CN116715463A - Composite modified pillared material and preparation method thereof, fluorine-free alkali-free accelerator based on composite modified pillared material and preparation method thereof - Google Patents
Composite modified pillared material and preparation method thereof, fluorine-free alkali-free accelerator based on composite modified pillared material and preparation method thereof Download PDFInfo
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- CN116715463A CN116715463A CN202310574766.XA CN202310574766A CN116715463A CN 116715463 A CN116715463 A CN 116715463A CN 202310574766 A CN202310574766 A CN 202310574766A CN 116715463 A CN116715463 A CN 116715463A
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 36
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 48
- 239000003381 stabilizer Substances 0.000 claims abstract description 43
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 20
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 239000004113 Sepiolite Substances 0.000 claims description 26
- 229910052624 sepiolite Inorganic materials 0.000 claims description 26
- 235000019355 sepiolite Nutrition 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 20
- 230000002687 intercalation Effects 0.000 claims description 19
- 238000009830 intercalation Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 238000002715 modification method Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 239000004567 concrete Substances 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 96
- 239000000306 component Substances 0.000 description 25
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000012966 insertion method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000011378 shotcrete Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- -1 fluoride ions Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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
-
- 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
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of concrete additives, and particularly discloses a composite modified pillared material modified by hyperbranched quaternary ammonium salt and a preparation method thereof. The composite modified pillared material takes hyperbranched quaternary ammonium salt with specific structures such as quaternary ammonium salt corresponding to hyperbranched polyamine shown in a formula I or hyperbranched quaternary ammonium salt shown in a formula II as a modified material, and the composite modified pillared material is different from a common modified material with a long-chain structure due to the fact that the composite modified pillared material contains a branched structure, so that the interlayer spacing of the laminated hyperbranched material is larger, and the CEC capacity is higher. The invention also discloses a fluorine-free alkali-free accelerator taking the composite modified pillared material as a stabilizer and a preparation method thereof. Compared with the traditional alkali-free accelerator, the fluorine-free alkali-free accelerator improves the aluminum sulfate consumption by more than 10%, so that the supersaturation degree of an accelerator solution system is obviously improved, and the excellent effect of the fluorine-free alkali-free accelerator in concrete materials is ensured.
Description
Technical Field
The invention belongs to the technical field of concrete additives, and particularly relates to a composite modified pillared material modified by hyperbranched quaternary ammonium salt and a preparation method thereof, and a fluorine-free alkali-free accelerator taking the composite modified pillared material as a stabilizer and a preparation method thereof.
Background
The accelerator is a concrete admixture technology for quickly setting and hardening cement and concrete. The development idea of the accelerator is to promote the increase of the concentration of aluminum salt through various forms by taking the aluminum salt as a core component. The fluorine-free alkali-free accelerator can avoid the harm of alkali aggregate reaction to concrete and the harm of fluorine-containing materials in preparation to production/life safety, so the development of the fluorine-free alkali-free accelerator is the key point of the current research, the improvement of aluminum phase content is the main stream scheme for improving the performance of the fluorine-free alkali-free accelerator, and meanwhile, the excessive aluminum salt content can bring the conditions of high supersaturation degree of a solution system, poor stability, layering of products and the like, so the proper stabilizer has stronger practical significance.
Unlike conventional stabilizer materials, the strut materials have been widely studied because they have porous/intercalated inorganic structures that can be widely modified to bring about different structural characteristics. At present, the common modification objects are generally rhombic crystal materials such as kaolin, montmorillonite, sepiolite, talcum and the like of lamellar silicate; modification techniques include ion exchange modification of metal ions, intercalation modification of organic anions and cations, and the like, wherein anion surface active modification such as sodium dodecyl sulfate or cationic cetyltrimethylammonium bromide and the like are widely reported.
Such as a suspension type alkali-free liquid accelerator supersaturated with aluminum sulfate and a preparation method thereof. Wherein the aluminum sulfate dosage is between 60 percent and 70 percent, and the stability of the supersaturated system is improved through superfine sepiolite powder and polyacrylamide. However, the system uses 1 to 4 percent of fluoride salt, the existence of fluoride ions is unfavorable for the early strength of the product, and the early strength is usually difficult to reach 10MPa; the use amount of the polyacrylamide is not suitable to exert the function of crosslinking and flocculation, which is disadvantageous to the stability of the system; the preferable superfine sepiolite powder has an average particle diameter of less than 10 mu m, and has a remarkable improvement effect on the stability of the system, but the system has an overall viscosity of up to 2000 mPas to 4000 mPas because of no modification treatment, which is unfavorable for practical application.
