The high high-early strength type polycarboxylic acids dehydragent of a kind of high diminishing and its without thermal source preparation method
Technical field
The present invention relates to concrete additive technical field in construction material, more particularly to a kind of high early-strength of high diminishing
Poly carboxylic acid series water reducer and its without thermal source preparation method.
Background technology
The maximum culture's material of consumption in the concrete world today.Concrete admixture is in mixing concrete mixing
The material for improving concrete performance is mixed during front or mix, can effectively improve the performance of concrete, become coagulation
Indispensable material in soil.
Modern age concrete admixture originates from early 1930s, experienced the common diminishing of the first generation that calcium lignosulfonate is representative
Agent, naphthalene system and melamine series be represent second generation high efficiency water reducing agent, polycarboxylic-acid as representative third generation high-performance diminishing
Agent three phases, the so far existing developing history of more than 80 years.Water reducer, slump retaining agent, rapid hardening are broadly divided into by the function of additive
Agent, retarder, defoamer, early strength agent etc..Polycarboxylate water-reducer is got over as third generation water reducer used in the engineering of China
Come more extensive, relative to water reducers such as naphthalene system and melamine series, its peptizaiton effect is good, and the retention time is long, can make coagulation
Soil has good service behaviour.
After mixing polycarboxylate water-reducer, concrete can be made to possess good service behaviour and mechanical property, it is at a high speed
Advantage is especially prominent in the engineering that the structure durabilities such as railway have high demands.Its excellent performance derives from its special comb shape molecule
Structure, main chain is adsorbed in cement particle surface, forms firm adsorption layer, is extended in villiform by polyethylene oxide side chains water-soluble
In liquid, strong sterically hindered effect is formed, make cement granules obtain significant peptizaiton.However, plain edition polycarboxylic acids subtracts
Aqua can significantly delay the aquation of cement, and especially under cryogenic, early strength slower development makes common polycarboxylic acids diminishing
Agent is constructed be restricted with the use of cold environment in the winter time, is also constrained in early strong engineering and concrete prefabricated element is required
Use.
In concrete prefabricated element production, in order to increase production efficiency, template turn-around speed is improved, do not require nothing more than polycarboxylic acids
Water reducer has good diminishing peptizaiton, is also required to improve early age strength of concrete;In addition, in order to accelerate low temperature bar
Speed of application under part, also requires that concrete has preferably morning epistasis energy.
At present, improving early age strength of concrete has three kinds of main paths:(1) used using extraordinary strength cement and increase cement
Amount (yield and price are restricted can not generally be adopted);(2) steam curing is adopted, or even the technological approaches of microwave curing is trying one's best
Improve early age strength of concrete.(it is unfavorable for the raising of volume stability of concrete and durability, steam curing and microwave curing are not
Beneficial to environmental protection, the requirement of energy-conservation);(3) using early-strength admixture (method of operating is simple, with low cost).
Early-strength admixture is generally using naphthalene water reducer (or melamine system water reducer) or common polycarboxylic-acid diminishing
The mode that agent is compounded with early strength agent (triethanolamine, sodium sulphate, sodium chloride etc.), but naphthalene water reducer (or melamine series diminishing
Agent) have the shortcomings that water-reducing rate is not high enough, concrete plasticity that is preparing is poor, slump-loss is big with early strength agent compounding;Using general
Logical poly carboxylic acid series water reducer is compounded with early strength agent (triethanolamine, sodium sulphate, sodium chloride etc.), be there is unstable product quality, is held
The shortcomings of being easily layered.
Patent CN201410220236 utilize isobutene alcohol APEO (HPEG), acrylic acid (AA), 2- acrylamides-
2- methyl propane sulfonic acids (AMPS) polymerization obtains a kind of high-early strength type polycarboxylic acids dehydragent, but needs to be closed at a temperature of 40-45 DEG C
Into;Patent CN201110291956 utilizes the modified polyoxyalkylenes ether containing unsaturated double-bond, (methyl) acrylic acid, unsaturation
The sulfonate of double bond, four kinds of monomers of acrylamide are carried out water-soluble under molecular weight regulator existence condition by free radical initiation
Liquid copolymerization and obtain high-early strength type polycarboxylic acids dehydragent, but need at a temperature of 50-70 DEG C synthesize.
