CN106380549A - Polycarboxyliy water reducer and preparation method thereof - Google Patents
Polycarboxyliy water reducer and preparation method thereof Download PDFInfo
- Publication number
- CN106380549A CN106380549A CN201610742895.5A CN201610742895A CN106380549A CN 106380549 A CN106380549 A CN 106380549A CN 201610742895 A CN201610742895 A CN 201610742895A CN 106380549 A CN106380549 A CN 106380549A
- Authority
- CN
- China
- Prior art keywords
- water
- reducer
- preparation
- polycarboxyliy
- water reducer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a polycarboxyliy water reducer and belongs to the technical field of concrete water reducers. According to the technical scheme of the invention, not only the polycarboxyliy water reducer is provided with high-performance water-reducing type carboxyls, sulfonic acid groups, poly(ethylene oxide)graft chains and other groups, but also acrylic esters, allyl alcohols and other small monomers, having the reduction function, are grafted onto the polycarboxyliy water reducer. Therefore, the polycarboxyliy water reducer is high in water-reducing rate and crack resistance, and good in reduction effect at the same time. The shrinkage stress of the concrete during different periods of the formation process is avoided, so that the generation and development of cracks is avoided. The impact resistance of the concrete/mortar is significantly enhanced. The polycarboxyliy water reducer can be applied to the engineering fields of waterproof projects, highways, ports, tunnels, reservoir dams, special impervious and antiknock projects and the like. Especially, the polycarboxyliy water reducer is especially applicable to the seamless design and the construction of expansive concretes, mass concretes and super-length reinforced concretes. Therefore, the polycarboxyliy water reducer has a wide application prospect.
Description
Technical field
The present invention relates to cement water reducing agent technical field, more particularly, to a kind of polycarboxylate water-reducer and preparation method thereof.
Background technology
Concrete is conventional material in the engineerings such as bridge, road, building, sends out with building industry and the rapid of hydraulic engineering
Exhibition, puts forward higher requirement to the performance of concrete.Adding water reducer is to improve one of means of concrete performance.Water reducer
Development have long history.Successfully develop respectively to Japan's sixties in last century and Germany from the lignosulfonates of early stage
Beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt (SNF) and sulfonated melamine compound condensation product (SMF) both high efficiency water reducing agents, make
The development of concrete technology rises to a stage.Start to develop the macromolecule diminishing of a new generation from last century the mid-80
Agent, the such as polycarboxylic-acid such as acrylic acid series, maleic acid system and modified polyether series high-efficiency water-reducing agent, water-reducing rate is up to more than 30%, mixes
Amount is less, function of slump protection is good, amount of air entrainment and the continuous index such as solidifying are relatively mild, proper formulation high fluidity, self-compacting concrete, thus
Favored by engineering circles.In recent years, the research of concrete admixture and produces day tend to high-performance, pollution-free direction is developed.
High-efficiency water-reducing agent of poly-carboxylic acid because water-reducing rate is high, function of slump protection is good, gain in strength is fast, proper formulation is high-strength, super high strength concrete,
High fluidity and self-compacting concrete, become the focus of domestic and international concrete admixture research and development.
And building trade generally existing concrete can produce the phenomenon in a large amount of cracks, concrete during hardening now
Shrink and produce the one of the main reasons that crack is concrete cracking, concrete shrinkage can be divided into：Contraction, plastic shrinkage, change are dried
Learn contraction, Carbonization contract and self-constriction.Concrete produces stress because of contraction in inside concrete, should insist on when this
Continue and will produce crack when increasing and cannot effectively discharge.At present, architectural engineering is generally using the method adding swelling agent
To reduce shrinkage stress, but to there is a problem of that volume is larger and needs long-time moisture-keeping maintaining.
Economization agent is the surface tension by reducing capillary in the hole solution in cement, reduces the body producing due to moisture evaporation
Long-pending contraction, to control, to slow down the cracking phenomena of concrete with this, improves crack resistance performance and the endurance quality of concrete.Existing
In technology, there is reducing property in the such as disclosed polycarboxylate water-reducer such as CN103193410A, CN104262545A, CN105622863A
The problem that can not simultaneously can take into account with water-reducing property.
