CN105330193B - Nuclear power ultra dense real concrete polycarboxylate water-reducer and preparation method thereof - Google Patents
Nuclear power ultra dense real concrete polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to nuclear power ultra dense real concrete polycarboxylate water-reducer and preparation method thereof, every 100 parts of the water reducer includes following components and parts by weight content：50 55 parts of decentralized ethers polycarboxylic acid water reducing agent, 20 25 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 35 parts of retarder, 0.01 0.05 parts of defoamer, 13 parts of water-loss reducer, 12 parts of economization agent, 0.1 0.3 parts of preservative, water is surplus；It is during preparation, described component is well mixed by weight.Compared with prior art, water reducer of the present invention, which has, improves concrete workability, improves mobility, reduce coagulation soil temperature peak value, concrete shrinkage value is reduced, reduces inside concrete porosity, improves concrete self compacting ability, the advantages that improving concrete durability, preparation method is simple, and raw material sources are wide, and cost is low, it is green, there is good application prospect.
Description
Technical field
The invention belongs to water reducer technical field, it is related to water reducer and preparation method thereof, more particularly, to nuclear power with ultra dense
Real concrete polycarboxylate water-reducer and preparation method thereof.
Background technology
AP1000 nuclear island raft foundations bottom plate is the reinforced concrete raft foundation that reactor bottom plate and auxiliary plant bottom plate join together, basic
Thick 1.83m, flat shape are polygon, and basis a length of 78.03m, the widest part 49.1m, most narrow place is only 27.7m.Whole bottom
Board concrete, which pours, to implement primary concreting.For typical variable cross-section large volume concrete structural.To the additive used
It can require high, such as：Concrete workability is good, one hour slump-loss within 40mm, air content loss 2% with
It is interior.
Polycarboxylate water-reducer can produce steric hindrance repulsion work because of its unique molecular characterization in cement slurry
With to the dispersed stronger of fresh concrete, volume is lower, and concrete slump gradual loss is smaller, the concrete prepared
Gain in strength amplitude is big and volume stability of concrete is good.Compared with conventional water reducer, polycarboxylate water-reducer is changed conventional
Chain polymerization is progressively polymerized to, this polymerisation does not have small molecule generation, does not produce the three wastes substantially, and simultaneous reactions are very fast, holds
Easily meet supply requirement.But the radical polymerization of alkene needs to trigger, generally used initiator, initiation temperature is often higher than
Room temperature, so needing raw material being heated to certain temperature ability initiated polymerization.However, Raolical polymerizable is that heat release is anti-
Should, so being difficult to control temperature in course of reaction.
With the continuous consumption of non-renewable energy resources, the earth will face lack of energy, in addition, being added by offers such as fire coals
Thermal energy can also cause serious environmental pollution.Thus, how poly carboxylic acid series water reducer is reduced in large-scale industrial production
Energy resource consumption in synthesis, make technological process more simple and efficient, turn into the major issue that polycarboxylic acids production faces.
Authorization Notice No. be the B of CN 102491677 Chinese invention patent disclose a kind of nuclear power concrete additive and
Its preparation method, the additive are made up by mass percentage of following raw material：Polycarboxylate water-reducer 30%-80%；Poly- carboxylic
Sour slump retaining agent 10%-30%；Retarder 1%-15%；Water-loss reducer 0-0.5%；Air entraining agent 0.1%-2%；Economization agent 1%-
20%；Preservative 0-0.5%；Defoamer 0.05%-0.5%；Water surplus.Wherein, described ester type polycarboxylate water-reducer is third
Olefin(e) acid macrogol ester or methacrylic acid macrogol ester, acrylic or methacrylic acid, the thing of methacrylic sulfonic acid three are total to
Polymers, described ether type polycarboxylic acid slump retaining agent be acrylic alcohol APEO or isoamyl alcohol polyoxyethylene ether with single (double) no
The copolymer of saturated carboxylic acid；Described retarder is selected from sodium gluconate, sucrose, citric acid and salt, calgon and phosphonic acids
One or more mixing in salt；Described water-loss reducer is biogum or cellulose ether compound；Described air entraining agent be selected from gleditsia sinensis,
One or more mixing in modified rosin pyrolytic polymer, AEO and alkyl sulfate；Described economization agent is
One or more mixing of the alcohols economization agent in methyl diethanolamine, ethyldiethanolamine, triethanolamine and diethanol amine.
