CN103664052A - Polycarboxylate superplasticizer for machine-made sand concrete - Google Patents
Polycarboxylate superplasticizer for machine-made sand concrete Download PDFInfo
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Abstract
The invention discloses a polycarboxylate superplasticizer for machine-made sand concrete. The polycarboxylate superplasticizer comprises a polycarboxylic acid copolymer, a mud-resistant component, a crack-resistant component, an air entraining agent, an antifoaming agent and a retarder. The polycarboxylate superplasticizer is low in mixing amount, and enables the machine-made sand concrete, in particular the machine-made sand concrete containing high amount of mud and powder to achieve excellent initial working performance, long-term slump holding capability, keep the surface of the hardened concrete from cracking, and improve the durability of the machine-made sand concrete.
Description
Technical field
The present invention relates to additives for building materials field, relate in particular to a kind of polycarboxylate water-reducer for machine-made sand concrete.
Background technology
Concrete is one of topmost material of construction of contemporary society, and it is comprised of gelling material, aggregate, water and admixture, and the polycarboxylate water-reducer with comb shaped structure is to prepare one of of paramount importance admixture of high performance concrete.Along with large-scale basis build flourish; the resource that concrete is commonly used fine aggregate-natural sand is reducing gradually; and exploitation natural sand pollution on the environment and destruction are also day by day serious; the catastrophic failures such as the river course thereupon bringing breaches a dyke also occur again and again; for the Sustainable development of environment, country also puts into effect relevant policies and controls natural exploitation.
Along with the decline of natural river sand produced quantity, Machine-made Sand has progressively replaced natural sand to become the important raw and processed materials of concrete production.Because its production process (as powder pug is not washed) lack of standardization causes having occurred that grain composition is bad, grain type flaking and powder containing quantity are crossed the problems such as high, wherein grating and grain type problem will seriously reduce concrete serviceability, make concrete easily occur the problems such as segregation, bleeding, this will lead scleratogenous machine-made sand concrete surface cracking, causes endurance issues.When powder containing quantity is too high, if main component is stone flour, favourable to concrete workability, but when contained powder main component is clay, can adsorb in a large number polycarboxylate water-reducer, and have a strong impact on concrete serviceability, existing research both at home and abroad shows, when clay component is the polynite of 2:1 laminate structure, the pore passage structure that it is abundant and interlamellar spacing adjustability, absorption polycarboxylate water-reducer that will be a large amount of.If utilize washing to remove clay, can bring that energy consumption increases, water loss increases and the environmental problem such as sewage disposal simultaneously, the Sustainable development of this and green concrete is runed counter to.Therefore, developing a kind of poly carboxylic acid that has good reducing property and improve workability of concrete advantage is applied in machine-made sand concrete, avoid newly mixing machine-made sand concrete and occur that water consumption is too high, the problems such as cracking and poor durability appear in maturing, industry development is had to positive effect.
CN102659338A discloses a kind of polycarboxylate water-reducer that is applicable to Machine-made Sand, with polycarboxylate water-reducer mother liquor and fatty alcohol sulphonate and polyether glycol is composite forms, this scheme is the mode of the compound defoamer of simple mother liquor and air entrapment agent, can improve concrete working order, but the high problem of argillaceous amount in cannot settlement mechanism sand.CN102250295A adopts water-soluble free radical copolymerization method to obtain the polymkeric substance that molecular weight is 10000-65000, and add alkali neutralization, the Concrete superplastizer obtaining can improve cohesiveness and the workability of newly mixing machine-made sand concrete, significantly reduce fresh concrete segregation, excreting water phenomenon, this water reducer is also failed the problems such as the high and poor durability of initial water requirement that settlement mechanism abrasive band comes.
