CN109575199A - A kind of polycarboxylate water-reducer and preparation method thereof containing beta-cyclodextrin - Google Patents
A kind of polycarboxylate water-reducer and preparation method thereof containing beta-cyclodextrin Download PDFInfo
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- CN109575199A CN109575199A CN201811487030.4A CN201811487030A CN109575199A CN 109575199 A CN109575199 A CN 109575199A CN 201811487030 A CN201811487030 A CN 201811487030A CN 109575199 A CN109575199 A CN 109575199A
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- polycarboxylate water
- reducer
- cyclodextrin
- monomer
- containing beta
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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
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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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of polycarboxylate water-reducer and preparation method thereof containing beta-cyclodextrin is to mix acryloyl chloride and metanitrophenol, is stirred to react, obtains acrylic acid m-nitro phenolic ester；Then β-CD is added in acrylic acid m-nitro phenolic ester, is stirred to react, obtain modified β-CD monomer；β-CD monomer, acrylic acid, polyethers polymeric monomer, initiator will be modified again to mix, heating reaction obtains the polycarboxylate water-reducer containing beta-cyclodextrin.The present invention does not add any organic solvent, and simple production process, post-processing operation is simple, safe and non-toxic, and production cost is low.
Description
Technical field
The present invention relates to water-reducing agent fields, in particular to a kind of containing the polycarboxylate water-reducer of beta-cyclodextrin and its preparation side
Method.
Background technique
Beta-cyclodextrin (β-CD) is that the hollow and annular that is combined by 7 glucosyl group units with β -1,4 glycosidic bond is oligomeric
Sugar compounds.There are many hydrophilic hydroxyls on the surface of β-CD, make it have good stability；Inside configuration is a cavity,
Suitable gas can be introduced and make it have microcellular structure, improve concrete durability and intensity well, and releasable
The Free water being wrapped in cavity out, so as to improve the mobility of cement slurry.β-CD unique structure, raw material sources are extensive and pacify
Atoxic makes it have a good application prospect in polycarboxylate water-reducer field.
Polycarboxylate high performance water-reducing agent is that a kind of molecular structure is combed, the carboxylic graft copolymer surface-active of packet
Agent specifically includes that carbon-carbon skeletal chain, highly polar group short-side chain and the long side chain of polyethers.Short-side chain hydrophilic radical polarity is got over
By force, density is higher, will be stronger in the anchorage effect of cement particle surface, plays deferred action；Main chain plays increase space bit
Resistance prevents hydrone from permeating and adjusting the effect of surface-active；The dispersibility and dispersion retentivity of long side chain enhancing water-reducing agent.Cause
This, can design the polycarboxylate water-reducer haveing excellent performance according to polycarboxylate water-reducer molecule design feature.
It is compared with traditional naphthalene system, aliphatic with sulfamate water reducer, polycarboxylate water-reducer presents more excellent
Different performance, but its existing some problem in application process, such as in concrete works are applied there is easy bleeding, from
It the problems such as analysis, increase high to the requirement of sandstone clay content and late strength of concrete and durability low than expected, hinders poly-
The further genralrlization of carboxylic acid water reducer and use.In order to solve the problems, such as polycarboxylate water-reducer and cement poor compatibility, China is specially
A kind of preparation method (CN102229479A) of the water-retaining type of-CD containing β poly carboxylic acid series water reducer of benefit is related to maleic anhydride-β-CD, alkene
Propyl polyethylene glycol, lignin, acrylic acid obtain the polycarboxylate water-reducer of excellent moisture retention and high-collapse-retentivity；But this method
Using organic solvent, it is unfavorable for environmental protection.But simple β-CD haves the shortcomings that dissolubility is bad, needs first to change it
Property, polycarboxylate water-reducer is prepared by the modified β-CD of high activity small molecule reaction object at present and is reported there has been no open.
Summary of the invention
It is an object of the invention to overcome disadvantage existing in the prior art, a kind of polymolecularity, high fluidity are provided
Polycarboxylate water-reducer and preparation method thereof containing beta-cyclodextrin.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of the polycarboxylate water-reducer containing beta-cyclodextrin, includes the following steps:
(1) acryloyl chloride and metanitrophenol are mixed, is stirred to react, obtains acrylic acid m-nitro phenolic ester；Then will
β-CD is added in acrylic acid m-nitro phenolic ester, is stirred to react, and modified β-CD monomer is obtained；
(2) β-CD monomer, acrylic acid, polyethers polymeric monomer, initiator will be modified to mix, heating reaction is obtained containing β-ring
The polycarboxylate water-reducer of dextrin.
In step (1), acryloyl chloride is 10~40 mass parts, and metanitrophenol is 10~50 mass parts, and β-CD is 100 matter
Measure part.