All kinds of components that the technical scheme of above-mentioned patent disclosure is included are complicated, and all kinds of materials not only can be to the suction of polycarboxylate water-reducer
Attached-dispersed and scattered retentivity is impacted, but also the mechanical property of concrete and durability etc. can be caused not
Good influence, therefore be further improved.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of workability is good, flowing
Property is good, and the amount of causing is small, and as age increases, the concrete of institute's mixing has that shrinkage factor is small, and the porosity is low, the core of density superelevation
Electricity ultra dense real concrete polycarboxylate water-reducer and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
The ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts of the water reducer includes following components and parts by weight contain
Amount：Decentralized ethers polycarboxylic acid water reducing agent 50-55 parts, collapse protection type ethers polycarboxylic acid water reducing agent 20-25 parts, retarder 3-5 parts, disappear
Infusion 0.01-0.05 parts, water-loss reducer 1-3 parts, economization agent 1-2 parts, preservative 0.1-0.3 parts, water is surplus.
The preparation method of described decentralized ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (1-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12-12.3 that (1-2), which presses unsaturated monomer I and the mass ratio of polyether macromonomer,:100, by unsaturated monomer I and water
It is mixed to prepare the material of solution A 1；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 1 by (1-3)；
The material of solution A 1, the material of solution B 1 are at the uniform velocity added dropwise in mixed solution by (1-4), and the rate of addition of the material of solution A 1 is 27-
50g/ hours, the rate of addition of the material of solution B 1 is 25-35g/ hours, in order to improve the polymerization ratio of reactant to greatest extent, control
The material of solution B 1 processed adds half an hour after in the gob of solution A 1 and is added dropwise to complete；
(1-5) continues stirring reaction 10-30 minutes, added in aqueous slkali after the material of solution A 1, the gob of solution B 1 add
Be 6.5-7 to pH, that is, described decentralized ethers polycarboxylic acid water reducing agent is made；
The preparation method of described collapse protection type ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (2-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12-12.3 that (2-2), which presses unsaturated monomer II and the mass ratio of polyether macromonomer,:100, by unsaturated monomer II with
Water is mixed to prepare the material of solution A 2；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 2 by (2-3)；
The material of solution A 2, the material of solution B 2 are at the uniform velocity added dropwise in mixed solution by (2-4), and the rate of addition of the material of solution A 2 is 27-
50g/ hours, the rate of addition of the material of solution B 2 is 25-35g/ hours, and the control material of solution B 2 adds half an hour after in the gob of solution A 2
It is added dropwise to complete；
(2-5) continues stirring reaction 10-30 minutes, added in aqueous slkali after the material of solution A 2, the gob of solution B 2 add
Be 6-6.5 to pH, that is, described collapse protection type ethers polycarboxylic acid water reducing agent is made.
Described unsaturated monomer I includes the one or more in acrylic acid, maleic anhydride or methylpropene sodium sulfonate, institute
The unsaturated monomer II stated includes the one or more in acrylic acid, maleic anhydride or methyl methacrylate.
Described unsaturated monomer I and unsaturated monomer II mass ratio is 1-2:1.
Described polyether macromonomer is the methyl allyl polyoxyethylene ether (abbreviation that relative molecular weight is 2000-3000
TPEG)。
Described oxidant is one or both of ammonium persulfate, hydrogen peroxide or potassium peroxydisulfate, and described reducing agent is
L-AA, described chain-transferring agent are one kind in mercaptopropionic acid or TGA.
The preferred purity of described hydrogen peroxide is 35% hydrogen peroxide.
The addition of described oxidant is the 1.5-2% of total monomer quality, and the addition of described reducing agent is total single
The 0.1-0.5% of weight, the addition of described chain-transferring agent are the 0.3-0.6% of total monomer quality.
Described decentralized ethers polycarboxylic acid water reducing agent is modified allyl polyethenoxy ether or modified poly (ethylene glycol) list first
One kind in ether, described collapse protection type ethers polycarboxylic acid water reducing agent are modified allyl polyethenoxy ether or modified poly (ethylene glycol) list
One kind in methyl ether.
Described modification allyl polyethenoxy ether is TPEG type polyether macromonomers, unsaturated double-bond value ＞ 0.37mmol/
G, hydroxyl value are 21~26mg KOH/g, and acid number ＜ 0.5mg KOH/g, molecular weight is 2160~2640；The poly- second two of described modification
Alcohol monomethyl ether is MPEG-2200 type polymeric monomers, and hydroxyl value is 25.5~31, and molecular weight is 2060~2440；PH value 5.0~7.0.
