CN106279702A - A kind of froth breaking type function monomer, polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of froth breaking type function monomer, polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN106279702A CN106279702A CN201610736255.3A CN201610736255A CN106279702A CN 106279702 A CN106279702 A CN 106279702A CN 201610736255 A CN201610736255 A CN 201610736255A CN 106279702 A CN106279702 A CN 106279702A
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- defoaming
- functional monomer
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- polyether
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- 239000000178 monomer Substances 0.000 title claims abstract description 82
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 67
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 63
- 229920000570 polyether Polymers 0.000 claims description 63
- 229920002545 silicone oil Polymers 0.000 claims description 51
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 21
- 150000008065 acid anhydrides Chemical class 0.000 claims description 18
- 239000003377 acid catalyst Substances 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000008030 superplasticizer Substances 0.000 abstract description 16
- -1 siloxane structure Chemical group 0.000 abstract description 11
- 238000013329 compounding Methods 0.000 abstract description 5
- 230000001603 reducing effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 229960005070 ascorbic acid Drugs 0.000 description 12
- 235000010323 ascorbic acid Nutrition 0.000 description 12
- 239000011668 ascorbic acid Substances 0.000 description 12
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 230000007935 neutral effect Effects 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 101100533558 Mus musculus Sipa1 gene Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical group CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical group CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
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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
- 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
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- 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
- C08F290/068—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明提供了一种消泡型功能单体、聚羧酸减水剂及其制备方法，所述消泡功能单体的制备方法是将具有消泡功能的硅氧烷链段引入消泡型功能单体分子结构，制得消泡功能单体；所述具有消泡功能的聚羧酸减水剂的制备方法是将具有消泡功能的硅氧烷链段通过聚合的方式引入聚羧酸减水剂分子结构中以得到具有消泡功能的聚羧酸减水剂。本发明中所制备的消泡型功能单体引入硅氧烷结构，具有更优异的消泡功能，且结构中不含Si‑O‑C结构，从而避免因Si‑O‑C结构水解出现的稳定性问题。本发明的聚羧酸减水剂在不影响减水效果的前提下，赋予减水剂消泡的功能，使聚羧酸减水剂具有减水、消泡一体的功能，避免复配所出现的相容性和稳定性等问题。The invention provides a defoaming functional monomer, a polycarboxylate water reducer and a preparation method thereof. The preparation method of the defoaming functional monomer is to introduce a siloxane segment with a defoaming function into a defoaming type The molecular structure of the functional monomer is used to obtain the defoaming functional monomer; the preparation method of the polycarboxylate water reducer with the defoaming function is to introduce the siloxane segment with the defoaming function into the polycarboxylic acid by polymerization In order to obtain the polycarboxylate superplasticizer with defoaming function in the molecular structure of the superplasticizer. The defoaming type functional monomer prepared in the present invention introduces a siloxane structure, which has a more excellent defoaming function, and does not contain a Si-O-C structure in the structure, thereby avoiding the occurrence of hydrolysis of the Si-O-C structure. Stability issues. The polycarboxylate water reducer of the present invention endows the water reducer with the function of defoaming without affecting the water reducing effect, so that the polycarboxylate water reducer has the functions of water reduction and defoaming, and avoids the occurrence of compounding compatibility and stability issues.
Description
技术领域technical field
本发明属于建筑材料中混凝土外加剂技术领域，具体来讲，涉及一种具有消泡功能的消泡型功能单体、聚羧酸减水剂及其制备方法。The invention belongs to the technical field of concrete admixtures in building materials, and specifically relates to a defoaming type functional monomer with defoaming function, a polycarboxylate water reducer and a preparation method thereof.
背景技术Background technique
在混凝土配置和施工中不免要引入气泡，其中直径在50nm以下的气泡可显著提高混凝土的抗冻、抗渗、耐久性，还可改善混凝土的流动性和施工性，从而提高混凝土质量。随着混凝土行业发展，对混凝土各种性能要求的提高，聚羧酸减水剂得到广泛迅速的应用，但聚羧酸减水剂由于自身分子结构特点，导致其引气能力强，在混凝土制备过程中引入大小不一的气泡，含气量过高，严重影响混凝土强度、外观和耐久等性能。It is inevitable to introduce air bubbles in concrete configuration and construction, and air bubbles with a diameter below 50nm can significantly improve the frost resistance, impermeability, and durability of concrete, and can also improve the fluidity and constructability of concrete, thereby improving the quality of concrete. With the development of the concrete industry and the improvement of various performance requirements of concrete, polycarboxylate superplasticizers have been widely and rapidly applied, but polycarboxylate superplasticizers have strong air-entraining ability due to their own molecular structure characteristics, so they are used in concrete preparation. Bubbles of different sizes are introduced during the process, and the air content is too high, which seriously affects the strength, appearance and durability of concrete.
针对此问题，许多研究提出向聚羧酸减水剂中加入适量消泡剂进行复配以达到控制含气量，但由于消泡剂与聚羧酸减水剂相容性和稳定性较差，此方法在控制含气量问题上效果欠佳。因此有研究尝试将消泡剂进行改性以解决相容性。In response to this problem, many studies have proposed to add an appropriate amount of defoamer to the polycarboxylate superplasticizer for compounding to control the air content. However, due to the poor compatibility and stability of the defoamer and polycarboxylate superplasticizer, This method is less effective in controlling air content problems. Therefore, some research attempts to modify the defoamer to solve the compatibility.
专利US6803396将聚氧乙烯聚氧丙烯进行胺基封端，增加与聚羧酸减水剂的相互作用力，此种聚醚价格较昂贵；文献《聚羧酸减水剂和混凝土含气量的调控方法》报道在制备酯类大单体时将聚氧乙烯聚氧丙烯醚引入体系，调节聚氧丙烯和聚氧乙烯链段的比例以控制聚羧酸减水剂的引气性。现有技术中都通过对聚醚改性以改善聚羧酸减水剂的含气量。In the patent US6803396, polyoxyethylene and polyoxypropylene are terminated with amine groups to increase the interaction force with polycarboxylate water reducers. Method" reported that polyoxyethylene polyoxypropylene ether was introduced into the system when preparing ester macromonomers, and the ratio of polyoxypropylene and polyoxyethylene chain segments was adjusted to control the air-entraining property of polycarboxylate water reducers. In the prior art, the air content of the polycarboxylate water reducer is improved by modifying the polyether.
