CN106365493B - Anti- chamotte mould dispersant of a kind of guarantor's modeling and preparation method thereof - Google Patents
Anti- chamotte mould dispersant of a kind of guarantor's modeling and preparation method thereof Download PDFInfo
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- CN106365493B CN106365493B CN201510438859.5A CN201510438859A CN106365493B CN 106365493 B CN106365493 B CN 106365493B CN 201510438859 A CN201510438859 A CN 201510438859A CN 106365493 B CN106365493 B CN 106365493B
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- dispersant
- monomethyl ether
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- glycol monomethyl
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Abstract
The invention discloses a kind of guarantors to mould anti-chamotte mould dispersant and preparation method thereof, the comb shaped structure of traditional carboxylic acid molecules is presented in the dispersant main chain, side chain is spherical super cladodification molecule and long-chain ethylene oxide polyethers dual structure, spherical super cladodification molecule provides soil encapsulating structure, esterified group offer sustained release guarantor's plasticity energy of long-chain ethylene oxide polyethers and main chain.For the dispersant of the present invention while with excellent guarantor's plasticity energy, anti-mud performance reaches 8% or more.
Description
Technical field
The present invention relates to a kind of dispersants, and in particular to a kind of to have both dispersant and its preparation side for protecting modeling and anti-mud performance
Method belongs to cement dispersants field.
Background technology
Cement powder is easy to reunite certainly since surface energy is high, thus its dispersion technology becomes the key technology ring of application
Section.The dispersant applied in cement-based material is commonly referred to as water-reducing agent, is that molecular weight arrives tens of thousands of water solubilitys thousands of mostly
High molecular polymer.What application performance was most excellent in existing market is high performance water reducing agent of polyocarboxy acid, polycarboxylate dispersant's molecule
In comb-type structure, main chain is hydrophobic carbochain, side chain be with hydrophilic carboxyl, sulfonic group, ester group and long polyether chain etc.,
Dispersion water-reducing mechanism is the space steric effect of electrostatic repulsion effect and long side chain, compared with linear water-reducing agent, steric hindrance effect
The presence answered makes the dispersion effect of polycarboxylate water-reducer greatly improve, and this kind of water-reducing agent gradually replaces naphthalene system, aliphatic, ammonia
The development trend of the linear additive such as base sulfonate, lignin salt.
Traditional carboxylic acids dispersant often occurs in the application to concrete raw material impurity soil bad adaptability and concrete
The features such as plasticity gradual loss is big, general anti-chamotte mould product are initially having soil powerful tolerance performance, but rear wall losses
It is generally all very big.Existing market also has the report of anti-chamotte mould dispersant, such as publication【CN201010574716】Although patent
Also referred to as anti-chamotte mould carboxylic acid super plasticizer, but in terms of patent document content, not data show the anti-mud effect of patented product,
It does not refer to that product has and protects plasticity energy.Patent【CN101209911A】A kind of preparation method of carboxylic acid plasticity-maintaining agent is disclosed, but
In terms of patent document content, the anti-mud effect of patented product not data show.Patent【CN201410492164】Although public
A kind of preparation method of anti-chamotte mould carboxylic acid water reducer is opened, but in terms of patent document content, the anti-mud effect of detection is less than 1%
(soil accounts for the mass percent of cement), at the same its data in literature also show product protect plasticity it is very poor, the anti-mud performance of product and
Guarantor's plasticity can also there is ample room for improvement.
Invention content
The object of the present invention is to provide a kind of carboxylic acids dispersants and its preparation side for having both and protecting plasticity energy with anti-mud characteristic
Method.
Realizing technical solution of the invention is：Traditional carboxylic acid point is presented in a kind of anti-chamotte mould dispersant of guarantor's modeling, main chain
The comb shaped structure of son, side chain are spherical super cladodification molecule and long-chain ethylene oxide polyethers dual structure, and spherical super cladodification molecule provides
The esterified group of soil encapsulating structure, long-chain ethylene oxide polyethers and main chain provides sustained release and protects plasticity energy, structure such as formula (1)：
In formula (1), x, y, z is the positive integer no more than 15, R1、R2、R3Separately it is selected from H or methyl, R4、R5、
R6Separately it is selected from
Wherein, m is the positive integer no more than 67.
