CN110372830A - A kind of super plasticizer and preparation method thereof - Google Patents
A kind of super plasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN110372830A CN110372830A CN201910676592.1A CN201910676592A CN110372830A CN 110372830 A CN110372830 A CN 110372830A CN 201910676592 A CN201910676592 A CN 201910676592A CN 110372830 A CN110372830 A CN 110372830A
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- China
- Prior art keywords
- preparation
- super plasticizer
- added dropwise
- polymeric monomer
- added
- 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.)
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- 239000008030 superplasticizer Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004359 castor oil Substances 0.000 claims abstract description 16
- 235000019438 castor oil Nutrition 0.000 claims abstract description 16
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical group O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004568 cement Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011083 cement mortar Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 235000004443 Ricinus communis Nutrition 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
Abstract
The invention discloses a kind of super plasticizers and preparation method thereof, dehydrated castor oil minor comonomer is added in deionized water and is mixed with polymeric monomer, chain-transferring agent, it is heated with stirring to 20~60 DEG C, then 20~60 DEG C are kept, initiator is persistently added dropwise, keeps reaction temperature after being added dropwise, stop reaction after continuing stirring 1~2 hour, sodium hydrate aqueous solution is added in reaction product so that the pH value of system be 7~8 to get.The present invention replaces acrylic acid, methacrylic acid as minor comonomer to prepare super plasticizer using dehydrated castor oil, has the advantages that cost of material is low, from a wealth of sources, environmentally protective, sustainable development；Flowing degree of net paste of cement and cement mortar water-reducing rate can be significantly improved, gradual loss is reduced.
Description
Technical field
The present invention relates to concrete admixture field, specifically a kind of super plasticizer and preparation method thereof.
Background technique
Super plasticizer is otherwise known as concrete admixture, its addition can be effectively improved the working performance and power of concrete
Property is learned, is primarily referred to as the high high efficiency water reducing agent and high-performance water reducing agent of water-reducing rate in China.Dosage is maximum currently on the market
It is poly carboxylic acid series water reducer, mainly by using acrylic or methacrylic acid as minor comonomer, with allyl polyethenoxy ether or first
Base allyl polyethenoxy ether is polymeric monomer, issues raw Raolical polymerizable in initiator effect and forms.But cost of material compared with
Height, especially acrylic acid, industrial production mainly passes through petroleum chemicals propylene catalysis oxidation and is made at present, and there are shortages of resources, ring
The disadvantages of border pollution, high production cost, becomes restriction using acrylic acid as the poly carboxylic acid series water reducer industry sustainable development of raw material
One of the main reason for.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide it is a kind of using dehydrated castor oil as
Minor comonomer replaces acrylic acid, and novel castor oil-base super plasticizer is made.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of preparation method of super plasticizer, includes the following steps:
Step 1: being added dehydrated castor oil minor comonomer in deionized water and mix with polymeric monomer, chain-transferring agent, agitating and heating
To 20~60 DEG C；
Step 2: keep 20~60 DEG C, initiator is persistently added dropwise, keeps reaction temperature after being added dropwise, continue stirring 1~
Stop reaction after 2 hours；
Step 3: being added sodium hydrate aqueous solution into step 2 reaction product, so that the pH value of system is 7~8, i.e.,
?.
Wherein, dehydrated castor oil can be made by castor oil catalytic and dehydration reaction, be preparation method commonly used in the art, no
Content as the application creative contribution.Castor oil category biomass energy can be obtained directly from castor seeds extraction, and being can be again
Production-goods source.Prepare super plasticizer using dehydrated castor oil as minor comonomer, have cost of material it is low, it is from a wealth of sources, environmentally protective, can
The advantages of sustainable development.
Preferably, in step 1, the polymeric monomer is allyl polyethenoxy ether or methyl allyl polyoxyethylene ether；It is small
Monomer and polymeric monomer mass ratio are (0.4~2.5): 1.
The chain-transferring agent is thioacetic acid, and dosage is the 0.2~1.0% of minor comonomer and polymeric monomer gross mass.
The ion water quality and minor comonomer and the ratio of polymeric monomer gross mass are (1.0~1.5): 1.
Preferably, in step 1, the stirring rate is 60~120 revs/min.
In step 2, the initiator is (1~3) according to mass ratio by hydrogen peroxide and ascorbic acid: 1 is mixed,
Dosage is the 30~80% of minor comonomer and polymeric monomer gross mass.
The initiator was added dropwise within 3~5 hours time.
Preferably, in step 3, the mass concentration of the sodium hydrate aqueous solution is 10~30%.
The super plasticizer that the above method is prepared is also within the protection scope of the present invention.