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Summary of the invention
The present invention take there is high diminishing, the polycarboxylate water-reducer mother liquor of low bleed, viscosity reduction is main body, compound anti-mud component and cracking resistance component, can prepare can be for the polycarboxylate water-reducer of machine-made sand concrete.The polycarboxylate water-reducer mother liquor that this water reducer adopts can make that fluidity of newly mixed concrete is good, thickness not, anti-mud component can effectively suppress the absorption of Machine-made Sand medium clay soil to polycarboxylate water-reducer molecule, cracking resistance component can improve newly mix the workability of machine-made sand concrete and extend the concrete slump hold-time, can avoid concrete surface in process of setting because dehydration is ftractureed, air entrapment agent, defoamer and retardant are as auxiliary conditioning agent, further to meet the application property of fresh concrete.Product of the present invention is for machine-made sand concrete, can obtain that workability is good, concrete parcel property is good and the slump keeps good fresh concrete, and the machine-made sand concrete surface cracking of can avoiding hardening, and improves concrete weather resistance.
The object of the present invention is achieved like this:
For a polycarboxylate water-reducer for machine-made sand concrete, it is characterized in that this polycarboxylate water-reducer is comprised of following substances in percentage by weight:
Co-poly carboxylic acid 5.00%～60.00%,
Anti-mud component 1.0%～30.00%,
Cracking resistance component 0.1%～10.00%,
Air entrapment agent 0.00%～1.00%,
Defoamer 0.00% ~ 1.00%,
The water of retardant 0.00%～10.00% and surplus, gross weight is in 100%;
Wherein:
The weight-average molecular weight of described co-poly carboxylic acid is 15000～120000;
Described anti-mud component is one or more in poly carboxylic acid ether copolymer or polyvinyl alcohol;
Described cracking resistance component is one or more in poly carboxylic acid ether thickening copolymer or sustained-release polycarboxylic water reducer;
Described air entrapment agent is one or more in alkyl-sulphate, alkyl alcohol ethers air entrapment agent;
Described froth breaking component is one or more in polysiloxane defoamer, organic silicone oil defoamer, polyethers defoamer, organic silicon modified by polyether defoamer, slow release type defoamer;
Described retardant is one or more in Sunmorl N 60S, sucrose, Trisodium Citrate, Seignette salt, sodium polyphosphate.
Described co-poly carboxylic acid contains the following structural unit that is derived from unsaturated polyester ether monomer (1) and the following structural unit that is derived from unsaturated carboxylic acid monomer (2), wherein:
Structural unit (1) is
Wherein: q represents the number of methylene radical, be the integer of 0-2; R
1represent hydrogen or methyl; R
2o represents the oxyalkylene group of 2-8 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 1-180; R
3the alkyl that represents hydrogen or 1-6 carbon atom;
Structural unit (2) is
Wherein: R
4represent hydrogen, methyl or group, R
5represent hydrogen, methyl or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.
Described poly carboxylic acid ether copolymer contains the following structural unit that is derived from unsaturated polyester ether monomer (3) and the following structural unit that is derived from unsaturated carboxylic acid monomer (4), and the mol ratio of structural unit (4) and structural unit (3) is between 1:1～2.5:1, wherein:
Structural unit (3) is
Wherein: p represents the number of methylene radical, be 1 or 2 integer; R
6represent hydrogen or methyl; R
7o represents the oxyalkylene group of 2-3 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 20-110; R
8the alkyl that represents hydrogen or 1-4 carbon atom;
Structural unit (4) is
Wherein: R
9represent hydrogen or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.
Described poly carboxylic acid ether thickening copolymer contains the following structural unit that is derived from unsaturated polyester ether monomer (5) and the following structural unit that is derived from unsaturated carboxylic acid monomer (6), wherein:
Structural unit (5) is
Wherein: R
1represent hydrogen or methyl; R
2represent hydrogen, methyl or ethyl; R
3the alkyl that represents hydrogen or 1-6 carbon atom; X is linking group, for
,
,
,
,
or
; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 4-300;
Structural unit 6 is
Wherein: R
13represent hydrogen, methyl or group, R
14represent hydrogen, methyl or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
Described poly carboxylic acid ether thickening material copolymer characteristic is to have the weight-average molecular weight of 150000-10000000.
