CN108586672A - A kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application - Google Patents
A kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application Download PDFInfo
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- CN108586672A CN108586672A CN201810394176.8A CN201810394176A CN108586672A CN 108586672 A CN108586672 A CN 108586672A CN 201810394176 A CN201810394176 A CN 201810394176A CN 108586672 A CN108586672 A CN 108586672A
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
Abstract
The invention belongs to the technical field of super plasticizer, a kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation method and application is disclosed.The cross-linking type polycarboxylic acid super-plasticizer is mainly prepared from the following components：Trimethylolpropane trimethacrylate, unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer, unsaturated sulfonic acid root monomer, molecular weight regulator, initiator and water.The polycarboxylic acid super-plasticizer of the present invention is interconnected using hydroxymethyl-propane triacrylate as crosslinking points by linear pectination molecule chain.The electrostatic adsorption that the super plasticizer is not only provided with pectination super plasticizer based on carboxylate radical, sulfonate radical, and the steric hindrance effect of polycarboxylic acid super-plasticizer is promoted to a certain extent, show very excellent mobility and slump retaining；And the plasticiser volume is low, water-reducing rate is high, dispersion performance is excellent, function of slump protection is good.
Description
Technical field
The invention belongs to the technical fields of super plasticizer, and in particular to a kind of cross-linking type polycarboxylic acid super-plasticizer and its preparation
Methods and applications.
Background technology
With the development of modern concrete technology, application of the high performance concrete in engineering construction is more and more extensive, gathers
Carboxylic acid super plasticizer for concrete provide good mobility and flowing retentivity, become prepare high performance concrete can not
Or scarce component.Currently, the molecular structure of most polycarboxylic acid super-plasticizers is linear comb structure, but ordinary lines sex comb
The polycarboxylic acid super-plasticizer steric hindrance effect of shape structure is weaker, dispersibility of the plasticiser in cement slurry, slump retaining, water conservation
Effect and its universality are to be improved.
The present invention is using trifunctional group cross-linking agent as crosslinking points, by simple free radical polymerization, finally synthesizes a kind of friendship
Connection type polycarboxylic acid super-plasticizer.In cement slurry, cross-linking type polycarboxylic acid super-plasticizer Molecular Adsorption of the invention is in cement
Grain surface, the steric hindrance compared to common pectinate texture super plasticizer bigger can be provided between cement granules, makes cement
Grain is evenly dispersed, improves the fluidity of cement slurry.In addition, under the alkaline condition of cement slurry, the poly- carboxylic of cross-linking type of the invention
Sour super plasticizer can hydrolyze at aquation initial stage, collapse to achieve the purpose that sustained release is protected.And the super plasticizer of the present invention has
The advantages that volume is low, water-reducing rate is high, function of slump protection is good.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of super modelings of cross-linking type polycarboxylic acids
Agent and preparation method thereof.
Another object of the present invention is to provide the applications of above-mentioned cross-linking type polycarboxylic acid super-plasticizer.
The purpose of the invention is achieved by the following technical solution：
A kind of cross-linking type polycarboxylic acid super-plasticizer, is mainly prepared from the following components：Trimethylolpropane tris acrylic acid
Ester, unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer, unsaturated sulfonic acid root monomer, molecular weight regulator, initiator and
Water；The structural formula of trimethylolpropane trimethacrylate is：
The unsaturated carboxylic acid monomer is acrylic acid (AA), methacrylic acid (MA), maleic anhydride (MAn) and itaconic acid
One or more of (IA)；
The unsaturated sulfonic acid root monomer is in sodium p styrene sulfonate, methylpropene sodium sulfonate and Sodium Allyl Sulfonate
More than one；
The unsaturated polyether polymeric monomer is allyl polyglycol, isobutenyl polyethylene glycol and the poly- second of isopentene group two
One or more of alcohol；Its molecular weight is 1000-3000.
The molecular weight regulator is more than one in thioacetic acid, mercaptopropionic acid or n- dodecyl mereaptan；The initiator
For more than one in inorganic peroxide initiator or redox type initiators.
The inorganic peroxide initiator is more than one in ammonium persulfate, ammonium persulfate potassium or sodium peroxydisulfate；Oxidation
Reduction class initiator is benzoyl peroxide/sucrose, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, N- bis-
Methylaniline, hydrogen peroxide/ascorbic acid.
