CN106608950A - Lactam polycarboxylic water reducing agent and preparation method thereof - Google Patents
Lactam polycarboxylic water reducing agent and preparation method thereof Download PDFInfo
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- CN106608950A CN106608950A CN201611199411.3A CN201611199411A CN106608950A CN 106608950 A CN106608950 A CN 106608950A CN 201611199411 A CN201611199411 A CN 201611199411A CN 106608950 A CN106608950 A CN 106608950A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a lactam polycarboxylic water reducing agent and a preparation method thereof. The lactam polycarboxylic water reducing agent is prepared by copolymerizing a monomer A, a monomer B and a monomer C; the monomer A has the structure represented by the formula (I), the monomer B has the structure represented by the formula (II), the monomer C has the structure represented by the formula (III), and the molar ratio of the monomer A to the monomer B to the monomer C is (1-5) to (10-50) to (5-30), wherein R1, R2 and R3 is C1-C6 alkyl, R4 is C1-C8 alkylene, M is H or Na, d is an integer from 1 to 4, and e is an integer from 30 to 120. The lactam polycarboxylic water reducing agent contains a lactam functional group, can effectively improve the hydration speed of cement, and improves the early strength of concrete; at the same time, the lactam polycarboxylic water reducing agent improves the steric hindrance between molecules, increases the cohesiveness of the concrete, and has obvious promoting effect on the workability and later strength of the concrete.
Description
Technical field
The present invention relates to technical field of concrete additives, more particularly to a kind of lactams polycarboxylate water-reducer and its system
Preparation Method.
Background technology
Polycarboxylate water-reducer due to volume it is little, water-reducing rate is high, function of slump protection is excellent, alkali content and the low advantage of shrinkage factor
And it is widely used in the construction of all kinds of engineerings such as high-speed railway water power, nuclear power.The concrete of 21 century is sent out with building industry
Resources conservation and environmental friendliness are more advocated in exhibition, and precast concrete technology is more and more wider in city's building engineering field application of having stable political situation,
The quality of overhead large-span prestressed bridge needs early strengthening and high strengthening precast concrete new technique to be ensured with outward appearance.Early strength
Development is fast, and stable long-term strength increase is a new technique of precast concrete industry concern.Therefore, to guarantee concrete final
Under conditions of performance, the technology for improving early age strength of concrete seems more and more important, needs further research to be adapted to prefabricated structure
The early strong concrete additive new technique of part.
The content of the invention
The purpose of the present invention is for the demand, there is provided a kind of lactams polycarboxylic acids containing lactams functional group
Water reducer and preparation method thereof, improves the cohesiveness of concrete.
On the one hand, the present invention provides a kind of lactams polycarboxylate water-reducer, and it is total to by monomer A, monomer B and monomer C Jing
It is poly- and be obtained, the wherein structure of monomer A as shown in formula I, the structure of monomer B as shown in formula II, the structure such as formula of monomer C
(III) shown in, the mol ratio of monomer A, monomer B and monomer C is (1～5)：(10～50)：(5～30),
Wherein, R1、R2And R3For H or C1-C6Alkyl, R4For C1-C8Alkylidene, M is H or Na, d for the integer of 1-4, and e is
30～120 integer.
In an embodiment of the lactams polycarboxylate water-reducer of the present invention, R1For C2-C5Alkyl, R2And R3For
C1-C3Alkyl, R4For C1-C5Alkylidene, d is the integer of 1-3, and e is 35～50 integer.
In another embodiment of the lactams polycarboxylate water-reducer of the present invention, the lactams polycarboxylic acids subtract
The structure of water preparation as shown in formula IV,
In another embodiment of the lactams polycarboxylate water-reducer of the present invention, the lactams polycarboxylic acids subtract
The weight average molecular weight of water preparation is 30000～50000.
On the other hand, the present invention provides the preparation method of above-mentioned lactams polycarboxylate water-reducer, comprises the following steps：
Monomer A and deionized water are configured to into aqueous solution, as 1# material；
Monomer B and deionized water are configured to into aqueous solution, as 2# material；
Initiator and chain-transferring agent are configured to into aqueous solution with deionized water, as 3# material；
Monomer C and deionized water are configured to into the aqueous solution that mass concentration is 30%～60%, are fed intake in reaction vessel,
Reaction vessel is inserted in microwave reactor afterwards, is to slowly warm up to 40～70 DEG C；
Deca 2# material and 3# material in reaction vessel, time for adding is 3～8 hours, after being added dropwise to complete 1～2.5 hour again
Deca 1# expects that time for adding is 4～10 hours, is incubated 2～8 hours afterwards, and the lactams are obtained after the completion of polyreaction
Polycarboxylate water-reducer.
