CN108033707B - Environment-friendly biodegradable wide-temperature-zone concrete retarder and preparation method and application thereof - Google Patents
Environment-friendly biodegradable wide-temperature-zone concrete retarder and preparation method and application thereof Download PDFInfo
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- CN108033707B CN108033707B CN201711471537.6A CN201711471537A CN108033707B CN 108033707 B CN108033707 B CN 108033707B CN 201711471537 A CN201711471537 A CN 201711471537A CN 108033707 B CN108033707 B CN 108033707B
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
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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
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of retarders, and particularly discloses an environment-friendly biodegradable wide-temperature-zone concrete retarder as well as a preparation method and application thereof. The retarder is at least one of polyaspartic acid or modified polyaspartic acid. The preparation method of the polyaspartic acid comprises the step of hydrolyzing polysuccinimide under the condition of alkali liquor to obtain the polyaspartic acid. The preparation method of the modified polyaspartic acid comprises the steps of preparing polysuccinimide into suspension, adding 2-aminoethanol, and uniformly stirring to obtain a solution system; and dropwise adding alkali liquor into the solution system to adjust the pH value to 9-11, and reacting until the solution system is clear to obtain the hydroxyl-modified polyaspartic acid derivative, namely the modified polyaspartic acid. The retarder prepared by the invention has excellent retarding effect in a temperature range of 10-200 ℃, can be biodegraded, does not pollute the environment, and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of retarders, in particular to an environment-friendly biodegradable wide-temperature-zone concrete retarder as well as a preparation method and application thereof.
Background
The deep stratum exploration field is increasing, deep wells, ultra-deep wells and geothermal wells with extremely high geothermal gradient are increasing, the static temperature of the bottom of the well is generally 100-. At such high temperature, the physical and chemical properties of cement slurry and set cement can be obviously changed, which mainly shows that the thickening time of the cement slurry is sharply shortened, the strength of the set cement is degenerated, the permeability is increased and other changes occur, which indicates that hydration products and structures of the cement are correspondingly changed, thereby influencing the well cementation construction and the well cementation quality. Therefore, higher requirements are put on the temperature adaptability of the cement admixture used in the common environment, especially in the high-temperature and ultra-high-temperature environment.
The retarder is the most important one of cement admixtures, and is added into cement paste under the ordinary environment to adjust thickening time. The high-temperature retarder is a chemical reagent capable of prolonging the setting time of cement slurry under a high-temperature condition, has the function of effectively prolonging the time of the cement slurry in a liquid state and pumpability, and is mainly applied to deep stratum well cementation concrete with higher temperature and temperature gradient, such as deep wells, ultra-deep wells and the like of land and offshore oil fields. At present, the domestic high-temperature resistant retarder is mainly focused on the research and development of polymers such as AMPS copolymer. In foreign countries, the commonly used retarder mainly comprises lignosulfonate and derivatives thereof, the effective use temperature reaches 121 ℃, the retarder is compounded with boric acid (salt) to use, and the effective use temperature can reach 316 ℃, but the retarder has the defect of strong high-temperature dispersibility; the effective use temperature of the low molecular weight cellulose and the derivatives thereof reaches 121 ℃, and the defects of increasing the consistency of cement paste and reducing the high-temperature strength of cement exist; hydroxycarboxylic acid (salts) such as sodium gluconate, sodium glucoheptonate, tartaric acid, citric acid and the like have the defects of relatively sensitive dosage, too strong dispersibility and the like; boric acid (salt), auxiliary retarder, self-retarding function and the like are not obvious.
With the increasing attention of people on environmental protection, foreign researchers have made many studies on environmental protection retarders in recent years. The environment-friendly retarder mainly refers to a retarder product with better biodegradability. The commonly used retarders such as lignosulfonate and AMPS copolymer are difficult to biodegrade at present, and cellulose retarders such as CMC are good in biodegradability, but have a plurality of defects and can only be used at medium and low temperature.
Disclosure of Invention
Aiming at the problems that the existing retarder is difficult to degrade and has narrow applicable temperature range and the like, the invention provides an environment-friendly biodegradable wide-temperature-range concrete retarder.
Furthermore, the invention also provides a preparation method of the environment-friendly biodegradable wide-temperature-zone concrete retarder.
Further, the invention also provides application of the environment-friendly biodegradable wide-temperature-zone concrete retarder.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
an environment-friendly biodegradable wide-temperature-range concrete retarder is at least one of polyaspartic acid or modified polyaspartic acid.
Compared with the prior art, the retarder can be biodegraded, cannot cause environmental pollution, and belongs to an environment-friendly concrete admixture; the dispersion of the cement paste is weak, and the single slow release effect is achieved, so that the excessive thinning of the cement paste in a high-temperature use environment is prevented; the retarder has a wide use temperature range.