发明内容Contents of the invention
针对现有技术中存在的不足，本发明的目的之一在于解决上述现有技术中存在的一个或多个问题。例如，本发明的目的之一在于提供一种减水性能优异且同时具有优良消泡功能的聚羧酸减水剂。In view of the deficiencies in the prior art, one purpose of the present invention is to solve one or more problems in the above prior art. For example, one of the objectives of the present invention is to provide a polycarboxylate water reducer with excellent water reducing performance and excellent defoaming function.
为了实现上述目的，本发明的一方面提供了一种消泡型功能单体的制备方法。所述消泡型功能单体的制备方法将具有消泡功能的硅氧烷链段及聚醚链段结构引入消泡型功能单体分子结构。In order to achieve the above object, one aspect of the present invention provides a method for preparing a defoaming functional monomer. The preparation method of the defoaming type functional monomer introduces the structure of the siloxane segment and the polyether segment having the defoaming function into the molecular structure of the defoaming type functional monomer.
根据本发明示例性实施例的消泡型功能单体的制备方法，所述消泡型功能单体的制备方法可以包括以下步骤：加热聚醚改性硅油，并将含有酸类催化剂的不饱和羧酸或酰氯滴加至所述聚醚改性硅油中进行酯化反应，或者将酸酐滴加至聚醚改性硅油中分散溶解并加热进行酯化反应，得到含硅氧烷和聚醚侧链的消泡型功能单体。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, the preparation method of the defoaming type functional monomer may include the following steps: heating the polyether modified silicone oil, Carboxylic acid or acid chloride is added dropwise to the polyether-modified silicone oil for esterification, or acid anhydride is added dropwise to polyether-modified silicone oil to disperse and dissolve and heated for esterification to obtain silicone- and polyether-containing Chain defoaming type functional monomer.
根据本发明示例性实施例的消泡型功能单体的制备方法，所述聚醚改性硅油与不饱和羧酸的摩尔比为1：1.05～1：1.10，所述酸类催化剂占所述聚醚改性硅油与不饱和羧酸总摩尔数的0.5％～3.0％，所述聚醚改性硅油与酰氯的摩尔比为1：1.05～1：1.10，所述聚醚改性硅油与酸酐的摩尔比为1：1.05～1：1.10。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, the molar ratio of the polyether modified silicone oil to the unsaturated carboxylic acid is 1:1.05-1:1.10, and the acid catalyst accounts for the 0.5%-3.0% of the total moles of polyether-modified silicone oil and unsaturated carboxylic acid, the molar ratio of polyether-modified silicone oil to acid chloride is 1:1.05-1:1.10, the polyether-modified silicone oil and acid anhydride The molar ratio is 1:1.05～1:1.10.
根据本发明示例性实施例的消泡型功能单体的制备方法，加热所述聚醚改性硅油至60～100℃。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, the polyether-modified silicone oil is heated to 60-100°C.
根据本发明示例性实施例的消泡型功能单体的制备方法，所述不饱和羧酸为丙烯酸、甲基丙烯酸、丁烯酸、2-丁烯酸中的至少一种，所述酰氯为丙烯酰氯、甲基丙烯酰氯中的至少一种，所述酸酐为顺丁烯二酸酐，所述酸类催化剂为浓硫酸和/或对甲苯磺酸。According to the preparation method of the defoaming type functional monomer in an exemplary embodiment of the present invention, the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, crotonic acid, and 2-butenoic acid, and the acid chloride is At least one of acryloyl chloride and methacryloyl chloride, the acid anhydride is maleic anhydride, and the acid catalyst is concentrated sulfuric acid and/or p-toluenesulfonic acid.
根据本发明示例性实施例的消泡型功能单体的制备方法，在1～2小时内通过恒压滴液漏斗向所述聚醚改性硅油中滴加酰氯或含有酸类催化剂的不饱和羧酸。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, acid chloride or unsaturated polyether containing acid catalyst is added dropwise to the polyether modified silicone oil through a constant pressure dropping funnel within 1 to 2 hours. carboxylic acid.
根据本发明示例性实施例的消泡型功能单体的制备方法，向所述聚醚改性硅油中滴加酰氯或含有酸类催化剂的不饱和羧酸完毕后，继续酯化反应1～2小时，或者直接加入酸酐分散溶解进行酯化反应1～2小时。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, after the acid chloride or the unsaturated carboxylic acid containing an acid catalyst is added dropwise to the polyether modified silicone oil, the esterification reaction is continued for 1-2 hours, or directly add acid anhydride to disperse and dissolve for esterification reaction for 1 to 2 hours.
根据本发明示例性实施例的消泡型功能单体的制备方法，所述制备方法还包括将不饱和羧酸和酸类催化剂、或酰氯滴加至所述聚醚改性硅油中时进行搅拌。According to the preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention, the preparation method also includes stirring when adding unsaturated carboxylic acid and acid catalyst, or acid chloride dropwise into the polyether modified silicone oil .
根据本发明示例性实施例的消泡型功能单体的制备方法，所述消泡型功能单体用于制备具有消泡功能的聚羧酸减水剂。According to the preparation method of a defoaming type functional monomer according to an exemplary embodiment of the present invention, the defoaming type functional monomer is used to prepare a polycarboxylate water reducer with a defoaming function.
本发明另一方面提供一种消泡型功能单体。所述消泡型功能单体含硅氧烷和聚醚侧链且无Si-O-C结构，所述消泡型功能单体的分子结构为：Another aspect of the present invention provides a defoaming functional monomer. The defoaming type functional monomer contains siloxane and polyether side chains and has no Si-O-C structure, and the molecular structure of the defoaming type functional monomer is:
根据本发明示例性实施例的消泡型功能单体，所述消泡型功能单体由上述消泡型功能单体的制备方法制备而成。According to the defoaming type functional monomer according to an exemplary embodiment of the present invention, the defoaming type functional monomer is prepared by the above-mentioned preparation method of the defoaming type functional monomer.
