CN108203489A - The hyperbranched poly carboxylic acid water reducing agent and its preparation method and application that a kind of hydrophobic grouping is modified - Google Patents
The hyperbranched poly carboxylic acid water reducing agent and its preparation method and application that a kind of hydrophobic grouping is modified Download PDFInfo
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- CN108203489A CN108203489A CN201711481919.7A CN201711481919A CN108203489A CN 108203489 A CN108203489 A CN 108203489A CN 201711481919 A CN201711481919 A CN 201711481919A CN 108203489 A CN108203489 A CN 108203489A
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- carboxylic acid
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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
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to cement additire field, hyperbranched poly carboxylic acid water reducing agent and its preparation method and application that a kind of hydrophobic grouping is modified are disclosed.The present invention introduces the side chain containing hydrophobic grouping on the basis of traditional poly carboxylic acid series water reducer, simultaneously dissaving structure is formed using the chain-transferring agent of polyfunctionality, one side hydrophobic segment can enhance the repulsion between the cement particle of attachment diminishing agent molecule, another aspect dissaving structure improves the bulk of water-reducing agent, the space steric effect of diminishing agent molecule is strengthened, the mobility for achieving the purpose that improve cement slurry is so as to improve the comprehensive performance of water-reducing agent.During solid content 40%, it is more than 285mm to make reference cement paste flowing degree in the ratio of mud 0.35, water-reducing agent volume 0.6%, and air content is more than 2.5% compression strength for ensureing solidified sample simultaneously.
Description
Technical field
The invention belongs to cement additire field, more particularly to a kind of hyperbranched poly carboxylic serials diminishing of hydrophobic grouping modification
Agent and its preparation method and application.
Background technology
Water-reducing agent is a kind of typical additives in cement works application.Cement can form wadding after being mixed in application with water
Concretio, these encapsulated by structures, which have lived Free water, to be caused also to need to add in excessive water to ensure that cement system has convenient for construction
Fluidity.Excessive water can leave hole in the structure after cement solidification causes concrete performance to reduce.By adding in diminishing
Agent can reduce the dosage of mixing water so as to the peptizaiton strengthened between cement particle in the case where ensureing fluidity, carry
The intensity of high concrete.
Water-reducing agent passes through the development of several generations, currently on the market based on poly carboxylic acid series water reducer product.Polycarboxylic-acid diminishing
Agent typical structure is the Grafting Structure of pectination, and the carboxylic acid group on main chain is interacted by the interionic after ionization so as to make
Water-reducing agent can be anchored at cement particle surface；Polyethers side long-chain then improves the dispersion of cement particle by steric hindrance repulsion
Property.The molecular structure of poly carboxylic acid series water reducer determines its designability height, in addition it has excellent performance, is environmentally protective, because forming
For the Main way of present water-reducing agent area research, high performance poly carboxylic acid series water reducer product emerges in an endless stream.But the opposing party
The traditional polycarboxylic acid water reducing agent in face there is also function of slump protection is for example caused during Various Seasonal to differ greatly to construction temperature sensitivity,
Being influenced big, viscosity height by clay content causes to be unfavorable for the problems such as construction.It is announced in Chinese disclosure CN107189021A
The formula and synthetic method of a kind of polycarboxylate water-reducer, with methoxy poly (ethylene glycol), methacrylic acid, acrylic acid hydroxy alkyl ester
For reaction monomers, the sodium hypophosphite and tartaric acid with reproducibility and chain tra nsfer are introduced in the reaction system, with oxidant
The redox initiation system of high activity is formed, can be reacted at 5~40 DEG C, production efficiency is improved, reduces production cost, but
Patent is not introduced the comprehensive performance of water-reducing agent obtained.Chinese disclosure CN107189026A discloses a kind of ester
First poly- second is obtained by the reaction with poly glycol monomethyl ether and methacrylic acid in ether composite polymeric polycarboxylate water-reducer and preparation method thereof
Glycol monomethyl ether methacrylate macromer, then by it with ethers polymeric monomer mixed configuration to carry out poly- carboxylic after mixing polymeric monomer
The synthesis of acid type water-reducing agent, the product of preparation can make fresh concrete keep the good easy property of work, but be also possible to will appear stream
The counter productives such as dynamic degree loss, Qinshui.A kind of poly- carboxylic of low entraining viscosity reduction type is disclosed in Chinese disclosure CN106883355A
Sour water-reducing agent and preparation method thereof is subtracted by being introduced on main chain containing the three fat structure of alkyl phosphoric acid there are two double bond so as to increase
Aqua adsorbent layer thickness to achieve the purpose that reduce concrete plastic viscosity, while also improve antifoam performance, reduces bleed
Property, but preparation process is complex, and fluidity retention property is general.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of hydrophobic grouping
Modified hyperbranched poly carboxylic acid water reducing agent.
