CN109021179A - A kind of phosphonic acids based polyalcohol and preparation method thereof and phosphate mother liquor - Google Patents
A kind of phosphonic acids based polyalcohol and preparation method thereof and phosphate mother liquor Download PDFInfo
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- CN109021179A CN109021179A CN201810763953.1A CN201810763953A CN109021179A CN 109021179 A CN109021179 A CN 109021179A CN 201810763953 A CN201810763953 A CN 201810763953A CN 109021179 A CN109021179 A CN 109021179A
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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
- C04B24/243—Phosphorus-containing polymers
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to chemical building material fields, and in particular to a kind of phosphonic acids based polyalcohol and preparation method thereof and phosphate water-reducing agent.The phosphonic acids based polyalcohol includes structural unit, the structural unit derived from unsaturated acids and the structural unit derived from unsaturated phosphonic acids derived from unsaturated polyether, the unsaturated polyether is isobutenyl polyoxyethylene ether, and the structural unit derived from unsaturated polyether relative to 185-205 parts by weight, the content of structural unit derived from unsaturated acids is 20-30 parts by weight, and the content of the structural unit derived from unsaturated phosphonic acids is 5-10 parts by weight.Phosphonic acid base water-reducing agent provided by the invention not only has water-reducing rate height, retarding effect good, well adapting to property is all had with the cement of different cultivars, side effect will not be generated because of the difference of cement type, and its preparation process is simple, reaction carries out at normal temperature, whole process temperature is without control, and the reaction time is short, and low energy consumption, it is at low cost, safety coefficient is high, pollution-free, easy to industrialized production.
Description
Technical field
The invention belongs to chemical building material fields, and in particular to a kind of phosphonic acids based polyalcohol and preparation method thereof and phosphoric acid
Base water-reducing agent.
Background technique
Polycarboxylate water-reducer is as one of modern high performance concrete important component, since it is with volume
It is low, diminishing is high, adaptability is good, adjustability of structure is strong and it is environmentally protective the advantages that, obtain huge development and wide in recent ten years
General application.But other performances of polycarboxylate water-reducer are often relatively simple, the construction requirement not being able to satisfy under specified conditions,
Such as concrete construction often requires that and delays setting time, especially in the hot summer, temperature is high, concrete coagulating time contracting
It is short, it loses flowability, brings greater inconvenience to construction soon, or be when pouring mass concrete, it is necessary to prolong
The setting time of long concrete avoids generating cracking because of temperature stress.But the retarding effect of polycarboxylate water-reducer itself is ratio
It is weaker, it is necessary to by reaching said effect with compounding for retarder.Although compounded technology can solve subproblem, but according to
By compounding the limitation solved the problems, such as, but also the original water-reducing property of water-reducing agent is made sacrifices, the retarder being additionally added
Also increase cost.In addition, compounding retarder diminishing agent solution be also possible that layering, precipitating, corruption, it is smelly phenomena such as,
Properties of product are unstable, therefore are badly in need of developing a kind of water-reducing rate height, and retarding effect is obvious, and properties of product are stablized, and to coagulation
The late-enhancement effect of soil also very ideal high-performance water reducing agent.
CN107337376A is disclosed using polycarboxylate water-reducer and water-retaining agent, defoaming agent, retarder, polydimethylsiloxanes
Alkane/Nano composite material of montmorillonite is compounded, and the polycarboxylate water-reducer with extra retarded set effect is obtained.CN102241489B is public
It has opened and allyl polyglycol is used (to count equal relative molecular mass as 600-2400), methyl acrylate, maleic anhydride, lignin
Sodium sulfonate, sucrose fatty ester, under the action of ammonium persulfate directly synthesis have retarding effect water-reducing agent, but lignin,
The reactivity of sucrose fatty ester is lower, and reaction is incomplete.
Summary of the invention
The purpose of the invention is to overcome existing polycarboxylate water-reducer presence that cannot combine diminishing and slow setting, and
It is used in compounding the defect that will affect water-reducing agent performance with retarder, and a kind of phosphonic acids based polyalcohol is provided and preparation method thereof and phosphorus
Acidic group water-reducing agent.
Specifically, the present invention provides a kind of phosphonic acids based polyalcohols, wherein the phosphonic acids based polyalcohol includes being derived from insatiable hunger
It is described with the structural unit, the structural unit derived from unsaturated acids and the structural unit derived from unsaturated phosphonic acids of polyethers
Unsaturated polyether is isobutenyl polyoxyethylene ether, and the structure derived from unsaturated polyether relative to 185-205 parts by weight
Unit, the content of the structural unit derived from unsaturated acids are 20-30 parts by weight, the structural unit derived from unsaturated phosphonic acids
Content is 5-10 parts by weight.
