CN102140020B - Concrete water reducing agent and preparation method thereof - Google Patents

Concrete water reducing agent and preparation method thereof Download PDF

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CN102140020B
CN102140020B CN 201010557744 CN201010557744A CN102140020B CN 102140020 B CN102140020 B CN 102140020B CN 201010557744 CN201010557744 CN 201010557744 CN 201010557744 A CN201010557744 A CN 201010557744A CN 102140020 B CN102140020 B CN 102140020B
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reducing agent
water reducing
cement water
polyamino acid
preparation
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CN102140020A (en
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朱建民
刘兆滨
董振鹏
仲崇纲
周立明
侯光
于连林
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LIAONING OXIRANCHEM GROUP CO Ltd
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

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

A kind of cement water reducing agent and preparation method thereof
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 and a series of effects such as with cement to be that main fine aggregate particulate successively takes place wetting, infiltration, absorption; The fine aggregate particulate is produced accurate parcel phenomenon, fine aggregate particulate inner cement and water 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 like (i).See that from chemical structure carboxyl and sulfonic group etc. is the main group that cement is produced chemisorption, 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.
Figure BDA0000034003890000011
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 through organic carboxyl acid that contains two keys such as materials such as vinylformic acid, methylacrylic 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 types material of sub-fraction such as methylpropene sodium sulfonate etc. in the main chain; This type of water reducer is difficult for obtaining through mass polymerization the product of high solid content; Actual production is made solvent with big water gaging often; Obtain solid content through 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 said cement water reducing agent is provided.
Above-mentioned purpose of the present invention realizes through following technical scheme:
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 said high molecular polymer has branched structure.
Described cement water reducing agent is preferably obtained through 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:
Figure BDA0000034003890000021
In the above-mentioned formula (I)～(VI), A represents
Figure BDA0000034003890000031
B represents
Figure BDA0000034003890000032
C represents
Figure BDA0000034003890000033
D represents
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 propylhomoserin that gathers that has a plurality of carboxyls can be through commercial acquisition; Perhaps can prepare, for example, can make through intermolecular amino and carboxyl polycondensation with the amino acids material that contains binary or the carboxyl more than the binary through existing several different methods; 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, through intermolecular amino and carboxyl polycondensation, and the described propylhomoserin that gathers of formation straight or branched with a plurality of carboxyls.
Figure BDA0000034003890000035
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:
Figure BDA0000034003890000041
In the above-mentioned formula (VII)～(XII), A represents
Figure BDA0000034003890000051
B represents
Figure BDA0000034003890000052
C represents
D represents
Figure BDA0000034003890000054
E representative---COOH;
F represents
Figure BDA0000034003890000055
G represents
Figure BDA0000034003890000056
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 said cement water reducing agent; Be to put into polyamino acid in the reactor drum with the MPEG and the catalyst for esterification reaction that have hydroxyl with a plurality of carboxyls; 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 accomplished through the amount of control adding MPEG.
Described preparation method specifically may further comprise the steps: in reactor drum, drop into described polyamino acid with a plurality of carboxylic acids, MPEG and catalyst for esterification reaction; Be warming up to 100～150 ℃; Esterification 2～6h; Reaction finishes the back and utilizes the band aqua or vacuumize and agingly remove the water that generates in the reaction process, treat that esterification fully after, cooling discharge obtains the said cement water reducing agent of solid; Described MPEG 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.
Gather 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---gather the propylhomoserin water reducer; See from 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 that a kind of novel solid gathers the propylhomoserin water reducer; 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
Below in conjunction with embodiment invention is done further to describe, but should not limit protection scope of the present invention with this, 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 SAP 73s (a described SAP 73 can according to synthetic the obtaining of SAP 73 compound method in " development of efficient coal water slurry dispersing agent-SAP 73 " literary composition of " clean coal technology " 2006 the 12nd volumes the 12nd phase Song Ying of the 52nd～53 page etc.), 2.74 parts of tosic acid, 27 parts of hexanaphthenes; Add and be equipped with in the there-necked flask of TM, water trap and spherical condensation tube; Be warming up to 110 ℃, react pressure reducing and steaming hexanaphthene after 4 hours, cooling obtains gathering propylhomoserin water reducer PAA-MPEG; Number-average molecular weight is 36000; Confirm structure suc as formula shown in (ii) through infrared spectroscopy, wherein the value of m * (x+y) is 10～40, n=54.
Figure BDA0000034003890000061
Embodiment two:
The input molecule amount is 115.50 parts of 1200 MPEG in round-bottomed flask, molecular weight be 3000 gather 28.30 parts in γ L-glutamic acid (commercially available prod), 1.72 parts of 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; Confirm structure suc as formula shown in (iii) through 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 instance 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 ".TP is that the result is following:
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 is seen table 1.
The clean slurry slump test of table 1 water reducer
Figure BDA0000034003890000072
Can know from table 1, of the present inventionly gather the propylhomoserin water reducer and polycarboxylate water-reducer has 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 is seen table 2.
Table 2 concrete mix
Figure BDA0000034003890000081
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, its result sees table 3.
Table 3 water reducer concrete test
Figure BDA0000034003890000082
Above-mentioned test shows that synthetic of the present invention gathers the concrete performance that the propylhomoserin water reducer has traditional polycarboxylate water-reducer, promptly under lower volume, just can obtain the higher slump, and has good slump hold facility.

