CN108084362A - A kind of solid polycarboxylic acid water reducing agent and its preparation method and application - Google Patents
A kind of solid polycarboxylic acid water reducing agent and its preparation method and application Download PDFInfo
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- CN108084362A CN108084362A CN201711464228.6A CN201711464228A CN108084362A CN 108084362 A CN108084362 A CN 108084362A CN 201711464228 A CN201711464228 A CN 201711464228A CN 108084362 A CN108084362 A CN 108084362A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds 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
- C04B2103/302—Water reducers
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Abstract
The present invention relates to technical field of concrete additives, and in particular to a kind of solid polycarboxylic acid water reducing agent and its preparation method and application.The present invention is by by unsaturated carboxylic acid and liquid pfpe monomer direct Raolical polymerizable in the environment without any solvent, the solid water-free polycarboxylate water-reducer being had excellent performance.The method uses bulk polymerization mode, without using any solvent or medium in whole process, effectively improves and adds in water or organic solvent, the method for later stage removing the early period routinely used；Obtained product not only convenient transportation, but also performance is better than commercial solid polycarboxylate water-reducer.
Description
Technical field
The present invention relates to technical field of concrete additives, and in particular to a kind of solid polycarboxylic acid water reducing agent and its preparation
Method and purposes.
Background technology
Fifth component of the polycarboxylate water-reducer as modern concrete is set by its excellent low-dosage, high-thin arch dam, molecule
The advantages that degree of freedom is big is counted, is used widely in concrete works technical field.The polycarboxylate water-reducer being widely used at present
The mostly solution product of 10-50% concentration, this causes very big cost problem to long-distance transportation.In dry powder and mortar, use
Before liquid water-reducing agent product need to be carried out to spray drying rear can be used, but drying process with atomizing process high energy consumption, spray drying
The comprehensive performance of product declines afterwards, and the performance of liquid polycarboxylate water-reducer is not achieved in practical applications.Therefore, develop anhydrous pure
The high performance water reducing agent of polyocarboxy acid of solid for reducing cost, accelerates the development of polycarboxylate water-reducer industry, popularization polycarboxylic acids subtracts
Aqua application has extremely important meaning.
Patent document CN102993387B reports the method that a step directly synthesizes pure solid high-performance polycarboxylate water-reducer.
The invention adds in molecular weight regulator, is drawing using acrylic compounds and unsaturated polyoxyethylene ether as polymerization reaction monomer
It is made under the action of hair agent in the environment of without any solvent by free radical bulk polymerization.The invention passes through bulk polymerization
Realize the preparation of complete anhydrous pure solid high-performance polycarboxylate water-reducer, but due under room temperature unsaturated polyoxyethylene ether be
Solid product under high temperature, it is necessary to be melted, in addition, system is sticky during its polymerization, monomer conversion is low.
In order to reduce polymerization system viscosity, patent document CN201611089616.6 and CN201611089676.8 are reported
The organic solvent of polymeric monomer 20-50% mass parts is added in polymerization system, synthesizes early strong or collapse protection type water-reducing agent.But it is polymerizeing
It needs to carry out solvent removal process after completion of the reaction.In addition, the organic solvent CCl used4It is of high cost, toxicity is larger, process is numerous
It is trivial.
Patent document CN106893047 is reported and polyglycol ether is added in prenol, and stirring makes its fusing, successively
Organic oxidizing agent and chain-transferring agent are added in, the mixture that acrylic acid and organic reducing agent is added dropwise prepares solid polycarboxylic acid water reducing agent
Method.However the low-molecular-weight polyethylene glycol used in this method disperses cement not help, and causes the waste of resource, and easily exist
Bubble is introduced in mortar architecture, strength of cement is caused to reduce.
Patent document CN201710293128.5 is reported adds in the water of electrolyte and 8-21% to drop in polymerization system
Low viscosity, synthesized high-performance solid polycarboxylic acid water reducing agent.However this method needs high temperature, high pressure-off after completion of the polymerization reaction
Water crushes section under liquid nitrogen cryogenics, and energy consumption is high, and preparation process is complicated.
Further, since the polyether macromonomer used at present in the synthesis of Conventional solid polycarboxylate water-reducer for solid, it is necessary to
High temperature melting, polymerization temperature is high, and viscosity is big, and technique is all to reduce fusion temperature and viscosity using thinner is added at present.This
Further increase manufacturing cost.
Based on the above problem, it is necessary to the preparation method of solid polycarboxylic acid water reducing agent is improved, subtracted with its satisfaction
The different use demand in aqua field.
The content of the invention
It is described to subtract the present invention provides a kind of solid polycarboxylic acid water reducing agent in order to improve the deficiencies in the prior art
Aqua includes passing through polymerisation, example by liquid unsaturated polyether compound and Formula Il compound represented, its salt or acid anhydrides
Such as free crowd polymer obtained by the reaction：
Wherein, A, B, C are identical or different, be independently from each other H ,-COOH, it is unsubstituted or optionally by it is one or more-
The following groups of COOH substitutions：C1-40Alkyl, C1-40Alkoxy, C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base,
3-20 circle heterocycles bases oxygroup, C6-20Aryl, C6-20Aryloxy, 5-20 unit's heteroaryls, 5-20 unit's heteroaryl oxygroups；
D is selected from OH；
The C1-40Alkyl, C1-40Alkoxy, C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base, 3-20 members
Heterocycle oxygroup, C6-20Aryl, C6-20Aryloxy, 5-20 unit's heteroaryls, 5-20 unit's heteroaryls oxygroup can also be further by one
A or multiple RSSubstitution；
Each RSCan be identical or different, it is independently from each other H, OH, SH, CN ,-SO3Na、C1-40Alkyl, C1-40Alcoxyl
Base, C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base, 3-20 circle heterocycles bases oxygroup, C6-20Aryl, C6-20Aryl oxide
Base, 5-20 unit's heteroaryls, 5-20 unit's heteroaryl oxygroups.
