CN102718428A - Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer - Google Patents
Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer Download PDFInfo
- Publication number
- CN102718428A CN102718428A CN2012102195895A CN201210219589A CN102718428A CN 102718428 A CN102718428 A CN 102718428A CN 2012102195895 A CN2012102195895 A CN 2012102195895A CN 201210219589 A CN201210219589 A CN 201210219589A CN 102718428 A CN102718428 A CN 102718428A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- polycarboxylic acid
- raw material
- parts
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the field of concrete additives and specifically relates to a polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and a preparation method of the polycarboxylic acid type concrete water reducer. The water reducer is prepared by a polymerization reaction of, by weight, 120-130 parts of allyl polyoxyethylene ether, 30-40 parts of maleic anhydride residues, 3-7 parts of chain transfer agents and 3-9 parts of initiating agents, wherein the maleic anhydride residues are crystals in waste residues and waster water which are produced in the process of maleic anhydride. The preparation method includes adding the allyl polyoxyethylene ether and the maleic anhydride residues into water according to an appropriate proportion, stirring a mixture and heating the mixture to 55 DEG C-65 DEG C, then adding the chain transfer agents and the initiating agents, subjecting the mixture to two-step heating, performing the polymerization reaction, and subjecting the mixture to cooling and PH value adjusting to obtain the water reducer. According to the polycarboxylic acid type concrete water reducer with the maleic anhydride residues as the raw materials and the preparation method of the polycarboxylic acid type concrete water reducer, the zero discharge of the maleic anhydride waste residues is achieved, the cost of the polycarboxylic acid water reducer is reduced, the maleic anhydride residues are recycled, useful components in the waste residues can be utilized to the maximum, the greening production of the maleic anhydride is achieved, and good social and economic benefits are achieved.
Description
Technical field
The present invention relates to the concrete additive field, specifically, relating to a kind of is the polycarboxylic acid series water reducing agent and preparation method thereof of raw material with the maleic anhydride residue.
Background technology
Produce the waste residue of cis-butenedioic anhydride, be similar in color, be acid, if directly discarded meeting bring great harm to environment in soil.The staple of cis-butenedioic anhydride waste residue is cis-butenedioic anhydride, maleic acid, FUMARIC ACID TECH GRADE and other micromolecular acid.One of main path of the recycling of maleic anhydride residue is to be used to produce fumaric acid at present; Maleic anhydride residue is produced fumaric acid need pass through isoversion, decolouring; And the technological processs such as regeneration of gac, process is loaded down with trivial details, and technology is complicated; Processing cost is higher relatively, and the oxidative coupling material that wherein contains is difficult to remove through decolorization.Maleic anhydride residue also is used to produce the ester class like the production of dimethyl fumarate, succinate, though the production of ester class can be reclaimed high value-added product, but needs through fractionation by distillation, and facility investment is big.
Maleic acid in the waste residue and FUMARIC ACID TECH GRADE all are one of main raw materials of synthetic polycarboxylate water-reducer; And cement water reducing agent is lower to the requirement of material color; Therefore maleic anhydride residue directly is used for the synthetic of polycarboxylate water-reducer and will reduces processing cost greatly; Simplify treatment process, the use field of widening maleic anhydride residue reduces the production cost of polycarboxylate water-reducer simultaneously; For the recycling of maleic anhydride residue and " popular " of polycarboxylate water-reducer bring wide development space, and environment protection and changing waste into resources had positive effect.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of high-performance, be the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue cheaply.
It is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue that another object of the present invention is to provide above-mentioned.
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue; It is characterized in that; Raw material following mass fraction is prepared from through polyreaction: 120 ~ 130 parts of allyl polyethenoxy ethers, 30 ~ 40 parts of maleic anhydride residues, 3 ~ 7 parts of chain-transfer agents and 3 ~ 9 parts of initiators
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
Wherein:
Said allyl polyethenoxy ether molecular weight is 1200 ~ 2400.