Content of the invention
In view of this, it is an object of the invention to provide a kind of polycarboxylate water-reducer, improve reducing of polycarboxylate water-reducer
Effect, prevents the shrinkage stress of concrete different times in forming process, stops generation and the development in crack, significantly enhances
The impact resistance of concrete/mortar.
In order to realize foregoing invention purpose, the present invention provides technical scheme below：
There is the polycarboxylate water-reducer of structure shown in Formulas I：
Wherein, M is Na+、K+Or NH4 +,
R is-H ,-CH3Or-CH2CH3,
50≤a≤500,1≤b≤100,20≤c≤150,10≤d≤100,1≤e≤100,0≤m≤3,30≤n≤
100.
Preferably, 100≤a≤300,30≤b≤60,50≤c≤100,40≤d≤60,50≤e≤80,1≤m≤2,
50≤n≤80.
Present invention also offers having the preparation side of the polycarboxylate water-reducer of structure shown in Formulas I described in technique scheme
Method, comprises the steps of：
Under conditions of initiator and molecular weight regulator exist, by APEO, acrylate, allyl alcohol, propylene
Acid and allylsulfonate carry out copolyreaction in water, obtain the water reducer of structure shown in Formulas I
Preferably, described APEO, acrylate, allyl alcohol, acrylic acid, the mass ratio of allylsulfonate are
(270～380)：(2～15)：(3～9)：(20～60)：(1～9).
Preferably, described APEO, initiator, molecular weight regulator, the mass ratio of water are (270～380)：(1～
8)：(1～7)：(580～660).
Preferably, described acrylate is included in methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate
The mixture of one or more.
Preferably, described molecular weight regulator includes 2- TGA, 3- mercaptopropionic acid, mercaptoethanol, metering system sulphur
The mixture of one or more of sour sodium and azodiisobutyronitrile.
Preferably, described initiator is redox initiator, comprises oxidation component and reduction components, described oxidation component
Comprise the mixture of one or more of hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate, described reduction components comprise Vitamin C
The mixture of one or more of acid, sodium bisulphite formaldehyde and sodium hydrogensulfite.
Preferably, the temperature of described copolyreaction is 20～35 DEG C, and the time of copolyreaction is 3～10h.
Preferably, also comprise isothermal holding after described copolyreaction, the temperature of described insulation is 20～35 DEG C, insulation when
Between be 1～5h.
The present invention provide the polycarboxylate water-reducer with structure shown in Formulas I, be not only grafted have high diminishing carboxyl,
The groups such as sulfonic group, APEO side chain, but also be grafted and there is the little list such as acrylate, allyl alcohol of reducing function
Body is so that polycarboxylate water-reducer has higher water-reducing rate and cracking resistance, and has while having higher water-reducing rate
The effect preferably reduced, prevents the shrinkage stress of concrete different times in forming process, stops generation and the development in crack,
Significantly enhance the impact resistance of concrete/mortar, can be used for waterproofing work, highway, harbour, tunnel, reservoir dam,
There is engineering of special impervious antiknock etc., be particularly well-suited to prepare expansive concrete, mass concrete, overlength reinforced concrete
Soil structure seamless design and construction, rigid structure self-waterproof concrete and other have the special engineering of anti-crack and anti-seepage technical requirements with
Position.
The preparation method of the polycarboxylate water-reducer with structure shown in Formulas I that the present invention provides, under normal temperature in initiator and
Under conditions of molecular weight regulator exists, by APEO, acrylate, allyl alcohol, acrylic acid and allylsulfonate exist
Carry out Raolical polymerizable, reaction condition is easily controllable, production equipment, simple production process, no " three wastes " discharge in water.
Brief description
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the infrared spectrogram of the polycarboxylate water-reducer with structure shown in Formulas I of the embodiment of the present invention 1 preparation.
Specific embodiment
The invention provides having the polycarboxylate water-reducer of structure shown in Formulas I：
Wherein, M is Na+、K+Or NH4 +, preferably Na+Or K+；More preferably Na+；
R is-H ,-CH3Or-CH2CH3, preferably-CH3Or-CH2CH3；More preferably-CH2CH3；
50≤a≤500,1≤b≤100,20≤c≤150,10≤d≤100,1≤e≤100,0≤m≤3,30≤n≤
100；Preferably, 100≤a≤300,30≤b≤60,50≤c≤100,40≤d≤60,50≤e≤80,1≤m≤2,50≤n
≤80；It is furthermore preferred that 150≤a≤250,40≤b≤50,60≤c≤80,50≤d≤55,60≤e≤70,60≤n≤70.