Embodiment according to the present invention, when Formula II compound represented is there are during chiral centre, the Formula II compound
Can also be its raceme, stereoisomer, tautomer；
Embodiment according to the present invention, the liquid unsaturated polyether compound can be selected from the liquid as shown in following formula I
Body unsaturated polyether polymeric monomer：
Wherein, each R1It is identical or different, hydrogen atom or the hydrocarbon with 1~20 carbon atom are represented independently of one another
Base；
R2Represent the alkyl with 1~20 carbon atom；
Each R3It is identical or different, alkyl or carbonyl with 1~10 carbon atom are represented independently of one another；
Each R5It is identical or different, hydrogen atom or the alkyl with 1~20 carbon atom are represented independently of one another；
Each R4O is identical or different, represents the oxyalkylene group with 2~18 carbon atoms independently of one another；
N represents the average addition molal quantity of oxyalkylene group, and 5≤n≤300；
X, Y, Z are identical or different, expression-N ,-O or H.
Embodiment according to the present invention, in the liquid unsaturated polyether polymeric monomer, oxyalkylene group be preferably have 2~
The oxyalkylene group of 8 carbon atoms；It is highly preferred that the oxyalkylene group can be oxyethylene group, oxypropylene group or oxidation fourth
Arbitrary two or three in alkenyl；It is further preferred that the oxyalkylene group can be oxyethylene group and oxypropylene group,
Or oxyethylene group and butylene oxide base；Such as the oxyalkylene group can be oxyethylene group and oxypropylene group.
Embodiment according to the present invention, the number-average molecular weight of the liquid unsaturated polyether polymeric monomer for 1400~
10000, it is preferably 2000~5000.
The preparation of heretofore described liquid unsaturated polyether polymeric monomer can refer to patent application CN201510041919.X
Described in method.The method is to use at least to contain there are one the unsaturated compound of reactive hydrogen atom for initiator and oxidation
Alkene carries out block, random or alternating addition obtains polymeric reaction product.Preferably with 2- methallyl alcohols or 3- methyl -3- fourths
Alkene -1- alcohol is initiator, and quality is than propylene oxide (PO)：Ethylene oxide (EO)=21.5:100, molecular weight, which is prepared, is
2400 liquid pfpe polymeric monomer.
Embodiment according to the present invention, A, B, C are identical or different in the Formula II compound represented, independently of one another
Selected from H ,-COOH, following groups that are unsubstituted or optionally being substituted by one or more-COOH：C1-12Alkyl or C1-12Alkoxy.
Embodiment according to the present invention, the Formula II compound represented are selected from following compounds or its acid anhydrides：Propylene
Acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid.
Embodiment according to the present invention, not containing in the polymerisation conventional makes when preparing solid polycarboxylic acid water reducing agent
Solvent, such as do not contain the one or more in the components such as the carbon tetrachloride additionally added, chloroform, acetone or water.
Embodiment according to the present invention does not contain the carbon tetrachloride additionally added, chloroform, acetone or water and refers to that reaction is former
The total mass fraction of component described in material is less than 0.5%.
The present invention also provides the preparation method of solid polycarboxylic acid water reducing agent as described above, including：By liquid unsaturated polyether
Compound carries out Raolical polymerizable with Formula II compound represented；
The liquid unsaturated polyether compound has definition described above with Formula II compound represented.
Embodiment according to the present invention, the quality of the Formula II compound represented and liquid unsaturated polyether compound
Than for (1-20):100, such as (2.5-15):100.
Embodiment according to the present invention, the reaction can carry out under the action of radical polymerization initiator；
The radical polymerization initiator can be selected from peroxide, azo type free radical initiator or its combination；Example
Such as in tert-butyl hydroperoxide, peroxidized t-butyl perbenzoate, sodium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide
One or more of combinations；
The radical polymerization initiator and the mass ratio of liquid unsaturated polyether compound are (0.1-1):100, such as
(0.2-0.8):100, such as (0.4-0.6):100.
Embodiment according to the present invention, the reaction can carry out under the action of molecular weight regulator；The molecule
The combination of one or more of following compound or its inorganic salts (when it is present) can be selected from by measuring conditioning agent：Mercaptoethanol,
Thioglycerin, thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, thiomalic acid, thioacetic acid monooctyl ester, 3- mercaptopropionic acids monooctyl ester,
Mistabrom, n-dodecyl mercaptan, octyl mercaptan, thioacetic acid butyl ester, isopropanol, sodium hypophosphite, potassium hypophosphite, Asia
The inclined sulfurous acid of sulfuric acid, bisulfites, hydrosulfurous acid, acid, sodium sulfite, potassium sulfite, sodium hydrogensulfite, bisulfite
Potassium, sodium dithionite, potassium hyposulfite, sodium metabisulfite or inclined potassium bisulfite；
Embodiment according to the present invention, the dosage of the molecular weight regulator and the matter of liquid unsaturated polyether compound
It can be (0.05-2) to measure ratio:100, such as (0.1-1.5):100, such as (0.5-1):100.
