CN113637123A - Hyperbranched concrete tackifier and preparation method and application thereof - Google Patents
Hyperbranched concrete tackifier and preparation method and application thereof Download PDFInfo
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- CN113637123A CN113637123A CN202110962118.2A CN202110962118A CN113637123A CN 113637123 A CN113637123 A CN 113637123A CN 202110962118 A CN202110962118 A CN 202110962118A CN 113637123 A CN113637123 A CN 113637123A
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- concrete
- unsaturated
- tackifier
- hyperbranched
- monomer
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- 239000004567 concrete Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 32
- -1 unsaturated maleic acid diester Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 8
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 6
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- ATXASKQIXAJYLM-UHFFFAOYSA-N 1-hydroxypyrrolidine-2,5-dione;prop-2-enoic acid Chemical group OC(=O)C=C.ON1C(=O)CCC1=O ATXASKQIXAJYLM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IUILQPUHQXTHQD-UHFFFAOYSA-N 1-hydroxypyrrolidine-2,5-dione;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.ON1C(=O)CCC1=O IUILQPUHQXTHQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000005394 methallyl group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 13
- 238000005204 segregation Methods 0.000 abstract description 11
- 239000004566 building material Substances 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract description 2
- 238000005345 coagulation Methods 0.000 abstract description 2
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 16
- 239000004568 cement Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- QXONIHMUSQFKJU-UHFFFAOYSA-N 2-(prop-1-enoxymethyl)oxirane Chemical compound CC=COCC1CO1 QXONIHMUSQFKJU-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- PYDQYQSHPJGKNR-UHFFFAOYSA-N 2-methyl-2-(propanoylamino)propane-1-sulfonic acid Chemical compound CCC(=O)NC(C)(C)CS(O)(=O)=O PYDQYQSHPJGKNR-UHFFFAOYSA-N 0.000 description 3
- DBMBAVFODTXIDN-UHFFFAOYSA-N 2-methylbutane-2-sulfonic acid Chemical compound CCC(C)(C)S(O)(=O)=O DBMBAVFODTXIDN-UHFFFAOYSA-N 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LLYKEHMXABZNQX-UHFFFAOYSA-N 2-(but-2-en-2-yloxymethyl)oxirane Chemical compound CC=C(C)OCC1CO1 LLYKEHMXABZNQX-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000001613 Gambling Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002986 polymer concrete Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C04B2103/44—Thickening, gelling or viscosity increasing agents
Abstract
The invention discloses a hyperbranched concrete tackifier and a preparation method and application thereof, belonging to the technical field of building material concrete admixtures, wherein the hyperbranched concrete tackifier is prepared by carrying out free radical polymerization on a hyperbranched polymer A, an unsaturated succinimide monoester monomer, an unsaturated maleic acid diester monomer and an unsaturated sulfonic acid monomer; the hyperbranched polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization reaction, and the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether. The tackifier of the invention can effectively improve the workability of fresh concrete, solve the problems of segregation, bleeding and settlement of the concrete, and has obvious water retention and tackifying effects, good slurry wrapping effect and no serious delayed coagulation or air entraining phenomenon.
Description
Technical Field
The invention belongs to the technical field of building material concrete additives, and particularly relates to a hyperbranched concrete tackifier, and a preparation method and application thereof.
