CN107936209A - A kind of high-adaptability disperses phosphonate group water-reducing agent and preparation method thereof soon - Google Patents
A kind of high-adaptability disperses phosphonate group water-reducing agent and preparation method thereof soon Download PDFInfo
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- CN107936209A CN107936209A CN201711323481.XA CN201711323481A CN107936209A CN 107936209 A CN107936209 A CN 107936209A CN 201711323481 A CN201711323481 A CN 201711323481A CN 107936209 A CN107936209 A CN 107936209A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Oc1ccccc1 Chemical compound Oc1ccccc1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0243—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing phosphorus
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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
- C04B24/30—Condensation polymers of aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/06—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
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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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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of high adaptation to disperse phosphonic acids based polyalcohol and its preparation method and application soon.The high molecular structure for adapting to fast scattered phosphonic acids based polyalcohol is comb shape, molecular backbone contains rigid phenyl ring, is formed for phenoxy compounds polycondensation, polyoxy alkane alkenyl structures are steric hindrance side chain, adsorption functional group is phosphonate radical and carboxylate radical, phosphate radical and carboxylate radical random distribution.The high scattered phosphonic acids based polyalcohol soon that adapts to can lift it to low-grade aggregate and low activity industrial residue adaptability, improve low water binder ratio concrete flowability energy, lift concrete mechanics and endurance quality.
Description
Technical field
The invention belongs to cement water reducing agent technical field in construction material, more particularly to a kind of phosphonic acids with novel structure
Based polyalcohol and preparation method thereof.
Background technology
Polycarboxylate water-reducer is a kind of high-performance water reducing agent, with molecular structure designability is strong, volume is low, water-reducing rate
High, the advantages that function of slump protection is good, concrete contraction percentage is low and volume stability is good, technique cleaning, from Japan's eighties in last century
Since catalyst company develops first, the research of poly carboxylic acid series water reducer at home and abroad has made great progress, and is increasingly becoming city
The application mainstream of field.At present poly carboxylic acid series water reducer almost all of country is great, key project, especially high ferro, airport,
All it is widely used in the engineerings such as water conservancy and hydropower, bridge.But as national basis Facilities Construction persistently promotes, traditional river sand and excellent
The resources such as matter flyash, miberal powder are increasingly in short supply, and the alternate resources such as Machine-made Sand and Desulphurization, denitration ash are increasingly becoming concrete former material
Expect mainstream, and these alternate resources are there are clay content is big, grading is poor, the low shortcoming of activity, polycarboxylate water-reducer is in different zones
In raw material, water-reducing rate and function of slump protection difference are obvious, the characteristics of having embodied bad adaptability, although country and professional standard are to mixed
Clay content, clod content's index have stringent limitation in solidifying soil, but are limited to residing natural environment and resource, and various regions concrete is used
Sand amount and species are different, or even threaten the regulation and control of concrete flowability energy.
To improve polycarboxylate water-reducer to the adaptability of concrete raw material, the researcher of colleges and universities, scientific research institutions and enterprise
Substantial amounts of expansion work is carried out to polycarboxylic acids molecular structure, to knots such as molecular weight, side chain lengths, sour ether ratio, main chain hard and softs
Structure parameter has carried out system optimization, has derived substantial amounts of upgrading products and technological innovation, is ground for domestic and international cement water reducing agent
The hot spot studied carefully and developed.
Patent CN 103467670A report a kind of preparation method of anti-chamotte mould polycarboxylate water-reducer.The water-reducing agent is by season
The copolymerizations such as ammonium salt oligomer, isoamyl alcohol polyoxyethylene ether, aminotrimethylene phosphoric acid, unsaturated carboxylic acid.The water-reducing agent
It is insensitive to the clay content problem of aggregate, concrete diminishing can be solved in the case where not improving water-reducing agent volume
Rate is not high, slump-loss is big and the problems such as low strength.Patent CN 103641963A, CN 104031217A are equally reported
The anti-mud performance of similar phosphorous acid groups water-reducing agent.
Patent CN 103848944A report a kind of preparation method of extra retarded set polycarboxylate water-reducer.The water-reducing agent is not by
Saturation polyether macromonomer, unsaturated carboxylic acid/acid anhydrides, unsaturated sulfonic acid class minor comonomer and unsaturated phosphonic acid minor comonomer pass through certainly
By base copolymerization.Manufactured water-reducing agent has obvious retarding effect, suitable for requiring setting time longer concrete
In, the process that avoids compounding retarder, and there is no the problem of homogeneity and storage stability in complex process, avoid
There is setting time exception in concrete.
Patent CN105175658A relate to a kind of method of pectination polycarboxylate water-reducer β-cyclodextrin silicon ash, including as follows
Step：(1) carry out reversible addition-fracture transfer polymerization in the case where chain-transferring agent closes initiator effect using TPEG and AA to react, (2)
It is carried out reversible addion-fragmentation chain transfer under chain-transferring agent and initiator effect with the mixture of AA conjunctions KH570 again to polymerize
Effect, the silicon ash that (3) are modified with surface hydroxylation again are reacted, and prepare comb block polycarboxylate water-reducer β-cyclodextrin silicon
Ash, the invention advantage：The narrow molecular weight distribution of the polycarboxylate water-reducer of preparation, structure-controllable, the polymer and surface hydroxylation
The silicon ash of processing is more easy to be bonded, and can use in batches, reduces labor intensity so that the application of concrete is more extensive.
Patent CN105713150A provides a kind of preparation method and applications of the polycarboxylate water-reducer of resistance to sulfate, this subtracts
Aqua carries out reversible addion-fragmentation chain transfer polymerization by monomer a, monomer b, monomer c.The present invention is bright by being distributed in sequential structure
Strong adsorption group-phosphate is introduced on true block polycarboxylic acids backbone structure so that the adsorption capacity of block polycarboxylic acids is stronger, because
And improve its patience to sulfate.Therefore, the polycarboxylate water-reducer that prepared by the present invention is with volume is low, water-reducing rate is high, collapses
The advantages that degree loss is small, cement adaptability is good, resistance to sulfate, and synthetic method of the present invention is simple, and technological requirement is low, is produced into
This is small, and environmental pollution is small.