Said chain-transfer agent is the mixture of one or both arbitrary proportions in sodium allyl sulfonate or the methallylsulfonic acid sodium.
Said initiator is the mixture of one or both arbitrary proportions in Potassium Persulphate or the ammonium persulphate.
The preparation method may further comprise the steps:
Allyl polyethenoxy ether, the maleic anhydride residue that 1) will meet ratio adds and stirs in the entry and be warming up to 60 ~ 65 ℃;
2) in the solution that step 1) obtains, add chain-transfer agent and initiator, carry out polyreaction;
3) cooling after reaction finishes is regulated the pH value with alkaline solution, obtains polycarboxylic acid series water reducing agent.
Wherein, said water is 200 ~ 230 weight parts.
Said polyreaction is divided two stages:
Fs: be warming up to 70 ~ 75 ℃ of isothermal reaction 1.0 ~ 1.5h;
Subordinate phase: be warming up to 75 ~ 80 ℃ of isothermal reaction 1.5 ~ 2.0h.
Said temperature is reduced to 25 ~ 30 ℃.
Said pH value is 6.0 ~ 8.0.
Said alkaline solution is 47% sodium hydroxide solution.
Method of use is: this water reducer mixes to roll over to measure admittedly and is 0.15% ~ 0.30% of cement weight in the clean slurry, and this water reducer incorporation is 0.25% ~ 0.45% of a gelling material weight in the concrete.
The beneficial effect that the present invention had is:
1, utilizes the polycarboxylic acid series water reducing agent of maleic anhydride residue preparation; Consumption instead of pure cis-butenedioic anhydride synthetic water reducer fully through the adjustment water reducer; Can alleviate the concrete admixture imbalance between supply and demand that causes owing to significantly improving of the prices of raw and semifnished materials, improve competitiveness of product; Owing to also contain other micromolecular acid and organism in the maleic anhydride residue, sandstone silt content susceptibility had positive meaning simultaneously to alleviating water reducer;
2, utilize the synthetic polycarboxylate water-reducer of maleic anhydride residue can reduce the pollution that maleic anhydride residue brings to environment;
3, maleic anhydride residue directly can reduce the processing cost of maleic anhydride residue greatly as the synthesis material of polycarboxylate water-reducer.
Embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, is prepared from through polyreaction the raw material of following mass fraction: 120 parts of allyl polyethenoxy ethers, 35 parts of maleic anhydride residues, 5 parts of methylpropene sodium sulfonates and 7 parts of Potassium Persulphates,
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 205 parts of water of maleic anhydride residue adding and being warming up to 55 ℃;
2) in the solution that step 1) obtains, add methylpropene sodium sulfonate and Potassium Persulphate, carry out polyreaction;
3) be cooled to 30 ℃ after reaction finishes, regulate pH value to 7, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 70 ℃ of isothermal reaction 1.5h;
Subordinate phase: be warming up to 80 ℃ of isothermal reaction 1.5h.
Embodiment 2
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, is prepared from through polyreaction the raw material of following mass fraction: 130 parts of allyl polyethenoxy ethers, 40 parts of maleic anhydride residues, 6 parts of sodium allyl sulfonates and 9 parts of ammonium persulphates,
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 215 parts of water of maleic anhydride residue adding and being warming up to 65 ℃;
2) in the solution that step 1) obtains, add sodium allyl sulfonate and ammonium persulphate, carry out polyreaction;
3) be cooled to 25 ℃ after reaction finishes, regulate pH value to 8, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 72 ℃ of isothermal reaction 1h;
Subordinate phase: be warming up to 75 ℃ of isothermal reaction 2h.
