CN105646794B - The preparation method and application of collapse protection type phosphate super plasticizer - Google Patents
The preparation method and application of collapse protection type phosphate super plasticizer Download PDFInfo
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- CN105646794B CN105646794B CN201511029522.5A CN201511029522A CN105646794B CN 105646794 B CN105646794 B CN 105646794B CN 201511029522 A CN201511029522 A CN 201511029522A CN 105646794 B CN105646794 B CN 105646794B
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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
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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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
- C04B2103/32—Superplasticisers
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Abstract
The invention provides a kind of preparation method and applications of collapse protection type phosphate super plasticizer, on the one hand the collapse protection type phosphate super plasticizer can keep the mobility of concrete for a long time, simultaneously when the content of mud is higher in Machine-made Sand, the service behaviour that can still keep.The preparation method is, free radicals copolymerization reaction is carried out by the ethers unsaturated polyether as monomer A, the esters unsaturated polyether as monomer B, the phosphorous acid groups esters of unsaturated carboxylic acids as monomer C and the esters of unsaturated carboxylic acids of group containing bis phosphoric acid as monomer D, the collapse protection type phosphate super plasticizer is obtained, wherein (monomer A+ monomer B)：Monomer C：Monomer D mol ratio is 1:(3~8):(4~12).
Description
Technical field
The present invention relates to a kind of preparation method and application of collapse protection type phosphate super plasticizer, belongs to concrete admixture technology
Field.
Background technology
With the fast development of China's economy, modern building shows super-span, high-rise development trend, to mixed
Coagulate the performances such as intensity and the durability of soil and propose higher requirement.And it is drop in concrete admixture high-performance polymer dispersant
Low cement content, improve industrial residue utilization rate, realize that concrete high-durability and performance boost are most effective, most economical, most simple
Just technological approaches.For now, due to the increase of cement content in the otherness and sandstone of different regions concrete raw material,
So that concrete slump loss is big, mobility is deteriorated, and abnormal setting occurs, and intensity increase is slow, and shrinking increases, easy to crack etc.
Phenomenon.These engineer applied problems caused by the deficiency of concrete slump retaining ability, which have become contemporary scientific man institute strategic point, to be needed
Solve the problems, such as.
In order to effectively solve the problems, such as the engineer applied caused by the deficiency of concrete slump retaining ability, the research of association area
Employee development has different molecular structures and the polycarboxylic acid slump retaining agent of performance characteristic, to adapt to the raw material needs of concrete
With the selection of requirement of engineering.Have numerous patents document at present and disclose the related system for having and protecting function polycarboxylate polymer of collapsing
Preparation Method.
Patent document CN101786824A discloses a kind of preparation method for protecting plastotype polycarboxylate water-reducer.This method be by
Unsaturated polyoxyalkyl ether monomer, unsaturated monocarboxylic acid and its derivatives monomer, unsaturated dicarboxylic acid and its derivative list
Body and unsaturated sulfonic acid and its salt monomer are formed by radical polymerization.Collapsed although such polymer is met to a certain extent
Degree of falling and divergence lose small engineer applied, but cement caused by the polymer of this structure but can not meet summer high temperature
Aquation accelerates the problem of concrete fluidity immediate loss brought.
Patent document CN102976655A discloses a kind of preparation method of the super plasticizer of collapse protective poly-carboxylic acid.This method
It is to be led to by unsaturated polyether polymeric monomer, unsaturated esterification polymeric monomer, unsaturated carboxylic acid or its salt and esters of unsaturated carboxylic acids small molecule
Water-based free radical polymerization is crossed to obtain.This method by main polymer chain introduce esters of unsaturated carboxylic acids comonomer, and
Under cement basic conditions slowly hydrolysis ester reaction mechanism come reach slowly release water reducer primary attachment group --- carboxyl,
Collapsed the effect of sustained release so as to reach the guarantor of different time.Such polymer design is ingenious, can meet short or long-time concrete stream
The engineer applied of dynamic property.However, when the content of mud is higher especially in Machine-made Sand in some cases, this kind of carboxylic acid polyalcohol according to
So there is a situation where to protect the scarce capacity that collapses.
Patent document CN103613308A discloses a kind of preparation method of water reducing type polycarboxylic acid concrete slump retaining agent, by
Hydroxyethyl Acrylate, styrene, methylpropene sodium sulfonate, itaconic acid, methyl allyl polyoxyethylene ether are copolymerized to obtain.Such
Water reducer, which introduces itaconic acid and improves its guarantor as adsorption group, to collapse ability；Steric hindrance is produced with phenyl ring in molecular configurational
Effect, water reducer dispersion stabilization can be strengthened.But when using primary attachment group as water reducer of carboxyl and sulfonic acid group, still
The guarantor of concrete based on Machine-made Sand that can not be when higher compared with the content for solving mud under low-dosage is collapsed problem.
(Cem.Concr.Res.2015,67,21-30.) is pointed out according to the SylviePourchet researchs taught, uses phosphoric acid
Group replaces carboxyl as adsorption group, be greatly improved polymer to product --- entringite in cement early stage hydration process
(AFt) and single sulfur type calcium aluminate hyrate (AFm) adsorption capacity.It is possible to prepare high-performance phosphatic type water reducer.
The current more disclosed Patents on phosphoric acid water reducer.