Background
Along with the continuous development of building structure design and super high-rise buildings, higher requirements are also put forward to concrete in building construction, the concrete is often required to have large fluidity due to the continuous complication of concrete members and the continuous increase of the density of reinforcing steel bars in the building members, but if the mixture is over-diluted, the concrete is easy to generate a delamination phenomenon, so that the problems of a gambling pump, the missing pouring of construction parts, the unqualified strength of a solidified body and the like are easily caused, and the quality and the service life of a concrete project are influenced. In addition, the exploitation of natural sand is limited, the use amount of machine-made sand is increased day by day, but the quality of machine-made sand is poor, the gradation is poor, the mud content is high, and the cohesiveness of concrete is poor. Therefore, there is a need for effective methods to provide fresh concrete with both good flow and segregation resistance. The method for adding the rheological control agent into the concrete system is a safe and effective method for improving the viscosity of the concrete and reducing the occurrence of bleeding and segregation phenomena at present, and most of the concrete rheological control agents are natural polymers such as rice hull ash, wen lu jiao, cellulose ether, cellulose derivatives and the like at present; however, the substances and the polycarboxylic acid water reducing agent have compatibility problems, in addition, the rheology regulating agent is sensitive to the mixing amount, has a good rheology modification effect when the mixing amount is low, but can obviously increase the viscosity of concrete when slightly over-mixing is carried out, so that the flowability of fresh concrete is reduced, the water requirement is increased, and the strength of the concrete is influenced;
a good concrete rheology modifier should have the following characteristics: firstly, the viscosity of the fresh concrete can be obviously increased when the mixing amount is low, so that the fresh concrete is reduced in sedimentation and does not bleed in a plastic state; secondly, the paint has good compatibility with other additives; finally, the concrete fluidity is slightly influenced, and the concrete has certain water retention and tackifying capability over time. The artificially synthesized polymer concrete rheology regulator has the advantages of diverse raw materials, rich synthesis modes, strong designability of molecular structures and the like, and has become a key research direction of many scientific researchers. At present, partial rheology regulator can solve the traditional problemA technical problem that the compatibility of a rheological regulator and a polycarboxylic acid water reducing agent is poor is solved, for example, Chinese patent CN 109369859B discloses a concrete tackifying type viscosity regulator and a preparation method thereof, and the preparation method comprises the following steps: dissolving a modified polyether monomer, an unsaturated amide monomer, an unsaturated carboxylic acid monomer and a crosslinking agent in deionized water to obtain a monomer mixed solution: dissolving an unsaturated amide monomer and an unsaturated carboxylic acid monomer in deionized water, and marking as solution A: in N2And slowly dripping the initiator solution and the solution A into the monomer mixed solution at the temperature of 40-60 ℃, continuously stirring and reacting at the temperature of 60-90 ℃, adjusting the pH value, and supplementing water for dilution to obtain the viscosity regulator. The viscosity regulator has good compatibility with the polycarboxylic acid water reducing agent, can effectively regulate the cohesiveness of concrete, solves the problems of segregation and bleeding of the concrete, and does not influence the maintaining performance and the setting time of the concrete. However, the viscosity regulator adopts the modified polyether monomer as the raw material, the modified polyether is a linear polymer, molecular chains are easy to bend, and the molecular chains are easy to wind, so that the capability of molecules of the viscosity regulator for binding water molecules and bridging cement and gravel particles is weakened, and the tackifying effect of the viscosity regulator is further reduced.
Therefore, the research on the tackifier capable of avoiding the intermolecular winding of the linear polymer can effectively solve the problems of segregation, bleeding and the like of fresh concrete, and has great significance in having good compatibility with the polycarboxylic acid water reducing agent.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a hyperbranched concrete tackifier, which is prepared from a hyperbranched polymer, an unsaturated succinimide monoester monomer, an unsaturated maleic diester monomer, and an unsaturated sulfonic acid monomer by radical polymerization. The problem of intermolecular winding caused by using linear polyether can be avoided, the cohesiveness of concrete can be effectively adjusted, and the problems of bleeding, segregation and the like of fresh concrete are solved.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a hyperbranched concrete tackifier is prepared by a hyperbranched polymer A, an unsaturated succinimide monoester monomer, an unsaturated maleic acid diester monomer and an unsaturated sulfonic acid monomer through free radical polymerization;
the hyperbranched polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization reaction, and the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether.