It is a kind of to protect the preparation method for moulding anti-chamotte mould dispersant, include the following steps：
1) polyethyleneimine polymeric monomer and hydroquinone, are added into acrylic or methacrylic acid, after stirring evenly
Reaction simultaneously extracts water vapour simultaneously at 130~190 DEG C, reacts 1~3 hour, and polymerizable polymeric monomer 1 is diluted with water to obtain after cooling；
2), using the concentrated sulfuric acid as catalyst, using hydroquinone as polymerization inhibitor, using hexamethylene as solvent and deicer, by poly- second
It is warming up to 105 DEG C~145 DEG C progress esterifications after glycol monomethyl ether and acrylic acid stirring, generates big with polymerizable unit
Monomer 2；
3), by polymeric monomer 2 and methylpropene sodium sulfonate mixing and water adding made from polymeric monomer made from step 1) 1 and step 2)
Mixed monomer solution is made, bottom material is used as after stirring evenly；Bottom material is warming up to 50~70 DEG C, by the water-soluble of initiator ammonium persulfate
Liquid is slowly added in bottom material, stirs copolyreaction, and after cooling plus alkali adjusts pH value 6~8 to get the dispersant.
Above-mentioned steps 1) in, the mass ratio of polyethyleneimine and acrylic or methacrylic acid is 10~90：1；Polyethylene
The molecular weight of imines is between 3500~25000；The mass ratio of polyethyleneimine and hydroquinone is 500~900：1.
Above-mentioned steps 2) in, the molecular weight of poly glycol monomethyl ether is 1000~3000.
Above-mentioned steps 2) in, the mass ratio of poly glycol monomethyl ether and acrylic or methacrylic acid is 3~10：1；Poly- second
The mass ratio of glycol monomethyl ether and the concentrated sulfuric acid is 100~500：1；The mass ratio of poly glycol monomethyl ether and hydroquinone is 300
~600：1；The mass ratio of poly glycol monomethyl ether and hexamethylene is 6~8：1；Poly glycol monomethyl ether and methylpropene sodium sulfonate
Mass ratio be 50~70：1；The mass ratio of poly glycol monomethyl ether and ammonium persulfate is 60~80：1；Poly glycol monomethyl ether
It is controlled 1~72 with the mass ratio of polyethyleneimine：1.
Above-mentioned steps 3) in, the mass concentration of the aqueous solution of ammonium persulfate is 5%.
Compared with existing other comb shape carboxylic dispersants, inventive dispersant has the characteristics that：
(1), side chain carries polyethyleneimine spherical shape group, improves space steric effect.
(2), fine mud particles can be encapsulated while spherical side chain forms space steric effect, it is significantly anti-to be formed
Mud effect, traditional carboxylic acids dispersant is in concrete in application, it can generally reach 3% hereinafter, working as to the tolerance of soil
When soil content is more than 5% in concrete raw material, the dispersion performance of carboxylic acids dispersant almost loses totally, product of the present invention
8% or more can be reached to soil tolerance performance.
(3), side chain carries ester group, protects modeling effect to have both sustained release while product has anti-mud effect, makes
Lasting plasticity retention property can be obtained by obtaining the cement-based materials such as fresh concrete.
(4), adaptability of the dispersant to soil can be adjusted by changing the molecular weight of spherical side chain, expands product
Application range meets a variety of construction environment requirements.