Described sustained-release polycarboxylic water reducer contains the following structural unit that is derived from unsaturated polyester ether monomer (7) and the following structural unit that is derived from unsaturated carboxylic acid monomer (8), wherein:
Structural unit (7) is
Wherein: q represents the number of methylene radical, be the integer of 0-2; R
15represent hydrogen or methyl; R
16o represents the oxyalkylene group of 2-4 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 20-110; R
17the alkyl that represents hydrogen or 1-6 carbon atom;
Structural unit (8) is
Wherein: R
18represent hydrogen or group, M represents the alkyl of hydrogen, monovalence metal, divalent metal, ammonium, organic amino group or 1-8 carbon atom; R
19the alkyl that represents 1-8 carbon atom.
Described slow release type defoamer is the represented compound of general structure (3):
Wherein: R
6represent HOOC-CH=CH-, HOOC-CH-CH-; Represent-COO-of X ,-CONHCH
2cH
2o-; R
7o represents the oxyalkylene group of 2-8 carbon atom; R
8the alkyl that represents 1-6 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 5-100.
Described polycarboxylate water-reducer volume be in concrete mix total gelling material weight 0.6%～2.5%.
Embodiment
By following examples, the present invention is further described, but the present invention is not produced to any restriction.
Used in an embodiment listed abbreviation below:
PC-1: the multipolymer of vinylformic acid, toxilic acid and methacrylic polyoxyethylene glycol (average EO adduct number 54), weight-average molecular weight 31200;
PC-2: the multipolymer of vinylformic acid and methacrylic polyoxyethylene glycol (average EO adduct number 54), weight-average molecular weight 39000;
CT-1: the multipolymer of vinylformic acid and 3-methyl-3-butenyl polyoxyethylene glycol (average EO adduct number 30), wherein, the mol ratio of vinylformic acid and 3-methyl-3-butenyl polyoxyethylene glycol is 1.2, weight-average molecular weight 46000;
The multipolymer of AT-1:3-methyl-3-butenyl polyoxyethylene glycol (average EO adduct number 54) and ethyl maleate, weight-average molecular weight 52000;
AT-2: the multipolymer of vinylformic acid and methacrylic polyoxyethylene glycol (average EO adduct number 54), weight-average molecular weight 450000;
DF-1: methoxyl group polypropylene glycol polyoxyethylene glycol, wherein the polypropylene glycol polymerization degree is 35, and the polymerization degree of polyoxyethylene glycol is 7, and polypropylene glycol polyoxyethylene glycol is random copolymerization.
Embodiment 1
Take water 50.00kg and be placed in reactor, then the co-poly carboxylic acid PC-1 that adds 35.00kg 40% solid content, then add successively the anti-mud component CT-1 of 10.00kg40% solid content, the cracking resistance component AC-1 of 5kg40% solid content, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-1.
Embodiment 2
Take water 43.95kg and be placed in reactor, then the co-poly carboxylic acid PC-1 that adds 45.00kg 40% solid content, then the cracking resistance component AC-1, the 0.05kg slow release type defoamer DF-1 that add successively the anti-mud component of 1kg polyvinyl alcohol, 10kg40% solid content, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-2.
Embodiment 3
Take water 39.70kg and be placed in reactor, then the co-poly carboxylic acid PC-2 that adds 30.00kg 40% solid content, then the cracking resistance component AC-2, the 0.20kg dodecyl alcohol ether air entrapment agent that add successively anti-mud component CT-1, the 0.1kg of 30kg40% solid content, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-3.
Embodiment 4
Take water 40.60kg and be placed in reactor, then under whipped state, add successively 2.00kg Sunmorl N 60S, 2.00kg sucrose, the co-poly carboxylic acid PC-2 that adds 55.00kg 40% solid content after salt dissolves completely, then the cracking resistance component AC-1,0.05kg dodecyl alcohol ether air entrapment agent, 0.05kg sodium lauryl sulphate air entrapment agent, the 0.10kg organic silicone oil defoamer TEGO Antifoam 204 that add successively the anti-mud component of 4kg polyvinyl alcohol, 5kg40% solid content, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-4.
