CN105712656A - Polyurethane reaction type cement concrete admixture and preparation method and application thereof - Google Patents
Polyurethane reaction type cement concrete admixture and preparation method and application thereof Download PDFInfo
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- CN105712656A CN105712656A CN201510987878.3A CN201510987878A CN105712656A CN 105712656 A CN105712656 A CN 105712656A CN 201510987878 A CN201510987878 A CN 201510987878A CN 105712656 A CN105712656 A CN 105712656A
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- diisocyanate
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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
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0054—Water dispersible polymers
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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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0062—Cross-linked polymers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane reaction type cement concrete admixture which is an emulsion. Solid content of the emulsion is 20-35%, the emulsion contains cross-linked polyurethane macromolecules using amino silane for end termination and chain extension, and the polyurethane macromolecules contain polyether type polyol chain segments. By improving own performance of the polyurethane reaction type cement concrete admixture, mechanical performance is improved, and toughness of the concrete is improved from the perspective of bend-press ratio.
Description
Technical field
The invention belongs to concrete building material industry chemical admixture field, particularly to a kind of polyurethane cement concrete admixture and its preparation method and application.
Technical background
Cement concrete is the construction material that the world today makes consumption maximum, has the advantage such as comprcssive strength height, extensive, the convenient construction of raw material sources.Cement concrete has high comprcssive strength according to after certain form molding hardening, but its bending resistance is relative with tensile strength very low, shows as high fragility, the feature of poor toughness.In engineering, conventional reinforcing bar makes up xoncrete structure bending resistance or the low defect of tensile strength.Along with the progress of science and technology, the especially development of cross discipline, multiple composite is widely used in improving Brittleness of Concrete；Wherein most study, most widely used is various fiber and macromolecule polymer solution and emulsion；Cardinal principle is the advantage utilizing high molecular polymer high tenacity, in conjunction with the feature of concrete high-strength degree, and the two synergism, and then improve Brittleness of Concrete, promote toughness of concrete.
Chinese patent (CN102603232B) discloses a kind of for concrete polyformaldehyde fibre, it is possible to concrete component generation bonding action, thus improving concrete performance.
Chinese patent (CN103641326B) discloses a kind of concrete modifying agent, is mainly made up of bentonite, acrylic emulsion, polypropylene fibre and nano-carbon powder.Fiber, mainly through physical bridge continuous cropping use, from matrix withdrawal process, is playing toughening effect by disperseing the stress of Near A Crack Tip to concentrate.Intensity and the elastic modelling quantity of fiber are most important to toughening effect, and the fiber of the low mould strong, low of tradition (< 10GPa) is only inhibited to plastic shrinkage cracking, it does not have toughening effect；It addition, a dispersion difficult problem for fiber and interface micro-crack, all govern the toughening effect of fiber.
Polymer modified cement-concrete utilizes the feature of cement rigidity and polymer flexibility, is connected and filling effect by the bridge of polymeric film, forms inierpeneirating network structure with cement gel, optimizes interfacial transition zone, thus realizing the lifting of cement-based material toughness.As a kind of composite, the mechanical property of polymer and be the key factor determining its performance in the dispersion within cement-based material, also therefore, for the polymer in cement concrete field mainly based on Water-borne modification product, i.e. polymer solution or polymer emulsion.
Chinese patent (CN101607807A) discloses a kind of bi-component cement composite grouting material containing oiliness polyurethane.Chinese patent (CN102358686A) discloses a kind of bi-component cement mortar containing water-base epoxy.Chinese patent (CN100528790C) discloses the composite modified cement concrete of multiple emulsion and construction method thereof.
But, the polymer being currently used for cement-based material modified is confined to the polymer such as styrene-butadiene emulsion, acrylic emulsion, this acrylic emulsion, and described polymer exists poor mechanical property, the shortcoming that structure adjustable extent is little, and tensile strength is only only 1-10MPa.For increasing cement-based material toughness, it is necessary to even 30%(polymer and cement weight compare to 10% to improve polymer volume), and high polymer cement ratio very easily causes the reduction of comprcssive strength.
Summary of the invention
For shortcomings such as the poor mechanical property that described cement concrete polymer emulsion exists, the present invention provides a kind of polyurethane reaction type cement concrete admixture, its preparation method and application thereof.