Also, as a modified sepiolite stabilizer for liquid accelerator and a preparation method thereof. The sepiolite modification method is specifically carried out by cetyl trimethyl ammonium bromide and sodium silicate. However, the sepiolite stabilizer prepared by the method has the problems that the surface active substances are gradually released in the process of preparing the accelerator by using the sepiolite modified by the surfactant cetyl trimethyl ammonium bromide, a large number of bubbles can be generated in the system, and the saturated salt system of the accelerator is easily disturbed to further generate the phenomenon of poor system stability.
And a special anti-settling agent for alkali-free accelerator, a preparation method and an application technology thereof, which introduce a method for modifying sepiolite by gamma-methacryloxypropyl trimethoxy silane. The sepiolite is modified by silane, and is mixed with a polymer obtained by free radical polymerization to be used as a special anti-settling agent, wherein the mechanism is that entanglement of a high molecular chain and a three-dimensional network structure of the sepiolite are cooperated. However, the technology has the problems that the sepiolite is easy to agglomerate and difficult to disperse in water because the silane forms a hydrophobic layer after affinity on the surface of the sepiolite, so that the dispersing effect is poor; in addition, in the scheme, the high polymer is obtained by copolymerization in the presence of the sepiolite, so that the existence of the sepiolite can influence the molecular weight of a finished product, the molecular weight of the polymer is low, the entanglement effect is weakened, and the anti-sedimentation effect is poor. In addition to the above-mentioned drawbacks in preparation and use, since the polymer obtained by in-situ polymerization improves stability by a three-dimensional crosslinking system, the overall viscosity of the system may be large, resulting in reduced thixotropy of the system, which is disadvantageous for pumping in application construction.
Disclosure of Invention
Aiming at the technical problems of the modifying agent of the pillared material in the prior art, the invention adopts two hyperbranched quaternary ammonium salts to modify the pillared material to obtain the composite modified pillared material, and the composite modified pillared material has larger pillared material capacity (CEC) and better effect of improving the long-term stability of the composite modified pillared material applied to an accelerator system as a stabilizing agent.
The invention adopts the following technical scheme:
a composite modified pillared material comprises an orthorhombic crystal system pillared material modified by a quaternary ammonium salt corresponding to hyperbranched polyamine shown in the following formula I or a hyperbranched quaternary ammonium salt shown in the formula II.
In the formula I, R is selected from a structure (a) or a structure (b) shown in a formula III, and the value range of n is 3-10; in the formula II, the value range of m is 3-9.
In the above formula I, the substituent R is not selected singly from the group consisting of the structure (a) and the structure (b), but is freely bonded to the structure (a) and the structure (b) in the preparation and synthesis.
The hyperbranched polyamine shown in the formula I and the corresponding quaternary ammonium salt thereof and the hyperbranched quaternary ammonium salt shown in the formula II can be prepared according to reported literature methods, the preparation methods of the hyperbranched polyamine shown in the formula I and the hyperbranched quaternary ammonium salt can be obtained by adopting the methods described in the literature of preparation and performance of amino-terminated hyperbranched polymer and quaternary ammonium salt thereof, and the hyperbranched polyamine in the formula I is further prepared into the corresponding hyperbranched quaternary ammonium salt according to the methods; the hyperbranched quaternary ammonium salt shown in the formula II can be prepared by adopting a method recorded in the literature of synthesis, performance and application of hyperbranched Gimmy (Gemini) quaternary ammonium salt.
The orthorhombic column support material may be sepiolite or hydrotalcite.
The preparation method of the composite modified pillared material comprises the following steps:
and mixing and modifying the hyperbranched quaternary ammonium salt and the orthorhombic crystal system pillared material according to the mass ratio of 5-10:100 to obtain the composite modified pillared material.
Specifically, the modification method may be any one of modification methods of conventional pillared materials such as a direct intercalation method, a solution-blended macromolecular intercalation method, a molten macromolecular intercalation method, and the like.
