CN117511106A - Organic-inorganic hybrid internal curing agent and preparation method and application thereof - Google Patents
Organic-inorganic hybrid internal curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN117511106A CN117511106A CN202311287091.7A CN202311287091A CN117511106A CN 117511106 A CN117511106 A CN 117511106A CN 202311287091 A CN202311287091 A CN 202311287091A CN 117511106 A CN117511106 A CN 117511106A
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- Prior art keywords
- gel
- organic
- curing agent
- inorganic
- internal curing
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 99
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 239000004567 concrete Substances 0.000 claims abstract description 60
- 239000000378 calcium silicate Substances 0.000 claims abstract description 32
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 32
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 229920006322 acrylamide copolymer Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 35
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002952 polymeric resin Substances 0.000 claims description 15
- 229920003002 synthetic resin Polymers 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- 230000001603 reducing effect Effects 0.000 abstract description 12
- 230000002411 adverse Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 61
- 239000000243 solution Substances 0.000 description 35
- 239000004570 mortar (masonry) Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 230000036571 hydration Effects 0.000 description 15
- 238000006703 hydration reaction Methods 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000007873 sieving Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005213 imbibition Methods 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007863 gel particle Substances 0.000 description 4
- -1 hydroxide ions Chemical class 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000000404 calcium aluminium silicate Substances 0.000 description 3
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 3
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 3
- 229940078583 calcium aluminosilicate Drugs 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000011083 cement mortar Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 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 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C08L33/24—Homopolymers or copolymers of amides or imides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/287—Calcium, strontium or barium nitrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to an organic-inorganic hybrid internal curing agent, a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a gel suspension from the organic-inorganic hybrid internal curing agent raw materials, reacting to obtain organic-inorganic hybrid gel, dehydrating and grinding to obtain the organic-inorganic hybrid internal curing agent; taking the organic-inorganic hybrid internal curing agent as 100%, wherein the dry weight of the composite calcium silicate inorganic gel is 1% -2%; the composite calcium silicate inorganic gel has a dry weight of 100% and comprises 1% -3% of acrylamide homopolymer or copolymer. The organic-inorganic hybrid internal curing agent provided by the invention has good shrinkage reducing effect by adding a small amount, and does not have adverse effects on the flowing effect and the strength after hardening when concrete is mixed.
Description
Technical Field
The invention relates to the field of internal curing agents for concrete, in particular to an organic-inorganic hybrid internal curing agent, a preparation method and application thereof.
Background
The mineral admixture concrete with low water-cement ratio and large mixing amount is widely applied to important infrastructures such as bridges and the like due to the advantages of high strength and high durability. However, because of its lower water-cement ratio, the risk of early self-shrinkage cracking of concrete is greater. Once early cracking occurs, harmful substances enter the concrete through cracks, so that the internal concrete structure, the reinforcing steel bars and the like are more damaged, and the durability of the concrete is seriously reduced. Because the concrete for the major infrastructure has higher strength and compactness, common external sprinkling, covering and moisturizing and other means can not effectively maintain the inside of the concrete, and in partial plateau areas, the bridge pier column has higher position, severe environment, difficult manual maintenance and higher maintenance cost. In order to effectively reduce the early self-shrinkage of concrete, particularly concrete for major foundation facilities, an effective internal curing means is required, and an internal curing material is generated.
The internal curing material can absorb a large amount of water, and is doped into concrete, and in the hydration hardening process of the concrete, the high-water internal curing material can release water when the humidity in the concrete is reduced due to hydration or water evaporation, so that the humidity in the concrete and the maximum water filling hole radius are improved, the shrinkage stress is reduced, the cracking risk of the concrete is effectively reduced, the durability of the concrete is improved, and the shrinkage reducing material has wide application prospect.
At present, the internal curing materials are mainly divided into two types: inorganic internal curing material and super absorbent resin. The inorganic internal curing material mainly comprises light aggregate and inorganic powder, and comprises porous ceramsite, zeolite, diatomite and the like, the liquid absorption rate of the inorganic internal curing material is generally 10% -80%, the dry shrinkage of concrete can be increased, and the self-shrinkage reducing capability of the concrete is limited. The super absorbent resin has obvious shrinkage reducing effect because the liquid absorption rate of the super absorbent resin can reach tens times or even hundreds times, and the super absorbent resin is more and more focused in the aspect of being used as an internal curing material in recent years. However, the volume of the high water absorption resin sold in the market at present is reduced after water is released, holes are left in the hardened concrete, and the strength of the concrete is affected to a certain extent; the existing widely used polyacrylic acid monomer sodium type super absorbent resin absorbs water rapidly at the initial stage of doping, so that the fluidity of concrete or mortar is reduced, calcium ions and the like in a concrete solution enter the super absorbent resin to crosslink after doping, a water back-absorption phenomenon is generated, the phenomena of concrete bleeding and the like are easily caused, the strength and the durability of the concrete are influenced, and the defects limit the application of the super absorbent resin type internal curing material.