Preferably, the number-average molecular weight of the unsaturated polyether is 600-3000, preferably 2400-3000.
Preferably, the unsaturated acids is acrylic acid and/or methacrylic acid.
Preferably, the unsaturated phosphonic acids is styryl phosphonic acid and/or vinyl phosphonic acid.
Preferably, the number-average molecular weight of the phosphonic acid base polycarboxylate water-reducer is 30000-50000.
The present invention also provides a kind of preparation methods of phosphonic acids based polyalcohol, wherein this method include by unsaturated polyether,
Unsaturated acids and unsaturated phosphonic acids carry out Raolical polymerizable in the presence of radical initiator and chain-transferring agent.
A kind of specific embodiment according to the present invention, the radical initiator are redox initiator, the phosphine
The preparation method of acid-based polymer the following steps are included:
(1) unsaturated acids and unsaturated phosphonic acids are configured to the aqueous solution that concentration is 60-70wt%, are denoted as first
Solution, and by redox initiator reducing agent and chain-transferring agent be configured to the aqueous solution that concentration is 1-5wt%, be denoted as the
Two solution；
(2) unsaturated polyether is configured to the aqueous solution that concentration is 30-50wt%, the Redox Initiator is added
First solution and the second solution is added dropwise simultaneously again later in oxidant in agent, and heat preservation carries out radical polymerization after completion of dropwise addition
Close reaction；
(3) pH value of the product of the Raolical polymerizable is adjusted to 6-7.
Preferably, the dosage of the unsaturated polyether is 185-205 parts by weight, and the dosage of the unsaturated acids is 20-30
Parts by weight, the dosage of the unsaturation phosphonic acids are 5-10 parts by weight, and the dosage of the oxidant is 1.5-2.5 parts by weight, described
The dosage of reducing agent is 0.2-0.8 parts by weight, and the dosage of the chain-transferring agent is 0.6-1.1 parts by weight.
Preferably, the number-average molecular weight of the unsaturated polyether is 600-3000, preferably 2400-3000.
Preferably, the unsaturated acids is acrylic acid and/or methacrylic acid.
Preferably, the unsaturated phosphonic acids is styryl phosphonic acid and/or vinyl phosphonic acid.
Preferably, the oxidant is selected from least one of hydrogen peroxide, potassium peroxydisulfate and ammonium persulfate；
Preferably, the reducing agent is selected from least one of ascorbic acid, sodium hydrogensulfite and tartaric acid；
Preferably, the chain-transferring agent is selected from least one of thioacetic acid, mercaptopropionic acid and methylpropene sodium sulfonate.
Preferably, it is 0-30 DEG C that the condition of the Raolical polymerizable, which includes temperature, time 3-6h.
The present invention also provides phosphonic acids based polyalcohols prepared by the above method.
In addition, the present invention also provides a kind of phosphate water-reducing agents, wherein diminishing contained in the phosphate water-reducing agent
Agent mother liquor is above-mentioned phosphoric acid based polyalcohol.
Preferably, the solid content of the phosphate water-reducing agent is 30-50wt%.
The beneficial effects of the present invention are:
1, the phosphonyl group with slow setting function is introduced in phosphonic acid base polycarboxylate water-reducer provided by the invention, it can be with
Ca effectively in chelating cement2+, the complexing deposition film of formation prevents the aquation of cement granules, the hydration rate of cement caused to subtract
Slowly, to be obviously prolonged the setting time of cement system, slow setting has been achieved the effect that.
2, phosphonic acid base polycarboxylate water-reducer provided by the invention has an advantage that water-reducing rate is high, retarding effect is good, and with not
Cement with kind all has well adapting to property, will not generate side effect because of the difference of cement type.
3, the preparation process of phosphonic acid base polycarboxylate water-reducer provided by the invention is simple, and reaction carries out at normal temperature, entirely
Process temperature is without control, and the reaction time is short, and low energy consumption, at low cost, and safety coefficient is high, pollution-free, easy to industrialized production.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.
The present invention will be described in detail by way of examples below.
Embodiment 1
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 15 parts by weight water and obtain the first solution, by reducing agent and chain-transferring agent
It is dissolved in 31.2 parts by weight water and obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 277.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after five minutes, while the first solution and the second solution is added dropwise in stirring, and time for adding is 2 hours, completion of dropwise addition
2 hours are kept the temperature afterwards, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 6.0, obtains
It is phosphate water-reducing agent, solid content 40wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 33629.