本发明再一方面一种具有消泡功能的聚羧酸减水剂的制备方法。所述具有消泡功能的聚羧酸减水剂的制备方法包括：a、将具有消泡功能的硅氧烷链段和聚醚链段结构引入消泡型功能单体分子结构，以制备消泡型功能单体；b、将所述消泡型功能单体引入聚合体系中，得到具有消泡功能的聚羧酸减水剂。Another aspect of the present invention is a preparation method of polycarboxylate water reducer with defoaming function. The preparation method of the polycarboxylate water reducer with defoaming function includes: a. introducing the siloxane segment and polyether segment structure with defoaming function into the molecular structure of defoaming functional monomer to prepare defoaming A foam-type functional monomer; b. introducing the defoaming-type functional monomer into the polymerization system to obtain a polycarboxylate water reducer with defoaming function.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述步骤b在引发剂和链转移剂的作用下使所述消泡型功能单体、聚醚大单体与不饱和羧酸和/或其衍生物(即不饱和羧酸的衍生物)进行水溶液自由基聚合反应，得到具有消泡功能的聚羧酸减水剂。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the step b makes the defoaming type functional monomer and polyether large under the action of an initiator and a chain transfer agent. The monomer and the unsaturated carboxylic acid and/or its derivatives (that is, the derivatives of the unsaturated carboxylic acid) are subjected to an aqueous radical polymerization reaction to obtain a polycarboxylic acid water reducer with a defoaming function.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述步骤b可以包括：将所述消泡型功能单体、聚醚大单体和水混合并加热，得到溶液A；将不饱和羧酸和/或其衍生物与引发剂、链转移剂和水配成溶液B；将所述溶液B滴加至所述溶液A中，完成水溶液自由基聚合反应，得到具有消泡功能的聚羧酸减水剂。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the step b may include: mixing and heating the defoaming functional monomer, polyether macromonomer and water , to obtain solution A; unsaturated carboxylic acid and/or its derivatives and initiator, chain transfer agent and water are made into solution B; said solution B is added dropwise in said solution A to complete the aqueous solution free radical polymerization reaction , to obtain a polycarboxylate water reducer with defoaming function.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，将4.0～24.4重量份的所述消泡型功能单体、300～400重量份的聚醚大单体和200～260重量份的水混合并加热，得到所述溶液A。According to the preparation method of the polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, 4.0-24.4 parts by weight of the defoaming-type functional monomer, 300-400 parts by weight of polyether macromonomer It is mixed with 200-260 parts by weight of water and heated to obtain the solution A.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，将40～60重量份的不饱和羧酸和/或其衍生物与0.3～3.0重量份的引发剂、1.0～4.0重量份的链转移剂和180～240重量份的水配成溶液B。According to the preparation method of polycarboxylate superplasticizer with defoaming function according to an exemplary embodiment of the present invention, 40-60 parts by weight of unsaturated carboxylic acid and/or its derivatives and 0.3-3.0 parts by weight of initiator, 1.0-4.0 parts by weight of chain transfer agent and 180-240 parts by weight of water are formulated into solution B.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述水溶液自由基聚合反应在40～60℃的温度条件下进行。According to the preparation method of the polycarboxylate superplasticizer with defoaming function according to an exemplary embodiment of the present invention, the radical polymerization reaction in the aqueous solution is carried out at a temperature of 40-60°C.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，将所述消泡型功能单体、聚醚大单体和水加热至40～60℃。According to the preparation method of the polycarboxylate superplasticizer with defoaming function according to an exemplary embodiment of the present invention, the defoaming type functional monomer, polyether macromonomer and water are heated to 40-60°C.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述溶液B在1.5～3.5小时以内通过恒压滴液漏斗滴加至所述溶液A中。According to the preparation method of the polycarboxylate superplasticizer with defoaming function according to an exemplary embodiment of the present invention, the solution B is added dropwise to the solution A through a constant pressure dropping funnel within 1.5 to 3.5 hours.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述方制备法还可以包括在所述水溶液自由基聚合反应完之后降温至40℃以下，并调节pH至中性。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the preparation method may also include cooling down to below 40°C after the radical polymerization reaction of the aqueous solution is completed, and adjusting the pH to neutral.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，采用碱性物质进所述调节pH至中性的步骤，所述碱性物质可以为氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。According to the preparation method of the polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the step of adjusting the pH to neutral is carried out by using an alkaline substance, and the alkaline substance can be sodium hydroxide, hydrogen At least one of potassium oxide and calcium hydroxide.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述聚醚大单体可以为分子量2200～2800的异戊烯醇聚氧乙烯聚氧丙烯醚、甲基烯丙基聚氧乙烯聚氧丙烯醚和4-羟丁基乙烯基聚氧乙烯聚氧丙烯醚中的至少一种。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the polyether macromonomer can be prenyl alcohol polyoxyethylene polyoxypropylene ether with a molecular weight of 2200-2800, methyl At least one of allyl polyoxyethylene polyoxypropylene ether and 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述链转移剂可以为巯基丙酸、巯基乙酸、甲基丙烯磺酸钠和苯乙烯磺酸钠中的至少一种。According to the preparation method of the polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the chain transfer agent can be mercaptopropionic acid, mercaptoacetic acid, sodium methacrylene sulfonate and sodium styrene sulfonate at least one of .
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述引发剂可以为过硫酸铵、过硫酸钾、抗坏血酸与过硫酸铵、抗坏血酸与过硫酸钾、或者抗坏血酸与双氧水。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the initiator can be ammonium persulfate, potassium persulfate, ascorbic acid and ammonium persulfate, ascorbic acid and potassium persulfate, or Ascorbic acid and hydrogen peroxide.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述步骤a包括：加热聚醚改性硅油，并将含有酸类催化剂的不饱和羧酸或酰氯滴加至所述聚醚改性硅油中进行酯化反应，或者将酸酐滴加至聚醚改性硅油中分散溶解并加热进行酯化反应，得到含硅氧烷和聚醚侧链的消泡型功能单体。According to the preparation method of polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the step a includes: heating polyether modified silicone oil, and dropping unsaturated carboxylic acid or acid chloride containing acid catalyst Add it to the polyether-modified silicone oil for esterification, or add the acid anhydride dropwise to the polyether-modified silicone oil to disperse and dissolve and heat for esterification to obtain a defoaming type containing siloxane and polyether side chains functional monomer.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述聚醚改性硅油与不饱和羧酸的摩尔比为1：1.05～1：1.10，所述酸类催化剂占所述聚醚改性硅油与不饱和羧酸总摩尔数的0.5％～3.0％，所述聚醚改性硅油与酰氯的摩尔比为1：1.05～1：1.10，所述聚醚改性硅油与酸酐的摩尔比为1：1.05～1：1.10。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the molar ratio of the polyether modified silicone oil to the unsaturated carboxylic acid is 1:1.05 to 1:1.10, and the acid Catalysts account for 0.5% to 3.0% of the total moles of polyether-modified silicone oil and unsaturated carboxylic acid, the molar ratio of polyether-modified silicone oil to acid chloride is 1:1.05-1:1.10, and the polyether The molar ratio of modified silicone oil to acid anhydride is 1:1.05～1:1.10.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，加热所述聚醚改性硅油至60～100℃。According to the preparation method of the polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the polyether-modified silicone oil is heated to 60-100°C.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，所述不饱和羧酸为丙烯酸、甲基丙烯酸、丁烯酸、2-丁烯酸中的至少一种，所述酰氯为丙烯酰氯、甲基丙烯酰氯中的至少一种，所述酸酐为顺丁烯二酸酐，所述酸类催化剂为浓硫酸和/或对甲苯磺酸。According to the preparation method of a polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention, the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, crotonic acid, and 2-butenoic acid , the acid chloride is at least one of acryloyl chloride and methacryloyl chloride, the acid anhydride is maleic anhydride, and the acid catalyst is concentrated sulfuric acid and/or p-toluenesulfonic acid.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，在1～2小时内通过恒压滴液漏斗向所述聚醚改性硅油中滴加酰氯或含有酸类催化剂的不饱和羧酸。According to the preparation method of the polycarboxylate water-reducer with defoaming function according to the exemplary embodiment of the present invention, acid chloride or acid containing unsaturated carboxylic acids as catalysts.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法，向所述聚醚改性硅油中滴加酰氯或含有酸类催化剂的不饱和羧酸完毕后，继续酯化反应1～2小时，或者直接加入酸酐分散溶解进行酯化反应1～2小时。According to the preparation method of the polycarboxylate water reducer with defoaming function according to the exemplary embodiment of the present invention, after adding acid chloride or unsaturated carboxylic acid containing acid catalyst dropwise to the polyether modified silicone oil, continue to esterify reaction for 1-2 hours, or directly add acid anhydride to disperse and dissolve for esterification reaction for 1-2 hours.