Another object of the present invention is to provide the preparation side for the hyperbranched poly carboxylic acid water reducing agent that above-mentioned hydrophobic grouping is modified
Method.
Still a further object of the present invention is to provide the application for the hyperbranched poly carboxylic acid water reducing agent that above-mentioned hydrophobic grouping is modified.
The purpose of the present invention is realized by following proposal：
The hyperbranched poly carboxylic acid water reducing agent that a kind of hydrophobic grouping is modified includes the raw material of following dosage：
(1) small molecule unsaturated carboxylic acid；
(2) unsaturated polyether class polymeric monomer；
(3) minor comonomer containing hydrophobic group；
(4) polycarboxylic acid macromolecule catalyst is synthesized；
(5) polyfunctionality chain-transferring agent；
Wherein, the dosage of each raw material meets：The small molecule unsaturated carboxylic acid and unsaturated polyether class polymeric monomer rub
You are than being 2.5~5：1；The molar ratio of described minor comonomer and unsaturated polyether class polymeric monomer containing hydrophobic group for 0.05~
0.2:1；The amount of the synthesis polycarboxylic acid macromolecule catalyst be unsaturated polyether class polymeric monomer mole 1%~
2%；The amount of the polyfunctionality chain-transferring agent is the 0.5%~1.5% of unsaturated polyether class polymeric monomer mole.
The small molecule unsaturated carboxylic acid is acrylic acid (AA), one or more in α-methacrylic acid (MAA).
Allyl polyethenoxy ether (APEG), different of the unsaturated polyether class polymeric monomer for molecular weight 500~2000
It is one or more in pentenol polyoxyethylene ether (TPEG), methyl allyl alcohol polyoxyethylene ether (HPEG).
The minor comonomer containing hydrophobic group is butyl methacrylate, isooctyl methacrylate, methacrylic acid
It is one or more in lauryl, methacrylic acid octadecane ester.
The synthesis polycarboxylic acid macromolecule is dibenzoyl peroxide (BPO), azodiisobutyronitrile with catalyst
(AIBN) one kind in thermal cracking catalysts such as.
The polyfunctionality chain-transferring agent is pentaerythrite four (thioacetic acid) ester, triethanolamine three (thioacetic acid) ester
One kind therein.
The preparation method of poly carboxylic acid series water reducer that a kind of above-mentioned hydrophobic grouping is modified, includes the following steps：
(1) by unsaturated polyether polymeric monomer, the minor comonomer containing hydrophobic group, synthesis polycarboxylic acid macromolecule catalyst
Solvent is dissolved in by proportioning, adds in heating stirring in reaction vessel；
(2) mixed solution of small molecule unsaturated carboxylic acid and polyfunctionality chain-transferring agent is added dropwise to step (1) reaction system,
The temperature of step (1) is kept during dropwise addition；
(3) system heats up and reacts a period of time after completion of dropwise addition；
(4) after reaction, stop heating, remove solvent postcooling to addition water after less than 50 DEG C and neutralizer and adjust pH
Value and solid content are to get final product：The hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping is modified.
Solvent described in step (1) is dioxane.
