CN106519143A - Preparation method of star-shaped polycarboxylate water reducer - Google Patents
Preparation method of star-shaped polycarboxylate water reducer Download PDFInfo
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- CN106519143A CN106519143A CN201611177921.0A CN201611177921A CN106519143A CN 106519143 A CN106519143 A CN 106519143A CN 201611177921 A CN201611177921 A CN 201611177921A CN 106519143 A CN106519143 A CN 106519143A
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- double bond
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 54
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- -1 polyoxylethylene Polymers 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- JCYTWBDAGJLEEB-UHFFFAOYSA-N hex-1-ene-3,3-diol Chemical compound CCCC(O)(O)C=C JCYTWBDAGJLEEB-UHFFFAOYSA-N 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 3
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims 2
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007983 Tris buffer Substances 0.000 abstract 2
- 239000002667 nucleating agent Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- BPQLWNNZYOMGGK-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;propanoic acid Chemical compound CCC(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O BPQLWNNZYOMGGK-BTVCFUMJSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 1
- 229960005205 prednisolone Drugs 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- JFVZTPIWVQKFFW-UHFFFAOYSA-N propanoate;tris(2-hydroxyethyl)azanium Chemical compound CCC([O-])=O.OCC[NH+](CCO)CCO JFVZTPIWVQKFFW-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
- 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
-
- 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
- C04B24/2605—Macromolecular compounds 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a preparation method of a star-shaped polycarboxylate water reducer and belongs to the technical field of polycarboxylate water reducers for concrete. According to the star-shaped polycarboxylate water reducer, double-bond monomers, a multi-perssad nucleating agent, an initiating agent and end double-bond polyoxylethylene ether are used as raw materials and subjected to a polymeric reaction to obtain the star-shaped polycarboxylate water reducer. According to the technical scheme provided by the invention, pentaerythritol tris(3-mercaptopropionic acid)ester, triethanolamine tris(3-mercaptopropionic acid)ester, glucose tetra(3-mercaptopropionic acid)ester and ethylene diamine(3-mercaptopropionic acid)ester serve as the nucleating agent, and the star-shaped polycarboxylate water reducer is prepared and obtained. The yield of a star-shaped structure can be increased. Meanwhile, the preparation method is simple in process and suitable for industrial production.
Description
Technical field
The present invention relates to concrete polycarboxylate water-reducer technical field, more particularly to a kind of star polycarboxylate water-reducer
Preparation method.
Background technology
Polycarboxylate water-reducer is big due to the molecular structure free degree, can carry out structure design according to required performance, is formed
Various polycarboxylic acids special products, can preferably meet the new demand that concrete is constantly proposed, thus with traditional diminishing
Agent is compared with powerful vitality.The polycarboxylate water-reducer of star-shaped molecule structure brings unlimited vigor for polycarboxylate water-reducer,
Raising for polycarboxylate water-reducer performance opens a fan gate, in practice it has proved that star polycarboxylate water-reducer molecule and comb shaped structure
Compare with higher water-reducing rate, more excellent function of slump protection and more preferable concrete workability.
The key of synthesis star polycarboxylate water-reducer is to obtain stable unidirectional growth group, is typically entered from three directions
Hand.One direction is that, using many radical initiators, such as CN104371077A is disclosed and closed using Transfer Radical Polymerization
Into star polycarboxylate water-reducer, there is initiator and prepare difficult, expensive shortcoming in the method；Another direction is using many
Group monomer, such as discloses methacrylic acid and polyalcohol and prepares the work of star polymerizable by esterification under catalyst action
Property end, then with polymeric monomer, molecular weight regulator, unsaturated carboxylic acid monomer in the presence of initiator pass through Raolical polymerizable
Prepared star polycarboxylate water-reducer, the method there are problems that easily forming cross-linked polymer, react uncontrollable；3rd direction is
Using many group chain terminations or chain-transferring agent, many radical chain transfer agents are referred in molecule to be had containing three or more than three
The group of chain transfer, also using glucose four (3- mercaptopropionic acids) ester, ethylenediamine tetraacetic (acetic acid -2- in prior art
Mercapto ethyl ester) can form four arm star structure polycarboxylate water-reducers, the method exist hub-and-spoke configuration yield it is low the drawbacks of.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of star polycarboxylate water-reducer, it is possible to increase
The yield of hub-and-spoke configuration, while the preparation method process is simple of the present invention, is adapted to industrialized production, makes in solving prior art
It is uncontrollable that the initiator that standby star polycarboxylate water-reducer is present prepares difficult, expensive, easily formation cross-linked polymer, reaction
Problem.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
The invention provides a kind of preparation method of star polycarboxylate water-reducer, comprises the following steps：
Double bond containing monomer, nucleator and water are mixed, monomer-nucleator mixed solution is obtained, the nucleator includes
Pentaerythrite three (3- mercaptopropionic acids) ester, triethanolamine three (3- mercaptopropionic acids) ester, four (3- mercaptopropionic acids) ester of glucose and second
One kind in diamines four (acetic acid -2- mercapto ethyl esters)；
Initiator solution is provided；
The terminal double bond APEO aqueous solution is provided；
The monomer-nucleator mixed solution and initiator solution are added drop-wise to into the terminal double bond APEO simultaneously
In the aqueous solution, polymerisation is carried out, obtain star polycarboxylate water-reducer.