Patent CN105175740A discloses a kind of preparation method of high workability esters polycarboxylate water-reducer, first by propylene
The acid activated monomer high with workability mixes, and adds oxidant and aided initiating, and unsaturated monomer, chain tra nsfer are added dropwise at low temperature
The mixed liquor of agent, reducing agent and water, reaction obtain block copolymer intermediate, it is rear add poly glycol monomethyl ether and catalyst into
Row graft esterification, finally neutralizes and is made.High workability esters polycarboxylate water-reducer prepared by the present invention by Molecular Design,
The good activated monomer of workability is introduced, the method for taking high temperature esterification after first low temperature polymerization, this method double bond destructive rate is low, copolymerization
Degree is high, and the water-reducing agent workability of production is good, and water-reducing rate is high；Industrialized producing technology is simple, the production cycle greatly shortens, and produces
Process is environmentally protective, pollution-free.
Although the research of polycarboxylate water-reducer derived product has carried out substantial amounts of innovation work, conventional molecular frame is confined to
In frame, deriving technology is limited to the lifting of the low activity industrial residue such as artificial aggregate and gangue, Desulphurization adaptability, still cannot
Fundamentally solve current low-grade or low activity alternate resources cause concrete initial dispersion efficiency is low, slump-loss is big,
A series of application problems such as system viscosity height, concrete flowability, which can regulate and control, is gradually absorbed in bottleneck, or even limits concrete skill
The development of art.
The content of the invention
It is contemplated that overcome existing carboxylic acids and sulphonic acids additive to Machine-made Sand and inferior suitability, to sulfate
It is sensitive with clay content, cause concrete initial dispersion efficiency deficiency, collapse and damage the problems such as serious, there is provided a kind of high-adaptability divides soon
Phosphonic acids based polyalcohol is dissipated, improves initial dispersion and scattered holding technology, reduces system viscosity, under the conditions of new raw material, regulation and control
Concrete flowability energy.
The high scattered phosphonic acids based polyalcohol soon that adapts to of the present invention is the graft polymers for having new molecules structure, described
Graft polymers adsorption capacity is strong and dispersion efficiency is high, can realize high mineral admixture concrete high dispersive and viscosity reduction, and sulfur resistive
Hydrochlorate and clay interference performance are strong, and preparation process can industrialize, and market application space is wide.
The high molecular structure for adapting to fast scattered phosphonic acids based polyalcohol is comb shape, and molecular backbone is by phenoxy group segment group
Into, or be made of the phenoxy group segment that C1~C6 aliphatic methylenes or methylene guanidine-acetic acid connect, polyoxy alkane alkenyl structures are
Steric hindrance side chain, adsorption functional group are phosphonate radical and carboxylate radical, phosphate radical and carboxylate radical random distribution；Phosphate radical and carboxylate radical rub
You are than being 1.0~9.0:1.0.
The high scattered phosphonic acids based polyalcohol soon that adapts to is existed by ether type side chain A, phosphonate group monomer B, carboxylic monomer C and aldehyde D
The effect of catalyst E, is made by copolycondensation, and wherein phosphonate group monomer B and carboxylic monomer C have synergistic effect, can carry
The adsorption efficiency on the admixture such as cement and flyash, miberal powder, silicon ash surface is risen, ether type side chain A provides space steric effect, into
And strengthen dispersibility, improve concrete flowability energy.
Contain phenoxy group structure in the molecule of ether type side chain A, phosphonate group monomer B and carboxylic monomer C.
Wherein the degree of polymerization of ether type side chain A is 2~80, and the degree of polymerization of monomer B is 4~200, the monomer C degree of polymerization for 1~
300, wherein (monomer B+ monomer C)/monomer A molar ratios are 1.0~5.0, the molar ratio of monomer C and monomer B are 1.0~9.0:1；
The ether type side chain A meets below general formula：
Wherein L1Can be straight chain or highly branched chain, wherein containing EO and PO fragments, EO and PO exist for polyoxy alkane alkenyl structures
Position random distribution in polyoxy alkane alkenyl structures, EO contents are not less than 60%, R1Satisfy for H or C1-C6 and/or unsaturation alcoxyl
Group, the molecular weight of ether type side chain A is 1200~4800, is preferably 1500~2500.The polymerization activity of the ether type side chain is high,
Polymerization efficiency can be obviously improved；
Side chain A can use commercialized simple raw material, in alkali (NaH/NaOMe/NaOH/KOH etc.) or metal composite
Under catalytic action such as (DMC, Mg/Al compounds etc.), alkoxylation occurs with ethylene oxide or propylene oxide and is made, the party
Method (end containing double alkoxy polyethers built and preparation method thereof, CN101712755B and is prepared ester terminated to be known in the industry
Allyl alcohol polyether method, CN200910234991.9)；
The monomer B meets below formula：
Wherein G is-N (CH2-PO3H2)2, or-OPO3H2, it is main adsorption group, L2For the alkyl or polyoxy of C2~C10
Alkane alkenyl structures, L2For linear chain structure, R2For H, OH ,-COOH ,-COOR3Or the alkyl of C1~C8, can be straight or branched knot
Structure, wherein R3For the linear chain structure of C1~C6.
