CN107265906B - A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof - Google Patents
A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof Download PDFInfo
- Publication number
- CN107265906B CN107265906B CN201710452555.3A CN201710452555A CN107265906B CN 107265906 B CN107265906 B CN 107265906B CN 201710452555 A CN201710452555 A CN 201710452555A CN 107265906 B CN107265906 B CN 107265906B
- Authority
- CN
- China
- Prior art keywords
- reducing agent
- high performance
- viscosity reduction
- reduction type
- water
- 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.)
- Active
Links
Classifications
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof, high performance water-reducer raw material are：Low molecule amount block modified unsaturated APEO comonomer A, unsaturated carboxylic acid comonomer B, APES C, initiator, reducing agent, chain-transferring agent, liquid caustic soda and water；The mass ratio of synthesis material is unsaturated APEO comonomer A：Unsaturated carboxylic acid comonomer B：APES C：Initiator：Reducing agent：Chain-transferring agent：Liquid caustic soda：Water is (320~420)：(24~36)：(3~10)：(1~5)：(0.5~3)：(0.5~4)：(20~50)：(400~500).The present invention have the characteristics that good dispersion property, viscosity reducing effect significantly, it is excellent with cement adaptability, Product Process is simple, securely and reliably, stable performance, not chloride ion-containing, to the harm of reinforcing bar non-corroding, it is environmentally safe the advantages that.
Description
Technical field
The invention belongs to technical field of concrete additives, more particularly to a kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid
And preparation method thereof.
Background technology
With the high speed development of China's building trade, high-grade concrete just with its bulk strength it is high, from heavy and light the features such as,
It is increasingly being applied in engineering construction.But the application environment of high-grade concrete, often building structure is complicated, and cloth muscle is close
Collection, this workability, mobility, self compacting ability and gain in strength to high-grade concrete are proposed higher requirement.
Presently mainly by reducing the ratio of mud, increase gel material content the methods of, improves the intensity of concrete, but
These methods can cause concrete viscosity to increase, and mobility declines, and so as to reduce pumpability of concrete, have impact on construction
Efficiency, largely limit the popularization and application of high-strength shale ceramsite.Viscosity reduction type polycarboxylate water-reducer can at present
To be effectively improved high-grade concrete viscosity problem, but the research country of this respect also compares shortcoming, the first-class product in market
Less, the mainly imported product such as viscosity reducing effect such as series of products of BASF RHEOPLUS 416 is preferable, but the product price is held high
It is expensive, also it is unfavorable for promoting the development of domestic polycarboxylic acids viscosity reduction technology.
At present, the patent report for viscosity reduction high performance water reducing agent of polyocarboxy acid is not also a lot, patent CN106279561A
Viscosity reduction type poly carboxylic acid series water reducer of a kind of high performance concrete and preparation method thereof is disclosed, first with polyethylene polyamine and third
Olefin(e) acid Arrcostab prepares a kind of comonomer A；Then by comonomer A, polyoxyethylene poly-oxygen propylene aether comonomer B, ethene
Base aromatic compound C and the lower progress aqueous phase Raolical polymerizable system of unsaturated carboxylic acid monomer D initiators and chain-transferring agent effect
Obtain viscosity reduction type poly carboxylic acid series water reducer.Although it has dispersive property by introducing polycarboxylate water-reducer made from hydrophobic grouping
The advantages that good, viscosity reducing effect is substantially and cement adaptability is good, but comonomer A needs the esterification by more than 5h and gone back
Needing to be evaporated under reduced pressure to be made, and contrast current polycarboxylate water-reducer preparation method, step is relative complex, undoubtedly adds economy
Cost.
Patent CN106008784A discloses a kind of concrete thinner and preparation method thereof, uses 4- hydroxyl butyl vinyls
Ether, unsaturated amides and unsaturated phosphate form for polymerizable raw material, although concrete thinner production prepared by the invention
Technique is simple, can effectively solve the problems, such as the big workability difference of concrete viscosity, but because the thinner molecular weight of synthesis is smaller, it is quiet
Electric repulsion and space steric effect are smaller, and its water-reducing rate is also corresponding relatively low, it is difficult to while meet high-grade concrete to water reducer
In water-reducing rate and the ambilateral demand of viscosity reduction.