Polyurethane reaction type cement concrete admixture of the present invention, for a kind of emulsion；Solid content is 20-35%, and containing by amino-silane terminated and chain extension cross-linked type polyurethane macromole in its emulsion, described polyurethane macromolecular contains polyether alcohol segment.
The preparation method of polyurethane reaction type cement concrete admixture of the present invention, use diisocyanate, Polyethylene Glycol, trimethylolpropane, dimethylolpropionic acid, after generating performed polymer by step-reaction polymerization, add amino silane chain extender and amino-silane terminated dose, add nertralizer, neutralize and prepare described polyurethane reaction type cement concrete admixture；
Described diisocyanate, Polyethylene Glycol, trimethylolpropane, dimethylolpropionic acid, chain extender, end-capping reagent and nertralizer mol ratio be: 100:(30-60): (1-5): (0.5-2): (20-40): (1-5): (0.5-2).
The mixture of the described diisocyanate more than one arbitrary proportions in toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
The number-average molecular weight of described Polyethylene Glycol is 200-1000.
Described chain extender more than one arbitrary proportion mixture in N-(β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane and N-(β-aminoethyl-γ-aminopropyl) trimethoxy silane.
The mixture of the described end-capping reagent more than one arbitrary proportions in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyltriethoxy diethoxy silane.
Described nertralizer more than one arbitrary proportion mixture in triethanolamine and triisopropanolamine compound.
Cement concrete is internal is strong basicity environment (pH > 10), the present invention relates to the polyurethane macromolecular of preparation and has good alkaline resistance properties, and not using polyester polyol for this is its soft section, but with the good polyether alcohol of alkaline resistance properties.
Described polyether alcohol segment is provided by Polyethylene Glycol, and the Polyethylene Glycol that the present invention uses is as soft section, while promoting alkaline resistance properties, also serves as hydrophilic section, plays the effect of stable emulsifying nanoparticle.
The present invention uses dimethylolpropionic acid as the hydrophilic chain extension monomer of anionic, it is therefore intended that increase the water solublity of polyurethane macromolecular.
Owing to being subject to hydrated cementitious impact, after adding water, cement concrete system is except showing highly basic character, possibly together with substantial amounts of metal ion, such as Al3+、Ca2+、Mg2+Deng, these ionic groups very easily cause general polymer emulsion breaking gel, especially contain anion or cationic emulsification system, and therefore in the present invention, the least possible use has the monomer of ionic emulsifying agent effect.
Dimethylolpropionic acid is as ionic emulsifying agent monomer, it is necessary to react with antalkali, forms ionic bond, improving stability.For the particularity of cement concrete, the present invention proposes to utilize the triethanolamine with early strength function and triisopropanolamine for nertralizer.
For increasing the mechanical property of polyaminoester emulsion, invention introduces trimethylolpropane as cross-linking monomer.
Hydrolysis product of cement is various silicate, containing silicate in structure, new Si-O-Si chemical covalent bonds can be formed with siloxane compound generation chemical reaction, it is chain extender and end-capping reagent that the present invention proposes to use amino silicone compounds, the polyaminoester emulsion making the present invention can with hydrolysis product of cement generation chemical reaction, by new Si-O-Si chemical covalent bonds, while the alkali resistance meeting polyurethane and mechanical property, increase the adhesion of polymer and hydrolysis product of cement, farthest improve the toughness of polymer.
The preparation method of described polyurethane reaction type cement concrete admixture, concrete preparation process is as follows:
1) dewater 1-2h by Polyethylene Glycol vacuum (0-0.01MPa) under 110-120 DEG C of condition, adds diisocyanate and catalyst after being cooled to 30-90 DEG C, and 100-500rpm stirs and keeps temperature 2-6h；Add trimethylolpropane and dimethylolpropionic acid, continue reaction 2-8h.Reaction adds anhydrous propanone, to keep reaction system viscosity less than 15000mPa.s.Described catalyst is selected from dibutyl tin laurate or stannous octoate, and addition is the 0.05%-1% of diisocyanate weight.
2) step 1) gained reactant liquor is down to 0-5 DEG C, it is separately added into chain extender aqueous solution and end-capping reagent aqueous solution that temperature is 0-5 DEG C successively, after keeping 0-5 DEG C of stirring to be not less than 10min, it is to slowly warm up to 30-35 DEG C, heating rate is not more than 1 DEG C/min, continuing stirring and be not less than 30min, continue stirring and be not less than 10min after adding nertralizer, vacuum (0-0.01MPa) removes organic solvent-acetone；Adding water, making emulsion solid content is 20-35%；Gained emulsion is polyurethanes response type cement concrete admixture.
