WO2024255217A1 - Chitosane modifié et son procédé de préparation, et agent réducteur d'eau de type retard et son utilisation - Google Patents

Chitosane modifié et son procédé de préparation, et agent réducteur d'eau de type retard et son utilisation Download PDF

Info

Publication number
WO2024255217A1
WO2024255217A1 PCT/CN2024/070560 CN2024070560W WO2024255217A1 WO 2024255217 A1 WO2024255217 A1 WO 2024255217A1 CN 2024070560 W CN2024070560 W CN 2024070560W WO 2024255217 A1 WO2024255217 A1 WO 2024255217A1
Authority
WO
WIPO (PCT)
Prior art keywords
chitosan
modified chitosan
acid
water
slow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/070560
Other languages
English (en)
Chinese (zh)
Inventor
吴传灯
林志群
李格丽
方云辉
柯余良
林添兴
郭元强
吴文贤
张加炎
谢非
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kezhijie New Material Group Co Ltd
Original Assignee
Kezhijie New Material Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kezhijie New Material Group Co Ltd filed Critical Kezhijie New Material Group Co Ltd
Publication of WO2024255217A1 publication Critical patent/WO2024255217A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B24/38—Polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • 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

Definitions

  • the invention belongs to the technical field of building materials, and in particular relates to a modified chitosan and a preparation method thereof, a slow-setting water reducing agent and application thereof.
  • polycarboxylate water-reducing agent As a commonly used chemical admixture in existing concrete, polycarboxylate water-reducing agent is widely used due to its advantages of low dosage, high water reduction, designable molecular structure, and green environmental protection.
  • the interaction between polycarboxylate water-reducing agent and concrete will affect the flow properties of cement paste and cause abnormal coagulation of cement paste.
  • retarding substances such as chitosan and polyether
  • the problem of deterioration of concrete paste flow properties caused by the addition of polycarboxylate water-reducing agent is expected to be improved.
  • the second object of the present invention is to provide a method for preparing modified chitosan.
  • a fourth object of the present invention is to provide a slow-setting water-reducing agent.
  • the catalyst is added in an amount of 0.01 to 0.5 wt % based on the total molar amount of the chitosan and the halogenated carboxylic acid.
  • C1-C4 haloalkylene groups include, but are not limited to, -CH(Cl)-, -CH(Br) CH2- , -C[Br( CH3 )]- , -CH( Br ) CH2CH2- , -C[ CH2 (Cl) CH3 ]-, or -CH2CH2CH (Br) CH2- .
  • C1-C4 carboxylic acid groups include, but are not limited to, -CH(COOH)-, -CH2CH (COOH)-, or -CH( CH3 )CH(COOH)-.
  • C2-C4 acyl groups include, but are not limited to, -CH2CO- , -CH2CH2CO- , -CH ( CH3 ) CO- , -CH2CH2CH2CO- , or -C( CH3 ) 2CO- .
  • C2-C4 haloacyl include, but are not limited to, -CH(Br)CO-, -CH2CH (Cl)CO-, or -CH( CH3 )CH(Br ) CO- .
  • the ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4, structural unit 5, structural unit 6 and structural unit 7 in the modified chitosan structure is not particularly limited, that is, the ratio of structural unit 1, structural unit 2, structural unit 3, structural unit 4, structural unit 5, structural unit 6 and structural unit 7 in the modified chitosan structure provided by the present invention can be
  • the ratio of the present invention is 1:2:1:1:3:6:2, 2:5:9:3:1:1:1, 9:1:8:2:1:7, 100:5:135:1:4:3:6 or any other ratio
  • the distribution of the structural unit one, structural unit two, structural unit three, structural unit four, structural unit five, structural unit six and structural unit seven in the modified chitosan structure is not particularly limited, that is, the structural unit one, structural unit two, structural unit three, structural unit four, structural unit five, structural unit six and structural unit seven in the modified chitosan structure provided in the present invention can be distributed in any manner.
  • the preparation method of the modified chitosan provided by the present invention comprises: taking chitosan and halogenated carboxylic acid to carry out halogenated carboxylation reaction under the action of a catalyst to obtain the modified chitosan
  • the weight average molecular weight of the chitosan is preferably 300-50000, such as 300, 500, 1000, 2000, 1000, 2000, 3000, 7500, 10000, 10200, 14600, 20000, 30000, 40000, 50000 or any value therebetween.
  • the halogenated carboxylic acid is a compound containing both a halogen atom and a carboxylic acid in the molecule, which can undergo a halogenated carboxylic acid reaction with chitosan, and the halogenated carboxylic acid can be directly purchased or prepared by conventional methods.
  • specific examples of the halogenated carboxylic acid include, but are not limited to, one or more of 3-chloropyruvic acid, 3-bromopyruvic acid, 2-dichlorosuccinic acid, 2,3-dichlorosuccinic acid, 3-chloropropionic acid, and 3-bromopropionic acid.