Monomer b can use commercialized simple raw material, be prepared by phosphitylation or phosphorylation reaction, when the bottom of G
Thing is-NH2When, it is made using the Mannich reaction of organic chemistry, specific method can refer to pertinent literature progress
(J.Org.Chem.1966；31:1603-1607；Synthesis.2012；44:1628-1630；J.Am.Chem.Soc.1952；
74:1528-1531), when X is O, prepared using common phosphorylation agent or reagent combination, such as sodium hypophosphite, tri-chlorination
Phosphorus, P4O6, dimethylphosphite, phosphorous acid etc., wherein common agents are phosphorus trichloride, and specific method can refer to pertinent literature (the Liao Dynasty
Ninghua work, 37 (8), 505-506；Hebei chemical industry, 2004,1,1~5 etc.), which is known in the industry.
The carboxylic monomer C meets below formula：
Wherein R4And R5Respectively H, OH, NH2Or CO2R6, independently of each other, wherein R6For H or C1~C6 saturated alkyls.
Carboxylic monomer C may be selected from conventional P-hydroxybenzoic acid, 4- hydroxyphenyl pyravates, 5- Hydroxy M Phthalic Acids, 2,
4- dihydroxycinnamic acids, salicylic acid, gallic acid, 4- coumaric acids, caffeic acid, 4- amino-2-hydroxybenzoic acids, 3,4- dihydroxy
Benzoic acid and 2,5- dihydroxy-benzoic acids etc.；
The aldehyde D is the alkyl aldehydes of C1~C6, the aromatic aldehyde or glyoxalic acid of C7~C12.
It should be noted that if the segment of aldehyde D is long, activity dies down.
The catalyst E mainly has a concentrated sulfuric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, 2- naphthalene sulfonic acids, phosphoric acid, oxalic acid, concentrated hydrochloric acid,
It is preferred that the concentrated sulfuric acid；
The copolycondensation carries out under solvent environment, and the reaction dissolvent E is the protic or aprotic of routine
Weak polar solvent, ethyl methyl ether, the ethyl methyl ether of the ethylene glycol derivative that can be water or ethylene glycol derivative are glycol dinitrate
Ether, ethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether
Deng,
The solvent of the copolycondensation is preferably water, diethylene glycol ethylmethyl ether or diethylene glycol dimethyl ether.
The high weight average molecular weight Mw for adapting to fast scattered phosphonic acids based polyalcohol is 10000~100000.
One of the high structural formula for adapting to fast scattered phosphonic acids based polyalcohol is as follows：
The preparation method of phosphonate group graft polymers of the present invention, includes the following steps：
(1) preparation of side chain A：Using the phenyl monomer containing activity hydroxy or amido as initiator, a certain amount of urge is added
Agent, is heated to certain temperature, is slowly introducing the ethylene oxide or propylene oxide of metering, controls certain temperature, and reaction is certain
After time, after curing, cooling is spare.
Wherein catalyst charge is the 5%~20% of monomer molar amount, depending on monomer hydroxyl or amido activity are different；
Wherein initiation temperature control is at 60~100 DEG C, preferably 80~90 DEG C；
Wherein reaction temperature control is at 100~160 DEG C, depending on different initiator and reaction raw materials；
Wherein curing time control is in 0.5~1.0h；
(2) synthesis of graft polymers：The side chain A of preparation, monomer B, monomer C and aldehyde D and catalyst E are sequentially added instead
Answer in container, then add a certain amount of water, as reaction dissolvent, be heated to 90~130 DEG C, reflux state or seal-off pressure
Under the conditions of, 1~8h is reacted, is cooled, then adds certain water and lye, adjustment solution pH value is 3.0~5.0, admittedly contain
For 20%~50%.
Wherein side chain A, monomer B, the molar ratio of monomer C and aldehyde D are 1:0.8~5.0:0.8~2.0:1.0~6.0；
Wherein the addition of catalyst E (presses H for the 5%~30% of side chain A, monomer B and monomer C moles+Adjust)；
The amount for wherein adding water is the 1%~40% of side chain A, monomer B and monomer C quality sums；
The fast dispersant graft polymer of high-adaptability of the present invention has two Typical molecular architectural features：1. main chain knot
Structure is aromatic radical alkane, enhances the rigidity of polymer solution conformation, helps to lift adsorption efficiency；2. adsorption group is phosphonic acids
Root/carboxylate radical, has synergistic effect, more traditional single carboxylate radical or sulfonate radical, significantly improve adsorption capacity.
The application process of graft polymers of the present invention, material Under Concrete diminishing is closed especially suitable for high mineral
Agent is used, its volume is the 0.08%~0.6% of total cementitious material weight, as an improvement, it is preferred that 0.1%~0.4%, if volume mistake
It is low, then it is initially unsatisfactory to the dispersion effect of low water binder ratio concrete, if volume is excessive, Slow setting time can be postponed,
Intensity is influenced, will also result in economic waste.
Graft polymers of the present invention and conventional water reducing agents have good compatibility, can with it is of the prior art
Know that aminosulfonic water-reducing agent, Lignins water-reducing agent, naphthalene water reducer and ester type carboxylic acid water reducer mix use, separately
Outside, except known cement water reducing agent presented above, wherein air entraining agent, swelling agent, retarder, early strength agent, increasing can also be added
Stick, economization agent and defoamer etc..
This technology has the following advantages that compared with prior art：
(1) it is aromatic radical alkane to design first and be prepared for main chain, and adsorption group is phosphonate radical/carboxylate radical blending structure,
And it is polycondensation reaction to prepare key technology；
(2) raw material are easy to purchase, and technique simple possible, and equipment investment is little, and having can industrial prospect；
(3) graft polymers prepared by technology using the present invention can be obviously improved the initial of high mineral admixture concrete
Dispersibility and dispersion rate, reduce system viscosity, or even can reduce cement consumption, to current cement, high clay and high sulfuric acid
The sandstone aggregate of salt content has good adaptability, has a extensive future.
Embodiment
Following embodiments have described in more detail a kind of molecular structure of graft polymers provided by the invention and had prepared
Journey, these embodiments provide by way of illustration, and its object is to allow person skilled in the art to understand the present invention's
Content is simultaneously implemented according to this, but these embodiments are in no way intended to limit the scope of the present invention.What all Spirit Essences according to the present invention were made etc.