Specific implementation mode
The preparation of 1 dispersant of embodiment
1), amidated polyethylene imine：By 10 grams of acrylic acid and 100 grams of aq. polyethyleneimine (molecular weight
3500, solid content 50%, polyethyleneimine polymeric monomer is configured to aqueous solution use in advance, and the concentration of aqueous solution is to product of the present invention
Quality influence it is little, can suitable control) and 0.2 gram of hydroquinone be mixed evenly, reaction and extract water simultaneously at 190 DEG C
Steam reacts 1~3 hour, cooling to obtain polymerizable polymeric monomer 1.In order to improve the reactivity of later product, polymerizable big list
Body 1 can be diluted with water into 60% aqueous solution being cooled to 98 DEG C or less, wait for that later stage polymerization uses；
2), it is esterified poly glycol monomethyl ether：It is added in the poly glycol monomethyl ether (molecular weight 3000) melted at 100 grams
After 0.33 gram of hydroquinone stirs evenly, it is slow added into 1 gram of concentrated sulfuric acid, it is equal to be stirring evenly and then adding into 33 grams of acrylic acid stirrings
It is even.Constant temperature esterification is reacted 30 minutes after being warming up to 105 DEG C, and 16.67 grams of hexamethylenes are added, and carrying out back flow reaction 4 hours, (reflux is anti-
Answer temperature at 102 DEG C), draining vacuumizes (vacuumizing present invention temperature can increase, but must not be higher than 130 DEG C) vacuum degree must not
Less than -0.09MPa), stop vacuumizing after 3 hours, it is cooling to obtain polymerizable polymeric monomer 2, in order to improve the anti-of later product
Ying Xing, polymerizable polymeric monomer 2 can be diluted with water into 60% aqueous solution being cooled to 50 DEG C or less, wait for that later stage polymerization uses；
3) 2 grams of methyl-props, will be added in 2 mixed solution of polymeric monomer made from polymeric monomer made from step 1) 1 and step 2)
Alkene sodium sulfonate stirring and dissolving is uniformly used as bottom material, bottom material to be warming up to 50~70 DEG C afterwards；1.67 grams of ammonium persulfates are configured to 5%
Aqueous solution, is slowly added in bottom material and (time control is added at 2 hours or so), continues insulation reaction 1 hour, adds alkali tune after cooling
PH value is saved 6~8.Up to dispersant of the present invention.
The preparation of 2 dispersant of embodiment
1), amidated polyethylene imine：7.93 grams of methacrylic acid and 714 grams of aq. polyethyleneimine (are divided
Son amount 25000, solid content 50%) and 0.79 gram of hydroquinone be mixed evenly, at 130 DEG C reaction and simultaneously extract water steaming
Vapour reacts 1~3 hour, cooling to obtain polymerizable polymeric monomer 1.In order to improve the reactivity of later product, polymerizable polymeric monomer
1 can be diluted with water into 60% aqueous solution being cooled to 98 DEG C or less, wait for that later stage polymerization uses；
2), it is esterified poly glycol monomethyl ether：It is added in the poly glycol monomethyl ether (molecular weight 1000) melted at 100 grams
After 0.167 gram of hydroquinone stirs evenly, it is slow added into 0.2 gram of concentrated sulfuric acid, is stirring evenly and then adding into 10 grams of methacrylic acids
It stirs evenly.Constant temperature esterification is reacted 30 minutes after being warming up to 145 DEG C, and 12.5 grams of hexamethylenes are added, and carries out back flow reaction 4 hours
(back flow reaction temperature is at 102 DEG C), it is true that draining vacuumizes (vacuumizing present invention temperature can increase, but must not be higher than 130 DEG C)
Reciprocal of duty cycle must not be less than -0.09MPa), stop vacuumizing after 3 hours, it is cooling to obtain polymerizable polymeric monomer 2, in order to improve the later stage
The reactivity of product, polymerizable polymeric monomer 2 can be diluted with water into 60% aqueous solution being cooled to 50 DEG C or less, wait for that the later stage poly-
It closes and uses；
3) 1.43 grams of methyl, will be added in 2 mixed solution of polymeric monomer made from polymeric monomer made from step 1) 1 and step 2)
Sodium allylsulfonate stirring and dissolving is uniformly used as bottom material, bottom material to be warming up to 50~70 DEG C afterwards；1.25 grams of ammonium persulfates are configured to 5%
Aqueous solution, be slowly added in bottom material (be added time control at 2 hours or so), continue insulation reaction 1 hour, after cooling plus alkali
PH value is adjusted 6~8.Up to dispersant of the present invention.