The molar ratio of the unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer and unsaturated sulfonic acid root monomer is 2:(2-
7):(0.5~1)；The initiator amount is the 1%~10% of all components gross mass；The molecular weight regulator dosage is
The 0.1%~2% of all components gross mass；The trimethylolpropane trimethacrylate dosage is all components gross mass
1%~3%.Dosage relation between total monomer and all components is：The all components of every 100~200g contain 0.045~
The total monomer of 0.1mol；Total monomer is unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer and unsaturated sulfonic acid root monomer.
The preparation method of the cross-linking type polycarboxylic acid super-plasticizer, includes the following steps：By unsaturated polyether polymeric monomer, divide
Son amount conditioning agent, unsaturated carboxylic acid monomer, unsaturated sulfonic acid root monomer are mixed with part water, obtain mixture；By initiator and
TMPTA is dissolved in remaining water, obtains mixed solution；Mixed solution is added dropwise in mixture, heating reaction after having reacted, is adjusted
The pH of solution is saved to neutrality, obtains cross-linking type polycarboxylic acid super-plasticizer.
The temperature of the heating reaction is 50~100 DEG C；The time of the heating reaction is 1~5h；
The speed of the dropwise addition is 0.5~1mL/min.
The pH for adjusting solution refers to being adjusted using alkaline solution；The alkaline solution is NaOH solution, KOH is molten
Liquid, hexamethylene diamine solution or triethanolamine solution；The mass concentration of alkaline solution is 10%~40%.
The cross-linking type polycarboxylic acid super-plasticizer of the present invention has crosslinking topological structure, trimethylolpropane trimethacrylate
(TMPTA) it is crosslinking center.
Application of the cross-linking type polycarboxylic acid super-plasticizer in concrete field.
It is light brown or colourless transparent liquid that the present invention, which prepares cross-linking type polycarboxylic acid super-plasticizer, and specific volume can basis
Practical situations adjust.
The principle of the present invention is：The cross-linking type polycarboxylic superplasticizer of the present invention is using trifunctional group cross-linking agent as topology
The tie point of structure, is synthesized using free radical polymerization.Polycarboxylic acid super-plasticizer passes through linear pectination using TMPTA as crosslinking points
Strand interconnects.The super plasticizer is not only inhaled with pectination super plasticizer based on the electrostatic that carboxylate radical, sulfonate radical are provided
Attached effect, and the steric hindrance effect of polycarboxylic acid super-plasticizer is promoted to a certain extent, show very excellent flowing
Property and slump retaining.
In cement slurry, cross-linking type polycarboxylic acid super-plasticizer Molecular Adsorption of the invention, can be in cement particle surface
Steric hindrance compared to common pectinate texture super plasticizer bigger is provided between cement granules, keeps cement granules evenly dispersed,
Improve the fluidity of cement slurry.In addition, under the alkaline condition of cement slurry, cross-linking type polycarboxylic acid super-plasticizer of the invention can
To be hydrolyzed at aquation initial stage, collapse to achieve the purpose that sustained release is protected.The present invention super plasticizer have volume is low, water-reducing rate is high,
The advantages that function of slump protection is good.
The present invention has the advantages that prominent and advantageous effect as follows compared with prior art：
(1) the cross-linking type polycarboxylic acid super-plasticizer prepared by the present invention, agent structure are using TMPTA as crosslinking points
The component part of cross-linking type topological structure, cross-linked network is containing the various features structure such as carboxylate group, sulfonate group
Pectinate texture long-chain；
(2) the cross-linking type polycarboxylic acid super-plasticizer excellent combination property prepared by the present invention, is provided simultaneously with low-dosage, height subtracts
Water rate, polymolecularity, high fluidity；
(3) the cross-linking type polycarboxylic acid super-plasticizer prepared by the present invention has slow release effect, has good function of slump protection.
Description of the drawings
Fig. 1 is the reaction process schematic diagram that Examples 1 to 2 prepares cross-linking type polycarboxylic acid super-plasticizer；
Fig. 2 is the reaction process schematic diagram that embodiment 3~4 prepares cross-linking type polycarboxylic acid super-plasticizer；
Fig. 3 is the reaction process schematic diagram that embodiment 5~7 prepares cross-linking type polycarboxylic acid super-plasticizer.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiment of the present invention is not limited to
This.