本发明再一方面提供一种具有消泡功能的聚羧酸减水剂。所述聚羧酸减水剂由上述具有消泡功能的聚羧酸减水剂的制备方法制备而成。Another aspect of the present invention provides a polycarboxylate water reducer with defoaming function. The polycarboxylate water reducer is prepared by the above preparation method of the polycarboxylate water reducer with defoaming function.
与现有技术相比，本申请的聚羧酸减水剂在不影响减水效果的前提下，赋予减水剂消泡的功能，即保证制备的混凝土流动性、施工性的基础上，消除混凝土内残留气泡。本申请中所制备的消泡型功能单体引入硅氧烷结构，比起聚醚类消泡单体具有更优异的消泡功能，且结构中不含Si-O-C结构，结构性能稳定。将其引入聚合体系，所制备的聚羧酸减水剂具有减水、消泡一体的功能，避免复配所出现的相容性和稳定性等问题。Compared with the prior art, the polycarboxylate water reducer of the present application endows the water reducer with the function of defoaming without affecting the water reducing effect, that is, on the basis of ensuring the fluidity and constructability of the prepared concrete, it eliminates Bubbles remain in the concrete. The defoaming type functional monomer prepared in this application is introduced into a siloxane structure, which has a better defoaming function than polyether defoaming monomers, and does not contain Si-O-C structure in the structure, so the structure and performance are stable. Introducing it into the polymerization system, the prepared polycarboxylate water reducer has the functions of water reduction and defoaming, and avoids the problems of compatibility and stability in compounding.
具体实施方式detailed description
在下文中，将结合示例性实施例详细地描述根据本发明的消泡型功能单体、具有消泡功能聚羧酸减水剂及其制备方法。Hereinafter, the defoaming type functional monomer, the polycarboxylate superplasticizer with defoaming function and the preparation method thereof according to the present invention will be described in detail with reference to exemplary embodiments.
本发明通过将具有消泡功能的硅氧烷链段及聚醚链段结构通过聚合的方式引入聚羧酸减水剂分子结构中以赋予聚羧酸减水剂消泡的功能。即首先制备含硅氧烷和聚醚侧链的消泡型功能单体，然后在引发剂和链转移剂的作用下使消泡型功能单体、聚醚大单体与不饱和羧酸和/或其衍生物进行水溶液自由基聚合反应，得到具有消泡功能的聚羧酸减水剂。In the present invention, the siloxane segment and the polyether segment structure having the defoaming function are introduced into the molecular structure of the polycarboxylate water reducer through polymerization to endow the polycarboxylate water reducer with the defoaming function. That is, first prepare the defoaming type functional monomer containing siloxane and polyether side chain, and then make the defoaming type functional monomer, polyether macromonomer and unsaturated carboxylic acid and / or its derivatives are subjected to aqueous radical polymerization reaction to obtain a polycarboxylate water reducer with defoaming function.
根据本发明示例性实施例的具有消泡功能的聚羧酸减水剂的制备方法包括以下步骤：The preparation method of the polycarboxylate water reducer with defoaming function according to an exemplary embodiment of the present invention comprises the following steps:
1)消泡型功能单体的制备：在装有搅拌杆、恒压滴液漏斗和温度计的三口瓶中加入聚醚改性硅油，将所述聚醚改性硅油加热至60～100℃，在1～2小时内通过恒压滴液漏斗向所述聚醚改性硅油中滴加含有酸类催化剂的不饱和羧酸或酰氯，滴加同时搅拌，滴加完毕后继续酯化反应1～2小时，或者将酸酐加入聚醚改性硅油中分散溶解并加热进行酯化反应1～2小时，反应后得到含硅氧烷和聚醚侧链的消泡型功能单体。1) Preparation of defoaming functional monomer: Add polyether-modified silicone oil into a three-necked bottle equipped with a stirring rod, a constant-pressure dropping funnel, and a thermometer, and heat the polyether-modified silicone oil to 60-100°C. Add unsaturated carboxylic acid or acyl chloride containing an acid catalyst to the polyether modified silicone oil dropwise through a constant pressure dropping funnel within 1 to 2 hours, stir while adding dropwise, and continue the esterification reaction after the dropwise addition is completed for 1~ 2 hours, or add the acid anhydride into the polyether modified silicone oil to disperse and dissolve and heat for 1 to 2 hours for esterification reaction, after the reaction, a defoaming type functional monomer containing siloxane and polyether side chains is obtained.
2)聚羧酸减水剂的制备：在装有搅拌杆、恒压滴液漏斗和温度计的四口瓶中加入所述消泡型功能单体、聚醚大单体和水，加热至40～60℃，搅拌溶解，形成溶液A；在1.5～3.5小时以内通过恒压滴液漏斗向溶液A中滴加由不饱和羧酸和/或其衍生物、引发剂、链转移剂和水配成的混合溶液B，滴加完毕后在40～60℃继续反应1.5～2.0小时，反应结束后降温至40℃以下，用碱性物质水溶液中和，调节溶液pH至中性，制得具有消泡功能的聚羧酸减水剂。2) Preparation of polycarboxylate water reducer: add the defoaming type functional monomer, polyether macromonomer and water into a four-necked bottle equipped with a stirring rod, a constant pressure dropping funnel and a thermometer, and heat to 40 ~60°C, stirring and dissolving to form solution A; within 1.5 to 3.5 hours, dropwise add the unsaturated carboxylic acid and/or its derivatives, initiator, chain transfer agent and water to the solution A through the constant pressure dropping funnel. The resulting mixed solution B was continued to react at 40-60°C for 1.5-2.0 hours after the completion of the dropwise addition. After the reaction was completed, the temperature was lowered to below 40°C, neutralized with an aqueous solution of an alkaline substance, and the pH of the solution was adjusted to neutral to obtain a Polycarboxylate superplasticizer with foam function.