Further, the invention also provides a preparation method of the environment-friendly biodegradable wide-temperature-zone concrete retarder.
The preparation method of the polyaspartic acid comprises the following steps: providing polysuccinimide, and hydrolyzing the polysuccinimide under the alkaline solution condition to obtain polyaspartic acid, wherein the alkaline solution condition is as follows: the pH value is 9-11.
The preparation method of the modified polyaspartic acid comprises the following steps:
preparing polysuccinimide into suspension, adding 2-aminoethanol, and uniformly stirring to obtain a solution system, wherein the molar ratio of the polysuccinimide to the 2-aminoethanol is 3-5: 1;
and dropwise adding alkali liquor into the solution system to adjust the pH value to 9-11, and reacting until the solution system is clear to obtain the hydroxyl-modified polyaspartic acid derivative, namely the modified polyaspartic acid.
Compared with the prior art, the preparation method of the environment-friendly biodegradable wide-temperature-range concrete retarder provided by the invention is simple, and the polysuccinimide can be prepared into polyaspartic acid with different molecular weights by self-making or commercial method; in the preparation process of the modified polyaspartic acid, the adding amount of the modifier 2-aminoethanol is controlled to obtain the modified polyaspartic acid with different hydroxyl contents,
correspondingly, the invention provides the application of the environment-friendly biodegradable wide-temperature-zone concrete retarder or the retarder prepared by the preparation method of the environment-friendly biodegradable wide-temperature-zone concrete retarder in the field of concrete operation with a temperature zone of 10-200 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides an environment-friendly biodegradable wide-temperature-range concrete retarder which is at least one of polyaspartic acid or modified polyaspartic acid.
Compared with the prior art, the retarder can be biodegraded, cannot cause environmental pollution, and belongs to an environment-friendly concrete admixture; the dispersion of the cement paste is weak, and the single slow release effect is achieved, so that the excessive thinning of the cement paste in a high-temperature use environment is prevented; the retarder has a wide use temperature range.
Preferably, the number average molecular weight of the polyaspartic acid is 2000-15000; the modified polyaspartic acid has a number average molecular weight of 2000-15000; the modifier of the modified polyaspartic acid is at least one of citric acid, 2-aminoethanol, diethanolamine, 2-aminoethanesulfonic acid and sodium aspartate.
The coagulant with different molecular weights and other components, temperature, auxiliary retarder and other factors of the concrete have certain influence on the retarding effect of the concrete because the retarder with different molecular weights is not prepared. In practical application, the retarder with specific molecular weight can be selected under the application condition to achieve the most excellent effect.
The invention further provides a preparation method of the environment-friendly biodegradable wide-temperature-zone concrete retarder on the premise of providing the environment-friendly biodegradable wide-temperature-zone concrete retarder.
In any embodiment, the preparation method of the environment-friendly biodegradable wide temperature zone concrete retarder comprises the following steps: providing polysuccinimide, and hydrolyzing the polysuccinimide under the alkaline solution condition to obtain polyaspartic acid, wherein the alkaline solution condition is as follows: the pH value is 9-11.
The preparation method of the polyaspartic acid provided by the invention is simple and the raw materials are easy to obtain.
The above preparation process is further explained below:
preferably, the preparation method of the polysuccinimide at least comprises the following steps:
mixing maleic anhydride and ammonium carbonate with the molar ratio of 1:2-2.5, and carrying out amination treatment for 2-6h at the temperature of 50-90 ℃ to obtain a polymeric precursor, wherein the ammonium carbonate can be replaced by ammonia water;
and (3) decompressing and drying the polymerization precursor to remove water, and heating to 180-200 ℃ in a nitrogen atmosphere for polymerization reaction for 3-6h to obtain polysuccinimide with different molecular weights.
Maleic anhydride and ammonium carbonate are used as raw materials, so that the method is simple and easy to obtain, low in price and simple in preparation process.
Preferably, the preparation method of the polysuccinimide at least comprises the following steps:
mixing L-aspartic acid with a molar ratio of 5-15: 1: mixing phosphoric acid, and carrying out thermal polycondensation reaction for 3-4h at the temperature of 200-240 ℃ to obtain polysuccinimide.
The polysuccinimide is prepared by adopting an L-aspartic acid thermal condensation method, and the method is simple and easy to control.
In any embodiment, the preparation method of the environment-friendly biodegradable wide-temperature-zone concrete retarder comprises the following steps:
preparing polysuccinimide into suspension, adding 2-aminoethanol, and uniformly stirring to obtain a solution system, wherein the molar ratio of the polysuccinimide to the 2-aminoethanol is 3-5: 1;
and dropwise adding alkali liquor into the solution system to adjust the pH value to 9-11, and reacting until the solution system is clear to obtain the hydroxyl-modified polyaspartic acid derivative, namely the modified polyaspartic acid.