Described retarder is one kind in sodium gluconate, calgon or sucrose, and described defoamer is polyethers
One kind in class defoamer or Polyether Modified Polysiloxanes Defoaming Agent, described water-loss reducer are that sodium tripolyphosphate or hydroxypropyl methyl are fine
One kind in dimension element, described economization agent are one kind in triethanolamine or triisopropanolamine, and described preservative is to hydroxyl
One kind in methyl benzoate or natrium nitrosum.
The preparation method of the ultra dense real concrete polycarboxylate water-reducer of nuclear power, this method be by described component by weight
Part, mixed under normal temperature environment, and stir.
In the present invention, described decentralized ethers polycarboxylic acid water reducing agent concrete newly the initial stage of mixing can quick adsorption in glue
Gel material particle surface, stronger absorption-peptizaiton is played, ensure the initial fluidity of fresh concrete；Described guarantor is collapsed
Type ethers polycarboxylic acid water reducing agent has slowly releasing effect, is progressively adsorbed in binder materials in the concrete mortar of continuous aquation
Grain surface, compensates the polycarboxylate water-reducer covered by hydrated product, and fresh concrete slurry workability is persistently maintained so as to play
Effect.By compatibility retarder, defoamer and water-loss reducer etc., bubble (hole) structure in optimised coagulation soil paste body can be cooperateed with
And binder materials degree of hydration is improved, improve concrete density.
Water reducer of the present invention can be used for each position, each concrete, the spies such as the nuclear island of nuclear power AP1000 units, conventional island
Not Shi Yongyu AP1000 unit nuclear island raft foundations position, this position volume of concrete is big, and amount of concrete is more, primary concreting, is made
Pour time length.
Compared with prior art, the invention has the characteristics that：
1) the decentralized ethers polycarboxylic acid water reducing agent employed in the present invention and collapse protection type ethers polycarboxylic acid water reducing agent are equal
Using normal temperature synthesis technique, the techniques such as heating pressurization are avoided, high degree reduces energy consumption, reduces equipment investment cost and energy
Source consuming cost；
2) water reducer made from has improvement concrete workability, improves mobility, reduces coagulation soil temperature peak value, reduces mixed
Coagulate native shrinkage value, reduce inside concrete porosity, improve concrete self compacting ability, improve concrete durability the advantages that, energy
Enough meet nuclear power engineering application demand；
3) when in use, as age increases, the concrete of institute's mixing has that shrinkage factor is small to water reducer made from, the porosity
It is low, the advantages that density superelevation；
4) preparation method is simple, and the synthesis technique of related component can be completed under normal temperature condition, and without heating, raw material comes
Source is wide, and cost is low, green, has good application prospect.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1：
A kind of ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts include following components and parts by weight content：
Decentralized ethers polycarboxylic acid water reducing agent：50 parts
Collapse protection type ethers polycarboxylic acid water reducing agent：20 parts
Sodium gluconate：5 parts
Polyether Modified Polysiloxanes Defoaming Agent：0.05 part
Hydroxypropyl methyl cellulose：2 parts
Triethanolamine：1 part
Natrium nitrosum：0.3 part
Water：Surplus
Wherein, decentralized ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 180g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Ammonium persulfate 2.5g, hydrogen peroxide (purity 35%) 1g, propylene are added to reaction system
Sour 3.3g, continuing stirring makes reaction system be sufficiently mixed uniformly.Homogeneous solution A1 material are configured to by 25g acrylic acid, with 18g water,
1g mercaptopropionic acids, 1gL- ascorbic acid and 50g water are configured to the material of solution B 1.By valve control device, by the material of solution A 1 and
The material of solution B 1 is progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 1 is 1 hour, the material time for adding of solution B 1
For 1.5 hours.After the material of solution A 1, the material of solution B 1 are added dropwise to complete completely, continue stirring reaction system 10 minutes or so, final profit
It is 7 to be neutralized reaction solution into pH with the sodium hydroxide solution of 25% concentration.
Collapse protection type ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 180g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Ammonium persulfate 2.5g, hydrogen peroxide (purity 35%) 1g, propylene are added to reaction system
Sour 3.3g, continuing stirring makes reaction system be sufficiently mixed uniformly.10g acrylic acid, 3g methyl methacrylates and 18g water are prepared
Expect into homogeneous solution A2,1g mercaptopropionic acids, 1gL- ascorbic acid and 50g water are configured to the material of solution B 2.Filled by Valve controlling
Put, the material of solution A 2 and the material of solution B 2 are progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 2 is 1 hour, molten
Liquid B2 material time for adding is 1.5 hours.After the material of solution A 2, the material of solution B 2 are added dropwise to complete completely, continue stirring reaction system 10
Minute or so, it is 6 that the final sodium hydroxide solution using 25% concentration, which neutralizes reaction solution into pH,.