Embodiment 2
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 19.32 parts by weight water and obtain the first solution, by reducing agent and chain tra nsfer
Agent, which is dissolved in 74.1 parts by weight water, obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 277.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after ten minutes, while the first solution and the second solution is added dropwise in stirring, and time for adding is 3 hours, and knot is added dropwise
1 hour is kept the temperature after beam, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 7.0, obtains
It is phosphate water-reducing agent, solid content 37wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 39143.
Embodiment 3
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 21 parts by weight water and obtain the first solution, by reducing agent and chain-transferring agent
It is dissolved in 50.7 parts by weight water and obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 277.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after stirring 8 minutes, while the first solution and the second solution is added dropwise, time for adding is 3 hours, completion of dropwise addition
1.5 hours are kept the temperature afterwards, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 6.5, obtains
It is phosphate water-reducing agent, solid content 40wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 42164.
Embodiment 4
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 19.2 parts by weight water and obtain the first solution, by reducing agent and chain tra nsfer
Agent, which is dissolved in 54.6 parts by weight water, obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 292.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after five minutes, while the first solution and the second solution is added dropwise in stirring, and time for adding is 4 hours, completion of dropwise addition
2 hours are kept the temperature afterwards, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 6.0, obtains
It is phosphate water-reducing agent, solid content 39wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 32931.
Embodiment 5
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 20.76 parts by weight water and obtain the first solution, by reducing agent and chain tra nsfer
Agent, which is dissolved in 39 parts by weight water, obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 307.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after stirring 8 minutes, while the first solution and the second solution is added dropwise, time for adding is 3 hours, completion of dropwise addition
2 hours are kept the temperature afterwards, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 6.5, obtains
It is phosphate water-reducing agent, solid content 40wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 38631.
Embodiment 6
(1) raw material composition is as follows:
(2) acrylic acid and styryl phosphonic acid are dissolved in 21 parts by weight water and obtain the first solution, by reducing agent and chain-transferring agent
It is dissolved in 42.9 parts by weight water and obtains the second solution；
(3) unsaturated polyether is added in reaction kettle together with the water of 277.5 parts by weight, the stirring and dissolving under room temperature
Afterwards, oxidant is added, after stirring 8 minutes, while the first solution and the second solution is added dropwise, time for adding is 3 hours, completion of dropwise addition
2 hours are kept the temperature afterwards, carries out Raolical polymerizable；
(4) it after Raolical polymerizable, with the sodium hydroxide solution adjustment pH value of 30% mass concentration to 6.5, obtains
It is phosphate water-reducing agent, solid content 40wt%, the equal molecule of number of phosphoric acid based polyalcohol contained therein to clear solution
Amount is 41187.
Comparative example 1
185g isobutenyl polyoxyethylene ether (number-average molecular weight 2400) and 277.5g water are added reaction kettle, under room temperature
Stirring to unsaturated polyoxyethylene ether dissolves, and 1.5g ammonium persulfate is added, then respectively to being added dropwise to 40g acrylic acid in reaction kettle
Aqueous solution (being mixed by 25g acrylic acid and 15g water) and 44g chain-transferring agent aqueous solution (by 0.7g mercaptopropionic acid,
0.4g ascorbic acid and 42.9g water mix), time for adding was controlled at 3 hours, and the reaction was continued 1 hour after being added dropwise to complete, and was made
Polymerization reaction is complete, and the sodium hydroxide solution that 30% mass concentration is added adjusts pH to 6.0, obtains phosphate water-reducing agent, Gu
Content is 39wt%, and the number-average molecular weight of phosphoric acid based polyalcohol contained therein is 42556.
Compliance test result
1, according to GB/T 1346-2011, " cement normal consistency water consumption, is stabilized at setting time for cement setting time measurement
Property the method for inspection " standard, wherein the volume of PC (polycarboxylate water-reducer) be solid weight 0.4%.The slow setting used in table 1
Agent is the sodium gluconate of Shanghai traditional Chinese medicines company purchase, and additional amount is the 2% of water-reducing agent weight.
1 cement setting time of table (20 DEG C of test temperature)
Note: the volume of retarder is measured on the basis of cement weight.
2, concrete water-reducing ratio test has been carried out to water-reducing agent prepared by the present invention referring to GB/T8076-2008 standard, coagulated
Knot time test and intensity test, concrete mix are shown in Table 1, and experimental result is shown in Table 2 and table 3.