In an embodiment of the preparation method of the present invention, the initiator is Ammonium persulfate., hydrogen peroxide, tertiary fourth
The mixture of one or more in base hydrogen peroxide, ascorbic acid and ferrous sulfate, by mass, its consumption is monomer C's
0.01～5%.
In another embodiment of the preparation method of the present invention, the chain-transferring agent is ethanol, mercaptoethanol and 3-
The mixture of one or more in mercaptopropionic acid, by mass, its consumption is the 0.001～5% of monomer C.
In another embodiment of the preparation method of the present invention, it is additionally included in after the completion of polyreaction and adds deionization
It is 30%～50% that water makes the solid content of the lactams polycarboxylate water-reducer.
The lactams polycarboxylate water-reducer of the present invention contains lactams functional group, can effectively improve the aquation speed of cement
Degree, lifts the early strength of concrete；The steric hindrance between molecule is improve simultaneously, the cohesiveness of concrete is improve, to coagulation
The workability and later strength of soil has obvious facilitation.Additionally, the preparation method of the present invention is friendly to bad border, do not produce useless
Water Litter, the starting monomer wide material sources for using, cost is relatively low, and the development to concrete admixture and Concrete Industry all has
It is significant.
Specific embodiment
Technical scheme is described further below according to specific embodiment.Protection scope of the present invention is not limited
In following examples, enumerate these examples and limit the present invention never in any form merely for exemplary purpose.
The present invention provides a kind of lactams polycarboxylate water-reducer, and it is by monomer A, monomer B and monomer C Jing random copolymerizations
Be obtained, the wherein structure of monomer A as shown in formula I, the structure of monomer B as shown in formula II, the structure such as formula III institute of monomer C
Show, the mol ratio of monomer A, monomer B and monomer C is (1～5)：(10～50)：(5～30),
In formula I, R1For H or C1-C6Alkyl (i.e. carbon number is 1～6 alkyl), preferably C2-C5Alkyl；D be 1～
4 integer, preferably 1～3.
In formula II, R2For H or C1-C6Alkyl, preferably C1-C3Alkyl；M is H or Na.
In formula III, R3For H or C1-C6Alkyl, preferably C1-C3Alkyl；R4For C1-C8Alkylidene, preferably C1-C5It is sub-
Alkyl；E is 30～120 integer, preferably 35～50.
The present invention lactams polycarboxylate water-reducer be lactams combed polycarboxylate water-reducer, a kind of structure such as formula
(IV) shown in,
The weight average molecular weight of the lactams polycarboxylate water-reducer of the present invention is 30000～50000.
The lactams polycarboxylate water-reducer of the present invention introduces lactams functional group, and this kind of group can significantly increase poly-
The cohesiveness of carboxylic acid water reducer, has obvious facilitation to the workability and later strength of concrete.
The present invention also provides the preparation method of above-mentioned lactams polycarboxylate water-reducer, including：
Monomer A and deionized water are configured to into aqueous solution, as 1# material；
Monomer B and deionized water are configured to into aqueous solution, as 2# material；
Initiator and chain-transferring agent are configured to into aqueous solution with deionized water, as 3# material；
At normal temperatures, monomer C and deionized water are configured to into the aqueous solution that mass concentration is 30%～60%, it is disposable to throw
Expect in reaction vessel (for example, flask), seal after nitrogen displacement three times, afterwards reaction vessel is inserted in microwave reactor,
It is to slowly warm up to 40～70 DEG C；
Simultaneously Deca 2# material and 3# material in reaction vessel, time for adding is 3～8 hours, 2# material and 3# gobs add 1～
Again Deca 1# is expected after 2.5 hours, and time for adding is 4～10 hours, after being added dropwise to complete, is incubated 2～8 hours, and makes monomer A, B
Mol ratio and C between is (1～5)：(10～50)：(5～30), finally mending a certain amount of deionized water makes lactams birds of the same feather flock together carboxylic
The solid content of sour water reducer is 30%～50%, you can obtain above-mentioned lactams polycarboxylate water-reducer.
The present invention is not limited for the concentration of 1#, 2#, 3# material, only needs the overall aforementioned proportion for meeting each monomer.
Initiator used by the present invention is that Ammonium persulfate., hydrogen peroxide, tert-butyl hydroperoxide, ascorbic acid and sulphuric acid are sub-
The mixture of one or more in ferrum, by mass, its consumption is the 0.01～5% of monomer C.
Chain-transferring agent used by the present invention is the mixing of one or more in ethanol, mercaptoethanol and 3- mercaptopropionic acids
Thing, by mass, its consumption is the 0.001～5% of monomer C.
The preparation method of the present invention is friendly to bad border, does not produce waste water and gas thing, the starting monomer wide material sources for using, into
This is relatively low, and the development to concrete admixture and Concrete Industry is all significant.