以上，如果酯化反应两个反应物是酸和醇的话，必须加酸类催化剂，且需要较高温度，通常在100℃左右。如果反应物是活性较高的酸酐或酰氯，反应过程不需要催化剂，且在较低温度就可进行反应。例如，酰氯直接滴加至聚醚改性硅油中。Above, if the two reactants of the esterification reaction are acid and alcohol, an acid catalyst must be added, and a higher temperature is required, usually around 100°C. If the reactant is an acid anhydride or acid chloride with higher activity, no catalyst is needed in the reaction process, and the reaction can be carried out at a lower temperature. For example, acid chlorides are directly added dropwise to polyether-modified silicone oil.
将不饱和羧酸和酸类催化剂、或酰氯滴加至所述聚醚改性硅油中的原因是因为摩尔比接近的时候，聚醚硅油分子量大，质量就大，滴加的时候为了方便操作，是少量液体滴入大量液体中。另一个方面是少量酸或酰氯与大量聚醚硅油接触，处于“饥饿”状态，避免酯化更多聚醚硅油链段上的羟基，以免形成交联结构。The reason for adding unsaturated carboxylic acid and acid catalyst, or acid chloride to the polyether modified silicone oil dropwise is because when the molar ratio is close, the polyether silicone oil has a large molecular weight and a large quality. , is a small amount of liquid dropped into a large amount of liquid. Another aspect is that a small amount of acid or acid chloride is in contact with a large amount of polyether silicone oil and is in a "starved" state to avoid esterification of more hydroxyl groups on the polyether silicone oil chain segment to avoid the formation of a cross-linked structure.
“在1～2小时内通过恒压滴液漏斗向所述聚醚改性硅油中滴加含有酸类催化剂的不饱和羧酸或酰氯”，这里，关于滴加时间，在不影响产物结构和性能的前提下时间越短越好，缩短流程，节约成本。但是滴太快容易分散不均匀，或者反应过快，与多个羟基反应。"Add unsaturated carboxylic acid or acyl chloride containing an acid catalyst to the polyether modified silicone oil dropwise through a constant pressure dropping funnel within 1 to 2 hours", here, regarding the dropping time, without affecting the product structure and Under the premise of performance, the shorter the time, the better, shorten the process and save costs. However, if the drop is too fast, it is easy to disperse unevenly, or the reaction is too fast, and it reacts with multiple hydroxyl groups.
滴加完毕后继续酯化反应1～2小时，在节省时间的前提下保证转化率。After the dropwise addition, continue the esterification reaction for 1 to 2 hours to ensure the conversion rate under the premise of saving time.
其中，所述不饱和羧酸为丙烯酸、甲基丙烯酸、丁烯酸、2-丁烯酸中的至少一种，所述酰氯为丙烯酰氯、甲基丙烯酰氯中的至少一种，所述酸酐为顺丁烯二酸酐，所述酸类催化剂为浓硫酸和/或对甲苯磺酸。Wherein, the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, crotonic acid, and 2-butenoic acid, the acid chloride is at least one of acryloyl chloride and methacryloyl chloride, and the acid anhydride is maleic anhydride, and the acid catalyst is concentrated sulfuric acid and/or p-toluenesulfonic acid.
因为衍生物有很多种，包括酯类、酰胺类，例如，甲基丙烯酸甲酯、丙烯酰胺，其跟醇类的反应较为复杂，一般酯化单体选择酸、酸酐或者酰氯。因此，在步骤(1)制备单体的时候，采用不饱和羧酸、酸酐或者酰氯，酰氯和酸酐酯化反应的时候不用加催化剂，在步骤(2)制备减水剂的时候，由于是自由基聚合，溶液B中可以是不饱和羧酸和/或其衍生物(包括酸酐)。Because there are many kinds of derivatives, including esters and amides, such as methyl methacrylate and acrylamide, the reaction with alcohols is more complicated, and the esterification monomer generally chooses acid, acid anhydride or acid chloride. Therefore, when the monomer is prepared in step (1), unsaturated carboxylic acid, acid anhydride or acid chloride is used, and no catalyst is added when the acid chloride and acid anhydride are esterified. When the water reducer is prepared in step (2), since it is free Based polymerization, solution B may be unsaturated carboxylic acid and/or its derivatives (including acid anhydride).
所述聚醚改性硅油为Si-C型结构，且具有一定的消泡功能。The polyether modified silicone oil has a Si-C structure and has a certain defoaming function.
所述引发剂为过硫酸铵、过硫酸钾、抗坏血酸与过硫酸铵、抗坏血酸与过硫酸钾、或者抗坏血酸与双氧水。即过硫酸铵、过硫酸钾都可以单独做引发剂，自身可以进行氧化还原反应，此时反应温度较高，也可与还原剂抗坏血酸一起使用，此时温度较低。双氧水只能与抗坏血酸一起使用。聚醚大单体溶解完全之后，向其溶液中加入氧化剂双氧水、过硫酸铵或过硫酸钾继续搅拌，还原剂抗坏血酸溶于不饱和羧酸和/或其衍生物溶液中。The initiator is ammonium persulfate, potassium persulfate, ascorbic acid and ammonium persulfate, ascorbic acid and potassium persulfate, or ascorbic acid and hydrogen peroxide. That is, both ammonium persulfate and potassium persulfate can be used as initiators alone, and can carry out redox reactions by themselves, and the reaction temperature is higher at this time, and they can also be used together with reducing agent ascorbic acid, and the temperature is lower at this time. Hydrogen peroxide should only be used with ascorbic acid. After the polyether macromonomer is completely dissolved, the oxidant hydrogen peroxide, ammonium persulfate or potassium persulfate is added to the solution to continue stirring, and the reducing agent ascorbic acid is dissolved in the solution of the unsaturated carboxylic acid and/or its derivatives.
所述链转移剂为巯基丙酸、巯基乙酸、甲基丙烯磺酸钠和苯乙烯磺酸钠中的至少一种。The chain transfer agent is at least one of mercaptopropionic acid, mercaptoacetic acid, sodium methacrylate and sodium styrene sulfonate.