Heating stirring described in step (1) refers in 65~80 DEG C of heating stirrings, preferably 80 DEG C；The stirring is
Finger mixing speed is 800r/min；
Dropwise addition described in step (2) refers to that time for adding is 1.5~3h；It is preferred that in 2.5h；
Heating and reaction described in step (3) refer to be warming up to 90~100 DEG C of reactions, and the time of reaction is 1~2h；It is excellent
It is selected in 90 DEG C of reaction 1.5h.
Removing solvent described in step (4) refers to the method removal solvent with vacuum distillation.
PH value described in step (4) is 7, solid content 40%.
Application of the hyperbranched poly carboxylic acid water reducing agent that above-mentioned hydrophobic grouping is modified in cement works construction.
The present invention mechanism be：
The present invention introduces the side chain containing hydrophobic grouping on the architecture basics of traditional poly carboxylic acid series water reducer, utilizes simultaneously
The chain-transferring agent of polyfunctionality forms dissaving structure, and one side hydrophobic segment can enhance the cement grain of attachment diminishing agent molecule
Repulsion between son, another aspect dissaving structure improve the bulk of water-reducing agent, strengthen the space of diminishing agent molecule
Steric effect, the mobility for achieving the purpose that improve cement slurry is so as to improve the comprehensive performance of water-reducing agent.
The present invention is had the following advantages and advantageous effect relative to the prior art：
(1) the more traditional polycarboxylate water-reducer of the present invention has preferable bleed, and do not influence the pressure resistance after cement solidification
Degree；
(2) the more traditional polycarboxylate water-reducer of the present invention can further improve cement slurry fluidity, work as polycarboxylate water-reducer
During solid content 40%, it is more than 285mm that can make reference cement paste flowing degree in the ratio of mud 0.35, water-reducing agent volume 0.6%.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Test is that concrete admixture examines dedicated fiducial cement, 42.5 silicates of model PI with cement in embodiment
Cement (rotary kiln), the ratio of mud 0.35, the solid volume of water-reducing agent folding is 0.6%, and cement solidification sample curing time is 28 days.Net slurry
Fluidity test method is according to GB/T 8077-2012《Methods for testing uniformity of concrete admixture》.Cement sample compression strength
Test method is according to GB/T 17671-1999《Test method for strength of hydraulic cement mortar》.Gassiness weight testing method is according to GB/
T50080-2016《Standard for test methods of properties of ordinary concrete mixture standard》.
Embodiment 1
(1) by HPEG-500 50g (0.1mol), butyl methacrylate 0.71g (0.005mol), AIBN 0.164g
(0.001mol) is dissolved in 150g dioxane and adds in four-hole boiling flask, heating stirring at 65 DEG C；
(2) acrylic acid 21.6g (0.3mol) and (thioacetic acid) ester of pentaerythrite four 0.216g is added dropwise to system
(0.0005mol) mixed solution, time for adding 1.5h, temperature are kept for 65 DEG C；
(3) after dripping acrylic acid and pentaerythrite four (thioacetic acid) ester, 90 DEG C are warming up to, keeps 2h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Embodiment 2
(1) by APEG-1000 50g (0.05mol), butyl methacrylate 0.355g (0.0025mol), BPO
0.242g (0.001mol) is dissolved in 150g dioxane and adds in four-hole boiling flask, heating stirring at 80 DEG C；
(2) methacrylic acid 17.2g (0.2mol) and (thioacetic acid) ester of pentaerythrite four 0.324g is added dropwise to system
(0.00075mol) mixed solution, time for adding 3h, temperature are kept for 80 DEG C；
(3) after dripping acrylic acid and pentaerythrite four (thioacetic acid) ester, 90 DEG C are warming up to, keeps 2h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Embodiment 3
(1) by APEG-1000 50g (0.05mol), isooctyl methacrylate 0.99g (0.005mol), AIBN
0.164g (0.001mol) is dissolved in 150g dioxane and adds in four-hole boiling flask, heating stirring at 65 DEG C；
(2) acrylic acid 18g (0.25mol) and (thioacetic acid) ester of triethanolamine three 0.186g is added dropwise to system
(0.0005mol) mixed solution, time for adding 2h, temperature are kept for 65 DEG C；
(3) after dripping acrylic acid and triethanolamine three (thioacetic acid) ester, 100 DEG C are warming up to, keeps 1h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Embodiment 4