The unsaturated ternary oxygen-containing heterocyclic monomer is polymerized through ring opening and multiple branches to form hyperbranched polymer A with multiple double bonds at the tail end, and compared with a linear polymer, the tackifier of the invention adopts the hyperbranched polymer A as a raw material, has small hydrodynamic gyration radius and less winding among molecular chains, and molecular chains can effectively generate a bridging effect between cement particles and sand stones, thereby increasing the cohesiveness of concrete and effectively solving the problems of bleeding, segregation and the like of fresh concrete.
Preferably, the hyperbranched polymer a comprises a repeating unit represented by the following general formula (r), or comprises a repeating unit represented by the following general formula (c):
in the general formula (I), R is allyl; in the general formula (II), R' is a methallyl group.
Preferably, the weight average molecular weight of the hyperbranched polymer A is 3000-4000.
Preferably, the mass ratio of the hyperbranched polymer A, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer and the unsaturated sulfonic acid monomer is as follows: 1 (0.15-0.3), (0.1-0.25) and (0.4-0.5).
Preferably, the unsaturated succinimide monoester monomer is N-hydroxysuccinimide acrylate or N-hydroxysuccinimide methacrylate.
Preferably, the unsaturated maleic acid diester monomer is one of polyethylene glycol maleic acid diester, diethylene glycol maleic acid diester, and triethylene glycol maleic acid diester.
Preferably, the unsaturated sulfonic acid monomer is 2-acrylamido-2-methylpropanesulfonic acid or methacrylamidopropyl-N, N-dimethylpropanesulfonic acid.
Preferably, the weight average molecular weight of the tackifier is 10 to 100 ten thousand.
The tackifier of the invention is obtained by carrying out free radical chain addition polymerization on monomers containing carbon-carbon double bonds, wherein the-C-C-bonds are used as main chains of polymer molecules, and functional groups on the monomers are generally on side chains of the polymers. The molecular weight of the polymerization product is larger, so that a bridge effect can be generated among cement particles, sand grains and stones, and the cohesiveness of the concrete is increased, namely the viscosity of the concrete is improved. Due to the amide groups and the ester groups on the side chains, hydrolysis reaction can occur in the alkaline environment of cement hydration to generate alcohols with the water retention function, so that the water retention and tackifying capability of fresh concrete can be improved.
The inventor finds that most of the current tackifiers are linear polymers which are easy to bend in the high-alkaline environment of concrete, so that the tackifier molecules lose the capacity of binding water molecules and bridging cement and sand particles; the unsaturated ternary oxygen-containing heterocyclic monomer can form a highly branched hydrophilic product with multiple double bonds at the terminal through ring-opening polymerization, and the terminal C ═ C can be grafted with a required functional group through free radical polymerization. Compared with linear polymers, the polymer has small hydrodynamic radius of gyration and less entanglement among molecular chains, can effectively bridge cement and sand particles, and increases the viscosity of concrete.
The inventor also finds that the unsaturated succinimide monoester monomer is a monoester with C ═ C, and the unsaturated succinimide monoester monomer is hydrolyzed in the concrete alkaline environment to generate carboxylic acid with strong adsorption capacity and alcohol with water retention performance, so that the tackifier has viscosity increasing and water retention performance over time. The unsaturated maleic diester monomer is diester with C ═ C, has two or more carbon-carbon double bonds, can play a role in slight crosslinking in a system, enables a polymer to form a spatial three-dimensional structure, and can enhance the interaction between the polymer and cement and sandstone particles by combining carboxyl, amido and other groups with strong adsorbability on the polymer, thereby endowing the tackifier with better tackifying performance.
The inventors have also found that the presence of water-soluble sulfonic acid groups in the unsaturated sulfonic acid monomers, which can form hydrogen bonds with water molecules, enhances the ability of S to attract electrons from water molecules, i.e., readily form stable hydrogen bonds with water molecules. The charge density is high, and the hydration ability is strong; in the negative ion-SO3In which two pi bonds and 2 oxygen atoms share a negative charge, SO that-SO3Stable and insensitive to attack by external cations, so that the tackifier has good salt resistance. Three pairs of arc pair electrons on carbonyl oxygen (C ═ O) in the monomer are easy to be adsorbed on the surface of solid particles in the cement liquid phase, and provide reaction sites for forming a space network structure in the cement liquid phase to a certain extent. Meanwhile, the unsaturated sulfonic acid monomer has huge side groups, and the rigidity of a macromolecular chain is enhanced, so that the temperature resistance, salt resistance, stability and shear resistance of the copolymer are improved; will give good overall performance to the tackifier.