Patent CN105924592A discloses a kind of viscosity reduction type poly carboxylic acid series water reducer and preparation method thereof, and the invention passes through
Synthesize the class water reducer of A, B two, and compounded and formed, have volume is small, viscosity reducing effect significantly, water-reducing rate and guarantor performance of collapsing it is excellent
The features such as different.But the modified APEO polymeric monomer of unsaturation that the high performance water-reducer process uses uses oxirane and epoxy
Propane random copolymerization forms, and molecular weight is larger, the hydrophilic and hydrophobic and viscosity reducing effect for adjusting molecular structure is difficult to have larger
Contribution.The preparation method compounded again using two-step process simultaneously is also relative complex, and follow-up industrialization and economy are still problem.
Therefore, in view of the shortcomings of the prior art, exploitation one kind both can guarantee that water-reducing rate and slump retaining, again with viscosity reduction function
Polycarboxylate water-reducer is significant.
The content of the invention
A kind of viscosity reduction type high-performance polycarboxylic acids is provided and subtracted it is an object of the invention to avoid the deficiencies in the prior art part
Aqua and preparation method thereof, with technical process is simple, good dispersion property, viscosity reducing effect are notable, excellent with cement adaptability
The features such as.
The above-mentioned purpose of the present invention is realized by following technological means.
A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid is provided, synthesis material is：Low molecule amount is block modified unsaturated poly-
Oxygen vinethene comonomer A, unsaturated carboxylic acid comonomer B, APES C, initiator, reducing agent, chain tra nsfer
Agent, liquid caustic soda and water；The mass ratio of synthesis material is unsaturated APEO comonomer A：Unsaturated carboxylic acid comonomer B：
APES C：Initiator：Reducing agent：Chain-transferring agent：Liquid caustic soda：Water is (320~420)：(24~36)：(3~
10)：(1~5)：(0.5~3)：(0.5~4)：(20~50)：(400~500).
Preferably, the block modified unsaturated APEO comonomer of above-mentioned low molecule amount, its molecule segment is by ring
Molecular structure is formed among Ethylene Oxide or epoxy butane segment insertion oxirane segment, its chemical structural formula is as follows：CH2
=C (CH2CH3)CH2O-(CH2CH2O)n1-(RO)m-(CH2CH2O)n2OH, R is-CH in formula2CH2CH3Or-CH2CH2CH2CH3
One kind, n1 and n2 are the addition molal quantitys of oxirane, and the scope of n1 and n2 sums is 4~22；M is expoxy propane or epoxy
The addition molal quantity of butane, m are 2~6.
Preferably, the block modified unsaturated APEO of above-mentioned low molecule amount, its relative molecular mass be 500~
1200。
Preferably, above-mentioned unsaturated carboxylic acid comonomer is in methacrylic acid, acrylic acid, itaconic acid, maleic anhydride
It is one or more.
Preferably, the chemical structural formula of abovementioned alkyl phenol polyethenoxy ether is RO (CH2CH2O)nH, wherein RO are nonyl phenol
Or octyl phenol, n represent the addition molal quantity of oxirane, n is 1~150, wherein, NPE NP-4, NP-
7th, at least one of NP-9 or NP-10, in OPEO OP-4, OP-7, OP-9 or OP-10 at least
It is a kind of.
Preferably, above-mentioned initiator is one kind or several of ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate or hydrogen peroxide
Kind.
Preferably, above-mentioned reducing agent is sodium sulfite, sodium hydrogensulfite, L-AA, sodium formaldehyde sulphoxylate
Or the one or more of ferrous sulfate.
Preferably, above-mentioned chain-transferring agent is isopropanol, sodium hypophosphite, lauryl mercaptan, mercaptoethanol or sulfydryl
Acetic acid and 3- mercaptopropionic acids are one or more of.
Present invention simultaneously provides a kind of preparation method of viscosity reduction type high performance water reducing agent of polyocarboxy acid, comprise the following steps：
To equipped with agitator, thermometer four-hole boiling flask in, put into the block modified unsaturated APEO of low molecule amount
Comonomer A and APES C, add water to open agitating and heating and be warming up to 35 DEG C~40 DEG C, treat that monomer is complete in flask
After fully dissolved, initiator is put into, I material solution and II material solution are added dropwise simultaneously after stirring 5min~10min, I material solution is by not
Saturated carboxylic acid comonomer B and water stir the solution being configured to, and II material solution is to be stirred by reducing agent, chain-transferring agent and water
The solution being uniformly configured to, I material solution be added dropwise 3h~4h, II material solution be added dropwise 3.5h~4.5h, after dripping off continue 40 DEG C~
45 DEG C of insulation 1h~2h, reaction terminate that rear moisturizing is cooled to 30 DEG C plus alkali is neutralized to pH value 6~7, finally the poly- carboxylic of obtained viscosity reduction type
Sour high-performance water reducing agent.