Embodiment 2：
A kind of ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts include following components and parts by weight content：
Decentralized ethers polycarboxylic acid water reducing agent：52 parts
Collapse protection type ethers polycarboxylic acid water reducing agent：25 parts
Sodium gluconate：3 parts
Polyether antifoam agent：0.01 part
Sodium tripolyphosphate：3 parts
Triisopropanolamine：1.5 part
Natrium nitrosum：0.2 part
Water：Surplus
Wherein, decentralized ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 230g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Hydrogen peroxide (purity 35%) 4g, maleic anhydride 2.3g is added to reaction system, is continued
Reaction system is sufficiently stirred.18g maleic anhydrides, 5g methylpropene sodium sulfonates and 18g water are configured to homogeneous solution A1 material, will
1g mercaptopropionic acids, 0.5gL- ascorbic acid and 50g water are configured to the material of solution B 1.By peristaltic-type pump arrangement, by the material of solution A 1 and molten
Liquid B1 material are progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 1 is 1.5 hours, the material time for adding of solution B 1
For 2 hours.After the material of solution A 1, the material of solution B 1 are added dropwise to complete completely, continue stirring reaction system 20 minutes or so, it is final to utilize
It is 7 that the sodium hydroxide solution of 25% concentration, which neutralizes reaction solution into pH,.
Collapse protection type ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 230g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Hydrogen peroxide (purity 35%) 4g, maleic anhydride 2.3g is added to reaction system, is continued
Reaction system is sufficiently stirred.9g maleic anhydrides, 7g methyl methacrylates and 18g water are configured to homogeneous solution A2 material, will
1g mercaptopropionic acids, 0.5gL- ascorbic acid and 50g water are configured to the material of solution B 2.By peristaltic-type pump arrangement, by the material of solution A 2 and molten
Liquid B2 material are progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 2 is 1.5 hours, the material time for adding of solution B 2
For 2 hours.After the material of solution A 2, the material of solution B 2 are added dropwise to complete completely, continue stirring reaction system 20 minutes or so, it is final to utilize
It is 6 that the sodium hydroxide solution of 25% concentration, which neutralizes reaction solution into pH,.
Embodiment 3：
A kind of ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts include following components and parts by weight content：
Decentralized ethers polycarboxylic acid water reducing agent：55 parts
Collapse protection type ethers polycarboxylic acid water reducing agent：20 parts
Sucrose：5 parts
Polyether antifoam agent：0.05 part
Hydroxypropyl methyl cellulose：1 part
Triisopropanolamine：1 part
Methyl hydroxybenzoate：0.2 part
Water：Surplus
Wherein, decentralized ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 200g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Potassium peroxydisulfate 2g, hydrogen peroxide (purity 35%) 1g, maleic acid are added to reaction system
Acid anhydride 2.5g, continue to be sufficiently stirred reaction system.28g maleic anhydrides, 3g methylpropene sodium sulfonates and 18g water are configured to uniformly
The material of solution A 1,1g mercaptopropionic acids, 0.2gL- ascorbic acid and 50g water are configured to the material of solution B 1., will be molten by peristaltic-type pump arrangement
Liquid A1 expects and the material of solution B 1 is progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 1 is 1 hour, the material of solution B 1
Time for adding is 1.5 hours.After the material of solution A 1, the material of solution B 1 are added dropwise to complete completely, it is left to continue stirring reaction system half an hour
The right side, it is 6.5 that the final sodium hydroxide solution using 25% concentration, which neutralizes reaction solution into pH,.
Collapse protection type ethers polycarboxylic acid water reducing agent is prepared using following methods：
TPEG polymeric monomer 180g, water 200g are added under normal temperature into the reactor equipped with agitating device, opens agitating device,
Stirring to TPEG polymeric monomers are completely dissolved.Potassium peroxydisulfate 2g, hydrogen peroxide (purity 35%) 1g, maleic acid are added to reaction system
Acid anhydride 2.5g, continue to be sufficiently stirred reaction system.10g maleic anhydrides, 20g methyl methacrylates and 18g water are configured to
The even material of solution A 2,1g mercaptopropionic acids, 0.2gL- ascorbic acid and 50g water are configured to the material of solution B 2., will by peristaltic-type pump arrangement
The material of solution A 2 and the material of solution B 2 are progressively at the uniform velocity added dropwise to reaction system, wherein, the material time for adding of solution A 2 is 1 hour, solution B 2
It is 1.5 hours to expect time for adding.After the material of solution A 2, the material of solution B 2 are added dropwise to complete completely, continue stirring reaction system half an hour
Left and right, it is 6 that the final sodium hydroxide solution using 25% concentration, which neutralizes reaction solution into pH,.