(1) by TPEG-2000 100g (0.05mol), butyl methacrylate 1.42g (0.01mol), AIBN 0.164g
(0.001mol) is dissolved in 300g dioxane and adds in four-hole boiling flask, heating stirring at 65 DEG C；
(2) methacrylic acid 10.75g (0.125mol) and (thioacetic acid) ester of triethanolamine three 0.186g is added dropwise to system
(0.0005mol) mixed solution, time for adding 2h, temperature are kept for 65 DEG C；
(3) after dripping acrylic acid and triethanolamine three (thioacetic acid) ester, 90 DEG C are warming up to, keeps 2h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Embodiment 5
(1) by APEG-2000 200g (0.1mol), lauryl methacrylate 2.54g (0.01mol), BPO 0.242g
(0.001mol) is dissolved in 600g dioxane and adds in four-hole boiling flask, heating stirring at 80 DEG C；
(2) acrylic acid 28.8g (0.4mol) and (thioacetic acid) ester of triethanolamine three 0.557g is added dropwise to system
(0.0015mol) mixed solution, time for adding 3h, temperature are kept for 80 DEG C；
(3) after dripping acrylic acid and triethanolamine three (thioacetic acid) ester, 90 DEG C are warming up to, keeps 1.5h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Embodiment 6
(1) by TPEG-2000 200g (0.1mol), methacrylic acid octadecane ester 6.76g (0.02mol), AIBN
0.328g (0.002mol) is dissolved in 300g dioxane and adds in four-hole boiling flask, heating stirring at 65 DEG C；
(2) methacrylic acid 21.6g (0.3mol) and (thioacetic acid) ester of pentaerythrite four 0.432g is added dropwise to system
(0.001mol) mixed solution, time for adding 2h, temperature are kept for 65 DEG C；
(3) after dripping acrylic acid and pentaerythrite four (thioacetic acid) ester, 90 DEG C are warming up to, keeps 2h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
Comparative example
(1) APEG-1000 50g (0.05mol), AIBN 0.164g (0.001mol) are dissolved in 150g dioxane to add in
In four-hole boiling flask, heating stirring at 75 DEG C；
(2) acrylic acid 14.4g (0.2mol), time for adding 2h is added dropwise to system, temperature is kept for 75 DEG C；
(3) after dripping acrylic acid, 90 DEG C are warming up to, keeps 1h；
(4) system vacuum distillation removes solvent postcooling to 50 DEG C hereinafter, adding in water and being neutralized to pH=7, body with NaOH
It is that solid content is adjusted to 40%.
The relevant test data of the polycarboxylate water-reducer of gained is as shown in table 1 below in Examples 1 to 6 and comparative example：
The relevant test data of the polycarboxylate water-reducer of gained in 1 Examples 1 to 6 of table and comparative example
| Sample | Flowing degree of net paste of cement (mm) | Cement solidification sample air content | Cement solidification sample compression strength (MPa) |
| Comparative example | 256 | 2.2% | 40.1 |
| Embodiment 1 | 292 | 2.6% | 40.4 |
| Embodiment 2 | 311 | 3.4% | 39.8 |
| Embodiment 3 | 297 | 3.0% | 41.2 |
| Embodiment 4 | 285 | 2.8% | 40.7 |
| Embodiment 5 | 308 | 3.1% | 39.3 |
| Embodiment 6 | 302 | 3.0% | 40.5 |
From above-described embodiment as can be seen that when polycarboxylate water-reducer solid content 40%, reference cement can be made in water ash
Paste flowing degree is more than 285mm during than 0.35, water-reducing agent volume 0.6%, and air content is more than 2.5% and does not have substantially to compression strength
There is negative effect.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the hyperbranched poly carboxylic acid water reducing agent that a kind of hydrophobic grouping is modified, it is characterised in that it includes the raw material of following dosage：
(1) small molecule unsaturated carboxylic acid；
(2) unsaturated polyether class polymeric monomer；
(3) minor comonomer containing hydrophobic group；
(4) polycarboxylic acid macromolecule catalyst is synthesized；
(5) polyfunctionality chain-transferring agent；
Wherein, the dosage of each raw material meets：The small molecule unsaturated carboxylic acid and the molar ratio of unsaturated polyether class polymeric monomer
It is 2.5~5：1；The molar ratio of described minor comonomer and unsaturated polyether class polymeric monomer containing hydrophobic group is 0.05~0.2:
1；The amount of the synthesis polycarboxylic acid macromolecule catalyst is the 1%~2% of unsaturated polyether class polymeric monomer mole；Institute
The amount of polyfunctionality chain-transferring agent stated is the 0.5%~1.5% of unsaturated polyether class polymeric monomer mole.
