CN104446100B - A kind of without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid and preparation method thereof - Google Patents
A kind of without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to high performance water reducing agent of polyocarboxy acid preparation field, protect plastotype high performance water reducing agent of polyocarboxy acid and preparation method thereof particularly to a kind of without thermal source.Plastotype high performance water reducing agent of polyocarboxy acid specific selection the first composition is protected without thermal source, acrylic acid, 2 acrylamide 2 methyl propane sulfonic acids, second composition, methylpropene sodium sulfonate is as reactant, with Ammonium persulfate. as oxidant, simultaneously using vitamin C as reducing agent, composition redox initiation system, and using mercaptopropionic acid as chain-transferring agent, obtain multiple copolymer, it is high that this product has early anti pressured intension, little loss of slump, the feature such as bleeding rate is little and shrinkage ratio is little, and with concrete raw material, there is being well adapted for property, concrete sand can be solved in the case of not improving original volume of product, stone material clay content is big and contains the difficult problem that the many using effects of stone powder are poor, in addition, also have in concrete is applied and protect plasticity ideally.
Description
Technical field
The present invention relates to high performance water reducing agent of polyocarboxy acid preparation field, in particular to one
Plant and protect plastotype high performance water reducing agent of polyocarboxy acid and preparation method thereof without thermal source.
Background technology
Along with the development of concrete admixture, the construction level of concrete is dashed forward
Fly the raising pushed ahead vigorously.After latest generation high performance water reducing agent of polyocarboxy acid is used widely,
Make self-leveling concrete, high-strength concrete, super high strength concrete, high performance concrete etc.
Obtain the accreditation of insider's height, but there is also some problems to have influence on it further simultaneously
Promote.At present, main problem is exactly in the case of concrete raw material worse becoming,
How to improve the adsorptivity of concrete admixture so that the use of high performance water reducing agent of polyocarboxy acid
Performance improves, thus beneficially market is further promoted.Additionally, country carries always
Advocate environmental protection, and polycarboxylic acid high-performance water reducer in process of production in the market
As use boiler plant produce this series products by steam-heated synthesis technique, this series products
Production do not meet country environmental requirement.
As Application No. 201410124010.6 discloses a kind of high performance water reducing agent of polyocarboxy acid,
It is prepared from by the raw material of following weight portion: acrylic acid 25-35 part, TGA 10-20
Part, isopentenol polyoxyethylene ether 30-50 part, hydrogen peroxide 1-10 part, vitamin C 1-10
Part, white sugar 1-5 part, dodecyl sodium sulfate 0.5-2 part, water 25-60 part.But obtain
The percentage ratio of the comprcssive strength of high performance water reducing agent of polyocarboxy acid, water-reducing rate, the slump through time damage
Mistake still needs to improve further.
Application No. 201310699091.8 disclose a kind of high performance water reducing agent of polyocarboxy acid and
Its preparation method, is by maleic acid Polyethylene Glycol mono-methyl (MaPEG), unsaturated alcohol, draws
Send out agent and water mixing, stir, under logical condition of nitrogen gas, be warming up to 80 DEG C of-90 DEG C of temperature,
After question response 2-2.5h, start to drip unsaturated sulfonic acid sodium solution, adjust effusion meter 1.5-2.5h
Drip off, continue reaction 0.5h；Add acrylamide solution, adjust effusion meter 1.5-2h and drip
Complete, continue reaction 4h, be cooled to room temperature, obtain high performance water reducing agent of polyocarboxy acid.But
To the Slump Time losing of Large of high performance water reducing agent of polyocarboxy acid need to promote, and this invention
Preparation method need heating, its production does not meets environmental requirement, and wastes the energy.
Based on the problems referred to above, how adsorptivity and the nothing of high performance water reducing agent of polyocarboxy acid will be improved
Thermal source synthetic technology organically combines so that the water reducer of production had both improved performance and met market need
Asking, production process environmental protection again is conducive to the sustainable development of country to become problem demanding prompt solution.
In view of this, the special proposition present invention.
