the unsaturated carboxylic acid monomer b and the unsaturated phosphate ester monomer c is 1 (3.0-4.5): (0.5-1.0), the amounts of the iron-based catalyst, the oxidant, the reductant and the chain transfer agent are respectively 0.2-1.0%, 0.4-1.2%, 0.1-0.5% and 0.2-0.8% of the total mass of the monomer a, the monomer b and the monomer c, the pH of the solution is adjusted to 5-7 by using a proper amount of liquid alkali, and the solid content is adjusted to 40-50% by using a proper amount of deionized water.
In a preferred embodiment of the present invention, the unsaturated polyoxyethylene ether monomer a in step S2 is ethylene glycol monovinyl polyethylene glycol ether (EPEG), and the molecular structural formula is: CH (CH)2＝CH-O-CH2-CH2-O-(C2H4O)n-H，n＝50-120。
As a preferred embodiment of the present invention, the unsaturated carboxylic acid monomer b in step S1 is one of acrylic acid, methacrylic acid, maleic acid, itaconic acid and/or fumaric acid, preferably acrylic acid.
As a preferred embodiment of the present invention, the molecular structure of the unsaturated phosphate ester monomer c in step S1 is:
r represents H or alkyl, X represents alkyl; or
R1、R2Represents H or alkyl, R3、R4Represents an alkyl group; is one of vinyl phosphate, diethyl vinyl phosphate, alkyl acrylate phosphate, end-capped amide phosphate and/or 2-hydroxyethyl methacrylate phosphate.
As a preferred embodiment of the present invention, the reducing agent in step S1 is one of L-ascorbic acid, sodium bisulfite, sodium sulfite and/or sodium hypophosphite, preferably L-ascorbic acid.
In a preferred embodiment of the present invention, the chain transfer agent in step S1 is one of mercaptoethanol, mercaptopropanol, mercaptoacetic acid, 3-mercaptopropionic acid and/or n-dodecyl mercaptan.
As a preferred embodiment of the present invention, the 1% concentration iron-based catalyst in step S3 is one of a ferrous sulfate solution, a ferric chloride solution and/or a ferrous chloride solution.
In a preferred embodiment of the present invention, the oxidizing agent in step S3 is one of hydrogen peroxide, ammonium persulfate, sodium persulfate, and/or potassium persulfate, preferably hydrogen peroxide.
As a preferred embodiment of the present invention, the liquid alkali in step S4 is one of 30% sodium hydroxide and/or 30% potassium hydroxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-adaptability polycarboxylate superplasticizer for low-quality aggregates provided by the invention takes ethylene glycol monovinyl polyethylene glycol ether (EPEG) as a polymerization macromonomer, compared with the existing vinyl alcohol 4C (HPEG) and 5C (TPEG) macromonomers, unsaturated double bonds in an EPEG molecular structure are directly connected with an oxygen atom to form a unique molecular structure of a group of C-O bonds, the shift of double bond electron cloud distribution enables the electron cloud density to be lower, the reaction activity of the double bonds to be higher, the polymerization reaction is easier to carry out, the reaction time can be shortened to 1-2h, and the production energy consumption is effectively reduced; (2) the phosphate group grafted on the side chain of the molecular structure of the high-adaptability polycarboxylate superplasticizer provided by the invention can release free phosphate ions and hydroxyl-containing micromolecule diol in an alkaline cement slurry environment by water explanation, and simultaneously release a large amount of carboxyl. Phosphate radical ions and micromolecular diol have the effect of delaying cement hydration, carboxyl is adsorbed on the surface of cement particles to play a dispersing role, and the dispersing and plasticity-maintaining performance of the water reducing agent is greatly improved under the synergistic effect of the phosphate radical ions, the micromolecular diol and the carboxyl; (3) the double bond in the EPEG molecule is a substituted structure, the structure is changed, the space resistance of swinging of the polyether side chain is reduced, the swinging freedom degree is increased, and the wrapping property and the winding property of the side chain are improved, so that the synthesized polycarboxylate superplasticizer has better adaptability, and particularly has obvious effects on the conditions of poor sand quality, high mud content, poor mechanical sand grading and high powder content.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates comprises the following steps:
s1: dispensing of the dripped liquid A, B: uniformly mixing 22.5g of acrylic acid, 7.5g of vinyl phosphate, 2.5g of thioglycolic acid and 25g of deionized water to obtain a dropping liquid A; 0.95g of L-ascorbic acid and 45g of deionized water are uniformly mixed to be used as a dropping liquid B for standby;
s2: adding 250g of deionized water and 300g of EPEG monomer (average molecular weight 3000) into a reaction kettle, stirring at normal temperature to fully dissolve the monomer, regulating the temperature to 15 ℃, adding 2.7g of acrylic acid to regulate the acidity of a base solution, and uniformly stirring;
s3: at the initial temperature of 15 ℃, sequentially adding 2.0g of 1% ferric chloride solution and 2.5g of 30% hydrogen peroxide solution into the mixed solution obtained in the step S2, stirring for 5min, then beginning to dropwise add the solution A and the solution B at a constant speed, dropwise adding the solution A for 60min, dropwise adding the solution B for 75min, controlling the temperature of the reaction solution to be 15-30 ℃, and carrying out a curing reaction for 45min after the dropwise addition is finished;
s4: and (3) adding 20g of 30% sodium hydroxide solution to adjust the pH value to 6.2, adding 80.5g of deionized water, and uniformly stirring to obtain the high-adaptability polycarboxylate superplasticizer with the solid content of 45%.