The utility model has the advantages that
The present invention replaces acrylic acid, methacrylic acid as minor comonomer using dehydrated castor oil and prepares super plasticizer, has original
Expect the advantages of at low cost, from a wealth of sources, environmentally protective, sustainable development；Flowing degree of net paste of cement and cement can be significantly improved
Glue sand water-reducing rate reduces gradual loss.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is castor oil-base super plasticizer infrared spectrogram prepared by embodiment 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Embodiment 1
4.0g dehydrated castor oil, 10.0g allyl polyethenoxy ether, 0.028g thioacetic acid are added to four-hole boiling flask
In, 14.0g deionized water is added, under the conditions of 20 DEG C of temperature, 60 revs/min of stirring rate, starts that initiator is added dropwise, at 3 hours
Left and right drips 4.2g, and initiator is mixed by 2.1g hydrogen peroxide and 2.1g ascorbic acid, after being added dropwise, keeps at 20 DEG C
Continue stirring 1 hour, then stop heating, stirring, it is water-soluble that the sodium hydroxide that mass concentration is 10% is added dropwise into four-hole boiling flask
Liquid, when mixed solution pH value be 7.0 when stop be added dropwise, be made castor oil-base super plasticizer, infrared spectrogram as shown in Figure 1,
Product yield is 83.6%.
Embodiment 2
25.0g dehydrated castor oil, 10.0g allyl polyethenoxy ether, 0.35g thioacetic acid are added to four-hole boiling flask
In, 52.5g deionized water is added, under the conditions of 40 DEG C of temperature, 100 revs/min of stirring rate, starts that initiator is added dropwise, at 5 hours
Left and right drips 28.0g, and initiator is mixed by 21.0g hydrogen peroxide and 7.0g ascorbic acid, after being added dropwise, is kept for 40 DEG C
Under continue stirring 2 hours, then stop heating, stirring, into four-hole boiling flask be added dropwise mass concentration be 20% sodium hydroxide water
Solution stops being added dropwise when mixed solution pH value is 7.0, castor oil-base super plasticizer, product yield 88.3% is made.
Embodiment 3
10.0g dehydrated castor oil, 10.0g methyl allyl polyoxyethylene ether, 0.1g thioacetic acid are added to four mouthfuls of burnings
In bottle, 25.0g deionized water is added, under the conditions of temperature 60 C, 120 revs/min of stirring rate, starts that initiator is added dropwise, it is small 5
When or so drip 15.6g, initiator is mixed by 10.4g hydrogen peroxide and 5.2g ascorbic acid, after being added dropwise, keep 60
Continue stirring 1 hour at DEG C, then stop heating, stirring, the sodium hydroxide that mass concentration is 10% is added dropwise into four-hole boiling flask
Aqueous solution stops being added dropwise when mixed solution pH value is 7.0, castor oil-base super plasticizer, product yield 87.8% is made.
Embodiment 4
15.0g dehydrated castor oil, 10.0g allyl polyethenoxy ether, 0.05g thioacetic acid are added to four-hole boiling flask
In, 25.0g deionized water is added, under the conditions of 23 DEG C of temperature, 120 revs/min of stirring rate, starts that initiator is added dropwise, at 5 hours
Left and right drips 12.5g, and initiator is mixed by 6.5g hydrogen peroxide and 6.0g ascorbic acid, after being added dropwise, is kept for 23 DEG C
Under continue stirring 2 hours, then stop heating, stirring, into four-hole boiling flask be added dropwise mass concentration be 30% sodium hydroxide water
Solution stops being added dropwise when mixed solution pH value is 7.0, castor oil-base super plasticizer, product yield 95.1% is made.
Embodiment 5
20.0g dehydrated castor oil, 10.0g methyl allyl polyoxyethylene ether, 0.15g thioacetic acid are added to four mouthfuls of burnings
In bottle, 39.0g deionized water is added, under the conditions of 35 DEG C of temperature, 120 revs/min of stirring rate, starts that initiator is added dropwise, it is small 5
When or so drip 21.0g, initiator is mixed by 14.0g hydrogen peroxide and 7.0g ascorbic acid, after being added dropwise, keep 35
Continue stirring 1 hour at DEG C, then stop heating, stirring, the sodium hydroxide that mass concentration is 20% is added dropwise into four-hole boiling flask
Aqueous solution stops being added dropwise when mixed solution pH value is 7.0, castor oil-base super plasticizer, product yield 91.3% is made.
Embodiment 6
8.0g dehydrated castor oil, 10.0g allyl polyethenoxy ether, 0.1g thioacetic acid are added in four-hole boiling flask,
20.0g deionized water is added, under the conditions of 25 DEG C of temperature, 80 revs/min of stirring rate, starts that initiator is added dropwise, at 4 hours or so
Drip 10.8g, initiator is mixed by 8.1g hydrogen peroxide and 2.7g ascorbic acid, after being added dropwise, keep 25 DEG C at after
Continuous stirring 1 hour, then stops heating, stirring, and the sodium hydrate aqueous solution that mass concentration is 20% is added dropwise into four-hole boiling flask,
Stop being added dropwise when mixed solution pH value is 7.0, castor oil-base super plasticizer, product yield 85.5% is made.
Embodiment 7
Castor oil-base super plasticizer obtained by Examples 1 to 6 and commercialization polycarboxylate water-reducer SPE-100 are subjected to performance pair
Than, according to flowing degree of net paste of cement in GB/T 8077-2012 " Methods for testing uniformity of concrete admixture ", gradual loss and
The measuring method of cement mortar water-reducing rate carries out performance evaluation, the results are shown in Table 1.