  • the added amount of the catalyst is preferably 0.01-0.5wt%, such as 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.35wt%, 0.4wt%, 0.5wt% or any value therebetween.
  • the present invention also provides a modified chitosan prepared by the above method, wherein the structure of the modified chitosan has at least one of the structural unit 1 represented by formula (1), the structural unit 2 represented by formula (2) and the structural unit 3 represented by formula (3); in addition, the modified chitosan may also have one or more of the structural unit 4 represented by formula (4), the structural unit 5 represented by formula (5), the structural unit 6 represented by formula (6) and the structural unit 7 represented by formula (7).
  • Embodiments of the present invention are described in detail below, and the examples of the embodiments are intended to be used to explain the present invention, but should not be construed as limiting the present invention.
  • specific techniques or conditions are not specified, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not specified for reagents or instruments used, they are all conventional products that can be obtained commercially.
  • Air entraining agent (manufacturer is Nanjing Xinyi Synthetic, product number is XY-A01); water retention agent (manufacturer is Ningbo Zhongshuike, product number is SK-530); polycarboxylic acid (manufacturer is Kezhijie, product number is Point-400S); PCE-S (manufacturer is Kezhijie, product number is Point-MS); Sika retarder H-1 (manufacturer is Sika, product number is POWDER P).
  • This preparation example is used for the modified chitosan and the preparation method thereof provided by the present invention.
  • the preparation of the modified chitosan is specifically as follows: 3-bromopyruvic acid and chitosan (weight average molecular weight is 2000) are dissolved in butyl acetate according to a molar ratio of 1:0.1, and 0.05wt% of Ziegler-Natta catalyst is added, and stirred at 90°C for reaction. After 6 hours, the mixture was filtered, washed and dried to obtain modified chitosan.
  • This preparation example is used for the modified chitosan and preparation method thereof provided by the present invention.
  • the preparation of the modified chitosan is specifically as follows: 2,3-dibromosuccinic acid and chitosan (weight average molecular weight is 7000) are dissolved in butyl acetate according to a molar ratio of 1:0.5, and 0.12wt% of Ziegler-Natta catalyst is added. After stirring and reacting at 90°C for 6h, the reaction is filtered, washed and dried to obtain the modified chitosan.
  • This preparation example is used for the modified chitosan and its preparation method provided by the present invention.
  • the preparation method is as follows: 3-bromopropionic acid and chitosan (weight average molecular weight of 5000) are dissolved in butyl acetate in a molar ratio of 1:1, and 0.2wt% of Ziegler-Natta catalyst is added. After stirring at 90°C for 6h, the mixture is filtered, washed and dried to obtain modified chitosan.
  • modified chitosan was prepared according to the method provided in Preparation Example 1, except that chitosan (weight average molecular weight: 2000) was replaced by chitosan (weight average molecular weight: 7000) in an equal molar amount, and other conditions were the same.
  • This example is used to illustrate the slow-setting water-reducing agent provided by the present invention and its preparation method.
  • the components and contents of the slow-setting water-reducing agent are specifically: 19.5 parts by mass of the modified chitosan provided in Preparation Example 1, 0.4 parts by mass of an air entraining agent, 0.1 parts by mass of a water retaining agent and 80 parts by mass of a polycarboxylic acid.
  • the preparation of the slow-setting water reducer specifically includes: taking the modified chitosan, air entraining agent and water retaining agent according to the above mass parts, adding them into the polycarboxylic acid and stirring them evenly to obtain the slow-setting water reducer.
  • This example is used to illustrate a slow-setting water reducing agent and its preparation method.
  • the components and contents of the slow-setting water reducing agent are specifically: 49.5 parts by weight of the modified chitosan provided in Preparation Example 1, 0.3 parts by weight of an air entraining agent, 0.2 parts by weight of a water retaining agent, and 50 parts by weight of a polycarboxylic acid.
  • the preparation of the slow-setting water reducer specifically includes: taking the modified chitosan, air entraining agent and water retaining agent according to the above mass parts, adding them into the polycarboxylic acid and stirring them evenly to obtain the slow-setting water reducer.
  • This example is used to illustrate a slow-setting water reducing agent and its preparation method.
  • the components and contents of the slow-setting water reducing agent are specifically: 29.2 parts by mass of the modified chitosan provided in Preparation Example 3, 0.4 parts by mass of an air entraining agent, 0.4 parts by mass of a water retaining agent, and 70 parts by mass of a polycarboxylic acid.