Effect change or modification, should be covered by the protection scope of the present invention.
In the embodiment of the present invention, reagent used is ommercially available AR, or synthesizes gained (mono phosphoric acid ester according to document
The source of body B)：(1) it is commercially available；(2)J.Org.Chem.1966；31:1603-1607；Synthesis.2012；44:1628-
1630；J.Am.Chem.Soc.1952；74:1528-1531；(3) Liaoning chemical industry, 37 (8), 505-506；Hebei chemical industry, 2004,
1,1~5.
Molecular weight test condition：The molecular weight of all condensation polymers uses aqueous gel chromatography (GPC) in the embodiment of the present invention
It is measured, experiment condition is as follows：
Gel column：Two root chromatogram columns of Shodex SB806+803 are connected；
Mobile phase：0.1MNaNO3 aqueous solutions；
Flow phase velocity：1.01ml/min；
Injection：20 μ l, 0.5% aqueous solutions；
Detector：Shodex RI-71 type differential refraction detectors；
Reference material：Polyethylene glycol GPC standard specimens (Sigma-Aldrich, molecular weight 1010000,478000,263000,
118000、44700、18600、6690、1960、628、232)。
In Application Example of the present invention, except special instruction, used cement is Jiangnan-small wild water in field mud
(P.O42.5), stone is the rubble that particle diameter is 5~20mm continuous gradings.Flowing degree of net paste of cement test is with reference to GB/T8077-
2000 standards carry out, amount of water 87g, and flowing degree of net paste of cement is measured on plate glass after stirring 3min.Air content, diminishing
Rate test method is with reference to GB8076-2008《Concrete admixture》Relevant regulations perform.The slump and slump-loss reference
JC473-2001《Concrete pump-feed agent》Relevant regulations perform.
The numbering and molecular structure of side chain A involved in embodiment：
The numbering and molecular structure of monomer B involved in embodiment：
Synthetic example 1
(1) preparation of pendant polyether A-1
In 1000mL autoclaves, Phenoxyethanol 0.10mol and sodium methoxide 0.006mol is added, is slowly heated to 50~60
DEG C, -0.08MPa is evacuated to, keeps 30min, is slowly added to ethylene oxide, keeps 0.2~0.3MPa of reaction pressure, reaction temperature
100~160 DEG C of degree, adds up to add ethylene oxide 3.60mol (158.0g) and propylene oxide 0.80mol (47.2g), insulation curing
30min is reacted, is deaerated, discharging, GPC tests：Weight average molecular weight Mw=2050.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-1 0.10mol, phosphonate group monomer B-1 0.20mol, monomer C P-hydroxybenzoic acid 0.10mol and reaction
Aqueous solvent 20.0g, is slowly added to sulfuric acid 0.05mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.60mol is slowly added dropwise, and drips
About 30min between added-time, then heats to 108 DEG C, reacts 3.0h, cools, and it is 4.0 or so to add liquid caustic soda and adjust pH value, is added
Enter water adjusting and be contained in 30% or so admittedly, obtain light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 15000, mesh
Mark product assay 90%, A-1 residual quantities 3%, B-1 residual quantities 1%, P-hydroxybenzoic acid residual quantity 2%.
Synthetic example 2
(1) preparation of pendant polyether A-2
In 1000mL autoclaves, 4- cumene oxyethanol 0.10mol and sodium methoxide 0.008mol, slow heating are added
To 50~60 DEG C, be evacuated to -0.08MPa, keep 30min, be slowly added to ethylene oxide, keep reaction pressure 0.2~
0.3MPa, 100~160 DEG C of reaction temperature, adds up to add ethylene oxide 5.60mol (246.4g) and propylene oxide 1.80mol
(106.2g), keeps the temperature slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=3500.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-3 0.10mol, phosphonate group monomer B-3 0.30mol, monomer C 5- Hydroxy M Phthalic Acids 0.20mol and
Reaction dissolvent water 50.0g, is slowly added to sulfuric acid 0.12mol, and stirring 10min is to being uniformly mixed, then formaldehyde is slowly added dropwise
0.30mol, time for adding about 30min, then heat to 110 DEG C, react 4.0h, cool, and add liquid caustic soda adjusting pH value and are
4.2 or so, add water adjusting and be contained in 30% or so admittedly, obtain light yellow and brown solution, GPC tests：Weight average molecular weight Mw
≈ 20000, target product content 91%, A-1 residual quantities 2%, B-1 residual quantities 1%, 5- Hydroxy M Phthalic Acids residual quantity 1%.
Synthetic example 3
(1) preparation of pendant polyether A-3
In 1000mL autoclaves, 4- methylenedioxy phenoxy ethanol 0.10mol and sodium methoxide 0.006mol are added, is slowly heated to
50~60 DEG C, -0.08MPa is evacuated to, keeps 30min, is slowly added to ethylene oxide, keeps 0.2~0.3MPa of reaction pressure,
100~160 DEG C of reaction temperature, adds up to add ethylene oxide 6.20mol (272.8g) and propylene oxide 2.40mol (141.6g),
Slaking reaction 30min is kept the temperature, is deaerated, discharging, GPC tests：Weight average molecular weight Mw=4100.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-3 0.10mol, phosphonate group monomer B-3 0.30mol, monomer C 4- hydroxyphenyl pyravates 0.10mol and anti-
Aqueous solvent 30.0g is answered, is slowly added to sulfuric acid 0.08mol, stirring 10min is to being uniformly mixed, then formaldehyde 0.20mol is slowly added dropwise,
Time for adding about 30min, then heats to 120 DEG C, reacts 4.0h, cools, and it is 4.6 or so to add liquid caustic soda and adjust pH value,
Add water adjusting and be contained in 30% or so admittedly, obtain light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 32000,
Target product content 92%, A-1 residual quantities 2%, B-1 residual quantities 1%, 4- hydroxyphenyl pyravates residual quantity 1%.
