WO2024124734A1 - Inhibiteur composite d'agrégats alcalins et procédé de préparation associé - Google Patents

Inhibiteur composite d'agrégats alcalins et procédé de préparation associé Download PDF

Info

Publication number
WO2024124734A1
WO2024124734A1 PCT/CN2023/083638 CN2023083638W WO2024124734A1 WO 2024124734 A1 WO2024124734 A1 WO 2024124734A1 CN 2023083638 W CN2023083638 W CN 2023083638W WO 2024124734 A1 WO2024124734 A1 WO 2024124734A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali
composite inhibitor
aggregate composite
polyethylene glycol
organic acid
Prior art date
Application number
PCT/CN2023/083638
Other languages
English (en)
Chinese (zh)
Inventor
倪涛
黄玉美
赵发香
杨晓锋
王进春
王龙
王龙飞
刘江涛
董树强
刘松光
袁海军
Original Assignee
石家庄市长安育才建材有限公司
四川砼道科技有限公司
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 石家庄市长安育才建材有限公司, 四川砼道科技有限公司 filed Critical 石家庄市长安育才建材有限公司
Publication of WO2024124734A1 publication Critical patent/WO2024124734A1/fr

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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0042—Powdery mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present disclosure relates to the field of concrete building materials, and in particular to an alkali-aggregate composite inhibitor.
  • the present disclosure also relates to a preparation method of the alkali-aggregate composite inhibitor.
  • Concrete has become the world's largest building material due to its excellent cost-effectiveness.
  • Concrete is a composite material obtained by mixing and hardening cementitious materials, coarse and fine aggregates and water.
  • the main type of cementitious materials is cement. Cement undergoes a hydration reaction when it comes into contact with water, bonding coarse and fine aggregates together. Since the international energy crisis in the 1970s, the cement industry has gradually changed from wet production to dry production, which has increased the alkali content of cement.
  • Alkali-aggregate reaction is the slow reaction between the alkali in cement and the active silica in aggregate to form silicate gel.
  • the silicate gel accumulates over a long period of time and its output increases. It has strong water absorption, causing the silicate gel to expand in volume, thereby inducing expansion stress from the inside to the outside of the concrete structure, causing concrete cracking, reducing the mechanical properties of concrete, and damaging the durability of concrete.
  • Alkali-aggregate reaction cracking has been found. Some urban highway traffic has cracks in its moist parts a few years after construction and sampling has confirmed that it is alkali-aggregate reaction.
  • the present disclosure proposes an alkali-aggregate composite inhibitor to inhibit the alkali-aggregate reaction of concrete.
  • An alkali aggregate composite inhibitor the raw materials for preparing the alkali aggregate composite inhibitor include the following components by weight: 0.5-2.0 parts of a titanate coupling agent, 15-30 parts of an ester of polyethylene glycol and an organic acid, and 200-260 parts of a medium-pore zeolite.
  • the titanate coupling agent includes di(triethanolamine)titanate diisopropyl ester, bis(di At least one of a chelate of octyl pyrophosphate) ethylene titanate and triolamine, isopropyl tri(dioctyl phosphate) titanate, and isopropyl dioleyloxy(dioctyl phosphate) titanate.
  • the molar ratio of the alcohol acid in the ester of polyethylene glycol and organic acid is (5-8): (12-18).
  • the weight average molecular weight of the polyethylene glycol is 200-600.
  • the organic acid is at least one of formic acid, acetic acid and propionic acid.
  • the medium pore zeolite includes at least one of ferrierite, Y-type zeolite and ZSM-5 zeolite.
  • the present disclosure also provides a method for preparing an alkali-aggregate composite inhibitor, the method comprising the following steps:
  • the preparation method of the ester of polyethylene glycol and organic acid comprises the following steps:
  • the catalyst is at least one of phosphotungstic heteropoly acid, SO 4 2- /SiO 2 -TiO 2 , cerium sulfate and zirconium sulfate.
  • the dehydrating agent is at least one of calcium oxide and anhydrous calcium sulfate.
  • the preparation of the ester of polyethylene glycol and organic acid is carried out by heating in an oil bath.
  • the amount of the catalyst is 0.1-0.3% of the amount of the reactants.
  • An alkali aggregate composite inhibitor the raw materials for preparing the alkali aggregate composite inhibitor include the following components by weight: 0.5-2.0 parts of a titanate coupling agent, 15-30 parts of an ester of polyethylene glycol and an organic acid, and 200-260 parts of a medium-pore zeolite.
  • the alkali-aggregate composite inhibitor disclosed in the present invention is composed of three main components: titanate coupling agent, esterification product of polyethylene glycol and organic acid, and medium-porous zeolite powder.