Unless otherwise defined, term used herein is the implication that those skilled in the art are generally understood that.
The present invention is described in further detail by the following examples.
Embodiment 1
3g vinyl pyrrolidones, 5g deionized waters are configured to into aqueous solution, 1# material are designated as.
8g acrylic acid and 10g water are configured to into aqueous solution, 2# material are designated as.
1.4g Ammonium persulfate .s, 1g mercaptopropionic acids and 20g water are configured to into aqueous solution, 3# material are designated as.
70g methyl butenes polyoxyethylenated alcohol and 70g deionized waters are loaded in flask and dissolve, it is close after nitrogen displacement three times
Envelope is inserted in microwave reactor, stirs and be to slowly warm up to 60 DEG C.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 5 hours.Start drop after 2# expects and 3# gobs add 1 hour
Plus 1# material, time for adding 4 hours.
Deionized water 15g is supplemented after being added dropwise to complete, that is, obtains lactams polycarboxylate water-reducer.
Embodiment 2
5gN, N- caprolactams, 5g deionized waters are configured to into aqueous solution, 1# material are designated as.
5g acrylic acid and 8g water are configured to into aqueous solution, 2# material are designated as.
1.3g Ammonium persulfate .s, 1.3g mercaptopropionic acids and 15g water are configured to into aqueous solution, 3# material are designated as.
80g allyl alcohol polyethenoxy ethers and 70g deionized waters are loaded in flask and is dissolved, nitrogen displacement is sealed afterwards for three times and put
In entering microwave reactor, 70 DEG C are stirred and are to slowly warm up to.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 4 hours.Start drop after 2# expects and 3# gobs add 1 hour
Plus 1# material, time for adding 4 hours.
Deionized water 30g is supplemented after being added dropwise to complete, that is, obtains lactams polycarboxylate water-reducer.
Embodiment 3
5g acrylic ketopyrrolidines, 5g deionized waters are configured to into aqueous solution, 1# material are designated as.
6g acrylic acid and 10g water are configured to into aqueous solution, 2# material are designated as.
0.9g Ammonium persulfate .s, 0.9g TGAs and 30g water are configured to into aqueous solution, 3# material are designated as.
75g methyl butenes polyoxyethylenated alcohol and 70g deionized waters are loaded in flask and dissolve, it is close after nitrogen displacement three times
Envelope is inserted in microwave reactor, stirs and be to slowly warm up to 65 DEG C.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 5.5 hours.Start after 2# expects and 3# gobs add 1 hour
Deca 1# material, time for adding 4 hours.
Deionized water 15g is supplemented after being added dropwise to complete, that is, obtains lactams polycarboxylate water-reducer.
Embodiment 4
6g vinyl pyrrolidones, 10g deionized waters are configured to into aqueous solution, 1# material are designated as.
10g methacrylic acids and 20g water are configured to into aqueous solution, 2# material are designated as.
1.35g Ammonium persulfate .s, 1g TGAs and 20g water are configured to into aqueous solution, 3# material are designated as.
80g methyl butenes polyoxyethylenated alcohol and 65g deionized waters are loaded in flask and dissolve, it is close after nitrogen displacement three times
Envelope is inserted in microwave reactor, stirs and be to slowly warm up to 60 DEG C.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 5 hours.Start drop after 2# expects and 3# gobs add 1 hour
Plus 1# material, time for adding 4 hours.
Deionized water 25g is supplemented after being added dropwise to complete, that is, obtains lactams polycarboxylate water-reducer.
Embodiment 5
5g vinyl pyrrolidones, 8g deionized waters are configured to into aqueous solution, 1# material are designated as.
8g acrylic acid and 15g water are configured to into aqueous solution, 2# material are designated as.
1.5g Ammonium persulfate .s, 1.1g mercaptopropionic acids and 30g water are configured to into aqueous solution, 3# material are designated as.
78g methyl allyl alcohol polyoxyethylene ethers and 70g deionized waters are loaded in flask and dissolve, it is close after nitrogen displacement three times
Envelope is inserted in microwave reactor, stirs and be to slowly warm up to 60 DEG C.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 3 hours.Start drop after 2# expects and 3# gobs add 1 hour
Plus 1# material, time for adding 4 hours.
Deionized water 10g is supplemented after being added dropwise to complete, that is, obtains lactams polycarboxylate water-reducer.
Comparative example 1
10g acrylic acid and 10g water are configured to into aqueous solution, 2# material are designated as.
1.4g Ammonium persulfate .s, 1.2g mercaptopropionic acids and 20g water are configured to into aqueous solution, 3# material are designated as.
80g methyl butenes polyoxyethylenated alcohol and 70g deionized waters are loaded in flask and dissolve, it is close after nitrogen displacement three times
Envelope is inserted in microwave reactor, stirs and be to slowly warm up to 60 DEG C.
