CN109956697A - A kind of more adsorption group intermediates, the preparation method and application of polymer - Google Patents
A kind of more adsorption group intermediates, the preparation method and application of polymer Download PDFInfo
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- CN109956697A CN109956697A CN201711415599.5A CN201711415599A CN109956697A CN 109956697 A CN109956697 A CN 109956697A CN 201711415599 A CN201711415599 A CN 201711415599A CN 109956697 A CN109956697 A CN 109956697A
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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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Abstract
The present invention provides a kind of more adsorption group intermediates, its polymer and preparation method thereof, by (methyl) acrylic acid autohemagglutination or copolymerization occur for more adsorption group intermediates, and esterification acquisition is carried out with mercaptoethanol, it carries out the polymer that polymerization obtains more adsorption group intermediates, the adsorption group of the polymer is concentrated, and independently of dispersion segment, solve the problems, such as that conventional polycarboxylic acid super-plasticizer adsorption group causes relative distribution degree larger by the separation of side chain connection site and causes adsorption capacity insufficient, also the relatively low problem for causing conversion ratio relatively low of activity to avoid ultrahigh molecular weight reactive polyether.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to a kind of more adsorption group intermediates, polymer
Preparation method and application.
Background technique
With the propulsion of national large-scale infrastructure and Urbanization Construction process, it is a series of include large bridge, nuclear power,
To concrete, more stringent requirements are proposed for the construction of the Important Projects such as water power, super high-rise building.Engineering construction difficulty is gradually increased,
Construction environment becomes increasingly complex, and the strength demand of especially high performance concrete is higher and higher, the usage amount of industrial residue component
It is increasing.Therefore, stable workability is just particularly important high performance concrete at different conditions.
Since Chinese Regional factor leads to the building materials quality of various regions, there are biggish differences, with the Aggregate in area
There is also a degree of fluctuations for quality.Currently, high performance concrete admixture have become prepare high performance concrete can not
The component lacked.The different performance that high performance concrete admixture shows under the conditions of different construction temperatures can all cause height
The quality fluctuation of performance concrete.Therefore also require high performance concrete admixture improve product dispersibility, to coagulation
More stringent requirements are proposed for the compatibility and adaptability of soil material, temperature sensitivity etc..
In numerous additive kinds, the polycarboxylic-acid dispersing agent of comb shaped structure has water-reducing rate height, Slump Time losing of Large
Small, the advantages such as volume is low become the hot spot studied both at home and abroad.
It is well known that poly carboxylic acid series concrete dispersing agent can be by adjusting the type and dosage of each component units of intramolecular
Ratio reaches different performances, and relevant polycarboxylic-acid dispersing agent and preparation method thereof has been disclosed in a large amount of Chinese patent,
It is essentially all to carry out copolymerization with the polyglycol ether or ester for having double bond using unsaturated carboxylic acid to form main comb-type structure.
The groups such as carboxyl, sulfonic group, the phosphate on conventional polycarboxylic-acid dispersant molecule main chain obtained according to these preparation methods
Absorption to cement granules is provided, dispersion repulsion is provided；Long side chain increases space steric effect, and forms thicker absorption water
Film keeps polycarboxylic-acid dispersing agent more obvious to the stably dispersing effect of cement granules, improves slump holding capacity.
Conventional polycarboxylic-acid dispersing agent still exposes partial properties defect in application process, such as temperature sensitivity, greatly
Dispersibility deficiency etc. under the conditions of volume industry admixture.
The molecular composition of analytic routines polycarboxylic-acid dispersing agent, it can be found that adsorption group component and side chain component are in molecule
In exist in a manner of alternate combinations, side chain is in curling state random distribution in main chain two sides.This combination makes molecule
The density of middle adsorption group decreases, and the state of curling of long side chain may also can hinder the exposure of adsorption group, makes its dispersion
Ability is affected, so as to cause the phenomenon of the dispersibility deficiency under the conditions of certain applications.In addition, due to high polymer itself
Property, under the conditions of different temperatures and ion concentration, different molecular conformations can be presented in polymer, be will also result in molecule and adsorbed
The decline of dispersibility caused by group exposure is insufficient.
The skeleton symbol of conventional comb-type structure polycarboxylic-acid dispersing agent is as follows:
To solve above-mentioned engineering application problem, construction personnel, which generallys use, to be increased admixture dosage or repeatedly adds additional
The mode of agent solves the problems, such as initial dispersion deficiency and temperature sensitivity, and this way undoubtedly increases difficulty of construction, also right
Concrete quality causes fluctuation.In view of the above-mentioned problems, scientific research personnel has carried out a large amount of improvement both at home and abroad, from following several
Aspect is studied, but is had certain problems.
(1) propose to increase the adsorption group quantity on main chain to improve the situation of adsorption capacity deficiency；Although solving portion
The problem of dividing initial dispersion under application conditions, but the excessively high later period apparent fluidity loss that will lead to of adsorption group shows in molecule
As；
(2) it proposes to improve dispersibility with the side chain of ultrahigh molecular weight；According to polycarboxylic acids dispersion theory, lengthening side chain should
Be conducive to improve dispersibility, but side chain is longer, reactivity can be deteriorated therewith, and polymerizable degree can be substantially reduced；
(3) it proposes block polymer concept, side chain in molecule is polymerized alone, backbone component is centrally located at the another of side chain
Side；This structure has feasibility in theory, but since synthesis process is extremely complex, requires very high to material quality and lacks
Commercial viability.