Embodiment 1
40mL water, 44g allyl polyethenoxy ethers (molecular weight 2200), 1.44g propylene are sequentially added into reaction vessel
Sour (AA), 1.15g methylpropene sodium sulfonates (SMAS), 0.5g thioacetic acid (TGA), stirring at normal temperature dissolving is complete, is mixed
Object solution；2.0g TMPTA and 1.5g ammonium persulfate (APS) are dissolved in 30mL water, obtain the solution of crosslinking agent and initiator；It will
The solution of crosslinking agent and initiator is added dropwise in mixture solution, is added dropwise in one hour, is reacted in 80 DEG C of insulated and stirreds
3h；After reaction, reaction product is slowly cooled to room temperature, the sodium hydroxide that obtained product mass concentration is 30% is molten
Liquid adjusts pH value to 7 or so to get cross-linking type polycarboxylic acid super-plasticizer, is labeled as PC1.The present embodiment prepares cross-linking type polycarboxylic acids
The reaction process schematic diagram of super plasticizer is as shown in Figure 1.
Embodiment 2
40mL water, 44g allyl polyethenoxy ethers (molecular weight 2200), 1.44g propylene are sequentially added into reaction vessel
Sour (AA), 1.15g methylpropenyls sodium sulfonate (SMAS), 0.5g thioacetic acid (TGA), stirring at normal temperature dissolving is complete, is mixed
Polymer solution；2.0g TMPTA and 1.5g ammonium persulfate (APS) are dissolved in 30mL water, obtain the solution of crosslinking agent and initiator；
The solution of crosslinking agent and initiator is added dropwise in mixture solution, and is started to warm up to being added dropwise in 80 DEG C, one hour,
Insulated and stirred reacts 5h；After reaction, reaction product is slowly cooled to room temperature, obtained product mass concentration is 30%
Sodium hydroxide solution adjust pH value to 7 or so to get cross-linking type polycarboxylic acid super-plasticizer, be labeled as PC2.It is prepared by the present embodiment
The reaction process schematic diagram of cross-linking type polycarboxylic acid super-plasticizer is as shown in Figure 1.
Embodiment 3
40mL water, 10g allyl polyethenoxy ethers (molecular weight 2000), 33g iso-amylene are sequentially added into reaction vessel
Base polyoxyethylene ether (TPEG) (molecular weight 2200), 1.96g maleic anhydrides, 1.15g methylpropene sodium sulfonates (SMAS),
0.5g thioacetic acid (TGA), stirring at normal temperature dissolving is complete, obtains mixture solution；By 2.0g TMPTA and 1.5g ammonium persulfates
(APS) it is dissolved in 30mL water, obtains the solution of crosslinking agent and initiator；Mixture is added dropwise in the solution of crosslinking agent and initiator
It in solution, and starts to warm up to being added dropwise in 80 DEG C, one hour, insulated and stirred reacts 3h；After reaction, by reaction product
It is slowly cooled to room temperature, the sodium hydroxide solution that obtained product mass concentration is 30% adjusts pH value to 7 or so to get friendship
Connection type polycarboxylic acid super-plasticizer is labeled as PC3.The present embodiment prepares the reaction process schematic diagram of cross-linking type polycarboxylic acid super-plasticizer
As shown in Figure 2.
Embodiment 4
40mL water, 10g allyl polyethenoxy ethers (molecular weight 2000), 33g iso-amylene are sequentially added into reaction vessel
Base polyoxyethylene ether (TPEG) (molecular weight 2200), 1.44g acrylic acid (AA), 1.15g methylpropene sodium sulfonates (SMAS), 0.5g
Thioacetic acid (TGA), stirring at normal temperature dissolving is complete, obtains mixture solution；By 2.0g TMPTA and 1.5g ammonium persulfate (APS)
It is dissolved in 30mL water, obtains the solution of crosslinking agent and initiator；Mixture solution is added dropwise in the solution of crosslinking agent and initiator
In, and start to warm up to being added dropwise in 80 DEG C, one hour, insulated and stirred reacts 5h；After reaction, reaction product is slow
It is cooled to room temperature, the sodium hydroxide solution that obtained product mass concentration is 30% adjusts pH value to 7 or so to get cross-linking type
Polycarboxylic acid super-plasticizer is labeled as PC4.The present embodiment prepares the reaction process schematic diagram of cross-linking type polycarboxylic acid super-plasticizer as schemed
Shown in 2.