In the high-early strength type polycarboxylic acids dehydragent synthetic method that above-mentioned patent is announced, steam or boiler heating are required for,
Energy resource consumption and equipment investment are increased, production cost is high, is unfavorable for energy-saving and emission-reduction and reduces cost.
The content of the invention
In order to overcome drawbacks described above, the present invention to carry out extensively and profoundly studying, by being with unsaturated APEO
Main macromonomer, is designed for poly carboxylic acid series water reducer comb shaped molecular structure, by select suitable polymeric monomer and
Polymerization technique, adjustment molecular architecture and functional group densities and species, synthesize high-early strength type polycarboxylic acids dehydragent mother liquor, are combined
With auxiliary materials such as various high-quality accelerating components, defoamers, the high early-strength polycarboxylic admixture of high diminishing is obtained.Make full use of height
The characteristics of high water reducing rate and works fine performance of diminishing high early-strength polycarboxylic admixture, changes poly carboxylic acid series water reducer pair
The hydration influences of cement, shorten concrete coagulating time, improve early age strength of concrete, and improve production efficiency is cost-effective.
It is an object of the invention to overcoming, conventional water reducer complex manufacturing, production power consumption are high, quality is unstable (such as divides
Layer etc.) the shortcomings of, there is provided a kind of process is simple, energy-conserving and environment-protective, the high high-early strength type polycarboxylic acids dehydragent of high diminishing of excellent performance
And its without thermal source preparation method.
The technical solution adopted for the present invention to solve the technical problems is:A kind of high early-strength polycarboxylic-acid diminishing of high diminishing
Agent, it is characterised in that:It is made up of the raw material of following weight percent, high-early strength type polycarboxylic acids dehydragent mother liquor 10%~30%;It is early
Strong component 1%~15%;Defoamer 0.005%~0.02%;Water surplus;
Wherein, high-early strength type polycarboxylic acids dehydragent mother liquor is made up of the raw material of following weight percent:
Unsaturated APEO 33%~37%;Unsaturated acids and/or unsaturated acids derivative 2%~6%;Chain tra nsfer
Agent 0.1%~0.8%;Oxidant 0.1%~0.3%;Reducing agent 0.03%~0.08%;Alkali 0.5%~1.0%;Remaining is
Water;
The mean molecule quantity of the unsaturated APEO is in 3800-4000.
The alkali is preferably NaOH.
The preparation method of the high-early strength type polycarboxylic acids dehydragent mother liquor comprises the steps:
1. get the raw materials ready:Reducing agent and water are mixed to prepare into reducing agent aqueous solution, a material are denoted as;By chain-transferring agent, unsaturated acids
And/or unsaturated acids derivative, water are mixed to prepare the aqueous solution, b material are denoted as;
2. it is polymerized:Unsaturated APEO and water are added in reactor, is stirred to dissolving, add oxidant;Stirring
After uniform, while adding a material and b to expect, it is 15~40 DEG C to control temperature in the kettle during charging, after charging is finished, continuation reaction 1.5~
3 hours, it was 7~9 to be neutralized to pH with aqueous slkali, obtains high-early strength type polycarboxylic acids dehydragent mother liquor.
The time control of the addition a material and b material was at 2~4 hours.
The accelerating component be triethanolamine, sodium sulphate and sodium chloride in one or more, preferably triethanolamine and
One or more in sodium sulphate.
The defoamer is at least one in machine silicon defoaming agent and polyethers defoamer.
It is preferred that b material are chain-transferring agent, unsaturated acids, unsaturated acids derivative and the aqueous solution obtained in water, so can obtain
To the more preferable water reducer of early strong effect.
The unsaturated acids is acrylic acid;Unsaturated acids derivative is in acrylamide, ethyl acrylate, butyl acrylate
One or more.
The oxidant is one or more in hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate, preferred oxygen
Agent is hydrogen peroxide.
The chain-transferring agent is one or more from mercaptopropionic acid, methylpropene sodium sulfonate, TGA.
The reducing agent is one or more in L-AA, ferrous sulfate and sodium hydrogensulfite.