Summary of the invention
Cause relative distribution degree larger to solve conventional polycarboxylic acid super-plasticizer adsorption group by the separation of side chain connection site
And lead to the problem of adsorption capacity deficiency, also to avoid the activity of ultrahigh molecular weight reactive polyether (molecular weight be greater than 5000) partially
The low problem for causing conversion ratio relatively low.The present invention provides a kind of more adsorption group intermediates, and polymer and preparation method thereof comes
It solves the above problems.
More its structure of adsorption group intermediate A of the present invention meets following general formula (1):
Wherein R1Represent H or CH3；A, the value of b, c meet the integer that (a+b+c) value is 5~100, and the value model of b
Enclose be limited to 1~3 any number ".
(a+b+c) value is preferably 10~70.
(a+b+c) value is more preferably 20~50.
More adsorption group midbody polymer A are by monomer B in toluene as solvent, azodiisobutyronitrile (English
Abridge AIBN) it is used as initiator, mercaptopropionic acid under conditions of chain-transferring agent as being polymerize；Then in p-methyl benzenesulfonic acid conduct
Catalyst under conditions of toluene is as water entrainer, carries out esterification with monomer C and obtains.
Monomer B is methacrylic acid or acrylic acid, and two kinds of monomers can be used alone or two kinds with the mixed of arbitrary proportion
Solvate form uses.
Monomer C is mercaptoethanol.
The polymer of aforementioned more adsorption group intermediates is provided with anionic group intensive in more adsorption group intermediates
Adsorption capacity；Small-molecular-weight polyethers is copolymerized to obtain branched polymer segment offer dispersibility；More adsorption group intermediates pass through
The chain tra nsfer effect of itself is connected with chain branching polymer segment, forms new molecular architecture of the present invention.
The small-molecular-weight polyethers refers to weight average molecular weight in 5000 unsaturated polyethers below.
Polymer prepared by the present invention has adsorption group, the backbone structure of stretching, extension and the large volume side chain of concentration concentrated
Structure has good dispersion performance under ultralow volume, while having good adaptability for materials, efficiently solves poly- carboxylic
The problem of dispersibility deficiency under the conditions of the temperature sensitivity and large dosage admixture of sour series plasticiser.
The polymer of aforementioned more adsorption group intermediates, molecule skeleton symbol are as follows:
In polymer of the present invention in main chain adsorption group complete set, side chain does not account for the adsorption potential on main chain substantially
Point；Side chain component high concentration prepares large volume of branching segment by the copolymerization of small-molecular-weight polyethers, solves super large point
The low problem of son amount polyethers polymerization activity.
The preparation method of the polymer of more adsorption group intermediates, among monomer D, monomer E and more adsorption groups
Body A in aqueous solution, existing for the redox initiator under the conditions of carry out polymerization reaction, after reaction in alkaline matter
With obtain.
The weight average molecular weight of the polymer of more adsorption group intermediates is 5,000~100,000.
Monomer D is indicated with general formula (2):
In general formula (2), R2Represent H or CH3；R3It is the alkyl of H or 1~4 carbon atom, X=O, CH2O、CH2CH2O or
PersonP is the average addition molal quantity of ethylene oxide, is 10~110 integer.
Monomer E is indicated with general formula (3):
R in general formula (3)4Represent H or CH3；R5It is NH2、
In general formula (3) of the present invention, monomer E must be in the molecular structure without Anion-adsorption group.
The monomer D is selected from vinyl polyglycol ether, allyl polyglycol ether, 3- butene-1-ol base polyethylene glycol
The poly- Asia of vinyl of ether, methylallyl polyglycol ether, 3- methyl-3-butene-1-alcohol base polyglycol ether, methoxy group
Alkyl glycol ether, the vinyl polyalkylene glycols ether of ethyoxyl sealing end, the vinyl polyalkylene second of propoxyl group sealing end
Glycol ethers, butoxy sealing end vinyl polyalkylene glycols ether, the allyl polyalkylene glycols ether of methoxy group,
The allyl polyalkylene glycols ether of ethyoxyl sealing end, the allyl polyalkylene glycols ether of propoxyl group sealing end, butoxy
Allyl polyalkylene glycols ether, the 3- butene-1-ol base polyalkylene glycols ether of methoxy group, ethyoxyl of sealing end
3- butene-1-ol base polyalkylene glycols ether, the 3- butene-1-ol base polyalkylene glycols of propoxyl group sealing end of sealing end
3- butene-1-ol base polyalkylene glycols ether, the methylallyl polyalkylene second of methoxy group of ether, butoxy sealing end
The methylallyl polyalkylene that glycol ethers, the methylallyl polyalkylene glycols ether of ethyoxyl sealing end, propoxyl group block
Glycol ether, butoxy sealing end methylallyl polyalkylene glycols ether, methoxy group 3- methyl-3- butene-1-
Alcohol radical polyalkylene glycols ether, the 3- methyl-3-butene-1-alcohol base polyalkylene glycols ether of ethyoxyl sealing end, propoxyl group
The 3- methyl-3-butene-1-alcohol base polyalkylene glycols ether of sealing end, the 3- methyl-3-butene-1-alcohol base of butoxy sealing end are poly-
(methyl) third that alkylidene glycol ether, (methyl) acrylic acid polyalkylene glycols ester of methoxy group, ethyoxyl block
What olefin(e) acid polyalkylene glycols ester, (methyl) acrylic acid polyalkylene glycols ester of propoxyl group sealing end or butoxy blocked
The mixture of one or more of (methyl) acrylic acid polyalkylene glycols ester arbitrary proportion.
