CN104478279B - A kind of polysulfonate type cement water reducing agent and preparation method thereof - Google Patents
A kind of polysulfonate type cement water reducing agent and preparation method thereof Download PDFInfo
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- CN104478279B CN104478279B CN201410833420.8A CN201410833420A CN104478279B CN 104478279 B CN104478279 B CN 104478279B CN 201410833420 A CN201410833420 A CN 201410833420A CN 104478279 B CN104478279 B CN 104478279B
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Abstract
The invention discloses a kind of polysulfonate type cement water reducing agent and preparation method thereof, belong to fine chemicals preparing technical field.This polysulfonate type cement water reducing agent is made up of following raw material: allyl polyethenoxy ether, anhydride, catalyst and NaHSO3.Preparation includes: after first being mixed with anhydride and catalyst by allyl polyethenoxy ether, heats up and is stirred continuously, and generates two ends and the middle polymer being respectively provided with double bond after reaction 6h～10h；Regulation temperature dropping NaHSO3,I.e. prepare polysulfonate type cement water reducing agent.The inventive method is easy and simple to handle, and process is easily-controllable, low for equipment requirements, environmental friendliness, is suitable for industrialization large-scale production；The polysulfonate type cement water reducing agent prepared through the inventive method has excellent diminishing and dispersive property.
Description
Technical field
The invention belongs to fine chemicals preparing technical field, be specifically related to a kind of polysulfonate type cement diminishing
Agent and preparation method thereof.
Background technology
At present, according to water reducer diminishing and the ability of enhancing, water reducer can be largely classified into four big classes: one be with
Lignins is main ordinary water-reducing agent, and such water reducer mostly is powdery low air-entraining performance retarder, has micro-drawing
Gas, can improve the impervious freeze thawing performance of concrete.But the molecular structure of such water reducer is based on aromatic rings,
Compliance is poor.Two is the high efficiency water reducing agent with naphthalene water reducer as representative, and this kind of water reducer is with environmental protection
Higher plasticity is resistance to by parent.But naphthalene water reducer is restricted by molecular structure, it is impossible to fundamentally improve
The function of slump protection of concrete and the excessive problem of volume.Three is polycarboxylic acid high-performance water reducer, this kind of diminishing
Agent has ultra-dispersed property becomes the focus of research at present, and development is swift and violent.But it is weak to hard water, volume can be affected.
Four is aliphatic sulfonic salt water reducer, and it has excellent diminishing characteristic, and wherein sulfonic group hydrophilic is strong, energy
Forceful electric power lotus is provided, also is able to resistance to hard water simultaneously.Aliphatic sulfonic salt water reducer grew up in recent years
One of main non-naphthalene water reducer, it be with acetone, formaldehyde, sodium sulfite, sodium pyrosulfite etc. be main
Raw material, its production technology is simple, with short production cycle.But many based on single sulfonic group and disulfonic acid base, it subtracts
Aqueous can not be good, and raw material has pollution, irritant abnormal smells from the patient simultaneously, does not meets the requirement of green production.
Summary of the invention
It is an object of the invention to provide a kind of polysulfonate type cement water reducing agent and preparation method thereof, this is prepared
Method is simple to operate, environmental friendliness, and the polysulfonate type cement water reducing agent prepared through the method has excellent
Diminishing and dispersive property.
The present invention is to be achieved through the following technical solutions:
A kind of polysulfonate type cement water reducing agent, is made up of following raw material: allyl polyethenoxy ether, anhydride,
Catalyst and NaHSO3；Wherein, anhydride is 1.0:(2.0～2.4 with the mol ratio of allyl polyethenoxy ether),
Catalyst accounts for the 0.5%～0.9% of anhydride and allyl polyethenoxy ether gross mass, anhydride and NaHSO3Mole
Ratio is 1.0:(3.0～3.6).
The molecular weight of described allyl polyethenoxy ether is 500～2500.
Described anhydride is phthalic anhydride or contains alkene, the anhydride of alkynes unsaturated bond.
The described anhydride containing alkene, alkynes unsaturated bond is maleic anhydride or hexene diacid acid anhydride.
Described catalyst is p-methyl benzenesulfonic acid, methanesulfonic acid or benzoic acid.
