CN102140020A - Concrete water reducing agent and preparation method thereof - Google Patents
Concrete water reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN102140020A CN102140020A CN 201010557744 CN201010557744A CN102140020A CN 102140020 A CN102140020 A CN 102140020A CN 201010557744 CN201010557744 CN 201010557744 CN 201010557744 A CN201010557744 A CN 201010557744A CN 102140020 A CN102140020 A CN 102140020A
- Authority
- CN
- China
- Prior art keywords
- reducing agent
- water reducing
- representative
- cement water
- polyamino acid
- 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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Links
- ACYFWRHALJTSCF-UHFFFAOYSA-N CC(C)(C)NC(C)=O Chemical compound CC(C)(C)NC(C)=O ACYFWRHALJTSCF-UHFFFAOYSA-N 0.000 description 1
- RFGFCICNGCPXQJ-UHFFFAOYSA-N CC(NC(C)=O)=C Chemical compound CC(NC(C)=O)=C RFGFCICNGCPXQJ-UHFFFAOYSA-N 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/287—Polyamides
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
Abstract
The invention provides a concrete water reducing agent which structurally contains macromolecular polymers with a main chain and side chains, wherein the main chain is a polyamino acid structure, and molecules of the water reducing agent are provided with dendritic structures. The water reducing agent has high solid-containing content and higher water reducing ratio and is convenient to use. The invention also provides a preparation method for the water reducing agent.
Description
Technical field
The invention belongs to technical field of concrete additives, be specifically related to a kind of cement water reducing agent of novel texture, and preparation method thereof.
Background technology
Polycarboxylate water-reducer is the important component part of concrete admixture, its basic reason that produces the effect of water reducer is in limited aqueous systems, water reducer with a series of effects such as wetting, infiltration, absorption successively take place based on the fine aggregate particulate of cement, the fine aggregate particulate is produced accurate parcel phenomenon, the cement and the water of fine aggregate particulate inside are separated, effectively stoped the hydrated reaction of cement process, thereby guaranteed that the slurry in the concrete can keep mobile, promptly good dispersiveness within a certain period of time.Polycarboxylic acids dehydragent is the comb type functional polymer with surfactant properties, and its general structure is as (i).On chemical structure, carboxyl and sulfonic group etc. is the main group that cement is produced chemisorption, and the long side chain of branched structure and Soxylat A 25-7 is to form the fundamental space of isolating the fine aggregate particulate to hinder the unit.
Wherein, R gets H or CH
3X, y, z, m and n are positive integer.
The preparation method of current polycarboxylate water-reducer forms comb shape water reducer molecular structure by organic carboxyl acid that contains two keys such as materials such as vinylformic acid, methacrylic acid with the polyethers polyreaction that contains the two keys of end group.Double bond containing carboxylic acid forms the short main chain of water reducer molecule, and the polyethers that contains the two keys of end group forms long side chain.For improving the performance of water reducer, can also add double bond containing other class materials of sub-fraction such as methylpropene sodium sulfonate etc. in the main chain, this type of water reducer is difficult for obtaining by mass polymerization the product of high solid content, actual production is made solvent with big water gaging often, obtain solid content by solution polymerization and be usually less than 50% water reducer solution, this makes it be restricted in application scenarios such as dry-mix concretes on the one hand, also makes products production and transportation cost increase because of the existence of big water gaging in the product on the other hand.
Summary of the invention
One object of the present invention is: a kind of cement water reducing agent is provided, not only can keeps good water reducer performance, and have higher solid content.
Another object of the present invention is: the preparation method that described cement water reducing agent is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of cement water reducing agent is provided, and it is the high molecular polymer that comprises main chain and side chain in the structure; Wherein, described main chain is the polyamino acid structure; And described high molecular polymer has branched structure.
Described cement water reducing agent is preferably obtained by the grafting of esterification mode by polyamino acid and methoxy poly (ethylene glycol) (MPEG) with a plurality of carboxyls.
In the preferred polyamino acid of following chemical structural formula shown in (I)～(VI) of described polyamino acid any one with a plurality of carboxyls:
In the above-mentioned formula (I)～(VI), the A representative
The B representative
The C representative
The D representative
E representative---COOH;
And the R among above-mentioned A～E
1, R
2, R
3Alkyl for H or C1～C5;
A, b, c, d, e, f and g are 0～6 integer;
H, i, j, k, l, m, n, o, p, q, r, s, t, u, v, x, y and z are positive integer.
The molecular weight ranges preferred 1000～10000 of described polyamino acid with a plurality of carboxyls.