The polycarboxylate water-reducer specifically with structure shown in Formulas I is exemplified below：
The invention provides the preparation method of structure water reducer shown in Formulas I described in technique scheme, comprise the steps of：
Under conditions of initiator and molecular weight regulator exist, by APEO, acrylate, allyl alcohol, propylene
Acid and allylsulfonate carry out copolyreaction in water, obtain the water reducer of structure shown in Formulas I.
In the present invention, described APEO, acrylate, allyl alcohol, acrylic acid, the mass ratio of allylsulfonate
It is preferably (270～380)：(2～15)：(3～9)：(20～60)：(1～9), more preferably (300～360)：(4～12)：(4
～8)：(30～50)：(3～8), most preferably (320～350)：(6～9)：(5～7)：(35～45)：(4～6).
In the present invention, the mass ratio of described APEO, initiator, molecular weight regulator and water be preferably (270～
380)：(1～8)：(1～7)：(580～660), more preferably (300～360)：(2～6)：(3～6)：(600～640),
It is preferably (320～350)：(4～5)：(4～5)：(610～630).
In the present invention, described acrylate preferably includes methyl acrylate, ethyl acrylate, propyl acrylate and propylene
The mixture of one or more of acid butyl ester, described mixture is preferably the mixture of 2～3 kinds of acrylate, more preferably
The mixture of the mixture of ethyl acrylate and propyl acrylate, propyl acrylate and butyl acrylate, in the present invention, to mixed
In compound, the mass ratio of each acrylate does not limit, and those skilled in the art can select any mass ratio according to actual needs
The mixture of acrylate.
In the present invention, the equal molecular mass of the number of described APEO is preferably 1379～4487, more preferably 2259
～4267, most preferably 2699～3167.
In the present invention, described molecular weight regulator preferably includes 2- TGA, 3- mercaptopropionic acid, mercaptoethanol, first
The mixture of one or more of base sodium allylsulfonate and azodiisobutyronitrile, described mixture is preferably 2～3 kinds of molecular weight
The mixture of conditioning agent, the more preferably mixture of 2- TGA and 3- mercaptopropionic acid, 3- mercaptopropionic acid and mercaptoethanol
The mixture of the mixture of mixture, 3- mercaptopropionic acid and methylpropene sodium sulfonate, 3- mercaptopropionic acid and azodiisobutyronitrile,
In the present invention, the mass ratio of molecular weight regulator each in mixture is not limited, those skilled in the art can be according to actual need
Select the mixture of the molecular weight regulator of any mass ratio.
In the present invention, described initiator is preferably redox initiator, comprises oxidation component and reduction components, described
Oxidation component preferably comprises the mixture of one or more of hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate, described oxidation group
The mixture dividing is preferably the mixture of 2～3 kinds of oxidation components, the more preferably mixture of hydrogen peroxide and ammonium persulfate, mistake
Hydrogen oxide and the mixture of potassium peroxydisulfate.In the present invention, the mass ratio of oxidation component each in mixture is not limited, ability
Field technique personnel can select the mixture of the oxidation component of any mass ratio, in the present invention, described peroxide according to actual needs
Change hydrogen to add in the form of hydrogen peroxide, there is no any particular determination to the weight/mass percentage composition of hydrogen peroxide, using art technology
Commercially available dioxygen Water Goods known to personnel；
In the present invention, described reduction components preferably comprise in ascorbic acid, sodium bisulphite formaldehyde and sodium hydrogensulfite
The mixture of one or more, described reduction components mixture be preferably 2～3 kinds of reduction components mixture, more preferably
The mixture of the mixture of ascorbic acid and sodium bisulphite formaldehyde, ascorbic acid and sodium hydrogensulfite.In the present invention, to mixed
In compound, the mass ratio of each reduction components does not limit, and those skilled in the art can select any mass ratio according to actual needs
The mixture of reduction components.
In the present invention, the temperature of described copolyreaction is preferably 20～35 DEG C, more preferably 25～30 DEG C, most preferably
27～28 DEG C；The time of described copolyreaction is preferably 3～10h, more preferably 5～9h, most preferably 6～8h.