1 present invention gained super plasticizer of table and commercialization SPE-100 performance comparison
As can be seen from Table 1: the super plasticizer and commercialization SPE-100 prepared according to the method and raw material of the invention patent
Performance is compared, and higher flowing degree of net paste of cement, lower gradual loss and higher cement mortar water-reducing rate are shown.
The present invention provides a kind of thinking of super plasticizer and preparation method thereof and methods, implement the technical solution
There are many method and approach, the above is only a preferred embodiment of the present invention, it is noted that for the common of the art
For technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these are improved and profit
Decorations also should be regarded as protection scope of the present invention.The available prior art of each component part being not known in the present embodiment is subject to reality
It is existing.
Claims (9)
1. a kind of preparation method of super plasticizer, which comprises the steps of:
Step 1: being added dehydrated castor oil minor comonomer and polymeric monomer, chain-transferring agent in deionized water and mix, be heated with stirring to
20~60 DEG C；
Step 2: it is kept for 20~60 DEG C, initiator is persistently added dropwise, keeps reaction temperature after being added dropwise, it is small to continue stirring 1~2
When after stop reaction；
Step 3: being added sodium hydrate aqueous solution into step 2 reaction product so that the pH value of system be 7~8 to get.
2. the preparation method of super plasticizer according to claim 1, which is characterized in that in step 1, the polymeric monomer is alkene
Propyl polyoxyethylene ether or methyl allyl polyoxyethylene ether；Minor comonomer and polymeric monomer mass ratio are (0.4~2.5): 1.
3. the preparation method of super plasticizer according to claim 2, which is characterized in that in step 1, the chain-transferring agent is
Thioacetic acid, dosage are the 0.2~1.0% of minor comonomer and polymeric monomer gross mass.
4. the preparation method of super plasticizer according to claim 2, which is characterized in that in step 1, the ion water quality
It is (1.0~1.5) with minor comonomer and the ratio of polymeric monomer gross mass: 1.
5. the preparation method of super plasticizer according to claim 1, which is characterized in that in step 1, the stirring rate is
60~120 revs/min.
6. the preparation method of super plasticizer according to claim 1, which is characterized in that in step 2, the initiator is by double
Oxygen water and ascorbic acid are (1~3) according to mass ratio: 1 mixes, dosage be minor comonomer and polymeric monomer gross mass 30~
80%.
7. the preparation method of super plasticizer according to claim 6, which is characterized in that in step 2, the initiator 3~
It is added dropwise in 5 hours time.
8. the preparation method of super plasticizer according to claim 1, which is characterized in that in step 3, the sodium hydroxide water
The mass concentration of solution is 10~30%.
9. the super plasticizer that any one of claim 1~8 preparation method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676592.1A CN110372830B (en) | 2019-07-25 | 2019-07-25 | Superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910676592.1A CN110372830B (en) | 2019-07-25 | 2019-07-25 | Superplasticizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110372830A true CN110372830A (en) | 2019-10-25 |
| CN110372830B CN110372830B (en) | 2021-12-31 |
Family
ID=68256000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910676592.1A Active CN110372830B (en) | 2019-07-25 | 2019-07-25 | Superplasticizer and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336845A (en) * | 2010-07-27 | 2012-02-01 | 上海台界化工有限公司 | Method for synthesizing polycarboxylic acid water reducer |
| CN102876453A (en) * | 2012-09-29 | 2013-01-16 | 淄博市淄川创业油脂化工厂 | Preparation method for dehydrated castor oil |
| CN105800986A (en) * | 2016-03-09 | 2016-07-27 | 河南工程学院 | Method for preparing concrete water reducing agent |
| CN107057003A (en) * | 2017-05-09 | 2017-08-18 | 山东华伟银凯建材科技股份有限公司 | Self-curing type poly carboxylic acid series water reducer and preparation method thereof |
| CN107245130A (en) * | 2017-06-08 | 2017-10-13 | 武汉理工大学 | A kind of polycarboxylate water-reducer of ginkgoic acid graft modification and preparation method thereof |
-
2019
- 2019-07-25 CN CN201910676592.1A patent/CN110372830B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336845A (en) * | 2010-07-27 | 2012-02-01 | 上海台界化工有限公司 | Method for synthesizing polycarboxylic acid water reducer |
| CN102876453A (en) * | 2012-09-29 | 2013-01-16 | 淄博市淄川创业油脂化工厂 | Preparation method for dehydrated castor oil |
| CN105800986A (en) * | 2016-03-09 | 2016-07-27 | 河南工程学院 | Method for preparing concrete water reducing agent |
| CN107057003A (en) * | 2017-05-09 | 2017-08-18 | 山东华伟银凯建材科技股份有限公司 | Self-curing type poly carboxylic acid series water reducer and preparation method thereof |
| CN107245130A (en) * | 2017-06-08 | 2017-10-13 | 武汉理工大学 | A kind of polycarboxylate water-reducer of ginkgoic acid graft modification and preparation method thereof |
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