To C30 pump concretes, the properties for filling the concrete of various embodiments above polycarboxylate water-reducer are shown in Table 2,
Table 1 is concrete mix.
The concrete mix of table 1
| Cement | Flyash | Water | Sand | Great Shi | Gravelstone | Glue material total amount | W/C | Sand coarse aggregate ratio |
| 307 | 45 | 172 | 789 | 413 | 619 | 352 | 0.49 | 43% |
Table 2 implements concrete performance data
Embodiment 4：
The ultra dense real concrete polycarboxylate water-reducer of the present embodiment nuclear power, every 100 parts of the water reducer include following components and
Parts by weight content：54 parts of decentralized ethers polycarboxylic acid water reducing agent, 21 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 4 parts of retarder, disappear
0.04 part of infusion, 2 parts of water-loss reducer, 2 parts of economization agent, 0.1 part of preservative, water is surplus.
Wherein, the preparation method of decentralized ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (1-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12 that (1-2), which presses unsaturated monomer I and the mass ratio of polyether macromonomer,:100, unsaturated monomer I is mixed with water
Obtained solution A1 expects；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 1 by (1-3)；
The material of solution A 1, the material of solution B 1 are at the uniform velocity added dropwise in mixed solution by (1-4), and the rate of addition of the material of solution A 1 is 50g/
Hour, the rate of addition of the material of solution B 1 is 35g/ hours, and the control material of solution B 1 adds half an hour after in the gob of solution A 1 and dripped
Into；
(1-5) continues stirring reaction 30 minutes after the material of solution A 1, the gob of solution B 1 add, and adds aqueous slkali neutralization
It is 6.5 to pH, that is, decentralized ethers polycarboxylic acid water reducing agent is made.
The preparation method of collapse protection type ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (2-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12.3 that (2-2), which presses unsaturated monomer II and the mass ratio of polyether macromonomer,:100, by unsaturated monomer II and water
It is mixed to prepare the material of solution A 2；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 2 by (2-3)；
The material of solution A 2, the material of solution B 2 are at the uniform velocity added dropwise in mixed solution by (2-4), and the rate of addition of the material of solution A 2 is 45g/
Hour, the rate of addition of the material of solution B 2 is 32g/ hours, and the control material of solution B 2 adds half an hour after in the gob of solution A 2 and dripped
Into；
(2-5) continues stirring reaction 10 minutes after the material of solution A 2, the gob of solution B 2 add, and adds aqueous slkali neutralization
It is 6 to pH, that is, collapse protection type ethers polycarboxylic acid water reducing agent is made.
Unsaturated monomer I is 1 in mass ratio by acrylic acid, maleic anhydride and methylpropene sodium sulfonate:1:2 mix,
Unsaturated monomer II is acrylic acid.
Unsaturated monomer I and unsaturated monomer II mass ratio is 1.5:1.
Polyether macromonomer is the methyl allyl polyoxyethylene ether that relative molecular weight is 3000.
Oxidant is 1 in mass ratio by ammonium persulfate and hydrogen peroxide:1 mixes, and reducing agent is L-AA, and chain turns
Shifting agent is TGA.
It should be noted that the addition of oxidant is the 2% of total monomer quality, the addition of reducing agent is total monomer matter
The 0.5% of amount, the addition of chain-transferring agent are the 0.6% of total monomer quality.
Retarder is calgon, and defoamer is Polyether Modified Polysiloxanes Defoaming Agent, and water-loss reducer is sodium tripolyphosphate, is subtracted
Contracting agent is triisopropanolamine, and preservative is methyl p-hydroxybenzoate.
The preparation method of the present embodiment water reducer is：Described component is well mixed by weight.
Embodiment 5：
The ultra dense real concrete polycarboxylate water-reducer of the present embodiment nuclear power, every 100 parts of the water reducer include following components and
Parts by weight content：53 parts of decentralized ethers polycarboxylic acid water reducing agent, 23 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 3 parts of retarder, disappear
0.03 part of infusion, 3 parts of water-loss reducer, 1.5 parts of economization agent, 0.2 part of preservative, water is surplus.