  • the medium-porous zeolite powder can rely on its own porous structure to produce adsorption effect on titanate coupling agent and esterification product of polyethylene glycol and organic acid, so that the adsorbed titanate coupling agent and esterification product of polyethylene glycol and organic acid are slowly released in the hardened concrete system to play a long-term effect.
  • the long carbon chain hydrophobic group of the titanate coupling agent is grafted onto the surface of the aggregate, which can hydrophobically modify the active silica on the surface of the aggregate, so that the silica on the surface of the aggregate has a hydrophobic effect, so that water cannot adhere to the surface of the aggregate, reducing the wetting effect of water molecules on the active silica in the hardened concrete under a humid environment, and alkaline substances cannot be ionized by water to produce hydroxide ions, which is helpful to inhibit the reaction between alkaline ions and active silica in the hardened concrete.
  • the titanium element contained in the titanate coupling agent can improve the durability of concrete, and an appropriate amount of titanium dioxide helps to improve the self-cleaning performance of concrete.
  • the titanate coupling agent may preferably be at least one of diisopropyl di(triethanolamine)titanate, a chelate of bis(dioctyl pyrophosphate)ethylene titanate and triolamine, isopropyl tri(dioctyl phosphate acyloxy) titanate, and isopropyl dioleyloxy(dioctyl phosphate acyloxy) titanate.
  • the ester of polyethylene glycol and organic acid undergoes hydrolysis reaction under alkaline conditions to generate organic acid, which neutralizes the alkali in the system, reduces the pH value of hardened concrete, and inhibits alkali-aggregate reaction.
  • the molar ratio of the alcohol acid in the ester of polyethylene glycol and organic acid is (5-8): (12-18).
  • the weight average molecular weight of the polyethylene glycol is 200-600. The molecular weight in this range is relatively small, the esterification efficiency is high, and more organic acid can be released by hydrolysis.
  • the organic acid can preferably be at least one of formic acid, acetic acid and propionic acid. This organic acid has a strong acidity and is more efficient in neutralization with alkali.
  • the present disclosure also provides a method for preparing an alkali-aggregate composite inhibitor, the method comprising the following steps:
  • 0.5-0.8 mol of polyethylene glycol is added to the reactor, the oil bath heater is turned on, the temperature is set to 60-65°C, stirring is turned on, 1.2-1.8 mol of organic acid monomer and catalyst are added, and after reacting for 2-3 hours, a dehydrating agent is added, and the reaction is continued for 2-3 hours. The dehydrating agent is continued to be added, and the reaction is cooled to room temperature to obtain a viscous paste of polyethylene glycol and organic acid ester.
  • the amount of catalyst used in this step is 0.1-0.3% of the mass of the reactants, and it can be preferably at least one of phosphotungstic heteropoly acid, SO 4 2- /SiO 2 -TiO 2 , cerium sulfate and zirconium sulfate, which has a high catalytic efficiency compared to ordinary concentrated sulfuric acid.
  • the total amount of the dehydrating agent is 0.5-1.0 mol, and it can be preferably at least one of calcium oxide and anhydrous calcium sulfate. The catalyst and the dehydrating agent do not need to be removed separately.
  • the preparation method of the ester of polyethylene glycol and an organic acid includes the following process steps: first, 0.8 mol of polyethylene glycol with a weight average molecular weight of 200 is added into a reactor, the oil bath heater is turned on, the temperature is set to 62° C., stirring is turned on, 1.8 mol of formic acid and 0.36 g of zirconium sulfate are added, and after reacting for 3 hours, 28 g of calcium oxide is added, the reaction is continued for 3 hours, 28 g of calcium oxide is added, and the mixture is cooled to room temperature to obtain a viscous paste, that is, the ester of polyethylene glycol and an organic acid is obtained.
  • alkali aggregate composite inhibitor Add 210g of medium-pore Y-type zeolite powder to a kneader, heat to 62°C, add 16g of ester of polyethylene glycol and organic acid, knead for 1.2 hours, then add 1.0g of isopropyl tri(dioctylphosphoyloxy) titanate, knead for 1.5 hours, cool to room temperature, and obtain powdery Alkali aggregate composite inhibitor.
  • the preparation method of the ester of polyethylene glycol and an organic acid comprises the following process steps: firstly, 0.6 mol of polyethylene glycol with a weight average molecular weight of 400 is added into a reactor, the oil bath heater is turned on, the temperature is set to 65° C., stirring is turned on, 1.4 mol of acetic acid and 0.32 g of phosphotungstic heteropoly acid are added, and after reacting for 2 hours, 35 g of calcium sulfate is added, and reacting for 3 hours, 35 g of calcium sulfate is continuously added, and the mixture is cooled to room temperature to obtain a viscous paste, that is, the ester of polyethylene glycol and an organic acid is obtained.