Preferably, the quality of the double bond containing monomer, nucleator, initiator and terminal double bond APEO for [9,
15]：[0.5,2]：[0.5,2]：100.
Preferably, the terminal double bond APEO includes methyl allyl alcohol polyoxyethylene ether, prenol polyoxyethylene
One kind in ether and vinyl butanediol APEO.
Preferably, the mass concentration of the terminal double bond APEO aqueous solution is 30～70%.
Preferably, in the monomer-nucleator mixed solution, the total mass concentration of double bond containing monomer and nucleator is 30
～90%；The mass concentration of the initiator solution is 3～20%.
Preferably, the double bond containing monomer include acrylic acid, methacrylic acid, maleic anhydride, methylene-succinic acid and
One kind in fumaric acid.
Preferably, during the initiator is persulfate initiator, including ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate
It is a kind of.
Preferably, the speed that the monomer-nucleator mixed solution and initiator solution are added dropwise independently selected from 1.5～
3 hours.
Preferably, the temperature of the polymerisation is 50～90 DEG C.
The invention provides a kind of preparation method of star polycarboxylate water-reducer, with double bond containing monomer, nucleator, initiation
Agent, terminal double bond APEO and water are raw material, and star polycarboxylate water-reducer has been obtained by polymerisation, and the present invention is provided
Technical scheme with pentaerythrite three (3- mercaptopropionic acids) ester, triethanolamine three (3- mercaptopropionic acids) ester, four (3- sulfydryls of glucose
Propionic acid) ester and ethylenediamine tetraacetic (acetic acid -2- mercapto ethyl esters) be nucleator, has prepared star polycarboxylate water-reducer, preparation side
Method process is simple, is adapted to industrialized production, prepares the initiator system that star polycarboxylate water-reducer is present in solving prior art
It is standby it is difficult, expensive, easily form cross-linked polymer, react uncontrollable problem.
Description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Infrared spectrum spectrograms of the Fig. 1 for star-like polycarboxylate water-reducer obtained in the embodiment of the present invention.
Specific embodiment
The invention provides a kind of preparation method of star polycarboxylate water-reducer, comprises the following steps：
Double bond containing monomer, nucleator and water are mixed, monomer-nucleator mixed solution is obtained, the nucleator includes
Pentaerythrite three (3- mercaptopropionic acids) ester, triethanolamine three (3- mercaptopropionic acids) ester, four (3- mercaptopropionic acids) ester of glucose and second
One kind in diamines four (acetic acid -2- mercapto ethyl esters)；
Initiator solution is provided；
The terminal double bond APEO aqueous solution is provided；
The monomer-nucleator mixed solution and initiator solution are added drop-wise to into the terminal double bond APEO simultaneously
In the aqueous solution, polymerisation is carried out, obtain star-like polycarboxylate water-reducer.
Double bond containing monomer, nucleator and water are mixed by the present invention, obtain monomer-nucleator mixed solution.In the present invention
In, in the monomer-nucleator mixed solution, the total mass concentration of double bond containing monomer and nucleator is preferably 30～90%, more
It is preferred that 40～80%, most preferably 50～60%.
In the present invention, the double bond containing monomer is preferably acrylic acid, methacrylic acid, maleic anhydride, methylene fourth
One kind in diacid and fumaric acid.
In the present invention, the nucleator is preferably pentaerythrite three (3- mercaptopropionic acids) ester, three (3- sulfydryls of triethanolamine
Propionic acid) one kind in ester, four (3- mercaptopropionic acids) ester of glucose and ethylenediamine tetraacetic (acetic acid -2- mercapto ethyl esters).