The present invention more unfolds free polycarboxylic acids using the block modified unsaturated APEO of low molecule amount to obtain
The hydrophobicity of water reducer side chain and regulation molecular structure, while further adjusted by introducing APES group
The hydrophilic and hydrophobic of polycarboxylate water-reducer molecule, final be made have that technical process is simple, good dispersion property, viscosity reducing effect show
Write, with cement adaptability it is excellent the features such as viscosity reduction type polycarboxylate water-reducer product, be particularly suitable for use in configuration high-strength concrete, from
Air-free concrete and high mineral admixture concrete etc..The present invention can with defoamer, air entraining agent, retarder, thickener, subtract
The functional form such as contracting agent auxiliary agent compounding use by a certain percentage, has good dispersion property, viscosity reducing effect significantly and cement adaptability
The features such as excellent, be particularly suitable for use in configuration high-strength concrete, self-compacting concrete and high mineral admixture concrete etc..Simultaneously
Product Process is simple, and securely and reliably, stable performance, chloride ion-containing, does not endanger reinforcing bar non-corroding, environmentally safe etc. excellent
Point.
Embodiment
Technical scheme is described further below by specific embodiment.
Embodiment 1.
A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid, synthesis material are：The block modified unsaturated polyoxy second of low molecule amount
Alkene ether comonomer A, unsaturated carboxylic acid comonomer B, APES C, initiator, reducing agent, chain-transferring agent, liquid
Alkali and water；The mass ratio of synthesis material is unsaturated APEO comonomer A：Unsaturated carboxylic acid comonomer B：Alkyl
Phenol polyethenoxy ether C：Initiator：Reducing agent：Chain-transferring agent：Liquid caustic soda：Water is (320~420)：(24~36)：(3~10)：(1
~5)：(0.5~3)：(0.5~4)：(20~50)：(400~500).
Wherein, the block modified unsaturated APEO comonomer of low molecule amount, its molecule segment by expoxy propane or
Molecular structure is formed among epoxy butane segment insertion oxirane segment, its chemical structural formula is as follows：CH2=C
(CH2CH3)CH2O-(CH2CH2O)n1-(RO)m-(CH2CH2O)n2OH, R is-CH in formula2CH2CH3Or-CH2CH2CH2CH3One
Kind, n1 and n2 are the addition molal quantitys of oxirane, and the scope of n1 and n2 sums is 4~22；M is expoxy propane or epoxy butane
Addition molal quantity, m be 2~6.
The block modified unsaturated APEO of the low molecule amount, its relative molecular mass is than usually used average molecular
Quality is that 2400 polyether monomers are small, is 500~1200.
Wherein, unsaturated carboxylic acid comonomer can be one kind in methacrylic acid, acrylic acid, itaconic acid, maleic anhydride
It is or a variety of.
Wherein, the chemical structural formula of APES is RO (CH2CH2O)nH, wherein RO are nonyl phenol or octyl group
Phenol, n represent the addition molal quantity of oxirane, and n is 1~150, wherein, NPE NP-4, NP-7, NP-9
Or at least one of at least one of NP-10, OPEO OP-4, OP-7, OP-9 or OP-10.
Initiator can be the one or more of ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate or hydrogen peroxide.Reducing agent can be
Sodium sulfite, sodium hydrogensulfite, L-AA, the one or more of sodium formaldehyde sulphoxylate or ferrous sulfate.Chain turns
It can be that isopropanol, sodium hypophosphite, lauryl mercaptan, mercaptoethanol or TGA and 3- mercaptopropionic acids are a kind of or several to move agent
Kind.
The preparation method of the viscosity reduction type high performance water reducing agent of polyocarboxy acid of the present invention, is made by the steps and forms：To dress
In the four-hole boiling flask for having agitator, thermometer, the block modified unsaturated APEO comonomer A of input low molecule amount and alkane
Base phenol polyethenoxy ether C, add water to open agitating and heating and be warming up to 35 DEG C~40 DEG C, after monomer is completely dissolved in flask, input
Initiator, stir and I material solution and II material solution be added dropwise after 5min~10min simultaneously, I material solution be copolymerized by unsaturated carboxylic acid it is single
Body B and water stir the solution being configured to, II material solution for stirred by reducing agent, chain-transferring agent and water be configured to it is molten
Liquid, I material solution are added dropwise 3h~4h, II material solution and 3.5h~4.5h are added dropwise, continues to be incubated 1h~2h at 40 DEG C~45 DEG C after dripping off,
Reaction terminates that rear moisturizing is cooled to 30 DEG C plus alkali is neutralized to pH value 6~7, finally obtained viscosity reduction type high performance water reducing agent of polyocarboxy acid.