Summary of the invention
The first object of the present invention is that providing a kind of subtracts without thermal source guarantor's plastotype poly-carboxylic high-performance
Water preparation, described protects plastotype high performance water reducing agent of polyocarboxy acid and existing like product phase without thermal source
Ratio, has early anti pressured intension height, little loss of slump, bleeding rate is little and shrinkage ratio is little
Etc. feature, this product and concrete raw material have being well adapted for property, are not improving product
Original volume in the case of can to solve concrete sand, stone material clay content big and many containing stone powder
The difficult problem of using effect difference, additionally, also have ideal guarantor in concrete is applied
Plasticity.
The second object of the present invention is to provide a kind of and described protects plastotype polycarboxylic acids height without thermal source
The preparation method of performance water reducer, the method technique is simple, eliminates tradition in production process
The boiler plant of technique, has saved coal fuel, and environmental protection, sustainable to national resources
Develop significant.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
One protects plastotype high performance water reducing agent of polyocarboxy acid without thermal source, is mainly made up of following raw material,
By weight, the first composition 43 parts-49 parts, Ammonium persulfate. 0.8 part-1.2 parts, dimension is raw
Element C 0.1 part-0.3 part, mercaptopropionic acid 0.3 part-0.7 part, 2.0 parts-5.0 parts of acrylic acid,
Methylpropene sodium sulfonate 0.3 part-0.5 part, 2-acrylamide-2-methyl propane sulfonic 0.5 part-1.0
Part, the second composition 1.0 parts-3.0 parts, 44 parts-49 parts of water；
Described first composition is isopentene group polyoxyethylene ether, methyl allyl polyoxyethylene ether
In one or both；
Described second composition is one or both in equisetic acid, ethyl aconitate.
The present invention provide without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid, specific selection the
One composition, acrylic acid, 2-acrylamide-2-methyl propane sulfonic, the second composition, metering system
Sodium sulfonate is as reactant, with Ammonium persulfate. as oxidant, simultaneously using vitamin C as also
Former dose, form redox initiation system, and using mercaptopropionic acid as chain-transferring agent, obtain
Multiple copolymer, this multiple copolymer is protects plastotype high performance water reducing agent of polyocarboxy acid without thermal source,
This product has that early anti pressured intension height, little loss of slump, bleeding rate be little and shrinkage ratio
The feature such as little, and with concrete raw material, there is being well adapted for property, do not improving product
Original volume in the case of can to solve concrete sand, stone material clay content big and many containing stone powder
The difficult problem of using effect difference, additionally, also have ideal guarantor in concrete is applied
Plasticity.
The comprehensive of plastotype high performance water reducing agent of polyocarboxy acid is protected without thermal source in order to promote further
Can, it is preferable that in parts by weight, the first composition 44 parts-46 parts, Ammonium persulfate. 0.9 part
-1.1 parts, vitamin C 0.1 part-0.3 part, mercaptopropionic acid 0.3 part-0.4 part, acrylic acid 2.0
Part-3.0 parts, methylpropene sodium sulfonate 0.4 part-0.5 part, 2-acrylamide-2-methyl-prop sulphur
Acid 0.8 part-1.0 parts, the second composition 1.0 parts-3.0 parts, 45 parts-48 parts of water.
It is highly preferred that in parts by weight, the first composition 45 parts, Ammonium persulfate. 1 part,
Vitamin C 0.2 part, mercaptopropionic acid 0.3 part, 3.0 parts of acrylic acid, metering system sulphur
0.5 part of sodium of acid, 2-acrylamide-2-methyl propane sulfonic 1.0 parts, the second composition 2.0
Part, 47 parts of water.
So that arrives is the most steady without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid performance
Fixed, and other impurity that undope, it is preferable that described water is deionized water.
Present invention also offers the above-mentioned system protecting plastotype high performance water reducing agent of polyocarboxy acid without thermal source
Preparation Method, comprises the following steps:
(a), by the first composition, Ammonium persulfate., the second composition and part water mix, continue
Stir 1.0～1.5 hours；
(b), while stirring be simultaneously added dropwise A material and B material；Described A material for vitamin C,
The solution that mercaptopropionic acid and water are made into, described B material for acrylic acid, methylpropene sodium sulfonate,
The solution that 2-acrylamide-2-methyl propane sulfonic and water are made into；
After (c), dropping, i.e. obtain described without thermal source after continuing stirring 1.0～1.5 hours
Protect plastotype high performance water reducing agent of polyocarboxy acid.