Synthetic example 4
(1) preparation of pendant polyether A-4
In 1000mL autoclaves, 3- propyl group Phenoxyethanol 0.10mol and sodium methoxide 0.010mol are added, is slowly heated to
50~60 DEG C, -0.08MPa is evacuated to, keeps 30min, is slowly added to ethylene oxide, keeps 0.2~0.3MPa of reaction pressure,
100~160 DEG C of reaction temperature, adds up to add ethylene oxide 6.80mol (300.0g) and propylene oxide 3.20mol (189.0g),
Slaking reaction 30min is kept the temperature, is deaerated, discharging, GPC tests：Weight average molecular weight Mw=4900.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-4 0.10mol, phosphonate group monomer B-4 0.20mol, monomer C 2,4- dihydroxycinnamic acids 0.30mol and
Reaction dissolvent water 45.0g, is slowly added to sulfuric acid 0.12mol, and stirring 10min is to being uniformly mixed, then formaldehyde is slowly added dropwise
0.40mol, time for adding about 30min, then heat to 130 DEG C, react 5.0h, cool, and add liquid caustic soda adjusting pH value and are
4.8 or so, add water adjusting and be contained in 30% or so admittedly, obtain light yellow and brown solution, GPC tests：Weight average molecular weight Mw
≈ 45000, target product content 90%, A-1 residual quantities 3%, B-1 residual quantities 2%, 2,4- dihydroxycinnamic acid residual quantities 1%.
Synthetic example 5
(1) preparation of pendant polyether A-5
In 1000mL autoclaves, 3- propenylbenzene oxyethanol 0.10mol and sodium methoxide 0.010mol, slow heating are added
To 50~60 DEG C, be evacuated to -0.08MPa, keep 30min, be slowly added to ethylene oxide, keep reaction pressure 0.2~
0.3MPa, 100~160 DEG C of reaction temperature, adds up to add ethylene oxide 6.20mol (272.8g) and propylene oxide 2.60mol
(153.4g), keeps the temperature slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=4300.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-5 0.10mol, phosphonate group monomer B-5 0.15mol, monomer C salicylic acids 0.20mol and reaction dissolvent water
50.0g, is slowly added to sulfuric acid 0.10mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.30mol, time for adding is slowly added dropwise
About 30min, then heats to 125 DEG C, reacts 6.0h, cools, and it is 5.0 or so to add liquid caustic soda and adjust pH value, adds water tune
Section is contained in 30% or so admittedly, obtains light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 60000, target product
Content 93%, A-1 residual quantities 2%, B-1 residual quantities 1%, salicylic acid residual quantity 1%.
Synthetic example 6
(1) preparation of pendant polyether A-6
In 1000mL autoclaves, 4- normal octane base Phenoxyethanol 0.10mol and sodium methoxide 0.010mol are added, is slowly added
Heat is evacuated to -0.08MPa to 50~60 DEG C, keeps 30min, is slowly added to ethylene oxide, keep reaction pressure 0.2~
0.3MPa, 100~160 DEG C of reaction temperature, adds up to add ethylene oxide 5.40mol (237.6g) and propylene oxide 2.20mol
(129.8g), keeps the temperature slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=3600.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-6 0.10mol, phosphonate group monomer B-6 0.12mol, monomer C gallic acids 0.12mol and reaction dissolvent
Water 40.0g, is slowly added to sulfuric acid 0.08mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.50mol is slowly added dropwise, during dropwise addition
Between about 30min, then heat to 120 DEG C, react 5.0h, cool, it is 5.6 or so to add liquid caustic soda and adjust pH value, adds water
Adjusting is contained in 30% or so admittedly, obtains light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 98000, target production
Thing content 88%, A-1 residual quantities 4%, B-1 residual quantities 3%, gallic acid allowance 2%.
Synthetic example 7
(1) preparation of pendant polyether A-7
In 1000mL autoclaves, 2- methyl 2- heptenyl Phenoxyethanol 0.10mol and sodium methoxide 0.010mol are added, is delayed
Slowly 50~60 DEG C are heated to, are evacuated to -0.08MPa, keep 30min, be slowly added to ethylene oxide, keep reaction pressure 0.2
~0.3MPa, 100~160 DEG C of reaction temperature, adds up to add ethylene oxide 4.40mol (193.6g) and propylene oxide 1.80mol
(106.2g), keeps the temperature slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=3000.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-7 0.10mol, phosphonate group monomer B-7 0.08mol, monomer C gallic acids 0.14mol and reaction dissolvent
Water 25.0g, is slowly added to sulfuric acid 0.03mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.20mol is slowly added dropwise, during dropwise addition
Between about 30min, then heat to 118 DEG C, react 4.0h, cool, it is 6.0 or so to add liquid caustic soda and adjust pH value, adds water
Adjusting is contained in 30% or so admittedly, obtains light yellow and brown solution, GPC tests：48000 target products of weight average molecular weight Mw ≈
Content 92%, A-1 residual quantities 4%, B-1 residual quantities 2%, gallic acid allowance 2%.
Synthetic example 8
(1) preparation of pendant polyether A-8
In 1000mL autoclaves, 2- heptyl Phenoxyethanol 0.10mol and sodium methoxide 0.010mol are added, is slowly heated to
50~60 DEG C, -0.08MPa is evacuated to, keeps 30min, is slowly added to ethylene oxide, keeps 0.2~0.3MPa of reaction pressure,
100~160 DEG C of reaction temperature, adds up to add ethylene oxide 3.60mol (158.4g) and propylene oxide 1.20mol (70.8g), protects
Warm slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=2300.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-8 0.10mol, phosphonate group monomer B-8 0.10mol, monomer C 4- coumaric acids 0.16mol and reaction dissolvent
Water 20.0g, is slowly added to sulfuric acid 0.02mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.15mol is slowly added dropwise, during dropwise addition
Between about 30min, then heat to 108 DEG C, react 4.0h, cool, it is 6.2 or so to add liquid caustic soda and adjust pH value, adds water
Adjusting is contained in 30% or so admittedly, obtains light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 36000, target production
Thing content 94%, A-1 residual quantities 2%, B-1 residual quantities 1%, 4- coumaric acids residual quantity are less than 1%.