Embodiment 5
40mL water, 44g allyl polyethenoxy ethers (molecular weight 2200), 1.15g methyl are sequentially added into reaction vessel
Sodium allylsulfonate (SMAS), 1.44g acrylic acid (AA), 1.96g maleic anhydrides, 0.5g thioacetic acid (TGA), stirring at normal temperature
Dissolving is complete, obtains mixture solution；2.0g TMPTA and 1.5g ammonium persulfate (APS) are dissolved in 30mL water, obtain crosslinking agent
With the solution of initiator；The solution of crosslinking agent and initiator is added dropwise in mixture solution, and is started to warm up to 80 DEG C, one
It is added dropwise in hour, insulated and stirred reacts 3h；After reaction, reaction product is slowly cooled to room temperature, obtained product
The sodium hydroxide solution for being 30% with mass concentration adjusts pH value to 7 or so to get cross-linking type polycarboxylic acid super-plasticizer, is labeled as
PC5.The reaction process schematic diagram that the present embodiment prepares cross-linking type polycarboxylic acid super-plasticizer is as shown in Figure 3.
Embodiment 6
40mL water, 44g allyl polyethenoxy ethers (molecular weight 2200), 1.15g methyl are sequentially added into reaction vessel
Acrylic sodium sulfonate (SMAS), 1.44g acrylic acid (AA), 1.96g maleic anhydrides, 0.5g thioacetic acid (TGA), room temperature stirs
It is complete to mix dissolving, obtains mixture solution；2.0g TMPTA and 1.5g ammonium persulfate (APS) are dissolved in 30mL water, are crosslinked
The solution of agent and initiator；The solution of crosslinking agent and initiator is added dropwise in mixture solution, and is started to warm up to 80 DEG C,
It is added dropwise in one hour, insulated and stirred reacts 5h；After reaction, reaction product is slowly cooled to room temperature, obtained production
The sodium hydroxide solution that object mass concentration is 30% adjusts pH value to 7 or so to get cross-linking type polycarboxylic acid super-plasticizer, label
For PC6.The reaction process schematic diagram that the present embodiment prepares cross-linking type polycarboxylic acid super-plasticizer is as shown in Figure 3.
Embodiment 7
40mL water, 44g allyl polyethenoxy ethers (molecular weight 2200), 1.15g methyl are sequentially added into reaction vessel
Acrylic sodium sulfonate (SMAS), 1.44g acrylic acid (AA), 1.96g maleic anhydrides, 0.5g thioacetic acid (TGA), room temperature stirs
It is complete to mix dissolving, obtains mixture solution；2.0g TMPTA and 2.0g ammonium persulfate (APS) are dissolved in 30mL water, are crosslinked
The solution of agent and initiator；The solution of crosslinking agent and initiator is added dropwise in mixture solution, and is started to warm up to 80 DEG C,
It is added dropwise in one hour, insulated and stirred reacts 5h；After reaction, reaction product is slowly cooled to room temperature, obtained production
The sodium hydroxide solution that object mass concentration is 30% adjusts pH value to 7 or so to get cross-linking type polycarboxylic acid super-plasticizer, label
For PC7.The reaction process schematic diagram that the present embodiment prepares cross-linking type polycarboxylic acid super-plasticizer is as shown in Figure 3.
Implementation result
1, paste flowing degree
Using reference cement, according to GB/T8077-2000《Methods for testing uniformity of concrete admixture》Test cement
Paste flowing degree, the ratio of mud 0.35, the volume (rolling over solid volume 0.15%) of super plasticizer is on the basis of the quality of cement.It chooses
Pectination polycarboxylic acid super-plasticizer (PC0) is used as reference, test result is as follows table 1.
The performance test results of cross-linking type polycarboxylic acid super-plasticizer prepared by 1 Examples 1 to 7 of table
2, retentivity is flowed
Using reference cement, according to GB/T8077-2000《Methods for testing uniformity of concrete admixture》Test cement
Paste flowing degree, the ratio of mud 0.35, super plasticizer volume is 0.15%, by 0min, the fluidity of 1h, 2h, test result
Such as the following table 2.
