CN106008854A - Preparation method of polycarboxylic acid water reducing agent - Google Patents
Preparation method of polycarboxylic acid water reducing agent Download PDFInfo
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- CN106008854A CN106008854A CN201610498950.0A CN201610498950A CN106008854A CN 106008854 A CN106008854 A CN 106008854A CN 201610498950 A CN201610498950 A CN 201610498950A CN 106008854 A CN106008854 A CN 106008854A
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- water
- unsaturated carboxylic
- carboxylic acid
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- polyethers
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 74
- 229920000570 polyether Polymers 0.000 claims abstract description 73
- 239000003999 initiator Substances 0.000 claims abstract description 43
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 229920005646 polycarboxylate Polymers 0.000 claims description 42
- 150000003254 radicals Chemical class 0.000 claims description 41
- 150000002148 esters Chemical class 0.000 claims description 29
- 150000001735 carboxylic acids Chemical class 0.000 claims description 25
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyoxy Polymers 0.000 claims description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 98
- 238000003756 stirring Methods 0.000 description 36
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 230000003467 diminishing effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- C04B2103/30—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 relates to the technical fields of building materials and cement concrete additives, particularly a preparation method of a polycarboxylic acid water reducing agent. The method comprises the following step: in the presence of water, a water-soluble chain-transfer agent and a free-radical initiator, carrying out reaction on the following substances at 5-45 DEG C: at least one unsaturated carboxylic acid, and at least one polyether with free hydroxyl capable of reacting with carboxyl functional group of the polymer formed by the unsaturated carboxylic acid. The preparation method of the polycarboxylic acid water reducing agent has the advantages of mild reaction and free selection of raw materials, and is convenient to operate.
Description
Technical field
The present invention relates to construction material and cement concrete admixture technical field, be specifically related to a kind of polycarboxylic acids
The preparation method of water reducer.
Background technology
Owing to poly-alkoxyl polycarboxylate (co) polymer (PCP) (also referred to as polycarboxylate water-reducer) has
Remarkable dispersive property so that concrete technology is able to rapid advances.Above-mentioned water reducer is for having pectinate texture
(co) polymer, its main polymeric chain comprises the side chain formed by polyether-type sequence that carboxyl carries.Existing
The preparation method having the polycarboxylate water-reducer in technology is the most at high temperature carried out, and reaction needs heating, needs pot
Stove or other heating sources, consersion unit requires height, needs enamel reaction still or stainless steel cauldron.Separately
Outward, also need to add slump retaining agent wherein to optimize the performance of water reducer, high to ingredient requirement, protect the diminishing that collapses
Polyethers is relatively fixed.
In consideration of it, overcome above defect of the prior art, it is provided that the preparation of a kind of new polycarboxylate water-reducer
Method becomes the technical problem that this area is urgently to be resolved hurrily.
Summary of the invention
Present invention aims to the drawbacks described above of prior art, it is provided that the system of a kind of polycarboxylate water-reducer
Preparation Method.
The purpose of the present invention can be realized by following technical measures:
A kind of preparation method of polycarboxylate water-reducer, compared with prior art, its difference is, water,
At a temperature of in the presence of water-soluble chain transfer agent and radical initiator, between 5 DEG C and 45 DEG C so that under
Row material reacts:
At least one unsaturated carboxylic acid；And
At least one polyethers, its carboxyl functional group with the polymer that can be formed with unsaturated carboxylic acid occurs
The free hydroxyl of reaction.
Preferably, this preparation method comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part is formed in water the unsaturated carboxylic that mass concentration is 25～100%
Acid solution；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
Being dropped to by unsaturated carboxylic acid solution in 1～8 hour in the first solution, in 1～8 hour will be from
Dropped to the first solution forms reactant liquor by base initiator solution；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
Preferably, described polyethers is 1:(1～8 with the mol ratio of unsaturated carboxylic acid)；Described water solublity chain tra nsfer
The quality of agent is (0.02～1.2) with the ratio of unsaturated carboxylic acid and the gross mass of polyethers: 100；Described freedom
The quality of base initiator is (0.01～15) with the ratio of unsaturated carboxylic acid and the gross mass of polyethers: 100.
Preferably, water, water-soluble chain transfer agent, radical initiator, unsaturated carboxylic acid and polyethers are formed
In polymeric system, solid content is 20～60%.