In the preparation method of the modified polyaspartic acid, the preparation method is simple and easy to control.
Preferably, the 2-aminoethanol may be replaced by one of citric acid, diethanolamine, 2-aminoethanesulfonic acid, sodium aspartate.
Can be R-NH such as diethanolamine, 2-aminoethanesulfonic acid, and sodium aspartate2And R1-NH-R2The functional monomer of (2) introduces functional groups such as hydroxyl, carboxyl, sulfonic group, amide group and the like through ring-opening polymerization.
Correspondingly, the invention provides the environment-friendly biodegradable wide-temperature-range concrete retarder or the retarder prepared by the preparation method of the environment-friendly biodegradable wide-temperature-range concrete retarder, and the application of the retarder in the field of concrete operation with a temperature range of 10-200 ℃.
Preferably, in the concrete operation with the temperature range of 80-120 ℃, the retarder with the molecular weight of 4000-6000 is 0.3-0.7 wt% by taking the cementing material as 100% as the basis.
Preferably, in the concrete operation at the temperature of 160-200 ℃, the retarder and tartaric acid are compounded according to the mass ratio of 3:1-1.2 to obtain a compound agent, wherein the compound agent is added in an amount of 1.0-1.5 wt% based on 100% of the gelled material, and the molecular weight of the retarder is 4000-6000.
The following examples are provided to better illustrate the embodiments of the present invention.
Example 1
The embodiment of the invention provides an environment-friendly biodegradable wide-temperature-range concrete retarder which is polyaspartic acid with the molecular weight of 4000-6000.
The preparation method of the polyaspartic acid comprises the following steps:
mixing maleic anhydride and ammonium carbonate with a molar ratio of 1:2, and carrying out amination treatment for 5 hours at 70 ℃ to obtain a polymeric precursor;
and (3) decompressing and drying the polymerization precursor to remove water, and heating to 200 ℃ in a nitrogen atmosphere for polymerization reaction for 5h to obtain polysuccinimide with the molecular weight of 5000-1000.
Washing the polysuccinimide with water, grinding the polysuccinimide into suspension, adding NaOH solution at normal temperature to regulate the pH value of the reaction system to 9.0-11.0, and obtaining polyaspartic acid with molecular weight of 4000-6000.
Example 2
The embodiment of the invention provides an environment-friendly biodegradable wide-temperature-range concrete retarder which is polyaspartic acid with the molecular weight of 4000-6000.
The preparation method of the polyaspartic acid comprises the following steps:
mixing L-aspartic acid with a molar ratio of 10: 1: mixing phosphoric acid, and carrying out thermal polycondensation reaction for 4h at 220 ℃ to obtain polysuccinimide with the molecular weight of 5000-1000.
Washing the polysuccinimide with water, grinding the polysuccinimide into suspension, adding NaOH solution at normal temperature to regulate the pH value of the reaction system to 9.0-11.0, and obtaining polyaspartic acid with molecular weight of 4000-6000.
Example 3
The embodiment of the invention provides an environment-friendly biodegradable wide-temperature-range concrete retarder which is modified polyaspartic acid with the molecular weight of 4000-6000.
The preparation method of the modified polyaspartic acid comprises the following steps:
suspending polysuccinimide in water to prepare suspension, adding 2-aminoethanol, and uniformly stirring to obtain a solution system, wherein the molar ratio of the polysuccinimide to the 2-aminoethanol is 5: 1;
and dropwise adding alkali liquor into the solution system to adjust the pH value to 9-11, and reacting until the solution system is clear to obtain the hydroxyl-modified polyaspartic acid derivative, namely the modified polyaspartic acid.
In order to better illustrate the characteristics of the environmentally-friendly biodegradable concrete retarder with wide temperature range provided by the embodiment of the invention, the retarder prepared in the embodiment 1, 2 and 3 is applied to concrete operation with the temperature range of 80-200 ℃, wherein the doping amount, and the initial setting time and the final setting time of the concrete are listed as follows.