  • the preparation of the slow-setting water reducer specifically includes: taking the modified chitosan, air entraining agent and water retaining agent according to the above mass parts, adding them into the polycarboxylic acid and stirring them evenly to obtain the slow-setting water reducer.
  • This example is used to illustrate a slow-setting water reducing agent and its preparation method.
  • the components and contents of the slow-setting water reducing agent are specifically: 19.5 parts by mass of the modified chitosan provided in Preparation Example 4, 0.4 parts by mass of an air entraining agent, 0.1 parts by mass of a water retaining agent, and 80 parts by mass of a polycarboxylic acid.
  • the preparation of the slow-setting water reducer specifically includes: taking the modified chitosan, air entraining agent and water retaining agent according to the above mass parts, adding them into the polycarboxylic acid and stirring them evenly to obtain the slow-setting water reducer.
  • a slow-setting water-reducing agent was prepared according to the method provided in Example 1, except that the modified chitosan provided in Preparation Example 1 was replaced by the modified chitosan provided in Preparation Example 5 in equal parts by weight, and other conditions were the same.
  • the comparative example provides a water reducing agent, which is prepared by uniformly mixing 40 parts by mass of PCE-S with 60 parts by mass of water.
  • This comparative example is prepared according to the method provided in Example 1, except that An equal amount of Sika retarder H-1 was used to replace the modified chitosan provided in Preparation Example 1, and other conditions were the same.
  • This comparative example prepares a slow-setting water-reducing agent according to the method provided in Example 1, except that the modified chitosan provided in Preparation Example 1 is replaced by an equal amount of polycarboxylic acid, and other conditions are the same.
  • This comparative example is used to illustrate a slow-setting water-reducing agent and a preparation method thereof, wherein the specific components and their weight parts are: 19.5 weight parts of modified chitosan, 0.4 weight parts of air entraining agent, 0.1 weight parts of water-retaining agent and 80 weight parts of polycarboxylic acid.
  • the preparation of the slow-setting water-reducing agent specifically comprises: taking the modified chitosan, air entraining agent and water-retaining agent according to the above weight parts, adding them to the polycarboxylic acid and stirring them evenly to obtain the slow-setting water-reducing agent.
  • the preparation of modified chitosan includes: taking propionic acid and chitosan (weight average molecular weight of 2000) to react according to the molar ratio of 1:0.1, firstly adding chitosan to acetic acid solution with a mass fraction of 75% for ultrasonic dispersion for 25 minutes, then adding propionic acid, stirring for reaction for 45 minutes, filtering, washing and drying to obtain modified chitosan.
  • the modified chitosan provided by the present invention can cooperate with polycarboxylic acid to achieve better water reduction effect, slow setting effect and collapse retention effect, and has good application prospects.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention relève du domaine technique des matériaux de construction. Sont divulgués un chitosane modifié et son procédé de préparation, et un agent réducteur d'eau de type retard et son utilisation. Le chitosane modifié selon la présente invention est un composé dans lequel une chaîne moléculaire de chitosane est liée à une structure chélatante de type acide aminé, la structure chélatante de type acide aminé pouvant jouer un rôle synergique avec un effet stérique d'une structure spatiale en trois dimensions du chitosane lui-même. L'ajout du chitosane modifié peut mettre dans un état d'équilibre dynamique la concentration d'ions métalliques dans un coulis de béton précoce, ce qui permet d'obtenir un effet de réduction du taux d'hydratation précoce. De plus, une certaine quantité d'hydroxyle est en outre réservée sur la chaîne moléculaire du chitosane modifié, de telle sorte qu'une grande quantité d'eau peut être adsorbée pendant la chélation d'ions métalliques, ce qui permet de favoriser une réaction d'hydratation ultérieure du béton. L'agent réducteur d'eau obtenu en mélangeant le chitosane modifié selon la présente invention à d'autres composants tels que l'acide polycarboxylique, présente de bonnes performances de réduction d'eau, de ralentissement des performances et des performances de rétention de l'affaissement, et présente de bonnes perspectives d'application.
PCT/CN2024/070560 2023-12-18 2024-01-04 Chitosane modifié et son procédé de préparation, et agent réducteur d'eau de type retard et son utilisation Pending WO2024255217A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202311736218.9 2023-12-18
CN202311736218.9A CN117720674A (zh) 2023-12-18 2023-12-18 一种改性壳聚糖及其制备方法、缓凝型减水剂和应用