2 concrete mix of table (unit :/kg/m3)
| Label | Fujian good fortune cement | Water | Sand | Stone | Miberal powder | Flyash |
| C30 snag | 242 | 165 | 792 | 988 | 62 | 86 |
3 concrete coagulating time of table and compression strength (20 DEG C of test temperature)
Upper table data show, phosphate water-reducing agent provided by the invention not only water-reducing rate with higher, but also can be with
Extend the setting time of concrete, and its concrete seven day and 28 days compression strength can satisfy construction requirement.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of phosphonic acids based polyalcohol, which is characterized in that the phosphonic acids based polyalcohol includes the structure list derived from unsaturated polyether
Member, the structural unit derived from unsaturated acids and the structural unit derived from unsaturated phosphonic acids, the unsaturated polyether are different
Cyclobutenyl polyoxyethylene ether, and the structural unit derived from unsaturated polyether relative to 185-205 parts by weight are derived from insatiable hunger
Content with the structural unit of acid is 20-30 parts by weight, and the content of the structural unit derived from unsaturated phosphonic acids is 5-10 weight
Part.
2. phosphonic acids based polyalcohol according to claim 1, wherein
The number-average molecular weight of the unsaturated polyether is 600-3000, preferably 2400-3000；
The unsaturated acids is acrylic acid and/or methacrylic acid；
The unsaturation phosphonic acids is styryl phosphonic acid and/or vinyl phosphonic acid.
3. phosphonic acids based polyalcohol according to claim 1 or 2, wherein the number-average molecular weight of the phosphonic acids based polyalcohol is
30000-50000。
4. a kind of preparation method of phosphonic acids based polyalcohol, which is characterized in that this method include by unsaturated polyether, unsaturated acids with
And unsaturated phosphonic acids carries out Raolical polymerizable in the presence of radical initiator and chain-transferring agent.
5. the preparation method according to claim 4, wherein the radical initiator is redox initiator, described
The preparation method of phosphonic acids based polyalcohol the following steps are included:
(1) unsaturated acids and unsaturated phosphonic acids are configured to the aqueous solution that concentration is 60-70wt%, it is molten is denoted as first
Liquid, and by redox initiator reducing agent and chain-transferring agent be configured to concentration be 1-5wt% aqueous solution, be denoted as second
Solution；
(2) unsaturated polyether is configured to the aqueous solution that concentration is 30-50wt%, be added in the redox initiator
Oxidant, later again simultaneously first solution and the second solution is added dropwise, after completion of dropwise addition heat preservation carry out free radical polymerization it is anti-
It answers；
(3) pH value of the product of the Raolical polymerizable is adjusted to 6-7.
6. preparation method according to claim 5, wherein the dosage of the unsaturated polyether is 185-205 parts by weight, institute
The dosage for stating unsaturated acids is 20-30 parts by weight, and the dosage of the unsaturation phosphonic acids is 5-10 parts by weight, the use of the oxidant
Amount is 1.5-2.5 parts by weight, and the dosage of the reducing agent is 0.2-0.8 parts by weight, and the dosage of the chain-transferring agent is 0.6-1.1
Parts by weight.
7. preparation method according to claim 5, wherein
The number-average molecular weight of the unsaturated polyether is 600-3000, preferably 2400-3000；
The unsaturated acids is acrylic acid and/or methacrylic acid；
The unsaturation phosphonic acids is styryl phosphonic acid and/or vinyl phosphonic acid；
The oxidant is selected from least one of hydrogen peroxide, potassium peroxydisulfate and ammonium persulfate；
The reducing agent is selected from least one of ascorbic acid, sodium hydrogensulfite and tartaric acid；
The chain-transferring agent is selected from least one of thioacetic acid, mercaptopropionic acid and methylpropene sodium sulfonate.
8. the preparation method according to any one of claim 5-7, wherein the condition packet of the Raolical polymerizable
Including temperature is 0-30 DEG C, time 3-6h.
9. the phosphonic acids based polyalcohol that the method as described in any one of claim 4-8 is prepared.
10. a kind of phosphate water-reducing agent, which is characterized in that water-reducing agent mother liquor contained in the phosphate water-reducing agent is wanted for right
Seek phosphoric acid based polyalcohol described in any one of 1-3 and 9.
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| CN115746217B (en) * | 2022-11-14 | 2024-04-26 | 清华大学 | Alkali-activated cementing material water reducer and application thereof |
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