Embodiment according to the present invention, the reaction can carry out under the effect of the catalyst；The catalyst can be with
Selected from organic amine, alkali metal sulfite, inorganic acid or its salt, ascorbic acid, arabo-ascorbic acid, ascorbic acid or different Vitamin C
The following derivative of acid：Salt or ester；Such as one or more of the catalyst in following compound：N, N- dimethyl second
Hydramine, N, N- lupetazins, tetramethylurea, N, N- dimethyl-ethylenediamines, N, N, N', N'- tetramethylethylenediamines, hypophosphorous acid,
Sodium hypophosphite, sodium hydrogensulfite, hyponitrous acid sodium, iron ammonium sulfate, sodium sulfoxylate formaldehyde, L-AA, L- Vitamin Cs
One or more in hydrochlorate, L-AA ester, arabo-ascorbic acid, erythorbate and arabo-ascorbic acid ester；
Embodiment according to the present invention, the catalyst and the mass ratio of liquid unsaturated polyether compound can be
(0.1-2):100, be, for example, (0.2-1):100, be such as (0.5-1):100.
Embodiment according to the present invention, when the reaction time can be 1-24 small, such as when 1.5-6 is small；It is described anti-
It can be 0-35 DEG C, such as 10-25 DEG C to answer temperature.
Embodiment according to the present invention, the method can also include further being ground into product after the completion of reacting suitable
Close the shape of different use demands, such as solid particle or powder.
Following steps may be employed in embodiment according to the present invention, the preparation method：At room temperature, by liquid insatiable hunger
It is added to polyether macromonomer in reactor, adds in molecular weight regulator, initiator into reactor successively, divided after stirring evenly
Not Di Jia Formula II compound represented or its salt, catalyst, reaction 1.5-6 it is small when, stop reaction, be cooled to 25-40 DEG C to get
To solid polycarboxylic acid water reducing agent.
It will be appreciated that though in the preparation method of the solid polycarboxylic acid water reducing agent, do not contain and conventional prepare solid and gather
The above-mentioned solvent used during carboxylic acid water reducer, however for easy to operation, cost-effective or other purposes, above-mentioned initiator divides
A small amount of water may be contained in the reagents such as son amount conditioning agent, catalyst, but the water content in these reagents should be controlled and can not made
For in the content range of reaction dissolvent.
The present invention also provides a kind of cement admixtures, such as grouting material, and it includes solid polycarboxylic acid water reducing agents as described above.
According to the present invention, the cement admixture can also include antifoaming agent；The antifoaming agent is defoamed selected from mineral oil system
Agent such as kerosene and atoleine；Oil and fat system antifoaming agent such as animal and vegetable oil such as sesame oil, castor oil and its oxyalkylene add
Into object；Fatty acid series antifoaming agent；Aliphatic ester system antifoaming agent；Epoxy methane series antifoaming agent；Alcohol system antifoaming agent；Amide system antifoaming agent；
Phosphate system antifoaming agent；One or more mixtures in metallic soap system antifoaming agent and silicone-based antifoaming agent；Such as described disappear
Infusion is selected from atoleine, animal and vegetable oil, oleic acid, single ricinoleic acid glyceride, octanol, acrylamide, tributyl phosphate, hard
One or more mixtures in ester acid aluminium, dimethicone.
The present invention also provides use of the solid polycarboxylic acid water reducing agent as described above in cement admixture, such as grouting material is prepared
On the way.
Term defines and explanation
Term " C1-40Alkyl " is interpreted as the preferred direct-connected or branch saturation monovalent hydrocarbon for representing to have 1~40 carbon atom
Base is preferably C1-10Alkyl.“C1-10Alkyl " is interpreted as preferred represent with 1,2,3,4,5,6,7,8,9 or 10 carbon atom
Direct-connected or branch saturation monovalent hydrocarbon.The alkyl be for example methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl,
Isobutyl group, sec-butyl, tertiary butyl, isopentyl, 2- methyl butyls, 1- methyl butyls, 1- ethyl propyls, 1,2- dimethyl propyls,
Neopentyl, 1,1- dimethyl propyls, 4- methyl amyls, 3- methyl amyls, 2- methyl amyls, 1- methyl amyls, 2- ethyl-butyls,
1- ethyl-butyls, 3,3- dimethylbutyls, 2,2- dimethylbutyls, 1,1- dimethylbutyls, 2,3- dimethylbutyls, 1,3- bis-
Methyl butyl or 1,2- dimethylbutyls etc. or their isomers.Particularly, the group have 1,2,3,4,5,6, a carbon
Atom (" C1-6Alkyl "), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl group, sec-butyl, tertiary butyl, more particularly,
The group has 1,2 or 3 carbon atom (" C1-3Alkyl "), such as methyl, ethyl, n-propyl or isopropyl.