The present invention also provides a kind of preparation method of the high high-early strength type polycarboxylic acids dehydragent of high diminishing, comprises the steps:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor is prepared
1. get the raw materials ready:Reducing agent and water are mixed to prepare into reducing agent aqueous solution, a material are denoted as;By chain-transferring agent, unsaturated acids
And/or unsaturated acids derivative, water are mixed to prepare the aqueous solution, b material are denoted as;
2. it is polymerized:Unsaturated APEO and water are added in reactor, is stirred to dissolving, add oxidant;Stirring
After uniform, while adding a material and b to expect, it is 15~40 DEG C to control temperature in the kettle during charging, after charging is finished, continuation reaction 1.5~
3 hours, it was 7~9 to be neutralized to pH with aqueous slkali, obtains high-early strength type polycarboxylic acids dehydragent mother liquor;
(2) the high high-early strength type polycarboxylic acids dehydragent of high diminishing is prepared
Water, defoamer, high-early strength type polycarboxylic acids dehydragent mother liquor, mixing and stirring are sequentially added in a reservoir, then are added
Enter accelerating component and be uniformly mixing to obtain the high high-early strength type polycarboxylic acids dehydragent of high diminishing.
It is preferred that the time control of the addition a material and b material was at 2~4 hours.
In this programme, the synthesis of high-early strength type polycarboxylic acids dehydragent mother liquor adds a material and b to be heat release when expecting without the need for thermal source
Reaction, it is 15~40 DEG C to control temperature in the kettle during charging, synthesizes the early-strength polycarboxylic-acid acted synergistically with accelerating component and subtracts
Aqua mother liquor, low cost, process is simple.
The present invention compared with like product and technique, with significant beneficial effect:
1st, early-strength type poly carboxylic acid series water reducer mother liquor is according to molecular design theory, by preferred polymeric monomer,
Adjustment polycarboxylate water-reducer molecule main chain and side-chain structure, because molecular side chain it is longer (it is relatively low to cement granules encapsulation, cause water
Muddy waterization accelerates) and introduce during polymerization there is early powerful monomer, high-early strength type polycarboxylic acids dehydragent mother liquor can be with early work(by force
Energy monomer is effectively polymerized, and than plain edition poly carboxylic acid series water reducer mother liquor concrete coagulating time is shortened, and improves concrete morning
Phase intensity, it is real so as to the shortcoming for solving traditional poly carboxylic acid series water reducer setting time length, early strength is low, quality is unstable
Show the high early strong dual-use function of the high diminishing of polycarboxylate water-reducer;
2nd, there is the high high-early strength type polycarboxylic acids dehydragent of high diminishing prepared by the present invention high diminishing, high early strong, cement to adapt to
Property wide, energy-conserving and environment-protective the advantages of, the ratio of mud of concrete can be greatly decreased, by compounding accelerating component after, can further shorten
Concrete coagulating time, improves early age strength of concrete, significantly improves service behaviour, mechanical property and the durability of concrete
Can, to improve production efficiency, construction cost is reduced, is saved and is reduced discharging, improves construction engineering quality and the aspect such as increase the service life
It is significant.
3rd, preparation process is simple of the present invention, and carry out in normal temperature, it is not necessary to steam or boiler provide thermal source, reaction system
It is stable, it is easily controlled, overcome the shortcoming for needing to heat in traditional high performance water reducing agent of polyocarboxy acid preparation process, whole course of reaction
Solvent-free, environmental protection belongs to clean manufacturing, is conducive to energy-saving and emission-reduction and environmental protection.
Specific embodiment
Comparative example 1
Common poly carboxylic acid series water reducer P-1 is prepared by following material quantities and technique, specially:
1. get the raw materials ready:L-AA 0.30g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 23.0g, 4.0 grams of methylpropene sodium sulfonate in adding 40g deionized waters, is well mixed, and B tanks are standby, is for b material;
2. it is polymerized:Deionized water 283.45g and alkene are added to being furnished with the glass reactor of thermometer and electric blender
Propyl group APEO (MW=2400) 200g, after stirring fully dissolving, is warming up to 60 DEG C, adds mass concentration to be 30%
H2O20.50g, stirs, and a material and b material are then added dropwise simultaneously, and a gobs add 3 hours, and b gobs add 2.5 hours, and a gobs are added
Continue reaction response 2 hours after finishing, 15 grams are neutralized to pH value to 6.8~7.2 with 30% sodium hydrate aqueous solution, obtain plain edition
Poly carboxylic acid series water reducer mother liquor P-1, its solid content is about 40%.
Comparative example 2
862.4 grams of deionized water, 0.1 gram of organic silicon defoamer, plain edition polycarboxylic-acid diminishing are sequentially added in container C
P-1125 gram of agent mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains polycarboxylic-acid diminishing
Agent F-1.