Patent document CN102439063B is disclosed a kind of has at least one phosphonic acids end containing straight chain polyglycereol
Compound.This compound, which is used as water reducer, can effectively keep the slump flow test of concrete, but this water reducer system
Standby cost is higher, and can cause set retardation, and set retardation extends with the increase of the dosage of additive.
Patent document CN103596993A discloses a kind of copolymer having together with bis phosphoric acid ester group, such polymer phase pair
There is low sensitiveness for polycarboxylate water-reducer to the clay in cement and alkaline sulfides.
Patent document CN101128495A discloses a kind of cement dispersants of phosphorous polyvinyl.This phosphoric acid
Water reducer is to pass through radical polymerization by poly- (alkylidene oxide) compound of vinyl and the unsaturated monomer containing phosphoric acid or its salt
Conjunction forms.This phosphoric acid class water reducer does not delay the setting time of concrete and can keep preferable initial water reducing ability.
Patent document CN101061151A discloses a kind of condensed phosphoric esters based on aromatics or heterocyclic aromatic compounds and gathered
The scattered application of the preparation method and cement of compound.Such condensation polymer is by aromatic phosphonic acid ester compound, aldehyde and with alcoxyl
The polycondensation under conditions of acid of the aromatic compound of base polyethers forms.The condensation polymer has preferable water-reducing effect.
Above-mentioned patent document discloses different types of phosphate water reducer, improves the phase of concrete to a certain extent
Capacitive, improve resistance of the super plasticizer to clay and alkaline sulfides.But the water reducer of the type can only keep concrete
Initial fluidity.The guarantor for not reaching the long period is collapsed effect.
The content of the invention
Goal of the invention
It is an object of the present invention to provide a kind of preparation method of collapse protection type phosphate super plasticizer, the collapse protection type phosphorus
On the one hand acidic group super plasticizer can keep the mobility of concrete for a long time, while the content of mud is higher in Machine-made Sand
When, the service behaviour that can still keep.
It is a further object to provide application of the collapse protection type phosphate super plasticizer as cement dispersants.
Summary of the invention
Experimental results demonstrate：Phosphate and carboxylate group can hydrolyze under the alkalescence condition of cement, discharge carboxylic
Base (- COO-) and phosphate (- PO3 2-)；The hydrolysis rate of carboxylate and phosphate is different simultaneously, it is ensured that when different
Between discharge adsorption group, the guarantor for reaching different time is collapsed effect.In addition, phosphate is as strong and effective adsorption group, one
Volume caused by aspect can avoid carboxylase gene absorption property weak is too high, on the other hand can also avoid because of concrete raw material mud
The phenomenon of traditional polycarboxylic acid slump retaining agent scarce capacity caused by too high levels.
In the first aspect of the present invention, there is provided a kind of preparation method of collapse protection type phosphate super plasticizer, by monomer A,
Monomer B, monomer C and monomer D carry out free radicals copolymerization reaction and obtain the collapse protection type phosphate super plasticizer, wherein：
Monomer A is represented with formula (1)：
Wherein, R1For-H or-CH3, X=O, CH2O、CH2CH2O；N=20~130, rubbed for the average addition of oxyethylene group
That number；
Monomer B is represented with formula (2)：
Wherein, R2For-H or-CH3, R3For C1~C4 alkyl, m=20~90, rubbed for the average addition of oxyethylene group
That number；
Monomer C is represented with formula (3)：
Wherein, R4For-H or-CH3, p=2 or 3, M are H atom, alkali metal ion, ammonium ion or organic amine group；
Monomer D is represented with formula (4)：
Wherein, R5、R6Independently of one another-H or-CH3, x, y be independently of one another 2 or 3, L be H atom, alkali metal from
Son, ammonium ion or organic amine group,
(monomer A+ monomer B)：Monomer C：Monomer D mol ratio is 1:(3~8):(4~12).
Preferably, monomer A and monomer B mol ratio is 1:(1~4).
The molecular weight requirement of anti-chamotte mould polycarboxylate water-reducer of the present invention subtracts compared with comb shaped structure polycarboxylic acids in technology
The conventional molecular weight ranges of aqua, those skilled in the art can also combine and further determine that preferable molecular weight ranges through experiment.
Weight average molecular weight (the M of collapse protection type phosphate super plasticizer of the present inventionw) it is preferably 20000~80000.
Monomer A representated by formula of (1) of the present invention is ethers unsaturated polyether polymeric monomer, is material commonly used in the art,
In formula (1), work as R1For H when, it represent unsaturated polymeric monomer include：Vinyl polyglycol ether, allyl polyglycol
Ether, 3- butene-1-ol base polyglycol ethers；Work as R1For CH3When, the unsaturated polymeric monomer that it is represented includes：The poly- second of methylallyl
Glycol ethers, 3- methyl-3-butene-1-alcohol base polyglycol ethers, the above monomer selection at least one use therein are that is, single
Solely select therein a kind of or used with two or more arbitrary proportion form of mixtures.
Monomer B representated by formula of (2) of the present invention is (methyl) esters of acrylic acid polyglycol ether polymeric monomer, is ability
Material is often used in domain, and the esters polymeric monomer representated by it includes：Methoxy polyethylene glycol acrylate, ethyoxyl polyethylene glycol propylene
Acid esters, propoxyl group polyethylene glycol acrylate, butoxy polyethylene glycol acrylate, methoxy poly (ethylene glycol) methacrylic acid
Ester, ethyoxyl polyethylene glycol methacrylate-styrene polymer, propoxyl group polyethylene glycol methacrylate-styrene polymer, butoxy polyethylene glycol methyl-prop
Olefin(e) acid ester.