The application process of described polyurethanes emulsion-type cement concrete admixture, in cement paste, mortar, concrete preparation, together adds with other component, and volume accounts for the 0.1-5%(of Binder Materials weight and calculates with amount of polymers).
Polyurethanes emulsion-type cement concrete admixture of the present invention, can significantly improve concrete every mechanical property, and described additive is type of latex type product, it is possible to mix mutually with water, is conducive to being uniformly dispersed in concrete；Solve conventional polyurethanes emulsion stability problem under cement concrete highly basic high salt；It is different from traditional low intensive acrylic emulsion, styrene-butadiene emulsion, from composite angle design, the lifting by self performance of the high-strength polyurethane of the present invention, improves concrete mechanical property further；Toughness of concrete is improved from bend-press ratio angle.
Specific embodiment
According to following embodiment, it is possible to be more fully understood that the present invention.But, as it will be easily appreciated by one skilled in the art that the concrete material proportion described by embodiment, process conditions and result thereof are merely to illustrate the present invention, and should without the present invention described in detail in restriction claims.
Number described in the following example is molal weight part.
Embodiment 1
30 parts of Polyethylene Glycol (number-average molecular weight is 200) are heated to 120 DEG C, and dewater under 0.005MPa vacuum 2h, adds 100 parts of isophorone diisocyanate and proper catalyst dibutyl tin laurate, stir and keep temperature 2h under 100rpm after being cooled to 90 DEG C；Add 1 part of trimethylolpropane and 0.5 part of dimethylolpropionic acid, continue reaction 2h.Reaction supplements suitable anhydrous propanone, keeps reaction system viscosity less than 15000mPa.s.
Described reactant liquor is down to 5 DEG C, it is separately added into N-(β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane aqueous solution 20 parts and 3-aminopropyl trimethoxysilane aqueous solution 1 part that temperature is 5 DEG C successively, after keeping 0 DEG C-5 DEG C stirring 10min, it is to slowly warm up to 35 DEG C, heating rate is 0.9 DEG C/min, continue stirring 30min, add triethanolamine 0.5 part, continue stirring 20min, removing organic solvent-acetone under 0.01MPa, the water of polishing surplus obtains the polyurethanes response type cement concrete admixture 1 that solid content is 20%.
Embodiment 2
60 parts of Polyethylene Glycol (number-average molecular weight is 1000) are heated to 110 DEG C, and dewater under 0.0095MPa vacuum 2h, adds 100 parts of toluene di-isocyanate(TDI)s and proper catalyst stannous octoate, stir and keep temperature 2h under 300rpm after being cooled to 40 DEG C；Add 5 parts of trimethylolpropanes and 2 parts of dimethylolpropionic acids, continue reaction 2h.Reaction supplements suitable anhydrous propanone, keeps reaction system viscosity less than 15000mPa.s.
Described reactant liquor is down to 0-5 DEG C, it is separately added into N-(β-aminoethyl-γ-aminopropyl) trimethoxy silane aqueous solution 20 parts and 3-aminopropyl triethoxysilane aqueous solution 5 parts that temperature is 0-5 DEG C successively, after keeping 0 DEG C-5 DEG C stirring 20min, it is to slowly warm up to 30 DEG C, heating rate is 0.5 DEG C/min, continue stirring 30min, add triethanolamine 2 parts, continue stirring 20min, removing organic solvent-acetone under 0.01MPa, the water of polishing surplus obtains the polyurethanes response type cement concrete admixture 2 that solid content is 35%.
Embodiment 3
40 parts of Polyethylene Glycol (number-average molecular weight is 600) are heated to 110 DEG C, and dewater under 0.0095MPa vacuum 2h, adds 100 parts of methyl diphenylene diisocyanates and proper catalyst stannous octoate, stir and keep temperature 2h under 300rpm after being cooled to 50 DEG C；Add 2.5 parts of trimethylolpropanes and 1.5 parts of dimethylolpropionic acids, continue reaction 2h.Reaction supplements suitable anhydrous propanone, keeps reaction system viscosity less than 15000mPa.s.