Embodiment 1
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-1 is prepared
1. get the raw materials ready:L-AA 0.20g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 12.0g, acrylamide 5.0g, 2.16 grams of methylpropene sodium sulfonate in adding 40g deionized waters, is well mixed, and B tanks are standby
With, be for b material;
2. it is polymerized:Deionized water 289.5g, insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=4000) 210g, after stirring fully dissolving, the H that mass concentration is 30% is added2O21.45g, stirring is equal
Even, to 15 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 15 grams of 30% sodium hydrate aqueous solution be neutralized to pH value to 6.8~
7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-1 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-1 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-1125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-1.
Embodiment 2
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-2 is prepared
1. get the raw materials ready:L-AA 0.35g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 16.0g, acrylamide 6.0g, 3- mercaptopropionic acid 0.45g, in adding 40g deionized waters, is well mixed, and B tanks are standby, are
For b material;
2. it is polymerized:Deionized water 187.3g and insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=4000) 140g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.57g, stirring is equal
Even, to 18 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 16 grams of 30% sodium hydrate aqueous solution be neutralized to pH value to 6.8~
7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-2 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-2 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-2125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-2.
Embodiment 3
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-3 is prepared
1. get the raw materials ready:L-AA 0.21g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 12.0g, acrylamide 5.0g, 2.28 grams of methylpropene sodium sulfonate is added in 40g deionized waters, is well mixed, and B tanks are standby
With, be for b material;
2. it is polymerized:Deionized water 228.7g, insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=3800) 170g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.57g, stirring is equal
Even, to 27 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 30% sodium hydrate aqueous solution, 14.5 grams are neutralized to pH value to 6.8
~7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-3 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-3 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-3125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-3.
Embodiment 4
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-4 is prepared
1. get the raw materials ready:L-AA 0.45g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 11.0g, acrylamide 3.0g, 0.39 gram of 2 mercaptopropionic acid in adding 40g deionized waters, is well mixed, and B tanks are standby, are
For b material;
2. it is polymerized:Deionized water 281.4g and insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=4000) 210g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.62g, stirring is equal
Even, to 13 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 16 grams of 30% sodium hydrate aqueous solution be neutralized to pH value to 6.8~
7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-4 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-4 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-4125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-4.
Embodiment 5
Sequentially add 862.3 grams of deionized water, 0.20 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-3125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-5.
Embodiment 6
Sequentially add 749.8 grams of deionized water, 0.20 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-3125 gram of aqua mother liquor, mixes, and adds 125 grams of accelerating component sodium sulphate, stirs, and obtains the high early-strength of high diminishing
Poly carboxylic acid series water reducer Z-6.
Embodiment 7
Sequentially add 737.3 grams of deionized water, 0.20 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-3125 gram of aqua mother liquor, mixes, and adds 125 grams of accelerating component sodium sulphate, 12.5 grams of triethanolamine, stirs, and obtains
To the high high-early strength type polycarboxylic acids dehydragent Z-7 of high diminishing.
Embodiment 8
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-5 is prepared
1. get the raw materials ready:L-AA 0.21g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 12.0g, 2.28 grams of methylpropene sodium sulfonate is added in 40g deionized waters, is well mixed, and B tanks are standby, is for b material;
2. it is polymerized:Deionized water 221.2g, insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=3800) 170g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.57g, stirring is equal
Even, to 27 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 30% sodium hydrate aqueous solution, 14.5 grams are neutralized to pH value to 6.8
~7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-5 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-8 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-5125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-8.
Embodiment 9
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-6 is prepared
1. get the raw materials ready:L-AA 0.45g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 11.0g, acrylamide 3.0g, 0.39 gram of 2 mercaptopropionic acid in adding 40g deionized waters, is well mixed, and B tanks are standby, are
For b material;
2. it is polymerized:Deionized water 281.4g and insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=4000) 210g, after stirring fully dissolving, the ammonium persulfate 0.62g that mass concentration is 30% is added,
Stir, to 13 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, b material
It is added dropwise 2.5 hours, reaction response is continued 2 hours after a material completion of dropping, 16 grams is neutralized to pH value with 30% sodium hydrate aqueous solution
To 6.8~7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-6 is obtained, its solid content is about 40%.
The ammonium persulfate can also be at least one of potassium peroxydisulfate and sodium peroxydisulfate.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-9 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of polyethers defoamer, early-strength polycarboxylic-acid in container C to subtract
T-6125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-9.