In step (1), the temperature of the reaction is room temperature, and the time of reaction is 3~8h.The rate of the stirring is 100
~300r/min.
In step (2), polyethers polymeric monomer is 100 mass parts, and acrylic acid is 2~40 mass parts, and modified β-CD monomer is 2
~50 mass parts, initiator are 0.1~20 mass parts.
In step (2), the initiator is azodiisobutyronitrile, ammonium persulfate, hydrogen peroxide, hydrogen peroxide/dimension life
Plain C.
In step (2), the temperature of the heating reaction is 60~120 DEG C, and the time of reaction is 5~15h.
In step (2), the polyethers polymeric monomer is TPEG-1000, TPEG-2400, APEG-1200 or APEG-
2400。
In step (2), after reaction, the pH of reaction system is adjusted to 6~8 with the solution of 30Wt%NaOH.
A kind of polycarboxylate water-reducer containing beta-cyclodextrin is to adopt to be prepared with the aforedescribed process.
The present invention has the following advantages that compared with prior art and effect:
(1) present invention is modified β-CD, and polymerize to have obtained polycarboxylic acids diminishing with acrylic acid, polyethers polymeric monomer
Agent.The polycarboxylate water-reducer introduces β-CD, and surface has many hydroxyls, the dispersibility of the water-reducing agent, and β-can be improved
There is CD inside configuration a hydrophobic cavity can coat hydrone, and releasing Free water can be improved the mobility of the water-reducing agent.
(2) preparation method of the invention does not add any organic solvent, and simple production process, post-processing operation is simple, peace
Atoxic, production cost are low.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
(1) metanitrophenol 25g is added in three-necked flask, acryloyl chloride 20g reacts about 6h at room temperature, obtains nitre
Base phenol ester.100g β-CD is added in m-nitro phenolic ester, reacts about 6h at room temperature, obtains modified β-CD monomer.
(2) the modification β-CD monomer 20g that above-mentioned steps obtain is placed in four-hole boiling flask, and 10g acrylic acid, 100g is added
APEG-1200,4g vitamin C and 8g H2O2Mixture.Heating stirring reacts about 6h at 80 DEG C, after reaction, uses
The pH of reaction system is adjusted to 6-8 by the solution of 30Wt%NaOH, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 2
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 10g acrylic acid, 100g is added
APEG-2400,4g vitamin C and 8g H2O2Mixture.Heating stirring 6h uses 30Wt% after reaction at 80 DEG C
The pH of reaction system is adjusted to 6-8 by the solution of NaOH, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 3
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 8g acrylic acid, 100g is added
TPEG-1000,4g vitamin C and 8g H2O2Mixture.Heating stirring 6h uses 30Wt% after reaction at 80 DEG C
The pH of reaction system is adjusted to 6-8 by the solution of NaOH, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 4
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 10g acrylic acid is added,
100gTPEG-2400,4 vitamin Cs and 8g H2O2Mixture.Heating stirring 6h uses 30Wt% after reaction at 80 DEG C
The pH of reaction system is adjusted to 6-8 by the solution of NaOH, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 5
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 10g acrylic acid, 100g is added
TPEG-2400,4g vitamin C and 8g H2O2Mixture.6h stirring is heated at 60 DEG C, after reaction, uses 30Wt%
The pH of reaction system is adjusted to 6-8 by the solution of NaOH, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 6
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100 β-CD will be added in metanitrophenol that above-mentioned steps obtain, react at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above the preparation of the polycarboxylate water-reducer of-CD containing β: is placed in four-hole boiling flask
In, and 10g acrylic acid, 100g TPEG-2400,4g vitamin C and 8g H is added2O2Mixture.The heating stirring at 100 DEG C
The pH of reaction system is adjusted to 6-8 with the solution of 30Wt%NaOH after reaction by 6h, obtains the polycarboxylic acids diminishing of-CD containing β
Agent.
Embodiment 7
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 10g acrylic acid, 100g is added
TPEG-2400,8g H2O2Mixture.The heating stirring 6h at 80 DEG C after reaction will be anti-with the solution of 30Wt%NaOH
It answers the pH of system to be adjusted to 6-8, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 8
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.100g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 10g acrylic acid, 100g is added
The mixture of TPEG-2400,8g ammonium persulfate.The heating stirring 6h at 80 DEG C, after reaction, with the solution of 30Wt%NaOH
The pH of reaction system is adjusted to 6-8, obtains the polycarboxylate water-reducer of-CD containing β.