The composite modified pillared material provided by the invention takes the hyperbranched quaternary ammonium salt with a specific structure as a modified material, and is different from a common modified material with a long-chain structure due to the fact that the hyperbranched quaternary ammonium salt contains a branched structure, so that the interlayer spacing of the orthorhombic pillared material after intercalation is ensured to be larger, and the CEC capacity is higher.
Modification with other conventional modified materials in the prior art (by Na + Exchange assay method) is compared as shown in table 1 below.
TABLE 1 CEC values before and after modification of different orthorhombic column support materials by different modification materials
In the composite modified pillared material, the hyperbranched quaternary ammonium salt structure has the characteristics of stronger acid resistance, alkali resistance and salt resistance, CEC of the modified pillared material is obviously improved, the composite modified pillared material is suitable for a high-concentration fluorine-free alkali-free accelerator, and is used as a stabilizer in the high-concentration fluorine-free alkali-free accelerator, wherein the CEC improvement amplitude of sepiolite and hydrotalcite after the hyperbranched quaternary ammonium salt intercalation modification is obviously larger than that of montmorillonite, and the hyperbranched quaternary ammonium salt is not suitable for each conventional orthorhombic crystal system pillared material. Therefore, the invention also provides a fluorine-free alkali-free accelerator and a preparation method thereof. Compared with the traditional alkali-free accelerator, the fluorine-free alkali-free accelerator improves the aluminum sulfate consumption by more than 10%, so that the supersaturation degree of an accelerator solution system is obviously improved.
The fluorine-free alkali-free accelerator comprises the following components in percentage by mass:
wherein the stabilizer is the composite modified pillared material.
In general, the maximum solubility of the core component aluminum sulfate of the alkali-free accelerator is 36g/L (20 ℃) under normal temperature, the performance requirement of practical application is far less than that of the core component aluminum sulfate, the dosage of the aluminum sulfate in the common alkali-free accelerator on the market can reach 40-50%, the aluminum sulfate is difficult to continuously increase, and the solid content of a final finished product is about 50%. Further improving the solid content can bring about a great reduction of the stability of the system, including the problems of easy delamination, excessive viscosity, easy crystallization and precipitation of the system, and the like. The special hyperbranched quaternary ammonium salt modified pillared material is particularly suitable for fluorine-free and alkali-free accelerator with aluminum sulfate concentration reaching more than 60%, and has the advantages that more complexing sites can be provided by modifying the multi-component quaternary ammonium salt, so that the high CEC of the composite modified pillared material can provide space for intercalation exchange for a large amount of supersaturated aluminum sulfate (exceeding the conventional solubility), the crystallization precipitation probability is reduced, and the characteristics of the pillared material are utilized, namely, the three-dimensional net structure is built, so that the stability of the whole system is improved. Therefore, the effect of preparing the high-concentration fluorine-free alkali-free accelerator product is achieved, and the finished product has good long-term stability and viscosity meeting the construction requirement.
Further, the complexing agent A is selected from diethanolamine or/and triethanolamine, and the complexing agent B is selected from at least one of EDTA, phosphoric acid, oxalic acid and urea.
Further, the ion inhibitor is at least one selected from glycerol, sodium hexametaphosphate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and cetyltrimethylammonium bromide.
The preparation method of the fluorine-free alkali-free accelerator specifically comprises the following steps:
mixing the above components according to a predetermined mass ratio, and dissolving uniformly.
The fluorine-free alkali-free accelerator provided by the invention takes the aluminum sulfate component as a main aluminum phase component, utilizes the synergistic effects of the components such as complexation, stabilization, viscosity reduction and the like, and simultaneously ensures that the fluorine-free alkali-free accelerator has the solid content increased by more than 10% compared with the traditional alkali-free accelerator by using the composite modified pillared material as a stabilizer, and the supersaturation degree of an accelerator solution system is obviously increased, thereby improving the performance. And alkali metal ions and fluoride are not used in the fluorine-free alkali-free accelerator, so that the influence of fluoride ions on early strength and the influence of alkali aggregate reaction on later strength in the applied concrete are avoided, and the fluorine-free alkali-free accelerator has remarkable value especially for early-strength sprayed concrete. The autonomous synthesized orthorhombic crystal column support stabilizer improves the supersaturation degree of a fluorine-free alkali-free accelerator system on the basis of ensuring the stability of products by utilizing charges and thixotropic properties, and ensures the excellent effect of the stabilizer in concrete materials.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application so that others skilled in the art will be able to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
Example 1
The embodiment provides a composite modified pillared material and a preparation method thereof.