Term " C3-20Cycloalkyl " is understood to mean that the monovalent monocyclic of saturation or bicyclic hydrocarbon ring, has 3~20 carbon
Atom, preferably " C3-10Cycloalkyl ".Term " C3-10Cycloalkyl " is understood to mean that the monovalent monocyclic of saturation or bicyclic hydrocarbon ring,
With 3,4,5,6,7,8,9 or 10 carbon atoms.The C3-10Cycloalkyl can be monocyclic alkyl, such as cyclopropyl, cyclobutyl, ring
Amyl, cyclohexyl, suberyl, cyclooctyl, cyclononyl or cyclodecyl or for example decahydronaphthalene naphthalene nucleus of bicyclic alkyl.
Term " 3-20 circle heterocycles base " means the monovalent monocyclic of saturation or bicyclic hydrocarbon ring, and it includes 1-5 to be independently selected from N, O
With the hetero atom of S, preferably " 3-10 circle heterocycles base ".Term " 3-10 circle heterocycles base " means the monovalent monocyclic or dicyclic hydrocarbon of saturation
Ring, the preferably 1-3 hetero atoms that are selected from N, O and S a it includes 1-5.The heterocycle can pass through appointing in the carbon atom
One or nitrogen-atoms (if present) are connected with the rest part of molecule.Particularly, the heterocycle can be included but not
It is limited to：4 yuan of rings, such as azetidinyl, oxetanyl；5 yuan of rings, such as tetrahydrofuran base, dioxa cyclopentenyl, pyrroles
Alkyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl；Or 6 yuan of rings, as THP trtrahydropyranyl, piperidyl, morpholinyl, dithiane base,
Thio-morpholinyl, piperazinyl or trithiane base；Or 7 yuan of rings, such as Diazesuberane base.Optionally, the heterocycle can be
Benzo-fused.The heterocycle can be bicyclic, such as, but not limited to 5,5 yuan of rings, such as hexahydro cyclopentano [c] pyrroles -2
(1H)-basic ring or 5,6 membered bicyclics, such as hexahydropyrrolo simultaneously [1,2-a] pyrazine -2 (1H)-basic ring.The ring of nitrogen atom can be
Part is undersaturated, i.e., it can include one or more double bonds, such as, but not limited to 2,5- dihydro -1H- pyrrole radicals, 4H- [1,
3,4] thiadiazine base, 4,5- dihydro-oxazoles base or 4H- [Isosorbide-5-Nitrae] thiazinyl, alternatively, it can be benzo-fused, such as but not
It is limited to dihydro-isoquinoline base.According to the present invention, the heterocycle is no armaticity.
Term " C6-20Aryl " is interpreted as the preferred monovalence armaticity or partial aromatic for representing to have 6~20 carbon atoms
The monocyclic, bicyclic or tricyclic hydrocarbon ring of property, preferably " C6-14Aryl ".Term " C6-14Aryl " be interpreted as it is preferred represent with 6,7,
8th, 9,10,11,12, the 13 or 14 monovalence armaticity of carbon atom or monocyclic, bicyclic or tricyclic hydrocarbon rings of partial aromatic
(“C6-14Aryl "), particularly the ring (" C with 6 carbon atoms6Aryl "), such as phenyl；Or xenyl or with 9
The ring (" C of carbon atom9Aryl "), such as indanyl or indenyl or the ring (" C with 10 carbon atoms10Aryl "), such as
Tetrahydro naphthyl, ihydro naphthyl or naphthalene or the ring (" C with 13 carbon atoms13Aryl "), such as fluorenyl, either
Ring (" C with 14 carbon atoms14Aryl "), such as anthryl.
Term " 5-20 unit's heteroaryls " is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring system：It has
There are 5~20 annular atoms and the hetero atom for being independently selected from N, O and S comprising 1-5, such as " 5-14 unit's heteroaryls ".Term " 5-14
Unit's heteroaryl " is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring system：It has 5,6,7,8,9,10,11,
12nd, 13 or 14 annular atoms, particularly 5 or 6 or 9 or 10 carbon atoms, and it includes 1-5, preferably 1-3 be respectively independently selected from N,
The hetero atom of O and S also, in addition can be benzo-fused at each occurrence.Particularly, heteroaryl is selected from thienyl, furan
It mutters base, pyrrole radicals, oxazolyls, thiazolyl, imidazole radicals, pyrazolyl, isoxazolyls, isothiazolyl, oxadiazolyls, triazolyl, thiophene
Di azoly, thiophene -4H- pyrazolyls etc. and their benzo derivative, such as benzofuranyl, benzothienyl, benzoxazole
Base, benzoxazine, benzimidazolyl, benzotriazole base, indazolyl, indyl, isoindolyl etc.；Or pyridyl group, pyridazine
Base, pyrimidine radicals, pyrazinyl, triazine radical etc. and their benzo derivative, such as quinolyl, quinazolyl, isoquinolyl
Deng；Or azocine base, indolizine base, purine radicals etc. and their benzo derivative；Or cinnoline base, phthalazinyl, quinazolyl, quinoline
Quinoline base, naphthyridines base, pteridyl, carbazyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazine groups etc..
Unless otherwise indicated, heterocycle, heteroaryl or inferior heteroaryl include its all possible isomeric form, such as its position
Put isomers.Therefore, pyridine -2- bases, sub- pyrrole are included for some illustrative non-limiting examples, pyridyl group or sub-pyridyl group
Pyridine -2- bases, pyridin-3-yl, sub- pyridin-3-yl, pyridin-4-yl and sub- pyridin-4-yl；Thienyl or sub- thienyl include thiophene
Fen -2- bases, Asia thiophene -2- bases, thiene-3-yl and sub- thiene-3-yl.