Generally speaking, the concrete tackifier disclosed by the invention is a cross-linked polymer, and compared with the traditional straight-chain polymer, the concrete tackifier has the advantages that the tackifying and water-retaining properties are improved, and the influence on the concrete fluidity is smaller, so that the concrete has a certain viscosity and also has better fluidity. And shows higher saturated doping amount and more excellent dispersion performance, temperature resistance and salt tolerance in a cement/concrete system.
The invention also aims to provide a preparation method of the hyperbranched concrete tackifier, which comprises the following steps:
s1, dissolving 50-70% of unsaturated ternary oxygen-containing heterocyclic monomer in a solvent, wherein the mass ratio of the monomer to the solvent is (1-2): 3; then adding an initiator to form a mixed solution, slowly dropwise adding the remaining 30-50% of unsaturated ternary oxygen-containing heterocyclic monomers into the mixed solution at the temperature of 110-120 ℃, reacting for 3-5 h under heat preservation, and purifying to obtain a hyperbranched polymer A;
s2, dissolving the hyperbranched polymer A into deionized water, wherein the mass ratio of the hyperbranched polymer A to the deionized water is1: (3-5), adding an unsaturated succinimide monoester monomer, an unsaturated maleic acid diester monomer and an unsaturated sulfonic acid monomer into the solution, uniformly stirring, and adjusting the pH value to 7-8 by using liquid alkali; in N2And slowly dripping an azo initiator into the monomer mixed solution at the temperature of 40-60 ℃, and reacting for 4-6 h at the temperature of 50-60 ℃ to obtain the hyperbranched concrete tackifier.
Preferably, in the step S1, the mass of the initiator is 1.0 to 1.5% of the total mass of the unsaturated ternary oxygen-containing heterocyclic monomer, and if the amount of the initiator is too large, the branching degree of the polymerization product is too small, which may adversely affect the product performance. The use of too little initiator can reduce the reaction rate and even stop the polymerization, the number of the molecules of the polymerization product is small, and the branching degree of individual single molecules can be too large, thereby affecting the tackifying performance.
Preferably, in step S1, the initiator of the ring-opening polymerization reaction of the unsaturated ternary oxygen-containing heterocyclic monomer is trimethylolpropane, the reaction temperature is 110 to 120 ℃, and the half-life of the initiator is changed when the temperature is too high or too low, so that the polymerization reaction rate and the polymerization degree are affected, and the comprehensive performance of the polymerization product is changed.
Preferably, in step S2, the mass of the azo initiator is 0.5 to 2.0% of the total mass of the hyperbranched polymer a, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer, and the unsaturated sulfonic acid monomer, and if the amount of the initiator is insufficient, the generated free radicals are less, the reaction rate is slowed, and even the polymerization is stopped. The excessive initiator can generate excessive free radicals to accelerate the reaction rate and increase the probability of double-radical termination, so that the molecular weight of the product is reduced.
Preferably, in step S2, the azo initiator is dissolved in deionized water, the mass percentage concentration of the initiator aqueous solution is adjusted to 0.5-1.0%, and the time for dropping the initiator aqueous solution into the monomer mixed solution is controlled to be 1-2.5 hours.
The invention controls the weight average molecular weight of the tackifier to be 10-100 ten thousand by reasonably controlling the components and the proportion of the synthetic raw materials and the synthetic conditions, and the tackifier with the molecular weight has the following beneficial effects.
The invention further aims to provide application of the tackifier in medium and low-grade strength concrete, which is characterized in that the blending amount of the tackifier is 0.01-0.1% of that of a concrete cementing material.