Embodiment 10
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-7 is prepared
1. get the raw materials ready:L-AA 0.45g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 14.0g, 0.39 gram of 2 mercaptopropionic acid in adding 40g deionized waters, is well mixed, and B tanks are standby, is for b material;
2. it is polymerized:Deionized water 281.4g and insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=4000) 210g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.62g, stirring is equal
Even, to 13 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 16 grams of 30% sodium hydrate aqueous solution be neutralized to pH value to 6.8~
7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-7 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-10 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of polyethers defoamer, early-strength polycarboxylic-acid in container C to subtract
T-7125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-10.
Embodiment 11
High diminishing high collapse protection type polycarboxylate high performance water-reducing agent is prepared by following material quantities and technique, specially:
(1) high-early strength type polycarboxylic acids dehydragent mother liquor T-8 is prepared
1. get the raw materials ready:L-AA 0.21g, in adding 13g deionized waters, is well mixed, and A tanks are standby, is for a material;Third
Olefin(e) acid 12.0g, acrylamide 5.0g, 3.80 grams of methylpropene sodium sulfonate is added in 40g deionized waters, is well mixed, and B tanks are standby
With, be for b material;
2. it is polymerized:Deionized water 228.7g, insatiable hunger are added to being furnished with the glass reactor of thermometer and electric blender
With APEO (MW=3800) 170g, after stirring fully dissolving, the H that mass concentration is 30% is added2O20.57g, stirring is equal
Even, to 27 DEG C, while a material and b material is added dropwise, at 15~40 DEG C, a gobs add 3 hours control polymerization temperature constant temperature, and b gobs add 2.5
Hour, continue reaction response 2 hours after a material completion of dropping, with 30% sodium hydrate aqueous solution, 14.5 grams are neutralized to pH value to 6.8
~7.2, high-early strength type polycarboxylic acids dehydragent mother liquor T-8 is obtained, its solid content is about 40%.
(2) the high high-early strength type polycarboxylic acids dehydragent Z-11 of high diminishing is prepared
Sequentially add 862.4 grams of deionized water, 0.05 gram of organic silicon defoamer, early-strength polycarboxylic-acid in container C to subtract
T-8125 gram of aqua mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing high early
Strong type poly carboxylic acid series water reducer Z-11.
Embodiment 12
687.45 grams of deionized water, 0.05 gram of machine silicon defoaming agent defoamer, early-strength polycarboxylic acids are sequentially added in container C
T-3300 gram of based water reducer mother liquor, mixes, and adds 12.5 grams of accelerating component triethanolamine, stirs, and obtains high diminishing
High high-early strength type polycarboxylic acids dehydragent Z-12.
Tests below is carried out respectively to the high high-early strength type polycarboxylic acids dehydragent of high diminishing prepared by above example:
1st, product of the present invention and domestic and international product cement mortar Experimental comparison
This experiment cement be little wild field 42.5R, cement 1000g, 2000 grams of normal sand, water 305g, specific experiment result is such as
Shown in table 1.
The cement mortar contrast experiment of table 1
As it can be seen from table 1 the high high-early strength type polycarboxylic acids dehydragent of high diminishing of the invention all has preferable water-reducing effect
Higher dispersibility, effect is suitable with external product effect.
2nd, product of the present invention is contrasted with domestic and international product concrete experiments
This experiment cement is little wild field 42.5R, and flyash is Huaneng Group second-level ash.Clay content is 2.2%, modulus of fineness 2.6
Middle sand.Clay content 0.5%, the stone of particle diameter 5~25.Mixing time is 90 seconds, vibrating time 15 seconds.Match ratio is cement:
Flyash:Breeze:Sand:Stone:Water=190:80:80:1000:840:160.Specific experiment result is as shown in table 2.
The concrete performance experimental result of table 2
From table 2 it can be seen that the high high-early strength type polycarboxylic acids dehydragent of high diminishing of the present invention have water-reducing effect it is good, early stage
Intensity is high, later strength is not lost, energy-conserving and environment-protective, good stability the advantages of, excellent combination property.
The specific embodiment of the present invention is the foregoing is only, the present invention is not limited to, to people in the art
For member, can be improved according to above-described embodiment or be converted, and all these modifications and variations should all be included in the present invention
In the protection domain of claims.