Disclosure of Invention
The invention mainly aims to provide an organic-inorganic hybrid internal curing agent, a preparation method and application thereof, and aims to solve the technical problems of providing the organic-inorganic hybrid internal curing agent which is added into concrete, has good shrinkage reducing effect on the concrete, does not have adverse effects on the flowing effect and the strength after hardening when the concrete is mixed, and is more suitable for practical use.
The aim and the technical problems of the invention are realized by adopting the following technical proposal. The preparation method of the organic-inorganic hybrid internal curing agent provided by the invention comprises the following steps:
preparing a gel suspension from the raw materials of the organic-inorganic hybrid internal curing agent, reacting to obtain organic-inorganic hybrid gel, dehydrating the organic-inorganic hybrid gel, and grinding to obtain the organic-inorganic hybrid internal curing agent;
the organic-inorganic hybrid internal curing agent comprises the following raw materials: a high molecular resin monomer, a composite silicon-calcium inorganic gel, a cross-linking agent and an initiator;
taking the organic-inorganic hybrid internal curing agent as 100%, and the dry weight of the composite calcium silicate inorganic gel is 1% -2%;
the dry weight of the composite silicon-calcium inorganic gel is 100 percent, and the composite silicon-calcium inorganic gel is added with acrylamide homopolymer or copolymer accounting for 1 to 3 percent during preparation.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the composite silica-calcium inorganic gel comprises the following components in percentage by mass, wherein the dry weight of the composite silica-calcium inorganic gel is 100 percent:
40% -50% of soluble silicate;
40% -55% of soluble calcium salt;
4% -11% of soluble aluminum salt; the method comprises the steps of,
acrylamide homo-or copolymer: 1 to 3 percent.
Preferably, the polymer resin monomer is 100% by mass and comprises:
acrylic monomer: 3% -11%;
sulfonic acid monomer: 30% -55%; the method comprises the steps of,
amide monomer: 35% -60%.
Preferably, the acrylic monomer is one or more of acrylic acid and methacrylic acid; the sulfonic acid monomer is one or more of 2-acrylamide-2-methylpropanesulfonic acid, propenesulfonic acid and sodium p-styrenesulfonate; the amide monomer is one or more of acrylamide and methacrylamide.
Preferably, the organic-inorganic hybrid internal curing agent is taken as 100%, and comprises 10% -20% of siliceous and aluminum powder in percentage by mass, wherein the particle size range of the siliceous and aluminum powder is 10-4000 nm.
Preferably, the aforementioned acrylamide homo-or copolymer is an uncrosslinked linear homo-or copolymer.
Preferably, the particle size of the organic-inorganic hybrid internal curing agent is 100 to 200 mesh.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The organic-inorganic hybrid internal curing agent provided by the invention comprises the following components: a high molecular resin monomer, a composite silicon-calcium inorganic gel, a cross-linking agent and an initiator; taking the organic-inorganic hybrid internal curing agent as 100%, and the dry weight of the composite calcium silicate inorganic gel is 1% -2%; the composite silicon-calcium inorganic gel comprises, by mass, 1% -3% of acrylamide homopolymer or copolymer based on 100% of the dry weight of the composite silicon-calcium inorganic gel.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The concrete material provided by the invention comprises the organic-inorganic hybrid internal curing agent.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The concrete building provided by the invention comprises the organic-inorganic hybrid internal curing agent.
By means of the technical scheme, the organic-inorganic hybrid internal curing agent and the preparation method and application thereof provided by the invention have at least the following advantages:
the invention provides a preparation method of an organic-inorganic hybrid internal curing agent, which is characterized in that acrylamide homopolymer or copolymer accounting for 1% -3% of the dry weight of the composite calcium silicate inorganic gel is added in the preparation process of the composite calcium silicate inorganic gel, so that inorganic particles are highly dispersed in the gel. The composite silica-calcium inorganic gel is dispersed in a high polymer resin monomer solution and is prepared into organic-inorganic hybrid gel by in-situ copolymerization with the monomer solution, so that the composite silica-calcium inorganic gel is uniformly dispersed in the high polymer resin with larger specific surface area, the inorganic gel particles have higher liquid absorption rate, and the high polymer resin also has higher liquid absorption rate, so that the internal curing agent prepared by the invention has good shrinkage reducing effect, and the alkali resistance of the material is improved by adding the inorganic gel material.