The present invention more unfolds free polycarboxylic acids using the block modified unsaturated APEO of low molecule amount to obtain
The hydrophobicity of water reducer side chain and regulation molecular structure, while further adjusted by introducing APES group
The hydrophilic and hydrophobic of polycarboxylate water-reducer molecule, finally give with technical process is simple, good dispersion property, viscosity reducing effect show
Write, with cement adaptability it is excellent the features such as viscosity reduction type polycarboxylate water-reducer product, be particularly suitable for use in configuration high-strength concrete, from
Air-free concrete and high mineral admixture concrete etc..The present invention can with defoamer, air entraining agent, retarder, thickener, subtract
The functional form such as contracting agent auxiliary agent compounding use by a certain percentage, has good dispersion property, viscosity reducing effect significantly and cement adaptability
The features such as excellent, be particularly suitable for use in configuration high-strength concrete, self-compacting concrete and high mineral admixture concrete etc..Simultaneously
Product Process is simple, and securely and reliably, stable performance, chloride ion-containing, does not endanger reinforcing bar non-corroding, environmentally safe etc. excellent
Point.
Embodiment 2.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 324.1 parts of molecular weight are 500
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)2-(CH2CH2CH2O)2-(CH2CH2O)5OH and 4.8
Part NPE NP-4, add 250.5 parts of water to open agitating and heatings and be warming up to 35 DEG C~40 DEG C, treat that monomer is complete in flask
After fully dissolved, 1.2 parts of ammonium persulfates are put into, I material and II material solution are added dropwise simultaneously after stirring 5min~10min, I is expected (by 34.7
Part acrylic acid and 40 parts of water stir the solution being configured to) be added dropwise 3h~4h, II material (by 2.1 parts of sodium hydrogensulfites, 1.8 parts
TGA and 58.7 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue after dripping off at 40 DEG C~45 DEG C
1h~2h is incubated, reaction mends 93.5 parts after terminating and is water-cooled to 30 DEG C or so and adds 39.2 parts of liquid caustic soda to be neutralized to pH value 6~7 or so,
Finally obtained viscosity reduction type high performance water reducing agent of polyocarboxy acid.
Embodiment 3.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 359.4 parts of molecular weight are 800
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)3-(CH2CH2CH2CH2O)4-(CH2CH2O)7OH and
5.7 parts of NPE NP-10, add 254.3 parts of water to open agitating and heating and be warming up to 35 DEG C~40 DEG C, treat single in flask
After body is completely dissolved, put into 1.9 parts of sodium peroxydisulfates, stir 5min~10min after simultaneously be added dropwise I material and II material solution, I material (by
25.4 parts of acrylic acid and 30 parts of water stir the solution being configured to) be added dropwise 3h~4h, II material (by 1.8 parts of L-AAs,
1.6 parts of mercaptoethanols and 72.4 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue after dripping off 40 DEG C~
50 DEG C of insulation 1h~2h, reaction mend 90.4 parts and are water-cooled to 30 DEG C or so to add 35.0 parts of liquid caustic soda to be neutralized to pH value 6~7 left after terminating
The right side, viscosity reduction type high performance water reducing agent of polyocarboxy acid is finally made.
Embodiment 4.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 391.2 parts of molecular weight are 1200
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)7-(CH2CH2CH2O)6-(CH2CH2O)10OH and 5.7
Part OPEO OP-7, add 254.3 parts of water to open agitating and heatings and be warming up to 35 DEG C~40 DEG C, treat that monomer is complete in flask
After fully dissolved, 1.9 parts of hydrogen peroxide are put into, I material and II material solution are added dropwise simultaneously after stirring 5min~10min, I is expected (by 32.6 parts
Methacrylic acid, 11.2 parts of ethyl acrylates stir the solution being configured to) 3h~4h, II material is added dropwise (is closed by 1.8 parts of formaldehyde
Sodium bisulphite, 2.3 parts of 3- mercaptopropionic acids and 96.7 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, drip off
After continue to be incubated 1h~2h at 40 DEG C~45 DEG C, reaction mends 102.5 parts after terminating and is water-cooled to 30 DEG C or so and adds 35.8 parts of liquid caustic soda
PH value 6~7 or so is neutralized to, finally obtained viscosity reduction type high performance water reducing agent of polyocarboxy acid.