2. the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 1 is modified, it is characterised in that：
The small molecule unsaturated carboxylic acid is acrylic acid, one or more in α-methacrylic acid.
3. the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 1 is modified, it is characterised in that：
The unsaturated polyether class polymeric monomer is allyl polyethenoxy ether, the prenol polyoxy of molecular weight 500~2000
It is one or more in vinethene, methyl allyl alcohol polyoxyethylene ether.
4. the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 1 is modified, it is characterised in that：
The minor comonomer containing hydrophobic group is butyl methacrylate, isooctyl methacrylate, lauryl
It is one or more in ester, methacrylic acid octadecane ester.
5. the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 1 is modified, it is characterised in that：
Synthesis polycarboxylic acid macromolecule one kind that catalyst is in dibenzoyl peroxide, azodiisobutyronitrile.
6. the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 1 is modified, it is characterised in that：
The polyfunctionality chain-transferring agent is pentaerythrite four (thioacetic acid) ester, in triethanolamine three (thioacetic acid) ester
It is a kind of.
7. a kind of system for the hyperbranched poly carboxylic acid water reducing agent being modified according to claim 1~6 any one of them hydrophobic grouping
Preparation Method, it is characterised in that include the following steps：
(1) by unsaturated polyether polymeric monomer, the minor comonomer containing hydrophobic group, synthesis polycarboxylic acid macromolecule catalyst by matching
Than being dissolved in solvent, heating stirring in reaction vessel is added in；
(2) small molecule unsaturated carboxylic acid and polyfunctionality chain-transferring agent mixed solution are added dropwise to step (1) reaction system, during dropwise addition
Keep the temperature of step (1)；
(3) system heats up and reacts a period of time after completion of dropwise addition；
(4) after reaction, stop heating, remove solvent postcooling to addition water and sodium hydroxide after less than 50 DEG C, be configured to
Aqueous solution be final product.
8. the preparation method for the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 7 is modified, feature
It is：
Heating described in step (1) refers in 65~80 DEG C of heating stirrings；The stirring refers to that mixing speed is 800r/
Min, the solvent described in step (1) are dioxane；
Dropwise addition described in step (2) refers to that time for adding is 1.5~3h；
Heating described in step (3), which refers to, is warming up to 90~100 DEG C of reactions, and the time of reaction is 1~2h；
Removing solvent described in step (4) refers to the method removal solvent with vacuum distillation；
PH value described in step (4) is 7, solid content 40%.
9. the preparation method for the hyperbranched poly carboxylic acid water reducing agent that hydrophobic grouping according to claim 8 is modified, feature
It is：
Heating described in step (1) refers in 80 DEG C of heating；
Dropwise addition described in step (2) refers to that time for adding is 2.5h；
Heating described in step (3) refers to rise to 90 DEG C of reaction 1.5h.
10. the hyperbranched poly carboxylic acid water reducing agent being modified according to claim 1~6 any one of them hydrophobic grouping is in cement work
Application in journey construction.
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| CN113929837A (en) * | 2021-11-03 | 2022-01-14 | 同济大学 | Shrinkage-reducing polycarboxylic acid water reducer and preparation method and application thereof |
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