Embodiment 3
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue; Raw material following mass fraction is prepared from through polyreaction: 125 parts of allyl polyethenoxy ethers, 38 parts of maleic anhydride residues, 2 parts of sodium allyl sulfonates, 4 parts of methylpropene sodium sulfonates and 6 parts of ammonium persulphates
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 225 parts of water of maleic anhydride residue adding and being warming up to 58 ℃;
2) in the solution that step 1) obtains, add sodium allyl sulfonate, methylpropene sodium sulfonate and ammonium persulphate, carry out polyreaction;
3) be cooled to 30 ℃ after reaction finishes, regulate pH value to 7.5, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 75 ℃ of isothermal reaction 1.5h;
Subordinate phase: be warming up to 80 ℃ of isothermal reaction 2h.
Embodiment 4
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue; Raw material following mass fraction is prepared from through polyreaction: 127 parts of allyl polyethenoxy ethers, 35 parts of maleic anhydride residues, 3 parts of methylpropene sodium sulfonates, 3 parts of sodium allyl sulfonates, 4 parts of Potassium Persulphates and 4 parts of ammonium persulphates
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 210 parts of water of maleic anhydride residue adding and being warming up to 62 ℃;
2) in the solution that step 1) obtains, add methylpropene sodium sulfonate, sodium allyl sulfonate, Potassium Persulphate and and ammonium persulphate, carry out polyreaction;
3) be cooled to 30 ℃ after reaction finishes, regulate pH value to 7.5, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 72 ℃ of isothermal reaction 1.5h;
Subordinate phase: be warming up to 78 ℃ of isothermal reaction 2h.
Embodiment 5
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, is prepared from through polyreaction the raw material of following mass fraction: 128 parts of allyl polyethenoxy ethers, 40 parts of maleic anhydride residues, 4 parts of sodium allyl sulfonates and 3 parts of Potassium Persulphates,
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 220 parts of water of maleic anhydride residue adding and being warming up to 62 ℃;
2) in the above-mentioned solution that obtains, add sodium allyl sulfonate and Potassium Persulphate, carry out polyreaction;
3) be cooled to 28 ℃ after reaction finishes, regulate pH value to 7.5, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 72 ℃ of isothermal reaction 1.2h;
Subordinate phase: be warming up to 78 ℃ of isothermal reaction 2h.
Embodiment 6
Of the present invention is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue; Raw material following mass fraction is prepared from through polyreaction: 122 parts of allyl polyethenoxy ethers, 32 parts of maleic anhydride residues, 3 parts of methylpropene sodium sulfonates, 2 parts of Potassium Persulphates and 3 parts of ammonium persulphates
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
The preparation method may further comprise the steps:
1) with stirring in allyl polyethenoxy ether, 230 parts of water of maleic anhydride residue adding and being warming up to 65 ℃;
2) in the solution that step 1) obtains, add methylpropene sodium sulfonate, Potassium Persulphate and ammonium persulphate, carry out polyreaction;
3) be cooled to 28 ℃ after reaction finishes, regulate pH value to 6.5, obtain polycarboxylate water-reducer with sodium hydroxide solution.
Wherein: polyreaction is divided two stages:
Fs: be warming up to 74 ℃ of isothermal reaction 1.6h;
Subordinate phase: be warming up to 80 ℃ of isothermal reaction 1.6h.
Be example with embodiment 1 to embodiment 4 below; The water reducer that cis-butenedioic anhydride is made is designated as PC2 appearance as a comparison; The water reducer of PC2 and above-mentioned four embodiment preparation is starched simultaneous test and concrete application performance evaluation experimental only, to estimate the water reducer performance of the present invention's preparation.
Wherein, PC2 is prepared from through polyreaction 130 parts of allyl polyethenoxy ethers, 30 parts of cis-butenedioic anhydrides, 5 parts of methylpropene sodium sulfonates and 8 parts of Potassium Persulphates, and the water reducer of four embodiment preparations is docile and obedient preface and is labeled as #1, #2, #3, #4 respectively.