The described poly-propylhomoserin that has a plurality of carboxyls can be by commercial acquisition, perhaps can prepare by existing several different methods, for example, can make by intermolecular amino and carboxyl polycondensation with the amino acids material that contains binary or the carboxyl more than the binary, such as, concrete grammar can be to be in the amino acids material of (1) or (2) one or more by a plurality of structural formulas, by intermolecular amino and carboxyl polycondensation, form the described poly-propylhomoserin of straight or branched with a plurality of carboxyls.
In formula (1) and the formula (2), R
1, R
2And R
3Alkyl for H or C1～C5; A, b, c, d, e, f and g are 0～6 integer.
The molecular weight 200～6000 of described MPEG.
The chemical structure of described cement water reducing agent can be with shown in the following formula (VII)～(XII) any one:
In the above-mentioned formula (VII)～(XII), the A representative
The B representative
The C representative
The D representative
E representative---COOH;
The F representative
The G representative
And the R among above-mentioned A～G
1, R
2And R
3Alkyl for H or C1～C5;
A, b, c, d, e, f and g are 0～6 integer;
Other small letter English alphabet labels are positive integer.
Described cement water reducing agent molecular weight is 5000～70000.
The present invention also provides the preparation method of described cement water reducing agent, be that the polyamino acid with a plurality of carboxyls is put in the reactor with the MPEG and the catalyst for esterification reaction that have hydroxyl, intermolecular dehydration esterification is carried out in intensification, behind the reaction certain hour, vacuumize and slough the water that generates in the reaction process, the direction that makes reaction generate ester is carried out.The side chain density that generates the water reducer molecule can be finished by the amount of control adding MPEG.
Described preparation method specifically may further comprise the steps: drop into described polyamino acid with a plurality of carboxylic acids, MPEG and catalyst for esterification reaction in reactor, be warming up to 100～150 ℃, esterification 2～6h, reaction finishes the back and utilizes the band aqua or vacuumize the aging water that generates in the reaction process of removing, after treating that esterification fully, cooling discharge obtains the described cement water reducing agent of solid; Described MPEG and be 20～5 with the polyamino acid and the mol ratio of a plurality of carboxylic acids; Described catalyst for esterification reaction consumption is MPEG and polyamino acid 0.001～0.1% of the quality that always feeds intake.
Preferred tosic acid of described catalyst for esterification reaction or solid acid catalyst.
The preferred load-type solid acid catalyst SO of described solid acid catalyst
4 2-/ SiO
2-TiO
2
Preferred hexanaphthene of described band aqua or toluene;
Describedly vacuumized digestion time preferred 1～3 hour.
Poly-propylhomoserin and a certain amount of MPEG that the present invention will have carboxyl carry out the graft esterification reaction on the part carboxyl, obtained structure and the similar polymkeric substance of existing polycarboxylate water-reducer---poly-propylhomoserin water reducer, on chemical structure, the carboxyl that can produce chemisorption to cement is arranged on its main chain, also have even surpass the branched structure (this will help forming more effective steric restriction) of the cladodification degree of existing polycarboxylate water-reducer, have the long side chain of the Soxylat A 25-7 that can form steric restriction equally.Compare with existing poly carboxylic acid series water reducer, cement water reducing agent of the present invention has following beneficial effect:
1. cement water reducing agent of the present invention is the poly-propylhomoserin water reducer of a kind of novel solid, it is the water-free solid water reducer of synthetic product under non-water meson reaction condition, overcome traditional polycarboxylate water-reducer and be not restricted in application scenarios such as dry-mix concretes, and produced and weak point such as transportation cost increase because of the existence of water in producing makes because of solid content is high.
2. cement water reducing agent of the present invention is when keeping even having improved the water reducer performance, for new raw material field has been opened up in the preparation of water reducer.
Embodiment
The invention is further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this, and the prepared polyethers Performance Detection index of following specific embodiment is listed in the table 1.
Embodiment one:
The input molecule amount is MPEG235.34 part of 2400 in round-bottomed flask, molecular weight is 38.50 parts of 4000 poly aspartic acids (a described poly aspartic acid can according to synthetic the obtaining of poly aspartic acid synthetic method in " development of efficient coal water slurry dispersing agent-poly aspartic acid " literary composition of " clean coal technology " 2006 the 12nd volumes the 12nd phase Song Ying of the 52nd～53 page etc.), 2.74 part tosic acid, 27 parts of hexanaphthenes, add thermometer is housed, in the there-necked flask of water trap and spherical condensation tube, be warming up to 110 ℃, react pressure reducing and steaming hexanaphthene after 4 hours, cooling obtains poly-propylhomoserin water reducer PAA-MPEG, number-average molecular weight is 36000, determine that by infrared spectroscopy structure is suc as formula shown in (ii), wherein the value of m * (x+y) is 10～40, n=54.