所述碱性物质为氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。The alkaline substance is at least one of sodium hydroxide, potassium hydroxide and calcium hydroxide.
所述聚醚大单体为分子量2200～2800的异戊烯醇聚氧乙烯聚氧丙烯醚、甲基烯丙基聚氧乙烯聚氧丙烯醚和4-羟丁基乙烯基聚氧乙烯聚氧丙烯醚中的至少一种。The polyether macromonomer is isopentenol polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene polyoxypropylene ether and 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether with a molecular weight of 2200-2800. at least one of propylene ethers.
聚醚改性硅油与不饱和羧酸的摩尔比为1：1.05～1：1.10，所述酸类催化剂占所述聚醚改性硅油与不饱和羧酸总摩尔数的0.5％～3.0％，所述聚醚改性硅油与酰氯的摩尔比为1：1.05～1：1.10，所述聚醚改性硅油与酸酐的摩尔比为1：1.05～1：1.10。The molar ratio of polyether-modified silicone oil to unsaturated carboxylic acid is 1:1.05-1:1.10, and the acid catalyst accounts for 0.5%-3.0% of the total moles of polyether-modified silicone oil and unsaturated carboxylic acid, The molar ratio of the polyether modified silicone oil to the acid chloride is 1:1.05˜1:1.10, and the molar ratio of the polyether modified silicone oil to the acid anhydride is 1:1.05˜1:1.10.
所述步骤(2)中的原料重量份为：消泡型功能单体4.0～24.4份，聚醚大单体300～400份，水200～260份；不饱和羧酸和/或其衍生物40～60份，引发剂0.3～3.0份，链转移剂1.0～4.0份，水180～240份。The weight parts of raw materials in the step (2) are: 4.0-24.4 parts of defoaming functional monomer, 300-400 parts of polyether macromonomer, 200-260 parts of water; unsaturated carboxylic acid and/or its derivatives 40-60 parts, 0.3-3.0 parts of initiator, 1.0-4.0 parts of chain transfer agent, 180-240 parts of water.
根据本发明示例性实施例的消泡型功能单体的制备方法即采用上述步骤1)。本发明中所制备的消泡型功能单体引入硅氧烷及聚醚链段结构，具有更优异的消泡功能，且结构中不含Si-O-C结构，结构性能稳定。本发明中所制备的消泡型功能单体的分子结构式为：The preparation method of the defoaming type functional monomer according to the exemplary embodiment of the present invention adopts the above step 1). The defoaming type functional monomer prepared in the present invention introduces siloxane and polyether segment structure, has more excellent defoaming function, does not contain Si-O-C structure in the structure, and has stable structure and performance. The molecular structural formula of the defoaming type functional monomer prepared in the present invention is:
将消泡型功能单体引入聚合体系，所制备的聚羧酸减水剂具有减水、消泡一体的功能，避免复配所出现的相容性和稳定性等问题。The defoaming functional monomer is introduced into the polymerization system, and the prepared polycarboxylate superplasticizer has the functions of water reduction and defoaming, and avoids the problems of compatibility and stability in compounding.
为了更好地理解本发明的上述示例性实施例，下面结合具体示例对其进行进一步说明。In order to better understand the above exemplary embodiments of the present invention, it will be further described below in conjunction with specific examples.
示例1Example 1
1)含硅氧烷和聚醚侧链消泡型功能单体的制备：在装有搅拌杆、恒压滴液漏斗和温度计的三口瓶中加入500重量份的聚醚改性硅油，加热至90℃。在7.9重量份丙烯酸中加入0.1重量份的98wt％的浓硫酸并在2小时通过恒压滴液漏斗向聚醚改性硅油中滴加，搅拌，滴加完毕后继续反应2小时，得到含硅氧烷和聚醚侧链的消泡型功能单体SPA-1。1) Preparation of defoaming type functional monomer containing siloxane and polyether side chain: Add 500 parts by weight of polyether modified silicone oil into a three-necked bottle equipped with a stirring rod, a constant pressure dropping funnel and a thermometer, and heat to 90°C. Add 0.1 parts by weight of 98 wt% concentrated sulfuric acid to 7.9 parts by weight of acrylic acid and add it dropwise to polyether modified silicone oil through a constant pressure dropping funnel in 2 hours, stir, and continue to react for 2 hours after the dropwise addition to obtain silicon-containing Antifoaming functional monomer SPA-1 of oxane and polyether side chain.
2)具有消泡功能的聚羧酸减水剂的制备：在装有搅拌杆、恒压滴液漏斗和温度计的四口瓶中加入4.0重量份的消泡型功能单体SPA-1、300重量份异戊烯醇聚氧乙烯聚氧丙烯醚和200重量份水，升温至60℃，搅拌溶解；将40重量份丙烯酸、0.3重量份过硫酸铵、1.0重量份甲基丙烯磺酸钠和180重量份水配成混合溶液，在1.5小时以内通过恒压滴液漏斗滴完，然后在60℃继续反应1.5小时；反应结束后降温至40℃以下，用氢氧化钠水溶液中和，调节溶液pH至中性，制得具有消泡功能的聚羧酸减水剂。2) Preparation of polycarboxylate water reducer with defoaming function: Add 4.0 parts by weight of defoaming functional monomer SPA-1, 300 Parts by weight of prenyl alcohol polyoxyethylene polyoxypropylene ether and 200 parts by weight of water are heated to 60°C and stirred to dissolve; 40 parts by weight of acrylic acid, 0.3 parts by weight of ammonium persulfate, 1.0 parts by weight of sodium methacrylate 180 parts by weight of water is made into a mixed solution, which is dropped through a constant pressure dropping funnel within 1.5 hours, and then the reaction is continued at 60°C for 1.5 hours; after the reaction is completed, the temperature is lowered to below 40°C, neutralized with aqueous sodium hydroxide solution, and the solution is adjusted pH to neutral to prepare polycarboxylate water reducer with defoaming function.
示例2Example 2
1)含硅氧烷和聚醚侧链消泡型功能单体的制备：在装有搅拌杆、恒压滴液漏斗和温度计的三口瓶中加入500重量份的聚醚改性硅油，称取10.3重量份顺丁烯二酸酐加入聚醚改性硅油中分散溶解，加热至60℃，搅拌，反应1小时，得到含硅氧烷和聚醚侧链的消泡型功能单体SPA-2。1) Preparation of defoaming type functional monomer containing siloxane and polyether side chain: Add 500 parts by weight of polyether modified silicone oil into a three-necked bottle equipped with a stirring rod, a constant pressure dropping funnel and a thermometer, and weigh Add 10.3 parts by weight of maleic anhydride to polyether-modified silicone oil to disperse and dissolve, heat to 60°C, stir, and react for 1 hour to obtain the defoaming functional monomer SPA-2 containing siloxane and polyether side chains.