In the present invention, preferably further proceed with isothermal holding after described copolyreaction, obtain the poly- carboxylic of structure shown in formula I
Sour water reducer.In the present invention, the temperature of described isothermal holding is preferably 20～35 DEG C, more preferably 25～30 DEG C, most preferably
For 27～28 DEG C；The time of described isothermal holding is preferably 1～5h, more preferably 2～4h, most preferably 2.5～3.5h.
In the present invention, the equipment described copolyreaction being adopted does not have special restriction, using those skilled in the art
Known to reactor.
In the present invention, the equipment described isothermal holding being adopted does not have special restriction, using those skilled in the art
Known to heat-preserving equipment, the mode preferably employing heating in embodiments of the present invention carries out isothermal holding.
The polycarboxylate water-reducer with structure shown in Formulas I that the present invention provides, can also may be used with stoste form admixture with directly
Used after pulvis with making.
The present invention provide the polycarboxylate water-reducer with structure shown in Formulas I be not only grafted have high diminishing carboxyl,
The groups such as sulfonic group, APEO side chain, but also be grafted and there is the little list such as acrylate, allyl alcohol of reducing function
So that having higher water-reducing rate and cracking resistance, water-reducing rate is up to 27.4% to body, and decrement is only 35.9%, has relatively
While high water-reducing rate, there is the effect preferably reduced, prevent the shrinkage stress of concrete different times in forming process,
Stop generation and the development in crack, significantly enhance the impact resistance of concrete/mortar, and there is relatively low air content, can
For waterproofing work, highway, harbour, tunnel, reservoir dam, there is engineering of special impervious antiknock etc., be particularly well-suited to join
Expansive concrete processed, mass concrete, over-long reinforced concrete structure seamless design and construction, rigid structure self waterproofing
Concrete and other special engineering and position having anti-crack and anti-seepage technical requirements.
The preparation method of the polycarboxylate water-reducer with structure shown in Formulas I that the present invention provides, under normal temperature in initiator and
Under conditions of molecular weight regulator exists, by APEO, acrylate, allyl alcohol, acrylic acid and allylsulfonate exist
Carry out Raolical polymerizable, reaction condition is easily controllable, production equipment, simple production process, no " three wastes " discharge in water.
Polycarboxylate water-reducer with structure shown in the Formulas I present invention being provided with reference to embodiment and preparation method thereof
It is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
In parts by mass, its preparation method comprises the steps raw material：
Under normal temperature condition, add the isobutene alcohol polyoxyethylene that the equal molecular mass of 270 numbers is 2699 in reactor
Ether APEO, 2 parts of propyl acrylates, 3 parts of allyl alcohols, 580 parts of water, stirring and dissolving, respectively 20 parts of acrylic acid of dropping, 1 part
The initiator of ALS and 1 part of hydrogen peroxide and ascorbic acid composition, 1 part of 3- mercaptopropionic acid molecular weight regulator are 20
Carry out free radicals copolymerization reaction 3h at DEG C, after the completion of be incubated 1h at 20 DEG C, that is, the polycarboxylic acids obtaining having structure shown in Formulas I subtracts
Aqua.
Fig. 1 is the infrared spectrogram of the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 1 is obtained, can by figure
To find out, in 3424cm-1An absworption peak in left and right, belongs to the characteristic peak of-OH association stretching vibration, and 1720cm-1Left and right
Characteristic absorption peak for-C=O-, 1250cm-1Left and right appearance-SO3Characteristic absorption peak, in 1100cm-1Appearance-C-O-C- nearby
Stretching vibration absworption peak.More than 3000cm-1The stretching vibration peak of-C-H in place, and in 1644cm-1- the C=C- at place
Characteristic absorption peak is weaker, shows that minor comonomer successfully there occurs copolyreaction.From infrared spectrogram, prepared polycarboxylic acids diminishing
Agent has the structure shown in Formulas I.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 1 is obtained
Carry out correlated performance test, result such as table 1.