Described reactant liquor is down to 0-5 DEG C, it is separately added into N-(β-aminoethyl-γ-aminopropyl) the trimethoxy silane aqueous solution 10 parts that temperature is 0-5 DEG C successively, N-(β-aminoethyl-γ-aminopropyl) trimethoxy silane aqueous solution 30 parts and 3-aminopropyltriethoxy diethoxy silane aqueous solution 2.5 parts, after keeping 0 DEG C-5 DEG C stirring 30min, it is to slowly warm up to 30 DEG C, heating rate is 0.5 DEG C/min, continue stirring 30min, add triisopropanolamine 1.0 parts, continue stirring 20min, organic solvent-acetone is removed under 0.01MPa, the water of polishing surplus obtains the polyurethanes response type cement concrete admixture 3 that solid content is 30%.
Embodiment 4
20 parts of Polyethylene Glycol (number-average molecular weight be 200 and 400 each 20 parts) are heated to 120 DEG C, and dewater under 0.005MPa vacuum 2h, adds 100 part 1 after being cooled to 65 DEG C, hexamethylene-diisocyanate and proper catalyst, stirring keep temperature 2h under 300rpm；Add 1.5 parts of trimethylolpropanes and 0.5 part of dimethylolpropionic acid, continue reaction 2h.Reaction supplements suitable anhydrous propanone, keeps reaction system viscosity less than 15000mPa.s.
Described reactant liquor is down to 0-5 DEG C, it is separately added into N-(β-aminoethyl-γ-aminopropyl) the trimethoxy silane aqueous solution 20 parts that temperature is 0-5 DEG C successively, N-(β-aminoethyl-γ-aminopropyl) trimethoxy silane aqueous solution 20 parts, 3-aminopropyl triethoxysilane aqueous solution 2.5 parts and 3-aminopropyltriethoxy diethoxy silane aqueous solution 2.5 parts, after keeping 0 DEG C-5 DEG C stirring 30min, it is to slowly warm up to 30 DEG C, heating rate is 0.5 DEG C/min, continue stirring 30min, add triethanolamine and each 0.25 part of triisopropanolamine, continue stirring 20min, organic solvent-acetone is removed under 0.01MPa, the water of polishing surplus obtains the polyurethanes response type cement concrete admixture 4 that solid content is 30%.
Described polyurethanes cement concrete admixture is converted polymer weight according to the 1wt%(of Binder Materials) volume carries out concrete formation and maintenance, according to its mechanical property of GB50081 standard testing after 28 days.
Joining the data in seeing the above table, compared with normal concrete, concrete crushing strength and two most important mechanical properties of rupture strength of having filled the present invention have had obvious increase, and the toughness of bend-press ratio reaction there has also been obvious raising.
Claims (5)
1. a polyurethane reaction type cement concrete admixture, for a kind of emulsion；It is characterized in that, solid content is 20-35%, and containing by amino-silane terminated and chain extension cross-linked type polyurethane macromole in emulsion, described polyurethane macromolecular contains polyether alcohol segment.
2. the preparation method of described polyurethane reaction type cement concrete admixture described in claim 1, it is characterized in that, use diisocyanate, Polyethylene Glycol, trimethylolpropane, dimethylolpropionic acid, after generating performed polymer by step-reaction polymerization, add amino silane chain extender and amino-silane terminated dose, add nertralizer, neutralize and prepare described polyurethane reaction type cement concrete admixture；
Described diisocyanate, Polyethylene Glycol, trimethylolpropane, dimethylolpropionic acid, chain extender, end-capping reagent and nertralizer mol ratio be: 100:(30-60): (1-5): (0.5-2): (20-40): (1-5): (0.5-2)；
The number-average molecular weight of described Polyethylene Glycol is 200-1000；
Described chain extender more than one arbitrary proportion mixture in N-(β-aminoethyl-γ-aminopropyl) methyl dimethoxysilane and N-(β-aminoethyl-γ-aminopropyl) trimethoxy silane；
The mixture of the described end-capping reagent more than one arbitrary proportions in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyltriethoxy diethoxy silane；
Described nertralizer more than one arbitrary proportion mixture in triethanolamine and triisopropanolamine compound.
3. method according to claim 2, it is characterised in that described diisocyanate selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1, the mixture of hexamethylene-diisocyanate and more than one arbitrary proportions in isophorone diisocyanate.