Wherein, the preparation method of decentralized ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (1-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12.3 that (1-2), which presses unsaturated monomer I and the mass ratio of polyether macromonomer,:100, unsaturated monomer I is mixed with water
Close obtained solution A1 material；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 1 by (1-3)；
The material of solution A 1, the material of solution B 1 are at the uniform velocity added dropwise in mixed solution by (1-4), and the rate of addition of the material of solution A 1 is 27g/
Hour, the rate of addition of the material of solution B 1 is 25g/ hours, and the control material of solution B 1 adds half an hour after in the gob of solution A 1 and dripped
Into；
(1-5) continues stirring reaction 10 minutes after the material of solution A 1, the gob of solution B 1 add, and adds aqueous slkali neutralization
It is 7 to pH, that is, decentralized ethers polycarboxylic acid water reducing agent is made.
The preparation method of collapse protection type ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (2-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12 that (2-2), which presses unsaturated monomer II and the mass ratio of polyether macromonomer,:100, unsaturated monomer II is mixed with water
Close obtained solution A2 material；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 2 by (2-3)；
The material of solution A 2, the material of solution B 2 are at the uniform velocity added dropwise in mixed solution by (2-4), and the rate of addition of the material of solution A 2 is 27g/
Hour, the rate of addition of the material of solution B 2 is 25g/ hours, and the control material of solution B 2 adds half an hour after in the gob of solution A 2 and dripped
Into；
(2-5) continues stirring reaction 15 minutes after the material of solution A 2, the gob of solution B 2 add, and adds aqueous slkali neutralization
It is 6.5 to pH, that is, collapse protection type ethers polycarboxylic acid water reducing agent is made.
Unsaturated monomer I is 18 in mass ratio by acrylic acid and methylpropene sodium sulfonate:5 mix, unsaturated monomer
II is maleic anhydride and methyl methacrylate is 9 in mass ratio:7 mix.
Unsaturated monomer I and unsaturated monomer II mass ratio is 2:1.
Polyether macromonomer is the methyl allyl polyoxyethylene ether that relative molecular weight is 2000.
Oxidant is 2 in mass ratio by potassium peroxydisulfate and hydrogen peroxide:1 mixes, and reducing agent is L-AA, and chain turns
Shifting agent is mercaptopropionic acid.
It should be noted that the addition of oxidant is the 1.5% of total monomer quality, the addition of reducing agent is total monomer
The 0.1% of quality, the addition of chain-transferring agent are the 0.3% of total monomer quality.
Retarder is sucrose, and defoamer is polyethers defoamer, and water-loss reducer is hydroxypropyl methyl cellulose, economization agent three
Monoethanolamine, preservative are natrium nitrosum.
The preparation method of the present embodiment water reducer is：Described component is well mixed by weight.
Embodiment 6：
The ultra dense real concrete polycarboxylate water-reducer of the present embodiment nuclear power, every 100 parts of the water reducer include following components and
Parts by weight content：51 parts of decentralized ethers polycarboxylic acid water reducing agent, 22 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 4.5 parts of retarder,
0.02 part of defoamer, 1.8 parts of water-loss reducer, 1.2 parts of economization agent, 0.3 part of preservative, water is surplus.
Wherein, the preparation method of decentralized ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (1-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12.1 that (1-2), which presses unsaturated monomer I and the mass ratio of polyether macromonomer,:100, unsaturated monomer I is mixed with water
Close obtained solution A1 material；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 1 by (1-3)；
The material of solution A 1, the material of solution B 1 are at the uniform velocity added dropwise in mixed solution by (1-4), and the rate of addition of the material of solution A 1 is 50g/
Hour, the rate of addition of the material of solution B 1 is 35g/ hours, and the control material of solution B 1 adds half an hour after in the gob of solution A 1 and dripped
Into；
(1-5) continues stirring reaction 25 minutes after the material of solution A 1, the gob of solution B 1 add, and adds aqueous slkali neutralization
It is 6.5 to pH, that is, decentralized ethers polycarboxylic acid water reducing agent is made.
The preparation method of collapse protection type ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (2-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12.2 that (2-2), which presses unsaturated monomer II and the mass ratio of polyether macromonomer,:100, by unsaturated monomer II and water
It is mixed to prepare the material of solution A 2；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 2 by (2-3)；
The material of solution A 2, the material of solution B 2 are at the uniform velocity added dropwise in mixed solution by (2-4), and the rate of addition of the material of solution A 2 is 42g/
Hour, the rate of addition of the material of solution B 2 is 28g/ hours, and the control material of solution B 2 adds half an hour after in the gob of solution A 2 and dripped
Into；
(2-5) continues stirring reaction 30 minutes after the material of solution A 2, the gob of solution B 2 add, and adds aqueous slkali neutralization
It is 6 to pH, that is, collapse protection type ethers polycarboxylic acid water reducing agent is made.