The preparation method of a kind of polysulfonate type cement water reducing agent, comprises the following steps:
1) raw material is taken: allyl polyethenoxy ether, anhydride, catalyst and NaHSO3；
Wherein, anhydride is 1.0:(2.0～2.4 with the mol ratio of allyl polyethenoxy ether), catalyst accounts for anhydride
With the 0.5%～0.9% of allyl polyethenoxy ether gross mass, anhydride and NaHSO3Mol ratio be 1.0:
(3.0～3.6)；
2) it is warming up to allyl polyethenoxy ether make it liquefy completely, is subsequently adding anhydride and catalyst,
Stirring reaction at 100～130 DEG C, then adds NaHSO in reaction system3；
3) make reaction system continuously stirred reaction at 80～100 DEG C, prepare polysulfonate type cement water reducing agent.
Step 2) in make allyl polyethenoxy ether liquefy completely intensification be that temperature is risen to 50 DEG C～75 DEG C.
Step 2) described in the stirring response time be 6～10h；Step 3) described in the continuously stirred response time
It is 3～5h.
Step 2) in reaction system add NaHSO3It is by NaHSO3It is configured to quality by proportioning raw materials
Mark is that the solution of 20% drips in reaction system.
The molecular weight of described allyl polyethenoxy ether is 500～2500；Described anhydride is phthalic anhydride, horse
Come anhydride or hexene diacid acid anhydride；Described catalyst is p-methyl benzenesulfonic acid, methanesulfonic acid or benzoic acid.
Compared with prior art, the present invention has a following useful technique effect:
The polysulfonate type cement water reducing agent of the present invention by allyl polyethenoxy ether, anhydride, catalyst and
NaHSO3Composition, the active stronger hydroxyl of allyl polyethenoxy ether and double bond, with anhydride reaction and
NaHSO3Effect under after sulfonation, prepare containing three sulfonic water-soluble polymers.Three sulfonic group energy
There is provided forceful electric power lotus, it is possible to be stretched in aqueous solution, be formed with certain thickness hydrophilic solid adsorption layer, from
And be formed with certain thickness hydrophilic solid adsorption layer at the cement particle surface adsorbed and preferably play it
Water-reduction, additionally it is possible to resistance to hard water.Meanwhile, contained polyethers key can strengthen sterically hindered and molecule is soft
Pliable, when cement granules near time, adsorption layer starts overlap, it is possible to produce sterically hindered between cement granules
Effect, overlap is the most, and sterically hindered repulsion is the biggest, the biggest to the obstruction of cohesion between cement granules,
Thus enhance the dispersive property of cement.
Polysulfonate type cement water reducing agent preparation method disclosed by the invention, first by allyl polyethenoxy ether
After mixing with anhydride and catalyst, heating up and be stirred continuously, reaction generates two ends and centre and is respectively provided with double bond
Polymer, then regulates temperature, by dropping NaHSO3Can be prepared by trisulfonic acid base cement water reducing agent.The party
Method is easy and simple to handle, and process is easily-controllable, low for equipment requirements, environmental friendliness, is suitable for industrialization large-scale production.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, described in the present invention
Explain rather than limit.
Embodiment 1
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, maleic anhydride, p-methyl benzenesulfonic acid and the NaHSO of 5003；
Wherein, maleic anhydride is 1.0:2.0 with the mol ratio of allyl polyethenoxy ether；P-methyl benzenesulfonic acid accounts for maleic acid
Acid anhydride and the 0.6% of allyl polyethenoxy ether gross mass；NaHSO3It is 3.6:1.0 with the mol ratio of maleic anhydride.
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 50 DEG C completely after liquefaction, is rapidly added maleic anhydride and right
Toluenesulfonic acid, control temperature be 100 DEG C, be stirred continuously reaction 10h after by NaHSO3It is formulated as quality to divide
Number is the solution dropping of 20%, and keeping temperature is 80 DEG C, and stir about 5h can be prepared by trisulfonic acid base water reducer.
Embodiment 2
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, maleic anhydride, p-methyl benzenesulfonic acid and the NaHSO of 15003；
Wherein, maleic anhydride is 1.0:2.1 with the mol ratio of allyl polyethenoxy ether；P-methyl benzenesulfonic acid accounts for maleic acid
Acid anhydride and the 0.6% of allyl polyethenoxy ether gross mass；NaHSO3It is 3.2:1.0 with the mol ratio of maleic anhydride.