4. method according to Claims 2 or 3, it is characterised in that concrete preparation process is as follows:
1) dewater 1-2h by Polyethylene Glycol vacuum (0-0.01MPa) under 110-120 DEG C of condition, adds diisocyanate and catalyst after being cooled to 30-90 DEG C, and 100-500rpm stirs and keeps temperature 2-6h；Add trimethylolpropane and dimethylolpropionic acid, continue reaction 2-8h；
Reaction adds anhydrous propanone, to keep reaction system viscosity less than 15000mPa.s；
Described catalyst is selected from dibutyl tin laurate or stannous octoate, and addition is the 0.05%-1% of diisocyanate weight；
2) step 1) gained reactant liquor is down to 0-5 DEG C, it is separately added into chain extender aqueous solution and end-capping reagent aqueous solution that temperature is 0-5 DEG C successively, after keeping 0-5 DEG C of stirring to be not less than 10min, it is to slowly warm up to 30-35 DEG C, heating rate is not more than 1 DEG C/min, continuing stirring and be not less than 30min, continue stirring and be not less than 10min after adding nertralizer, vacuum (0-0.01MPa) removes organic solvent-acetone；Adding water, making emulsion solid content is 20-35%；Gained emulsion is polyurethanes response type cement concrete admixture.
5. the application process of polyurethanes emulsion-type cement concrete admixture described in claim 1, in cement paste, mortar, concrete preparation, together adds with other component；In the quality of polymer, volume accounts for the 0.1-5% of Binder Materials weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510987878.3A CN105712656B (en) | 2015-12-25 | A kind of polyurethane reaction type cement concrete admixture and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510987878.3A CN105712656B (en) | 2015-12-25 | A kind of polyurethane reaction type cement concrete admixture and its preparation method and application |
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| CN105712656A true CN105712656A (en) | 2016-06-29 |
| CN105712656B CN105712656B (en) | 2018-08-31 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018053108A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
| CN108316667A (en) * | 2018-02-05 | 2018-07-24 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of protection and the system of reparation for concrete base layer surface |
| CN109265062A (en) * | 2018-08-08 | 2019-01-25 | 王阳 | A kind of concrete construction compound curing agent and preparation method |
| CN110563393A (en) * | 2019-09-06 | 2019-12-13 | 徐州山溪建筑材料有限公司 | Uneven-load working condition anti-crack concrete |
| CN111848067A (en) * | 2020-07-30 | 2020-10-30 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN116947404A (en) * | 2023-05-10 | 2023-10-27 | 湖南中大设计院有限公司 | Concrete for mountain gas tunnel and preparation method thereof |
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| CN102219886A (en) * | 2011-05-23 | 2011-10-19 | 福州大学 | Preparation method of aqueous polyurethane emulsion with high solid content |
| CN103897649A (en) * | 2014-03-12 | 2014-07-02 | 南京艾布纳密封技术有限公司 | Method for preparing single-component silane modified polyurethane sealant |
| CN105037680A (en) * | 2015-06-23 | 2015-11-11 | 上海东和胶粘剂有限公司 | Permeable modified waterborne polyurethane waterproof agent |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102219886A (en) * | 2011-05-23 | 2011-10-19 | 福州大学 | Preparation method of aqueous polyurethane emulsion with high solid content |
| CN103897649A (en) * | 2014-03-12 | 2014-07-02 | 南京艾布纳密封技术有限公司 | Method for preparing single-component silane modified polyurethane sealant |
| CN105037680A (en) * | 2015-06-23 | 2015-11-11 | 上海东和胶粘剂有限公司 | Permeable modified waterborne polyurethane waterproof agent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018053108A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
| CN108316667A (en) * | 2018-02-05 | 2018-07-24 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of protection and the system of reparation for concrete base layer surface |
| CN109265062A (en) * | 2018-08-08 | 2019-01-25 | 王阳 | A kind of concrete construction compound curing agent and preparation method |
| CN110563393A (en) * | 2019-09-06 | 2019-12-13 | 徐州山溪建筑材料有限公司 | Uneven-load working condition anti-crack concrete |
| CN111848067A (en) * | 2020-07-30 | 2020-10-30 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN111848067B (en) * | 2020-07-30 | 2022-02-01 | 石家庄铁道大学 | Grouting material for large bridge support and preparation method thereof |
| CN116947404A (en) * | 2023-05-10 | 2023-10-27 | 湖南中大设计院有限公司 | Concrete for mountain gas tunnel and preparation method thereof |
| CN116947404B (en) * | 2023-05-10 | 2024-04-16 | 湖南中大设计院有限公司 | Concrete for mountain gas tunnel and preparation method thereof |
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