Embodiment 5
Take water 39.85kg and be placed in reactor, then under whipped state, add successively 2.00kg sucrose, 1.00kg Trisodium Citrate and 1.00kg sodium polyphosphate, the co-poly carboxylic acid PC-2 that adds 40.00kg 40% solid content after salt dissolves completely, then the anti-mud component CT-1 that adds successively 5kg40% solid content, the cracking resistance component polyvinyl alcohol of 1kg, the cracking resistance component AC-1 of 10kg40% solid content, 0.05kg sodium lauryl sulphate, 0.05kg polysiloxane defoamer BYK-065, 0.05kg slow release type defoamer DF-1, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-5.
Embodiment 6
Take water 23.00kg and be placed in reactor, then under whipped state, add successively 2.00kg Sunmorl N 60S and 1.00kg Trisodium Citrate, the co-poly carboxylic acid PC-2 that adds 60.00kg 40% solid content after salt dissolves completely, then the anti-mud component polyvinyl alcohol that adds successively 5kg, the cracking resistance component AC-1 of 5kg40% solid content, the cracking resistance component AC-2 of 2kg, 1.00kg dodecyl alcohol ether air entrapment agent, 0.30kg slow release type defoamer DF-1, 0.20kg organic silicon modified by polyether defoamer LM-110, 0.50 polyethers defoamer HT-606, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-6.
Embodiment 7
Take water 71.75kg and be placed in reactor, then under whipped state, add 1.00kg Sunmorl N 60S and 2.00kg Seignette salt, the co-poly carboxylic acid PC-2 that adds until completely dissolved 5.00kg 40% solid content, then the anti-mud component AT-1 that adds successively 10kg40% solid content, the cracking resistance component AC-1 of 10kg40% solid content, 0.05kg dodecyl alcohol ether air entrapment agent, 0.10kg slow release type defoamer DF-1, 0.05kg organic silicon modified by polyether defoamer LM-110, 0.05 polyethers defoamer HT-606, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-7.
Embodiment 8
Take water 39.90kg and be placed in reactor, then under whipped state, add 8.00kg Sunmorl N 60S and 2.00kg sucrose, the co-poly carboxylic acid PC-2 that adds until completely dissolved 30.00kg 40% solid content, then add successively the anti-mud component AT-1 of 10kg40% solid content, the cracking resistance component AC-1 of 10kg40% solid content, 0.05kg slow release type defoamer DF-1,0.05 polyethers defoamer HT-606, after continuing to stir, obtain polycarboxylate water-reducer of the present invention, be designated as MCPC-5.
Comparative example 1
Take water 57.80kg and be placed in reactor, then under whipped state, add 2.00kg sodium tartrate, the co-poly carboxylic acid PC-1 that adds until completely dissolved 50.00kg 40% solid content, then add 0.10kg dodecyl alcohol ether air entrapment agent, 0.05kg polyethers defoamer HT-606, after continuing to stir, obtain relatively using polycarboxylate water-reducer, be designated as PCE-1.
Polycarboxylate water-reducer MCPC-1～MCPC-8 in above embodiment, comparative example polycarboxylate water-reducer PCE-1 and commercially available collapse protective poly-carboxylic acid water reducing agent PCE-2 are carried out to water-reducing rate, air content detection according to GB8076-2008 < < cement water reducing agent > >, volume is fixed as 1.0%, obtains the results are shown in Table 1.