2)具有消泡功能的聚羧酸减水剂的制备：在装有搅拌杆、恒压滴液漏斗和温度计的四口瓶中加入6.5重量份的消泡型功能单体SPA-2、360重量份甲基烯丙基聚氧乙烯聚氧丙烯醚和240重量份水，升温至45℃，搅拌溶解；将45重量份甲基丙烯酸、15重量份甲基丙烯酸甲酯，0.5重量份抗坏血酸、3.5重量份巯基乙酸和220重量份水配成混合溶液，在2.5小时以内通过恒压滴液漏斗滴完(滴加之前在大单体溶液中加入2.5份过硫酸钾，搅拌溶解10分钟)，并在45℃继续反应1.5小时；反应结束后降温至40℃以下，用氢氧化钾水溶液中和，调节溶液pH至中性，制得具有消泡功能的聚羧酸减水剂。2) Preparation of polycarboxylate water reducer with defoaming function: Add 6.5 parts by weight of defoaming functional monomer SPA-2, 360 Parts by weight of methallyl polyoxyethylene polyoxypropylene ether and 240 parts by weight of water are heated to 45°C and stirred to dissolve; 45 parts by weight of methacrylic acid, 15 parts by weight of methyl methacrylate, 0.5 parts by weight of ascorbic acid, 3.5 parts by weight of mercaptoacetic acid and 220 parts by weight of water are made into mixed solution, drop by constant pressure dropping funnel within 2.5 hours (add 2.5 parts of potassium persulfate in macromonomer solution before dropping, stir and dissolve 10 minutes), And continue to react at 45°C for 1.5 hours; after the reaction, cool down to below 40°C, neutralize with potassium hydroxide aqueous solution, adjust the pH of the solution to neutral, and prepare a polycarboxylate water reducer with defoaming function.
示例3Example 3
1)含硅氧烷和聚醚侧链消泡型功能单体的制备：在装有搅拌杆、恒压滴液漏斗和温度计的三口瓶中加入500重量份的聚醚改性硅油，加热至100℃。在9.5重量份甲基丙烯酸中加入0.6重量份的98wt％的浓硫酸并在2小时通过恒压滴液漏斗向聚醚改性硅油中滴加，搅拌，滴加完毕后继续反应2小时，得到含硅氧烷和聚醚侧链的消泡型功能单体SPA-3。1) Preparation of defoaming type functional monomer containing siloxane and polyether side chain: Add 500 parts by weight of polyether modified silicone oil into a three-necked bottle equipped with a stirring rod, a constant pressure dropping funnel and a thermometer, and heat to 100°C. In 9.5 parts by weight of methacrylic acid, add 0.6 parts by weight of 98wt% concentrated sulfuric acid and add dropwise to polyether modified silicone oil through a constant pressure dropping funnel in 2 hours, stir, and continue to react for 2 hours after the dropwise addition is completed, to obtain Defoaming functional monomer SPA-3 containing siloxane and polyether side chains.
2)具有消泡功能的聚羧酸减水剂的制备：在装有搅拌杆、恒压滴液漏斗和温度计的四口瓶中加入24.4重量份的消泡型功能单体SPA-3、400重量份4-羟丁基乙烯基聚氧乙烯聚氧丙烯醚中和260重量份水，升温至40℃，搅拌溶解；将52重量份甲基丙烯酸，0.7重量份抗坏血酸、3.0重量份巯基丙酸和220重量份水配成混合溶液，在3.5小时以内通过恒压滴液漏斗滴完(滴加之前在大单体溶液中加入3.0份30％质量浓度的双氧水，搅拌10分钟)，并在40℃继续反应2.0小时；反应结束后降温至40℃以下，用氢氧化钙水溶液中和，调节溶液pH至中性，制得具有消泡功能的聚羧酸减水剂。2) Preparation of polycarboxylate water reducer with defoaming function: Add 24.4 parts by weight of defoaming functional monomer SPA-3, 400 Parts by weight of 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether neutralize 260 parts by weight of water, heat up to 40 ° C, stir and dissolve; 52 parts by weight of methacrylic acid, 0.7 parts by weight of ascorbic acid, 3.0 parts by weight of mercaptopropionic acid Be made into mixed solution with 220 parts by weight of water, drop by constant pressure dropping funnel within 3.5 hours (add the hydrogen peroxide of 3.0 parts of 30% mass concentration in macromonomer solution before dropping, stir 10 minutes), and in 40 ℃ to continue the reaction for 2.0 hours; after the reaction, cool down to below 40 ℃, neutralize with calcium hydroxide aqueous solution, adjust the pH of the solution to neutral, and obtain a polycarboxylate superplasticizer with defoaming function.
示例4Example 4
1)含硅氧烷和聚醚侧链消泡型功能单体的制备：在装有搅拌杆、恒压滴液漏斗和温度计的三口瓶中加入500重量份的聚醚改性硅油，加热至60℃。将9.9重量份丙烯酰氯在2小时通过恒压滴液漏斗向聚醚改性硅油中滴加，搅拌，滴加完毕后继续反应1小时，得到含硅氧烷和聚醚侧链的消泡型功能单体SPA-4。1) Preparation of defoaming type functional monomer containing siloxane and polyether side chain: Add 500 parts by weight of polyether modified silicone oil into a three-necked bottle equipped with a stirring rod, a constant pressure dropping funnel and a thermometer, and heat to 60°C. Add 9.9 parts by weight of acryloyl chloride dropwise to the polyether modified silicone oil through a constant pressure dropping funnel in 2 hours, stir, and continue to react for 1 hour after the dropwise addition, to obtain a defoaming type containing siloxane and polyether side chains. Functional monomer SPA-4.