Compared with the prior art, the invention has the advantages that:
(1) the tackifier of the invention can effectively improve the workability of fresh concrete, solve the problems of segregation, bleeding and settlement of the concrete, has good slurry wrapping effect, obvious water retention and tackifying effects and no serious delayed coagulation or air entraining phenomenon.
(2) Compared with the traditional straight-chain polymer, the tackifier of the invention improves the water retention and tackifying performance and has small loss on the fluidity of concrete; the method can effectively solve the contradiction between the flowability of the fresh concrete and the segregation resistance and the bleeding resistance, and has good flowability while improving the viscosity of the concrete.
(3) The tackifier disclosed by the invention is insensitive to the mixing amount, and the optimal using amount of the tackifier is 0.01-0.1% of that of a concrete cementing material.
(4) The tackifier disclosed by the invention is simple in synthesis method, good in compatibility with the polycarboxylic acid water reducing agent and free from precipitation.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The hyperbranched concrete tackifier of the embodiment is prepared by carrying out free radical polymerization on hyperbranched polymer A, N-hydroxysuccinimide acrylate, polyethylene glycol maleic acid diester and 2-propionamido-2-methylpropanesulfonic acid; the hyperbranched polymer A is prepared from allyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
s1, adding 150ml of DMAC solution and 68.48g of propenyl glycidyl ether into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, setting the oil bath temperature to be 60 ℃, and uniformly stirring; then 1.14g trimethylolpropane is added, and 2.85g potassium carbonate is added after complete dissolution; the temperature was raised to 120 ℃, and then 45.66g of propenyl glycidyl ether was slowly dropped into the four-necked flask using a peristaltic pump; after the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, followed by neutralization with a cation exchange resin, and the solution was transferred to acetone of 10 times the volume and precipitated, and the crude product was dissolved with methanol, and the methanol was removed with a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 51.75g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, stirring for dissolving, adding 14.51g N-hydroxysuccinimide acrylate, 12.47g of polyethylene glycol maleic diester and 24.75g of 2-propionamido-2-methylpropanesulfonic acid into the solution, stirring uniformly, and adjusting the pH value to 7-8 by using 14.8g of 32 mass percent sodium hydroxide solution; purging the inside of the four-necked flask with nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.72g of azobisisobutylamidine hydrochloride is dissolved in deionized water to prepare a solution with the mass percent concentration of 0.5%, and the solution is dropwise added into a four-neck flask within 2 h. After the end of the dropwise addition, the temperature was raised to 60 ℃ and the reaction was continued for 4h and aged at 40 ℃ for 1 h. Finally 666ml of water were added to give a polymer with a solids content of 10%.
Example 2
The hyperbranched concrete tackifier of the embodiment is prepared by carrying out free radical polymerization on a hyperbranched polymer A, N-hydroxysuccinimide methyl propylene, diethylene glycol maleic acid diester and methacrylamide propyl-N, N dimethyl propane sulfonic acid; the hyperbranched polymer A is prepared from allyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
s1, adding 150ml of DMAC solution and 57.07g of propenyl glycidyl ether into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, setting the oil bath temperature to be 60 ℃, and uniformly stirring; then 1.71g trimethylolpropane is added, and 2.85g potassium carbonate is added after complete dissolution; the temperature was raised to 120 ℃, and then 57.07g of propenyl glycidyl ether was slowly added dropwise into the four-necked flask using a peristaltic pump; after the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, followed by neutralization with a cation exchange resin, and the solution was transferred to acetone of 10 times the volume and precipitated, and the crude product was dissolved with methanol, and the methanol was removed with a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 51.75g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, stirring for dissolving, adding 10.07g N-hydroxysuccinimide methacrylate, 6.31g of diethylene glycol maleic diester and 24.75g of methacrylamide propyl-N, N-dimethyl propane sulfonic acid into the solution, stirring uniformly, and adjusting the pH value to 7-8 by using 14.8g of sodium hydroxide solution with the mass concentration of 32%; purging the inside of the four-necked flask with nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.56g of azobisisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the end of the dropwise addition, the temperature was raised to 50 ℃ and the reaction was continued for 4h and aged at 40 ℃ for 1 h. Finally 601ml of water is added to obtain a polymerization product with the solid content of 10 percent.