The preparation side protecting plastotype high performance water reducing agent of polyocarboxy acid without thermal source that the present invention provides
Method, the method technique is simple, eliminates the boiler plant of traditional handicraft in production process,
Having saved coal fuel, and environmental protection, the sustainable development to national resources has important
Meaning.Prepare protects plastotype high performance water reducing agent of polyocarboxy acid and existing similar product without thermal source
Condition ratio, have early anti pressured intension height, little loss of slump, bleeding rate little and
The features such as shrinkage ratio is little, this product and concrete raw material have being well adapted for property,
Can solve concrete sand in the case of not improving original volume of product, stone material contains
Mud amount is big and contains the difficult problem that the many using effects of stone powder are poor, additionally, apply at concrete
In also have and protect plasticity ideally.
Further, described A material and B material are simultaneously added dropwise complete, and the time of dropping is
3～4h.A material and B material are added with certain speed, offer between each raw material is provided
Free radical more fully carries out copolyreaction, and prepared protects plastotype polycarboxylic acids height without thermal source
Performance water reducer molecule side chain is more, and not easy entanglement, performance more stable homogeneous.
In order to make being more uniformly distributed of each stock dispersion, fully to react, obtain
Plastotype high performance water reducing agent of polyocarboxy acid molecule side chain is protected more without thermal source, not easy entanglement, surely
Qualitative more preferably, it is preferable that the speed of the stirring during whole is maintained at 100～200
r/min.It is highly preferred that the speed of the stirring during whole is maintained at 150～200r/min.
Part water is the total amount of water used by raw material with the summation of A material and B material water used, in step
Suddenly, in (a), part water is first to be disperseed by part material, by the stirring of a period of time,
Between each composition fully dispersed.It is homogeneous in order to part material is sufficiently disperseed, it is preferable that
In step (a), the 50%-70% that weight is total Water of described part water.
In order to make each composition in A material preferably be uniformly dispersed, it is beneficial to the carrying out of reaction, enters
One step ground, in step (b), the weight of another part water used in A material is total Water
15%-25%.
In order to make each composition in B material preferably be uniformly dispersed, it is beneficial to the carrying out of reaction, enters
One step ground, in step (b), the weight of excess water used in B material is total Water
15%-25%.
Compared with prior art, the invention have the benefit that
(1) present invention is by selecting specific raw material as reactant, and selects specific
Oxidant, reducing agent and chain-transferring agent, prepare multiple copolymer, i.e. without thermal source protect mould
Type high performance water reducing agent of polyocarboxy acid, this product early anti pressured intension height, little loss of slump,
Bleeding rate is little and shrinkage ratio is little, has extraordinary performance.
(2) proportioning of all raw materials is optimized by the present invention, with certain content
What each material composition prepared protects plastotype high performance water reducing agent of polyocarboxy acid combination property more without thermal source
Good, with concrete raw material, there is being well adapted for property, also have non-in concrete is applied
Often protect plasticity ideally.
(3) system protecting plastotype high performance water reducing agent of polyocarboxy acid without thermal source that the present invention provides
Preparation Method, technique is simple, is not required to heating, environmental protection, saves the energy in production process,
The good combination property of the product prepared.
(4) A material and B material are simultaneously added dropwise by the present invention, and the time of dropping is 3～4
H, makes the free radical provided between each raw material more fully carry out copolyreaction, prepares
To protect plastotype high performance water reducing agent of polyocarboxy acid molecule side chain without thermal source more, and not easy entanglement,
Performance more stable homogeneous.
(5) preparation process of the present invention selects specific mixing speed, make each raw material divide
Dissipate is more uniformly distributed, and obtain protects plastotype high performance water reducing agent of polyocarboxy acid molecule without thermal source
Side chain is more, not easy entanglement, and stability is more preferable.