Embodiment 5.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 329.4 parts of molecular weight are 600
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)3-(CH2CH2CH2CH2O)2-(CH2CH2O)5OH and
7.8 parts of OPEO OP-4, add 250.5 parts of water to open agitating and heating and be warming up to 35 DEG C~40 DEG C, treat single in flask
After body is completely dissolved, put into 2.3 parts of hydrogen peroxide, stir 5min~10min after simultaneously be added dropwise I material and II material solution, I material (by
26.7 parts of methacrylic acids and 30 parts of water stir the solution being configured to) be added dropwise 3h~4h, II material (by 1.6 parts of sodium sulfites,
1.4 parts of 3- mercaptopropionic acids and 65.4 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue after dripping off at 40 DEG C
~45 DEG C insulation 1h~2h, reaction terminate after mend 101.7 parts be water-cooled to 30 DEG C or so add 32.6 parts of liquid caustic soda be neutralized to pH value 6~
7 or so, viscosity reduction type high performance water reducing agent of polyocarboxy acid is finally made.
Embodiment 6.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 405.4 parts of molecular weight are 1000
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)6-(CH2CH2CH2O)3-(CH2CH2O)11OH and 4.8
Part OPEO OP-9, add 254.0 parts of water to open agitating and heatings and be warming up to 35 DEG C~40 DEG C, treat that monomer is complete in flask
After fully dissolved, 3.5 parts of hydrogen peroxide are put into, I material and II material solution are added dropwise simultaneously after stirring 5min~10min, I is expected (by 32.0 parts
Itaconic acid and 40 parts of water stir the solution being configured to) 3h~4h, II material is added dropwise (by 2.2 parts of ferrous sulfate, 1.8 parts of isopropyls
Alcohol and 100.0 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue to be incubated 1h at 40 DEG C~45 DEG C after dripping off
~2h, reaction mend 74.2 parts after terminating and are water-cooled to 30 DEG C or so and add 36.8 parts of liquid caustic soda to be neutralized to pH value 6~7 or so, final system
Obtain viscosity reduction type high performance water reducing agent of polyocarboxy acid.
Embodiment 7.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 350.0 parts of molecular weight are 800
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)3-(CH2CH2CH2O)5-(CH2CH2O)6OH and 3.2
Part OPEO NP-9, add 248.6 parts of water to open agitating and heatings and be warming up to 35 DEG C~40 DEG C, treat that monomer is complete in flask
After fully dissolved, 4.2 parts of ammonium persulfates are put into, I material and II material solution are added dropwise simultaneously after stirring 5min~10min, I is expected (by 28.4
Part maleic anhydride and 30 parts of water stir the solution being configured to) 3h~4h, II material is added dropwise (by 1.9 parts of L-AAs, 1.2
Part sodium hypophosphite and 78.2 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue after dripping off 40 DEG C~45
DEG C insulation 1h~2h, reaction mend 99.0 parts and are water-cooled to 30 DEG C or so to add 29.4 parts of liquid caustic soda to be neutralized to pH value 6~7 left after terminating
The right side, viscosity reduction type high performance water reducing agent of polyocarboxy acid is finally made.
Embodiment 8.
To equipped with agitator, thermometer four-hole boiling flask in, put into the low molecule amount block that 337.5 parts of molecular weight are 1200
Modified unsaturated APEO CH2=C (CH2CH3)CH2O-(CH2CH2O)4-(CH2CH2CH2CH2O)3-(CH2CH2O)16OH and
8.6 parts of OPEO NP-7, add 252.2 parts of water to open agitating and heating and be warming up to 435 DEG C~40 DEG C, treat single in flask
After body is completely dissolved, put into 1.8 parts of hydrogen peroxide, stir 5min~10min after simultaneously be added dropwise I material and II material solution, I material (by
35.2 parts of methacrylic acids and 40 points of solution being configured to that stir) be added dropwise 3h~4h, II material (by 0.9 part of L-AA,
0.7 part of sodium hypophosphite and 65.8 parts of water stir the solution being configured to) 3.5h~4.5h is added dropwise, continue after dripping off 40 DEG C~
45 DEG C of insulation 1h~2h, reaction mend 96.4 parts and are water-cooled to 30 DEG C or so to add 31.4 parts of liquid caustic soda to be neutralized to pH value 6~7 left after terminating
The right side, viscosity reduction type high performance water reducing agent of polyocarboxy acid is finally made.
Comparative example 1.