Embodiment 2
In parts by mass, its preparation method comprises the steps raw material：
Under normal temperature condition, add the prenol polyoxyethylene that the equal molecular mass of 380 numbers is 3100 in reactor
Ether APEO, 15 parts of ethyl acrylates, 9 parts of allyl alcohols, 660 parts of water, stirring and dissolving, respectively 60 parts of acrylic acid of dropping, 9 parts
The initiator of allyl sulphonic acid potassium and 8 parts of hydrogen peroxide and ascorbic acid composition, 7 parts of azodiisobutyronitrile molecular weight regulators exist
Carry out free radicals copolymerization reaction 10h at 35 DEG C, after the completion of at 35 DEG C be incubated 5h, that is, obtain the poly- carboxylic with structure shown in Formulas I
Sour water reducer.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 2 is obtained
Carry out correlated performance test, result such as table 1.
Embodiment 3
In parts by mass, its preparation method comprises the steps raw material：
Under normal temperature condition, add in reactor the allyl alcohol polyethenoxy ether that the equal molecular mass of 300 numbers is 2400,
2 parts of propyl acrylates, 2 parts of ethyl acrylates, 4 parts of allyl alcohols, 600 parts of water, stirring and dissolving, respectively 30 parts of acrylic acid of dropping, 3 parts
ALS and 4 parts of hydrogen peroxide, ammonium persulfate, ascorbic acid, the initiator of sodium bisulphite formaldehyde composition, 3 parts of 3-
Mercaptopropionic acid and azodiisobutyronitrile composition molecular weight regulator carry out free radicals copolymerization reaction 5h at 25 DEG C, after the completion of
It is incubated 2h at 25 DEG C, that is, obtain the polycarboxylate water-reducer with structure shown in Formulas I.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 3 is obtained
Carry out correlated performance test, result such as table 1.
Embodiment 4
In parts by mass, its preparation method comprises the steps raw material：
Under normal temperature condition, add in reactor the allyl alcohol polyethenoxy ether that the equal molecular mass of 200 numbers is 1500,
The equal molecular mass of 120 numbers be 1700 isobutene alcohol APEO, 3 parts of propyl acrylates, 3 parts of butyl acrylates, 5 parts of alkene
Propyl alcohol, 620 parts of water, stirring and dissolving, drip 35 parts of acrylic acid, 4 parts of ALSs and 5 parts of hydrogen peroxide, persulfuric acid respectively
Potassium, ascorbic acid, the molecular-weight adjusting of the initiator of sodium hydrogensulfite composition, 5 parts of 3- mercaptopropionic acids and 2- TGA composition
Agent carries out free radicals copolymerization reaction 6h at 27 DEG C, after the completion of at 27 DEG C be incubated 2.5h, that is, obtain that there is structure shown in Formulas I
Polycarboxylate water-reducer.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 4 is obtained
Carry out correlated performance test, result such as table 1.
Embodiment 5
In parts by mass, its preparation method comprises the steps raw material：
Under normal temperature condition, add in reactor the allyl alcohol polyethenoxy ether that the equal molecular mass of 250 numbers is 4400,
The equal molecular mass of 100 numbers be 3000 isopentenol polyoxyethylene ether, 5 parts of propyl acrylates, 4 parts of butyl acrylates, 7 parts of alkene
Propyl alcohol, 610 parts of water, stirring and dissolving, drip 45 parts of acrylic acid, 6 parts of ALSs and 2 parts of hydrogen peroxide, persulfuric acid respectively
Potassium, ascorbic acid, the molecular weight regulator of the initiator of sodium hydrogensulfite composition, 4 parts of 3- mercaptopropionic acids and mercaptoethanol composition
Carry out free radicals copolymerization reaction 6h at 28 DEG C, after the completion of be incubated 3.5h at 28 DEG C, that is, obtain having the poly- of structure shown in Formulas I
Carboxylic acid water reducer.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 4 is obtained
Carry out correlated performance test, result such as table 1.
Embodiment 6
Under normal temperature condition, add in reactor the allyl alcohol polyethenoxy ether that the equal molecular mass of 180 numbers is 2259,
The equal molecular mass of 180 numbers be 4267 isobutene alcohol APEO, 2 parts of propyl acrylates, 10 parts of butyl acrylates, 8 parts
Allyl alcohol, 640 parts of water, stirring and dissolving, drip 45 parts of acrylic acid, 8 parts of ALSs and 6 parts of hydrogen peroxide, over cures respectively
Sour potassium, ascorbic acid, the molecule of the initiator of sodium hydrogensulfite composition, 6 parts of 3- mercaptopropionic acids and methylpropene sodium sulfonate composition
Amount conditioning agent carry out free radicals copolymerization reaction 9h at 28 DEG C, after the completion of at 28 DEG C be incubated 4h, that is, obtain with Formulas I Suo Shi knot
The polycarboxylate water-reducer of structure.