It is above-mentioned to term " alkyl ", such as " C1-40The definition of alkyl " is equally applicable to containing " C1-40Other terms of alkyl ",
Such as term " C1-40Alkyl oxy " and " C1-40Alkoxy ".Similarly, it is above-mentioned to term " C3-20Cycloalkyl ", " 3-20 circle heterocycles
Base ", " C6-20The definition of aryl " and " 5-20 unit's heteroaryls " is correspondingly equally applicable to other terms containing it, such as term
“C3-20Cycloalkyl oxy ", " 3-20 circle heterocycles base ", " 3-20 circle heterocycles bases oxygroup " and " C6-20Aryloxy " etc..
Advantageous effect：
(1) present invention passes through unsaturated carboxylic acid and liquid unsaturated polyether polymeric monomer is straight in the environment without any solvent
Raolical polymerizable is connect, the anhydrous solid polycarboxylate water-reducer being had excellent performance.The method uses bulk polymerization mode,
Without using any solvent or medium in whole process, effectively improve and add in water or organic solvent, later stage the early period routinely used
The method of removing；Obtained product not only convenient transportation, but also performance is better than commercial solid polycarboxylate water-reducer.
(2) present invention prepares high performance water reducing agent of polyocarboxy acid under conditions of completely without using solvent, and reaction is at room temperature
It carries out, overcomes in previous solid polycarboxylic acids building-up process the shortcomings that must polymerizeing under high temperature melting, high temperature, avoid high temperature and gather
The shortcomings that local temperature is uneven in conjunction, and properties of product are low.Synthesis technology is simple and efficient, safety and environmental protection is pollution-free, production cost
And low energy consumption, product can be with batch application in multiple fields such as dry powder and mortar, commerical ready-mixed concretes, and can be according to live needs
The water for adding in respective amount is configured to the solution of any concentration, greatly reduces transportation cost, have the good market competitiveness and
Application prospect.
(3) present invention prepares high performance water reducing agent of polyocarboxy acid using liquid unsaturated polyether polymeric monomer with Formula II compound,
System viscosity is small, without using water or organic solvent viscosity reduction, compared to traditional preparation and post processing mode, reduces relatively numerous
Trivial processing step makes entire building-up process simple and easy to control, and it is apparent efficiently convenient to have the characteristics that, it is easy to accomplish industrial metaplasia
Production.
(4) from the perspective of production application, safe preparation process of the invention is environmentally friendly, solvent-free murder by poisoning, cleaning
Pollution-free, reaction raw materials used are simply common, and building-up process is protected without nitrogen, greatly reduces production cost.Synthesis gained
Water-reducing agent has excellent diminishing dispersion effect, compared with remaining to show preferable mobility and holding capacity under low-dosage, and
And very strong adaptability is shown to the cement of different cultivars.
Specific embodiment
Further detailed description is done to technical scheme below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on the above of the present invention are encompassed by it is contemplated that protecting.
Unless otherwise indicated, the raw materials and reagents used in following embodiment is commercial goods or can be by
It is prepared by perception method.
The preparation of heretofore described liquid unsaturated polyether polymeric monomer can refer to patent application CN201510041919.X
Described in method.The method is to use at least to contain there are one the unsaturated compound of reactive hydrogen atom for initiator and oxidation
Alkene carries out block, random or alternating addition obtains polymeric reaction product.Preferably with 2- methallyl alcohols or 3- methyl -3- fourths
Alkene -1- alcohol is initiator, and quality is than propylene oxide (PO)：Ethylene oxide (EO)=21.5:100, molecular weight, which is prepared, is
2400 liquid pfpe polymeric monomer.
Preparation example 1
The method that embodiment 3 and embodiment 4 are recorded in referenced patent document CN201510041919.X, with 2- methallyls
Alcohol or 3- methyl-3-butene-1-alcohols are initiator, and quality is than propylene oxide (PO)：Ethylene oxide (EO)=21.5:100, it prepares
Obtain the liquid unsaturated polyether polymeric monomer that molecular weight is 2400.
Embodiment 1
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 2.0g thioacetic acid, and 0.2gL- ascorbic acid then begins to that 15g third is added dropwise
The mixed liquor of olefin(e) acid, 0.1g peroxidized t-butyl perbenzoates, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature
It is afterwards solid granular by grinding.Product is through infrared spectrum characterization, in infrared spectrum spectrogram, 3440.79cm-1For O-H's
Stretching vibration, 2871.40cm-1And 2873.53cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1705.89cm-1For the stretching vibration of C=O, 1105.58cm-1And 1259.99cm-1The very strong absworption peak in place is stretched for-C-O-C-
Contracting vibration；Infrared results show the successful synthesis of solid water-reducing agent.
Embodiment 2
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 0.05g thioacetic acid, and 1.0gL- ascorbic acid then begins to that 2.5g is added dropwise
The mixed liquor of acrylic acid, 1g peroxidized t-butyl perbenzoates, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature
It is afterwards solid granular by grinding.Product is through infrared spectrum characterization, in infrared spectrum spectrogram, 3440.85cm-1For O-H's
Stretching vibration, 2871.45cm-1And 2873.60cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1705.5cm-1For the stretching vibration of C=O, 1260.15cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；Infrared knot
Fruit shows the successful synthesis of solid water-reducing agent.