Publications (1)

Publication Number Publication Date
WO2024255217A1 true WO2024255217A1 (fr) 2024-12-19

Family

ID=90199402

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2024/070560 Pending WO2024255217A1 (fr) 2023-12-18 2024-01-04 Chitosane modifié et son procédé de préparation, et agent réducteur d'eau de type retard et son utilisation

Country Status (2)

Country Link
CN (1) CN117720674A (fr)
WO (1) WO2024255217A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120607380A (zh) * 2025-08-07 2025-09-09 德州润德混凝土有限公司 一种混凝土防冻剂制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619995A (en) * 1984-12-24 1986-10-28 Nova Chem Limited N,O-carboxymethyl chitosan and preparative method therefor
CN113150771A (zh) * 2021-03-04 2021-07-23 齐鲁工业大学 一种检测二氧化硫的壳聚糖基荧光探针及其制备方法和应用
JP2021172727A (ja) * 2020-04-24 2021-11-01 大日精化工業株式会社 キトサン誘導体及びその製造方法、ｏ／ｗ型乳化組成物、並びに化粧料
CN114316143A (zh) * 2021-12-28 2022-04-12 科之杰新材料集团有限公司 一种壳聚糖-聚甘油复合型醚类聚羧酸减水剂的制备方法
CN116854945A (zh) * 2023-07-11 2023-10-10 中国海洋大学 一种壳聚糖基温敏水凝胶的制备方法及其应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114249555A (zh) * 2021-12-29 2022-03-29 科之杰新材料集团有限公司 一种降粘缓释型聚羧酸减水剂及其应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4619995A (en) * 1984-12-24 1986-10-28 Nova Chem Limited N,O-carboxymethyl chitosan and preparative method therefor
JP2021172727A (ja) * 2020-04-24 2021-11-01 大日精化工業株式会社 キトサン誘導体及びその製造方法、ｏ／ｗ型乳化組成物、並びに化粧料
CN113150771A (zh) * 2021-03-04 2021-07-23 齐鲁工业大学 一种检测二氧化硫的壳聚糖基荧光探针及其制备方法和应用
CN114316143A (zh) * 2021-12-28 2022-04-12 科之杰新材料集团有限公司 一种壳聚糖-聚甘油复合型醚类聚羧酸减水剂的制备方法
CN116854945A (zh) * 2023-07-11 2023-10-10 中国海洋大学 一种壳聚糖基温敏水凝胶的制备方法及其应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SKORIK, YURY A. ET AL.: "Carboxyalkylation of Chitosan in the Gel State", CARBOHYDRATE POLYMERS, vol. 90, no. 2, 1 October 2012 (2012-10-01), XP028931974, ISSN: 0144-8617, DOI: 10.1016/j.carbpol.2012.06.072 *
YUAN WEN, YIN XUE-QIONG, HE YONG-NING, LIN QIANG: "Progress in the Research of Carboxyl-Chitosan", HUAXUE SHIJI - CHEMICAL REAGENTS, BEIJING : HUAXUE HUAXUE SHIJI KEJI QINGBAO ZHONGXINZHAN, CN, vol. 29, no. 5, 1 January 2007 (2007-01-01), CN , XP093248607, ISSN: 0258-3283, DOI: 10.13822/j.cnki.hxsj.2007.05.007 *
ZHAOSHENG CAI, ZHAN-QIAN SONG, CHUN-SHEN YANG AND SHI-BIN SHANG: "Synthesis of N,O-(2-Carboxyethyl)-Chitosan and its Properties", JOURNAL OF THE CHEMICAL SOCIETY OF PAKISTAN., CHEMICAL SOCIETY OF PAKISTAN, KARACHI., PK, vol. 31, no. 2, 1 April 2009 (2009-04-01), PK , pages 279 - 283, XP009559357, ISSN: 0253-5106 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120607380A (zh) * 2025-08-07 2025-09-09 德州润德混凝土有限公司 一种混凝土防冻剂制备方法