Claims (10)

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; Described cement water reducing agent is obtained through the grafting of esterification mode by polyamino acid and the methoxy poly (ethylene glycol) with a plurality of carboxyls; Described polyamino acid with a plurality of carboxyls is selected from any one in the polyamino acid of following structure shown in (I) ~ (VI):
Figure FDA00001815225800012
or?
Figure FDA00001815225800013
In above-mentioned formula I ~ (VI), A represents
Figure FDA00001815225800014
B represents
Figure FDA00001815225800015
C represents
Figure FDA00001815225800021
D represents
Figure FDA00001815225800022
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.
2. the described cement water reducing agent of claim 1 is characterized in that: the molecular weight ranges of described polyamino acid with a plurality of carboxyls is 1000 ~ 10000.
3. the described cement water reducing agent of claim 1, it is characterized in that: the molecular weight ranges of described MPEG is 200 ~ 6000.
4. 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 following formula (VII) ~ (XII) any one:
Figure FDA00001815225800023
Figure FDA00001815225800031
Perhaps
Figure FDA00001815225800032
In above-mentioned formula I ~ (XII), A represents
Figure FDA00001815225800033
B represents
Figure FDA00001815225800034
C represents
D represents
Figure FDA00001815225800036
E representative-CO OH;
F represents
Figure FDA00001815225800037
G representative-CO OH or
Figure FDA00001815225800041
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.
5. 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.
6. the preparation method of the described cement water reducing agent of claim 1; May further comprise the steps: in reactor drum, 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 said cement water reducing agent of solid; Described methoxy poly (ethylene glycol) be 20 ~ 5 with the polyamino acid 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.
7. the described preparation method of claim 6, it is characterized in that: described catalyst for esterification reaction is tosic acid or solid acid catalyst.
8. the described preparation method of claim 7, it is characterized in that: described solid acid catalyst is load-type solid acid catalyst SO 4 2-/ SiO 2-TiO 2
9. the described preparation method of claim 6, it is characterized in that: described band aqua is hexanaphthene or toluene.
10. the described preparation method of claim 6, it is characterized in that: the described digestion time that vacuumizes is 1 ~ 3 hour.
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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
CN109897178B (en) * 2019-02-22 2021-06-25 临沂大学 Polyamino acid carboxylic acid 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
CN112500018B (en) * 2020-12-04 2022-09-06 河北协同环保科技股份有限公司 Degradable efficient gypsum retarder 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
CN115160577B (en) * 2022-07-07 2023-07-28 河北思动环保科技有限公司 Polylysine function-based modified macromolecular water reducer and preparation method and application thereof

Citations (2)

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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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

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