CN103058561B - Environmentally-friendly low-energy-consumption polycarboxylic acid high-performance reducer as well as preparation method and application thereof - Google Patents
Environmentally-friendly low-energy-consumption polycarboxylic acid high-performance reducer as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to an environmentally-friendly low-energy-consumption polycarboxylic acid high-performance reducer and the technical field of preparation methods. The reducer is formed by a polymeric monomer I, a polymeric active monomer II and a polymeric small monomer III under the effect of an initiator by means of graft copolymerization, wherein the polymeric monomer is prepared by a short velveteen black liquor or a vegetation pulping black liquor; the polymeric active monomer II is unsaturated organic acid polyoxyethylene ether; and the polymeric small monomer III is one or combination of more of styrene, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, 2-acrylamide-2-methyl propanesulfonic acid, maleic acid, itaconic acid, maleic anhydride and phenylacetic acid. The reducer provided by the invention has the maximal advantage that the production cost is lowered by 5-8%, and the application performance of concrete is improved, so that concrete is not tacky and does not scrabbled. The reducer has good market prospect.
Description
Technical field
The present invention relates to high-performance polycarboxylic acids water reducing agent and preparation method thereof technical field.
Background technology
Polycarboxylate high performance water-reducing agent is the third generation high-performance water reducing agent that development in recent years is swift and violent.Due to his superior dispersing property and the controllability of use, be subject to manufacturing enterprise and users' high praise.But current poly carboxylic acid remains in some problems in producing and applying, and has affected its development, if his main raw material is from the derived product of refining of petroleum, supply day is becoming tight, and price has larger fluctuation.In high-intensity concrete uses, can produce again concrete and be clamminess, take off the phenomenons such as the end.These problems have caused users and the producer's concern and attention, impel people to reducing raw materials cost, price stabilization and improve further thinking and research and development of aspect of performance.
Equally, at present in textile mills, the pulp mill in a lot of areas, all can produce a large amount of cotton linter black liquors and black liquor of pulp making every day needs to process.Cotton linter black liquor is cotton process liquid caustic soda and water high temperature steaming, has extracted the waste liquid of remainder after cotton fibre, and major ingredient is xylogen sodium, a small amount of fiber and sodium salt.Black liquor of pulp making is a large amount of waste black liquors that pulp mill produces while using the raw materials such as timber, forage to prepare paper making pulp.These enterprises all need to be delivered to costly sewage work and focus on, and have so not only wasted manpower financial capacity but also have wasted mass energy.
Summary of the invention
Object of the present invention is exactly to solve the problems referred to above that existing polycarboxylate high performance water-reducing agent exists, and a kind of new low cost high performance water reducing agent of polyocarboxy acid is provided, and has not only improved performance, has also saved cost.
For reaching above-mentioned purpose, the technical scheme that the present invention takes is as follows:
A kind of high performance water reducing agent of polyocarboxy acid, is formed by polymerization single polymerization monomer I, polymerization activity monomer II and polymerization minor comonomer III graft copolymerization under the effect of initiator, wherein
Polymerization single polymerization monomer I: first, by containing with phenolic hydroxyl group, Syringa oblata Lindl. base or/and then the aromatic polymer compound oxidation of guaiacyl structure carries out methylolation and become active aromatic polymer compound, finally become polymerization single polymerization monomer I with unsaturated acid grafting;
Polymerization activity monomer II is unsaturated organic acid polyoxyethylene ether-ester;
Polymerization minor comonomer III is selected from one or more the combination in vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, toxilic acid, methylene-succinic acid, maleic anhydride, toluylic acid.
Above-mentioned high performance water reducing agent of polyocarboxy acid, described contain with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound of guaiacyl structure can be by containing similar xylogen or/and the industrial waste of lignin structure obtain, as cotton linter black liquor, vegetation class black liquor of pulp making etc.These cotton linter black liquors are the makers' production waste liquid of cotton fibre, and vegetation class black liquor of pulp making is mainly Pulp And Papermaking Mill forage or timber are prepared to the waste black liquor discharging after paper pulp for copy paper, and main component is xylogen.Because such black liquor contains a large amount of xylogen and salkali waste spent acid, environmental pollution is more serious, processes so all need to focus on Sewage Plant, and the energy expending is large, and cost is high.Cotton linter black liquor that factory is directly discharged, vegetation class black liquor of pulp making are through filtering after pre-treatment, obtaining content through evaporation concentration is 30.0 ~ 40.0% concentrated black liquor, this concentrated black liquor just can directly replace and containing with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer raw materials of compound of guaiacyl structure is prepared polymerization single polymerization monomer I.Therefore, containing with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer raw materials of compound of guaiacyl structure described in this patent, not only comprise and containing with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound of guaiacyl structure itself, also comprise and contain similar xylogen or/and the Industry Waste black liquor of lignin structure, foregoing cotton linter black liquor or vegetation class black liquor of pulp making etc.