The present invention provides initiator solution, and the mass concentration of the initiator solution is preferably 3～20%, more preferably
For 5～15%, most preferably 8～10%.
In the present invention, the initiator is preferably persulfate initiator, more preferably including ammonium persulfate, sodium peroxydisulfate
With the one kind in potassium peroxydisulfate.
The present invention provides the terminal double bond APEO aqueous solution, the mass concentration of the terminal double bond APEO aqueous solution
Preferably 30～70%, more preferably 40～60%, most preferably 50～55%.
In the present invention, the terminal double bond APEO preferably includes methyl allyl alcohol polyoxyethylene ether, prenol
One kind in APEO and vinyl butanediol APEO.
In the present invention, the methyl allyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether and vinyl butanediol
The degree of polymerization of APEO is independently preferably 20～75, more preferably 30～60, most preferably 40～55.
After obtaining monomer-nucleator mixed solution, initiator solution and the APEO aqueous solution, the present invention will be described
Monomer-nucleator mixed solution and initiator solution are added drop-wise in the APEO aqueous solution simultaneously, carry out being polymerized instead
Should, obtain star-like polycarboxylate water-reducer.
In the present invention, the mass ratio of the double bond containing monomer, nucleator, initiator and terminal double bond APEO is excellent
Elect [9,15] as：[0.5,2]：[0.5,2]：100, more preferably [10,13]：[1,1.5]：[1,1.5]：100, most preferably
[11,12]：[1.1,1.3]：[1.1,1.3]：100.
In the present invention, when the monomer-nucleator mixed solution and initiator solution are added dropwise, monomer-nucleator is mixed
The temperature for closing solution and initiator solution preferably independently is selected from 50～75 DEG C, more preferably 55～70 DEG C, and most preferably 60～65
℃；The speed that the monomer-nucleator mixed solution and initiator solution are added dropwise independently preferably is selected from 2.5～3.3kg/min,
More preferably 2.7～3kg/min.
In the present invention, to be added drop-wise to APEO water-soluble for the monomer-nucleator mixed solution and initiator solution
When in liquid, the temperature of the APEO aqueous solution is preferably 50～75 DEG C, more preferably 55～70 DEG C, and most preferably 60～65
℃。
In the present invention, to be added drop-wise to APEO water-soluble for the monomer-nucleator mixed solution and initiator solution
Polymerisation is carried out in liquid, the temperature of the polymerisation is preferably 50～90 DEG C, more preferably 60～80 DEG C, most preferably 70
～75 DEG C；After the monomer-nucleator mixed solution and initiator solution are added drop-wise to the APEO aqueous solution completely, after
Continuous to carry out isothermal holding, the temperature of the insulation is preferably 50～90 DEG C, more preferably 60～80 DEG C, and most preferably 70～75
DEG C, the time of the insulation is preferably 1～5h, most preferably more preferably 2～4h, 3～3.5h.
The present invention is added drop-wise to the APEO aqueous solution to the monomer-nucleator mixed solution and initiator solution
Mode does not have any special restriction, using dropwise addition mode well known to those skilled in the art；In embodiments of the present invention
It is preferred that being carried out by the way of being added dropwise using quantifier control.
The present invention does not have any special restriction to the device of the polymerisation, using well known to those skilled in the art
Polymerizing reactor；Preferably carry out in a kettle. in embodiments of the present invention.
After the polymerisation, the product of the polymerisation is preferably cooled to room temperature by the present invention, obtains star-like poly- carboxylic
Sour water reducer.In the present invention, in the present invention, the rate of temperature fall of the cooling is preferably 0.25～1 DEG C/min, more preferably
0.33～0.5 DEG C/min；The time for being cooled to room temperature needs is preferably 0.5～2h, more preferably 1～1.5h.
The present invention does not have to the source by double bond containing monomer, nucleator, initiator, terminal double bond APEO and water
There is any special restriction, using commercial goods well known to those skilled in the art.
The invention provides a kind of preparation method of star-like polycarboxylate water-reducer, with double bond containing monomer, nucleator, initiation
Agent, APEO and water are raw material, polymerisation occurs star-like polycarboxylate water-reducer, the technology that the present invention is provided has been obtained
Scheme preparation method process is simple, is adapted to industrialized production, prepares star polycarboxylate water-reducer and exist in solving prior art
Initiator prepare it is difficult, expensive, easily form cross-linked polymer, react uncontrollable problem.