Synthetic example 9
(1) preparation of pendant polyether A-9
In 1000mL autoclaves, 4- methyl -2- heptyl Phenoxyethanol 0.10mol and sodium methoxide 0.010mol are added, is delayed
Slowly 50~60 DEG C are heated to, are evacuated to -0.08MPa, keep 30min, be slowly added to ethylene oxide, keep reaction pressure 0.2
~0.3MPa, 100~160 DEG C of reaction temperature, adds up to add ethylene oxide 2.80mol (123.2g) and propylene oxide 0.80mol
(47.2g), keeps the temperature slaking reaction 30min, deaerates, discharging, GPC tests：Weight average molecular weight Mw=1600.
(2) preparation of graft polymers
Stirred at one equipped with motor machine, in the 1000ml four-hole boiling flasks of heated at constant temperature oil bath, sequentially add foregoing system
Standby pendant polyether A-9 0.10mol, phosphonate group monomer B-9 0.30mol, monomer C caffeic acids 0.10mol and reaction dissolvent water
10.0g, is slowly added to sulfuric acid 0.14mol, and stirring 10min is to being uniformly mixed, then formaldehyde 0.20mol, time for adding is slowly added dropwise
About 30min, then heats to 110 DEG C, reacts 2.0h, cools, and it is 6.2 or so to add liquid caustic soda and adjust pH value, adds water tune
Section is contained in 30% or so admittedly, obtains light yellow and brown solution, GPC tests：Weight average molecular weight Mw ≈ 10000, target product
Content 95%, A-1 residual quantities 2%, B-1 residual quantities 1%, caffeic acid residual quantity 1%.
Comparative example 1 (traditional ether type polycarboxylic acid)
Iso-amylene alcohol radical polyoxyethylene ether (Mw=1500) 300g (0.2mol) and water 61g is mixed to three mouthfuls of 1000mL
In flask, 65 DEG C are warming up to, while it is molten that methacrylic acid solution 42.5g (70% concentration, 0.5mol), ammonium persulfate is slowly added dropwise
Liquid 30.6g (30% concentration), thioacetic acid 10.3g, time for adding 2h, after being added dropwise, the reaction was continued 3h obtains the poly- carboxylic of ether type
Acid mother liquor A, is colourless transparent solution, and after tested, the conversion ratio of monomer a is up to 86%, the weight average molecular weight of ether type polycarboxylic acid A
32000.
Comparative example 2 (traditional ester type polycarboxylic acids)
Ester type polyether macromonomer (Mw=1200) 240g (0.2mol) and water 60g is mixed to the three-necked flask of 1000mL
In, 65 DEG C are warming up to, while acrylic acid solution 41.8g (70% concentration, 0.5mol), ammonium persulfate solution 30.0g is slowly added dropwise
(30% concentration), thioacetic acid 9.8g, time for adding 2h, after being added dropwise, the reaction was continued 3h obtains ester type polycarboxylic acids mother liquor A,
For colourless transparent solution, after tested, for the conversion ratio of monomer a up to 89%, the weight average molecular weight of ester type polycarboxylic acids A is 31000.
Application example 1
In order to evaluate dispersion performance of the graft polymers prepared by the present invention to cement paste, according to GB/T8077-
2000 standards have carried out flowing degree of net paste of cement test, and experimental result is shown in Table 1.
In Application Example of the present invention, except special instruction, used cement is small wild field 52.5R.P.II cement, sand
For the middle sand of modulus of fineness Mx=2.6, cobble-stone diameter is the rubble of 5~20mm continuous gradings.Flowing degree of net paste of cement test ginseng
Carried out according to GB/T8077-2000 standards, amount of water 87g, stirring measures flowing degree of net paste of cement after 3 minutes on plate glass.
The slump and slump-loss are with reference to JC473-2001《Concrete pump-feed agent》Relevant regulations perform.
The flowing degree of net paste of cement of 1 sample of table
As shown by data in table 1, the graft polymers that the technology of the present invention provides has excellent initial water reducing ability, when mixing
When amount is 0.14%, compared with traditional ether type or ester type polycarboxylate water-reducer (comparative sample 1 and comparative sample 2), cement original net
Slurry fluidity has a clear superiority, but the function of slump protection of 60min is general, at the beginning of showing that the condensation polymer has excellent cement paste
Beginning dispersibility.
Application example 2
In order to evaluate the graft polymers of the present invention to the adaptability of cement, according to GB/T8077-2000≤concrete outside
Add the method for agent homogeneity test method >=middle measure flowing degree of net paste of cement, cement 300g, amount of water 87g, contrast sample is
Ether type or ester type polycarboxylate water-reducer (PCA) prepared by conventional art, test original net slurry flowing is carried out using net slurry mixer
Degree, result of the test are shown in Table 2.
Adaptability of 2 sample of table to different cement
As shown by data in table 2, graft polymers provided by the invention have good cement adaptability, are given birth in different regions
Stable flowing degree of net paste of cement is shown in production cement, and contrasts sample and although shows relatively low initial cement paste
Fluidity, has cashed larger floating in different cement, and the adaptability of cement is poor.Application example 3
In order to evaluate adaptability of the polymer of the present invention to clay, according to GB/T8077-2000≤concrete admixture
The method of homogeneity test method >=middle measure flowing degree of net paste of cement, cement 300g (crane woods cement), amount of water 87g, respectively
The montmorillonite of 0.5% and 1% content of cementitious material is added, contrast sample is traditional ether type and ester type polycarboxylic acids (PCA), is used
Net slurry mixer carries out testing initial paste flowing degree, and result of the test is shown in Table 3.