Example 2
A preparation method of a high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates comprises the following steps:
s1: dispensing of the dripped liquid A, B: uniformly mixing 24.3g of acrylic acid, 11.5g of 2-hydroxyethyl methacrylate phosphate, 1.75g of mercaptopropionic acid and 30g of deionized water to obtain a dropping liquid A; 1.05g of L-ascorbic acid and 50g of deionized water are uniformly mixed to be used as a dropping liquid B for standby;
s2: adding 300g of deionized water and 360g of EPEG monomer (average molecular weight of 3600) into a reaction kettle, stirring at normal temperature to fully dissolve the monomer, regulating the temperature to 20 ℃, adding 4.5g of acrylic acid to regulate the acidity of the base solution, and uniformly stirring;
s3: at the initial temperature of 20 ℃, sequentially adding 2.5g of 1% ferrous sulfate solution and 3.0g of 30% hydrogen peroxide solution into the mixed solution obtained in the step S2, stirring for 5min, then beginning to dropwise add the solution A and the solution B at a constant speed, dropwise adding the solution A for 60min and the solution B for 75min, controlling the temperature of the reaction solution to be between 20 and 35 ℃ during the period, and carrying out aging reaction for 30min after the dropwise addition is finished;
s4: adding 25g of 30% sodium hydroxide solution to adjust the pH value to 6.5, adding 97.5g of deionized water, and uniformly stirring to obtain the high-adaptability polycarboxylate superplasticizer with the solid content of 45%.
Example 3
A preparation method of a high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates comprises the following steps:
s1: dispensing of the dripped liquid A, B: uniformly mixing 21.0g of acrylic acid, 10.5g of diethyl vinylphosphate, 1.5g of mercaptopropionic acid and 25g of deionized water to obtain a dropping liquid A; uniformly mixing 1.35g of sodium bisulfite and 60g of deionized water to obtain a dropping liquid B for later use;
s2: adding 250g of deionized water and 300g of EPEG monomer (average molecular weight 3000) into a reaction kettle, stirring at normal temperature to fully dissolve the monomer, regulating the temperature to 15 ℃, adding 2.5g of acrylic acid to regulate the acidity of a base solution, and uniformly stirring;
s3: at the initial temperature of 15 ℃, sequentially adding 2.0g of 1% ferrous sulfate solution and 2.5g of ammonium persulfate into the mixed solution obtained in the step S2, stirring for 5min, then beginning to dropwise add the solution A and the solution B at a constant speed, dropwise adding the solution A for 75min, dropwise adding the solution B for 90min, controlling the temperature of the reaction solution to be 15-30 ℃, and carrying out aging reaction for 30min after dropwise adding;
s4: and (3) adding 20g of 30% sodium hydroxide solution to adjust the pH value to 6.2, adding 65g of deionized water, and uniformly stirring to obtain the high-adaptability polycarboxylate superplasticizer with the solid content of 45%.
Comparative example 1
The same procedure as described in example 2 was followed except that no unsaturated phosphate ester monomer was added to the monomer mixture.
Performance testing
Working performance and slump change of fresh concrete are measured by referring to GB/T50080-2016 (common concrete mixture performance test method) of examples 1-3, comparative example 1 (a 40% liquid common polycarboxylic acid water reducing agent sold in the market) and comparative example 2 (a 40% liquid anti-mud polycarboxylic acid water reducing agent sold in the market); the strength of the concrete at each age is determined by referring to GB/T50081-2002 'test method for mechanical properties of common concrete'.
P.O42.5 kumquat cement, II-grade fly ash, river sand with fineness modulus of 2.7 (mud content of 5%) and continuous graded broken stones with particle size of 5-25 mm are adopted. The concrete mixing ratio (kg/m) used in the test3) Comprises the following steps: cement, fly ash, river sand, pebble, water, 250:120:800:1050:165 and the broken solid content of the water reducing agent is 0.2 percent of the total amount of the cementing material. The test results are shown in table 1.
TABLE 1 comparison of Natural Sand concrete Properties
As can be seen from Table 1, the initial workability and the slump constant of the concrete doped with the high-adaptability polycarboxylate superplasticizers of the examples 1-3 are obviously superior to those of the liquid ordinary polycarboxylate superplasticizer of the comparative example 1 when the natural sand content is high due to the same water reducer doping amount; compared with the liquid anti-mud polycarboxylate superplasticizer in the comparative example 2, the concrete slump loss resistance over time is obviously improved, which shows that the high-adaptability polycarboxylate superplasticizer can obviously improve the working performance of the high-mud content natural sand concrete, and obviously improve the fluidity and the plasticity over time.