Preferably, unsaturated carboxylic acid is acrylic acid, and polyethers is methyl allyl alcohol polyoxyethylene ether or isopentene group
Polyoxyethylene ether or the mixture of the two.
Present invention also offers the preparation method of a kind of polycarboxylate water-reducer, compared with prior art, they are different
Part is, in the presence of water, water-soluble chain transfer agent and radical initiator, between 5 DEG C and 45 DEG C
At a temperature of so that following material reacts:
At least one unsaturated carboxylic acid；
At least one esters of unsaturated carboxylic acids, it is the ester that unsaturated carboxylic acid is formed with ethylene glycol；And
At least one polyethers, it has can be with the polymer of unsaturated carboxylic acid and esters of unsaturated carboxylic acids formation
The free hydroxyl that carboxyl functional group reacts.
Preferably, this preparation method comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part and esters of unsaturated carboxylic acids are formed in water the second solution, wherein,
In second solution, the mass concentration of unsaturated carboxylic acid is the matter of 25～100%, second esters of unsaturated carboxylic acids in solution
Amount concentration is 0～100%；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
In 1～8 hour, the second solution dropped in the first solution, in 1～8 hour, free radical drawn
Send out agent solution and drop to the first solution is formed reactant liquor；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
Preferably, described polyethers is 1:(1～8 with the mol ratio of unsaturated carboxylic acid)；Described water solublity chain tra nsfer
The quality of agent is (0.02～1.2) with the ratio of the gross mass of unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers:
100；The gross mass of the quality of described radical initiator and unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers
Ratio is (0.01～15): 100.
Preferably, water, water-soluble chain transfer agent, radical initiator, unsaturated carboxylic acid, unsaturated carboxylic acid
In the polymeric system that ester and polyethers are formed, solid content is 20～60%.
Preferably, unsaturated carboxylic acid is acrylic acid, and esters of unsaturated carboxylic acids is 2-(Acryloyloxy)ethanol, and polyethers is first
Base allyl alcohol polyethenoxy ether or isopentene group polyoxyethylene ether or the mixture of the two.
The preparation method reaction of the polycarboxylate water-reducer of the present invention is gentle, easy to operate, material choice free.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with being embodied as
The present invention is described in further detail by example.Should be appreciated that specific embodiment described herein only in order to
Explain the present invention, be not intended to limit the present invention.
For some problems in the presence of overcoming conventional polycarboxylate water-reducer to synthesize, such as: 1, heating, need
Want boiler or other heating sources；2, consersion unit requires height, enamel reaction still or stainless steel cauldron；
3, high to ingredient requirement, protect the diminishing polyethers that collapses and be relatively fixed.The present invention provides a kind of reaction gentleness, operation side
Just, raw material have relative to unrestricted choice simultaneously high diminishing, high-thin arch dam low temperature synthesis polycarboxylate water-reducer side
Method.
Above-mentioned target is to be realized by the preparation method of a kind of polycarboxylate water-reducer, in described preparation method
In, the temperature in the presence of water, water-soluble chain transfer agent and radical initiator, between 5 DEG C and 45 DEG C
Under so that following material reacts:
At least one unsaturated carboxylic acid；And
At least one polyethers, its carboxyl functional group with the polymer that can be formed with unsaturated carboxylic acid occurs
The free hydroxyl of reaction.
In one preferred embodiment, this preparation method specifically comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part is formed in water the unsaturated carboxylic that mass concentration is 25～100%
Acid solution；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
Being dropped to by unsaturated carboxylic acid solution in 1～8 hour in the first solution, in 1～8 hour will be from
Dropped to the first solution forms reactant liquor by base initiator solution；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
In aqueous, unsaturated carboxylic acid and polyethers are in water-soluble chain transfer agent and the effect of radical initiator
Under, the unsaturated bond polymerization in unsaturated carboxylic acid forms main chain, and main chain has carboxyl, and polyethers passes through carboxyl
It is bound on main chain form side chain.After completion of the reaction, add aqueous slkali and carry out pH value adjustment, pH value is adjusted
Whole is 6～8.