Example 3
The hyperbranched concrete tackifier of the embodiment is prepared by carrying out free radical polymerization on a hyperbranched polymer A, N-hydroxysuccinimide methyl propylene, diethylene glycol maleic acid diester and methacrylamide propyl-N, N dimethyl propane sulfonic acid; the hyperbranched polymer A is prepared from allyl glycidyl ether through ring-opening polymerization reaction.
The preparation method of the concrete tackifier specifically comprises the following steps:
s1, adding 150ml of DMAC solution and 89.69g of methyl propenyl glycidyl ether into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, setting the oil bath temperature to be 60 ℃, and uniformly stirring; then 1.71g trimethylolpropane is added, and 2.85g potassium carbonate is added after complete dissolution; the temperature was raised to 120 ℃, and then 38.44g of methacryl glycidyl ether was slowly added dropwise to the four-necked flask using a peristaltic pump; after the dropwise addition, stirring was continued for 3 hours. The reaction product was dissolved with anhydrous methanol, followed by neutralization with a cation exchange resin, and the solution was transferred to acetone of 10 times the volume and precipitated, and the crude product was dissolved with methanol, and the methanol was removed with a rotary evaporator at 45 ℃ to obtain hyperbranched polymer a.
S2, adding 35.2g of hyperbranched polymer A and 160ml of deionized water into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, stirring for dissolving, adding 10.55g N-hydroxysuccinimide methacrylate, 3.52g of diethylene glycol maleic diester and 17.59g of methacrylamide propyl-N, N-dimethyl propane sulfonic acid into the solution, stirring uniformly, and adjusting the pH value to 7-8 by using 10.56g of sodium hydroxide solution with the mass concentration of 32%; purging the inside of the four-necked flask with nitrogen, and raising the temperature of the water bath to 50 ℃ while stirring; 0.48g of azobisisobutylamidine hydrochloride was dissolved in deionized water to prepare a 0.5% by mass solution, which was added dropwise to a four-necked flask over 2 hours. After the end of the dropwise addition, the temperature was raised to 50 ℃ and the reaction was continued for 4h and aged at 40 ℃ for 1 h. Finally 373ml of water were added to obtain a polymer product having a solids content of 10%.
Comparative example 1
The concrete tackifier of the comparative example is prepared by free radical polymerization of methyl allyl polyoxyethylene ether, N-hydroxysuccinimide methyl propylene, diethylene glycol maleic acid diester and methacrylamide propyl-N, N dimethyl propane sulfonic acid;
the preparation method of the concrete tackifier specifically comprises the following steps:
adding 51.75g of methallyl polyoxyethylene ether and 160ml of deionized water into a four-neck flask provided with an electric stirrer, a dropping device, a thermometer and nitrogen circulation, stirring for dissolving, adding 14.51g N-hydroxysuccinimide acrylate, 12.47g of polyethylene glycol maleic diester and 24.75g of 2-propionamido-2-methylpropanesulfonic acid into the solution, stirring uniformly, purging the inside of the four-neck flask by using nitrogen, and raising the water bath temperature to 50 ℃ while stirring; 0.72g of azobisisobutylamidine hydrochloride is dissolved in deionized water to prepare a solution with the mass percent concentration of 0.5%, and the solution is dropwise added into a four-neck flask within 2 h. After the dropwise addition, the temperature was raised to 50 ℃ and the reaction was continued for 4h, followed by aging at 40 ℃ for 1 h. Then, 14.8g of sodium hydroxide solution with the mass concentration of 32% is used for adjusting the pH value to 7-8; finally 666ml of water were added to give a polymer with a solids content of 10%.