Monomer E can be selected from (methyl) acrylamide, (methyl) hydroxy-ethyl acrylate, one in (methyl) hydroxypropyl acrylate
The mixture of kind or two or more arbitrary proportions.
The polymer molecular structure of more adsorption group intermediates meets following general formula (4) according to the present invention:
Wherein a, b, c represent the corresponding number of repeat unit of monomer B in more adsorption group intermediates, wherein the contemporary list of b
The quantity of body C counter structure unit；D represents the corresponding number of repeat unit of monomer D, and p is the repetition list of monomer D epoxide epoxy group group
First number；E represents the corresponding number of repeat unit of monomer E.
Monomer D: monomer E in the polymer of more adsorption group intermediates of the present invention: more adsorption group intermediate As are rubbed
You are than being 1:1~3:0.02~0.15.R1~R5Functional group respectively in monomer has described clear in monomer introduction；R6
The alkali metal ion or amido brought into for neutralization stage after the completion of polymerization reaction.
Most suitable trigger rate of the present invention according to free radical polymerization, oxidant is in the redox initiator
The hydrogen peroxide that mass concentration is 30%, reducing agent is L-AA.Oxidizer accounts for monomer D and monomer E total mole number
0.5~10%, reducing agent dosage accounts for the 0.2~5% of monomer D and monomer E total mole number.Oxidant in the redox system
It is added in reaction vessel before starting the reaction, the aqueous solution of reducing agent is added to reaction after reaction starts in a manner of dropwise addition
In container.
In the present invention, the weight average molecular weight of the polymer of more adsorption group intermediates must control 5000~
100000, if molecular weight is too small and too big, to the dispersion performance, slump-retaining energy and adaptability for materials etc. of concrete
Performance can bring undesirable effect.
In order to improve product quality, in carrying out the present invention, monomer D and oxidant are then added to reaction before starting the reaction
In container, the aqueous solution of monomer E, more adsorption group intermediate As and reducing agent are added in the form of dropwise addition after reaction starts
In reaction vessel, to improve the conversion ratio and Copolymerization activity of monomer D.Rate of addition and each monomer for each monomer
Molar ratio can synthesize being total to for different composition distributions by changing above-mentioned rate of addition and molar ratio in polymerization reaction system
Copolymer mixture.
In carrying out the present invention, control that higher polymerization concentration is 30~60wt% and lower polymerization temperature is 30~60
It is carried out at DEG C, the aqueous solution time for adding of monomer E, more adsorption group intermediate As and reducing agent are controlled in 2~6h, polymerization reaction
Time controls in 5~10h.After polymerization reaction, it is 6~8 that alkali compounds adjustment pH value is added into reaction product, described
Alkali compounds selection ammonium hydroxide, organic amine, monovalent metal or divalent metal hydroxide or its carbonate.
The polycarboxylic-acid hyper-dispersant that the polymer of more adsorption group intermediates of the present invention can be used as concrete uses,
Its conventional volume is the 0.03~0.4% of cement concrete glue material gross mass.If additive amount is less than 0.03%, dispersion
Performance and reinforcing effect are unsatisfactory.If opposite additive amount is more than 0.4%, it is only to pass through that proof, which is excessively added,
Waste in Ji, because not bringing the corresponding growth in effect.
The polymer of more adsorption group intermediates of the present invention can also be at least one selected from known in the state of the art
Aminosulfonic water-reducing agent, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent mix.In addition, except mentioning above
Outside the known cement water reducing agent arrived, wherein can also be added according to actual needs air entraining agent, swelling agent, retarder, early strength agent,
Tackifier, economization agent and defoaming agent etc..
The polymer of more adsorption group intermediates of the present invention compared with present technology, has as polycarboxylate water-reducer
There is advantage below:
(1) this method significantly improves the water reducing ability of existing polycarboxylate dispersant, effectively reduces in concrete and disperses
The dosage of agent reduces Cost of Concrete.
This new structure that the present invention realizes makes the conformation of molecule curl curling for structure optimization solid by flat
Structure increases space steric effect, forms bigger water film thickness in cement surface, effectively increases polymer in cement
Dispersibility in system also just brings the promotion of water reducing ability, the reduction of volume, the reduction of Cost of Concrete.