Drip alternatively, it is also possible to water-soluble chain transfer agent is made into together with mixed solution with radical initiator,
That is, this preparation method specifically comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively the unsaturated carboxylic acid of the first molar part is added to polyether solutions, form the first solution；
The unsaturated carboxylic acid of the second molar part is formed in water the unsaturated carboxylic that mass concentration is 25～100%
Acid solution；
Water-soluble chain transfer agent and radical initiator are formed the mixing that mass concentration is 10～50% in water
Solutions Solution；
Being dropped to by unsaturated carboxylic acid solution in 1～8 hour will be mixed in the first solution, in 1～8 hour
Close solution and drop to the first solution is formed reactant liquor；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
In a preferred embodiment, described polyethers is 1:(1～8 with the mol ratio of unsaturated carboxylic acid)；Institute
Stating the quality of water-soluble chain transfer agent with the ratio of unsaturated carboxylic acid and the gross mass of polyethers is (0.02～1.2):
100；The ratio of the gross mass of the quality of described radical initiator and unsaturated carboxylic acid and polyethers be (0.01～
15): 100.
In order to obtain better polycarboxylate water-reducer, water, water-soluble chain transfer agent, radical initiator,
In the polymeric system that unsaturated carboxylic acid and polyethers are formed, solid content is 20～60%.
In a preferred embodiment, unsaturated carboxylic acid is acrylic acid, and polyethers is methallyl alcohol polyoxy second
Alkene ether or isopentene group polyoxyethylene ether or the mixture of the two." radical initiator " in this specification
Refer to can produce the reagent of free radical in radical reaction, can be described as again free-radical initiator, be produced from by
The process of base becomes chain and causes.Conventional radical initiator has: Cl2, Br2, organic peroxide, as
Cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide etc.；Azo-initiator, such as azo
Bis-isobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.." water-soluble chain transfer agent " in this specification refers to effectively to make
The material of propagating radical generation radical transfer, in order to regulate the relative molecular mass of polymer, therefore again
Name relative nonlinear error.Adding response speed without big impact of chain-transferring agent, simply shorten chain
Length.Chain-transferring agent may be used for controlling the chain length of polymer, that is the degree of polymerization of control polymer,
Or the viscosity of polymer.Generally chain-transferring agent addition is the most, and the chain of polymer is the shortest, and viscosity is the least.
" water " in this specification refers to deionized water, refers to the pure water after eliminating in ionic species impurity.
In order to optimize the performance of polycarboxylate water-reducer, reducing and even avoid using slump retaining agent, the present invention is at main chain
Upper introducing hydroxyl ethyl ester, above-mentioned target is to be realized by the preparation method of a kind of polycarboxylate water-reducer, in institute
State in preparation method, in the presence of water, water-soluble chain transfer agent and radical initiator, at 5 DEG C and 45 DEG C
At a temperature of between so that following material reacts:
At least one unsaturated carboxylic acid；
At least one esters of unsaturated carboxylic acids, it is the ester that unsaturated carboxylic acid is formed with ethylene glycol；And
At least one polyethers, it has can be with the polymer of unsaturated carboxylic acid and esters of unsaturated carboxylic acids formation
The free hydroxyl that carboxyl functional group reacts.
In one preferred embodiment, this preparation method specifically comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part and esters of unsaturated carboxylic acids are formed in water the second solution, wherein,
In second solution, the mass concentration of unsaturated carboxylic acid is the matter of 25～100%, second esters of unsaturated carboxylic acids in solution
Amount concentration is 0～100%；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
In 1～8 hour, the second solution dropped in the first solution, in 1～8 hour, free radical drawn
Send out agent solution and drop to the first solution is formed reactant liquor；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
Drip alternatively, it is also possible to water-soluble chain transfer agent is made into together with mixed solution with radical initiator,
That is, this preparation method specifically comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively the unsaturated carboxylic acid of the first molar part is added to polyether solutions, form the first solution；
The unsaturated carboxylic acid of the second molar part and esters of unsaturated carboxylic acids are formed in water the second solution, wherein,
In second solution, the mass concentration of unsaturated carboxylic acid is the matter of 25～100%, second esters of unsaturated carboxylic acids in solution
Amount concentration is 0～100%；
Water-soluble chain transfer agent and radical initiator are formed the mixing that mass concentration is 10～50% in water
Solution；
In 1～8 hour, the second solution is dropped to mixed solution in the first solution, in 1～8 hour
Drop to the first solution is formed reactant liquor；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
In a preferred embodiment, described polyethers is 1:(1～8 with the mol ratio of unsaturated carboxylic acid)；Institute
State the quality of water-soluble chain transfer agent and the ratio of the gross mass of unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers
For (0.02～1.2): 100；The quality of described radical initiator and unsaturated carboxylic acid, esters of unsaturated carboxylic acids
It is (0.01～15) with the ratio of the gross mass of polyethers: 100.