Monomer C representated by formula of (3) of the present invention is mono phosphoric acid ester esters monomer or its salt.Monomer C is as in polymer
The supplier of initial adsorption group, make collapse protection type phosphate super plasticizer that there is certain initial dispersion ability and polymer molecule
Polarity, it ensure that good water-reducing rate and water reducer compatibility.Meanwhile the absorption property of phosphate group is far longer than carboxyl；And
And phosphate group has low sensitiveness to the clay in cement and alkaline sulfides, so as to ensure the sandstone aggregate situation in difference
Lower concrete has preferable workability and service behaviour.
Monomer D representated by formula of (4) of the present invention is phosphate diester class monomer or its salt.Monomer D is regulation and control polymer
Molecule sustained release protects the important component for ability of collapsing.First, monomer D is the special compound containing carboxylate and phosphate.Should
Compound dilutes the charge density in molecular backbone to a certain extent, reduces the initial adsorption power of polymer molecule,
So as to which the long period is remained in cement system solution, in favor of used in later stage dispersion compensation；Secondly, the phosphate in monomer D
Key and carboxylic acid ester bond can gradually hydrolyze generation carboxylic acid and phosphate group, and phosphate diester hydrolysis can be gradually formed by an exposed phosphorus
Sour hydroxyl to exposed two phosphoric acid hydroxyls hydrolytic process, it is this gradually increase main chain in adsorption group content stepwise hydrolysis
It order, can gradually increase the absorption power of polymer molecule, be advantageous to the lasting absorption power that polymer remains strong, so as to reach
The effect persistently disperseed to cement slurry.
Monomer C and monomer D can be made by known method, such as according to document CN1158132A and US20090258969
The method of record, react to obtain by alcohol and phosphorylation agent, specifically, monomer C by the alcohol F1 containing unsaturated carboxylic acid ester group with
Phosphorylation agent carries out phosphorylation reaction and obtained, and monomer D is by the alcohol F2 containing unsaturated carboxylic acid ester group and contains unsaturated carboxylic acid
The alcohol F3 of ester group carries out phosphorylation reaction with phosphorylation agent and obtained, described alcohol F1, F2, F3's containing unsaturated carboxylic acid ester group
Structural formula is respectively as shown in (5a), (5b), (5c)：
Wherein, the phosphorylation agent is at least one of phosphorus pentoxide, phosphoric acid, polyphosphoric acids, pyrophosphoric acid.
In the phosphorylation reaction, the phosphorylation agent is expressed as P2O5·nH2O (such as：Polyphosphoric acids can represent
For P2O5·xH2O, orthophosphoric acid can be expressed as [1/2 (P2O5·3H2The molal quantity of its reclaimed water is designated as l when O)]), is expressed as
P2O5·nH2The molal quantity of O phosphorylation agent is designated as k, and the molal quantity of alcohol is designated as j in reaction, setting parameter x, it is specified that
X=(l+j)/k
As known technology, the structure of final product can be controlled by controlling x, specifically,
In the phosphorylation reaction for generating monomer C, x=2.0~4.0；
In the phosphorylation reaction for generating monomer D, x=6.0；
The phosphorylation reaction carries out 1~6h at 50~120 DEG C.
Preferably, R5=R6。
Those skilled in the art can select according to monomer reactivity and the molecular weight of target product with reference to prior art
Specific Raolical polymerizable condition.Common water-based free radical copolymerization in being synthesized present invention preferably employs polycarboxylate water-reducer
Reaction.While in order to form monomer polymer chain architecture arranged in a uniform as far as possible (it has been generally acknowledged that such properties of product are more
It is excellent), following reactant addition manners are proposed with very much, i.e.,：The relatively low monomer of polymerization activity is disposable before starting with reaction to be added
Enter in reaction vessel, the higher monomer of polymerization activity is slowly added dropwise at the reaction temperatures, and this is the usual means of this area.This hair
Monomer A is added in reaction vessel in disposable before reaction starts in the bright free radicals copolymerization reaction, monomer B, monomer C, monomer D
It is added dropwise at the reaction temperatures in reaction vessel.
Preferably, the water-based free radical copolyreaction uses water soluble oxidized-reduction initiator system and water-soluble chain
Transfer agent, in the oxidation-reduction trigger system, oxidant is hydrogen peroxide, and reducing agent is sodium hydrogensulfite, pyrosulfurous acid hydrogen
Sodium, sodium hypohosphate, Mohr's salt, L-AA, arabo-ascorbic acid or rongalite；Described chain-transferring agent is mercapto
Base ethanol, TGA, 2 mercaptopropionic acid, at least one of 3- mercaptopropionic acids, oxidant, reducing agent, the dosage of chain-transferring agent
Respectively 2%~10%, 0.5%~5%, the 0.5%~5% of monomer (A+B+C+D) total mole number.
Specific reaction temperature and insulation reaction time are selected according to monomer reactivity and initiator, such as upper
In the presence of stating preferable oxidation-reduction initiator, preferably set reaction temperature as 30~60 DEG C, the control of solution time for adding 2~
6h, 4~8h, polymerization concentration 30%~60% are reacted after completion of dropwise addition.The polymerization concentration refers to own in reaction mixture
The mass percent concentration sum of monomer.