(2) the polycarboxylic-acid hyper-dispersant of this method preparation effectively reduces temperature sensitivity, in large dosage industrial residue
Dispersibility is remarkably reinforced in concrete system, improves the adaptability of concrete material.
The present invention realizes the separation of absorbed component and steric hindrance component, concentrates the adsorption group of polymer more more
Add exposure, improve main chain rigidity, to improve the adsorption capacity of polymer.The polymer of this structure is in cryogenic conditions
Lower have a conformation more stretched compared to conventional polycarboxylate water-reducer, adsorption capacity is insufficient under effective solution cryogenic conditions asks
Topic.Equally, with the enhancing of itself adsorption capacity, bigger point is also shown when applying in large dosage industry admixture system
The ability of dissipating, improves the adaptability of material.
(3) it improves polymer and is saturated volume point, concrete viscosity is effectively reduced.
Polymer molecular weight can be accomplished relatively small range by the method for the invention, and cooperation is with point of opposite stretching, extension
Sub- conformation can obviously reduce concrete viscosity while guaranteeing that polymer plays effective dispersibility, improve saturation volume point.
Specific embodiment
Following embodiment has described in more detail the process for preparing polymerizate according to the method for the present invention, and these realities
It applies example to provide by way of illustration, its object is to those skilled in the art can understand the contents of the present invention and accordingly
Implement, but these embodiments are in no way intended to limit the scope of the present invention.Equivalence changes made by all Spirit Essences according to the present invention are repaired
Decorations, should be covered by the protection scope of the present invention.
Monomer used in following examples is as shown in table 1, and the polycarboxylic-acid hyper-dispersant of synthesis is abbreviated as SDP.
In the embodiment of the present invention, the weight average molecular weight of polymer is measured using 1260 chromatograph of Agilent.(gel column:
The series connection of two root chromatogram column of Shodex SB806+803；Elutriant: 0.1M NaNO3Solution；Flow phase velocity: 1.0ml/min；Note
It penetrates: 20 μ l, 0.5% aqueous solution；Detector: differential refraction detector；Reference substance: polyethylene glycol GPC standard specimen (Sigma-
Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232).
In Application Example of the present invention, except illustrating, used cement is small open country II cement of field 52.5R.P., sand
For the middle sand of fineness modulus Mx=2.6, stone is the rubble that partial size is 5~20mm continuous grading.
Compound numbers described in table 1 are used in synthetic example of the present invention:
1 embodiment compound numbers of table
Embodiment 1
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 650g deionization is added
Water, while 500g D-1 (1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 40 DEG C of dissolutions, it is rear to be added
Hydrogen peroxide (mass concentration 30%) 1.15g, stirs evenly.By 71g E-1 (1mol), 14.7g A-1 (0.03mol), water
500g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 2h, and be added dropwise simultaneously
200g contains the aqueous solution of 0.7g L-AA, and time for adding about 2.5h is added dropwise rear insulation reaction 3h and is cooled to room
Temperature adds alkali neutralization to pH value 7.0, and obtaining solid content is 30% light yellow clear liquid, molecular weight 13,000 (SDP-1).
Embodiment 2
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 400g deionization is added
Water, while 400g D-2 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 30 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 4.55g, stirs evenly.By 25.5g E-2 (0.3mol), 17.7g A-2
(0.002mol), water 135g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 4h,
And the aqueous solution that 100g contains 3.52g L-AA is added dropwise simultaneously, rear insulation reaction is added dropwise in time for adding about 4.5h
3h is cooled to room temperature, and adds alkali neutralization to pH value 7.0, obtaining solid content is 40% light yellow clear liquid, molecular weight 98,000
(SDP-2)。
Embodiment 3
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 300g deionization is added
Water, while 400g D-3 (0.4mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 60 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 1.8g, stirs evenly.By 46.4g E-3 (0.4mol), 48g A-3 (0.06mol),
Water 80g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 3h, and be added dropwise simultaneously
50g contains the aqueous solution of 1.4g L-AA, and time for adding about 3.5h is added dropwise rear insulation reaction 4h and is cooled to room temperature,
Add alkali neutralization to pH value 7.0, obtaining solid content is 50% light yellow clear liquid, molecular weight 5,000 (SDP-3).