The internal curing agent prepared by the invention is doped into concrete or mortar, is in a gel state after absorbing water, has large specific surface area of highly dispersed inorganic gel particles mixed in high polymer resin before hardening the concrete, avoids the phenomenon of concrete bleeding caused by water back absorption, is beneficial to improving the saline-alkali resistance and water retention capacity of the internal curing agent, ensures that the internal curing agent gel keeps in a high water-containing state before hardening the concrete, and has good water storage stability; in the hardening process of the concrete, the water in the concrete is gradually reduced, the gel is also gradually dehydrated, at the moment, inorganic salt particles dispersed in the gel play a role of crystal nucleus, substances such as calcium ions, hydroxide ions, silicate ions and the like entering into water release holes of the gel are promoted to generate hydration products, and the hydration products fill holes formed after the internal curing agent gel releases water in situ, so that the influence on the strength of the concrete caused by the fact that holes are left in the hardened concrete is avoided.
In conclusion, the internal curing material has higher imbibition rate, saline-alkali resistance, water storage stability and in-situ pore filling capability, has no obvious back-suction phenomenon during use, has good shrinkage reducing effect, does not cause adverse effects on the flowing effect before concrete reinforcement and the strength after hardening, and overcomes the defects of poor water retention and strength influence of the traditional internal curing agent.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Detailed Description
In order to further illustrate the technical means and effects adopted by the invention to achieve the preset aim, the following is a detailed description of the organic-inorganic hybrid internal curing agent, the preparation method thereof, the specific implementation, the structure, the characteristics and the effects thereof, which are provided by the invention, in combination with the preferred embodiment. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The invention provides a preparation method of an organic-inorganic hybrid internal curing agent, which comprises the following steps: preparing a gel suspension from the raw materials of the organic-inorganic hybrid internal curing agent, reacting to obtain organic-inorganic hybrid gel, dehydrating the organic-inorganic hybrid gel, and grinding to obtain the organic-inorganic hybrid internal curing agent; the organic-inorganic hybrid internal curing agent comprises the following raw materials: a high molecular resin monomer, a composite silicon-calcium inorganic gel, a cross-linking agent and an initiator; taking the organic-inorganic hybrid internal curing agent as 100%, and the dry weight of the composite calcium silicate inorganic gel is 1% -2%; the dry weight of the composite silicon-calcium inorganic gel is 100 percent, and the composite silicon-calcium inorganic gel is added with acrylamide homopolymer or copolymer with the proportion of 1 to 3 percent during preparation.
The composite calcium silicate inorganic gel is added in a gel state with high water content (the water content is more than 90%), if the inorganic gel material is dried, the inorganic gel material is agglomerated and hardened, the specific surface area and the activity of the inorganic gel material are seriously reduced, and the water absorption capacity and the gel effect of the inorganic gel material are limited. But in calculating its mass, for greater accuracy, it is calculated as the dry weight of the inorganic gel material. Too much of the composite calcium silicate inorganic gel can influence the strength of the concrete mortar, and too little of the composite calcium silicate inorganic gel can not play the roles of salt and alkali resistance, water storage stability and in-situ pore filling. Therefore, the content of the composite calcium silicate inorganic gel is limited to 1-2%.
Crosslinking agents such as N, N' -methylenebisamide monomers are capable of crosslinking the polymeric resin monomers to form a polymeric resin. Too much addition can lead to too tight crosslinking of the polymer chain, so that the imbibition rate of the internal curing agent is too low; too little addition and too loose monomer crosslinking result in too large imbibition rate of the internal curing agent, and the internal curing agent also forms larger pores, which affects the strength of the concrete mortar. Therefore, the content of the crosslinking agent is limited to 0.5% to 1.5%.
The initiator is used for initiating polymerization reaction, excessive addition leads to excessively high polymerization speed of the internal curing agent, influences the imbibition rate, and has excessively high cost; too little addition does not initiate the reaction. Therefore, the content of the initiator is limited to 0.5% to 2%. Specifically, the initiator is one or more of sodium persulfate, potassium persulfate or ammonium persulfate.
The acrylamide homopolymer or copolymer plays a role of a dispersing agent and a stabilizing agent, so that inorganic salt particles are dispersed in the gel with a larger specific surface area, the water absorption rate of the composite calcium silicate inorganic gel is improved, and the water content of the gel after suction filtration is more than 90%. The acrylamide copolymer is acrylamide and 2-acrylamide-2-methylpropanesulfonic acid copolymer, etc. Meanwhile, the inorganic salt particles in the gel are highly dispersed, and the high specific surface area can improve the liquid absorption rate, the salt and alkali resistance, the water storage stability and the in-situ pore filling capability of the internal curing material prepared from the inorganic salt particles. If the addition amount is too small, the gel dispersibility and stability are poor; if too much is added, the cost is high. Therefore, the content of acrylamide homopolymer or copolymer is limited to 1-3%.