The fundamental property of the various water reducers of table 1
| Water reducer | MCPC-1 | MCPC-2 | MCPC-3 | MCPC-4 | MCPC-5 | MCPC-6 | MCPC-7 | MCPC-8 | PCE-1 | PCE-2 |
| Water-reducing rate/% | 28.1 | 31.0 | 30.0 | 35.1 | 28.5 | 37.8 | 12.6 | 27.5 | 32.7 | 24.7 |
| Air content/% | 4.6 | 4.1 | 4.0 | 3.8 | 3.6 | 4.3 | 3.6 | 3.8 | 4.3 | 4.7 |
| 1h slump-loss/mm | 10 | 5 | 10 | 15 | 10 | 5 | 10 | 0 | 10 | 5 |
MCPC-1 prepared by the embodiment of the present invention, MCPC-2, MCPC-3, MCPC-4, MCPC-5, MCPC-6, MCPC-7, MCPC-8 polycarboxylate water-reducer and comparative example water reducer PCE-1 are spiked among machine-made sand concrete with polycarboxylate water-reducer PCE-2, the slump and the degree of mobilization of the initial and 1h of test fresh concrete, moulding test block, observes surface cracking situation.Test the good magnificent P.O42.5 cement of cement used, flyash is Green Dragon gorge, Kunming power plant II level flyash, breeze is good magnificent S95 breeze, fine aggregate is Machine-made Sand, wherein content of stone powder is 15-20%, methylene blue number 1.4, and fineness modulus is 2.9, the rubble of 5-20mm, proportioning is: C:F:K:S:G:W=360:48:72:725:887:157.Test result is in Table 2.
The various water reducers of table 2 are in the application performance test result of machine-made sand concrete
By test-results, can be found out: polycarboxylate water-reducer of the present invention has good initial dispersion ability, and there is good slump hold facility, when for machine-made sand concrete, the fresh concrete workability of preparation, parcel property are good, do not ftracture in maturing surface; Polycarboxylate water-reducer of the present invention is compared with comparative example 1, in good concrete material, water-reducing rate and the slump retaining of two class water reducers are more or less the same, and in the machine-made sand concrete high containing mud powder containing quantity, existence because of mud, cause the consumption of comparative example 1 to increase, slump retaining variation, and concrete surface simultaneously produces crack; Polycarboxylate water-reducer of the present invention is compared with commercially available collapse protective poly-carboxylic acid water reducing agent, still performance is to the good adaptability of Machine-made Sand containing powder containing mud, the consumption of commercially available collapse protection type product in machine-made sand concrete also increasing, although protecting collapses, be better than comparative example 1, but still can not meet application property, and concrete surface has crack.Therefore, use polycarboxylate water-reducer of the present invention can make newly to mix machine-made sand concrete and obtain good serviceability, particularly containing mud powder containing quantity high in Machine-made Sand effect more obvious, can significantly reduce the slump-loss of machine-made sand concrete, avoid maturing surface cracking, improve the weather resistance of machine-made sand concrete.
Claims (7)
1. for a polycarboxylate water-reducer for machine-made sand concrete, it is characterized in that this polycarboxylate water-reducer is comprised of following substances in percentage by weight:
Co-poly carboxylic acid 5.00%～60.00%,
Anti-mud component 1.0%～30.00%,
Cracking resistance component 0.1%～10.00%,
Air entrapment agent 0.00%～1.00%,
Defoamer 0.00% ~ 1.00%,
The water of retardant 0.00%～10.00% and surplus, gross weight is in 100%;
Wherein:
The weight-average molecular weight of described co-poly carboxylic acid is 15000～120000;
Described anti-mud component is one or more in poly carboxylic acid ether copolymer or polyvinyl alcohol;
Described cracking resistance component is one or more in poly carboxylic acid ether thickening copolymer or sustained-release polycarboxylic water reducer;
Described air entrapment agent is one or more in alkyl-sulphate, alkyl alcohol ethers air entrapment agent;
Described defoamer is one or more in polysiloxane defoamer, organic silicone oil defoamer, polyethers defoamer, organic silicon modified by polyether defoamer, slow release type defoamer;
Described retardant is one or more in Sunmorl N 60S, sucrose, Trisodium Citrate, Seignette salt, sodium polyphosphate.
2. polycarboxylate water-reducer according to claim 1, is characterized in that described co-poly carboxylic acid contains the following structural unit that is derived from unsaturated polyester ether monomer (1) and the following structural unit that is derived from unsaturated carboxylic acid monomer (2), wherein:
Structural unit (1) is
Wherein: q represents the number of methylene radical, be the integer of 0-2; R
1represent hydrogen or methyl; R
2o represents the oxyalkylene group of 2-8 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 1-180; R
3the alkyl that represents hydrogen or 1-6 carbon atom;
Structural unit (2) is
Wherein: R
4represent hydrogen, methyl or group, R
5represent hydrogen, methyl or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.