Simultaneously Deca 2# material and 3# expect in flask, time for adding 5 hours.Deionized water 15g is supplemented after being added dropwise to complete, i.e.,
Obtain contrasting water reducer.
Application examples
According to GB8076-2008《Concrete admixture》Middle assay method, the lactams polycarboxylic acids during comparison is of the invention
Application performance of the water reducer (embodiment 1～5) with common polycarboxylate water-reducer (comparative example 1), admittedly volume is water reducer folding
0.2%, experimental result is shown in Table 1.
The performance test results of table 1
As it can be seen from table 1 under conditions of identical volume, the lactams polycarboxylic acids diminishing of embodiment of the present invention 1-5
Agent is compared with common polycarboxylate water-reducer, and the workability and later strength of concrete are obviously improved.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be
Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the invention is not restricted to above-mentioned embodiment, and only
It is defined by the claims.
Claims (8)
1. a kind of lactams polycarboxylate water-reducer, it is obtained by monomer A, monomer B and monomer C Jing copolymerization, wherein monomer A's
Structure as shown in formula I, the structure of monomer B as shown in formula II, the structure of monomer C as shown in formula III, monomer A, monomer B and
The mol ratio of monomer C is (1～5)：(10～50)：(5～30),
Wherein, R1、R2And R3For H or C1-C6Alkyl, R4For C1-C8Alkylidene, M is H or Na, d for the integer of 1-4, e is 30～
120 integer.
2. lactams polycarboxylate water-reducer according to claim 1, wherein R1For C2-C5Alkyl, R2And R3For C1-C3Alkane
Base, R4For C1-C5Alkylidene, d is the integer of 1-3, and e is 35～50 integer.
3. lactams polycarboxylate water-reducer according to claim 1, wherein the lactams polycarboxylate water-reducer
Structure as shown in formula IV,
4. lactams polycarboxylate water-reducer according to any one of claim 1 to 3, wherein the poly- carboxylic of the lactams
The weight average molecular weight of sour water reducer is 30000～50000.
5. the preparation method of lactams polycarboxylate water-reducer according to any one of claim 1 to 4, including following step
Suddenly：
Monomer A and deionized water are configured to into aqueous solution, as 1# material；
Monomer B and deionized water are configured to into aqueous solution, as 2# material；
Initiator and chain-transferring agent are configured to into aqueous solution with deionized water, as 3# material；
Monomer C and deionized water are configured to into the aqueous solution that mass concentration is 30%～60%, are fed intake in reaction vessel, afterwards
Reaction vessel is inserted in microwave reactor, 40～70 DEG C are to slowly warm up to；
Deca 2# material and 3# material in reaction vessel, time for adding is 3～8 hours, Deca again after being added dropwise to complete 1～2.5 hour
1# expects that time for adding is 4～10 hours, is incubated 2～8 hours afterwards, the lactams is obtained after the completion of polyreaction and is birdsed of the same feather flock together carboxylic
Sour water reducer.
6. preparation method according to claim 5, wherein the initiator is Ammonium persulfate., hydrogen peroxide, tert-butyl group mistake
The mixture of one or more in hydrogen oxide, ascorbic acid and ferrous sulfate.
7. preparation method according to claim 5, wherein the chain-transferring agent is ethanol, mercaptoethanol and 3- mercaptopropionic acids
In the mixture of one or more.
8. preparation method according to claim 5, wherein be additionally included in after the completion of polyreaction adding deionized water to make institute
The solid content for stating lactams polycarboxylate water-reducer is 30%～50%.
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|---|---|---|---|---|
| CN101333092A (en) * | 2007-06-25 | 2008-12-31 | 深圳市海川实业股份有限公司 | Cement concrete superplasticizer and method for preparing same |
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| CN105504184A (en) * | 2016-01-15 | 2016-04-20 | 江苏苏博特新材料股份有限公司 | Preparation method and application of mud-resistant polycarboxylate superplasticizer |
-
2016
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| CN101333092A (en) * | 2007-06-25 | 2008-12-31 | 深圳市海川实业股份有限公司 | Cement concrete superplasticizer and method for preparing same |
| CN104446105A (en) * | 2014-11-04 | 2015-03-25 | 上海三瑞高分子材料有限公司 | Polycarboxylic super plasticizer |
| CN105367721A (en) * | 2015-11-30 | 2016-03-02 | 江苏苏博特新材料股份有限公司 | Method for preparing viscosity-reduction-type polycarboxylic acid superplasticizer and application of viscosity-reduction-type polycarboxylic acid superplasticizer |
| CN105504184A (en) * | 2016-01-15 | 2016-04-20 | 江苏苏博特新材料股份有限公司 | Preparation method and application of mud-resistant polycarboxylate superplasticizer |
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