Unsaturated monomer I is 28 in mass ratio by maleic anhydride and methylpropene sodium sulfonate:3 mix, unsaturated single
Body II is 1 in mass ratio by maleic anhydride and methyl methacrylate:2 mix.
Unsaturated monomer I and unsaturated monomer II mass ratio is 1:1.
Polyether macromonomer is the methyl allyl polyoxyethylene ether that relative molecular weight is 2800.
Oxidant is hydrogen peroxide, and reducing agent is L-AA, and chain-transferring agent is mercaptopropionic acid.
It should be noted that the addition of oxidant is the 1.8% of total monomer quality, the addition of reducing agent is total monomer
The 0.3% of quality, the addition of chain-transferring agent are the 0.5% of total monomer quality.
Retarder is sodium gluconate, and defoamer is polyethers defoamer, and water-loss reducer is hydroxypropyl methyl cellulose, decrement
Agent is triethanolamine, and preservative is natrium nitrosum.
The preparation method of the present embodiment water reducer is：Described component is well mixed by weight.
Embodiment 7：
The ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts of the water reducer includes following components and parts by weight contain
Amount：54 parts of decentralized ethers polycarboxylic acid water reducing agent, 24 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 4 parts of retarder, defoamer 0.05
Part, 1 part of water-loss reducer, 2 parts of economization agent, 0.3 part of preservative, water is surplus.
Wherein, decentralized ethers polycarboxylic acid water reducing agent is modified allyl polyethenoxy ether, and collapse protection type ethers polycarboxylic acids subtracts
Aqua is modified poly (ethylene glycol) monomethyl ether, and retarder is calgon, and defoamer is Polyether Modified Polysiloxanes Defoaming Agent, water conservation
Agent is sodium tripolyphosphate, and economization agent is triisopropanolamine, and preservative is methyl p-hydroxybenzoate.
The preparation method of the present embodiment water reducer is：Described component is well mixed by weight.
Embodiment 8：
The ultra dense real concrete polycarboxylate water-reducer of nuclear power, every 100 parts of the water reducer includes following components and parts by weight contain
Amount：52 parts of decentralized ethers polycarboxylic acid water reducing agent, 21 parts of collapse protection type ethers polycarboxylic acid water reducing agent, 4.8 parts of retarder, defoamer
0.05 part, 1.2 parts of water-loss reducer, 1.5 parts of economization agent, 0.3 part of preservative, water is surplus.
Wherein, decentralized ethers polycarboxylic acid water reducing agent is modified poly (ethylene glycol) monomethyl ether, collapse protection type ethers polycarboxylic acids diminishing
Agent is modified allyl polyethenoxy ether, and retarder is calgon, and defoamer is Polyether Modified Polysiloxanes Defoaming Agent, water conservation
Agent is sodium tripolyphosphate, and economization agent is triisopropanolamine, and preservative is methyl p-hydroxybenzoate.
The preparation method of the present embodiment water reducer is：Described component is well mixed by weight.
Claims (7)
1. the ultra dense real concrete polycarboxylate water-reducer of nuclear power, it is characterised in that every 100 parts of the water reducer include following components and
Parts by weight content：Decentralized ethers polycarboxylic acid water reducing agent 50-55 parts, collapse protection type ethers polycarboxylic acid water reducing agent 20-25 parts, retarder
3-5 parts, defoamer 0.01-0.05 parts, water-loss reducer 1-3 parts, economization agent 1-2 parts, preservative 0.1-0.3 parts, water is surplus；
The preparation method of described decentralized ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (1-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12-12.3 that (1-2), which presses unsaturated monomer I and the mass ratio of polyether macromonomer,:100, unsaturated monomer I is mixed with water
Obtained solution A1 expects；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 1 by (1-3)；
The material of solution A 1, the material of solution B 1 are at the uniform velocity added dropwise in mixed solution by (1-4), and the rate of addition of the material of solution A 1 is 27-50g/
Hour, the rate of addition of the material of solution B 1 is 25-35g/ hours, and the control material of solution B 1 adds half an hour after in the gob of solution A 1 and is added dropwise
Complete；
(1-5) continues stirring reaction 10-30 minutes, adds aqueous slkali and be neutralized to after the material of solution A 1, the gob of solution B 1 add
PH is 7, that is, described decentralized ethers polycarboxylic acid water reducing agent is made；