2)具有消泡功能的聚羧酸减水剂的制备：在装有搅拌杆、恒压滴液漏斗和温度计的四口瓶中加入8.1重量份的消泡型功能单体SPA-4、390重量份4-羟丁基乙烯基聚氧乙烯聚氧丙烯醚中和240重量份水，升温至40℃，搅拌溶解；将50重量份丙烯酸，0.6重量份抗坏血酸、2.3重量份巯基丙酸和220重量份水配成混合溶液，在3.0小时以内通过恒压滴液漏斗滴完(滴加之前在大单体溶液中加入2.8份30％质量浓度的双氧水，搅拌10分钟)，并在40℃继续反应1.5小时；反应结束后降温至40℃以下，用氢氧化钙水溶液中和，调节溶液pH至中性，制得具有消泡功能的聚羧酸减水剂。2) Preparation of polycarboxylate water reducer with defoaming function: Add 8.1 parts by weight of defoaming functional monomer SPA-4, 390 Parts by weight of 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether neutralize 240 parts by weight of water, heat up to 40 ° C, stir and dissolve; 50 parts by weight of acrylic acid, 0.6 parts by weight of ascorbic acid, 2.3 parts by weight of mercaptopropionic acid and 220 parts by weight Parts by weight of water are made into a mixed solution, which is dropped through a constant pressure dropping funnel within 3.0 hours (add 2.8 parts of 30% mass concentration of hydrogen peroxide in the macromonomer solution before the dropwise addition, and stir for 10 minutes), and continue at 40°C React for 1.5 hours; after the reaction, cool down to below 40°C, neutralize with calcium hydroxide aqueous solution, adjust the pH of the solution to neutral, and prepare a polycarboxylate water reducer with defoaming function.
以上示例1-4所制备具有消泡功能的聚羧酸减水剂的实验数据如下表所示。表1为示例1-4所得聚羧酸减水剂的净浆流动度测试结果，根据GB/T8077-2012混凝土外加剂匀质性试验方法，水胶比为0.29。表2为混凝土配合比，表3为混凝土实验数据。以上实验中减水剂掺量(按有效固体算)都为胶凝材料的0.2％。The experimental data of the polycarboxylate water reducer with defoaming function prepared in the above examples 1-4 are shown in the table below. Table 1 shows the test results of the net slurry fluidity of the polycarboxylate superplasticizer obtained in Examples 1-4. According to the GB/T8077-2012 test method for homogeneity of concrete admixtures, the water-binder ratio is 0.29. Table 2 is the concrete mix ratio, and Table 3 is the concrete experimental data. In the above experiments, the dosage of water reducer (calculated as effective solid) is 0.2% of the gelling material.
表1示例1-4所得聚羧酸减水剂的净浆流动度The net pulp fluidity of table 1 example 1-4 gained polycarboxylate superplasticizer
表2混凝土配合比Table 2 concrete mix ratio
表3混凝土实验数据Table 3 concrete experimental data
从表1可以看出，本申请的聚羧酸减水剂初始净浆流动度≥300,1小时后其净浆流动度≥270。It can be seen from Table 1 that the initial pulp fluidity of the polycarboxylate superplasticizer of the present application is ≥300, and its clean pulp fluidity is ≥270 after 1 hour.
从表3可以看出，采用本申请的减水剂后，混凝土的减水率≥31％，含气量≤2.6％，3天的抗压强度比≥224，7天的抗压强度比≥190，3天的抗压强度比≥133。It can be seen from Table 3 that after using the water reducing agent of this application, the water reducing rate of concrete is ≥ 31%, the air content is ≤ 2.6%, the compressive strength ratio of 3 days is ≥ 224, and the compressive strength ratio of 7 days is ≥ 190 , 3-day compressive strength ratio ≥ 133.
综上所述，本发明的聚羧酸减水剂在不影响减水效果的前提下，赋予减水剂消泡的功能，即保证制备的混凝土流动性、施工性的基础上，消除混凝土内残留气泡。本发明中所制备的消泡型功能单体引入硅氧烷结构，具有更优异的消泡功能，且结构中不含Si-O-C结构，从而避免因Si-O-C结构水解出现的稳定性问题。将其引入聚合体系，所制备的含硅基团的具有消泡功能的的聚羧酸减水剂具有减水、消泡一体的功能，避免复配所出现的相容性和稳定性等问题。In summary, the polycarboxylate water-reducer of the present invention endows the water-reducer with the function of defoaming without affecting the water-reducing effect, that is, on the basis of ensuring the fluidity and constructability of the prepared concrete, it eliminates the Air bubbles remain. The defoaming type functional monomer prepared in the present invention is introduced into a siloxane structure, which has a more excellent defoaming function, and does not contain a Si-O-C structure in the structure, thereby avoiding the stability problem caused by the hydrolysis of the Si-O-C structure. Introduce it into the polymerization system, and the prepared polycarboxylate superplasticizer containing silicon groups with defoaming function has the functions of water reduction and defoaming, avoiding the problems of compatibility and stability in compounding .
尽管上面已经通过结合示例性实施例描述了本发明，但是本领域技术人员应该清楚，在不脱离权利要求所限定的精神和范围的情况下，可对本发明的示例性实施例进行各种修改和改变。Although the present invention has been described above in conjunction with the exemplary embodiments, it should be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope defined in the claims. Change.
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| CN112159151A (en) * | 2020-10-16 | 2021-01-01 | 吉安市金羧科技有限公司 | Pumping agent and preparation method thereof |
| CN113501918A (en) * | 2021-09-08 | 2021-10-15 | 江苏福吉利亚建材有限公司 | Easily-stored high-performance polycarboxylate superplasticizer and preparation method thereof |
| CN114276550A (en) * | 2021-12-22 | 2022-04-05 | 东南大学 | Organic-inorganic composite additive for fair-faced concrete and preparation method and application thereof |
| CN115368517A (en) * | 2022-09-30 | 2022-11-22 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylic acid water reducing agent |
| CN115611565A (en) * | 2022-09-07 | 2023-01-17 | 云南筑辉建材有限公司 | Formula and preparation method of novel nano composite material UHPC |
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| CN111019054A (en) * | 2019-11-25 | 2020-04-17 | 中建西部建设股份有限公司 | A kind of low air entraining polycarboxylate water reducing agent and preparation method thereof |
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| CN113501918A (en) * | 2021-09-08 | 2021-10-15 | 江苏福吉利亚建材有限公司 | Easily-stored high-performance polycarboxylate superplasticizer and preparation method thereof |
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| CN114276550A (en) * | 2021-12-22 | 2022-04-05 | 东南大学 | Organic-inorganic composite additive for fair-faced concrete and preparation method and application thereof |
| CN115611565A (en) * | 2022-09-07 | 2023-01-17 | 云南筑辉建材有限公司 | Formula and preparation method of novel nano composite material UHPC |
| CN115368517A (en) * | 2022-09-30 | 2022-11-22 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylic acid water reducing agent |
| CN115368517B (en) * | 2022-09-30 | 2024-10-15 | 安徽海螺材料科技股份有限公司 | Preparation method of siloxane modified polyether and solid polycarboxylate superplasticizer |
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