After copolyreaction terminates, the principal component that reaction product can be directly used as cement dispersants uses, and is more preferably into one
Step uses after being neutralized with alkaline matter, to strengthen the storage stability of product.This is techniques known.Alkaline matter can
From ammoniacal liquor commonly used in the art, organic amine, the hydroxide of alkali metal or its carbonate, (concentration can be according to final product concentration
Requirement be determined), the preferably hydroxide of alkali metal, the now corresponding collapse protection type phosphate super plasticizer structure
In M can be converted into alkali metal ion.The dosage of alkaline matter is advisable using the pH value for adjusting reaction product as 6~8.After neutralization,
Contained carboxyl can partly or entirely be converted into carboxylate in said structure formula.Due to neutralizing to the super modeling of the collapse protection type phosphate
The molecular weight effects very little of agent, the present invention ignore to it.
In another aspect of this invention, application of the collapse protection type phosphate super plasticizer as cement dispersants is additionally provided.
The conventional volume (pure solid volume) of collapse protection type phosphate super plasticizer of the present invention is cement concrete glue
More than the 0.02% of material gross mass, its optimum amount must according to engineering be actually needed carry out on-site concrete mixing test into
Row checking.If addition is less than 0.02%, then it is unsatisfactory that it, which protects effect of collapsing,.If opposite addition mistake
Greatly, then it can occur to collapse hyperenergia due to protecting and cause later concrete fluidity the anti-phenomenon increased occur, or even can cause
Concrete disintegration, bleeding etc. deteriorate the situation of concrete performance.
Collapse protection type phosphate super plasticizer of the present invention can be used alone, and can also be selected from existing skill with least one
Known aminosulfonic water-reducing agent, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent mix use in art,
To improve the slump holding capacity of prior art water reducer product.In addition, in addition to known cement water reducing agent above-mentioned,
Air entraining agent, swelling agent, retarder, early strength agent, tackifier, economization agent and defoamer etc. wherein can also be added according to being actually needed
Functional form additive etc..
The collapse protection type phosphate super plasticizer obtained using preparation method of the present invention just has good under conditions of low-dosage
Good slump holding capacity, effectively increase the action effect and adaptability of collapse protection type phosphate super plasticizer.It is even more important
Be that the present invention can realize the service behaviour that can have still kept and excellent concrete in the higher Machine-made Sand of cement content
Workability.
Embodiment
The present invention is described in detail below by example, and these examples are merely illustrative, do not represent the limitation present invention
The scope of application, according to disclosure herein, those skilled in the art can be within the scope of the present invention to reagent and reaction process condition
It is changed.All equivalence changes made according to spirit of the invention or modification, it should all cover the protection model in the present invention
Within enclosing.
The compound described in table 1 is used in synthetic example of the present invention.Wherein monomer A, monomer B are commercially available prod, and
Monomer A, monomer B purity are all more than 98%.
The embodiment compound numbers of table 1
Monomer C, monomer D are self-control, react to obtain by corresponding (5a), (5b), the alcohol of (5c) structure and phosphorylation agent,
Phosphorylation agent is 85% phosphoric acid solution and P2O5React the mixture of the polyphosphoric acids of generation.After reaction terminates, alcohol is converted into
Monomer C or monomer D, but a small amount of phosphoric acid is remained in system.Without purification, the copolyreaction of next step can be directly used for；Monomer
C, monomer D metering is then using the conversion ratio of alcohol as 100% dosage for being converted to phosphorylation reaction product, for example, with following C-1
Exemplified by, during phosphorylation reaction, 1.0mol hydroxyethyl methacrylate is completely converted into monomer C-1, and reaction need not carry after terminating
It is pure, if necessary to add 0.3mol monomer C-1 in free radicals copolymerization reaction, then 30% phosphorylation reaction product is added after converting
.So operation, eliminates purification step, while free radicals copolymerization reaction and final collapse protection type phosphate super plasticizer
Performance will not be also significantly affected.It is obvious also possible to purify monomer C, monomer D, or commercially available (such as C-1 is commercially available, C-1
Materials Co., Ltd can be learned by essence Dehua, Guangzhou to provide, its commercial disignation is PM1000).
In the embodiment of the present invention, the weight average molecular weight of polymer is surveyed using Wyatt Technology of U.S. glue penetration chromatograph
It is fixed.Wherein, gel column：The root chromatogram columns of Shodex SB806+803 two are connected；Elutriant：0.1M NaNO3Solution；Flow phase velocity
Degree：0.8ml/min；Injection：The aqueous solution of 20 μ l 0.5%；Detector：Shodex RI-71 type differential refraction detectors；Standard
Thing：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,
18600,6690,1960,628,232)
In Application Example of the present invention, except special instruction, used cement is reference cement (P.042.5), and sand is
Modulus of fineness Mx=2.6 middle sand, stone are the rubble that particle diameter is 5~20mm continuous gradings.Flowing degree of net paste of cement test ginseng
Carried out according to GB/T8077-2000 standards, amount of water 87g, flowing degree of net paste of cement is determined on plate glass after stirring 3min.
Air content, water-reducing rate test method are with reference to GB8076-2008《Concrete admixture》Relevant regulations perform.The slump and slump
Degree loss is with reference to JC473-2001《Concrete pump-feed agent》Relevant regulations perform.