The invention provides a preparation method of an organic-inorganic hybrid internal curing agent, which comprises the steps of dispersing composite calcium silicate inorganic gel in a high polymer resin monomer solution, and carrying out in-situ copolymerization with the monomer solution to prepare the organic-inorganic hybrid gel, so that the composite calcium silicate inorganic gel is uniformly dispersed in the high polymer resin with a larger specific surface area, the inorganic gel particles have higher liquid absorption rate, and the high polymer resin also has higher liquid absorption rate, so that the internal curing agent prepared by the preparation method has good shrinkage reducing effect, and meanwhile, the alkali resistance of the material is improved by adding the inorganic gel material.
The internal curing agent prepared by the invention is doped into concrete or mortar, is in a gel state after absorbing water, has large specific surface area of highly dispersed inorganic gel particles mixed in high polymer resin before hardening the concrete, can generate a pre-ion crosslinking effect, avoids the phenomenon of bleeding of the concrete caused by water back suction, is beneficial to improving the saline-alkali resistance and water retention capacity of the internal curing agent, and ensures that the internal curing agent gel keeps a high water-containing state all the time before hardening the concrete, and has good water storage stability; in the hardening process of the concrete, the water in the concrete is gradually reduced, the gel is also gradually dehydrated, at the moment, inorganic salt particles dispersed in the gel play a role of crystal nucleus, substances such as calcium ions, hydroxyl ions, silicate ions and the like entering into water release holes of the gel are promoted to generate hydration products, and the hydration products fill holes formed after the internal curing agent gel releases water in situ, so that the influence on the strength of the concrete caused by the fact that holes are left in the hardened concrete is avoided.
In conclusion, the organic-inorganic hybrid internal curing agent has higher imbibition rate, saline-alkali resistance, water storage stability and in-situ pore filling capacity, has no obvious reverse suction phenomenon during use, has good shrinkage reducing effect, does not have adverse effects on the flowing effect before reinforcing the concrete and the strength after hardening, and overcomes the defects of poor water retention and strength influence of the traditional internal curing agent.
In some embodiments, the specific preparation method is: preparing a gel suspension from the organic-inorganic hybrid internal curing agent raw materials, placing the suspension in a container, carrying out ultrasonic vibration for 5min, after vibration, heating the suspension in a water bath at 50-70 ℃, stirring and reacting for 1-3 h to obtain an organic-inorganic hybrid gel, drying the gel at 60-80 ℃ for 3h, and grinding to obtain the organic-inorganic hybrid internal curing agent.
In some embodiments, the composition of the aforementioned composite calcium silicate inorganic gel is 100% by dry weight, and the composition of the aforementioned composite calcium silicate inorganic gel comprises, in mass percent: 40% -60% of soluble silicate; 40% -55% of soluble calcium salt; 4% -10% of soluble aluminum salt; and, acrylamide homo-or copolymers: 1 to 3 percent.
The soluble silicate, the soluble calcium salt and the soluble aluminum salt form the hydrated calcium aluminosilicate composite inorganic gel together. The soluble silicate provides a silicon source for forming the hydrated calcium silicate composite inorganic gel, and too little silicon source can not be provided for participating in forming a silicon-oxygen tetrahedral skeleton of the inorganic gel, and too much silicon source is added, so that part of the soluble silicate does not participate in the reaction, thereby causing waste. Therefore, the soluble silicate content is limited to 40% -50%. Too little addition of soluble calcium salt can not provide enough calcium source to participate in the reaction and cause too low calcium-silicon ratio of the inorganic gel and reduced activity; if too much soluble calcium salt is added, part of the soluble calcium salt does not participate in the reaction, so that waste is caused. Therefore, the soluble calcium salt content is limited to 40% -55%. The soluble aluminum salt, the soluble silicate and the soluble calcium salt can jointly form hydrated calcium aluminosilicate composite inorganic gel, the activity of the hydrated calcium aluminosilicate composite inorganic gel is higher than that of the hydrated calcium silicate composite inorganic gel, and the effect of promoting the generation of hydration products is better. The inorganic gel is mainly hydrated calcium silicate gel, so that the gel activity is affected; adding excessive aluminum salt to generate calcium aluminate hydrate, and affecting gel activity. Therefore, the content of the soluble aluminum salt is limited to 4% to 10%. Specifically, the soluble calcium salt is one or more of calcium nitrate tetrahydrate, calcium nitrate and calcium chloride; the soluble silicate is one or more of sodium metasilicate nonahydrate and potassium silicate; the soluble aluminum salt is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.