The preparation of 3 dispersant of embodiment
1), amidated polyethylene imine：By 6 grams of methacrylic acid and 300 grams of polyethyleneimine (molecular weight 15000,
Solid content 50%) and 0.43 gram of hydroquinone aqueous solution be mixed evenly, at 150 DEG C reaction and simultaneously extract water vapour, instead
It answers 1~3 hour, it is cooling to obtain polymerizable polymeric monomer 1.In order to improve the reactivity of later product, polymerizable polymeric monomer 1 is cold
But it can be diluted with water into 60% aqueous solution to 98 DEG C or less, waits for that later stage polymerization uses；
2), it is esterified poly glycol monomethyl ether：It is added in the poly glycol monomethyl ether (molecular weight 2400) melted at 100 grams
After 0.222 gram of hydroquinone stirs evenly, it is slow added into 0.333 gram of concentrated sulfuric acid, is stirring evenly and then adding into 16.67 grams of acrylic acid
It stirs evenly.Constant temperature esterification is reacted 30 minutes after being warming up to 130 DEG C, and 14.3 grams of hexamethylenes are added, and carries out back flow reaction 4 hours
(back flow reaction temperature is at 102 DEG C), it is true that draining vacuumizes (vacuumizing present invention temperature can increase, but must not be higher than 130 DEG C)
Reciprocal of duty cycle must not be less than -0.09MPa), stop vacuumizing after 3 hours, it is cooling to obtain polymerizable polymeric monomer 2, in order to improve the later stage
The reactivity of product, polymerizable polymeric monomer 2 can be diluted with water into 60% aqueous solution being cooled to 50 DEG C or less, wait for that the later stage poly-
It closes and uses；
3) 1.67 grams of methyl, will be added in 2 mixed solution of polymeric monomer made from polymeric monomer made from step 1) 1 and step 2)
Sodium allylsulfonate stirring and dissolving is uniformly used as bottom material, bottom material to be warming up to 50~70 DEG C afterwards；1.43 grams of ammonium persulfates are configured to 5%
Aqueous solution, be slowly added in bottom material (be added time control at 2 hours or so), continue insulation reaction 1 hour, after cooling plus alkali
PH value is adjusted 6~8.Up to dispersant of the present invention.
To examine application performance of the product of the present invention in cement-based material, by the other carboxylic acids of products and marketing of the present invention
Dispersant is the anti-mud performance comparison test of mortar, cement paste respectively.Dispersant presses solid volume 0.2% (i.e. and cement weight
Percentage) it executes.Test method is with reference to GB8076-2008, normal sand, conch P.O42.5 Portland cements.Determination data
See contrast table 1.
1 product of the present invention of table is with carboxylic acids dispersant in mortar, cement paste moderate resistance mud performance comparison
In order to detect the anti-mud performance of dispersant, replace equivalent water with 5% and 8% soil superfines respectively in experiment
Mud.It can be seen that from the testing result of three comparison examples, inventive dispersant has excellent anti-mud performance, when soil in cement
The content of powder at 5%, almost lose, and the anti-mud performance of product of the present invention is reachable by traditional anti-mud performance of carboxylic acids product
8%, this illustrates that product of the present invention has excellent anti-mud performance.Can also significantly it find out from table 1, product of the present invention is 8%
Still there is excellent guarantor's plasticity energy, this carboxylic dispersants for having both anti-mud and protecting plasticity energy to have no text at present when clay content
Offer report.