Specifically, 5 parts of hyperbranched quaternary ammonium salt corresponding to hyperbranched polyamine (n=3) shown in the formula I and 100 parts of sepiolite powder are subjected to a solution blending macromolecule insertion method to prepare the composite modified pillared material.
Example 2
The embodiment provides a composite modified pillared material and a preparation method thereof.
Specifically, 10 parts of hyperbranched quaternary ammonium salt (m=3) shown in the formula II and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the composite modified pillared material.
Example 3
The embodiment provides a composite modified pillared material and a preparation method thereof.
Specifically, 8 parts of hyperbranched quaternary ammonium salt (m=9) shown in the formula II and 100 parts of hydrotalcite powder are subjected to a melting macromolecular intercalation method to prepare the composite modified pillared material.
Example 4
The embodiment provides a composite modified pillared material and a preparation method thereof.
Specifically, 9 parts of hyperbranched quaternary ammonium salt corresponding to hyperbranched polyamine (n=10) shown in the formula I and 100 parts of sepiolite powder are subjected to a molten macromolecule insertion method to prepare the composite modified pillared material.
Example 5
Based on the composite modified pillared material provided in the embodiment 1, the embodiment takes the composite modified pillared material as a stabilizer, and provides a fluorine-free alkali-free accelerator and a preparation method thereof.
Specifically, the fluorine-free alkali-free accelerator is prepared by heating, dissolving and cooling according to the mass ratio of 62% of aluminum sulfate octadecanoate, 7% of diethanolamine, 0.5% of phosphoric acid, 0.8% of stabilizer and the balance of water.
That is, the fluorine-free alkali-free accelerator provided in this embodiment comprises the following components uniformly mixed:
example 6
Based on the composite modified pillared material provided in the embodiment 2, the embodiment takes the composite modified pillared material as a stabilizer, and provides a fluorine-free alkali-free accelerator and a preparation method thereof.
Specifically, the fluorine-free alkali-free accelerator is prepared by heating, dissolving and cooling aluminum sulfate octadecanoate 66%, diethanolamine 9%, phosphoric acid 0.5%, EDTA 1%, oxalic acid 0.5%, urea 0.5%, glycerin 0.3%, stabilizer 0.6% and the balance of water according to mass proportions.
That is, the fluorine-free alkali-free accelerator provided in this embodiment comprises the following components uniformly mixed:
example 7
Based on the composite modified pillared material provided in example 3, the present example uses the composite modified pillared material as a stabilizer, and provides a fluorine-free alkali-free accelerator and a preparation method thereof.
Specifically, the fluorine-free alkali-free accelerator is prepared by heating, dissolving and cooling aluminum sulfate octadecanoate 60%, diethanolamine 4%, triethanolamine 1.5%, phosphoric acid 0.5%, glycerin 0.2%, sodium hexametaphosphate 0.1%, stabilizer 0.7% and the balance of water according to mass proportions.
That is, the fluorine-free alkali-free accelerator provided in this embodiment comprises the following components uniformly mixed:
example 8
Based on the composite modified pillared material provided in example 3, the present example uses the composite modified pillared material as a stabilizer, and provides a fluorine-free alkali-free accelerator and a preparation method thereof.
Specifically, according to the mass ratio of 62% of aluminum sulfate octadecanoate, 4.5% of diethanolamine, 0.5% of phosphoric acid, 0.5% of EDTA, 0.2% of glycerin, 0.2% of cetyltrimethylammonium bromide, 0.2% of sodium dodecyl sulfate, 0.7% of stabilizer and the balance of water, the fluorine-free alkali-free accelerator is prepared after heating, dissolving and cooling.
That is, the fluorine-free alkali-free accelerator provided in this embodiment comprises the following components uniformly mixed:
example 9
Based on the composite modified pillared material provided in the embodiment 1, the embodiment takes the composite modified pillared material as a stabilizer, and provides a fluorine-free alkali-free accelerator and a preparation method thereof.
Specifically, the fluorine-free alkali-free accelerator is prepared by heating, dissolving and cooling aluminum sulfate octadecanoate 61%, diethanolamine 6%, phosphoric acid 0.3%, glycerin 0.3%, sodium dodecyl benzene sulfonate 0.3%, stabilizer 1% and the balance water according to the mass ratio.