Meanwhile, the 3d strength and the 7d strength of the concrete added with the high-adaptability polycarboxylate superplasticizers in the examples 1 to 3 are well developed, and the 28d strength is slightly increased, which shows that the concrete does not have adverse effect on the strength development of the concrete at each age.
The samples were tested for concrete performance using S95 grade ore fines and machine-made sand with a fineness modulus of 3.5 (10% stone fines content, MB value 0.5), concrete mix ratio (kg/m)3) Comprises the following steps: cement, pulverized coal ash, mineral powder, machine-made sand, pebbles, water, 410, 50, 75, 675, 1065 and 150, wherein the folded solid content of the water reducing agent is 0.25 percent of the total amount of the cementing material. The test results are shown in table 2.
TABLE 2 machine-made Sand concrete Performance comparison
As can be seen from Table 2, the highly adaptable polycarboxylate superplasticizers provided in examples 1 to 3 can significantly improve the workability of low-quality machine-made sand concrete and improve the segregation and bleeding problems of concrete, have more excellent plasticity retention performance over time compared with the common polycarboxylate superplasticizers and anti-mud polycarboxylate superplasticizers synthesized from HPEG and TPEG, and have no adverse effect on the strength development of machine-made sand concrete at all ages.
The embodiments of the present invention have been described in detail with reference to the examples, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates is characterized by comprising the following steps:
s1: configuration of the drip solution A, B: uniformly mixing an unsaturated carboxylic acid monomer b, an unsaturated phosphate ester c, a chain transfer agent and deionized water to obtain a dropping liquid A; uniformly mixing a reducing agent and deionized water to be used as a dropping liquid B for later use;
s2: adding deionized water and an unsaturated polyoxyethylene ether monomer a into a reaction kettle, stirring at normal temperature to fully dissolve the monomers, regulating the temperature to 10-30 ℃, adding a small amount of an unsaturated carboxylic acid monomer b with an acidity regulating effect, and uniformly stirring;
s3: sequentially adding 1% concentration iron catalyst and oxidant into the mixed solution obtained in step S2 at an initial reaction temperature of 10-30 ℃, stirring for 5min, then beginning to dropwise add solution A and solution B at a constant speed, wherein the dropwise adding time is 45-90min, the highest temperature of the reaction solution is controlled not to exceed 40 ℃, the solution B is 15min later than the solution A and completely dropwise added, and after the dropwise adding is finished, carrying out aging reaction for 30-60 min;
s4: and adding a proper amount of alkali liquor for neutralization, adjusting the pH to 5-6, and adding deionized water for dilution until the solid content is 40-50%, thus obtaining the high-adaptability polycarboxylate superplasticizer suitable for the low-quality aggregate.
2. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the molar ratio of the unsaturated polyoxyethylene ether monomer a to the unsaturated carboxylic acid monomer b to the unsaturated phosphate ester monomer c is 1 (3.0-4.5) to (0.5-1.0), the dosages of the iron catalyst, the oxidant, the reducing agent and the chain transfer agent are respectively 0.2-1.0%, 0.4-1.2%, 0.1-0.5% and 0.2-0.8% of the total mass of the monomer a, the monomer b and the monomer c, the pH of the solution is adjusted to 5-7 by proper amount of liquid alkali, and the solid content is 40-50% by proper amount of deionized water.
3. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: in S2, the unsaturated polyoxyethylene ether monomer a is ethylene glycol monovinyl polyethylene glycol ether (EPEG), and the molecular structural formula is as follows: CH (CH)2＝CH-O-CH2-CH2-O-(C2H4O)n-H，n＝50-120。
4. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the unsaturated carboxylic acid monomer b in S1 is one of acrylic acid, methacrylic acid, maleic acid, itaconic acid and/or fumaric acid.
5. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the molecular structure of the unsaturated phosphate ester monomer c in S1 is as follows:
r represents H or alkyl, X represents alkyl; or
R1、R2Represents H or alkyl, R3、R4Represents an alkyl group(ii) a Is one of vinyl phosphate, diethyl vinyl phosphate, alkyl acrylate phosphate, end-capped amide phosphate and/or 2-hydroxyethyl methacrylate phosphate.
6. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the reducing agent in S1 is one of L-ascorbic acid, sodium bisulfite, sodium sulfite and/or sodium hypophosphite.
7. The preparation method of the high-activity polyether synthesized ultra-slow-release type polycarboxylate superplasticizer according to claim 1, is characterized in that: the chain transfer agent in S1 is one of mercaptoethanol, mercaptopropanol, mercaptoacetic acid, 3-mercaptopropionic acid and/or n-dodecyl mercaptan.
8. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the 1% concentration iron-based catalyst in S3 is one of ferrous sulfate solution, ferric chloride solution and/or ferrous chloride solution.
9. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the oxidant in S3 is one of hydrogen peroxide, ammonium persulfate, sodium persulfate and/or potassium persulfate.
10. The preparation method of the high-adaptability polycarboxylate superplasticizer suitable for low-quality aggregates according to claim 1, characterized by comprising the following steps: the liquid alkali in S4 is one of 30% sodium hydroxide and/or 30% potassium hydroxide.
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Application publication date: 20201117 |