One, starch simultaneous test only:
Select mountain aluminium cement PO-42.5600g for use, water 174g, the concentration of water reducer is that 45%, 5 kind of water reducer volume is 2.4g, experimental result is seen table 1:
The water reducer of table 1 cis-butenedioic anhydride and maleic anhydride residue preparation is starched the degree of mobilization contrast only
Two, concrete application performance evaluation experimental:
1, slump-loss
The water reducer that maleic anhydride residue is made is designated as PC1, and the water reducer that cis-butenedioic anhydride makes is designated as PC2 appearance as a comparison.The mass ratio of cement, sand, stone is 1.0:2.0:2.6 in the concrete, and the solid volume of the folding of PC2 is 0.24%, and the volume of PC1 is 1.10 times of PC2.PC1 and PC2 fresh concrete slump-loss comparative test result are seen table 2.
Table 2 fresh concrete slump-loss situation
Visible by table 2, the initial slump of concrete and the divergence of mixing PC2 are bigger, but it is less to mix the concrete slump loss of PC1 behind the 0.5h, explain that volume as PC1 can reach the effect identical with PC2 when being 1.10 times of PC2 basically.
2, water-reducing rate and ultimate compression strength
The mass ratio of cement, sand, stone is 1.0:2.3:3.5 in the concrete, and PC1, the solid volume of PC2 folding are respectively 0.264% and 0.240%, mix PC1 and PC2 concrete water-reducing ratio and ultimate compression strength comparative test result and see table 3.
Table 3 is mixed PC1 and concrete water-reducing rate of PC2 and ultimate compression strength contrast
Can find out that by table 3 intensity of concrete 3d and 28d of mixing PC1 and PC2 is basic identical, shows when PC1 substitutes PC2 with 1.10 times of volumes, can reach same effect.
Claims (10)
1. one kind is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue; It is characterized in that; Raw material following mass fraction is prepared from through polyreaction: 120 ~ 130 parts of allyl polyethenoxy ethers, 30 ~ 40 parts of maleic anhydride residues, 3 ~ 7 parts of chain-transfer agents and 3 ~ 9 parts of initiators
Wherein, maleic anhydride residue is a crystallisate in the waste residue that produces in the cis-anhydride production process and the waste water, and effective constituent comprises cis-butenedioic anhydride, toxilic acid and fumaric acid.
2. according to claim 1 is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said allyl polyethenoxy ether molecular weight is 1200 ~ 2400.
3. according to claim 1 is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said chain-transfer agent is the mixture of one or both arbitrary proportions in sodium allyl sulfonate or the methylpropene sodium sulfonate.
4. according to claim 1 is the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said initiator is the mixture of one or both arbitrary proportions in Potassium Persulphate or the ammonium persulphate.
5. according to claim 1 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, comprises step:
Allyl polyethenoxy ether, the maleic anhydride residue that 1) will meet ratio adds and stirs in the entry and be warming up to 55 ~ 65 ℃;
2) in the solution that step 1) obtains, add chain-transfer agent and initiator, carry out polyreaction;
3) cooling after reaction finishes is regulated pH value with alkaline solution, obtains polycarboxylate water-reducer.
6. according to claim 5 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said water is 200 ~ 230 weight parts.
7. according to claim 5 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, churning time is 10 ~ 15min in the said step 1).
8. according to claim 5 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that said step 2) polyreaction divides two stages:
Fs: be warming up to 70 ~ 75 ℃ of isothermal reaction 1.0 ~ 1.5h;
Subordinate phase: be warming up to 75 ~ 80 ℃ of isothermal reaction 1.5 ~ 2.0h.
9. according to claim 5 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said step 3) temperature is reduced to 25 ~ 30 ℃.