Monomer C-1 synthesis
After hydroxyethyl methacrylate (130g, 1.0mol) and 85% phosphoric acid solution (77g, 0.67mol) are mixed,
P is slowly added in 20 minutes2O5(24g, 0.17mol), x=4.0.1h is reacted at 120 DEG C, obtains hydroxyethyl methacrylate
Phosphate ester monomer C-1.
Monomer C-2 synthesis
After hydroxy-ethyl acrylate (116g, 1.0mol) and 85% phosphoric acid solution (77g, 0.67mol) are mixed, at 20 points
P is slowly added in clock2O5(24g, 0.17mol), x=4.0.6h is reacted at 50 DEG C, obtains hydroxyethyl methacrylate phosphate
Monomer C-2.
Monomer C-3 synthesis
After hydroxy propyl methacrylate (144g, 1.0mol) and 85% phosphoric acid solution (77g, 0.67mol) are mixed,
P is slowly added in 20 minutes2O5(24g, 0.17mol), x=4.0.4h is reacted at 80 DEG C, obtains hydroxyethyl methacrylate phosphorus
Acid ester monomer C-3.
Monomer C-4 synthesis
After hydroxypropyl acrylate (130g, 1.0mol) and 85% phosphoric acid solution (77g, 0.67mol) are mixed, at 20 points
P is slowly added in clock2O5(24g, 0.17mol), x=4.0.4h is reacted at 80 DEG C, obtains hydroxy-ethyl acrylate phosphate ester monomer
C-4。
Monomer D-1 synthesis
After hydroxyethyl methacrylate (130g, 1.0mol) and 85% phosphoric acid solution (38g, 0.33mol) are mixed,
P is slowly added in 20 minutes2O5(11.7g, 0.083mol), x=6.0.1h is reacted at 120 DEG C, obtains hydroxyethyl methacrylate second
Ester phosphate diester monomer D-1.
Monomer D-2 synthesis
After hydroxy-ethyl acrylate (116g, 1.0mol) and 85% phosphoric acid solution (38g, 0.33mol) are mixed, at 20 points
P is slowly added in clock2O5(11.7g, 0.083mol), x=6.0.6h is reacted at 50 DEG C, obtains hydroxy propyl methacrylate phosphorus
Acid diester binary D-2.
Monomer D-3 synthesis
After hydroxy propyl methacrylate (144g, 1.0mol) and 85% phosphoric acid solution (38g, 0.33mol) are mixed,
P is slowly added in 20 minutes2O5(11.7g, 0.083mol), x=6.0.And 4h is reacted at 80 DEG C, obtain hydroxyethyl methacrylate
Ethyl ester phosphate diester monomer D-3.
Monomer D-4 synthesis
After hydroxypropyl acrylate (130g, 1.0mol) and 85% phosphoric acid solution (38g, 0.33mol) are mixed, at 20 points
P is slowly added in clock2O5(11.7g, 0.083mol), x=6.0.4h is reacted at 80 DEG C, it is double to obtain hydroxypropyl acrylate phosphoric acid
Ester monomer D-4.
Embodiment 1
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 100g deionizations are added
Water, while add 50gA-1 (0.05mol), while stirring with nitrogen purge reaction vessel, and 30 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 1.81g, stirs.Then by 50g B-1 (0.05mol), C-1 (0.30mol), D-
1 (0.40mol), 0.37g TGAs, water 50g phases are mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor,
Time for adding is 2h, and the aqueous solution that 50g contains 0.71g L-AAs is added dropwise simultaneously, time for adding about 2h, is added dropwise
Insulation reaction 4h afterwards, room temperature is cooled to, adds alkali to neutralize and arrive pH value 6.8, obtain the yellow transparent liquid that solid content is 59.6%, point
Son amount is 30,000.
Embodiment 2
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 300g deionizations are added
Water, while add 75gA-2 (0.03mol), while stirring with nitrogen purge reaction vessel, and 45 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 3.37g, stirs.Then by 120g B-2 (0.06mol), C-2 (0.36mol),
D-2 (0.54mol), 0.53g2- mercaptopropionic acids, 0.46g TGAs, water 130g phases are mixed, and it is water-soluble that uniform monomer is made in stirring
Liquid, reactor, time for adding 6h are added dropwise to, and the aqueous solution that 100g contains 1.17g sodium sulfoxylate formaldehydes are added dropwise simultaneously,
Time for adding about 6h, rear insulation reaction 4h is added dropwise, is cooled to room temperature, add alkali to neutralize and arrive pH value 7.2, obtaining solids content is
44.8% yellow transparent liquid, molecular weight 38,000.
Embodiment 3
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 350g deionizations are added
Water, while add 100g A-3 (0.025mol), while stirring with nitrogen purge reaction vessel, and the 50 DEG C of dissolvings that heat up, it is rear plus
Enter hydrogen peroxide (mass concentration 30%) 8.2g, stir.Then by 300gB-4 (0.075mol), C-4 (0.50mol),
D-3 (1.2mol), 2.48g TGAs, water 400g phases are mixed, and uniform monomer solution is made in stirring, is added dropwise to reaction
Device, time for adding 4h, and the aqueous solution that 200g contains 4.8g L-AAs is added dropwise simultaneously, time for adding about 4h, drip
Insulation reaction 8h, is cooled to room temperature after finishing, and adds alkali to neutralize and arrives pH value 7.0, obtains the yellow transparent liquid that solid content is 49.8%,
Molecular weight is 78,000.