Embodiment 4
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 240g deionization is added
Water, while 480g D-4 (0.2mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 50 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 5.44g, stirs evenly.By 52g E-4 (0.4mol), 15.3g A-4
(0.005mol), water 80g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 6h,
And the aqueous solution that 40g contains 4.2g L-AA is added dropwise simultaneously, rear insulation reaction is added dropwise in time for adding about 6.5h
3.5h is cooled to room temperature, and adds alkali neutralization to pH value 7.0, and obtaining solid content is 60% light yellow clear liquid, molecular weight 75,
000(SDP-4)。
Embodiment 5
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 200g deionization is added
Water, while 300g D-5 (0.2mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 40 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 1.81g, stirs evenly.By 26g E-5 (0.2mol), 16.7g A-5
(0.01mol), water 100g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 5h,
And the aqueous solution that 40g contains 1.76g L-AA is added dropwise simultaneously, rear insulation reaction 2h is added dropwise in time for adding about 6.5h
It is cooled to room temperature, adds alkali neutralization to pH value 7.0, obtaining solid content is 50% light yellow clear liquid, molecular weight 31,000
(SDP-5)。
Embodiment 6
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 400g deionization is added
Water, while 300g D-6 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 45 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 1.36g, stirs evenly.By 43.2g E-6 (0.3mol), 31.8g A-6
(0.006mol), water 200g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 2h,
And the aqueous solution that 90g contains 1.1g L-AA is added dropwise simultaneously, rear insulation reaction 4h is added dropwise in time for adding about 2.5h
It is cooled to room temperature, adds alkali neutralization to pH value 7.0, obtaining solid content is 35% light yellow clear liquid, molecular weight 57,000
(SDP-6)。
Embodiment 7
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 350g deionization is added
Water, while 440g D-7 (0.2mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 35 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 3.4g, stirs evenly.By 28.4g E-1 (0.4mol), 46.9g A-7
(0.02mol), water 200g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 4h,
And the aqueous solution that 70g contains 1.6g L-AA is added dropwise simultaneously, rear insulation reaction 3h is added dropwise in time for adding about 4.5h
It is cooled to room temperature, adds alkali neutralization to pH value 7.0, obtaining solid content is 45% light yellow clear liquid, molecular weight 24,000
(SDP-7)。
Embodiment 8
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 400g deionization is added
Water, while 500g D-8 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 55 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 2.7g, stirs evenly.By 43.2g E-6 (0.3mol), 15.85g A-8
(0.004mol), water 100g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 6h,
And the aqueous solution that 40g contains 1.9g L-AA is added dropwise simultaneously, rear insulation reaction 2h is added dropwise in time for adding about 6.5h
It is cooled to room temperature, adds alkali neutralization to pH value 7.0, obtaining solid content is 50% light yellow clear liquid, molecular weight 83,000
(SDP-8)。
Embodiment 9
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 600g deionization is added
Water, while 400g D-9 (0.4mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 30 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 1.4g, stirs evenly.By 34g E-2 (0.4mol), 39g A-3 (0.05mol), water
300g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 5h, and be added dropwise simultaneously
200g contains the aqueous solution of 0.7g L-AA, and time for adding about 5.5h is added dropwise rear insulation reaction 2h and is cooled to room
Temperature adds alkali neutralization to pH value 7.0, and obtaining solid content is 30% yellowish-brown transparency liquid, molecular weight 8,100 (SDP-9).
Embodiment 10
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 300g deionization is added
Water, while 300g D-10 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 50 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 2.4g, stirs evenly.By 26g E-4 (0.2mol), 11g A-7 (0.004mol),
Water 130g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 4h, and be added dropwise simultaneously
70g contains the aqueous solution of 1.6g L-AA, and time for adding about 4.5h is added dropwise rear insulation reaction 3h and is cooled to room temperature,
Add alkali neutralization to pH value 7.0, obtaining solid content is 40% yellowish-brown transparency liquid, molecular weight 24,000 (SDP-10).
Comparative example 1
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 200g deionization is added
Water, while 400g D-2 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 30 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 6.3g, stirs evenly.Then by 51.6g methacrylic acid (0.6mol), 3.7g mercapto
Base propionic acid, water 70g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 4h, and same
When 30g be added dropwise contain the aqueous solution of 3.7g L-AA, rear insulation reaction 3h is added dropwise in time for adding about 4.5h, cooling
To room temperature, add alkali neutralization to pH value 7.0, obtaining solid content is 60% light yellow clear liquid, molecular weight 58,000 (PC-1).
Comparative example 2
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 230g deionization is added
Water, while 300g D-5 (0.2mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 40 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 1.6g, stirs evenly.Then by 36g acrylic acid (0.5mol), 2.2g mercaptoethanol,
Water 70g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 5h, and be added dropwise simultaneously
30g contains the aqueous solution of 1.3g L-AA, and time for adding about 5.5h is added dropwise rear insulation reaction 2h, is cooled to room
Temperature adds alkali neutralization to pH value 7.0, and obtaining solid content is 50% light yellow clear liquid, molecular weight 17,000 (PC-2).
Comparative example 3
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 300g deionization is added
Water, while 300g D-6 (0.1mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 50 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 2g, stirs evenly.Then by 43g methacrylic acid (0.5mol), 1g mercaptopropionic acid,
Water 100g phase is mixed, and uniform monomer solution is made in stirring, is added dropwise to reactor, time for adding 2h, and be added dropwise simultaneously
100g contains the aqueous solution of 3.7g L-AA, and time for adding about 2.5h is added dropwise rear insulation reaction 4h, is cooled to room
Temperature adds alkali neutralization to pH value 7.0, and obtaining solid content is 40% light yellow clear liquid, molecular weight 87,000 (PC-3).