In some embodiments, the specific preparation method of the composite calcium silicate inorganic gel comprises the following steps: the solution is prepared by respectively preparing the solution of soluble calcium salt, soluble silicate, soluble aluminum salt and polyacrylamide, and the temperature of the solution is heated to 30-40 ℃ to ensure that the temperature of the soluble calcium salt solution is consistent with that of the soluble silicate solution. Adding a soluble calcium salt solution, a soluble silicate solution, a soluble aluminum salt solution and a polyacrylamide solution into the soluble silicate solution, uniformly mixing, stirring the mixed suspension in a nitrogen-filled sealed container at 30-40 ℃ for reaction for 1-3 hours to obtain an inorganic gel material suspension, carrying out suction filtration by using a vacuum pump and a filter device, washing for more than 2 times by using a mixed solution of ethanol and water, and carrying out suction filtration for 5min to obtain the composite calcium silicate inorganic gel.
In some embodiments, the polymer resin monomer comprises, by mass percentage, 100% of the polymer resin monomer: acrylic monomer: 3% -11%; sulfonic acid monomer: 30% -55%; and, an amide monomer: 35% -60%.
The acrylic acid monomer is a water-releasing monomer, the sulfonic acid monomer is a water-retaining monomer, the amide monomer is a nonionic monomer, the water-releasing monomer, the nonionic monomer and the water-retaining monomer are reasonably matched, the water storage stability can be ensured while the high imbibition rate is achieved, meanwhile, the water can be timely released when the concrete is hardened, and the self-shrinkage is reduced. Excessive water release monomer is added to cause the premature release of the internal curing agent, so that the strength of the mortar is affected; too little additive is added, and the shrinkage reducing effect of the internal curing agent is reduced. Too much or too little water retention monomer addition results in too low of the internal curing agent imbibition rate. Too much nonionic monomer can cause the imbibition multiplying power of the internal curing agent to be too low, and too little can cause the water release property of the internal curing agent to be poor, thereby influencing the effect of reducing self-shrinkage.
In some embodiments, the acrylic monomer used is one or more of acrylic acid, methacrylic acid; the sulfonic acid monomer is one or more of 2-acrylamide-2-methylpropanesulfonic acid, propenesulfonic acid and sodium p-styrenesulfonate; the amide monomer is one or more of acrylamide and methacrylamide.
In some embodiments, the organic-inorganic hybrid internal curing agent is taken as 100% and comprises 10% -20% of siliceous and/or aluminum powder in percentage by mass, wherein the particle size of the siliceous and/or aluminum powder ranges from 10 nm to 4000nm.
Ultrafine siliceous and/or aluminum powder in the internal curing agent and the composite silica-calcium inorganic gel cooperate to jointly promote the generation of hydration products in the gel water release holes. Too little addition to produce sufficient hydration product; excessive addition can affect the normal progress of the polymerization reaction and the strength of the mortar. Specifically, the superfine siliceous and aluminum powder is one or more of nanometer silicon dioxide, nanometer aluminum oxide, superfine calcined clay and superfine silica fume
In some embodiments, the aforementioned acrylamide homo-or copolymer is an uncrosslinked linear homo-or copolymer.
In some embodiments, the particle size of the organic-inorganic hybrid internal curing agent is 100-200 mesh.
The excessive particle size of the internal curing agent can cause voids formed by the internal curing agent in the concrete, which can have adverse effects on the strength of the concrete.
In another aspect, the present invention provides an organic-inorganic hybrid internal curing agent, in some embodiments, made by any of the methods of preparation described above.
The invention also provides a concrete material which comprises the organic-inorganic hybrid internal curing agent.
The invention also provides a concrete building, which comprises the organic-inorganic hybrid internal curing agent.
The invention will be further described with reference to specific examples, which are not to be construed as limiting the scope of the invention, but rather as falling within the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will now occur to those skilled in the art in light of the foregoing disclosure.
Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Inorganic gel A
500mL of a sodium silicate nonahydrate solution with the mass concentration of 50.0g/L, 250mL of a calcium nitrate tetrahydrate solution with the mass concentration of 90.0g/L, 100mL of an aluminum nitrate solution with the mass concentration of 30.0g/L and 100mL of a polyacrylamide solution with the mass concentration of 10.0g/L are heated to 30 ℃, then the four solutions are mixed, and the mixture is stirred and incubated for 1.5 hours at the water bath temperature of 30 ℃ to obtain an inorganic gel suspension. Filtering the suspension, washing with ethanol and water in the mass ratio of 1:1 for three times, and filtering for 5min to obtain 241.8g of composite calcium silicate inorganic gel with water content of 92.0%, which is denoted as inorganic gel A.