The anti-clay performance test of 3 sample of table
As shown by data in table 3, graft polymers provided by the invention have anti-montmorillonite ability, when respectively fill glue material water
Mud amount 0.5%, 1.0% montmorillonite when, compared with its paste flowing degree value is not when mixing montmorillonite, divergence is substantially suitable, nothing
It is obvious to reduce phenomenon；Comparative sample tradition polycarboxylate water-reducer (PCA) is rapid with the increase of montmorillonite volume, its paste flowing degree
Decline, fall is even up to more than 50%., should under the market environment that aggregate and admixture quality are gradually deteriorated
Condensation polymer water-reducing agent has wide engineer application space, its anti-clay ability can be subject to market to be approved by gradually.
Application example 4
In order to evaluate adaptability of the graft polymers of the present invention to sulfate, according to GB/T8077-2000≤concrete
The method of additive homogeneity test method >=middle measure flowing degree of net paste of cement, cement 300g (crane woods cement), amount of water
87g, adds the sodium sulphate of 0.5% and 1% content of cementitious material respectively, and test original net slurry stream is carried out using net slurry mixer
Dynamic degree, result of the test are shown in Table 4.
The sulfate resistance aptitude tests of 4 sample of table
As shown by data in table 4, graft polymers provided by the invention has sulfur resistive acid ion interference performance, due to phosphonic acids
The combination of root and carboxylic acid ion, significant increase adsorption efficiency and adsorbance, in the cement paste system, when filling glue respectively
Material cement amount 0.5%, 1.0% sodium sulphate when, compared with its paste flowing degree value is not when mixing sulfate, its divergence is without obvious
Reduce phenomenon；Traditional ether type or ester type polycarboxylate water-reducer (PCA) has one with the increase of sulfuric acid salt volume, its paste flowing degree
Determine the reduction of degree, showing sulfate ion, there occurs competitive adsorption in cement particle surface with polycarboxylate water-reducer.Mixed
In solidifying soil admixture inferior quality, supersulphated cement system, the Sulphate-resistant property which has has
There is potential huge applications space.
Application example 5
According to the test request of high-performance water reducing agent in GB8076-2008≤concrete admixture >=standard, using crane woods
Cement, clay content be 1.8% modulus of fineness be 3.3 mechanism mountain sand, clay content be 0.6% nominal particle diameter 5-10mm and 10-
20mm continuous gradings rubble is material, according to match ratio as defined in table 5 test the water-reducing rate of condensation polymer water-reducing agent, air content,
The indexs such as slump holding capacity, test result are shown in Table 6.
5 concrete mix of table
Table 6 mixes graft polymers concrete performance
Note：/ represent that concrete does not have the slump and extension angle value
Concrete flowability as shown by data in table 6, in the stone that clay content is 1.8% mechanism mountain sand and clay content is 0.6%
Son is under conditions of aggregate and low water binder ratio, in the case of similar in air content, the more traditional ether type of graft polymers that newly synthesizes
Or ester type polycarboxylate water-reducer (PCA) shows higher slump value and divergence, the inverted slump test tube time reduces by 50%
More than, illustrate that the phosphate block polycondensate water-reducing agent Machine-made Sand higher to clay content, stone have and well adapt to ability,
Effectively lifting initial dispersion ability.
Graft polymers provided by the invention, structure is novel, and preparation process can industrialize, and introduces phosphate moieties and replaces passing
The primary attachment group as water-reducing agent such as carboxyl of system, it is dramatically different with traditional ether type or ester type polycarboxylic acids backbone structure, entirely
Face improves the initial dispersion ability of low water binder ratio concrete, and can effectively reduce concrete viscosity more than 50%, is conducive to surpass
High-strength concrete pumping construction under high-rise, overlength distance and hot environment, in addition, show good cement adaptability,
Anti- clay ability and sulfur resistive acid ion competitive Adsorption ability, in current aggregate and the market ring of admixture inferior quality
Under border, which has stronger advantage and market application space.
Claims (12)
1. a kind of height adapts to scattered phosphonic acids based polyalcohol soon, it is characterised in that the high fast scattered phosphonic acids based polyalcohol of adaptation
Molecular structure is comb shape, and molecular backbone is made of phenoxy group segment, or by C1~C6 aliphatic methylenes or methylene guanidine-acetic acid
The phenoxy group segment composition of connection, polyoxy alkane alkenyl structures are steric hindrance side chain, and adsorption functional group is phosphonate radical and carboxylate radical, phosphoric acid
Root and carboxylate radical random distribution；The molar ratio of phosphate radical and carboxylate radical is 1.0~9.0:1.0.
2. high adaptation according to claim 1 disperses phosphonic acids based polyalcohol soon, it is characterised in that by ether type side chain A, phosphonic acids
Base monomer B, carboxylic monomer C and aldehyde D are made, ether type side chain A, phosphonate group monomer by copolycondensation in the effect of catalyst E
Contain phenoxy group structure in the molecule of B and carboxylic monomer C；
The ether type side chain A meets below general formula：
Wherein L1It is straight chain or highly branched chain for polyoxy alkane alkenyl structures, it contains EO and PO fragments, EO and PO in polyoxy alkane alkenyl
Position random distribution in structure, EO contents are not less than 60%, R1For H or C1-C6 saturations or unsaturation alkoxy grp, ether type side
The molecular weight of chain A is 1200~4800；
The monomer B meets below formula：
Wherein G is-N (CH2-PO3H2)2, or-OPO3H2, it is main adsorption group, L2For the alkyl or polyoxy alkane alkenyl of C2~C10
Structure, L2For linear chain structure, R2For H, OH ,-COOH ,-COOR3Or the alkyl of C1~C8, can be straight or branched structure, its
Middle R3For the linear chain structure of C1~C6；
The carboxylic monomer C meets below formula：
Wherein R4And R5Respectively H, OH, NH2Or CO2R6, independently of each other, wherein R6For H or C1~C6 saturated alkyls；
The aldehyde D is the alkyl aldehydes of C1~C6, the aromatic aldehyde or glyoxalic acid of C7~C12；
Wherein the degree of polymerization of ether type side chain A is 2~80, and the degree of polymerization of monomer B is 4~200, and the monomer C degree of polymerization is 1~300, its
In (monomer B+ monomer C)/monomer A molar ratios be 1.0~5.0, monomer C/ monomer B molar ratios be 1.0~9.0:1；
The catalyst E mainly has a concentrated sulfuric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, 2- naphthalene sulfonic acids, phosphoric acid, oxalic acid, concentrated hydrochloric acid,
3. high adaptation according to claim 2 disperses phosphonic acids based polyalcohol soon, it is characterised in that the weight of ether type side chain A is equal
Molecular weight is 1500~2500.