Comparative example 4
In the glass reactor equipped with thermometer, blender, dropping funel and nitrogen ingress pipe, 600g deionization is added
Water, while 440g D-7 (0.2mol) is added, nitrogen purge reaction vessel is used while stirring, and is warming up to 60 DEG C of dissolutions, it is rear to add
Enter hydrogen peroxide (mass concentration 30%) 5.7g, stirs evenly.Then by 57.6g acrylic acid (0.8mol), 2.3g sulfydryl second
Alcohol, water 300g phase are mixed, and uniform monomer solution is made in stirring, are added dropwise to reactor, time for adding 4h, and drip simultaneously
200g is added to contain the aqueous solution of 5.3g L-AA, time for adding about 4.5h is added dropwise rear insulation reaction 2h, is cooled to
Room temperature adds alkali neutralization to pH value 7.0, and obtaining solid content is 30% light yellow clear liquid, molecular weight 24,000 (PC-4).
Application examples 1:
Flowing degree of net paste of cement test: it is carried out referring to GB/T8077-2000 standard, using small open country II cement of field 52.5R.P.
300g, amount of water 87g, measures flowing degree of net paste of cement on plate glass after stirring.Flowing degree of net paste of cement test
It the results are shown in Table 2.
The test of 2 paste flowing degree of table
Polycarboxylic-acid hyper-dispersant of the invention is under the conditions of low-dosage to cement it can be seen from the test result of table 2
There is good dispersibility.Effective volume of the polymer of the method for the present invention preparation, which compares conventional polycarboxylic acid super-plasticizer, to be had very greatly
Decline, can substantially reduce volume 20~30%, while still showing better dispersion holding capacity.
In order to characterize the temperature sensitivity of polycarboxylic-acid hyper-dispersant prepared by the method for the present invention, contrived experiment is in 5 DEG C, 20
DEG C and 35 DEG C under the conditions of respectively the paste flowing degree of test sample and through when fluidity, experimental result is shown in Table 3
Paste flowing degree is tested under 3 condition of different temperatures of table
Conventional polycarboxylate water-reducer shows initial dispersion ability under cryogenic it can be seen from the test result of table 3
Not by force, the phenomenon that but rising appreciably at any time.It is inclined that this phenomenon will cause concrete initial flow degree on engineer application
It is small, and later period fluidity is excessive and leads to isolate bleeding, influences construction quality.Under the high temperature conditions, conventional water-reducing agent
Show obviously fluidity loss phenomenon.Polycarboxylic-acid hyper-dispersant of the invention is shown under condition of different temperatures
Good dispersibility and dispersion holding capacity out especially show as initial dispersion ability abundance under low temperature, and later period fluidity is not
The advantage to rise appreciably, and do not occur apparent fluidity loss under the high temperature conditions.Compared to conventional polycarboxylate dispersant, originally
Invention polymer, which reaches effective volume under the conditions of similar performance, which compares conventional water-reducing agent, apparent reduction.
Application examples 2:
Air content, compression strength and slump test: it is tried referring to the relevant regulations of GB8076-2008 " concrete admixture "
Proved recipe method has carried out the measurement of air content；Referring to GB/T50081-2016 " standard for test methods of mechanical properties of ordinary concrete "
Relevant regulations carried out concrete crushing strength test；Referring to GB50080-2016 " normal concrete mixture performance test
Method standard " relevant regulations have carried out slump consistancy test and Slump Time losing of Large test, and have carried out inversion slump cone row
Sky test.Fixing concrete water-cement ratio in test, and adjust copolymer volume make fresh concrete initial slump 21 ±
1cm, experimental result are shown in Table 4.Reference
4 concrete performance of table
It is above-mentioned experiments have shown that, using polycarboxylic-acid hyper-dispersant prepared by the present invention significantly lower than conventional polycarboxylic acids dispersion
It is obtained with very strong water reducing ability under the volume of agent, and shows in terms of slump-retaining energy obviously excellent
Gesture.With comparison concrete 28d compression strength data under the conditions of water-cement ratio it is found that polycarboxylic acid super-plasticizer prepared by the present invention has
The effect of better concrete enhancing.It can be seen that with the time correlation data of decaying under the conditions of fluidity prepared by the present invention
Concrete viscosity can be effectively reduced in polycarboxylic-acid hyper-dispersant, be more advantageous to pumping construction.
Polycarboxylic-acid of the present invention under the conditions of flyash in great mixed amount (substitution cement 40%) is demonstrated using above-mentioned test method
The performance difference of hyper-dispersant and conventional polycarboxylate dispersant, and decaying the time for concrete is tested, experimental result is shown in Table 5.
5 concrete performance of table
Flyash in great mixed amount system experiments have shown that, using polycarboxylic-acid hyper-dispersant prepared by the present invention in the system with
Conventional polycarboxylate dispersant, which compares, to be had the effect of bigger volume advantage and reduces concrete viscosity, it was demonstrated that in large dosage industry
Waste residue system has better adaptability.