In cotton linter black liquor or vegetation class black liquor of pulp making, contain a large amount of and similar macromolecular compound of vegetation class lignin structure, be summarised as following three kinds: 1 band phenolic hydroxyl group, 2 are with Syringa oblata Lindl. bases, 3 aromatics with guaiacyl structure.Structural formula is as follows:
This compounds is during without chemical treatment, and its aromatic structure is very stable, active low, is difficult for participating in reaction.By oxidizing reaction, make the macromole generation spallation reaction of xylogen aromatic structure, molecular mass reduces, and phenolic hydroxyl group increases.After methylolation, at ortho position and the formaldehyde generation hydroxymethylation of phenolic hydroxyl group.Use sulphonating agent Na
2sO
3or SO
2, NaHSO
3make used time generation sulfomethylation, introduce sulfonic group, all make the activity of black liquor improve, and can participate in next step graft reaction.The methylolation having activated or sulfonation black liquor and unsaturated organic acid carry out graft reaction, further improve the dispersive ability of these macromolecular compounds, and reduce soltion viscosity, increase the content of carboxyl, have therefore obtained the better polymerization single polymerization monomer I of performance.
Above-mentioned high performance water reducing agent of polyocarboxy acid, said oxygenant is for comprising H
2o
2, O
2, KMnO
4and KCr
2o
7.
Above-mentioned high performance water reducing agent of polyocarboxy acid, the condensing agent that said hydroxymethylation uses comprises formaldehyde, acetaldehyde and furfural.
Above-mentioned high performance water reducing agent of polyocarboxy acid, methylolation carries out sulfonation processing after becoming active aromatic polymer compound, and the sulphonating agent that said sulfonation reaction is used comprises Na
2sO
3, SO
2and NaHSO
3.
Polymerization activity monomer II described in this patent is known product, available existing disclosed method preparation, the ester class surface-active macromonomer that the production technique being provided in granted patent CN200710045863 as acquired in the applicant of this patent makes.Can be Methylacrylic acid polyethylene glycol single armor ether ester, polyalkylene glycol acrylate monomethyl ether ester or maleic anhydride polyethyleneglycol ether-ether etc.
Polymerization minor comonomer III refers to one or more the combination in vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, toxilic acid, methylene-succinic acid, maleic anhydride, toluylic acid etc.
Above polymerization single polymerization monomer I, polymerization activity monomer II and polymerization minor comonomer III, by initiator effect, carry out multi-grafted polyreaction and obtain this patent target product, the polycarboxylate water-reducer of more optimizing than currently available products.
Described in this patent, the preparation method of high performance water reducing agent of polyocarboxy acid, comprises the steps:
1) first will contain with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound oxidation of guaiacyl structure, then carry out methylolation and be processed into active aromatic polymer compound, finally become to obtain polymerization single polymerization monomer I with unsaturated acid graft polymerization reaction;
2), under initiator effect, unsaturated organic acid polyoxyethylene ether-ester polymerization activity monomer II, polymerization single polymerization monomer I and polymerization minor comonomer III graft copolymerization obtain target product high performance water reducing agent of polyocarboxy acid; Wherein polymerization minor comonomer III refers to one or more the combination in vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, toxilic acid, methylene-succinic acid, maleic anhydride, toluylic acid.
The preparation method of above-mentioned high performance water reducing agent of polyocarboxy acid, can also add chain-transfer agent, increases the polycarboxylate water-reducer that the performance that generating needs is more optimized by Quality Initiative.Described chain-transfer agent comprises sodium allyl sulfonate and methylpropene sodium sulfonate etc.
The preparation method of above-mentioned high performance water reducing agent of polyocarboxy acid, methylolation carries out sulfonation reaction again, further processes active aromatic polymer compound.The sulphonating agent that said sulfonation reaction is used comprises Na
2sO
3, SO
2and NaHSO
3.
The preparation method of above-mentioned high performance water reducing agent of polyocarboxy acid, described initiator adopts redox system, comprises ammonium persulphate and hydrogen peroxide, hydrogen peroxide and vitamins C etc.
The preparation method of above-mentioned high performance water reducing agent of polyocarboxy acid, the oxygenant that oxidation step uses comprises H
2o
2, O
2, KMnO
4and KCr
2o
7; The condensing agent that hydroxymethylation uses comprises formaldehyde, acetaldehyde and furfural.The sulphonating agent that sulfonation reaction is used comprises Na
2sO
3, SO
2and NaHSO
3.