To equipped with agitator, thermometer four-hole boiling flask in, put into the isopentene group polyoxy that 370.5 parts of molecular weight are 2400
Vinethene, add 245 parts of water to open agitating and heating and be warming up to 40 DEG C~50 DEG C, after monomer is completely dissolved in flask, put into 1.8 parts
Hydrogen peroxide, I material and II material solution are added dropwise simultaneously after stirring 5min~10min, I material (add 50 parts of water by 35.2 parts of methacrylic acids
Stir the solution being formulated) 3h~4h, II material is added dropwise (by 1.1 parts of L-AAs, 1.2 parts of mercaptoethanols and 105.8
Part water stirs the solution being configured to) 3.5h~4.5h is added dropwise, continue to be incubated 1h~2h, reaction at 40 DEG C~50 DEG C after dripping off
95.8 parts are mended after end to be water-cooled to 30 DEG C or so and add 37.5 parts of liquid caustic soda to be neutralized to pH value 6~7 or so, finally obtained viscosity reduction type gathers
Carboxylic acid high-performance water reducing agent.
Comparative example 2.
To equipped with agitator, thermometer four-hole boiling flask in, put into the methacrylic that 350.5 parts of molecular weight are 2400 and gather
Oxygen vinethene, add 225 parts of water to open agitating and heating and be warming up to 60 DEG C~70 DEG C, after monomer is completely dissolved in flask, input 2.2
Part ammonium persulfate, I material are added dropwise simultaneously after stirring 5min~10min and II expects solution, I material (add 50 parts of water by 34.7 parts of acrylic acid
Stir the solution being formulated) 3h~4h, II material is added dropwise (by 1.7 parts of sodium formaldehyde sulfoxylates, 1.4 parts of mercaptopropionic acids and 102.4 parts of water
Stir the solution being configured to) 3.5h~4.5h is added dropwise, continue to be incubated 1h~2h at 60 DEG C~70 DEG C after dripping off, reaction terminates
Mend 94.7 parts afterwards to be water-cooled to 30 DEG C or so and add 35.9 parts of liquid caustic soda to be neutralized to pH value 6~7 or so, finally obtained viscosity reduction type polycarboxylic acids
High-performance water reducing agent.
Application Example 1.
Viscosity reduction type high-performance polycarboxylic acids water reducing agent prepared by the embodiment of the present invention 2~8 is newly mixed with comparative example 1~2
Concrete application performance contrasts, with reference to standard GB/T 8076-2018《Concrete admixture》Relevant regulations, experiment use glue
Than the high-performance concrete mix for 0.28,1 is shown in Table, experiment uses Guangdong show P.O.42.5 cement；The sensible I levels powder in Foshan South Sea
Coal ash, the sensible miberal powder in Foshan South Sea；The middle sand of modulus of fineness 2.5；The rubble of 5mm~20mm continuous gradings, concrete 's air-containing
Control is 2.0%~3.0%.Using the viscosity of the bucket of falling slump method test concrete：Slump cone is inverted, fills concrete
And it is floating, while lifting slump cone rapidly, the time of concrete emptying is recorded with stopwatch, if concrete flows out slump cone
Time it is smaller, it is corresponding represent concrete viscosity it is smaller.Concrete crushing strength experiment according to《Normal concrete mechanical property
Test method standard》GB/T 50081-2002 are carried out.
Concrete mix (the kg/m of table 13)
| Strength grade | Cement | Flyash | Miberal powder | Sand | Stone | Water |
| C50 | 380 | 60 | 60 | 660 | 1100 | 140 |
The concrete performance of table 2 contrasts
Shown by the result of table 2, under conditions of control concrete initial slump degree (divergence) is basically identical, with contrast
The plain edition polycarboxylate water-reducer of example 1~2 is compared, and fills the inverted slump test tube emptying that the present invention prepares the concrete of embodiment 2~8
Time is significantly smaller, illustrates the viscosity and tool that concrete can be effectively reduced by poly carboxylic acid series water reducer prepared by the inventive method
There is more excellent guarantor to collapse performance, while the concrete strength of embodiment 2~8 and comparative example 1~2 increases preferably, 7d can reach
More than 50%, 28d substantially exceed 60MPa, are demonstrated by good combination property.
The preferred embodiments of the present invention are the foregoing is only, but they are not used to limit the present invention, it is any in the present invention
Any modification made within principle, equivalent substitution and improvement should be included in the scope of the protection.