Embodiment two:
The input molecule amount is 115.50 parts of 1200 MPEG in round-bottomed flask, molecular weight is 28.30 parts in 3000 a poly-γ L-glutamic acid (commercially available prod), 1.72 part tosic acid, be warming up to 120 ℃, react and be cooled to 100 ℃ after 4 hours and vacuumized 2 hours, cooling obtains polyglutamic acid water reducer PGA-MPEG, number-average molecular weight is 18600, determine structure suc as formula shown in (iii) by infrared spectroscopy, wherein the value of m * (x+y) is 10～40, n=54.
Performance Detection:
Choose market finished product type polycarboxylate water-reducer product 1 and 2 as reference (they all belong to structure suc as formula the existing polycarboxylate water-reducer shown in (i)), do simultaneous test with the PAA-MPEG of example one preparation and the PGA-MPEG of embodiment two preparations, use reference cement to carry out the mortar degree of mobilization and measure.Measuring method is with reference to GB/T 2419-1994 " Test method for fluidity of cement mortar ".Test method is that the result is as follows:
1. clean slurry test
Clean slurry degree of mobilization test (GB/T 8077-2000): adopt reference cement, according to the degree of mobilization of GB8077-87 test to cement paste.Test result sees Table 1.
The clean slurry slump test of table 1 water reducer
As known from Table 1, poly-propylhomoserin water reducer of the present invention and polycarboxylate water-reducer have suitable cement dispersing property.
2. concrete test
Gelatinous material adopts ordinary Portland cement, and fine aggregate adopts medium sand (fineness modulus 2.7, silt content 0.18%), and coarse aggregate uses rubble (particle diameter 5-25mm, continuous grade, porosity 43%).Concrete mix sees Table 2.
Table 2 concrete mix
Under above-mentioned condition, use the water reducer mix concrete of one and embodiment two preparations of the reference water reducer and the embodiment of the invention, and measure the concrete slump, air content, slump retention value, it the results are shown in Table 3.
Table 3 water reducer concrete test
Above-mentioned test shows that the poly-propylhomoserin water reducer of synthetic of the present invention has the concrete performance of traditional polycarboxylate water-reducer, promptly under lower volume, just can obtain the higher slump, and have good slump hold facility.
Claims (12)
1. cement water reducing agent, it is characterized in that: it is the high molecular polymer that comprises main chain and side chain in the structure; Wherein, described main chain is the polyamino acid structure; And described water reducer molecule has branched structure.
2. the described cement water reducing agent of claim 1, it is characterized in that: described cement water reducing agent is obtained by the grafting of esterification mode by polyamino acid and the methoxy poly (ethylene glycol) with a plurality of carboxyls.
3. the described cement water reducing agent of claim 2, it is characterized in that: described polyamino acid with a plurality of carboxyls is selected from any one in the polyamino acid of following structure shown in (I)～(VI):
In the above-mentioned formula (I)～(VI), the A representative
The B representative
The C representative
The D representative
E representative-COOH;
And the R among above-mentioned A～E
1, R
2, R
3Alkyl for H or C1～C5;
A, b, c, d, e, f and g are 0～6 integer;
H, i, j, k, l, m, n, o, p, q, r, s, t, u, v, x, y and z are positive integer.
4. the described cement water reducing agent of claim 2 is characterized in that: the molecular weight ranges of described polyamino acid with a plurality of carboxyls is 1000～10000.
5. the described cement water reducing agent of claim 2, it is characterized in that: the molecular weight ranges of described MPEG is 200～6000.
6. the described cement water reducing agent of claim 1 is characterized in that: the chemical structure of described cement water reducing agent is with shown in the following formula (VII)～(XII) any one:
In the above-mentioned formula (I)～(XII), the A representative
The B representative
The C representative
The D representative
E representative-COOH;
The F representative
The G representative
And the R among above-mentioned A～G
1, R
2And R
3Alkyl for H or C1～C5;
A, b, c, d, e, f and g are 0～6 integer;
Other small letter English alphabet labels are positive integer.
7. the described cement water reducing agent of claim 1, it is characterized in that: the molecular weight of described cement water reducing agent is 5000～70000.
8. the preparation method of the described cement water reducing agent of claim 2, may further comprise the steps: in reactor, drop into described polyamino acid, methoxy poly (ethylene glycol) and catalyst for esterification reaction with a plurality of carboxylic acids, be warming up to 100～150 ℃, esterification 2～6h, reaction finishes the back and utilizes the band aqua or vacuumize the aging water that generates in the reaction process of removing, after treating that esterification fully, cooling discharge obtains the described cement water reducing agent of solid; Described methoxy poly (ethylene glycol) and be 20～5 with the polyamino acid and the mol ratio of a plurality of carboxylic acids; Described catalyst for esterification reaction consumption is methoxy poly (ethylene glycol) and polyamino acid 0.001～0.1% of the quality that always feeds intake.