Inventive dispersant can be with existing naphthalene water reducer in the market, aminosulfonic water-reducing agent and other carboxylic acids
Based water reducer is used in combination, and is not only effectively improved the soil loss effect of fresh concrete, while not influencing the condensation of concrete
Time and early strength, in addition it can with the compound uses such as other air entraining agents, retarder, early strength agent, antifoaming agent, further carry
The comprehensive performance of high product.
Claims (7)
1. a kind of protecting the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that include the following steps：
1）, polyethyleneimine and hydroquinone are added into acrylic or methacrylic acid, after stirring evenly at 130 ~ 190 DEG C
It reacts and extracts water vapour simultaneously, react 1 ~ 3 hour, be diluted with water to obtain polymeric monomer 1 after cooling；
2）, using the concentrated sulfuric acid as catalyst, using hydroquinone as polymerization inhibitor, using hexamethylene as solvent and deicer, by polyethylene glycol
It is warming up to 105 DEG C ~ 145 DEG C progress esterifications after monomethyl ether and acrylic acid stirring, obtains polymeric monomer 2；
3）, by step 1）Polymeric monomer 1 obtained and step 2）Polymeric monomer 2 and methylpropene sodium sulfonate mixing and water adding obtained are made
Mixed monomer solution is used as bottom material after stirring evenly；Bottom material is warming up to 50~70 DEG C, and the aqueous solution of initiator ammonium persulfate is delayed
It is slow to be added in bottom material, copolyreaction is stirred, after cooling plus alkali adjusts pH value 6 ~ 8 to get the dispersant.
2. as described in claim 1 protect the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that step 1）In, polyethylene
Imines and the mass ratio of acrylic or methacrylic acid are 10~90：1；The molecular weight of polyethyleneimine 3500~25000 it
Between；The mass ratio of polyethyleneimine and hydroquinone is 500~900：1.
3. as described in claim 1 protect the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that step 2）In, poly- second two
The molecular weight of alcohol monomethyl ether is 1000~3000.
4. as described in claim 1 protect the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that step 2）In, poly- second two
The mass ratio of alcohol monomethyl ether and acrylic acid is 3~10：1；The mass ratio of poly glycol monomethyl ether and the concentrated sulfuric acid is 100~500：1；
The mass ratio of poly glycol monomethyl ether and hydroquinone is 300~600：1；The mass ratio of poly glycol monomethyl ether and hexamethylene is
6~8：1.
5. as described in claim 1 protect the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that poly glycol monomethyl ether with
The mass ratio of methylpropene sodium sulfonate is 50~70：1；The mass ratio of poly glycol monomethyl ether and ammonium persulfate is 60~80：1；
The mass ratio of poly glycol monomethyl ether and polyethyleneimine is controlled 1~72：1.
6. as described in claim 1 protect the preparation method for moulding anti-chamotte mould dispersant, which is characterized in that step 3）In, persulfuric acid
The mass concentration of the aqueous solution of ammonium is 5%.
7. guarantor prepared by the preparation method as described in claim 1-6 is any moulds anti-chamotte mould dispersant.
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| CN108816152B (en) * | 2018-04-11 | 2020-11-10 | 中山大学 | Polyether and carboxylic acid double-modified polyethyleneimine water-based dispersant, and preparation method and application thereof |
| CN112029563B (en) * | 2020-09-09 | 2022-08-02 | 中铁一局集团有限公司 | High-molecular water-soluble polymer muck dispersant |
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| CN101450984A (en) * | 2008-08-13 | 2009-06-10 | 大连市铭源全科技开发有限公司 | Most simple method for producing concrete polycarboxylate high performance dehydragent |
| CN101817657A (en) * | 2009-02-26 | 2010-09-01 | 北京东方雨虹防水技术股份有限公司 | Polycarboxylic acid slump retaining agent |
| CN103145928A (en) * | 2012-08-29 | 2013-06-12 | 成都理工大学 | Low-cost polyester polycarboxylic acid water reducer |
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