  • alkali-aggregate composite inhibitor Add 260g of medium-pore ferrous alkali zeolite powder into a kneader, heat to 62°C, add 30g of ester of polyethylene glycol and organic acid, knead for 1.5 hours, then add 2.0g of chelate of bis(dioctyloxypyrophosphate)ethylene titanate and triolamine, knead for 2 hours, cool to room temperature, and obtain a powdery alkali-aggregate composite inhibitor.
  • the preparation method of the esterification product of polyethylene glycol and organic acid includes the following process steps: first, 0.5 mol of polyethylene glycol with a weight average molecular weight of 600 is added into a reactor, the oil bath heater is turned on, the temperature is set to 65°C, stirring is turned on, 0.6 mol of formic acid and 0.2 g of SO42- / SiO2 - TiO2 catalyst are added, after reacting for 2.5 hours, 30 g of calcium oxide are added, 0.6 mol of acetic acid and 0.18 g of SO42- / SiO2 - TiO2 catalyst are added, the reaction is continued for 2.5 hours, 30 g of calcium oxide are added, and the reaction is cooled to room temperature to obtain a viscous paste, that is, the esterification product of polyethylene glycol and organic acid is obtained.
  • the preparation method of the alkali-aggregate composite inhibitor is as follows: 230 g of ZSM-5 medium-pore zeolite powder is added to a kneader, heated to 60° C., 25 g of an ester of polyethylene glycol and an organic acid is added, kneaded for 1.5 hours, and then 2 g of a chelate of bis(dioctyloxypyrophosphate)ethylene titanate and triolamine is added, kneaded for 1.5 hours, and cooled to room temperature to obtain a powdery alkali-aggregate composite inhibitor.
  • the method for preparing the ester of polyethylene glycol and organic acid comprises the following process steps: firstly, 0.4 mol of polyethylene glycol with weight average molecular weight of 200 and 400 respectively is added into the reactor, the oil bath heater is turned on, the temperature is set to 63°C, stirring is turned on, 1.8 mol of propionic acid and 0.3 g of SO42- / SiO2 - TiO2 catalyst are added, after reacting for 3 hours, 36 g of calcium sulfate is added, and 0.2 g of SO42-/SiO2-TiO2 catalyst is added , and the reaction is continued for 3 hours. When the mixture was stirred for 2 hours, 36 g of calcium sulfate was added and the mixture was cooled to room temperature to obtain a viscous paste, that is, an ester of polyethylene glycol and an organic acid.
  • Preparation of alkali-aggregate composite inhibitor Add 260 g of ZSM-5 zeolite medium-pore zeolite powder into a kneader, heat to 65°C, add 20 g of an ester of polyethylene glycol and an organic acid, knead for 1.5 hours, then add 1 g each of a chelate of bis(dioctylpyrophosphate)ethylene titanate and triolamine and isopropyl tri(dioctylphosphoacyl) titanate, knead for 1.8 hours, cool to room temperature, and obtain a powdery mixture.
  • Examples 1-4 were used for alkali-aggregate reaction test. Before the test, petrographic analysis of the machine-made sand in the stockpile showed that it was granite, and the active mineral contained was strained quartz with a content of about 38%. According to GB/T14684-2011, the samples of Examples 1-4 were used for alkali-aggregate reaction test, the cement used was Esheng PO.42.5 ordinary Portland cement, and the fly ash used was primary ash. First, the sand was graded and sieved with a square hole sieve to remove sand with a particle size greater than 4.75 mm and less than 0.15 mm. The mass of each particle size of sand used in the alkali-aggregate reaction experiment is shown in Table 1:
  • the mortar mixing should be carried out according to the provisions of GB/T 17671. After the mixing is completed, the mortar is immediately loaded into the test mold equipped with the expansion probe in two times, and each layer is tamped 40 times. Note that the expansion probe should be carefully tamped around. After pouring, use a steamed knife to scrape off the excess mortar, smooth it, number it and indicate the measurement direction. Each group of tests is formed into 3 groups.
  • test results are shown in Table 2:
  • the test block showed brittleness after 180 days, and its expansion rate reached 0.5%, and the expansion rate after 14 days was 0.12%, which was much higher than the requirement of less than 0.1% in GB14684-2011 for an expansion rate of less than 0.1% after 180 days, indicating that its alkali-aggregate reaction was very serious.
  • 1st-grade fly ash was used to replace 30% of cement. In the first 30 days, the expansion rate of the test block was less than 0.1%, but the expansion rate of the test block after 60 days reached 0.1%, and the expansion rate of the test block after 180 days reached 0.18%, indicating that fly ash reduced the alkali-aggregate reaction to a certain extent, but still could not meet the standard requirements.
  • the alkali-aggregate composite inhibitor provided by the present disclosure has the advantages of low dosage and good inhibition effect, which plays an energy-saving and efficiency-enhancing role in construction projects.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Polyethers (AREA)