In order to obtain better polycarboxylate water-reducer, water, water-soluble chain transfer agent, radical initiator,
In the polymeric system that unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers are formed, solid content is 20～60%.
In a preferred embodiment, unsaturated carboxylic acid is acrylic acid, and esters of unsaturated carboxylic acids is acrylic acid hydroxyl
Ethyl ester, polyethers is methyl allyl alcohol polyoxyethylene ether or isopentene group polyoxyethylene ether or the mixture of the two.
React complete and be directly added into alkaline conditioner adjustment system pH to 6～8 without cooling.
Embodiment 1
(room temperature is at 5-15 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 350 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 350 parts of water, stirring, to melting formation polyether solutions completely, adds 10 parts of propylene
Acid, after stirring 5min, adds 4 parts of chain-transferring agents, after stirring and dissolving, respectively 40 parts of acrylic acid of dropping and
The solution B that the acrylic acid aqueous solution A of 40 parts of water configurations and 2 parts of Ammonium persulfate .s and 150 parts of water configure, A is molten
The dropping duration of liquid and B solution is respectively 2 hours and 2.5 hours, and after dripping, insulation carries out copolymerization in 2 hours
Reaction, after question response, adds the sodium hydrate aqueous solution of 55 part 32%, adjusts system pH=6.2, stirring
10min, discharging obtains polycarboxylate water-reducer.
Embodiment 2
(room temperature 15-25 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 350 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 250 parts of water, stirring, to melting formation polyether solutions completely, adds 8 parts of propylene
Acid, after stirring 5min, adds 4 parts of chain-transferring agents, after stirring and dissolving, respectively 42 parts of acrylic acid of dropping and
The solution B that the acrylic acid aqueous solution A of 90 parts of water configurations and 2.2 parts of Ammonium persulfate .s and 200 parts of water configure, A
The dropping duration of solution and B solution is respectively 3 hours and 3.5 hours, and after dripping, insulation is carried out altogether for 2 hours
Poly-reaction, after question response, adds the sodium hydrate aqueous solution of 55 part 32%, adjusts system pH=6.2, stir
Mixing 10min, discharging obtains polycarboxylate water-reducer.
Embodiment 3
(room temperature ＞ 25 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 350 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 250 parts of water, stirring, to melting formation polyether solutions completely, adds 8 parts of propylene
Acid, after stirring 5min, adds 4.2 parts of chain-transferring agents, after stirring and dissolving, respectively 40 parts of acrylic acid of dropping and
The solution B that the acrylic acid aqueous solution A of 90 parts of water configurations and 2.2 parts of Ammonium persulfate .s and 200 parts of water configure, A
The dropping duration of solution and B solution is respectively 4 hours and 4.5 hours, and after dripping, insulation is carried out altogether for 1 hour
Poly-reaction, after question response, adds the sodium hydrate aqueous solution of 60 part 32%, adjusts system pH=6.3, stir
Mixing 10min, discharging obtains polycarboxylate water-reducer.
Embodiment 4
(room temperature 5-15 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 320 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 320 parts of water, stirring, to melting formation polyether solutions completely, adds 3.7 parts of chains and turns
Move agent, after stirring and dissolving, 50 parts of 2-(Acryloyloxy)ethanols of dropping, 20 parts of acrylic acid solutions and 160 parts of water respectively
The solution B that the solution A of configuration and 1.8 parts of Ammonium persulfate .s and 100 parts of water configure, solution A and B solution
Dropping duration is respectively 4 hours and 4.5 hours, and after dripping, insulation carries out copolyreaction, question response in 1 hour
After, stir 10min, discharging obtains polycarboxylate water-reducer.