Embodiment 9
(1) metanitrophenol 25g, acryloyl chloride 20g are added in three-necked flask, reacts 6h at room temperature and obtains m-nitro
Phenolic ester.20g β-CD is added in the metanitrophenol that above-mentioned steps are obtained, reacts at room temperature, obtains modified β-after reacting 6h
CD monomer.
(2) modified β-CD monomer 20g obtained above is placed in four-hole boiling flask, and 8g acrylic acid, 100g is added
The mixture of TPEG-2400,8g azodiisobutyronitrile.The heating stirring 6h at 80 DEG C, after reaction, with 30Wt%NaOH's
The pH of reaction system is adjusted to 6-8 by solution, obtains the polycarboxylate water-reducer of-CD containing β.
Test case
Table 1 is the paste flowing degree of the polycarboxylate water-reducer of-CD containing β.When test, using reference cement, according to GB/T8077-
2000 " Methods for testing uniformity of concrete admixture " test the paste flowing degree of cement, the ratio of mud 0.35.
The paste flowing degree of the 1 polycarboxylate water-reducer of-CD containing β of table
Seen from table 1, when volume is 0.1wt% and 0.2wt%, corresponding is the-CD containing β of different polymeric monomer preparations
The paste flowing degree of polycarboxylate water-reducer.As it can be seen that polycarboxylate water-reducer produced by the present invention has good fluidity.
Table 2 is the GPC characterization for changing the type of catalyst and obtaining.
The GPC of the 2 polycarboxylate water-reducer of-CD containing β of table is characterized
As can be seen from Table 2, the type for changing catalyst will affect the profile exponent of polymerization.It is learnt from the data of table 2, the present invention
Polycarboxylate water-reducer distribution uniform obtained.
As seen from the above-described embodiment, appropriate initiator type, the selection of polymeric monomer and dosage are chosen, controls reaction temperature
Degree and reaction time, so that it may obtain excellent polycarboxylate water-reducer.By the modified β-CD of high activity small molecule reaction object, pass through
It is that a big innovative point and the present invention of the invention seek weight that the structure of monomer, which introduces steric hindrance and the method for electrostatic repulsion,
The range of point protection.
The above description is only an embodiment of the present invention, but embodiment of the present invention are not limited by the above embodiments,
It is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications, be
The substitute mode of effect, is included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of the polycarboxylate water-reducer containing beta-cyclodextrin, it is characterised in that include the following steps:
(1) acryloyl chloride and metanitrophenol are mixed, is stirred to react, obtains acrylic acid m-nitro phenolic ester；Then by β-CD
It is added in acrylic acid m-nitro phenolic ester, is stirred to react, obtain modified β-CD monomer；
(2) β-CD monomer, acrylic acid, polyethers polymeric monomer, initiator will be modified to mix, heating reaction is obtained containing beta-cyclodextrin
Polycarboxylate water-reducer.
2. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(1) in, acryloyl chloride is 10~40 mass parts, and metanitrophenol is 10~50 mass parts, and β-CD is 100 mass parts.
3. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(1) in, the temperature of the reaction is room temperature, and the time of reaction is 3~8h；The rate of stirring is 100~300r/min.
4. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(2) in, polyethers polymeric monomer is 100 mass parts, and acrylic acid is 2~40 mass parts, and modified β-CD monomer is 2~50 mass parts,
Initiator is 0.1~20 mass parts.
5. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(2) in, the initiator is azodiisobutyronitrile, ammonium persulfate, hydrogen peroxide, hydrogen peroxide/vitamin C.
6. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(2) in, the temperature of the heating reaction is 60~120 DEG C, and the time of reaction is 5~15h.
7. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(2) in, the polyethers polymeric monomer is TPEG-1000, TPEG-2400, APEG-1200 or APEG-2400.
8. the preparation method of the polycarboxylate water-reducer according to claim 1 containing beta-cyclodextrin, it is characterised in that: step
(2) in, after reaction, the pH of reaction system is adjusted to 6~8 with the solution of 30Wt%NaOH.
9. a kind of polycarboxylate water-reducer containing beta-cyclodextrin, it is characterised in that: using any one of claim 1~8 method system
It is standby to obtain.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113583190A (en) * | 2021-07-12 | 2021-11-02 | 武汉理工大学 | 4-tert-butylcalix [4] arene modified polycarboxylic acid water reducer and preparation method thereof |
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2018
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| CN103333300A (en) * | 2013-06-27 | 2013-10-02 | 合肥工业大学 | Polycarboxylate-type water reducing agent with star topology and synthetical method thereof |
| CN108373522A (en) * | 2018-02-12 | 2018-08-07 | 中交二航武汉港湾新材料有限公司 | The polycarboxylate water-reducer and preparation method thereof of modified cyclodextrin side-chain structure |
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Application publication date: 20190405 |