Also Published As

Publication number Publication date
CN117720674A (zh) 2024-03-19

Similar Documents

Publication Publication Date Title
CN106188456B (zh) 一种适用于含泥骨料的改性萘系减水剂的制备方法
CN115448625B (zh) 一种改善高碱水泥性能的助磨剂及其制备方法
CN110818308A (zh) 一种用于高石粉含量的混凝土增效剂及其制备方法
CN113307571B (zh) 一种含机制砂的超保坍混凝土及其制备方法
WO2024198014A1 (fr) Agent de modification de béton et son procédé de préparation, mélange de béton et composition de béton
WO2024255217A1 (fr) Chitosane modifié et son procédé de préparation, et agent réducteur d'eau de type retard et son utilisation
CN111302695A (zh) 一种复合早强减水剂及其制备方法和应用
CN109608632B (zh) 一种混凝土抗泥牺牲剂及其制备方法
CN112430015B (zh) 一种大掺量粉煤灰混凝土及其制备方法
CN108975755A (zh) 再生混凝土专用外加剂
CN109320707B (zh) 一种超支化型公路混凝土缓凝剂及其制备方法及应用
CN120025509B (zh) 一种有机膦酸盐缓凝剂及其制备方法与应用
CN110563376B (zh) 一种适于机制砂配制的混凝土的强效剂及其母液的制备方法
CN118652069B (zh) 一种适用于高寒地区的防渗抗冻混凝土复合外加剂及其制备方法
CN117303784B (zh) 一种复合醇胺酯型混凝土减胶剂及其制备方法与应用
CN116199469B (zh) 一种提高有机料与水泥凝结强度的方法及其制备得到的水泥
CN117865550A (zh) 一种混凝土用环保减胶剂及其制备方法
CN116589245B (zh) 一种超缓凝混凝土及其制备方法
CN115448633B (zh) 一种聚羧酸降敏剂及其制备方法
CN118878273A (zh) 一种四元复掺绿色高性能混凝土
CN105503141A (zh) 一种废渣磷酸镁水泥自流平砂浆
CN113443879B (zh) 一种利用再生轻骨料生产的轻骨料混凝土及其生产工艺
CN115124327A (zh) 复合增塑耐火可塑料及其制备方法
JPS60131855A (ja) セメント添加剤
CN113024153A (zh) 一种液态水泥增效剂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24822178

Country of ref document: EP

Kind code of ref document: A1