The preparation method of described collapse protection type ethers polycarboxylic acid water reducing agent specifically includes following steps：
Polyether macromonomer is added to the water by (2-1) together with oxidant, is sufficiently stirred dissolving, and mixed solution is made；
It is 12-12.3 that (2-2), which presses unsaturated monomer II and the mass ratio of polyether macromonomer,:100, unsaturated monomer II is mixed with water
Close obtained solution A2 material；
Reducing agent, chain-transferring agent and water are mixed to prepare the material of solution B 2 by (2-3)；
The material of solution A 2, the material of solution B 2 are at the uniform velocity added dropwise in mixed solution by (2-4), and the rate of addition of the material of solution A 2 is 27-50g/
Hour, the rate of addition of the material of solution B 2 is 25-35g/ hours, and the control material of solution B 2 adds half an hour after in the gob of solution A 2 and is added dropwise
Complete；
(2-5) continues stirring reaction 10-30 minutes, adds aqueous slkali and be neutralized to after the material of solution A 2, the gob of solution B 2 add
PH is 6, that is, described collapse protection type ethers polycarboxylic acid water reducing agent is made；
Described unsaturated monomer I is methylpropene sodium sulfonate, and described unsaturated monomer II is methyl methacrylate；
Described oxidant is ammonium persulfate, and described reducing agent is L-AA, and described chain-transferring agent is mercaptopropionic acid.
2. the ultra dense real concrete polycarboxylate water-reducer of nuclear power according to claim 1, it is characterised in that described insatiable hunger
Mass ratio with monomer I and unsaturated monomer II is 1-2:1.
3. the ultra dense real concrete polycarboxylate water-reducer of nuclear power according to claim 1, it is characterised in that described polyethers
Polymeric monomer is the methyl allyl polyoxyethylene ether that relative molecular weight is 2000-3000.
4. the ultra dense real concrete polycarboxylate water-reducer of nuclear power according to claim 1, it is characterised in that described oxidation
The addition of agent is the 1.5-2% of total monomer quality, and the addition of described reducing agent is the 0.1-0.5% of total monomer quality,
The addition of described chain-transferring agent is the 0.3-0.6% of total monomer quality.
5. the ultra dense real concrete polycarboxylate water-reducer of nuclear power according to claim 1, it is characterised in that described is scattered
Type ethers polycarboxylic acid water reducing agent is one kind in modified allyl polyethenoxy ether or modified poly (ethylene glycol) monomethyl ether, described guarantor
The type that collapses ethers polycarboxylic acid water reducing agent is one kind in modified allyl polyethenoxy ether or modified poly (ethylene glycol) monomethyl ether.
6. the ultra dense real concrete polycarboxylate water-reducer of nuclear power according to claim 1, it is characterised in that described slow setting
Agent is one kind in sodium gluconate, calgon or sucrose, and described defoamer is polyethers defoamer or polyether-modified
One kind in organic silicon defoamer, described water-loss reducer is one kind in sodium tripolyphosphate or hydroxypropyl methyl cellulose, described
Economization agent be one kind in triethanolamine or triisopropanolamine, described preservative is methyl p-hydroxybenzoate or nitrous acid
One kind in sodium.
7. the nuclear power as claimed in claim 1 preparation method of ultra dense real concrete polycarboxylate water-reducer, it is characterised in that should
Method is that described component is well mixed by weight.
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| CN105819729A (en) * | 2016-03-30 | 2016-08-03 | 山东净金新能源有限公司 | Standard polycarboxylate water reducer and preparing method and application thereof |
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| CN110606924B (en) * | 2019-09-04 | 2021-11-05 | 西安建筑科技大学 | Polycarboxylate superplasticizer mother liquor for hydraulic concrete and preparation method thereof |
| CN111647115A (en) * | 2020-06-15 | 2020-09-11 | 安徽海螺新材料科技有限公司 | Polycarboxylate superplasticizer mother liquor and preparation method thereof, and polycarboxylate superplasticizer and preparation method thereof |
| CN113321438B (en) * | 2021-05-29 | 2023-04-07 | 石家庄市长安育才建材有限公司 | Slurry-rich concrete additive and preparation method thereof |
| CN113461362A (en) * | 2021-07-27 | 2021-10-01 | 深圳市三绿科技有限公司 | Concrete water-retaining agent and preparation method thereof |
| CN114735963A (en) * | 2022-03-17 | 2022-07-12 | 山东科润赢新材料科技有限公司 | Polycarboxylic acid super-retarding water reducer with small slump and production method thereof |
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