Table 1 examples 1-3 test data
As is apparent from the data in Table 1, the environmentally-friendly biodegradable wide-temperature-range concrete retarder provided by the invention has an obvious retarding effect under the concrete operation condition of a high-temperature range of 80-200 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The environment-friendly biodegradable wide-temperature-range concrete retarder is characterized in that: the retarder is modified polyaspartic acid with the number average molecular weight of 4000-6000; wherein the content of the first and second substances,
the preparation method of the modified polyaspartic acid comprises the following steps:
mixing maleic anhydride, ammonium carbonate or ammonia water with the molar ratio of 1 (2-2.5), and carrying out amination treatment for 2-6h at the temperature of 50-90 ℃ to obtain a polymerization precursor;
decompressing the polymerization precursor and evaporating the water to dryness, and heating to 180-200 ℃ for polymerization reaction for 3-6h under the nitrogen atmosphere to obtain polysuccinimide;
preparing the polysuccinimide into suspension, adding 2-aminoethanol, and uniformly stirring to obtain a solution system, wherein the molar ratio of the polysuccinimide to the 2-aminoethanol is (3-5) to 1;
and dropwise adding alkali liquor into the solution system to adjust the pH value to 9-11, and reacting until the solution system is clear to obtain the hydroxyl-modified polyaspartic acid derivative, namely the modified polyaspartic acid.
2. The environmentally friendly biodegradable wide temperature band concrete retarder of claim 1, wherein: the 2-aminoethanol can be replaced by one of citric acid, diethanolamine, 2-aminoethanesulfonic acid and sodium aspartate.
3. The environmentally friendly biodegradable wide temperature range concrete retarder according to any one of claims 1 to 2, which is applied to the field of concrete work with a temperature range of 10 to 200 ℃.
4. The use of the environmentally friendly biodegradable wide temperature band concrete retarder according to any one of claims 1 to 2 in the field of concrete work at a temperature band of 10 to 200 ℃, characterized in that: in the concrete operation with the temperature range of 80-120 ℃, the addition amount of the retarder with the molecular weight of 4000-6000 is 0.3-0.7 wt% based on 100% of the cementing material.
5. The use of the environmentally friendly biodegradable wide temperature band concrete retarder according to any one of claims 1 to 2 in the field of concrete work at a temperature band of 10 to 200 ℃, characterized in that: in the concrete operation at the temperature of 160-200 ℃, the retarder and the tartaric acid are compounded according to the mass ratio of 3:1-1.2 to obtain the compound agent, the mixing amount of the compound agent is 1.0-1.5 wt% based on 100% of the gelled material, and the molecular weight of the retarder is 4000-6000.
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| CN109020293A (en) * | 2018-09-18 | 2018-12-18 | 济南大学 | A kind of preparation and application of hyperbranched type retarder |
| CN109824893A (en) * | 2019-01-11 | 2019-05-31 | 吉林省产品质量监督检验院(吉林省农产品认证中心) | The preparation method of more gap polysuccinimides |
| CN110551283B (en) * | 2019-09-06 | 2021-05-11 | 南京林业大学 | Polyaspartic acid derivative and preparation method and application thereof |
| CN112408844B (en) * | 2020-12-04 | 2022-06-24 | 河北协同环保科技股份有限公司 | Gypsum retarder and preparation method and application thereof |
| CN112500018B (en) * | 2020-12-04 | 2022-09-06 | 河北协同环保科技股份有限公司 | Degradable efficient gypsum retarder and preparation method and application thereof |
| CN115448631B (en) * | 2022-10-31 | 2023-10-20 | 济宁无内新材料技术研发中心(有限合伙) | Amino acid gypsum retarder with strong alkali resistance |
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| DE3626672A1 (en) * | 1986-08-07 | 1988-02-11 | Bayer Ag | POLYASPARAGINAMID ACID |
| US6419016B1 (en) * | 2000-09-29 | 2002-07-16 | Halliburton Energy Services, Inc. | Methods of cementing in subterranean zones |
| CN1123588C (en) * | 2001-10-08 | 2003-10-08 | 北京化工大学 | Synthesis method of polyaspartic acid |
| CN1160397C (en) * | 2001-11-12 | 2004-08-04 | 南京南大表面和界面化学工程技术研究中心有限责任公司 | Polyasparagine derivative containing high-activity hydroxy radical |
| US7166160B2 (en) * | 2003-04-22 | 2007-01-23 | Halliburton Energy Services, Inc. | Biodegradable cement retarder compositions and methods of cementing in a subterranean formation |
| JP5339857B2 (en) * | 2008-11-05 | 2013-11-13 | ユニチカ株式会社 | Resin composition for foaming biodegradable flame retardant polyester, foam obtained therefrom, and molded product thereof |
| CN106279572A (en) * | 2016-07-26 | 2017-01-04 | 上海台界化工有限公司 | A kind of retarder for building containing poly-aspartate and preparation method thereof |
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Effective date of registration: 20230414 Address after: No. 209 Alishan Street, High tech Zone, Shijiazhuang City, Hebei Province, 050000, 900 Patentee after: Hebei Yuansheng Concrete Technology Co.,Ltd. Address before: 050000 No. 209 Alishan street, hi tech Zone, Shijiazhuang City, Hebei Province Patentee before: HEBEI TIEYUAN SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd. |