Claims (8)
1. a kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid, it is characterised in that synthesis material is：The block modified insatiable hunger of low molecule amount
With APEO comonomer A, unsaturated carboxylic acid comonomer B, APES C, initiator, reducing agent, chain
Transfer agent, liquid caustic soda and water；The mass ratio of synthesis material is unsaturated APEO comonomer A：Unsaturated carboxylic acid copolymerization is single
Body B：APES C：Initiator：Reducing agent：Chain-transferring agent：Liquid caustic soda：Water is (320~420)：(24~36)：(3
~10)：(1~5)：(0.5~3)：(0.5~4)：(20~50)：(400~500)；
The block modified unsaturated APEO comonomer of described low molecule amount, its molecule segment is by expoxy propane or epoxy
Molecular structure is formed among butane segment insertion oxirane segment, its chemical structural formula is as follows：CH2=C (CH2CH3)
CH2O-(CH2CH2O)n1-(RO)m-(CH2CH2O)n2OH, R is-CH in formula2CH2CH3Or-CH2CH2CH2CH3One kind, n1 and
N2 is the addition molal quantity of oxirane, and the scope of n1 and n2 sums is 4~22；M is the addition of expoxy propane or epoxy butane
Molal quantity, m are 2~6.
2. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 1, it is characterised in that described low molecule amount block
Modified unsaturated APEO, its relative molecular mass are 500~1200.
3. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 2, it is characterised in that the unsaturated carboxylic acid copolymerization
Monomer is the one or more in methacrylic acid, acrylic acid, itaconic acid, maleic anhydride.
4. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 3, it is characterised in that the alkylphenol-polyethenoxy
The chemical structural formula of ether is RO (CH2CH2O)nH, wherein RO are nonyl phenol or octyl phenol, and n represents the addition mole of oxirane
Number, n are 1~150, wherein, at least one of NPE NP-4, NP-7, NP-9 or NP-10, octyl group
Phenol polyethenoxy ether is at least one of OP-4, OP-7, OP-9 or OP-10.
5. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 4, it is characterised in that described initiator is over cure
Sour ammonium, sodium peroxydisulfate, the one or more of potassium peroxydisulfate or hydrogen peroxide.
6. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 5, it is characterised in that described reducing agent is sulfurous
Sour sodium, sodium hydrogensulfite, L-AA, the one or more of sodium formaldehyde sulphoxylate or ferrous sulfate.
7. viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 6, it is characterised in that described chain-transferring agent is different
Propyl alcohol, sodium hypophosphite, lauryl mercaptan, mercaptoethanol or TGA and 3- mercaptopropionic acids are one or more of.
8. the preparation method of viscosity reduction type high performance water reducing agent of polyocarboxy acid as claimed in claim 1, it is characterised in that including as follows
Step：
To equipped with agitator, thermometer four-hole boiling flask in, the block modified unsaturated APEO copolymerization of input low molecule amount
Monomer A and APES C, add water to open agitating and heating and be warming up to 35 DEG C~40 DEG C, treat that monomer is completely molten in flask
Xie Hou, initiator is put into, I material solution and II material solution are added dropwise simultaneously after stirring 5min~10min, I material solution is by unsaturation
Carboxylic acid comonomers B and water stir the solution being configured to, and II material solution is stirs by reducing agent, chain-transferring agent and water
The solution being configured to, I material solution are added dropwise 3h~4h, II material solution and 3.5h~4.5h are added dropwise, continues after dripping off at 40 DEG C~45 DEG C
It is incubated 1h~2h, reaction terminates that rear moisturizing is cooled to 30 DEG C plus alkali is neutralized to pH value 6~7, and finally obtained viscosity reduction type polycarboxylic acids is high
Performance water reducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710452555.3A CN107265906B (en) | 2017-06-15 | 2017-06-15 | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710452555.3A CN107265906B (en) | 2017-06-15 | 2017-06-15 | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107265906A CN107265906A (en) | 2017-10-20 |
| CN107265906B true CN107265906B (en) | 2018-02-23 |
Family
ID=60067739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710452555.3A Active CN107265906B (en) | 2017-06-15 | 2017-06-15 | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107265906B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041472B (en) * | 2018-01-15 | 2022-03-29 | 辽宁奥克化学股份有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN108585572B (en) * | 2018-02-05 | 2019-12-31 | 武汉优城科技有限公司 | Polymer surface modified calcium sulphoaluminate expanding agent and preparation method thereof |
| CN108822262A (en) * | 2018-05-25 | 2018-11-16 | 湖北工业大学 | 1200 molecular weight polyether polycarboxylate water-reducers of one kind and preparation method |