The performance test results of cross-linking type polycarboxylic acid super-plasticizer prepared by 2 Examples 1 to 7 of table
Data above shows that cross-linking type super plasticizer has preferable water-reducing effect, and water-reducing rate is compared to common super plasticizer
(PC0) it greatly improves；The slump has basic free of losses in two hours, shows excellent water-reducing effect and guarantor is collapsed effect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of cross-linking type polycarboxylic acid super-plasticizer, it is characterised in that：Mainly it is prepared from the following components：Trimethylolpropane
Triacrylate, unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer, unsaturated sulfonic acid root monomer, molecular weight regulator cause
Agent and water；The structural formula of trimethylolpropane trimethacrylate is：
The unsaturated polyether polymeric monomer is in allyl polyglycol, isobutenyl polyethylene glycol and isopentene group polyethylene glycol
More than one.
2. cross-linking type polycarboxylic acid super-plasticizer according to claim 1, it is characterised in that：The unsaturated carboxylic acid monomer is third
One or more of olefin(e) acid, methacrylic acid, maleic anhydride and itaconic acid；
The unsaturated sulfonic acid root monomer is one kind in sodium p styrene sulfonate, methylpropene sodium sulfonate and Sodium Allyl Sulfonate
More than.
3. cross-linking type polycarboxylic acid super-plasticizer according to claim 1, it is characterised in that：The molecular weight regulator is sulfydryl
More than one in acetic acid, mercaptopropionic acid or n- dodecyl mereaptan；The initiator is inorganic peroxide initiator and redox
More than one in class initiator.
4. cross-linking type polycarboxylic acid super-plasticizer according to claim 3, it is characterised in that：The inorganic peroxide initiator
For more than one in ammonium persulfate, ammonium persulfate potassium or sodium peroxydisulfate；Redox type initiators are benzoyl peroxide/sugarcane
Sugar, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, accelerine, hydrogen peroxide/ascorbic acid.
5. cross-linking type polycarboxylic acid super-plasticizer according to claim 1, it is characterised in that：The unsaturated polyether polymeric monomer,
The molar ratio of unsaturated carboxylic acid monomer and unsaturated sulfonic acid root monomer is 2:(2-7):(0.5~1)；The trimethylolpropane tris
Acrylate dosage is the 1%~3% of all components gross mass.
6. cross-linking type polycarboxylic acid super-plasticizer according to claim 1, it is characterised in that：The initiator amount is all groups
Divide the 1%~10% of gross mass；The molecular weight regulator dosage is the 0.1%~2% of all components gross mass；
Dosage relation between total monomer and all components is：The all components of every 100~200g contain the total of 0.045~0.1mol
Monomer；Total monomer is unsaturated polyether polymeric monomer, unsaturated carboxylic acid monomer and unsaturated sulfonic acid root monomer.
7. according to the preparation method of any one of the claim 1~6 cross-linking type polycarboxylic acid super-plasticizer, it is characterised in that：Packet
Include following steps：By unsaturated polyether polymeric monomer, molecular weight regulator, unsaturated carboxylic acid monomer and unsaturated sulfonic acid root monomer with
Part water mixing, obtains mixture；After initiator and hydroxymethyl-propane triacrylate are dissolved in remaining water, by mixed solution
It is added dropwise in mixture, heating reaction, after having reacted, adjusts the pH of solution to neutrality, obtain cross-linking type polycarboxylic acid super-plasticizer.
8. the preparation method of cross-linking type polycarboxylic acid super-plasticizer according to claim 7, it is characterised in that：The heating reaction
Temperature be 50~100 DEG C；The time of the heating reaction is 1~5h；
The speed of the dropwise addition is 0.5~1mL/min.
9. the preparation method of cross-linking type polycarboxylic acid super-plasticizer according to claim 7, it is characterised in that：The adjusting solution
PH refer to being adjusted using alkaline solution；The alkaline solution is NaOH solution, KOH solution, hexamethylene diamine solution or three second
Alkanolamine solution.
10. according to application of any one of the claim 1~6 cross-linking type polycarboxylic acid super-plasticizer in concrete field.
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