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 60 DEG C completely after liquefaction, is rapidly added maleic anhydride and right
Toluenesulfonic acid, control temperature be 110 DEG C, be stirred continuously reaction 8h after by NaHSO3It is formulated as mass fraction
It it is the solution dropping of 20%,Keeping temperature is 90 DEG C, and stir about 4h can be prepared by trisulfonic acid base water reducer.
Embodiment 3
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, maleic anhydride, p-methyl benzenesulfonic acid and the NaHSO of 25003；
Wherein, maleic anhydride is 1.0:2.4 with the mol ratio of allyl polyethenoxy ether；P-methyl benzenesulfonic acid accounts for maleic acid
Acid anhydride and the 0.9% of allyl polyethenoxy ether gross mass；NaHSO3It is 3.4:1.0 with the mol ratio of maleic anhydride.
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 75 DEG C completely after liquefaction, is rapidly added maleic anhydride and right
Toluenesulfonic acid, control temperature be 130 DEG C, be stirred continuously reaction 6h after by NaHSO3It is formulated as mass fraction
Being the solution dropping of 20%, keeping temperature is 100 DEG C, and stir about 3h can be prepared by trisulfonic acid base water reducer.
Embodiment 4
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, hexene diethyl anhydride, p-methyl benzenesulfonic acid and the NaHSO of 15003；
Wherein, hexene diethyl anhydride is 1.0:2.3 with the mol ratio of allyl polyethenoxy ether；P-methyl benzenesulfonic acid accounts for oneself
Alkene diethyl anhydride and the 0.8% of allyl polyethenoxy ether gross mass；NaHSO3With rubbing of hexene diethyl anhydride
That ratio is 3.5:1.0.
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 65 DEG C completely liquefaction after, be rapidly added hexene diethyl anhydride
And p-methyl benzenesulfonic acid, control temperature be 120 DEG C, be stirred continuously reaction 7h after by NaHSO3It is formulated as quality
Mark is the solution dropping of 20%, and keeping temperature is 85 DEG C, and stir about 4h can be prepared by trisulfonic acid base diminishing
Agent.
Embodiment 5
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, phthalic anhydride, benzoic acid and the NaHSO of 15003；
Wherein, benzoic acid is 1.0:2.2 with the mol ratio of allyl polyethenoxy ether；Benzoic acid accounts for phthalic anhydride
With allyl polyethenoxy ether gross mass 0.7%；NaHSO3With the mol ratio of phthalic anhydride it is
3.0:1.0。
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 50 DEG C completely liquefaction after, be rapidly added phthalic anhydride
And benzoic acid, control temperature be 100 DEG C, be stirred continuously reaction 10h after by NaHSO3It is formulated as quality to divide
Number is the solution dropping of 20%, and keeping temperature is 95 DEG C, and stir about 4h can be prepared by trisulfonic acid base water reducer.
Embodiment 6
A kind of polysulfonate type cement water reducing agent, its raw material components and consumption are as follows:
Molecular weight is allyl polyethenoxy ether, phthalic anhydride, methanesulfonic acid and the NaHSO of 15003；
Wherein, phthalic anhydride is 1.0:2.0 with the mol ratio of allyl polyethenoxy ether；Methanesulfonic acid accounts for adjacent benzene two
Formic anhydride and the 0.5% of allyl polyethenoxy ether gross mass；NaHSO3Mol ratio with phthalic anhydride
For 3.3:1.0.
The preparation technology of this polysulfonate type cement water reducing agent:
Allyl polyethenoxy ether is to slowly warm up to 65 DEG C completely liquefaction after, be rapidly added phthalic anhydride
And methanesulfonic acid, control temperature be 130 DEG C, be stirred continuously reaction 6h after by NaHSO3It is formulated as mass fraction
It it is the solution dropping of 20%,Keeping temperature is 100 DEG C, and stir about 3h can be prepared by trisulfonic acid base water reducer.