That is, the fluorine-free alkali-free accelerator provided in this embodiment comprises the following components uniformly mixed:
in order to verify the effect of the fluorine-free and alkali-free accelerator provided in each of the above examples, in particular, the stabilizing effect of the stabilizer therein, the following comparative experiments were conducted.
Comparative example 1
The comparative example was set up to illustrate the effect of the stabilizer on the performance of the fluorine-free and alkali-free accelerator by forming a comparison with example 5 lacking the stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
because the modified pillared material is absent to provide stability for the supersaturated accelerator, the compared fluorine-free alkali-free accelerator is quickly coagulated and separated out after being cooled and placed, and the whole accelerator loses fluidity and cannot be used.
Comparative example 2
The comparative example was set up to illustrate the effect of the amount of aluminum sulfate on the performance of the fluorine-free and alkali-free accelerator by comparing with example 5 to form an excess of aluminum sulfate.
This comparative example provides a comparative fluorine-free and alkali-free accelerator which differs from example 5 only in that: adjusting the dosage of aluminum sulfate octadecatydrate to 67 percent, and correspondingly reducing the dosage of water; the remainder are described in reference to example 5.
Although the supersaturation degree is improved to form a high-concentration system under the synergistic effect of the complexing agent, the ion inhibitor and the stabilizer, when the aluminum sulfate usage exceeds a critical point, excessive aluminum sulfate can serve as crystal nucleus to reduce the stability of the system, so that the comparative fluorine-free alkali-free accelerator in the comparative example is quickly coagulated and separated out after being cooled and placed, and the whole body loses fluidity and cannot be used.
Comparative example 3
The comparative example was set up to form a comparison lacking complexing agent a to illustrate the effect of complexing agent a on the performance of a fluorine-free and alkali-free accelerator.
This comparative example provides a comparative fluorine-free and alkali-free accelerator in which the composite modified pillared material provided in example 2 above was used as a stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
because of the lack of the complexing agent A, aluminum sulfate exceeding the solubility in water in the process of synthesizing the accelerator cannot be completely dissolved, a supersaturated stable system finished product cannot be effectively constructed, and the preparation of the finished product fails.
Comparative example 4
The comparative example was set up to form a comparison lacking complexing agent B to illustrate the effect of complexing agent B on the performance of a fluorine-free and alkali-free accelerator.
This comparative example provides a comparative fluorine-free and alkali-free accelerator in which the composite modified pillared material provided in example 2 above was used as a stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the contrast fluorine-free alkali-free accelerator is too high in viscosity of a supersaturated finished product solution system due to the lack of the complexing agent B, is greatly influenced by temperature, is easy to precipitate, solidify and lose fluidity after being cooled, and a finished product cannot be used.
Comparative example 5
This comparative example provides a comparative fluorine-free and alkali-free accelerator in which the composite modified pillared material provided in example 1 above was used as a stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the comparative fluorine-free alkali-free accelerator has the advantages that the accelerator does not contain an ion inhibitor, the stability of the system is reduced, partial components are easy to separate out, and the viscosity of the system is high.
Comparative example 6
The comparative example was set up to form a comparison of excess complexing agent B to illustrate the effect of complexing agent B on the performance of a fluorine-free and alkali-free accelerator.
This comparative example provides a comparative fluorine-free and alkali-free accelerator in which the composite modified pillared material provided in example 1 above was used as a stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the use amount of the complexing agent B of the comparative fluorine-free alkali-free accelerator exceeds the recommended range, and the stability is improved, but the viscosity is too high, so that the complexing agent B cannot be used, and the negative effect appears to influence the strength of the concrete.
Comparative example 7
The comparative example was set up to form a comparison of hyperbranched quaternary ammonium salts having a higher degree of branching as shown in formula II to illustrate the effect of the degree of branching of the hyperbranched quaternary ammonium salts on the performance of fluorine-free and alkali-free accelerators.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 10 parts of hyperbranched quaternary ammonium salt (m=10) shown in the formula II and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the comparative composite modified pillared material.
The prepared contrast composite modified pillared material is used for preparing contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the contrast fluorine-free alkali-free accelerator has poor stability due to the high branching degree of hyperbranched quaternary ammonium salt, insufficient water solubility and poor intercalation effect, so that the contrast fluorine-free alkali-free accelerator is obviously layered after being placed for 1d and has high viscosity and cannot be used.