According to the relevant criterion of cement concrete, the polycarboxylate water-reducer with structure shown in Formulas I that embodiment 4 is obtained
Carry out correlated performance test, result such as table 1.
Comparative example 1
According to the relevant criterion of cement concrete, correlated performance survey is carried out using commercially available STB-05 polycarboxylate water-reducer
Examination, result such as table 1.
Comparative example 2
According to the relevant criterion of cement concrete, correlated performance survey is carried out using commercially available FS-2080 polycarboxylate water-reducer
Examination, result such as table 1.
Table 1 embodiment 1～6 and the polycarboxylate water-reducer the performance test results of comparative example 1～2
As can be seen from Table 1, the polycarboxylate water-reducer in the present invention is compared with commercially available polycarboxylate water-reducer, has higher
Water-reducing rate, relatively low air content and preferably reduce performance.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for 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 (10)
1. there is the polycarboxylate water-reducer of structure shown in Formulas I：
Wherein, M is Na+、K+Or NH4 +, R is-H ,-CH3Or-CH2CH3, 50≤a≤500,1≤b≤100,20≤c≤150,10
≤ d≤100,1≤e≤100,0≤m≤3,30≤n≤100.
2. polycarboxylate water-reducer according to claim 1 is it is characterised in that 100≤a≤300,30≤b≤60,50≤c
≤ 100,40≤d≤60,50≤e≤80,1≤m≤2,50≤n≤80.
3. the preparation method of polycarboxylate water-reducer described in claim 1 or 2 is it is characterised in that comprise the steps of：
Under conditions of initiator and molecular weight regulator exist, by APEO, acrylate, allyl alcohol, acrylic acid and
Allylsulfonate carries out copolyreaction in water, obtains the water reducer of structure shown in Formulas I.
4. preparation method according to claim 3 is it is characterised in that described APEO, acrylate, allyl alcohol,
Acrylic acid, the mass ratio of allylsulfonate are (270～380)：(2～15)：(3～9)：(20～60)：(1～9).
5. the preparation method according to claim 3 or 4 is it is characterised in that described APEO, initiator, molecular weight
Conditioning agent, the mass ratio of water are (270～380)：(1～8)：(1～7)：(580～660).
6. preparation method according to claim 3 is it is characterised in that described acrylate includes methyl acrylate, propylene
The mixture of one or more of acetoacetic ester, propyl acrylate and butyl acrylate.
7. preparation method according to claim 3 it is characterised in that described molecular weight regulator include 2- TGA,
The mixture of one or more of 3- mercaptopropionic acid, mercaptoethanol, methylpropene sodium sulfonate and azodiisobutyronitrile.
8. preparation method according to claim 3, it is characterised in that described initiator is redox initiator, comprises
Oxidation component and reduction components, described oxidation component comprises one or more of hydrogen peroxide, ammonium persulfate and potassium peroxydisulfate
Mixture, described reduction components comprise one or more of ascorbic acid, sodium bisulphite formaldehyde and sodium hydrogensulfite
Mixture.
9. preparation method according to claim 3 is it is characterised in that the temperature of described copolyreaction is 20～35 DEG C, altogether
The time of poly- reaction is 3～10h.