Embodiment 4
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 250g deionizations are added
Water, while add 120g A-4 (0.02mol), while stirring with nitrogen purge reaction vessel, and be warming up to 60 DEG C of dissolvings, it is rear plus
Enter hydrogen peroxide (mass concentration 30%) 6.23g, stir.Then by 240gB-3 (0.08mol), C-3 (0.6mol),
D-4 (0.4mol), 2.34g3- mercaptopropionic acids, water 300g phases are mixed, and uniform monomer solution is made in stirring, are added dropwise to anti-
Device, time for adding 5h are answered, and the aqueous solution that 50g contains 2.6g sodium sulfoxylate formaldehydes is added dropwise simultaneously, time for adding about 5h, is added dropwise
After insulation reaction 5h, be cooled to room temperature, add alkali neutralize arrive pH value 6.5, obtain solid content for 51.4% yellow transparent liquid
Body, molecular weight 42,000.
Embodiment 5
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 200g deionizations are added
Water, while add 30gA-1 (0.03mol), while stirring with nitrogen purge reaction vessel, and 60 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 12.24g, stirs.Then by 210g B-3 (0.07mol), C-2 (0.7mol), g
D-1 (1.0mol), 4.15g TGAs, water 200g phases are mixed, and uniform monomer solution is made in stirring, is added dropwise to reaction
Device, time for adding 4h, and the aqueous solution that 200g contains 5.32g sodium sulfoxylate formaldehydes is added dropwise simultaneously, time for adding about 4h, it is added dropwise
After insulation reaction 6h, be cooled to room temperature, add alkali neutralize arrive pH value 7.1, obtain solid content for 54.6% yellow transparent liquid
Body, molecular weight 22,000.
Embodiment 6
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 300g deionizations are added
Water, while add 125gA-2 (0.05mol), while stirring with nitrogen purge reaction vessel, and be warming up to 40 DEG C of dissolvings, it is rear plus
Enter hydrogen peroxide (mass concentration 30%) 13.5g, stir.Then by 50g B-1 (0.05mol), C-3 (0.80mol),
D-4 (0.80mol), 5.41g2- mercaptopropionic acids, water 700g phases are mixed, and uniform monomer solution is made in stirring, are added dropwise to anti-
Device, time for adding 3h are answered, and the aqueous solution that 200g contains 9.0gL- ascorbic acid is added dropwise simultaneously, time for adding about 3h, is dripped
Insulation reaction 7h after finishing, add alkali to neutralize and arrive pH value 7.4, obtain solid content as 34.8% yellow transparent liquid, molecular weight 69,
000。
Embodiment 7
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 350g deionizations are added
Water, while 10gA-1 (0.01mol) is added, 120gA-3 (0.03mol) uses nitrogen purge reaction vessel while stirring, and heats up
To 40 DEG C of dissolvings, hydrogen peroxide (mass concentration 30%) 14.5g is added afterwards, is stirred.Then by 240gB-4
(0.06mol), C-3 (0.30mol), D-2 (1.20mol), 6.80g 3- mercaptopropionic acids, water 600g phases are mixed, and stirring is made uniformly
Monomer solution, be added dropwise to reactor, time for adding 5h, and 150g is added dropwise simultaneously and contains 11.3g L-AAs
The aqueous solution, time for adding about 5h, rear insulation reaction 4.5h is added dropwise, is cooled to room temperature, add alkali neutralize arrive pH value 7.5, obtain
To the yellow transparent liquid that solid content is 42.8%, molecular weight 55,000.
Embodiment 8
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 400g deionizations are added
Water, while add 80gA-3 (0.02mol), while stirring with nitrogen purge reaction vessel, and 40 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 14.7g, stirs.Then by 60g B-2 (0.03mol), 150gB-3
(0.05mol), C-4 (0.80mol), D-4 (0.40mol), 6.90g 3- mercaptopropionic acids, water 800g phases are mixed, and stirring is made uniformly
Monomer solution, be added dropwise to reactor, time for adding 5h, and 200g is added dropwise simultaneously and contains 8.8g L-AAs
The aqueous solution, time for adding about 5h, rear insulation reaction 6h is added dropwise, is cooled to room temperature, add alkali neutralize arrive pH value 7.5, obtain
Solid content be 30.6% yellow transparent liquid, molecular weight 21,000.
Comparative example 1
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 120g deionizations are added
Water, while 100g allyl polyglycol ethers (molecular weight 6000,0.04mol) are added, purging reaction with nitrogen while stirring holds
Device, and 50 DEG C of dissolvings are warming up to, hydrogen peroxide (mass concentration 30%) 13.4g is added afterwards, is stirred.Then by 240g second
Epoxide polyethylene glycol acrylate (molecular weight 3000,0.08mol), 51.6g methacrylic acids (0.6mol), 111.4g acrylic acid
Hydroxyl ethyl ester (0.96mol), 0.9g 2 mercaptopropionic acids, water 350g phases are mixed, and uniform monomer solution is made in stirring, is added dropwise
Enter reactor, time for adding 2h, and the aqueous solution that 100g contains 11.6g sodium sulfoxylate formaldehydes is added dropwise simultaneously, time for adding is about
2h, rear insulation reaction 2h is added dropwise, then the aqueous solution that 20g contains 1.3g sodium sulfoxylate formaldehydes is added into reaction bulb, and after
Continue insurance warm 1h, is cooled to room temperature, adds alkali to neutralize and arrives pH value 7.2, obtains the yellow transparent liquid that solid content is 46.67%, molecule
Measure as 43,000.