(6) present invention is by distributing the amount of water, makes each composition preferably disperse, and reaction is more
For fully, the properties of product prepared are more stable.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but this
Skilled person is it will be appreciated that the following example is merely to illustrate the present invention, and should not regard
For limiting the scope of the present invention.Unreceipted actual conditions person in embodiment, according to normal condition
Or the condition of manufacturer's suggestion is carried out.Agents useful for same or instrument unreceipted production firm person, all
For can be by the conventional products of commercially available acquisition.
Embodiment 1
Take following raw material: by weight, isopentene group polyoxyethylene ether 43 parts,
Ammonium persulfate. 0.8 part, vitamin C 0.3 part, mercaptopropionic acid 0.7 part, 5.0 parts of acrylic acid,
Methylpropene sodium sulfonate 0.3 part, 2-acrylamide-2-methyl propane sulfonic 0.5 part, equisetic acid
1.0 parts, 44 parts of water；
A expects: the water mixing of the 15% of vitamin C, mercaptopropionic acid and total Water be made into
Solution；
B expects: by acrylic acid, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic
With the 15% of total Water water mix the solution being made into；
Add in a kettle. total Water 70% water, be sequentially added into isopentene group under stirring
Polyoxyethylene ether, Ammonium persulfate., equisetic acid, continue stirring 1.0 hours；
Being simultaneously added dropwise A material while stirring and B expects, the time of dropping is 3h；
After dropping, i.e. obtain described poly-without thermal source guarantor's plastotype after continuing stirring 1.5 hours
Carboxylic acid high-performance water reducing agent；
Wherein, the speed of the stirring during whole is maintained at 100r/min.
Embodiment 2
Take following raw material: by weight, methyl allyl polyoxyethylene ether 44
Part, Ammonium persulfate. 1.1 parts, vitamin C 0.1 part, mercaptopropionic acid 0.3 part, acrylic acid 2.0
Part, methylpropene sodium sulfonate 0.4 part, 2-acrylamide-2-methyl propane sulfonic 1.0 parts, Aconitum carmichjaelii Debx.
Acetoacetic ester 1.0 parts, 45 parts of water；
A expects: the water mixing of the 20% of vitamin C, mercaptopropionic acid and total Water be made into
Solution；
B expects: by acrylic acid, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic
With the 20% of total Water water mix the solution being made into；
Add in a kettle. total Water 60% water, be sequentially added into methallyl under stirring
Base polyoxyethylene ether, Ammonium persulfate., ethyl aconitate, continue stirring 70 minutes；
Being simultaneously added dropwise A material while stirring and B expects, the time of dropping is 3.5h；
After dropping, i.e. obtain described poly-without thermal source guarantor's plastotype after continuing stirring 1.0 hours
Carboxylic acid high-performance water reducing agent；
Wherein, the speed of the stirring during whole is maintained at 150r/min.
Embodiment 3
Take following raw material: by weight, isopentene group polyoxyethylene ether 25 parts,
Methyl allyl polyoxyethylene ether 20 parts, Ammonium persulfate. 1 part, vitamin C 0.2 part, mercapto
Base propanoic acid 0.3 part, 3.0 parts of acrylic acid, methylpropene sodium sulfonate 0.5 part, 2-acrylamide
-2-methyl propane sulfonic acid 1.0 parts, equisetic acid 1.0 parts, ethyl aconitate 1.0 parts, 47 parts of water；
A expects: the water mixing of the 20% of vitamin C, mercaptopropionic acid and total Water be made into
Solution；
B expects: by acrylic acid, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic
With the 20% of total Water water mix the solution being made into；
Add in a kettle. total Water 60% water, be sequentially added into isopentene group under stirring
Polyoxyethylene ether, methyl allyl polyoxyethylene ether, Ammonium persulfate., equisetic acid, equisetic acid
Ethyl ester, continues stirring 80 minutes；
Being simultaneously added dropwise A material while stirring and B expects, the time of dropping is 4h；
After dropping, i.e. obtain described poly-without thermal source guarantor's plastotype after continuing stirring 1.0 hours
Carboxylic acid high-performance water reducing agent.
Wherein, the speed of the stirring during whole is maintained at 200r/min.