4. high adaptation according to claim 2 disperses phosphonic acids based polyalcohol soon, it is characterised in that phosphonate group monomer B is used
Commercialized raw material, is prepared by phosphitylation or phosphorylation reaction, when the substrate of G is-NH2When, it is anti-using Mannich
It should be made, when X is O, be prepared using phosphorylation agent or reagent combination, the phosphorylation agent is sodium hypophosphite, tri-chlorination
Phosphorus, P4O6, dimethylphosphite and/or phosphorous acid.
5. high adaptation according to claim 2 disperses phosphonic acids based polyalcohol soon, it is characterised in that the carboxylic monomer C choosings
From P-hydroxybenzoic acid, 4- hydroxyphenyl pyravates, 5- Hydroxy M Phthalic Acids, 2,4- dihydroxycinnamic acids salicylic acid, nutgall
Acid, 4- coumaric acids, caffeic acid, 4- amino-2-hydroxybenzoic acids, 3,4- dihydroxy-benzoic acids and 2,5- dihydroxy-benzoic acids.
6. high adaptation according to claim 2 disperses phosphonic acids based polyalcohol soon, it is characterised in that the catalyst D is dense
Sulfuric acid.
7. the high adaptation according to any one of claim 1-6 disperses phosphonic acids based polyalcohol soon, it is characterised in that described
Copolycondensation carries out under solvent environment, and the reaction dissolvent E is the protic or aprotic weak polar solvent of routine, can
Ethyl methyl ether for the ethyl methyl ether of water or ethylene glycol derivative, the ethylene glycol derivative is glycol dimethyl ether, ethylene glycol first and second
Ether, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether.
8. the high adaptation according to any one of claim 1-6 disperses phosphonic acids based polyalcohol soon, it is characterised in that described
The weight average molecular weight Mw that height adapts to fast scattered phosphonic acids based polyalcohol is 10000~100000.
9. the high adaptation according to any one of claim 1-6 disperses phosphonic acids based polyalcohol soon, it is characterised in that described
It is as follows that height adapts to one of the structural formula of fast scattered phosphonic acids based polyalcohol：
The X is the sum of degree of polymerization of monomer ether type side chain A, monomer B and monomer C, is 7~500；
10. the high preparation method for adapting to fast scattered phosphonic acids based polyalcohol described in any one of claim 1-6, its feature exist
In including the following steps：
(1) preparation of side chain A：Using the phenyl monomer containing activity hydroxy or amido as initiator, catalyst is added, is heated, is delayed
It is slow to be passed through ethylene oxide or propylene oxide, temperature is controlled, reaction, after curing, cooling is spare.
Wherein catalyst charge is the 5%~20% of monomer molar amount, depending on monomer hydroxyl or amido activity are different；
Wherein initiation temperature control is at 60~100 DEG C, preferably 80~90 DEG C；
Wherein reaction temperature control is at 100~160 DEG C, depending on different initiator and reaction raw materials；
Wherein curing time control is in 0.5~1.0h；
(2) synthesis of graft polymers：The side chain A of preparation, monomer B, monomer C and aldehyde D and catalyst E are sequentially added reaction to hold
In device, water is then added, as reaction dissolvent, is heated to 90~130 DEG C, under the conditions of reflux state or seal-off pressure, reaction 1
~8h, cools, and then adds lye, and adjustment solution pH value is 3.0~5.0, and solid content is 20%~50%.
Wherein side chain A, monomer B, the molar ratio of monomer C and aldehyde D are 1:0.8~5.0:0.8~2.0:1.0~6.0；
Wherein the addition of catalyst E (presses H for the 5%~30% of side chain A, monomer B and monomer C moles+Adjust)；
The amount for wherein adding water is the 1%~40% of side chain A, monomer B and monomer C quality sums.
11. the high application process for adapting to fast scattered phosphonic acids based polyalcohol described in any one of claim 1-6, its feature exist
In, suitable for high mineral close material under the conditions of cement water reducing agent use, its volume for total cementitious material weight 0.08%~
0.6%.
12. application process according to claim 11, it is characterised in that its volume is the 0.1% of total cementitious material weight
~0.4%.
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| CN112321784A (en) * | 2019-12-26 | 2021-02-05 | 联泓(江苏)新材料研究院有限公司 | Bulk polymer and preparation method and application thereof |
| CN113968976A (en) * | 2020-07-22 | 2022-01-25 | 南京博特新材料有限公司 | Arborescent phosphonic acid water reducing agent and preparation method and application thereof |
| CN113968949B (en) * | 2020-07-24 | 2023-11-07 | 博特新材料泰州有限公司 | High-adaptability water reducer based on biological amino acid, and preparation method and application thereof |
| CN113968949A (en) * | 2020-07-24 | 2022-01-25 | 博特新材料泰州有限公司 | High-adaptability water reducing agent based on biological amino acid and preparation method and application thereof |
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