The preparation method of above-mentioned high performance water reducing agent of polyocarboxy acid, contains with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound of guaiacyl structure can by factory, directly cotton linter black liquor, the vegetation class black liquor of pulp making of discharge obtain after filtering pre-treatment.
The high performance water reducing agent of polyocarboxy acid of this patent is through expert determination, and putative structure formula is as follows:
Hydroxyl or carboxyl that wherein R is C1-10, a, b, c, d, n are 0 integer while being difference.
Beneficial effect of the present invention:
This patent can be processed by the xylogen waste black liquor that factory is directly discharged, extract effective composition and carry out chemical modification, make active princlple change in waste liquid become active ingredient, utilize the active ingredient after modification to participate in the graft polymerization reaction in poly carboxylic acid series water reducer production process as a kind of polymerization component, made the new modified high performance water reducing agent of polyocarboxy acid product of the present invention.Both reduced the production cost of polycarboxylate water-reducer, processed again a large amount of waste black liquors, turned waste into wealth.
Meanwhile, the modified polycarboxylic acid water reducer of this patent has not only reduced production cost 5 ~ 8%, and has improved concrete application performance, makes concrete not be clamminess, not take off at the end, has solved prior art problem, has good market outlook.
Concrete case study on implementation
Example 1: the preparation of polymerization single polymerization monomer I
The concentrated concentration of learning from else's experience is 33% cotton linter black liquor 600g, adds 1000ml in four-hole boiling flask, opens stirring, and is warming up to 60～65 DEG C, adds green vitriol FeSO
47H
2o22.5g.Stir 15 minutes, then add the H of 30% content
2o
x5g, controlling the reaction times is 3 hours, reaction finishes.Temperature is down to 25～30 DEG C, and the black liquor by this through oxide treatment, with rare H of 20%
2sO
4adjust the P of solution
hbe 12.Then temperature is risen to 90 DEG C, add the formaldehyde 32g of 37% content, insulation reaction 3 hours, obtains methylolation black liquor.With 20% rare H
2sO
4adjust the P of black liquor
hbe 2.0 ~ 2.5.Temperature is risen to 92 DEG C, then drip the mixed solution of methacrylic acid 25g and pure water 100g, the time is 2 ~ 2.5 hours.Once add H simultaneously
2o
2the mixed solution of 3.5g and water 20g, continues reaction and finishes after 1 hour.Obtain polymerization single polymerization monomer I.
Example 2: the preparation of polymerization single polymerization monomer I
The concentrated concentration of learning from else's experience is 33% cotton linter black liquor 600g, adds 1000ml in four-hole boiling flask, opens stirring, and is warming up to 60～65 DEG C, adds green vitriol FeSO
47H
2o22.5g.Stir 15 minutes, then add the H of 30% content
2o
25g, controlling the reaction times is 3 hours, reaction finishes.Temperature is down to 25～30 DEG C, and the black liquor by this through oxide treatment, with rare H of 20%
2sO
4adjust the P of solution
hbe 12.Then temperature is risen to 90 DEG C, add the formaldehyde 32g of 37% content, insulation reaction 3 hours, obtains methylolation black liquor.Continue to add Na
2sO
350g also adds FeCl
37g is the sulfonation reaction of catalyzer, and reaction solution is warming up to 110 DEG C, reacts 4 ~ 5 hours, obtains sulfomethylation black liquor.With 20% rare H
2sO
4adjust the P of black liquor
hbe 2.0 ~ 2.5.Temperature is risen to 92 DEG C, then drip the mixed solution of methacrylic acid 25g and pure water 100g, the time is 2 ~ 2.5 hours.Once add H simultaneously
2o
2the mixed solution of 3.5g and water 20g, continues reaction and finishes after 1 hour.Obtain polymerization single polymerization monomer I.
Embodiment 3: the preparation of polymerization single polymerization monomer I
The concentrated concentration of learning from else's experience is 33% black liquor 632g, adds 1000ml in four-hole boiling flask, opens stirring, first adds the KMnO of 26g
4oxygenant, stirs the FeSO that adds 18.6g after 10 minutes
47H
2o, as catalyzer, is then warming up to 60 DEG C, reacts 3 hours.Then directly add Na
2sO
3the 51g 105g that adds water, temperature rises to 85～90 DEG C, and insulation reaction 4 hours, directly makes sulfonation black liquor.Use rare H
2sO
4adjust the P of black liquor
hbe 2.0 ~ 2.5, temperature is risen to 90～92 DEG C, add H
2o
2the mixed solution of 3.8g and water 25g, churning time is 10 minutes.Then the mixed solution that drips 28g vinylformic acid and pure water 95g, the time is controlled at 2 ~ 2.5 hours, then insulation reaction finishes for 1 hour.Obtain polymerization single polymerization monomer I.