Comparative example 2
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 200g deionizations are added
Water, while 350g methylallyls polyglycol ether (molecular weight 10000,0.03mol) is added, purged while stirring with nitrogen anti-
Container is answered, and is warming up to 60 DEG C of dissolvings, hydrogen peroxide (mass concentration 30%) 2.9g is added afterwards, stirs.Then will
17.3g acrylic acid (0.24mol), 31.2g methacrylic acids (0.24mol), 1.4g TGAs, water 100g phases are mixed, stirring system
Into uniform monomer solution, reactor, time for adding 4h are added dropwise to, and 120g is added dropwise simultaneously contains 2.4g L- and resist
The aqueous solution of bad hematic acid, time for adding about 4h, rear insulation reaction 2h is added dropwise, then adds 20g into reaction bulb and contain 0.31g
The aqueous solution of L-AA, and continue to be incubated 1h, room temperature is cooled to, adds alkali to neutralize and arrives pH value 7.3, obtaining solid content is
48.34% yellow transparent liquid, molecular weight 52,000.
Comparative example 3
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 200g deionizations are added
Water, while add 40gA-1 (0.04mol), while stirring with nitrogen purge reaction vessel, and 30 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 4.4g, stirs.Then by 360g B-3 (0.12mol), 94.2gC-2
(0.48mol), 2.7g 3- mercaptopropionic acids, water 400g phases are mixed, and uniform monomer solution is made in stirring, is added dropwise to reaction
Device, time for adding 3h, and the aqueous solution that 400g contains 4.1g L-AAs is added dropwise simultaneously, time for adding about 3h, drip
Insulation reaction 2h after finishing, then add 50g into reaction bulb and contain the aqueous solution of 0.45g L-AAs, and continue to be incubated 1h,
Room temperature is cooled to, adds alkali to neutralize and arrives pH value 6.8, obtains solid content as 17.29% yellow transparent liquid, molecular weight 23,
000。
Comparative example 4
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 100g deionizations are added
Water, while add 60gA-1 (0.06mol), while stirring with nitrogen purge reaction vessel, and 30 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 1.81g, stirs.Then by 40g B-1 (0.04mol), 42.02gC-1
(0.20mol), 96.67gD-1 (0.30mol), 0.37g TGAs, water 50g phases are mixed, and it is water-soluble that uniform monomer is made in stirring
Liquid, reactor, time for adding 2h are added dropwise to, and the aqueous solution that 50g contains 0.71g L-AAs is added dropwise simultaneously, dripped
About 2h between added-time, rear insulation reaction 3h is added dropwise, is cooled to room temperature, add alkali to neutralize and arrive pH value 6.8, obtaining solid content is
54.7% yellow transparent liquid, molecular weight 22,000.
Comparative example 5
In the glass reactor equipped with thermometer, agitator, dropping funel and nitrogen ingress pipe, 350g deionizations are added
Water, while add 80gA-3 (0.02mol) and use nitrogen purge reaction vessel while stirring, and 40 DEG C of dissolvings are warming up to, it is rear to add
Hydrogen peroxide (mass concentration 30%) 14.5g, stirs.Then by 400gB-4 (0.1mol), 242gC-3
(1.08mol), 458gD-2 (1.56mol), 6.80g3- mercaptopropionic acids, water 600g phases are mixed, and it is water-soluble that uniform monomer is made in stirring
Liquid, reactor, time for adding 5h are added dropwise to, and the aqueous solution that 150g contains 11.3g L-AAs are added dropwise simultaneously,
Time for adding about 5h, rear insulation reaction 3h is added dropwise, is cooled to room temperature, add alkali to neutralize and arrive pH value 7.5, obtaining solid content is
52.6% yellow transparent liquid, molecular weight 31,000.
Application Example 1
Flowing degree of net paste of cement is tested：With reference to GB/T8077-2000, using reference cement 300g, amount of water 87g, in detail
Data are shown in Table 2.
As can be seen from Table 2, collapse protection type phosphate super plasticizer of the invention can not only be kept under extremely low volume
Cement is disperseed, while good initial flow has been embodied relative to traditional carboxylic acid slump retaining agent (comparative example 1 and comparative example 2)
Property.In addition we have found that phosphorus acid monomer D is the key factor for making cement keep long-term mobility in the invention.
The paste flowing degree of table 2 is tested
Note：" -- " indicates no fluidity.
Application Example 2
Setting time, air content and slump test：With reference to GB8076-2008《Concrete admixture》Correlation test side
Method has carried out the measure of air content；With reference to JC473-2001《Concrete pump-feed agent》Correlation technique is determined mixed with of the present invention
The slump of the fresh concrete of collapse protection type phosphate super plasticizer and 60min, 120min, 180min through when the slump become
Change, super plasticizer volume is fixed as the 0.12% of cement consumption, and adjusting water consumption makes fresh concrete initial slump be 15
± 1cm, experimental result are as shown in table 3.As a result show, collapse protection type phosphate super plasticizer of the invention is can be with compared with low-dosage
The excellent slump is obtained to keep.