| CN109749020B (en) * | 2018-12-26 | 2021-11-16 | 广西红墙新材料有限公司 | Alkyl-containing early-strength viscosity-reduction type polycarboxylate superplasticizer and preparation method thereof |
| CN109928661A (en) * | 2019-04-15 | 2019-06-25 | 山西格瑞特建筑科技股份有限公司 | A kind of viscosity reduction type solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN110218018A (en) * | 2019-06-14 | 2019-09-10 | 杭州中齐新材料科技有限公司 | A kind of viscosity reduction type concrete admixture |
| CN110240697B (en) * | 2019-06-19 | 2020-06-12 | 北京金隅水泥节能科技有限公司 | Functional monomer and preparation method thereof, polycarboxylic acid water reducing agent and preparation method and application thereof |
| CN110358023B (en) * | 2019-07-31 | 2021-10-08 | 科之杰新材料集团有限公司 | Low-surface-tension reduction type polycarboxylate superplasticizer and preparation method thereof |
| CN111268935B (en) * | 2019-11-22 | 2022-07-01 | 中交二航武汉港湾新材料有限公司 | Additive for ultra-high performance concrete and preparation method thereof |
| CN113999348A (en) * | 2021-11-24 | 2022-02-01 | 湖南金华达建材有限公司 | Viscosity reduction type ester ether copolymerization polycarboxylate superplasticizer and normal-temperature preparation method thereof |
| CN117164770B (en) * | 2023-08-08 | 2024-06-14 | 长江三峡技术经济发展有限公司 | High-dispersion water reducer with shrinkage reducing function and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6875801B2 (en) * | 1999-12-10 | 2005-04-05 | Construction Research & Technology Gmbh | Solubilized defoamers for cementitious compositions |
| CN103553413B (en) * | 2013-09-25 | 2016-05-04 | 中国建筑材料科学研究总院 | A kind of sticky type polycarboxylate water-reducer and preparation method thereof of adjusting |
| CN103965460A (en) * | 2014-05-20 | 2014-08-06 | 武汉理工大学 | Polycarboxylate-type water reducing agent |
| CN104446099A (en) * | 2014-11-06 | 2015-03-25 | 贵州恒一新材料有限公司 | Polycarboxylic acid water reducing agent and preparation method thereof |
| CN105504261A (en) * | 2016-01-04 | 2016-04-20 | 鑫统领建材集团有限公司 | Random copolyether macromonomer, water reducing agent prepared from same, and preparing method and application of random copolyether macromonomer |
-
2017
- 2017-06-15 CN CN201710452555.3A patent/CN107265906B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107265906A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107265906B (en) | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof | |
| TWI540153B (en) | Polycarboxylic acid copolymers, cement dispersants, cement mixtures and cement compositions | |
| JP5769930B2 (en) | Dispersant | |
| KR101288145B1 (en) | Ultrarapid hardening cement composition and dispersant for ultrarapid hardening cement composition | |
| CN107337766B (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| CN107652405B (en) | Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof | |
| CN109608594A (en) | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN108003301A (en) | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer | |
| CN106279561B (en) | A kind of viscosity reduction type poly carboxylic acid series water reducer for high performance concrete | |
| CN109651566A (en) | A kind of viscosity reduction type polycarboxylate water-reducer and preparation method thereof | |
| CN107337765A (en) | Phosphonic acids based polyalcohol with strong adaptability and function of slump protection and its preparation method and application | |
| CN112694574A (en) | Novel high-mud-resistance high-slump-resistance polycarboxylic acid water reducer and preparation method thereof | |
| CN106565921B (en) | A kind of nanometer of polycarboxylate water-reducer and preparation method thereof | |
| CN107586366A (en) | A kind of modified polycarboxylic acid water reducer and preparation method thereof | |
| CN105601155A (en) | Additive special for limestone powder concrete | |
| JP2003221266A (en) | Cement admixture | |
| CN112661914A (en) | Novel polycarboxylate superplasticizer special for machine-made sand and preparation method thereof | |
| CN104193215B (en) | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof | |
| CN111378083B (en) | Polycarboxylic acid dispersant with star structure and preparation method and application thereof | |
| CN102936112B (en) | Polycarboxylic acid water reducing agent suitable for high-strength self-compacting concrete and preparation method of polycarboxylic acid water reducing agent | |
| CN111378078A (en) | Star-shaped polycarboxylate superplasticizer with viscosity reducing effect and preparation method and application thereof | |
| CN107987228A (en) | A kind of preparation method of low hydration heat Early-strength polycarboxylate superplasticizer | |
| CN107903361A (en) | A kind of preparation method of high-adaptability concrete flowability stabilizer | |
| CN104592457A (en) | Preparation method for sulfate-compatible polycarboxylic water reducer | |
| JP4877691B2 (en) | Method of constructing cement admixture and cement composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |