CN106565969A - Preparation method and application of organic and inorganic hybrid additive - Google Patents
Preparation method and application of organic and inorganic hybrid additive Download PDFInfo
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- CN106565969A CN106565969A CN201610988150.7A CN201610988150A CN106565969A CN 106565969 A CN106565969 A CN 106565969A CN 201610988150 A CN201610988150 A CN 201610988150A CN 106565969 A CN106565969 A CN 106565969A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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Abstract
The invention provides a preparation method and application of an organic and inorganic hybrid additive. The organic and inorganic hybrid additive is formed by hybridizing hyperbranched polymer and calcium silicon composite oxide. The preparation method comprises the steps that a compound a and a compound b are subjected to ring opening polymerization under a catalyst, then, the polymerization product and a compound c are subjected to an esterification reaction, and the hyperbranched polymer is obtained; the hyperbranched polymer is dissolved in water, pH is adjusted to be 9-11, a calciferous inorganic component d and a silicious inorganic component e are added, a sufficient reaction is carried out under reaction conditions, and therefore the organic and inorganic hybrid additive is obtained. By means of the organic and inorganic hybrid additive, the early strength of cement materials can be improved, the water-reducing rate is high, the long-term strength of concrete is not affected, and meanwhile the conveying cost of an early strength agent is reduced.
Description
Technical field
The invention belongs to technical field of concrete additives, more particularly to a kind of cement base of hybrid is additional
Agent, can accelerate cement-based material early hydration speed, improve the early strength of concrete.
Background technology
The construction of the Large Infrastructure Projects such as the nuclear power, water conservancy, high ferro, subway, bridge, tunnel of China is maked rapid progress, in order to
Accelerate the template turn around time of concrete, improve construction speed and efficiency, the early strength of cement-based material is proposed higher
Requirement.The fragment-free track slab requirement concrete 16h compression strength of high ferro construction is more than 48MPa；Subway and tunnel it is mixed
Solidifying soil shield duct piece requires that 10h demoulding strengths are more than 20MPa；Heavy caliber steel cylinder concrete water transmission pipe in hydraulic engineering
(PCCP), high-strength prestressed (PHC) pile tubes of the C80 of skyscraper, the large scale prefabricated concrete box girder of bridge construction, two nets
Transformation and communicating such as builds at the high-strength annular prestressed concrete electric pole of engineering, and runway, super highway etc. are urgent
Salvaging etc. all proposes requirement to the early strength of cement-based material.In addition, substantial amounts of mineral admixture be applied to it is mixed
Improve agent on crack resistance of concrete environmental attack degree in solidifying soil, but most of mineral admixture can significantly reduce the early stage of concrete
Mechanical property, have impact on it and widely applies in building materials field.
In order to improve the early strength of concrete, current approach mainly has change cement composition or fineness, additional morning strong
The method such as additive and thermal curing system, increase early strength polymer, the early strong nano-particle of addition.
(1) the early strong technology regulated and controled based on cement composition or fineness：In order to improve early age strength of concrete, using ultra-fine water
Mud and change cement minerals composition.The fineness of cement is thinner, and its early hydration speed is faster, and early strength is higher, but concrete
Workability is poor, contraction is big, easy to crack.Lumnite cement, sulphur aluminium can be produced by the phase composition of adjustment cement minerals in addition
The special cements such as hydrochlorate super-early strength cement are improving early strength, but early hydration heat is high, early stage contract with dry rate is big, and later strength
And hydraulic performance decline；
2) the early strong technology based on additional early strength agent：Inorganic early strength agent early strong effect is good, but volume is higher, and coagulation
Native later strength retraction is serious, and concrete drying shrinkage is big, is unfavorable for concrete durability, and alkaline metal salt early strength agent can also increase
The risk of big alkali-aggregate Reaction of Concrete, it is using increasingly being restricted.Then addition content is difficult to control to organic early strength agent, makes
The serious slow setting of concrete and concrete strength decline are easily caused with improper, and price is higher；
3) the early strong technology regulated and controled based on maintaining process：Widely used thermal curing technique improves early in prefabricated components production
Phase intensity, accelerates form cycling rate.Steam curing declines concrete component later stage mechanical property and durability, while maintenance
Energy consumption is very high；
4) the super hardening technology based on co-poly carboxylic acid molecular structure.Polycarboxylic admixture is newly mixed except giving
The high initial fluidity of concrete and high workability keep outer, can also give maturing using modern molecular tailoring technique and surpass
Early strong, lower shrinkage, or even meet the several functions such as the requirement of aquation control.Polycarboxylic admixture in the market substantially draws
Enter carboxyl as adsorption group, the aquation of cement can be delayed to a certain extent, when particularly curing temperature is low, due to its early stage
Strength development is slow, limits its use in cold climates.
5) the early strong technology based on nano material：Nano-meter SiO_2 is added in concrete2Or Nano-meter CaCO33, there is provided cement
Nucleus required for aquation, accelerates hydrated cementitious, its can permeate be filled into it is thin in hardened cement paste and rough aggregate interface
Little space, so as to reduce porosity, makes maturing more closely knit, and intensity is higher, but individually nano particle is easily reunited,
Certain difficulty is brought to application；ZL201410231260.X, ZL201410182656.X, ZL201110366521.5 introduce powder
Shape Nano-meter CaCO33Or SiO2Particle, the performance of concrete is improved by simple blending, and the nano particle of this powdery holds
Easily reunite, it is impossible to give full play to the humidification of nano particle.US20120216724、US20150291474、
US20150148456 etc. employ sulfonated acetone formaldehyde polycondensate, sulfamate condensation polymer, naphthalene sulfonic acid-formaldehyde condensation product, three
Melamine-formaldehyde condensation product, polycarboxylic-acid comb-shaped copolymer etc. carry out dispersed inorganic particles, due to these polymer for linear or
Dispersion of the comb shaped structure to inorganic particulate is limited, and the concentration of inorganic particulate can not be too high, too high that inorganic particulate can be caused to settle.
Therefore, the early strong technology for being regulated and controled using cement composition or fineness easily causes concrete shrinkage, cracking, and durability is not
It is high；It is unsafty to improve early age strength of concrete using inorganic salts or organic early strength agent, and its volume is high, reduces mixed
Solidifying soil later strength；Technology power consumption using high temperature, autoclave curing is high, is unfavorable for concrete durability.Conventional report
The solution concentration of linear or comb polymer dispersed inorganic particles is low, reduces production efficiency, while increasing cost of transportation.
The content of the invention
Based on above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of hybrid additive
Preparation method and applications, can not only improve the early strength of cement material, with high water reducing rate, not affect after concrete
Phase intensity, while also reducing the cost of transportation of early strength agent.
The organic inorganic hybridization additive is formed with calcium Si composite oxide hydridization by dissaving polymer, its system
Preparation Method is：
Step (1)：Compound a is carried out after ring-opening polymerisation in the presence of catalyst with compound b, then again with chemical combination
Thing c carries out esterification, obtains dissaving polymer.
Compound a is the dendritic molecule with multiple terminal hydroxy groups or Amino End Group, and number-average molecular weight is 3500-12000,
Structural formula is as follows：
Compound b is epoxide, shown in its structural formula such as formula (3)：
Wherein, R1For H ,-CH3,-CH (CH3) etc.
Compound c is the monomer containing acid anhydride structure.
Compound a：Compound b：The mol ratio of compound c is 1:50-250:30-100, gained has the super of core shell structure
The weight average molecular weight of branched polymer is between 10000-30000.
Step (2)：The dissaving polymer that step (1) is obtained is dissolved in into water, the inorganic component d of calcic and siliceous is added
Inorganic component e, it is 2-15% to adjust to the mass percent of dissaving polymer, and the mass percent of water-soluble Ca salt d is 5-
The mass percent of 25%, water-soluble silicate e is 5-20%, and regulation pH is 9-11, that is, obtain organic inorganic hybridization additive.
Described inorganic component d is water-soluble Ca salt, such as calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium citrate,
Calcium gluconae, calcium hydroxide, calcium nitrate, calcium oxalate, calcium phosphate, calcium propionate, calcium sulfate, they be it is known, it is commercially available.
Described inorganic component e is water-soluble silicate, such as sodium metasilicate, potassium silicate, prodan, magnesium fluosilicate, inclined silicon
Sour sodium, potassium metasilicate, they be it is known, it is commercially available.
Compound a is dendroid polyglycidyl ether, dendroid polyethyleneimine, has different molecular weight, the compound
Can be directly commercially available, it is also possible to according to open report document oneself synthesis (Macromolecules, 1999,32:4240；
MacromolSymp,2001,163:67；Journal of the American Chemical Society,1951,78:
2118-2121)。
The compound b is any one in oxirane, expoxy propane, methyloxetane or arbitrary proportion mixing
Mixture.
The described preferred glutaric anhydrides of compound c, maleic anhydride, succinic anhydride, 2- methyl maleic anhydrides, 2,3- dimethyl
Maleic anhydride, adipic anhydride, dimethyl maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, phthalic anhydride, phenyl
Succinyl oxide, isatoic anhydride, tetrafluoro phthalate anhydride, homophthalic acid acid anhydride, two Kui acid anhydrides, quinolinic anhydride, Yikang acid anhydrides, trimellitic acid
Acid anhydride.
It is known to above compound is or commercially available, or can be according to the side described in disclosed document or patent
It is prepared by method
The weight average molecular weight of described dissaving polymer is 10000-30000, and molecular weight is too low, polymer it is hyperbranched
Low degree, it is impossible to form the structure of dendroid core and linear shell well, the ability of dispersion inorganic particulate is weak, and molecular weight is too
Height, the water-soluble variation of polymer, can not well disperse inorganic particulate.
Ring-opening polymerisation described in step (1) be reaction well-known to those having ordinary skill in the art, preferred catalyst be metallic sodium,
Potassium, sodium hydride, hydrofining, sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide, NaOH, potassium hydroxide, the quality of catalyst is
The 0.1%-1% of compound a and compound b gross masses.
The reaction temperature of ring-opening polymerisation is 100-160 DEG C, and reaction pressure is to carry out open loop under 0-0.2MPa, oxygen free condition to gather
Reaction is closed, the feed time of compound b is 6-10h, and charging is incubated 2-4h after finishing.
Above-mentioned ring-opening polymerization must be carried out under anaerobic, according to material be lower boiling material, then adjust
System pressure between 0.1-0.2MPa, according to material be high boiling liquid, then using lower pressure react because pressure
Power affects little to reaction, as shielding gas after vacuumizing and with high pure nitrogen.Polymerisation is exothermic reaction, is needed to temperature
It is controlled between 100-160 DEG C, temperature is too low, decomposition induction time is elongated, reaction efficiency is low, temperature is too high, accessory substance increases
Plus, properties of product are deteriorated.The feed time of compound b is 6-10h, is fed too fast, and reaction speed is fast and violent, and temperature is difficult control
System, charging rate is excessively slow, and reaction efficiency is low.
After ring-opening polymerisation is finished, esterification catalyst, preferred p-methyl benzenesulfonic acid will be added in system, consumption is the total consumption of material
0.01-0.5%, add compound c, maintain the temperature at the temperature of ring-opening polymerisation, after reaction 2-5h, cooling discharge is surpassed
Branched polymer.
When preparing the solution of dissaving polymer dispersion inorganic particulate, first dissaving polymer is scattered in after the aqueous solution,
Reaction temperature is maintained at 20～60 DEG C, and water-soluble Ca salt and water-soluble silicate are configured to into the aqueous solution, while being added drop-wise to polymerization
In thing solution, time for adding is 6-12h, in final solution the mass percent of polymer be 2-15%, the matter of water-soluble Ca salt d
Amount percentage is 5-25%, and the mass percent of water-soluble silicate e is 5-20%, and remaining is water.The drop of inorganic particulate solution
Plus the time can not be too short, too short-range missile cause reaction speed is too fast, and inorganic particulate is easily settled, time oversize impact production efficiency.
Present invention also offers the application of described organic inorganic hybridization additive.
Organic inorganic hybridization additive of the present invention can be compounded with high-performance water reducing agent, it is also possible to defoamer, draw
The functional form auxiliary agent such as gas agent, retarder, thickener, economization agent is used after being compounded by a certain percentage, to adjust concrete
Combination property；Its conventional volume is the 1～6% of total Binder Materials, and optimum adding quantity of pulverized is 2～5%.If addition is less than 1%, that
Its early strong effect is unsafty；Conversely, if addition is more than 5%, it is only economically that proof is excessively added
Waste, do not bring the corresponding growth in effect.
The organic inorganic hybridization additive of the patented invention is by dissaving polymer and calcium Si composite oxide hydridization
Into, using dissaving polymer as organic component, compared with conventional linear polymer, this has organic component highly branched,
There are good surface-active and internal cavities, can be good at dispersion and contain calcium Si composite oxide, its dispersion efficiency is higher, nothing
The particle-stabilised more difficult sedimentation of machine, the concentration of the inorganic particulate of preparation is high, is more beneficial for improving early strength, while also can drop
Low cost of transportation.And inorganic component calcium Si composite oxide can provide the nucleus needed for hydrated cementitious, accelerate hydrated cementitious, together
When can reduce the porosity at cement slurry and interface, and then make hardened cement paste and concrete is more closely knit, intensity is higher.This is special
The hybrid additive of profit invention, the early strength effect to improving cement-based material is more excellent, especially low temperature early stage
Enhancing effect is very notable, is applicable to the production of non-evaporating foster section of jurisdiction concrete.
Specific embodiment
Following examples have described in more detail the process that the method according to the invention prepares polymerizate, and these realities
Apply example to be given by way of illustration, its object is to allow person skilled in the art to will appreciate that present disclosure and according to this
Implement, but these embodiments are in no way intended to limit the scope of the present invention.
During the present invention is implemented, compound a, compound b, compound c and inorganic component d, the inorganic component e described in table 1 is
For commercially produced product, can be buying on market.
B) in the embodiment of the present invention, the weight average molecular weight of polymer is swashed using the gel permeation chromatography-multi-angle of Waters
Light light scattering combined instrument is determined.Gel column：SWXL3000+SWXL5000；Elutriant：0.1MNaNO3 solution；Flowing phase velocity
Degree：0.8ml/min；Injection：The aqueous solution of 20 μ l 0.5%；Reference material：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecule
Measure 1010000,478000,263000,118000,44700,18600,6690,1960,628,2 32).
C) in Application Example of the present invention, cement：The little wild water in field mud PII 52.5 in the south of the River；Sand：Sand in II areas, 0～
5mm, modulus of fineness 2.6；Stone：Big stone 10～20mm, 5～10mm of handstone.Flyash:I level flyash, breeze (density
For 2520Kg/m3, specific surface area 448.9m2/kg), the high-performance water reducing agent PCA100 of Su Bote productions, is polyacrylate
Material, weight average molecular weight 35200.
Compound used therefor inventory in the embodiment of table 1
Synthetic example 1
In the 2L reactors for being furnished with the drying of mechanical agitation, measuring pump and high pure nitrogen, addition compound a -1 (750g,
0.12mol), 15.93g sodium methoxides, open stirring, seal reactor, are evacuated to below -0.2MPa, and are warming up to 100-120
After DEG C, b-1 (330g, 7.5mol) is at the uniform velocity added in reactor, feed time is 6h, while keeping reaction temperature 100-120
℃.After charging terminates, continue constant temperature and keep after 2h, after emptying, compound c-1 (513g, 4.5mol) is added in reactor, it is right
Toluenesulfonic acid 7.96g, stirring 2h is carried out after esterification, cooling discharge, and the molecular weight of sample is measured by laser light scattering instrument
10600.The 159.3g samples of above-mentioned synthesis are dissolved in 250g water and 20 DEG C are warming up to, the pH value for adjusting solution is 9.0, will
53.1g d-1 are dissolved in 250g water as dropping liquid A, 52.5g e-1 are dissolved in 260g water as dropping liquid B, are started simultaneously at
Solution A and B 6h, completion of dropping insulation 2h, cooling discharge (SX-1) is added dropwise.
Synthetic example 2
In the 2L reactors for being furnished with the drying of mechanical agitation, measuring pump and high pure nitrogen, addition compound a -2 (350g,
0.1mol), 10.32g sodium methoxides, open stirring, seal reactor, are evacuated to below -0.1MPa, and are warming up to 120-140
After DEG C, b-1 (880g, 20mol) is at the uniform velocity added in reactor, feed time is 8h, while keeping reaction temperature 120-140
℃.After charging terminates, continue constant temperature and keep after 3h, after emptying, compound c-2 (490g, 5mol) is added in reactor, to first
Benzene sulfonic acid 3.44g, stirring 3h is carried out after esterification, cooling discharge, and the molecular weight of sample is measured by laser light scattering instrument
17200.The 206.4g samples of above-mentioned synthesis are dissolved in 400g water and 20 DEG C are warming up to, the pH value for adjusting solution is 10.0, will
206.4g d-1 are dissolved in 200g water as dropping liquid A, and 137.6g e-2 are dissolved in as dropping liquid B in 200g water, while opening
Begin that solution A and B 10h, completion of dropping insulation 3h, cooling discharge (SX-2) is added dropwise.
Synthetic example 3
In the 2L reactors for being furnished with the drying of mechanical agitation, measuring pump and high pure nitrogen, addition compound a -3 (600g,
0.05mol), 4.48g sodium methoxides, open stirring, seal reactor, are evacuated to below -0.02MPa, and are warming up to 140-160
After DEG C, b-1 (550g, 12.5mol) is at the uniform velocity added in reactor, feed time is 10h, while keeping reaction temperature 140-
160℃.Charging terminate after, continue constant temperature keep 4h after, after emptying, in reactor add compound c-2 (343g,
3.5mol), p-methyl benzenesulfonic acid 0.15g, stirring 5h is carried out after esterification, cooling discharge, sample measured by laser light scattering instrument
Molecular weight be 29800.The 298.6g samples of above-mentioned synthesis are dissolved in 400g water and 20 DEG C are warming up to, the pH value of adjustment solution
For 11.0,497g d-1 are dissolved in 200g water as dropping liquid A, 398g e-1 are dissolved in 200g water as dropping liquid B, together
When start that solution A and B 12h, completion of dropping insulation 4h, cooling discharge (SX-3) is added dropwise.
Synthetic example 4
In the 2L reactors for being furnished with the drying of mechanical agitation, measuring pump and high pure nitrogen, compound a -4 is added
(454.2g, 0.06mol), 1.48g sodium methoxides open stirring, seal reactor, are evacuated to below -0.05MPa, and heat up
To after 140-160 DEG C, b-4 (384g, 6mol) is at the uniform velocity added in reactor, feed time is 8h, while keeping reaction temperature
140-160℃.Charging terminate after, continue constant temperature keep 4h after, after emptying, in reactor add compound c-1 (684g,
4.5mol), p-methyl benzenesulfonic acid 0.74g, stirring 4h is carried out after esterification, cooling discharge, sample measured by laser light scattering instrument
Molecular weight be 24800.The 247.7g samples of above-mentioned synthesis are dissolved in 500g water and 20 DEG C are warming up to, the pH value of adjustment solution
For 10.5,189.1g d-2 are dissolved in 260g water as dropping liquid A, 165.1g e-1 are dissolved in 260g water as dropping liquid
B, starts simultaneously at dropwise addition solution A and B 8h, completion of dropping insulation 3h, cooling discharge (SX-4).
Synthetic example 5
In the 2L reactors for being furnished with the drying of mechanical agitation, measuring pump and high pure nitrogen, addition compound a -2 (420g,
0.12mol), 7.57g sodium methoxides, open stirring, seal reactor, are evacuated to below -0.1MPa, and are warming up to 120-140
After DEG C, b-1 (633.6g, 14.4mol) is at the uniform velocity added in reactor, feed time is 8h, while keeping reaction temperature 120-
140℃.Charging terminate after, continue constant temperature keep 2h after, after emptying, in reactor add compound c-3 (460.8g,
3.6mol), p-methyl benzenesulfonic acid 1.51g, stirring 3h is carried out after esterification, cooling discharge, sample measured by laser light scattering instrument
Molecular weight be 14900.The 189.3g samples of above-mentioned synthesis are dissolved in 400g water and 20 DEG C are warming up to, the pH value of adjustment solution
For 10.0,126.2g d-1 are dissolved in 200g water as dropping liquid A, 100.9g e-1 are dissolved in 200g water as dropping liquid
B, starts simultaneously at dropwise addition solution A and B 8h, completion of dropping insulation 2h, cooling discharge (SX-5).
Comparative example 1：
It is used to disperse the copolymer 2 of inorganic particulate to substitute gathering in synthetic example 5 in patent US20140256857
Compound, the additive of synthesis is designated as CP-1
Application Example 1
Using the little wild cement of field P II 52.5, match ratio cement 450g, normal sand 1350g, the ratio of mud is 0.40, fixed
The high-performance water reducing agent PCA100 volumes of Su Bote productions are 0.12%, and the admixture dosage of invention is shown in following form,
Volume is that the folding on the basis of Binder Materials measures calculating admittedly, controls each group mortar unit weight by defoamer basically identical.Control sample 1
In the additive of synthesis, there is solid particles sediment, lamination occurs in sample.Control sample 2 is that Su Bote is commercially availableIt is poly-
Carboxylic acid super hardening water reducer, and individually fill the early-strength water reducer.