Embodiment 5
(room temperature 15-25 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 320 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 320 parts of water, stirring, to melting formation polyether solutions completely, adds 4 parts of chains and turns
Move agent, after stirring and dissolving, 52 parts of 2-(Acryloyloxy)ethanols of dropping, 18 parts of acrylic acid solutions and 160 parts of water respectively
The solution B that the solution A of configuration and 1.8 parts of Ammonium persulfate .s and 100 parts of water configure, solution A and B solution
Dropping duration is respectively 3 hours and 3.5 hours, and after dripping, insulation carries out copolyreaction, question response in 2 hours
After, stir 10min, discharging obtains polycarboxylate water-reducer.
Embodiment 6
(room temperature ＞ 25 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 320 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 320 parts of water, stirring, to melting formation polyether solutions completely, adds 4 parts of chains and turns
Move agent, after stirring and dissolving, 52 parts of 2-(Acryloyloxy)ethanols of dropping, 18 parts of acrylic acid solutions and 160 parts of water respectively
Dripping of the solution B that the solution A of configuration and 2 parts of Ammonium persulfate .s and 100 parts of water configure, solution A and B solution
Adding duration to be respectively 2 hours and 2.5 hours, after dripping, insulation carries out copolyreaction in 2 hours, and question response is complete
Bi Hou, stirs 10min, and discharging obtains polycarboxylate water-reducer.
Comparative example 1
(heating 60 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 350 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 350 parts of water, be heated to 60 DEG C and stir to melting formation polyether solutions completely, add
Enter 10 parts of acrylic acid, after stirring 5min, add 4 parts of chain-transferring agents, after stirring and dissolving, drip 40 respectively
It is molten that part acrylic acid and the acrylic acid aqueous solution A of 40 parts of water configurations and 2 parts of Ammonium persulfate .s and 150 parts of water configure
The dropping duration of liquid B, solution A and B solution is respectively 2 hours and 2.5 hours, is incubated 2 after dripping
Hour carry out copolyreaction, after question response, cool to 40 DEG C and add the sodium hydrate aqueous solution of 55 part 32%,
Adjustment system pH=6.2, stirs 10min, and discharging obtains polycarboxylate water-reducer.
Comparative example 2
(being heated to 60 DEG C)
In the four-hole boiling flask of 1000ml band stirring, put into 320 parts of methyl allyl polyoxyethylene ethers or different
Pentenyl polyoxyethylene ether and 320 parts of water, be heated to 60 DEG C and stir to melting formation polyether solutions completely, add
Enter 4 parts of chain-transferring agents, after stirring and dissolving, 52 parts of 2-(Acryloyloxy)ethanols, 18 parts of acrylic acid solutions of dropping respectively
The solution B that the solution A configured with 160 parts of water and 2 parts of Ammonium persulfate .s and 100 parts of water configure, solution A and B
The dropping duration of solution is respectively 2 hours and 2.5 hours, and after dripping, insulation carries out copolyreaction in 2 hours,
After question response, stirring 10min, cooling discharge obtains polycarboxylate water-reducer.
Experimental result
Index contrast 1 starched only by table 1.
Index contrast 2 starched only by table 2.
Table 3.GPC surveys product macromolecule effective content 1
Table 4.GPC surveys product macromolecule effective content 2
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. the preparation method of a polycarboxylate water-reducer, it is characterised in that water, water-soluble chain transfer agent and
At a temperature of in the presence of radical initiator, between 5 DEG C and 45 DEG C so that following material reacts:
At least one unsaturated carboxylic acid；And
At least one polyethers, its carboxyl functional group with the polymer that can be formed with unsaturated carboxylic acid occurs
The free hydroxyl of reaction.
The preparation method of polycarboxylate water-reducer the most according to claim 1, it is characterised in that this is prepared
Method comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part is formed in water the unsaturated carboxylic that mass concentration is 25～100%
Acid solution；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
Being dropped to by unsaturated carboxylic acid solution in 1～8 hour in the first solution, in 1～8 hour will be from
Dropped to the first solution forms reactant liquor by base initiator solution；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
The preparation method of polycarboxylate water-reducer the most according to claim 1 and 2, it is characterised in that institute
The mol ratio stating polyethers and unsaturated carboxylic acid is 1:(1～8)；The quality of described water-soluble chain transfer agent and insatiable hunger
It is (0.02～1.2) with the ratio of carboxylic acid and the gross mass of polyethers: 100；The quality of described radical initiator
It is (0.01～15) with the ratio of unsaturated carboxylic acid and the gross mass of polyethers: 100.