10. preparation method according to claim 3 is it is characterised in that also comprise isothermal holding, institute after described copolyreaction
The temperature stating insulation is 20～35 DEG C, and the time of insulation is 1～5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742895.5A CN106380549A (en) | 2016-08-27 | 2016-08-27 | Polycarboxyliy water reducer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742895.5A CN106380549A (en) | 2016-08-27 | 2016-08-27 | Polycarboxyliy water reducer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106380549A true CN106380549A (en) | 2017-02-08 |
Family
ID=57917479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610742895.5A Pending CN106380549A (en) | 2016-08-27 | 2016-08-27 | Polycarboxyliy water reducer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380549A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913318A (en) * | 2018-07-25 | 2018-11-30 | 刘滔 | A kind of concrete parting agent and preparation method thereof |
| CN113929837A (en) * | 2021-11-03 | 2022-01-14 | 同济大学 | Shrinkage-reducing polycarboxylic acid water reducer and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000034151A (en) * | 1998-07-15 | 2000-02-02 | Lion Corp | Cement admixture |
| CN102826784A (en) * | 2012-09-12 | 2012-12-19 | 江苏奥莱特新材料有限公司 | Polycarboxylate water reducer and preparation method thereof |
| CN102936109A (en) * | 2011-12-08 | 2013-02-20 | 江苏奥莱特新材料有限公司 | Polycarboxylic acid water reducing agent, preparation method and application thereof |
| CN103755895A (en) * | 2013-12-19 | 2014-04-30 | 聊城大学 | Polycarboxylic acid high performance water reducing agent and preparation method thereof |
| CN104693435A (en) * | 2013-12-06 | 2015-06-10 | 辽宁奥克化学股份有限公司 | Preparation method of polycarboxylate water reducer containing polyether side chains |
-
2016
- 2016-08-27 CN CN201610742895.5A patent/CN106380549A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000034151A (en) * | 1998-07-15 | 2000-02-02 | Lion Corp | Cement admixture |
| CN102936109A (en) * | 2011-12-08 | 2013-02-20 | 江苏奥莱特新材料有限公司 | Polycarboxylic acid water reducing agent, preparation method and application thereof |
| CN102826784A (en) * | 2012-09-12 | 2012-12-19 | 江苏奥莱特新材料有限公司 | Polycarboxylate water reducer and preparation method thereof |
| CN104693435A (en) * | 2013-12-06 | 2015-06-10 | 辽宁奥克化学股份有限公司 | Preparation method of polycarboxylate water reducer containing polyether side chains |
| CN103755895A (en) * | 2013-12-19 | 2014-04-30 | 聊城大学 | Polycarboxylic acid high performance water reducing agent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913318A (en) * | 2018-07-25 | 2018-11-30 | 刘滔 | A kind of concrete parting agent and preparation method thereof |
| CN108913318B (en) * | 2018-07-25 | 2021-04-20 | 刘滔 | Concrete release agent and preparation method thereof |
| CN113929837A (en) * | 2021-11-03 | 2022-01-14 | 同济大学 | Shrinkage-reducing polycarboxylic acid water reducer and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105367720B (en) | A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| US9365669B2 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN102976655B (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN109021181A (en) | A kind of poly carboxylic acid series water reducer and preparation method thereof for having both viscosity reduction and protecting function of collapsing | |
| CN102910855B (en) | Super plasticizer for precast concrete component | |
| CN106008853A (en) | Preparation method of mud resisting and slump retaining type phosphate group containing polycarboxylate superplasticizer | |
| CN104262548A (en) | Preparation method of mud-resistant polycarboxylate-type water reducer | |
| CN101333091A (en) | Method for preparing high-efficiency water-reducing agent of poly-carboxylic acid | |
| CN110642987B (en) | Ether ester copolymerization viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN105461866B (en) | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof | |
| CN103373831B (en) | Early-strength polycarboxylate superplasticizer and high-early-strength cement | |
| CN107892736A (en) | The method that compound oxidizing reduction initiating system produces high performance water reducing agent of polyocarboxy acid | |
| CN108840587A (en) | A kind of anti-chamotte mould cement water reducing agent and preparation method thereof | |
| CN104496253B (en) | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer | |
| CN106519137A (en) | Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof | |
| CN109776021A (en) | A kind of low entraining type clear-water concrete additive and preparation method thereof | |
| CN104371074A (en) | Low-temperature high-concentration polycarboxylate superplasticizer and preparation method thereof | |
| CN105036596B (en) | Low-temperature synthesis polycarboxylate superplasticizer and preparation method thereof | |
| CN104497230A (en) | Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof | |
| CN105949409A (en) | Polycarboxylate-series concrete water reducing agent containing chitosan, and preparation method thereof | |
| CN106380549A (en) | Polycarboxyliy water reducer and preparation method thereof | |
| CN114656600A (en) | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer | |
| KR102223222B1 (en) | Concrete admixtures composition and the manufacturing method thereof | |
| CN102910856A (en) | Super plasticizer for precast concrete component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170208 |
|
| RJ01 | Rejection of invention patent application after publication |