Inorganic gel B
500mL of a sodium silicate nonahydrate solution with the mass concentration of 40.0g/L, 250mL of a calcium nitrate tetrahydrate solution with the mass concentration of 110g/L, 100mL of an aluminum nitrate solution with the mass concentration of 20.0g/L and 100mL of a polyacrylamide solution with the mass concentration of 5.0g/L are heated to 30 ℃, then the four solutions are mixed, and the mixture is stirred and incubated for 1.5 hours at the water bath temperature of 30 ℃ to obtain an inorganic gel suspension. And (3) carrying out suction filtration on the suspension, washing the suspension three times by using a solution with the mass ratio of ethanol to water being 1:1, and carrying out suction filtration for 5 minutes to obtain 251.3g of composite calcium silicate inorganic gel, wherein the water content of the composite calcium silicate inorganic gel is 90.9%, and the composite calcium silicate inorganic gel is marked as inorganic gel B.
Inorganic gel C
500mL of a sodium silicate nonahydrate solution with a mass concentration of 42.0g/L, 250mL of a calcium nitrate tetrahydrate solution with a mass concentration of 80.0g/L, 100mL of an aluminum nitrate solution with a mass concentration of 50.0g/L and 100mL of a polyacrylamide solution with a mass concentration of 15.0g/L are heated to 30 ℃, then the four solutions are mixed, and the mixture is stirred and incubated for 1.5 hours at a water bath temperature of 30 ℃ to obtain an inorganic gel suspension. And (3) carrying out suction filtration on the suspension, washing the suspension three times by using a solution with the mass ratio of ethanol to water being 1:1, and carrying out suction filtration for 5 minutes to obtain 256.1g of composite calcium silicate inorganic gel, wherein the water content of the composite calcium silicate inorganic gel is 90.0%, and the composite calcium silicate inorganic gel is marked as inorganic gel C.
Example 1
10.0g of acrylic acid and 30.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, the aqueous solutions are uniformly mixed and stirred, 1.0g (calculated by dry weight of gel) of inorganic gel A,57.0g of acrylamide, 0.5g of N, N' -methylenebisacrylamide and 1.5g of potassium persulfate are added, and the aqueous solutions are stirred and dissolved to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 60 ℃ oven for drying for 72 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 2
5.0g of acrylic acid and 50.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, after being uniformly stirred, 2.0g (calculated by dry weight of gel) of inorganic gel B,41.0g of acrylamide, 1.5g of N, N' -methylene bisacrylamide and 0.5g of ammonium persulfate initiator are added, and stirred and dissolved to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 70 ℃ oven for drying for 48 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 3
6.5g of acrylic acid and 40.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, 1.5g (calculated by dry weight of gel) of inorganic gel C,50.0g of acrylamide, 0.8g of N, N' -methylenebisacrylamide and 1.2g of potassium persulfate are added after being uniformly stirred, and dissolved, so as to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 70 ℃ oven for drying for 48 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 4
3.0g of acrylic acid and 30.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, the aqueous solutions are mixed, 1g (calculated by dry weight of gel) of inorganic gel C,14.0g of nano silicon dioxide, 4.0g of nano aluminum oxide, 46.0g of acrylamide, 1.5g of N, N' -methylene bisacrylamide and 0.5g of potassium persulfate are added after uniform stirring, and the aqueous solutions are stirred and dissolved to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 70 ℃ oven for drying for 48 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 5
8.0g of acrylic acid and 45.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, the aqueous solutions are uniformly mixed, 1.0g (calculated by dry weight of gel) of inorganic gel C,8.0g of nano silicon dioxide, 2.0g of nano aluminum oxide, 34.0g of acrylamide, 0.5g of N, N' -methylene bisacrylamide and 1.5g of potassium persulfate are added, and the aqueous solutions are stirred and dissolved to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 70 ℃ oven for drying for 48 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving with 100 meshes, sieving the samples under the 100 meshes with 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 6
5.0g of acrylic acid and 36.0g of 2-acrylamido-2-methylpropanesulfonic acid are respectively prepared into aqueous solutions with the neutralization degree of 70% and 100%, the aqueous solutions are uniformly mixed, 1.5g (calculated by dry weight of gel) of inorganic gel C,12.0g of nano silicon dioxide, 3.5g of nano aluminum oxide, 40.0g of acrylamide, 1.0g of N, N' -methylene bisacrylamide and 1.0g of potassium persulfate are added, and stirring and dissolving are carried out to obtain gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 70 ℃ oven for drying for 48 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Example 7
The same as in example 1, except that methacrylic acid was used as the acrylic monomer and methacrylamide was used as the amide monomer.