Embodiment 4
Take following raw material: by weight, isopentene group polyoxyethylene ether 16 parts,
Methyl allyl polyoxyethylene ether 30 parts, Ammonium persulfate. 0.9 part, vitamin C 0.3 part,
Mercaptopropionic acid 0.4 part, 3.0 parts of acrylic acid, methylpropene sodium sulfonate 0.5 part, 2-acryloyl
Amine-2-methyl propane sulfonic acid 0.8 part, equisetic acid 2.0 parts, ethyl aconitate 1.0 parts, water 48
Part；
A expects: the water mixing of the 25% of vitamin C, mercaptopropionic acid and total Water be made into
Solution；
B expects: by acrylic acid, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic
With the 25% of total Water water mix the solution being made into；
Add in a kettle. total Water 50% water, be sequentially added into isopentene group under stirring
Polyoxyethylene ether, methyl allyl polyoxyethylene ether, Ammonium persulfate., equisetic acid, equisetic acid
Ethyl ester, continues stirring 1.5 hours；
Being simultaneously added dropwise A material while stirring and B expects, the time of dropping is 4h；
After dropping, i.e. obtain described poly-without thermal source guarantor's plastotype after continuing stirring 1.0 hours
Carboxylic acid high-performance water reducing agent.
Wherein, the speed of the stirring during whole is maintained at 150r/min.
Embodiment 5
Take following raw material: by weight, methyl allyl polyoxyethylene ether 49
Part, Ammonium persulfate. 1.2 parts, vitamin C 0.3 part, mercaptopropionic acid 0.7 part, acrylic acid 5.0
Part, methylpropene sodium sulfonate 0.5 part, 2-acrylamide-2-methyl propane sulfonic 1.0 parts, Aconitum carmichjaelii Debx.
Acid 3.0 parts, 49 parts；
A expects: the water mixing of the 20% of vitamin C, mercaptopropionic acid and total Water be made into
Solution；
B expects: by acrylic acid, methylpropene sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic
With the 20% of total Water water mix the solution being made into；
Add in a kettle. total Water 60% water, be sequentially added into methallyl under stirring
Base polyoxyethylene ether, Ammonium persulfate., equisetic acid, continue stirring 1.5 hours；
Being simultaneously added dropwise A material while stirring and B expects, the time of dropping is 4h；
After dropping, i.e. obtain described poly-without thermal source guarantor's plastotype after continuing stirring 1.5 hours
Carboxylic acid high-performance water reducing agent.
Wherein, the speed of the stirring during whole is maintained at 150r/min.
Embodiment 1-5 prepared is carried out without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
The slump, comprcssive strength, bleeding rate, the performance test of shrinkage factor；Meanwhile, with application number
Be 201310699091.8 embodiments 2 preparation high performance water reducing agent of polyocarboxy acid as a control group
1；Poly-carboxylic high-performance diminishing with the preparation of Application No. 201410124010.6 embodiment 3
Agent as a control group 2.Method of testing is right according to GB8076-2008 " concrete admixture "
The physical property of concrete batching is carried out, and wherein, volume is 1%.The result obtained is such as
Shown in table 1.
The result of each performance test of table 1
As it can be seen from table 1 the present invention provide without thermal source guarantor plastotype poly-carboxylic high-performance subtract
The combination property of water preparation is apparently higher than matched group 1 and matched group 2.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that
May be made that without departing from the spirit and scope of the present invention many other change and
Amendment.It is, therefore, intended that include in the following claims belonging in the scope of the invention
All such changes and modifications.
Claims (10)
1. protect plastotype high performance water reducing agent of polyocarboxy acid without thermal source for one kind, it is characterised in that main
To be made up of following raw material, by weight, the first composition 43 parts-49 parts, Ammonium persulfate.
0.8 part-1.2 parts, vitamin C 0.1 part-0.3 part, mercaptopropionic acid 0.3 part-0.7 part, propylene
Acid 2.0 parts-5.0 parts, methylpropene sodium sulfonate 0.3 part-0.5 part, 2-acrylamide-2-methyl
Propane sulfonic acid 0.5 part-1.0 parts, the second composition 1.0 parts-3.0 parts, 44 parts-49 parts of water；
Described first composition is isopentene group polyoxyethylene ether, methyl allyl polyoxyethylene ether
In one or both；
Described second composition is one or both in equisetic acid, ethyl aconitate.