Application examples 3:
By taking polycarboxylic-acid hyper-dispersant SDP-5 of the present invention and comparative example PC-2 as an example, referring to GB8076-2008 " concrete
Additive " relevant regulations test method carried out the measurement of water-reducing rate.Referring to GB50080-2016 " normal concrete mixture
Method for testing performance standard " relevant regulations test the performances of two kinds of dispersing agent fresh concretes under the conditions of different addition quantity, and it is real
It tests and the results are shown in Table 6:
6 fresh mixing concrete property of table
Under the conditions of same volume be can be seen that from the test data of table 6, the water reducing ability of SDP-5 is apparently higher than comparative example PC-
2, especially slump holding capacity are even more to have significant advantage.Therefore, the polycarboxylic acid super-plasticizer of the method for the present invention preparation
The dosage of dispersing agent in concrete can be effectively reduced, reduce Cost of Concrete while guaranteeing concrete quality.In addition, two
The water reducing ability of person can be improved with the increase of volume, and the saturation volume of the SDP-5 of the method for the present invention preparation is apparently higher than pair
Ratio PC-2.
The bound value of each raw material and each raw material cited by the present invention, can realize the present invention, herein not one by one
Enumerate embodiment.
Inventor: Zhou Dongliang, Liu Jiaping, Ran Qianping, Yang Yong, Yan Han, Zhai Shuying, Li Shentong.
Claims (13)
1. a kind of more adsorption group intermediates, which is characterized in that its structure meets following general formula (1):
Wherein R1Represent H or CH3；A, the value of b, c meet the integer that (a+b+c) value is 5~100, and the value range of b is 1
~3 any number.
2. more adsorption group intermediates according to claim 1, which is characterized in that (a+b+c) value is 10~70.
3. more adsorption group intermediates according to claim 1, which is characterized in that (a+b+c) value is 20~50.
4. the preparation method of more adsorption group intermediates described in any one of claim 1-3, which is characterized in that pass through list
Body B is in toluene as solvent, and azodiisobutyronitrile (AIBN) is used as initiator, and mercaptopropionic acid is polymerize as chain-transferring agent；
Then in p-methyl benzenesulfonic acid as catalyst, under conditions of toluene is as water entrainer, esterification is carried out with monomer C and is obtained；
Monomer B is methacrylic acid or acrylic acid, and two kinds of monomers can be used alone or two kinds of mixtures with arbitrary proportion
Form uses；
Monomer C is mercaptoethanol.
5. using the polymer of more adsorption group intermediates described in claim 1, which is characterized in that the absorption of the polymer
The position of group and the chain fragment position for providing steric hindrance are respectively independent；With anion base intensive in more adsorption group intermediates
Group provides adsorption capacity；Small-molecular-weight polyethers is copolymerized to obtain branched polymer segment offer dispersibility；Among more adsorption groups
Body is connected by the chain tra nsfer effect of itself with chain branching polymer segment；
Small-molecular-weight polyethers refers to weight average molecular weight in 5000 unsaturated polyethers below.
6. the polymer of more adsorption group intermediates according to claim 5, which is characterized in that its molecule skeleton symbol is as follows:
7. the preparation method of the polymer of more adsorption group intermediates described in claim 5 or 6, which is characterized in that
As monomer D, monomer E and more adsorption group intermediate As in aqueous solution, existing for the redox initiator under the conditions of into
Row polymerization reaction is neutralized with alkaline matter after reaction；
Monomer D: monomer E: the molar ratio of more adsorption group intermediate As is 1:1~3:0.02~0.15；
Monomer D is indicated with general formula (2):
In general formula (2), R2Represent H or CH3；R3It is the alkyl of H or 1~4 carbon atom, X=O, CH2O、CH2CH2O or
P is the average addition molal quantity of ethylene oxide, is 10~110 integer；
Monomer E is indicated with general formula (3):
R in general formula (3)4Represent H or CH3；R5It is NH2、
Oxidant is the hydrogen peroxide that mass concentration is 30% in the redox initiator, and reducing agent is L- Vitamin C
Acid；Oxidizer accounts for the 0.5~10% of monomer D and monomer E total mole number, and reducing agent dosage accounts for monomer D and monomer E total moles
Several 0.2~5%；Oxidant is added in reaction vessel before starting the reaction in the redox system, reducing agent it is water-soluble
Liquid is added in reaction vessel in a manner of dropwise addition after reaction starts.
8. the method according to the description of claim 7 is characterized in that monomer E must be in the molecular structure in the general formula (3)
Without Anion-adsorption group.