In sum, for aliphatic sulfonic salt water reducer, if sulfonic group quantity in individual molecule is increased,
Then hydrophilic, elecrtonegativity can be greatly increased so that electrostatic repulsion is greatly improved, and water-reduction significantly improves；
Molecule introduces ehter bond simultaneously and is conducive to strengthening the compliance of polymer, and intermolecular space bit can be strengthened
Resistance, makes the dispersibility of water reducer strengthen, and preferably plays its water-reduction.Through many sulfonic acid that the present invention prepares
Salt form cement water reducing agent structure has three sulfonic groups, is stretched in aqueous solution, thus at the water adsorbed
Mud particle surface is formed with certain thickness hydrophilic solid adsorption layer and preferably plays its water-reduction.And shape
Become polyethers key with its distinctive compliance when cement granules near time, adsorption layer starts overlap, it is possible to
Producing sterically hindered effect between cement granules, overlap is the most, and sterically hindered repulsion is the biggest, between cement granules
The obstruction of cohesion is the biggest, thus enhances the dispersive property of cement.
Claims (5)
1. a polysulfonate type cement water reducing agent, it is characterised in that be made up of following raw material: pi-allyl gathers
Oxygen vinyl Ether, anhydride, catalyst and NaHSO3；Wherein, anhydride and the mol ratio of allyl polyethenoxy ether
For 1.0:(2.0～2.4), catalyst accounts for the 0.5%～0.9% of anhydride and allyl polyethenoxy ether gross mass, acid
Acid anhydride and NaHSO3Mol ratio be 1.0:(3.0～3.6)；
The molecular weight of described allyl polyethenoxy ether is 500～2500；
Described anhydride is phthalic anhydride or contains alkene, the anhydride of alkynes unsaturated bond；
The described anhydride containing alkene, alkynes unsaturated bond is maleic anhydride or hexene diacid acid anhydride；
Described catalyst is p-methyl benzenesulfonic acid, methanesulfonic acid or benzoic acid.
2. the preparation method of a polysulfonate type cement water reducing agent, it is characterised in that comprise the following steps:
1) raw material is taken: allyl polyethenoxy ether, anhydride, catalyst and NaHSO3；
Wherein, anhydride is 1.0:(2.0～2.4 with the mol ratio of allyl polyethenoxy ether), catalyst accounts for anhydride
With the 0.5%～0.9% of allyl polyethenoxy ether gross mass, anhydride and NaHSO3Mol ratio be 1.0:
(3.0～3.6)；
2) it is warming up to allyl polyethenoxy ether make it liquefy completely, is subsequently adding anhydride and catalyst,
Stirring reaction at 100～130 DEG C, then adds NaHSO in reaction system3；
3) make reaction system continuously stirred reaction at 80～100 DEG C, prepare polysulfonate type cement water reducing agent；
The molecular weight of described allyl polyethenoxy ether is 500～2500；Described anhydride is phthalic anhydride, horse
Come anhydride or hexene diacid acid anhydride；Described catalyst is p-methyl benzenesulfonic acid, methanesulfonic acid or benzoic acid.
The preparation method of a kind of polysulfonate type cement water reducing agent the most according to claim 2, its feature
Be, step 2) in make allyl polyethenoxy ether liquefy completely intensification be that temperature is risen to 50 DEG C～75 DEG C.
The preparation method of a kind of polysulfonate type cement water reducing agent the most according to claim 2, its feature
Be, step 2) described in the stirring response time be 6～10h；Step 3) described in continuously stirred reaction time
Between be 3～5h.
The preparation method of a kind of polysulfonate type cement water reducing agent the most according to claim 2, its feature
Be, step 2) in reaction system add NaHSO3It is by NaHSO3It is configured to matter by proportioning raw materials
Amount mark is that the solution of 20% drips in reaction system.
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| CN107501482A (en) * | 2017-09-20 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of low responsive type polycarboxylate water-reducer |
| CN109694446B (en) * | 2018-12-14 | 2021-03-30 | 上海台界化工有限公司 | Synthesis method of solid polycarboxylate superplasticizer |
| CN111777721B (en) * | 2020-07-30 | 2021-07-02 | 天津市飞龙砼外加剂有限公司 | Enhanced polycarboxylate superplasticizer and preparation method thereof |
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| CN103159899B (en) * | 2012-12-21 | 2015-01-07 | 新疆德蓝股份有限公司 | Preparing method for polycarboxylate water reducing agent |
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