9. the described preparation method of claim 8, it is characterized in that: described catalyst for esterification reaction is tosic acid or solid acid catalyst.
10. the described preparation method of claim 9, it is characterized in that: described solid acid catalyst is load-type solid acid catalyst SO
4 2-/ SiO
2-TiO
2
11. the described preparation method of claim 8 is characterized in that: described band aqua is hexanaphthene or toluene.
12. the described preparation method of claim 8 is characterized in that: the described digestion time that vacuumizes is 1～3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010557744 CN102140020B (en) | 2010-11-24 | 2010-11-24 | Concrete water reducing agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010557744 CN102140020B (en) | 2010-11-24 | 2010-11-24 | Concrete water reducing agent and preparation method thereof |
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|---|---|
| CN102140020A true CN102140020A (en) | 2011-08-03 |
| CN102140020B CN102140020B (en) | 2012-12-26 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897178A (en) * | 2019-02-22 | 2019-06-18 | 临沂大学 | A kind of polyaminoacid class carboxylic acid water reducer and preparation method thereof |
| CN110642993A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of retarding ether polycarboxylate superplasticizer |
| CN110643003A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of retarding type ester polycarboxylate superplasticizer |
| CN112011050A (en) * | 2020-09-01 | 2020-12-01 | 中国建材检验认证集团北京天誉有限公司 | Ultrahigh-performance water reducing agent and preparation method thereof |
| CN112500018A (en) * | 2020-12-04 | 2021-03-16 | 河北协同环保科技股份有限公司 | Degradable efficient gypsum retarder and preparation method and application thereof |
| CN113801274A (en) * | 2021-09-17 | 2021-12-17 | 临沂大学 | Poly-like amino acid and preparation method and application thereof |
| CN115160577A (en) * | 2022-07-07 | 2022-10-11 | 临沂大学 | Polylysine function-based modified macromolecular water reducing agent and preparation method and application thereof |
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| CN1268101A (en) * | 1997-06-25 | 2000-09-27 | 格雷斯公司 | Admixture and method for optimizing addition of EO/PO superplasticizer to concrete containing smectite clay-containing aggregates |
| CN1784368A (en) * | 2003-05-07 | 2006-06-07 | 株式会社日本触媒 | Cement admixture and cement admixture composite |
-
2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268101A (en) * | 1997-06-25 | 2000-09-27 | 格雷斯公司 | Admixture and method for optimizing addition of EO/PO superplasticizer to concrete containing smectite clay-containing aggregates |
| CN1784368A (en) * | 2003-05-07 | 2006-06-07 | 株式会社日本触媒 | Cement admixture and cement admixture composite |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642993A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of retarding ether polycarboxylate superplasticizer |
| CN110643003A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of retarding type ester polycarboxylate superplasticizer |
| CN110642993B (en) * | 2018-06-26 | 2021-05-07 | 科之杰新材料集团有限公司 | Preparation method of retarding ether polycarboxylate superplasticizer |
| CN110643003B (en) * | 2018-06-26 | 2022-02-22 | 科之杰新材料集团有限公司 | Preparation method of retarding type ester polycarboxylate superplasticizer |
| CN109897178A (en) * | 2019-02-22 | 2019-06-18 | 临沂大学 | A kind of polyaminoacid class carboxylic acid water reducer and preparation method thereof |
| CN109897178B (en) * | 2019-02-22 | 2021-06-25 | 临沂大学 | Polyamino acid carboxylic acid water reducing agent and preparation method thereof |
| CN112011050A (en) * | 2020-09-01 | 2020-12-01 | 中国建材检验认证集团北京天誉有限公司 | Ultrahigh-performance water reducing agent and preparation method thereof |
| CN112011050B (en) * | 2020-09-01 | 2022-05-27 | 中国建材检验认证集团北京天誉有限公司 | Ultrahigh-performance water reducing agent and preparation method thereof |
| CN112500018A (en) * | 2020-12-04 | 2021-03-16 | 河北协同环保科技股份有限公司 | Degradable efficient gypsum retarder and preparation method and application thereof |
| CN113801274A (en) * | 2021-09-17 | 2021-12-17 | 临沂大学 | Poly-like amino acid and preparation method and application thereof |
| CN113801274B (en) * | 2021-09-17 | 2024-01-26 | 河北思动环保科技有限公司 | Polyamino acid and preparation method and application thereof |
| CN115160577A (en) * | 2022-07-07 | 2022-10-11 | 临沂大学 | Polylysine function-based modified macromolecular water reducing agent and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102140020B (en) | 2012-12-26 |
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