The mortar performance of table 2 tests table
Find out from result of the test, the additive of this patent synthesis has excellent early strong effect, than conventional polycarboxylate water-reducer
Significantly improve with the early strength of the 12h and 24h of early-strength polycarboxylic acids diminishing, and 28d compression strength is also slightly lifted.It is molten in addition
The stability of liquid is good, the drawbacks of there is no sedimentation.
Application Example 2
Metro shield Concrete precast pipe element generally uses C50 strong concretes, and section of jurisdiction is prefabricated in punching block, is
Raising form cycling rate, typically carries out steam curing after casting and compacting of concrete terminates, concrete strength reach after 20MPa from
Hang out in mould, be placed on after workshop cooling 4h and hang in pond immersion maintenance.For saving energy consumption, section of jurisdiction concrete is proposed
Non-evaporating foster requirement, using conventional match ratio cement：Breeze：Flyash：Sand：Stone：Water=308:44:88:701:1097:
140, the additive of fixed invention mixes 0.3%, and the high-performance water reducing agent PCA100 produced using Su Bote is mixed to adjust
The initial slump for coagulating soil is basically identical.Compression strength of the concrete under low temperature and normal temperature is tested, wherein, control sample
2 is the Early-strength polycarboxylate superplasticizer of Su Bote productions, is not spiked with high-performance water reducing agent, only participates in the early-strength water reducer.It is mixed
Solidifying soil result of the test is shown in Table 3.Test result indicate that：The additive of the present invention can significantly improve the intensity of concrete early stage, especially
It is that under cryogenic conditions, early strong effect becomes apparent from, and enables in particular to meet the demoulding requirement of 12h under the concrete normal temperature of section of jurisdiction, is improved
Mould turn around time, accelerates manufacturing schedule, reducing energy consumption.
Table 3
Claims (9)
1. a kind of preparation method of organic inorganic hybridization additive, the organic inorganic hybridization additive is by dissaving polymer
Form with calcium Si composite oxide hydridization, it is characterised in that its preparation method is：
Step (1)：Compound a is carried out after ring-opening polymerisation in the presence of catalyst with compound b, is then entered with compound c again
Row esterification, obtains dissaving polymer；
Compound a is the dendritic molecule with multiple terminal hydroxy groups or Amino End Group, and number-average molecular weight is 3500-12000, its knot
Structure formula is as follows：
Compound b is epoxide, shown in its structural formula such as formula (3)：
Wherein, R1For H ,-CH3,-CH (CH3)；
Compound c is the monomer containing acid anhydride structure；
Compound a：Compound b：The mol ratio of compound c is 1:50-250:30-100, gained dissaving polymer is divided equally again
Son amount is between 10000-30000；
Step (2)：The dissaving polymer that step (1) is obtained is dissolved in into water, regulation pH is 9-11, adds the inorganic component of calcic
D and siliceous inorganic component e, adjust to dissaving polymer mass percent be 2-15%, the quality hundred of water-soluble Ca salt d
Divide than being 5-25%, the mass percent of water-soluble silicate e is 5-20%, obtains the organic-inorganic after fully reacting miscellaneous
Change additive；
Described inorganic component d is water-soluble Ca salt, such as calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium citrate, grape
Calciofon, calcium hydroxide, calcium nitrate, calcium oxalate, calcium phosphate, calcium propionate, calcium sulfate；
Described inorganic component e be water-soluble silicate, such as sodium metasilicate, potassium silicate, prodan, magnesium fluosilicate, sodium metasilicate,
Potassium metasilicate.
2. method according to claim 1, it is characterised in that compound a is dendroid polyglycidyl ether, the poly- second of dendroid
Alkene imines.
3. method according to claim 1, the compound b is in oxirane, expoxy propane, methyloxetane
The mixture that any one or arbitrary proportion mix.