Example 8
The same as in example 2, except that sodium p-styrenesulfonate was used as the sulfonic acid-based monomer.
Example 9
The same procedure as in example 1 was repeated except that acrylamide was used as the whole polymer resin monomer. Specifically, 97.0g of acrylamide, 1g (calculated by dry weight of gel) of inorganic gel A,0.5g of N, N' -methylenebisacrylamide, and 1.5g of potassium persulfate were prepared into a gel suspension; transferring the mixture into a reaction kettle, heating to 60 ℃, and stirring and reacting for 2 hours to obtain organic-inorganic hybrid gel; cutting gel into blocks, putting the blocks into a 60 ℃ oven for drying for 72 hours to obtain block-shaped samples, finally putting the block-shaped materials into a ball mill for grinding, sieving by using 100 meshes, sieving the samples under the 100 meshes by using 200 meshes, and collecting the samples on the 200 meshes to obtain the organic-inorganic hybrid internal curing agent.
Comparative example 1
Comparative example 1 differs from example 3 in that the internal curing agent prepared does not contain inorganic gel C. The rest of the experimental conditions were the same as in example 3.
Comparative example 2
Comparative example 2 is different from example 3 in that the inorganic gel added to the prepared internal curing agent is prepared by the following method:
500mL of a sodium silicate nonahydrate solution with the mass concentration of 42.0g/L, 250mL of a calcium nitrate tetrahydrate solution with the mass concentration of 80.0g/L, 100mL of an aluminum nitrate solution with the mass concentration of 50.0g/L and 100mL of deionized water are heated to 30 ℃, then the four solutions are mixed, stirred and kept at the water bath temperature of 30 ℃ for 1.5h, and an inorganic gel suspension is obtained. And (3) carrying out suction filtration on the suspension, washing with a solution with the mass ratio of ethanol to water being 1:1 for three times, and carrying out suction filtration for 5min to obtain 229.0g of the composite calcium silicate inorganic gel with the water content of 78%.
The rest of the experimental conditions were the same as in example 3.
Comparative example 3
The purchased super absorbent resin produced in Xinyuan chemical industry is used as an internal curing agent.
Mortar was prepared according to the formulation in Table 1 using the organic-inorganic hybrid internal curing agent of examples 1 to 9 and the internal curing agent of comparative examples 1 to 2, respectively, and the fluidity was controlled at 230mm by adding an appropriate amount of water reducer to each mortar group, and the mortar was tested for 28d compressive strength and 28d self-shrinkage, and the test results are shown in Table 2. The formulation of the mortar used in the blank set differs from the formulation in table 1 in that no internal curing agent is added.
Table 1 mortar formulation
| Reference cement | ISO standard sand | Water and its preparation method | Water reducing agent | Internal curing agent dosage |
| 675g | 1350g | 246g | Proper amount of | 1.35g |
TABLE 2 mortar Performance test results
| 28d compressive Strength/MPa | 28d self-shrinkage μm/m | |
| Example 1 | 57.7 | 54 |
| Example 2 | 57.4 | 57 |
| Example 3 | 58.0 | 53 |
| Example 4 | 59.6 | 59 |
| Example 5 | 59.5 | 58 |
| Example 6 | 60.3 | 59 |
| Example 7 | 57.5 | 55 |
| Example 8 | 57.2 | 58 |
| Example 9 | 56.3 | 64 |
| Comparative example 1 | 53.5 | 56 |
| Comparative example 2 | 54.7 | 57 |
| Comparative example 3 | 50.3 | 63 |
| Blank group | 57.5 | 97 |
As can be seen from table 2: compared with the performance test results of the blank group mortar, the organic-inorganic hybrid internal curing agent prepared by the invention has lower self-shrinkage under the condition of less doping amount after being doped into the cement mortar, and can obviously reduce the self-shrinkage, so that the internal curing agent can release water in the cement hydration process, and the internal curing effect is achieved.
Compared with the mortar performance test results of the embodiment 3, the internal curing agent prepared by adding the composite silica-calcium inorganic gel in the embodiment 1 ensures that the cement mortar has better mechanical properties, and can obviously improve the 28d strength of the mortar, which shows that the internal curing agent in the embodiment 3 not only can release water to play an internal curing effect in the cement hydration process, but also can utilize the composite silica-calcium inorganic gel in-situ generated hydration product to fill internal pores, thereby reducing the influence of the pores formed by the release of the internal curing agent on the concrete strength.