10. according to claim 5 is the preparation method of the polycarboxylic acid series water reducing agent of raw material with the maleic anhydride residue, it is characterized in that, said step 3) pH value is 6.0 ~ 8.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102195895A CN102718428A (en) | 2012-06-29 | 2012-06-29 | Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102195895A CN102718428A (en) | 2012-06-29 | 2012-06-29 | Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102718428A true CN102718428A (en) | 2012-10-10 |
Family
ID=46944335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102195895A Pending CN102718428A (en) | 2012-06-29 | 2012-06-29 | Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718428A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496446A (en) * | 2016-11-15 | 2017-03-15 | 湖北工业大学 | A kind of method of expired HEA Material synthesis polycarboxylic acid slump retaining agent masterbatch |
| CN111574636A (en) * | 2019-06-12 | 2020-08-25 | 郑秀旗 | Starch maleate, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
-
2012
- 2012-06-29 CN CN2012102195895A patent/CN102718428A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
Non-Patent Citations (2)
| Title |
|---|
| 《混凝土外加剂生产技术和应用新进展学术交流会议论文集》 20120414 王景华等 "富马酸型聚羧酸减水剂的工艺研究" 第78-83页 1-8 , * |
| 王景华等: ""富马酸型聚羧酸减水剂的工艺研究"", 《混凝土外加剂生产技术和应用新进展学术交流会议论文集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496446A (en) * | 2016-11-15 | 2017-03-15 | 湖北工业大学 | A kind of method of expired HEA Material synthesis polycarboxylic acid slump retaining agent masterbatch |
| CN106496446B (en) * | 2016-11-15 | 2018-11-13 | 湖北工业大学 | A kind of method of expired HEA Material synthesis polycarboxylic acid slump retaining agent masterbatch |
| CN111574636A (en) * | 2019-06-12 | 2020-08-25 | 郑秀旗 | Starch maleate, preparation method and application thereof |
| CN111574636B (en) * | 2019-06-12 | 2023-02-17 | 郑秀旗 | Starch maleate, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102757211B (en) | Aerated concrete block produced by specially-made mineral waste residue and tailings steel slag and production method of aerated concrete block | |
| CN102408199B (en) | Method for preparing active admixture for concrete and cement by building waste | |
| CN101798198B (en) | Polycarboxylic acid cement activation reinforced grinding aid and preparation method thereof | |
| CN110885203A (en) | Composite mineral admixture and preparation method thereof | |
| CN103435288A (en) | Novel grinding enhancer and preparation and application thereof | |
| CN102765906B (en) | Method for producing aerated hollow bricks by fluorite slag | |
| CN104261723A (en) | Dry powder additive for masonry and rendering mortar and production technique thereof | |
| CN107056200B (en) | A method of environment friendly pervious brick is prepared using industrial melting waste slag | |
| CN103570259A (en) | Geopolymer dry powder material as well as preparation method thereof | |
| CN103539417A (en) | Method for manufacturing steam-pressing bricks by using iron tailings and steel slag | |
| CN102964082B (en) | High molecular synthetic cement grinding aid | |
| CN101805147B (en) | Preparation method of liquid cement grinding aid | |
| CN107352824B (en) | Industrial synthetic sulfur gypsum and preparation method thereof | |
| CN104119098A (en) | Autoclaved aerated partition plate taking red mud as raw material | |
| CN102718428A (en) | Polycarboxylic acid type concrete water reducer with maleic anhydride residues as raw materials and preparation method of polycarboxylic acid type concrete water reducer | |
| CN102690093A (en) | High-strength water resistance phosphogypsum steam-cured brick and preparation method thereof | |
| CN102303975A (en) | Ultralow-porosity refractory brick and preparation method thereof | |
| CN102795815B (en) | Cullet-doped aerated block production method | |
| CN103011881A (en) | Method for increasing quartz sand tailing powder content in aerated concrete product | |
| CN109650803A (en) | Machine-made sand concrete and its preparation process | |
| CN104150802A (en) | Synthesis method of crystal nucleus for promoting high-belite cement hydration progress | |
| KR100441640B1 (en) | Admixture of Powder for Concrete by used Industrial byproduct | |
| KR101147985B1 (en) | Cementless concrete using blast slag and producing method therof | |
| CN105481313B (en) | Construction and the continual and steady wet mixing mortar of mechanical property | |
| CN104370506A (en) | Concrete with improved construction performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121010 |