Comparative example 8
The comparative example was set up to form a comparison of hyperbranched quaternary ammonium salts having a lower degree of branching as shown in formula II to illustrate the effect of the degree of branching of the hyperbranched quaternary ammonium salts on the performance of fluorine-free and alkali-free accelerators.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 10 parts of hyperbranched quaternary ammonium salt (m=2) shown in the formula II and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the comparative composite modified pillared material.
The prepared contrast composite modified pillared material is used for preparing contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the stability of the comparative fluorine-free alkali-free accelerator is slightly poor as the branching degree of the hyperbranched quaternary ammonium salt is lower, so that the comparative fluorine-free alkali-free accelerator is obviously layered after being placed for 1d and has high viscosity and cannot be used.
Comparative example 9
The comparative example was set up to form a comparison of hyperbranched quaternary ammonium salts having a higher degree of branching as shown in formula I to illustrate the effect of the degree of branching of the hyperbranched quaternary ammonium salts on the performance of fluorine-free and alkali-free accelerators.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 8 parts of hyperbranched quaternary ammonium salt (n=11) shown in the formula I and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the comparative composite modified pillared material.
The prepared contrast composite modified pillared material is used for preparing contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the contrast fluorine-free alkali-free accelerator has the advantages that the molecular is too large to realize good intercalation due to the high branching degree of the hyperbranched quaternary ammonium salt, and the stability is slightly poor as a whole, so that the contrast fluorine-free alkali-free accelerator is obviously layered after being placed for 1d, has too high viscosity and cannot be used.
Comparative example 10
The comparative example was set up to form a comparison of hyperbranched quaternary ammonium salts having a lower degree of branching as shown in formula I to illustrate the effect of the degree of branching of the hyperbranched quaternary ammonium salts on the performance of fluorine-free and alkali-free accelerators.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 8 parts of quaternary ammonium salt (n=2) prepared from hyperbranched polyamine shown in the formula I and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the comparative composite modified pillared material.
The prepared contrast composite modified pillared material is used for preparing contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
the contrast fluorine-free alkali-free accelerator has the advantages that the branching degree of the hyperbranched quaternary ammonium salt is lower, the intercalation effect is close to that of the conventional common surface active intercalation, and the intercalation effect is not obvious, so that the stability is slightly poor as a whole, and the contrast fluorine-free alkali-free accelerator is obviously layered after being placed for 1d and has too high viscosity to be used.
Comparative example 11
The arrangement of the comparative example aims at changing the orthorhombic column support material in the composite modified column support material so as to embody the influence of the type of the orthorhombic column support material on the performance of the fluorine-free alkali-free accelerator.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 8 parts of quaternary ammonium salt corresponding to hyperbranched polyamine (n=3) shown in the formula I and 100 parts of kaolin powder are subjected to a solution blending macromolecule insertion method to prepare the comparative composite modified pillared material.
The prepared contrast modified pillared material is used for preparing a contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
as the kaolin is taken as the triclinic material, intercalation modification can not be carried out between layers under the action of strong hydrogen bonds, so that the effect of the kaolin as a pillared material is poor, and when the contrast composite modified pillared material prepared based on the above is applied to contrast fluorine-free alkali-free accelerator, delamination after 1d is remarkable, the viscosity is high, and engineering application can not be realized.
Comparative example 12
The arrangement of the comparative example aims at changing the intercalation material of the orthorhombic column support material in the composite modified column support material so as to embody the influence of the type of the intercalation material on the performance of the fluorine-free alkali-free accelerator.
The comparative example provides a comparative composite modified pillared material and a preparation method thereof.
Specifically, 5 parts of Sodium Dodecyl Benzene Sulfonate (SDBS) and 100 parts of sepiolite powder are subjected to a solution blending macromolecular insertion method to prepare the comparative composite modified pillared material.
The prepared contrast composite modified pillared material is used for preparing contrast fluorine-free alkali-free accelerator and is used as a contrast stabilizer.
The comparative fluorine-free alkali-free accelerator provided in this comparative example comprises the following components uniformly mixed:
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the stability of the comparative fluorine-free alkali-free accelerator is slightly poor, layering is obvious after the accelerator is placed for 1d, and the accelerator is too high in viscosity and cannot be used.