3. polycarboxylate water-reducer according to claim 1, it is characterized in that described poly carboxylic acid ether copolymer contains the following structural unit that is derived from unsaturated polyester ether monomer (3) and the following structural unit that is derived from unsaturated carboxylic acid monomer (4), and the mol ratio of structural unit (4) and structural unit (3) is between 1:1～2.5:1, wherein:
Structural unit (3) is
Wherein: p represents the number of methylene radical, be 1 or 2 integer; R
6represent hydrogen or methyl; R
7o represents the oxyalkylene group of 2-3 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 20-110; R
8the alkyl that represents hydrogen or 1-4 carbon atom;
Structural unit (4) is
Wherein: R
9represent hydrogen or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group.
4. polycarboxylate water-reducer according to claim 1, is characterized in that described poly carboxylic acid ether thickening copolymer contains the following structural unit that is derived from unsaturated polyester ether monomer (5) and the following structural unit that is derived from unsaturated carboxylic acid monomer (6), wherein:
Structural unit (5) is
Wherein: R
1represent hydrogen or methyl; R
2represent hydrogen, methyl or ethyl; R
3the alkyl that represents hydrogen or 1-6 carbon atom; X is linking group, for
,
,
,
,
Or
; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 4-300;
Structural unit (6) is
Wherein: R
13represent hydrogen, methyl or group, R
14represent hydrogen, methyl or group, M represents hydrogen, monovalence metal, divalent metal, ammonium or organic amino group;
Described poly carboxylic acid ether thickening material copolymer characteristic is to have the weight-average molecular weight of 150000-10000000.
5. polycarboxylate water-reducer according to claim 1, is characterized in that described sustained-release polycarboxylic water reducer contains the following structural unit that is derived from unsaturated polyester ether monomer (7) and the following structural unit that is derived from unsaturated carboxylic acid monomer (8), wherein:
Structural unit (7) is
Wherein: q represents the number of methylene radical, be the integer of 0-2; R
15represent hydrogen or methyl; R
16o represents the oxyalkylene group of 2-4 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 20-110; R
17the alkyl that represents hydrogen or 1-6 carbon atom;
Structural unit (8) is
Wherein: R
18represent hydrogen or group, M represents the alkyl of hydrogen, monovalence metal, divalent metal, ammonium, organic amino group or 1-8 carbon atom; R
19the alkyl that represents 1-8 carbon atom.
6. polycarboxylate water-reducer according to claim 1, is characterized in that described slow release type defoamer is the represented compound of general structure (9):
（9）
Wherein: R
6represent HOOC-CH=CH-, HOOC-CH-CH-; Represent-COO-of X ,-CONHCH
2cH
2o-; R
7o represents the oxyalkylene group of 2-8 carbon atom; R
8the alkyl that represents 1-6 carbon atom; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 5-100.
7. polycarboxylate water-reducer according to claim 1, it is characterized in that described polycarboxylate water-reducer volume be in concrete mix total gelling material weight 0.6%～2.5%.
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2013
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| CN109796149A (en) * | 2019-03-18 | 2019-05-24 | 云南富龙高速公路建设指挥部 | A kind of thickening type water-reducing agent and preparation method thereof for machine-made sand concrete |
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| CN111574104A (en) * | 2020-05-28 | 2020-08-25 | 中交一公局集团有限公司 | Water reducing agent and preparation method and application thereof |
| CN114195421A (en) * | 2020-09-17 | 2022-03-18 | 江苏尼高科技有限公司 | Preparation method of polycarboxylic acid admixture for machine-made sand concrete |
| CN114195421B (en) * | 2020-09-17 | 2023-08-29 | 江苏尼高科技有限公司 | Preparation method of polycarboxylic acid additive for machine-made sand concrete |
| CN113087470A (en) * | 2021-04-12 | 2021-07-09 | 贵州省公路工程集团有限公司 | Machine-made sand high-performance concrete |
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