Comparative example 2
The concrete tackifier of this comparative example was a commercially available hydroxypropyl methylcellulose ether available from Hubei Hengheng science and technology, Inc. model 172, 10 million viscosity.
Comparative example 3
The concrete tackifier of the comparative example is a commercially available diutan, available from the scientific and biological Co., Ltd, of Jiangsu vitamin, at an industrial level.
Test examples
Firstly, the concrete tackifiers in the embodiments 1 to 3 and the comparative examples 1 to 3 are applied to a mortar system, and the time-dependent bleeding amount of the mortar system is tested. The test method is as follows: mixing 450g of cement, 1350g of standard sand, 180g of water, 1.2g of water reducing agent and 0.23g of tackifier with solid content of 10%, uniformly stirring, and placing in a square container; recording the total mass M1 of the mortar and the container, standing, removing the water secreted from the surface by using absorbent paper at 15min and 30min, respectively measuring the total mass M2 and M3 of the mortar and the container, and calculating the bleeding amount at 15min and 30min, wherein the specific test result is shown in Table 1.
TABLE 1 bleeding amount (g) of mortar system
Group of | 15min bleeding amount | Bleeding amount of 30min |
Blank group | 6 | 8 |
Example 1 | 0 | 0 |
Example 2 | 0 | 0 |
Example 3 | 0 | 1 |
Comparative example 1 | 2 | 3 |
Comparative example 2 | 2 | 5 |
Comparative example 3 | 1 | 3 |
As can be seen from the data in Table 1, compared with the blank group and the comparative examples 1 to 3, the tackifier of the examples 1 to 3 can effectively improve the bleeding problem of the mortar, and has an obvious water retention effect.
Secondly, the concrete tackifiers of examples 1 to 3 and comparative examples 1 to 3 are applied to C30 concrete, the mixing ratio of the concrete is shown in Table 2, and the performance test of the concrete is carried out.
Table 2 shows the mixing ratio (kg/m) of C30 concrete3)
Cement | Fly ash | Sand | Stone (stone) | Water (W) | Water reducing agent |
265 | 80 | 870 | 1000 | 170 | 5.6 |
Wherein the cement is Huaxin P.O 42.5 grade cement; the fly ash is II-grade fly ash; the fineness modulus of the sand is 2.8, and the mud content is less than 2%; the stone is 5-25 mm continuous graded broken stone, and the water reducing agent is a Ujion-PC polycarboxylic acid water reducing agent produced by Wuhanyuan brocade building materials Limited.
According to the regulation in GB/T50080-2016 standard of common concrete mixture performance test method, the working performance of the fresh concrete of the blank group, examples 1-3 and comparative examples 1-3 is detected; detecting the mechanical property of the concrete according to the regulation in GB/T50081-2002 Standard for testing the mechanical property of the common concrete; testing the emptying time of the concrete mixture in the inverted slump cone according to a test method in appendix A of JGJ/T281 and 2012 'high-strength concrete application technical Specification'; the test results are shown in table 3.
TABLE 3 concrete Performance test results
Wherein the mixing amount of the tackifier accounts for the mass percent of the cementing material; the "v" indicates the degree of bleeding, and the more "v", the more severe the bleeding.