Compared with the mortar performance test results of the embodiment 3, the internal curing agent prepared from the composite silica-calcium inorganic gel added with the polyacrylamide during preparation ensures that the cement mortar has better mechanical properties and can obviously improve the 28d strength of the mortar. The polyacrylamide is proved to enable inorganic particles to be more dispersed in the composite calcium silicate inorganic gel, so that the effect of filling the internal pores with hydration products generated in situ in the cement hydration process is better, and the influence of the pores formed by water release of the internal curing agent on the strength of concrete is reduced.
Compared with the mortar performance test results of examples 4-6 and examples 1-3, the strength of the mortar can be improved by adding the composite silica-calcium inorganic gel and the silica and alumina nano powder into the internal curing agent, compared with the independent addition of the composite silica-calcium inorganic gel, the internal curing agent can be used for filling internal pores by utilizing inorganic gel materials to cooperate with nano silica and nano alumina in-situ generated hydration products, and the influence of the pores formed by water release of the internal curing agent on the strength of the concrete is further reduced.
In conclusion, the organic-inorganic hybrid internal curing agent provided by the invention is obviously reduced, has no adverse effect on the mechanical properties of cement-based materials, and has wide application prospects in the field of high-performance concrete.
The technical features of the claims and/or the description of the present invention may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the invention.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the organic-inorganic hybrid internal curing agent is characterized by comprising the following steps of:
preparing a gel suspension from the organic-inorganic hybrid internal curing agent raw materials;
the gel suspension reacts to obtain organic-inorganic hybrid gel;
dehydrating and grinding the organic-inorganic hybrid gel to obtain an organic-inorganic hybrid internal curing agent;
the organic-inorganic hybrid internal curing agent comprises the following raw materials: a high molecular resin monomer, a composite silicon-calcium inorganic gel, a cross-linking agent and an initiator;
taking the organic-inorganic hybrid internal curing agent as 100%, wherein the dry weight of the composite calcium silicate inorganic gel is 1% -2%;
the dry weight of the composite silicon-calcium inorganic gel is 100 percent, and the composite silicon-calcium inorganic gel is added with acrylamide homopolymer or copolymer accounting for 1 to 3 percent during preparation.
2. The preparation method according to claim 1, wherein the components of the composite silica-calcium inorganic gel in mass percent are as follows, based on the dry weight of the composite silica-calcium inorganic gel as 100%:
40% -50% of soluble silicate;
40% -55% of soluble calcium salt;
4% -11% of soluble aluminum salt; the method comprises the steps of,
acrylamide homo-or copolymer: 1 to 3 percent.
3. The production method according to claim 1, wherein the polymer resin monomer is 100% by mass, and comprises:
acrylic monomer: 3% -11%;
sulfonic acid monomer: 30% -55%; the method comprises the steps of,
amide monomer: 35% -60%.
4. The method according to claim 3, wherein the acrylic monomer is one or more of acrylic acid and methacrylic acid; the sulfonic acid monomer is one or more of 2-acrylamide-2-methylpropanesulfonic acid, propenesulfonic acid and sodium p-styrenesulfonate; the amide monomer is one or more of acrylamide and methacrylamide.
5. The preparation method according to claim 1, wherein the organic-inorganic hybrid internal curing agent is taken as 100%, and the organic-inorganic hybrid internal curing agent further comprises 10% -20% of siliceous and aluminum powder in percentage by mass, and the particle size of the siliceous and aluminum powder ranges from 10 nm to 4000nm.
6. The method according to claim 1, wherein the particle size of the organic-inorganic hybrid internal curing agent is 50 to 300 mesh.
7. The method of claim 1, wherein the acrylamide homo-or copolymer is an uncrosslinked linear homo-or copolymer.
8. An organic-inorganic hybrid internal curing agent is characterized by comprising the following components:
a high molecular resin monomer, a composite silicon-calcium inorganic gel, a cross-linking agent and an initiator;
taking the organic-inorganic hybrid internal curing agent as 100%, wherein the dry weight of the composite calcium silicate inorganic gel is 1% -2%;
the composite silicon-calcium inorganic gel comprises, by mass, 1% -3% of an acrylamide homopolymer or copolymer, wherein the dry weight of the composite silicon-calcium inorganic gel is 100%.
9. A concrete material comprising the organic-inorganic hybrid internal curing agent according to claim 8.
10. A concrete building comprising the organic-inorganic hybrid internal curing agent according to claim 8.
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