The preparation method of the star-like polycarboxylate water-reducer provided to the present invention with reference to embodiment is described in detail,
But they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
In with stirring and the dropping tank measured, acrylic acid 135kg, pentaerythrite three (3- mercaptopropionic acids) ester are added
7.5kg and water 332.5kg, obtains monomer-nucleator mixed solution, standby after stirring and dissolving.
In another dropping tank with stirring and quantifier, ammonium persulfate 7.5kg and water 242.5kg is added, is drawn
Send out the agent aqueous solution, be heated to after stirring and dissolving 50 DEG C it is standby.
Isopentenol polyoxyethylene ether (n=20) 1500kg and water 3500kg are added in reactor, stirring is opened, is heated to
50℃.After bottom temperature control is accurate, while monomer-nucleator mixed solution and initiator solution is added dropwise, control is added dropwise
Speed is 3kg/min, be heated to after being added dropwise to complete 50 DEG C reaction 1h, obtain star-like polycarboxylate water-reducer, then with 0.33 DEG C/
The speed cooling 1.5h of min is cooled to room temperature, that is, obtain star-like polycarboxylate water-reducer.
Obtained star high performance water reducing agent of polyocarboxy acid is dried to constant weight in 80 DEG C of baking ovens, infrared spectrum survey is done in sampling
Examination, as a result as shown in Figure 1.From figure 1 it appears that 1685cm-1No absworption peak near place, illustrates that residual double bonds are less, gathers
Close reaction to be well on.Star-like water reducer is in 1727cm-1Place occurs in that ester group (- COO-) characteristic peak.1566cm-1And 1650cm-1
Place has obvious absworption peak to prove that star-type polymer side chain has the functional group of carboxylate, wherein 1566cm-1The strong suction in place
Receive the asymmetric stretching vibration peak that peak is C=O in acrylic acid, 1375cm-1Another strong absworption peak at place is carboxylate anion
Symmetrical stretching vibration peak, this has also further demonstrated that the presence of carboxylate functionality in polymer；3445cm-1Significantly inhale at place
Receive stretching vibration peak of the peak for hydroxyl；In 1456,1352cm-1And 2845cm-1Locate as-CH ,-CH2,-CH3Stretching vibration absorb
Peak；1115cm-1Stretching vibration peak of the characteristic absorption peak at place from-C-O-C in middle polyoxyethylene groups long-chain.Obtained star
The polycarboxylate water-reducer of structure, activity " core " surface of synthesis contain a large amount of polymerisable double bond ends, then by polycarboxylic-acid chemical combination
Thing polymerization is connected on " core " surface, can form the multi-arm copolymer of star, so as to ensure the anchoring with more high energy efficiency
Absorption affinity and side chain space steric effect.
Embodiment 2
In the dropping tank with stirring and quantifier, maleic anhydride 225kg, glucose four (3- mercaptopropionic acids) ester are added
30kg and water 280kg, obtains monomer-nucleator mixed solution, be heated to after stirring and dissolving 75 DEG C it is standby.
In another dropping tank with stirring and quantifier, sodium peroxydisulfate 30kg and water 120kg is added, initiator is obtained
The aqueous solution, be heated to after stirring and dissolving 75 DEG C it is standby.
Methyl allyl alcohol polyoxyethylene ether (n=75) 1500kg and water 2282kg are added in reactor, stirring, heating is opened
To 75 DEG C.After bottom temperature control is accurate, while monomer-nucleator mixed solution and initiator solution are added dropwise, control drop
Acceleration is 3kg/min, be heated to after being added dropwise to complete 90 DEG C reaction 5h, obtain star-like polycarboxylate water-reducer, then with 0.5 DEG C/
The speed cooling of min, 1.5h are cooled to room temperature, that is, obtain star-like polycarboxylate water-reducer.
Embodiment 3
In the dropping tank with stirring and quantifier, methacrylic acid 150kg, three (3- sulfydryls third of triethanolamine are added
Acid) ester 12.5kg and water 230kg, obtain monomer-nucleator mixed solution, be heated to after stirring and dissolving 55 DEG C it is standby.
In another dropping tank with stirring and quantifier, ammonium persulfate 12.5kg and water 296kg is added, is caused
The agent aqueous solution, be heated to after stirring and dissolving 60 DEG C it is standby.
Vinyl butanediol APEO (n=40) 1500kg and water 3682kg are added in reactor, stirring is opened, plus
Heat is to 65 DEG C.After bottom temperature control is accurate, while monomer-nucleator mixed solution and initiator solution are added dropwise, control
Rate of addition is 3kg/min, is heated to 60 DEG C of reaction 4h, obtains star-like polycarboxylate water-reducer, then with 0.33 after being added dropwise to complete
DEG C/cooling of the speed of min, 1.5h is cooled to room temperature, that is, obtains star-like polycarboxylate water-reducer.