Comparative example 13
The comparative example provides a commercially available mature fluorine-containing alkali-free accelerator as a comparison, and the specific model is Su Bo specialty SBT-N (II).
To verify the effect of the above-described applications of each accelerator, the fluorine-free and alkali-free accelerators provided in examples 5 to 9, and the comparative fluorine-free and alkali-free accelerators provided in comparative examples 2 to 11 and the conventional modified materials provided in comparative example 12 were prepared and tested for application with the fluorine-containing and alkali-free accelerators commercially available in comparative example 13.
The proportions of each sprayed concrete used for the application test are shown in table 2 below; the corresponding amounts (amounts after the amounts of cement in the compositions were reduced), as well as the rebound in the project field injection experiments and the 8h core strength are shown in Table 3 below.
Table 2 application test of accelerator sprayed concrete mix ratio
TABLE 3 corresponding dosage, rebound Rate and 8h core strength at the time of application test of each accelerator
As can be seen from table 3, in comparative example 2, the stability cannot be ensured due to the higher amount of aluminum sulfate therein, and the rebound rate of up to 15% to 25% is obtained at the actual mixing amount of 4% to 6% under the actual working pump pressure; in comparative example 3, the viscosity is too high due to the high stabilizer dosage, so that the rebound rate of up to 20% -25% can be obtained under the condition that the actual mixing amount of the sprayer is only 4% -5% under full load, and the actual mixing amount cannot be ensured; in comparative example 4, on one hand, the viscosity of the stabilizer is larger, so that the rebound rate of up to 20% -25% can be obtained under the condition that the actual mixing amount of the sprayer is only 4% -5% under full load, and on the other hand, the long-term stability is reduced due to the lower mixing amount of the stabilizer; and the 8h drill core strength in each embodiment is obviously higher than that of the comparative example, which shows that the fluorine-free alkali-free accelerator based on the composite modified pillared material has positive effect on the strength increase of early sprayed concrete.
In general, the rebound rate of sprayed concrete should be controlled within 15%, less than 10% being an excellent level, while approaching 5% is a very excellent level. From this, it can be seen that each fluorine-free alkali-free accelerator of the present invention has very excellent application effects.
Meanwhile, the performance and stability of the accelerator provided in each of the above examples and comparative examples were tested. The test method specifically comprises the following steps: the setting time and the mortar strength are tested by adopting reference cement, and the mixing amount of the accelerator is 8%.
The test results are shown in table 4 below.
TABLE 4 Performance and stability of the accelerators
Note that: mortar testing according to QCR-807-2020 index
From the data in table 4, it can be seen that the embodiment can achieve the purpose of early high strength through the synergistic effect of the high aluminum phase and other complexing agents, and has more reasonable viscosity under the condition of high solid content, generally close to or lower than 500cp and very good stability (28 d water extraction rate < 5%), and the viscosity higher than 600cp may have the adverse effects of insufficient mixing amount, uneven dispersion, even pipe blockage and the like for actual injection. In addition, in the mortar experiment, the results of the test on the standard cement in the example product show that the 6h mortar strength is more than 1MPa and the 1d strength is more than 8MPa, so that the early strength and the high strength are met.
Comparative examples 1 to 6 are comparative fluorine-free and alkali-free accelerators prepared using the composite modified pillared materials of examples 1 to 4, the necessity of components in the above-mentioned compounding ratio, the influence of the complexing agent A on the system stabilizer is as important as the amount of aluminum sulfate; other components such as complexing agent B, ion inhibiting material and the like can also have significant effects on the viscosity, stability and the like of the system.
Comparative examples 7 to 12, which are the same proportions, show that the viscosity and the water separation rate are not the same, and the kaolin brings about the maximum viscosity improvement because of the high viscosity, so the water separation rate is relatively small, although the proportions are the same; the SDBS modified preparation of the pillared material has a certain effect, but the viscosity and the stability are weaker than those of the examples; while the unsuitable I, II structure is also weaker for modification than the reference product.
Comparative example 13 is a comparison of a commercially available fluorine-containing product, with lower solids content, low viscosity, good stability, fast setting but significantly weaker early strength than the fluorine-free and alkali-free product.