Embodiment 3
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 0.5g mercaptoethanols, and 0.5gL- ascorbic acid then begins to that 8.9g third is added dropwise
The mixed liquor of olefin(e) acid, 0.6g peroxidized t-butyl perbenzoates, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature
It is afterwards solid granular by grinding.Product is through infrared spectrum characterization, 3440.65cm in infrared spectrum spectrogram-1For stretching for O-H
Contracting vibration, 2871.55cm-1And 2873.33cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1704.86cm-1For the stretching vibration of C=O, 1259.85cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；It is infrared
The result shows that the successful synthesis of solid water-reducing agent.
Embodiment 4
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, addition 0.5g thioacetic acid, 0.5g N, N, N', N'- tetramethylethylenediamines, then
Start that 8.9g methacrylic acids, the mixed liquor of 0.6g peroxidized t-butyl perbenzoates, time for adding 2h, after being added dropwise to complete is added dropwise
1h is cured, it is solid granular to be cooled to after room temperature by grinding.Product is through infrared spectrum characterization, in infrared spectrum spectrogram
3440.75cm-1For the stretching vibration of O-H, 2871.32cm-1And 2873.23cm-1Strong absworption peak be-CH2- stretching vibration
With-CH3Bending vibration；1704.86cm-1For the stretching vibration of C=O, 1259.70cm-1The very strong absworption peak in place is-C-O-C-
Stretching vibration；Infrared results show the successful synthesis of solid water-reducing agent.
Embodiment 5
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 0.5g thioacetic acid, and 0.5gL- ascorbic acid then begins to that 8.9g horses are added dropwise
Come acid anhydrides, the mixed liquor of 0.6g peroxidized t-butyl perbenzoates, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room
After temperature by grinding be solid granular.Product is through infrared spectrum characterization, 3440.66cm in infrared spectrum spectrogram-1For O-H's
Stretching vibration, 2871.25cm-1And 2873.20cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1704.75cm-1For the stretching vibration of C=O, 1259.79cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；It is infrared
The result shows that the successful synthesis of solid water-reducing agent.
Embodiment 6
The liquid unsaturated polyether polymeric monomer that will be prepared in 100g preparation examples 1 using 2- methyl allyls alcohol as initiator
(molecular weight 2400) is placed in kettle, adds in 0.5g thioacetic acid, and 0.5gL- ascorbic acid then begins to that 8.9g propylene is added dropwise
Acid, the mixed liquor of 0.6g peroxidized t-butyl perbenzoates, time for adding 2h are added dropwise to complete post curing 1h, after being cooled to room temperature
It is solid granular by grinding.Product is through infrared spectrum characterization, 3440.75cm in infrared spectrum spectrogram-1For the flexible of O-H
Vibration, 2871.42cm-1And 2873.50cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1705.05cm-1For the stretching vibration of C=O, 1259.78cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；It is infrared
The result shows that the successful synthesis of solid water-reducing agent.
Embodiment 7
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 0.5g mercaptopropionic acids, and 0.5gL- ascorbic acid then begins to that 8.9g third is added dropwise
The mixed liquor of olefin(e) acid, 0.6g peroxidized t-butyl perbenzoates, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature
It is afterwards solid granular by grinding.Product is through infrared spectrum characterization, 3440.70cm in infrared spectrum spectrogram-1For stretching for O-H
Contracting vibration, 2871.20cm-1And 2873.45cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1705.06cm-1For the stretching vibration of C=O, 1259.82cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；It is infrared
The result shows that the successful synthesis of solid water-reducing agent.
Embodiment 8
It will be big as the liquid unsaturated polyether that initiator is prepared using 3- methyl-3-butene-1-alcohols in 100g preparation examples 1
Monomer (molecular weight 2400) is placed in kettle, adds in 0.5g thioacetic acid, and 0.5g ammonium persulfates then begin to that 8.9g propylene is added dropwise
Acid, 0.6gN, N, N', the mixed liquor of N'- tetramethylethylenediamines, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room
After temperature by grinding be solid granular.Product is through infrared spectrum characterization, 3440.72cm in infrared spectrum spectrogram-1For O-H's
Stretching vibration, 2871.35cm-1And 2873.26cm-1Strong absworption peak be-CH2- stretching vibration and-CH3Bending vibration；
1705.08cm-1For the stretching vibration of C=O, 1259.76cm-1The very strong absworption peak in place is-C-O-C- stretching vibrations；It is infrared
The result shows that the successful synthesis of solid water-reducing agent.
Test case 1
1. flowing degree of net paste of cement
To investigate mobility effect of the high-performance solid polycarboxylate water-reducer of the invention synthesized to different cement, examination
It tests and determines paste flowing degree of the solid polycarboxylic acid water reducing agent under identical volume in each embodiment to different cement types.Examination
It tests by GB/T8077-2000《Methods for testing uniformity of concrete admixture》Described in method carry out, W/C=0.29, volume
For 0.2%.Existing commercially available performance preferably high-performance solid polycarboxylate water-reducer is selected as control.Result of the test is shown in Table 1.
1 pulp flowage results of property of table
From table 1 it follows that high-performance solid polycarboxylate water-reducer and commercial solid polycarboxylic-acid that the present invention synthesizes
Water-reducing agent is compared, and has superior net slurry dispersion performance in solid volume 0.2%.