The preparation method of polycarboxylate water-reducer the most according to claim 1 and 2, it is characterised in that water,
The polymeric system that water-soluble chain transfer agent, radical initiator, unsaturated carboxylic acid and polyethers are formed contains admittedly
Amount is 20～60%.
The preparation method of polycarboxylate water-reducer the most according to claim 1 and 2, it is characterised in that no
Saturated carboxylic acid is acrylic acid, and polyethers is methyl allyl alcohol polyoxyethylene ether or isopentene group polyoxyethylene ether or two
The mixture of person.
6. the preparation method of a polycarboxylate water-reducer, it is characterised in that water, water-soluble chain transfer agent and
At a temperature of in the presence of radical initiator, between 5 DEG C and 45 DEG C so that following material reacts:
At least one unsaturated carboxylic acid；
At least one esters of unsaturated carboxylic acids, it is the ester that unsaturated carboxylic acid is formed with ethylene glycol；And
At least one polyethers, it has can be with the polymer of unsaturated carboxylic acid and esters of unsaturated carboxylic acids formation
The free hydroxyl that carboxyl functional group reacts.
The preparation method of polycarboxylate water-reducer the most according to claim 6, it is characterised in that this is prepared
Method comprises the steps:
Polyethers is dissolved in the water and forms the polyether solutions that mass concentration is 40～70%；
Respectively unsaturated carboxylic acid and the water-soluble chain transfer agent of the first molar part are added to polyether solutions,
Form the first solution；
The unsaturated carboxylic acid of the second molar part and esters of unsaturated carboxylic acids are formed in water the second solution, wherein,
In second solution, the mass concentration of unsaturated carboxylic acid is the matter of 25～100%, second esters of unsaturated carboxylic acids in solution
Amount concentration is 0～100%；
Radical initiator is formed in water the radical initiator solution that mass concentration is 10～50%；
In 1～8 hour, the second solution dropped in the first solution, in 1～8 hour, free radical drawn
Send out agent solution and drop to the first solution is formed reactant liquor；
At 5～45 DEG C, reactant liquor carries out copolyreaction and obtains polycarboxylate water-reducer, and the response time is 4～12
Hour.
8. according to the preparation method of the polycarboxylate water-reducer described in claim 6 or 7, it is characterised in that institute
The mol ratio stating polyethers and unsaturated carboxylic acid is 1:(1～8)；The quality of described water-soluble chain transfer agent and insatiable hunger
It is (0.02～1.2) with the ratio of the gross mass of carboxylic acid, esters of unsaturated carboxylic acids and polyethers: 100；Described freedom
The ratio of the gross mass of the quality of base initiator and unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers be (0.01～
15): 100.
9. according to the preparation method of the polycarboxylate water-reducer described in claim 6 or 7, it is characterised in that water,
It is poly-that water-soluble chain transfer agent, radical initiator, unsaturated carboxylic acid, esters of unsaturated carboxylic acids and polyethers are formed
In compound system, solid content is 20～60%.
10. according to the preparation method of the polycarboxylate water-reducer described in claim 6 or 7, it is characterised in that no
Saturated carboxylic acid is acrylic acid, and esters of unsaturated carboxylic acids is 2-(Acryloyloxy)ethanol, and polyethers is methallyl alcohol polyoxy second
Alkene ether or isopentene group polyoxyethylene ether or the mixture of the two.
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| CN101993210A (en) * | 2010-03-04 | 2011-03-30 | 山西大学 | Prenyl polyether polycarboxylate water reducing agent and synthesis method thereof |
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| CN104496256A (en) * | 2014-12-19 | 2015-04-08 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN105037648A (en) * | 2015-08-25 | 2015-11-11 | 科之杰新材料集团有限公司 | Slump-retaining water-reducing polycarboxylic acid water reducing agent and low-temperature quick preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101993210A (en) * | 2010-03-04 | 2011-03-30 | 山西大学 | Prenyl polyether polycarboxylate water reducing agent and synthesis method thereof |
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