The concrete test result of table 3
Application Example 3
In order to evaluate collapse protection type phosphate super plasticizer of the present invention to the sensitiveness of clay, test containing clay
The fluidity of the mortar of sand configuration.Wherein the divergence test of mortar is with reference to GB/T17671-1999《Flow of cement mortar
Assay method》Tested, wherein cement on the basis of cement used, cement mortar rate 1：3；The quality of clay substitution sand
0.5%；The ratio of mud is 0.44.Determine the fluidity of the fresh mortar mixed with collapse protection type phosphate super plasticizer of the present invention
And 1 hour, 2 hours through when fluidity change.
The mortar test result of table 4
It is above-mentioned test result indicates that, collapse protection type phosphate super plasticizer of the present invention compared with low-dosage in sand
Clay illustrate low sensitiveness.
Claims (10)
1. a kind of preparation method of collapse protection type phosphate super plasticizer, it is characterised in that by monomer A, monomer B, monomer C and monomer
D carries out free radicals copolymerization reaction and obtains collapse protection type phosphate super plasticizer, wherein：
Monomer A is represented with formula (1)：
Wherein, R1For-H or-CH3, X=O, CH2O、CH2CH2O；N=20~130；
Monomer B is represented with formula (2)：
Wherein, R2For-H or-CH3, R3For C1~C4 alkyl, m=20~90；
Monomer C is represented with formula (3)：
Wherein, R4For-H or-CH3, p=2 or 3, M are H atom, alkali metal ion, ammonium ion or organic amine group；
Monomer D is represented with formula (4)：
Wherein, R5、R6Independently of one another-H or-CH3, x, y are independently of one another 2 or 3, L are H atom, alkali metal ion, ammonium
Ion or organic amine group,
(monomer A+ monomer B)：Monomer C：Monomer D mol ratio is 1:(3~8):(4~12).
2. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 1, it is characterised in that monomer A and monomer B
Mol ratio be 1:(1~4).
3. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 1, it is characterised in that the collapse protection type phosphorus
The weight average molecular weight of acidic group super plasticizer is 20000~80000.
4. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 1, it is characterised in that monomer C by containing
The alcohol F1 of unsaturated carboxylic acid ester group carries out phosphorylation reaction with phosphorylation agent and obtained, and monomer D is by containing unsaturated carboxylic acid ester group
Alcohol F2 and alcohol F3 containing unsaturated carboxylic acid ester group carry out phosphorylation reaction with phosphorylation agent and obtain, it is described to contain unsaturation
Alcohol F1, F2, F3 of carboxylic acid ester groups structural formula are respectively as shown in (5a), (5b), (5c)：
Wherein, the phosphorylation agent is at least one of phosphorus pentoxide, phosphoric acid, polyphosphoric acids, pyrophosphoric acid.
5. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 4, it is characterised in that the phosphorylation is anti-
Ying Zhong, the phosphorylation agent are expressed as P2O5·nH2The molal quantity of its reclaimed water is designated as l during O, is expressed as P2O5·nH2O phosphoric acid
Change reagent molal quantity be designated as k, the molal quantity of alcohol is designated as j in reaction, setting parameter x, it is specified that
X=(l+j)/k
In the phosphorylation reaction for generating monomer C, x=2.0~4.0；
In the phosphorylation reaction for generating monomer D, x=6.0；
The phosphorylation reaction carries out 1~6h at 50~120 DEG C.
6. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 1, it is characterised in that R5=R6, x=y.
7. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 1, it is characterised in that the free radical is total to
Poly- reaction is water-based free radical copolyreaction.
8. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 7, it is characterised in that the free radical is total to
Monomer A is added in reaction vessel in disposable before reaction starts in poly- reaction, and monomer B, monomer C, monomer D drip at the reaction temperatures
Add in reaction vessel.
9. the preparation method of collapse protection type phosphate super plasticizer as claimed in claim 7, it is characterised in that the water-based freedom
Base copolyreaction uses water soluble oxidized-reduction initiator system and water-soluble chain transfer agent, the oxidation-reduction trigger system
In, oxidant is hydrogen peroxide, and reducing agent is sodium hydrogensulfite, pyrosulfurous acid hydrogen sodium, sodium hypohosphate, Mohr's salt, L- anti-bad
Hematic acid, arabo-ascorbic acid or rongalite；Described chain-transferring agent be mercaptoethanol, TGA, 2 mercaptopropionic acid,
At least one of 3- mercaptopropionic acids, oxidant, reducing agent, the dosage of chain-transferring agent are respectively monomer (A+B+C+D) total mole number
2%~10%, 0.5%~5%, 0.5%~5%.
10. collapse protection type phosphate super plasticizer obtained by any one of claim 1~9 preparation method should as cement dispersants
With.
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| CN113072668A (en) * | 2021-03-17 | 2021-07-06 | Sika技术股份公司 | Copolymers useful for maintaining high slump flow of mineral binder compositions, their preparation and use |
| CN115215982B (en) * | 2021-04-16 | 2023-09-08 | 博特新材料泰州有限公司 | Low-sensitivity type phosphate-based water reducer and preparation method thereof |
| CN117164274B (en) * | 2023-11-03 | 2024-01-05 | 四川蜀道建筑科技有限公司 | Water reducer for mass concrete, preparation method and concrete |
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