Embodiment 4
By the star-like polycarboxylate water-reducer synthesized by embodiment 1, embodiment example 2 and embodiment example 3 in normal temperature (15～25
DEG C) under storage 30 days after, determine its implementation result.Flowing degree of net paste of cement is the hub-and-spoke configuration polycarboxylic acids for investigating present invention synthesis
The mobility of high-performance water reducing agent, test determine the paste flowing degree gradual loss under identical fluidity.GB/ is pressed in test
T8077-2000《Methods for testing uniformity of concrete admixture》Carry out.From existing commercially available traditional combed polycarboxylic-acid diminishing
Agent (comparative example) is as a comparison sample, and result of the test is shown in Table 1.
The rheological parameters' change with time test result of 1 flowing degree of net paste of cement of table
From table 1 it follows that the star-like polycarboxylate water-reducer synthesized by the inventive method is respectively provided with preferably net slurry just
Beginning divergence agent keeps good mobility, and its effect is more excellent than selected combed polycarboxylate water-reducer control sample.
By star-like polycarboxylate water-reducer obtained in the present embodiment and traditional combed poly carboxylic acid series water reducer respectively with concrete
Mixing, as shown in table 3, table 2 is detection concrete mix to test result, and cement is conch cement, and sandstone is the commercially available bone in Guizhou
Material, wherein sand are Machine-made Sand.
2 concrete material match ratio of table
3 polycarboxylate water-reducer concrete performance of table
From table 3 it can be seen that the star-like polycarboxylate water-reducer synthesized by the inventive method can table in concrete system
Reveal the holding performance of excellent divergence and the slump.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of star polycarboxylate water-reducer, it is characterised in that comprise the following steps：
Double bond containing monomer, nucleator and water are mixed, monomer-nucleator mixed solution is obtained, the nucleator includes season penta
Tetrol three (3- mercaptopropionic acids) ester, triethanolamine three (3- mercaptopropionic acids) ester, four (3- mercaptopropionic acids) ester of glucose and ethylenediamine
One kind in four (acetic acid -2- mercapto ethyl esters)；
Initiator solution is provided；
The terminal double bond APEO aqueous solution is provided；
The monomer-nucleator mixed solution and initiator solution are added drop-wise to into the terminal double bond APEO simultaneously water-soluble
In liquid, polymerisation is carried out, obtain star polycarboxylate water-reducer.
2. preparation method according to claim 1, it is characterised in that the double bond containing monomer, nucleator, initiator with
The quality of APEO is [9,15]：[0.5,2]：[0.5,2]：100.
3. preparation method according to claim 1 and 2, it is characterised in that the terminal double bond APEO includes methyl
One kind in allyl alcohol polyethenoxy ether, isopentenol polyoxyethylene ether and vinyl butanediol APEO.
4. preparation method according to claim 3, it is characterised in that the quality of the terminal double bond APEO aqueous solution
Concentration is 30～70%.
5. preparation method according to claim 2, it is characterised in that contain double bond in the monomer-nucleator mixed solution
Monomer and nucleator total mass concentration be 30～90%；
The mass concentration of the initiator solution is 3～20%.
6. preparation method according to claim 1 or 5, it is characterised in that the double bond containing monomer includes acrylic acid, first
One kind in base acrylic acid, maleic anhydride, methylene-succinic acid and fumaric acid.
7. preparation method according to claim 1 or 5, it is characterised in that the initiator is persulfate initiator.
8. the preparation method according to claim 1,4 or 5, it is characterised in that the monomer-nucleator mixed solution and draw
The speed of agent aqueous solution dropwise addition is sent out independently selected from 1.5～3 hours
9. preparation method according to claim 1, it is characterised in that the temperature of the polymerisation is 50～90 DEG C.
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| CN111560104A (en) * | 2020-06-29 | 2020-08-21 | 贵州师范学院 | Star polycarboxylic acid water reducing agent prepared by using tannic acid azo compound as initiator |
| CN111690101A (en) * | 2020-07-28 | 2020-09-22 | 陕西大开建材有限公司 | Strong-adaptability polycarboxylate superplasticizer with star-shaped long branched chain structure and preparation method thereof |
| CN111978487A (en) * | 2020-09-01 | 2020-11-24 | 广州市建筑科学研究院有限公司 | Homograph arm star type polycarboxylate superplasticizer and preparation method and application thereof |
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