9. the method according to the description of claim 7 is characterized in that the monomer D is selected from vinyl polyglycol ether, allyl
Polyglycol ether, 3- butene-1-ol base polyglycol ether, methylallyl polyglycol ether, 3- methyl-3-butene-1-alcohol base
Polyglycol ether, the vinyl polyalkylene glycols ether of methoxy group, the vinyl polyalkylene second two of ethyoxyl sealing end
Alcohol ether, the vinyl polyalkylene glycols ether of propoxyl group sealing end, vinyl polyalkylene glycols ether, the first of butoxy sealing end
The allyl polyalkylene glycols ether of oxygroup sealing end, the allyl polyalkylene glycols ether of ethyoxyl sealing end, propoxyl group envelope
The allyl polyalkylene glycols ether at end, the allyl polyalkylene glycols ether of butoxy sealing end, methoxy group 3-
Butene-1-ol base polyalkylene glycols ether, the 3- butene-1-ol base polyalkylene glycols ether of ethyoxyl sealing end, propoxyl group
3- butene-1-ol base polyalkylene glycols ether, the 3- butene-1-ol base polyalkylene glycols of butoxy sealing end of sealing end
Ether, the methylallyl polyalkylene glycols ether of methoxy group, the methylallyl polyalkylene second two of ethyoxyl sealing end
Alcohol ether, the methylallyl polyalkylene glycols ether of propoxyl group sealing end, the methylallyl polyalkylene second of butoxy sealing end
3- methyl-the 3- that glycol ethers, the 3- methyl-3-butene-1-alcohol base polyalkylene glycols ether of methoxy group, ethyoxyl block
Butene-1-ol base polyalkylene glycols ether, propoxyl group sealing end 3- methyl-3-butene-1-alcohol base polyalkylene glycols ether,
The 3- methyl-3-butene-1-alcohol base polyalkylene glycols ether of butoxy sealing end, (methyl) acrylic acid of methoxy group are poly- sub-
(methyl) propylene that alkyl glycol ester, (methyl) acrylic acid polyalkylene glycols ester of ethyoxyl sealing end, propoxyl group block
Sour polyalkylene glycols ester or butoxy sealing end (methyl) acrylic acid polyalkylene glycols ester in any one or
The mixture of any two or more arbitrary proportions；
Monomer E can be selected from one of (methyl) acrylamide, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate or
The mixture of two or more arbitrary proportions.
10. the method according to the description of claim 7 is characterized in that the weight of the polymer of more adsorption group intermediates is equal
Molecular weight is 5,000~100,000.
11. the method according to the description of claim 7 is characterized in that the polymer molecule knot of more adsorption group intermediates
Structure meets following general formula (4):
Wherein a, b, c represent the corresponding number of repeat unit of monomer B in more adsorption group intermediates, wherein contemporary C pairs of list body of b
Answer the quantity of structural unit；D represents the corresponding number of repeat unit of monomer D, and p is the number of repeat unit of monomer D epoxide epoxy group group；
E represents the corresponding number of repeat unit of monomer E；
R1~R5Functional group respectively in monomer has described clear in monomer introduction；R6 is neutralization after the completion of polymerization reaction
The alkali metal ion or amido that the stage of reaction is brought into.
12. the method according to the description of claim 7 is characterized in that monomer D and oxidant are then added to instead before starting the reaction
It answers in container, the aqueous solution of monomer E, more adsorption group intermediate As and reducing agent are added in the form of dropwise addition after reaction starts
Into reaction vessel,
In polymerization reaction, control polymerization concentration is 30~60wt% and polymerization temperature is to carry out at 30~60 DEG C, monomer E, more suctions
The control of the aqueous solution time for adding of attached group intermediate A and reducing agent is controlled in 2~6h, polymerization reaction time in 5~10h；
After polymerization reaction, it is 6~8 that alkali compounds adjustment pH value is added into reaction product, the alkali compounds
Select the hydroxide or its carbonate of ammonium hydroxide, organic amine, monovalent metal or divalent metal.
13. the application method of the polymer of more adsorption group intermediates described in claim 5 or 6, which is characterized in that as mixed
The polycarboxylic-acid hyper-dispersant for coagulating soil uses, in an amount of from the 0.03~0.4% of cement concrete glue material gross mass.
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| CN112979867A (en) * | 2021-02-07 | 2021-06-18 | 中铝环保生态技术(湖南)有限公司 | Heavy metal sulfydryl adsorption material and preparation method thereof |
| CN117417542A (en) * | 2023-10-18 | 2024-01-19 | 湖北英采化学有限公司 | High-strength Wen Jiangnian early-strength-resistant dispersing agent |
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| CN102093520A (en) * | 2010-12-22 | 2011-06-15 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant |
| US20130231415A1 (en) * | 2012-03-05 | 2013-09-05 | Ruetgers Polymers Ltd. | Slump Retaining and Dispersing Agent for Hydraulic Compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093520A (en) * | 2010-12-22 | 2011-06-15 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant |
| US20130231415A1 (en) * | 2012-03-05 | 2013-09-05 | Ruetgers Polymers Ltd. | Slump Retaining and Dispersing Agent for Hydraulic Compositions |
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| CN112979867A (en) * | 2021-02-07 | 2021-06-18 | 中铝环保生态技术(湖南)有限公司 | Heavy metal sulfydryl adsorption material and preparation method thereof |
| CN112979867B (en) * | 2021-02-07 | 2023-07-21 | 中铝环保生态技术(湖南)有限公司 | Heavy metal sulfhydryl adsorption material and preparation method thereof |
| CN117417542A (en) * | 2023-10-18 | 2024-01-19 | 湖北英采化学有限公司 | High-strength Wen Jiangnian early-strength-resistant dispersing agent |
| CN117417542B (en) * | 2023-10-18 | 2024-04-19 | 湖北英采化学有限公司 | High-resistant Wen Jiangnian early-strength dispersing agent |
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