As can be seen from the test results in Table 3: compared with a blank group and a comparative example, the tackifier of the embodiment 1-3 can obviously improve the bleeding segregation problem of concrete, has obvious water retention and tackifying effects, does not have obvious air entraining phenomenon, has no negative influence on the compressive strength of the concrete, and can effectively improve the workability of fresh concrete; compared with comparative examples, the tackifier of comparative examples 1-3 can obviously reduce the expansion degree and the slump of concrete and influence the working performance of the concrete. The evacuation time of comparative example 1 was shorter than that of example, indicating that the thickening effect was inferior to that of example, and the slump and the spread were smaller than those of example; the thickening effect of comparative example 2 is also inferior to that of example, and bleeding phenomenon occurs; comparative example 3 showed good thickening effect, but had large slump and expansion loss. In conclusion, the tackifier of the embodiments 1 to 3 of the present invention has good compatibility with other additives, can effectively improve the problems of poor wrapping property, segregation, bleeding and the like of low-strength grade fresh concrete, can effectively improve the viscosity of concrete, can effectively improve the workability of concrete, and does not affect the working performance of concrete; in addition, the tackifier of the invention has low sensitivity to the mixing amount, does not cause sharp increase of viscosity after the mixing amount is increased, and does not reduce the slump and the expansion degree of concrete.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A hyperbranched concrete tackifier is characterized in that the tackifier is prepared by free radical polymerization reaction of hyperbranched polymer A, unsaturated succinimide monoester monomer, unsaturated maleic acid diester monomer and unsaturated sulfonic acid monomer;
the hyperbranched polymer A is prepared from unsaturated ternary oxygen-containing heterocyclic monomers through ring-opening polymerization reaction, and the unsaturated ternary oxygen-containing heterocyclic monomers are allyl glycidyl ether or methallyl glycidyl ether.
2. The hyperbranched concrete tackifier according to claim 1, wherein the hyperbranched polymer a comprises a repeating unit represented by the following general formula (r), or comprises a repeating unit represented by the following general formula (ii):
in the general formula (I), R is allyl; in the general formula (II), R' is a methallyl group.
3. The hyperbranched concrete tackifier of claim 1, wherein the mass ratio of the hyperbranched polymer A, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer and the unsaturated sulfonic acid monomer is 1 (0.15-0.3): (0.1-0.25): 0.4-0.5).
4. The hyperbranched concrete tackifier of claim 1, wherein the unsaturated succinimide monoester monomer is N-hydroxysuccinimide acrylate or N-hydroxysuccinimide methacrylate.
5. The hyperbranched concrete tackifier of claim 1, wherein the unsaturated maleic acid diester monomer is one of polyethylene glycol maleic acid diester, diethylene glycol maleic acid diester, and triethylene glycol maleic acid diester.
6. The hyperbranched concrete tackifier of claim 1, wherein the unsaturated sulfonic acid monomer is 2-acrylamido-2-methylpropanesulfonic acid or methacrylamidopropyl-N, N-dimethylpropanesulfonic acid.
7. The hyperbranched concrete tackifier according to claim 1, wherein the weight average molecular weight of the tackifier is 10 to 100 ten thousand.
8. The preparation method of the hyperbranched concrete tackifier according to any one of claims 1 to 7, characterized by comprising the following steps:
s1, dissolving a part of unsaturated ternary oxygen-containing heterocyclic monomers in a solvent, adding an initiator to form a mixed solution, slowly dripping the other part of unsaturated ternary oxygen-containing heterocyclic monomers into the mixed solution at the temperature of 110-120 ℃, reacting for 3-5 hours in a heat preservation manner, and purifying to obtain a hyperbranched polymer A;
s2, dissolving the hyperbranched polymer A, the unsaturated succinimide monoester monomer, the unsaturated maleic acid diester monomer and the unsaturated sulfonic acid monomer in deionized water to form a monomer mixed solution, and adjusting the pH value to 7-8; in N2And slowly dripping an azo initiator into the monomer mixed solution at the temperature of 40-60 ℃, and reacting for 4-6 h at the temperature of 50-60 ℃ to obtain the hyperbranched concrete tackifier.
9. The preparation method of the hyperbranched concrete tackifier of claim 8, wherein in the step S1, the mass of the initiator is 1.0-1.5% of the total mass of the unsaturated ternary oxygen-containing heterocyclic monomer.
10. The application of the hyperbranched concrete tackifier of any one of claims 1 to 7 or the tackifier prepared by the preparation method of claim 8 or 9 in medium and low-grade strength concrete is characterized in that the dosage of the tackifier is 0.01 to 0.1 percent of the concrete cementing material.
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