Abstract

La présente divulgation concerne un inhibiteur composite d'agrégats alcalins, ainsi qu'un procédé de préparation associé. Les matières premières de préparation de l'inhibiteur composite d'agrégats alcalins comprennent les composants suivants, en parties en poids : de 0,5 à 2,0 parties d'un agent de couplage au titanate, de 15 à 30 parties d'un produit estérifié de polyéthylène glycol et d'un acide organique et de 200 à 260 parties d'une zéolite mésoporeuse. L'inhibiteur composite d'agrégats alcalins est avantageux pour inhiber une réaction d'agrégats alcalins du béton à un stade ultérieur, réduisant ainsi le risque de fissuration du béton à un stade ultérieur, améliorant la durabilité de l'ingénierie et des bâtiments en béton, et réduisant les coûts d'entretien ultérieurs des projets d'ingénierie.
PCT/CN2023/083638 2022-12-16 2023-03-24 Inhibiteur composite d'agrégats alcalins et procédé de préparation associé WO2024124734A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211621255.0A CN115611551B (zh) 2022-12-16 2022-12-16 碱骨料复合抑制剂及其制备方法
CN202211621255.0 2022-12-16

Publications (1)

Publication Number Publication Date
WO2024124734A1 true WO2024124734A1 (fr) 2024-06-20

Family

ID=84879629

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/083638 WO2024124734A1 (fr) 2022-12-16 2023-03-24 Inhibiteur composite d'agrégats alcalins et procédé de préparation associé

Country Status (2)

Country Link
CN (1) CN115611551B (fr)
WO (1) WO2024124734A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115611551B (zh) * 2022-12-16 2023-03-14 石家庄市长安育才建材有限公司 碱骨料复合抑制剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169144A (ja) * 2005-11-04 2007-07-05 Tokuyama Corp アルカリ性低減剤
JP2008247686A (ja) * 2007-03-30 2008-10-16 Taiheiyo Cement Corp アルカリ骨材反応抑制剤
JP2010024112A (ja) * 2008-07-23 2010-02-04 Denki Kagaku Kogyo Kk セメント混和材及びセメント組成物
JP2022134233A (ja) * 2021-03-03 2022-09-15 Ｕｂｅ三菱セメント株式会社 セメント組成物及びその製造方法、アルカリシリカ反応抑制剤、アルカリシリカ反応抑制方法
CN115611551A (zh) * 2022-12-16 2023-01-17 石家庄市长安育才建材有限公司 碱骨料复合抑制剂及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100509684C (zh) * 2007-04-13 2009-07-08 俞锡贤 一种阻裂抗渗剂及其生产方法
CN102515606B (zh) * 2012-01-09 2016-05-04 水利部交通运输部国家能源局南京水利科学研究院 可抑制碱-硅酸反应的混凝土掺合料
CN103864336B (zh) * 2014-02-09 2015-08-12 郑州市公路工程公司 一种水泥复合添加剂的制备方法
CN108341619B (zh) * 2018-05-03 2020-07-07 黄河勘测规划设计研究院有限公司 一种混凝土内外部水分迁移抑制剂
CN109608085B (zh) * 2018-12-28 2020-03-06 内蒙古自治区水利水电勘测设计院 一种碱骨料反应抑制剂