Claims (8)
1. A composite modified pillared material is characterized by comprising an orthorhombic crystal system pillared material modified by a quaternary ammonium salt corresponding to hyperbranched polyamine shown in the following formula I or a hyperbranched quaternary ammonium salt shown in the formula II,
in the formula I, R is selected from a structure (a) or a structure (b) shown in a formula III, and the value range of n is 3-10; in the formula II, the value range of m is 3-9;
wherein the orthorhombic column support material is sepiolite or hydrotalcite.
2. The method for preparing the composite modified pillared material of claim 1, comprising the steps of:
mixing and modifying quaternary ammonium salt corresponding to hyperbranched polyamine shown in the following formula I or hyperbranched quaternary ammonium salt shown in the formula II with an orthorhombic crystal system pillared material according to the mass ratio of 5-10:100 to obtain the composite modified pillared material;
in the formula I, R is selected from a structure (a) or a structure (b) shown in a formula III, and the value range of n is 3-10; in the formula II, the value range of m is 3-9;
the orthorhombic column support material is sepiolite or hydrotalcite.
3. The method according to claim 2, wherein the modification method is selected from the group consisting of a direct intercalation method, a solution-blended macromolecular intercalation method and a molten macromolecular intercalation method.
4. The fluorine-free alkali-free accelerator is characterized by comprising the following components in percentage by weight:
the balance being water;
wherein the stabilizer is the composite modified pillared material of claim 1.
5. The fluorine-free alkali-free accelerator according to claim 4, wherein the complexing agent a is selected from diethanolamine or triethanolamine.
6. The fluorine-free alkali-free accelerator according to claim 4, wherein the complexing agent B is at least one selected from EDTA, phosphoric acid, oxalic acid and urea.
7. The fluorine-free alkali-free accelerator according to claim 4, wherein the ion inhibitor is at least one selected from the group consisting of glycerin, sodium hexametaphosphate, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, and cetyltrimethylammonium bromide.
8. The method for preparing a fluorine-free alkali-free accelerator according to any one of claims 4 to 7, comprising the steps of:
uniformly dissolving 60% -66% of aluminum sulfate, 4.5% -9% of complexing agent A, 0.3% -3% of complexing agent B, 0.2% -0.6% of ion inhibitor and 0.6% -1% of stabilizer in the balance of water to obtain the fluorine-free alkali-free accelerator; taking the total amount of the fluorine-free alkali-free accelerator as 100 percent;
wherein the stabilizer is the composite modified pillared material of claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717090A (en) * | 2009-12-07 | 2010-06-02 | 上海工程技术大学 | Hyperbranched quaternary ammonium salt modified organo montmorillonite and preparation method thereof |
| CN104672374A (en) * | 2013-11-27 | 2015-06-03 | 中国石油大学(北京) | Controllable dispersion method of nano-micron structural intermediate micro-particles and composite material prepared by nano-micron structural intermediate micro-particles |
| CN105107477A (en) * | 2015-08-26 | 2015-12-02 | 河南科技大学 | Hyperbranched polymer/clay mineral hybrid material and preparation method thereof |
| CN112745056A (en) * | 2021-01-14 | 2021-05-04 | 佛山市凯隽新建材科技有限公司 | Suspension type alkali-free liquid accelerator and preparation method thereof |
| CN115466075A (en) * | 2022-08-25 | 2022-12-13 | 中建西部建设建材科学研究院有限公司 | Preparation method and application of alkali-free and fluorine-free liquid accelerator |
-
2023
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717090A (en) * | 2009-12-07 | 2010-06-02 | 上海工程技术大学 | Hyperbranched quaternary ammonium salt modified organo montmorillonite and preparation method thereof |
| CN104672374A (en) * | 2013-11-27 | 2015-06-03 | 中国石油大学(北京) | Controllable dispersion method of nano-micron structural intermediate micro-particles and composite material prepared by nano-micron structural intermediate micro-particles |
| CN105107477A (en) * | 2015-08-26 | 2015-12-02 | 河南科技大学 | Hyperbranched polymer/clay mineral hybrid material and preparation method thereof |
| CN112745056A (en) * | 2021-01-14 | 2021-05-04 | 佛山市凯隽新建材科技有限公司 | Suspension type alkali-free liquid accelerator and preparation method thereof |
| CN115466075A (en) * | 2022-08-25 | 2022-12-13 | 中建西部建设建材科学研究院有限公司 | Preparation method and application of alkali-free and fluorine-free liquid accelerator |
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