4. method according to claim 1, described compound c is glutaric anhydride, maleic anhydride, succinic anhydride, 2- methyl
Maleic anhydride, 2,3- dimethyl maleic anhydrides, adipic anhydride, dimethyl maleic anhydride, glutaric anhydride, hexahydrophthalic acid
Acid anhydride, phthalic anhydride, phenylsuccinic acid acid anhydride, isatoic anhydride, tetrafluoro phthalate anhydride, homophthalic acid acid anhydride, two Kui acid anhydrides, quinolinic acid
Acid anhydride, Yikang acid anhydrides or trimellitic anhydride.
5. according to any one of Claims 1-4 methods described, it is characterised in that ring-opening polymerisation described in step (1) is urged
Agent be metallic sodium, potassium, sodium hydride, hydrofining, sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide, NaOH, potassium hydroxide,
The quality of catalyst is the 0.1%-1% of compound a and compound b gross masses；
The reaction temperature of ring-opening polymerisation is 100-160 DEG C, and reaction pressure is anti-to carry out ring-opening polymerisation under 0-0.2MPa, oxygen free condition
Should, the feed time of compound b is 6-10h, and charging is incubated 2-4h after finishing.
6. according to any one of Claims 1-4 methods described, it is characterised in that after ring-opening polymerisation is finished, esterification step
Suddenly esterification catalyst is also added, the esterification catalyst is p-methyl benzenesulfonic acid, and consumption is the 0.01-0.5% of the total consumption of material,
Compound c is added, the temperature of ring-opening polymerisation is maintained the temperature at, after reaction 2-5h, cooling discharge obtains hyperbranched polymer.
7. according to any one of Claims 1-4 methods described, it is characterised in that prepare dissaving polymer dispersion inorganic
During the solution of particle, first dissaving polymer is scattered in after the aqueous solution, reaction temperature is maintained at 20～60 DEG C, by water-soluble calcium
Salt and water-soluble silicate are configured to the aqueous solution, while being added drop-wise in polymer solution, time for adding is 6-12h.
8. the application process of the organic inorganic hybridization additive obtained by any one of claim 1-7 method, it is characterised in that
Described organic inorganic hybridization additive can be compounded with high-performance water reducing agent, it is also possible to defoamer, air entraining agent, retarder, increasing
Thick dose, use after economization agent functional form additive compound, to adjust the combination property of concrete；The organic inorganic hybridization additive
Volume be the 1～6% of total Binder Materials.
9. according to weighing 8 methods describeds, it is characterised in that the volume of the organic inorganic hybridization additive is 2～5%.
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| CN106986572A (en) * | 2017-04-25 | 2017-07-28 | 北京工业大学 | A kind of method that concrete intensifier is prepared with dissaving polymer |
| CN107555829A (en) * | 2017-08-14 | 2018-01-09 | 山西格瑞特建筑科技股份有限公司 | A kind of nucleus type for concrete promotees solidifying early strength agent and preparation method thereof |
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| CN106986572B (en) * | 2017-04-25 | 2020-08-14 | 北京工业大学 | Method for preparing concrete reinforcing agent by using hyperbranched polymer |
| CN107555829A (en) * | 2017-08-14 | 2018-01-09 | 山西格瑞特建筑科技股份有限公司 | A kind of nucleus type for concrete promotees solidifying early strength agent and preparation method thereof |
| CN108178549B (en) * | 2017-12-29 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Preparation method and application of composite type super early strength additive |
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| CN109206609B (en) * | 2018-09-04 | 2020-10-30 | 济南大学 | Preparation and application of hyperbranched polyether air entraining agent |
| CN112358222A (en) * | 2020-11-17 | 2021-02-12 | 陈小龙 | Environment-friendly concrete early strength agent and preparation method thereof |
| CN115626805A (en) * | 2022-10-31 | 2023-01-20 | 山东高速工程建设集团有限公司 | Slag gypsum-based cementing material and preparation method thereof |
| CN115626805B (en) * | 2022-10-31 | 2023-09-15 | 山东高速工程建设集团有限公司 | Slag gypsum-based cementing material and preparation method thereof |
| CN116082001A (en) * | 2023-02-16 | 2023-05-09 | 北京中建瑞特新材料股份有限公司 | Permeable crystallization type waterproof plugging material and preparation method thereof |
| CN116082001B (en) * | 2023-02-16 | 2024-06-28 | 北京中建瑞特新材料股份有限公司 | Permeable crystallization type waterproof plugging material and preparation method thereof |
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Application publication date: 20170419 |