Example 4: the preparation of polycarboxylate water-reducer
Polymerization single polymerization monomer I90g, the chain-transfer agent that adds end water 360g, example 1 in 1000ml four-hole boiling flask is sodium allyl sulfonate 5g, 2-acrylamide-2-methyl propane sulfonic 4g.Under the protection of nitrogen, temperature is risen to 85 DEG C, first add H
2o
2the mixed solution of 2.8g and water 10g starts to drip the mixed solution that surface-active macromonomer II is methacrylic acid poly(ethylene oxide)polymers monomethyl ether ester 180g and 200g water simultaneously, the mixed solution of initiator A PS6g and water 100g, and the time is respectively 3 hours and 3.5 hours.After all dropwising, temperature rises to 92～95 DEG C, and the insulation reaction time is 1 hour, and after reaction finishes, temperature is cooled to 45 ~ 50 DEG C, adjusts P with NaOH
hbe 6.5 ~ 7.5.Obtain polycarboxylate water-reducer product.
Example 5: the preparation of polycarboxylate water-reducer
In 1000ml four-hole boiling flask, adding polymerization single polymerization monomer I86g, the chain-transfer agent of end water 358g, example 2 is sodium allyl sulfonate 7g.Under the protection of nitrogen, temperature is risen to 80 DEG C, first add H
2o
2the mixed solution of 2.5g and water 15g, start to drip the mixed solution that surface-active macromonomer II is methacrylic acid poly(ethylene oxide)polymers monomethyl ether ester 180g, methyl methacrylate 8g and 200g water simultaneously, the mixed solution of initiator A PS9g and water 110g, the time is respectively 3 hours and 3.5 hours.After all dropwising, temperature rises to 95～98 DEG C, and the insulation reaction time is 1 hour, and after reaction finishes, temperature is cooled to 45 ~ 50 DEG C, adjusts P with NaOH
hbe 6.5 ~ 7.5.Obtain polycarboxylate water-reducer product.
One, product performance detect
Participate in the detected result of the synthetic polycarboxylate high performance dehydragent of modification through rare linters
1, homogeneity index, sees the following form one:
Table one
| ? | Project | Index |
| 1 | Outward appearance | Bright brown liquid |
| 2 | Solid content | 21.2% |
| 3 | Chloride ion content % | 0.02 |
| 4 | Density g/mol | 1．07 |
| 5 | Flowing degree of net paste of cement mm | 215 |
| 6 | PH value | 8.6 |
| 7 | Alkali content % | 2.02 |
2, after the polycarboxylate water-reducer of admixture this patent its concrete performance in table two:
Table two
Detect foundation: GB8076-1997 " concrete admixture "
GB/T8077-2000 " Methods for testing uniformity of concrete admixture "
Inspection cement: reference cement
Volume %:1%(is in cement quality)
Inspection rubble: 5～10mm
Note: at present one day compressive strength rate of product reach >=170%.
3, engineering application: apply thousands of tons of in the railway engineering project of Hebei, due to ground material and cement, used several proportionings.
Pile foundation
Case beam
Building site feedback opinion after application:
1, product performance are good, steady quality, and relative price is low.
2 and local cement and ground material adaptability good.
3, the concrete of mix is relatively loose, solved viscosity large, take off the problems such as the end.
Claims (18)
1. a high performance water reducing agent of polyocarboxy acid, by polymerization single polymerization monomer I, polymerization activity monomer II and polymerization minor comonomer III
Under the effect of initiator, graft copolymerization forms, wherein
Polymerization single polymerization monomer I: first will contain with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound oxidation of guaiacyl structure, then carry out methylolation and become active aromatic polymer compound, finally with methacrylic acid or acrylic acid-grafted become polymerization single polymerization monomer I; Described contain with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound of guaiacyl structure by containing similar xylogen or/and the industrial waste of lignin structure obtain;
Reactive monomer II is unsaturated organic acid polyoxyethylene ether-ester;
Polymerization minor comonomer III is one or more the combination in vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, toxilic acid, methylene-succinic acid, maleic anhydride, toluylic acid.
2. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: contain similar xylogen or/and the industrial waste of lignin structure is cotton linter black liquor or vegetation class black liquor of pulp making.
3. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: the oxygenant that oxidation step uses comprises H
2o
2, O
2, KMnO
4and KCr
2o
7.
4. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: the condensing agent that said hydroxymethylation uses comprises formaldehyde, acetaldehyde and furfural.
5. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: after hydroxymethylation, carry out sulfonation processing.
6. high performance water reducing agent of polyocarboxy acid as claimed in claim 5, is characterized in that: the sulphonating agent that sulfonation reaction is used comprises Na
2sO
3, SO
2and NaHSO
3.
7. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: polymerization activity monomer II is Methylacrylic acid polyethylene glycol single armor ether ester, polyalkylene glycol acrylate monomethyl ether ester or maleic anhydride polyethyleneglycol ether-ether.
8. high performance water reducing agent of polyocarboxy acid as claimed in claim 1, is characterized in that: polymerization minor comonomer III refers to methacrylic acid or vinylformic acid.
9. the preparation method of the arbitrary described high performance water reducing agent of polyocarboxy acid of claim 1-8, comprises the steps:
1) first will contain with phenolic hydroxyl group, Syringa oblata Lindl. base or/and the aromatic polymer compound oxidation of guaiacyl structure, then carry out methylolation and be processed into active aromatic polymer compound, finally become to obtain polymerization single polymerization monomer I with unsaturated acid graft polymerization reaction;
2), under initiator effect, unsaturated organic acid polyoxyethylene ether-ester polymerization activity monomer II, polymerization single polymerization monomer I and polymerization minor comonomer III graft copolymerization obtain target product high performance water reducing agent of polyocarboxy acid; Wherein polymerization minor comonomer III refers to one or more the combination in vinylbenzene, methacrylic acid, vinylformic acid, methyl methacrylate, methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamide, 2-acrylamide-2-methyl propane sulfonic, toxilic acid, methylene-succinic acid, maleic anhydride, toluylic acid.
10. the preparation method of high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: after hydroxymethylation, carry out sulfonation reaction.
The preparation method of 11. high performance water reducing agent of polyocarboxy acid as claimed in claim 10, is characterized in that: the sulphonating agent that sulfonation reaction is used comprises Na
2sO
3, SO
2and NaHSO
3.
The preparation method of 12. high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: graft reaction adds chain-transfer agent Quality Initiative to increase.
The preparation method of 13. high performance water reducing agent of polyocarboxy acid as claimed in claim 12, is characterized in that: described chain-transfer agent comprises sodium allyl sulfonate and methylpropene sodium sulfonate.
The preparation method of 14. high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: described initiator adopts redox system, comprises ammonium persulphate and hydrogen peroxide, hydrogen peroxide and vitamins C.
The preparation method of 15. high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: the oxygenant that oxidation step uses comprises H
2o
2, O
2, KMnO
4and KCr
2o
7.
The preparation method of 16. high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: the condensing agent that hydroxymethylation uses comprises formaldehyde, acetaldehyde and furfural.
The preparation method of 17. high performance water reducing agent of polyocarboxy acid as claimed in claim 9, is characterized in that: contain with phenolic hydroxyl group, Syringa oblata Lindl. base that directly cotton linter black liquor, the vegetation class black liquor of pulp making of discharge obtain after filtering pre-treatment or/and the aromatic polymer compound of guaiacyl structure is by factory.
18. a high performance water reducing agent of polyocarboxy acid, its structural formula is as follows:
Hydroxyl or carboxyl that wherein R is C1-10, a, b1 or b2, c, d, n are 0 integer while being difference.
19. claim 1-8,18 application of arbitrary described high performance water reducing agent of polyocarboxy acid in concrete.
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| CN104587891A (en) * | 2013-10-30 | 2015-05-06 | 上海是大高分子材料有限公司 | Comb type carboxylate ternary copolymer and preparation technology thereof |
| CN106084152A (en) * | 2016-06-28 | 2016-11-09 | 四川宇砼建材有限公司 | Water reducing type high performance water reducing agent of polyocarboxy acid and production technology thereof |
| CN106967200A (en) * | 2017-03-31 | 2017-07-21 | 刘翠芬 | It is a kind of to have poly carboxylic acid series water reducer that guarantor is collapsed with viscosity-reducing performance and preparation method thereof concurrently |
| CN108793894B (en) * | 2018-08-25 | 2020-11-06 | 北京建工新型建材有限责任公司 | Barite radiation-proof concrete |
| CN109384892B (en) * | 2018-10-25 | 2021-02-09 | 山东理工大学 | Preparation method of sulfonated bio-oil-based phenol polycarboxylic acid water reducer |
| CN113651552A (en) * | 2021-09-17 | 2021-11-16 | 南京福盛新材料有限公司 | Polycarboxylic acid high-performance pumping agent and production process and preparation device thereof |
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