2. testing concrete performance
Experiment is with reference to GB8076-2008《Concrete admixture》To sample obtained by embodiment and the preferably high property of commercially available performance
It can solid polycarboxylic acid water reducing agent (reference examples) progress concrete strength inspection.Solid volume of the sample in cement is 0.25%,
Reference cement is selected, cement on the basis of concrete mix：Sand：Stone：Water=360：812：1033：195.Result of the test is shown in Table 2.
2 concrete slump of table, divergence and compression strength
From Table 2, it can be seen that high-performance solid polycarboxylate water-reducer prepared by the present invention, more commercially available under low-dosage
High-performance solid polycarboxylate water-reducer superior diminishing dispersion performance is shown in concrete.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of solid polycarboxylic acid water reducing agent, wherein the water-reducing agent is included by liquid unsaturated polyether compound and Formula Il institute
Compound, its salt or the acid anhydrides shown passes through polymerisation, such as free crowd polymer obtained by the reaction：
Wherein, A, B, C are identical or different, are independently from each other H ,-COOH, unsubstituted or optionally by one or more-COOH
Substituted following groups：C1-40Alkyl, C1-40Alkoxy, C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base, 3-20
Circle heterocycles base oxygroup, C6-20Aryl, C6-20Aryloxy, 5-20 unit's heteroaryls, 5-20 unit's heteroaryl oxygroups；
D is selected from OH；
The C1-40Alkyl, C1-40Alkoxy, C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base, 3-20 circle heterocycles bases
Oxygroup, C6-20Aryl, C6-20Aryloxy, 5-20 unit's heteroaryls, 5-20 unit's heteroaryls oxygroup can also be further by one or more
A RSSubstitution；
Each RSCan be identical or different, it is independently from each other H, OH, SH, CN ,-SO3Na、C1-40Alkyl, C1-40Alkoxy,
C3-20Cycloalkyl, C3-20Cycloalkyl oxy, 3-20 circle heterocycles base, 3-20 circle heterocycles bases oxygroup, C6-20Aryl, C6-20Aryloxy,
5-20 unit's heteroaryls, 5-20 unit's heteroaryl oxygroups.
2. solid polycarboxylic acid water reducing agent described in claim 1, wherein, when Formula II compound represented is there are during chiral centre, institute
It can also be its raceme, stereoisomer, tautomer to state Formula II compound.
3. the solid polycarboxylic acid water reducing agent of claim 1 or 2, wherein, the liquid unsaturated polyether compound can be selected from
Liquid unsaturated polyether polymeric monomer as shown in following formula I：
Wherein, each R1It is identical or different, hydrogen atom or the alkyl with 1~20 carbon atom are represented independently of one another；
R2Represent the alkyl with 1~20 carbon atom；
Each R3It is identical or different, alkyl or carbonyl with 1~10 carbon atom are represented independently of one another；
Each R5It is identical or different, hydrogen atom or the alkyl with 1~20 carbon atom are represented independently of one another；
Each R4O is identical or different, represents the oxyalkylene group with 2~18 carbon atoms independently of one another；
N represents the average addition molal quantity of oxyalkylene group, and 5≤n≤300；
X, Y, Z are identical or different, expression-N ,-O or H；
Preferably, in the liquid unsaturated polyether polymeric monomer, oxyalkylene group is the oxyalkylene group with 2~8 carbon atoms；More
Preferably, the oxyalkylene group can be arbitrary two or three in oxyethylene group, oxypropylene group or butylene oxide base；
It is further preferred that the oxyalkylene group can be oxyethylene group and oxypropylene group or oxyethylene group and oxidation fourth
Alkenyl；Such as the oxyalkylene group can be oxyethylene group and oxypropylene group；
Preferably, the number-average molecular weight of the liquid unsaturated polyether polymeric monomer is 1400~10000, also preferably 2000~
5000。
4. any one of the claim 1-3 solid polycarboxylic acid water reducing agents, wherein, A, B, C in the Formula II compound represented
It is identical or different, it is independently from each other H ,-COOH, following groups that are unsubstituted or optionally being substituted by one or more-COOH：
C1-12Alkyl or C1-12Alkoxy；
Preferably, the Formula II compound represented is selected from following compounds or its acid anhydrides：Acrylic acid, methacrylic acid, clothing health
Acid, maleic acid, maleic anhydride, fumaric acid.
5. any one of the claim 1-4 solid polycarboxylic acid water reducing agents, wherein, conventional preparation is not contained in the polymerisation
The solvent used during solid carboxylic acid water-reducing agent, such as do not contain in the components such as the carbon tetrachloride additionally added, chloroform, acetone or water
One or more；
Preferably, total matter that the carbon tetrachloride additionally added, chloroform, acetone or water refer to component described in reaction raw materials is not contained
It measures fraction and is less than 0.5%.
6. the preparation method of any one of the claim 1-5 solid polycarboxylic acid water reducing agents, including：By liquid unsaturated polyether
It closes object and carries out Raolical polymerizable with Formula II compound represented；
The liquid unsaturated polyether compound has any one of the claim 1-5 definition with Formula II compound represented.