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007169144A (ja) * 2005-11-04 2007-07-05 Tokuyama Corp アルカリ性低減剤
JP2008247686A (ja) * 2007-03-30 2008-10-16 Taiheiyo Cement Corp アルカリ骨材反応抑制剤
JP2010024112A (ja) * 2008-07-23 2010-02-04 Denki Kagaku Kogyo Kk セメント混和材及びセメント組成物
JP2022134233A (ja) * 2021-03-03 2022-09-15 Ｕｂｅ三菱セメント株式会社 セメント組成物及びその製造方法、アルカリシリカ反応抑制剤、アルカリシリカ反応抑制方法
CN115611551A (zh) * 2022-12-16 2023-01-17 石家庄市长安育才建材有限公司 碱骨料复合抑制剂及其制备方法

Also Published As

Publication number Publication date
CN115611551B (zh) 2023-03-14
CN115611551A (zh) 2023-01-17

Similar Documents

Publication Publication Date Title
Ahmad et al. Influence of different admixtures on the mechanical and durability properties of one-part alkali-activated mortars
RU2517729C2 (ru) Геополимерные композиционные связущие с заданными характеристиками для цемента и бетона
WO2019080527A1 (fr) Mortier de plâtre à base de gypse pour pulvérisation mécanique, son procédé de préparation et suspension à base de gypse pour pulvérisation mécanique
CN101265069A (zh) 一种高强度耐水粉刷石膏及其生产方法
CN111792902B (zh) 一种高强耐水型磷石膏复合胶凝材料及其制备方法
CN105777035A (zh) 一种利用水化硅酸钙晶种粉制备的混凝土裂缝灌浆修补材料及其使用方法
JP7047634B2 (ja) モルタル・コンクリート用混和材、これを含むセメント組成物、モルタル組成物及びコンクリート組成物、並びに、モルタル硬化物及びコンクリート硬化物の製造方法
CN112939561B (zh) 一种磷石膏基轻质抹灰石膏及其制备方法
JP7014063B2 (ja) モルタル・コンクリート用混和材、これを含むセメント組成物、モルタル組成物及びコンクリート組成物、並びに、モルタル硬化物及びコンクリート硬化物の製造方法
WO2024124734A1 (fr) Inhibiteur composite d'agrégats alcalins et procédé de préparation associé
CN103979866A (zh) 一种含玛雅蓝加气砖及其制备方法
CN111285654A (zh) 一种脱硫建筑石膏基复合胶凝材料的制备方法
CN111943626A (zh) 石膏基墙体找平材料及其制备方法和使用方法
CN111807770A (zh) 生态水泥高强灌浆料及制备方法
CN115353361A (zh) 一种复合胶凝材料及其制备方法和应用
RU2361833C2 (ru) Комплексный модификатор бетона полифункционального действия (варианты)
KR101579790B1 (ko) 탈황반수석고를 포함하는 건축용 모르타르 조성물
JP2020128315A (ja) モルタル・コンクリート用混和材、これを含むセメント組成物、モルタル組成物及びコンクリート組成物、並びに、モルタル硬化物及びコンクリート硬化物の製造方法
RU2448921C2 (ru) Комплексная модифицирующая добавка для бетонных растворов
JPH11246260A (ja) セメント組成物およびそれを用いた硬化体の製造方法
JPH07267704A (ja) セルフレベリング性水性組成物
CN103011743B (zh) 钠沸石无机人造石制备工艺
CN110436870A (zh) 一种适于装配式建筑的调湿功能磷石膏墙体材料及其制备方法
WO2020238158A1 (fr) Stabilisateur de mortier pour mélange humide et son procédé de préparation
JP4197363B2 (ja) 調湿性石膏、その製造方法および石膏硬化体