The most according to claim 1 without thermal source guarantor's plastotype poly-carboxylic high-performance diminishing
Agent, it is characterised in that by weight, the first composition 44 parts-46 parts, Ammonium persulfate. 0.9
Part-1.1 parts, vitamin C 0.1 part-0.3 part, mercaptopropionic acid 0.3 part-0.4 part, acrylic acid
2.0 parts-3.0 parts, methylpropene sodium sulfonate 0.4 part-0.5 part, 2-acrylamide-2-methyl-prop
Sulfonic acid 0.8 part-1.0 parts, the second composition 1.0 parts-3.0 parts, 45 parts-48 parts of water.
The most according to claim 1 without thermal source guarantor's plastotype poly-carboxylic high-performance diminishing
Agent, it is characterised in that by weight, the first composition 45 parts, Ammonium persulfate. 1 part, dimension
Raw element C 0.2 part, mercaptopropionic acid 0.3 part, 3.0 parts of acrylic acid, methylpropene sodium sulfonate 0.5
Part, 2-acrylamide-2-methyl propane sulfonic 1.0 parts, the second composition 2.0 parts, 47 parts of water.
4. according to described in any one of claim 1-3 without thermal source protect plastotype polycarboxylic acids height
Energy water reducer, it is characterised in that described water is deionized water.
5. subtracting without thermal source guarantor's plastotype poly-carboxylic high-performance described in any one of claim 1-4
The preparation method of water preparation, it is characterised in that comprise the following steps:
(a), by the first composition, Ammonium persulfate., the second composition and part water mix, continue
Stir 1.0～1.5 hours；
(b), while stirring be simultaneously added dropwise A material and B material；Described A material for vitamin C,
The solution that mercaptopropionic acid and another part water are made into, described B material is acrylic acid, metering system
The solution that sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic and excess water are made into；
After (c), dropping, i.e. obtain described without thermal source after continuing stirring 1.0～1.5 hours
Protect plastotype high performance water reducing agent of polyocarboxy acid.
The most according to claim 5 without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
Preparation method, it is characterised in that described A material and B material be simultaneously added dropwise complete, dropping
Time is 3～4h.
The most according to claim 5 without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
Preparation method, it is characterised in that the speed of the stirring during whole is maintained at 100～200
r/min。
The most according to claim 5 without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
Preparation method, it is characterised in that in step (a), the weight of described part water is total
The 50%-70% of the water yield.
The most according to claim 5 without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
Preparation method, it is characterised in that in step (b), another part used in A material
The weight of water is the 15%-25% of total Water.
The most according to claim 5 without thermal source guarantor's plastotype high performance water reducing agent of polyocarboxy acid
Preparation method, it is characterised in that in step (b), excess water used in B material
Weight is the 15%-25% of total Water.
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| CN105585272A (en) * | 2015-10-22 | 2016-05-18 | 湖州绿色建材开发有限公司 | Novel concrete reinforcing agent |
| CN106397682B (en) * | 2016-08-29 | 2018-07-17 | 江苏中铁奥莱特新材料股份有限公司 | The preparation method of collapse protective poly-carboxylic acid water reducing agent |
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| GB1101204A (en) * | 1965-08-12 | 1968-01-31 | Ici Ltd | Cementing compositions |
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| CN102675557A (en) * | 2011-12-16 | 2012-09-19 | 天津冶建特种材料有限公司 | Slow-release type concrete slump retaining agent and preparation method thereof |
| CN102826784A (en) * | 2012-09-12 | 2012-12-19 | 江苏奥莱特新材料有限公司 | Polycarboxylate water reducer and preparation method thereof |
| CN103804610B (en) * | 2014-02-13 | 2016-10-05 | 科之杰新材料集团有限公司 | A kind of preparation method of the high-performance polycarboxylic acids water reducing agent of technique without thermal source |
| CN103992443B (en) * | 2014-05-19 | 2016-06-22 | 科之杰新材料集团有限公司 | The method that room temperature batch mixing method prepares polycarboxylate water-reducer |
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