7. the preparation method of solid polycarboxylic acid water reducing agent described in claim 6, wherein, the Formula II compound represented and liquid
The mass ratio of unsaturated polyether compound is (1-20):100, such as (2.5-15):100；
Preferably, the reaction can carry out under the action of radical polymerization initiator；
The radical polymerization initiator can be selected from peroxide, azo type free radical initiator or its combination；Such as it selects
One from tert-butyl hydroperoxide, peroxidized t-butyl perbenzoate, sodium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide
Kind or several combinations；
Preferably, the radical polymerization initiator and the mass ratio of liquid unsaturated polyether compound are (0.1-1):100, example
Such as (0.2-0.8):100, such as (0.4-0.6):100；
Preferably, the reaction can carry out under the action of molecular weight regulator；The molecular weight regulator can be selected from such as
The combination of one or more of lower compound or its inorganic salts (when it is present)：Mercaptoethanol, thioglycerin, thioacetic acid, 2-
Mercaptopropionic acid, 3- mercaptopropionic acids, thiomalic acid, thioacetic acid monooctyl ester, 3- mercaptopropionic acids monooctyl ester, mistabrom, positive ten
Dialkyl group mercaptan, octyl mercaptan, thioacetic acid butyl ester, isopropanol, sodium hypophosphite, potassium hypophosphite, sulfurous acid, bisulfites,
The inclined sulfurous acid of hydrosulfurous acid, acid, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, sodium dithionite,
Potassium hyposulfite, sodium metabisulfite or inclined potassium bisulfite；
The dosage of the molecular weight regulator and the mass ratio of liquid unsaturated polyether compound can be (0.05-2):100, example
Such as (0.1-1.5):100, such as (0.5-1):100；
Preferably, the reaction can carry out under the effect of the catalyst；It is sub- that the catalyst can be selected from organic amine, alkali metal
Sulfate, inorganic acid or its salt, ascorbic acid, arabo-ascorbic acid, the following derivative of ascorbic acid or arabo-ascorbic acid：Salt or
Ester；
Such as one or more of the catalyst in following compound：N, N- dimethylethanolamine, N, N- dimethyl piperazines
Piperazine, tetramethylurea, N, N- dimethyl-ethylenediamines, N, N, N', N'- tetramethylethylenediamines, hypophosphorous acid, sodium hypophosphite, bisulfite
Sodium, hyponitrous acid sodium, iron ammonium sulfate, sodium sulfoxylate formaldehyde, L-AA, L-AA salt, L-AA ester,
One or more in arabo-ascorbic acid, erythorbate and arabo-ascorbic acid ester；
Preferably, the catalyst and the mass ratio of liquid unsaturated polyether compound can be (0.1-2):100, be, for example,
(0.2-1):100, be such as (0.5-1):100；
Preferably, the reaction temperature can be 0-35 DEG C, such as 10-25 DEG C；
Preferably, the method can also include the shape that product is further ground into suitable different use demands after the completion of reacting
Shape, such as solid particle or powder.
8. the preparation method of the solid polycarboxylic acid water reducing agent of claim 6 or 7, wherein, the preparation method may be employed as
Lower step：At room temperature, liquid unsaturated polyether polymeric monomer is added in reactor, adds in molecular weight into reactor successively
Formula II compound represented or its salt, catalyst is added dropwise in conditioning agent, initiator respectively after stirring evenly, when reaction 1.5-6 is small,
Stop reaction, be cooled to 25-40 DEG C to get to solid polycarboxylic acid water reducing agent.
9. a kind of cement admixture, such as grouting material, it includes any one of the claim 1-5 solid polycarboxylic acid water reducing agents；
Preferably, the cement admixture can also include antifoaming agent；The antifoaming agent is selected from mineral oil system antifoaming agent such as kerosene
And atoleine；Oil and fat system antifoaming agent such as animal and vegetable oil such as sesame oil, castor oil and its alkylen oxide adducts；Fat
Fat acid system antifoaming agent；Aliphatic ester system antifoaming agent；Epoxy methane series antifoaming agent；Alcohol system antifoaming agent；Amide system antifoaming agent；Phosphate system
Antifoaming agent；One or more mixtures in metallic soap system antifoaming agent and silicone-based antifoaming agent；Such as the antifoaming agent is selected from
Atoleine, animal and vegetable oil, oleic acid, single ricinoleic acid glyceride, octanol, acrylamide, tributyl phosphate, aluminum foil stearate, two
One or more mixtures in methyl-silicone oil.
10. use of any one of the claim 1-5 solid polycarboxylic acid water reducing agents in cement admixture, such as grouting material is prepared
On the way.
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| CN111718447A (en) * | 2019-03-19 | 2020-09-29 | 江苏奥莱特新材料股份有限公司 | Fluorescent polycarboxylic acid water reducer and preparation method thereof |
| CN111378110B (en) * | 2018-12-27 | 2023-08-11 | 联泓(江苏)新材料研究院有限公司 | Polyether with high ignition point and preparation method and application thereof |
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| CN108821633B (en) * | 2018-07-09 | 2021-03-30 | 山西佳维新材料股份有限公司 | Water-reducing solid polycarboxylate superplasticizer and preparation method thereof |
| CN111378110B (en) * | 2018-12-27 | 2023-08-11 | 联泓(江苏)新材料研究院有限公司 | Polyether with high ignition point and preparation method and application thereof |
| CN111718447A (en) * | 2019-03-19 | 2020-09-29 | 江苏奥莱特新材料股份有限公司 | Fluorescent polycarboxylic acid water reducer and preparation method thereof |
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