CN107325234A - A kind of anti-chamotte mould phosphate modified polycarboxylic acid water reducer and preparation method thereof - Google Patents
A kind of anti-chamotte mould phosphate modified polycarboxylic acid water reducer and preparation method thereof Download PDFInfo
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- CN107325234A CN107325234A CN201710550760.3A CN201710550760A CN107325234A CN 107325234 A CN107325234 A CN 107325234A CN 201710550760 A CN201710550760 A CN 201710550760A CN 107325234 A CN107325234 A CN 107325234A
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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
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
-
- 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
Abstract
The invention discloses a kind of anti-chamotte mould phosphate modified polycarboxylic acid water reducer and preparation method thereof, comprise the following steps that：By unsaturated carboxylic acid class minor comonomer, unsaturated polyether polymeric monomer in the presence of initiator, reducing agent and chain-transferring agent, carry out redox Raolical polymerizable and obtain the polycarboxylate water-reducer performed polymer containing carboxyl；The partially modified copolymerization product for obtaining phosphoric acid ester group is carried out to the polycarboxylate water-reducer performed polymer containing carboxyl using diphenyl phosphoryl chloride, it is 6~7 that pH value is adjusted after the completion of reaction, adds water and obtains poly carboxylic acid series water reducer.The present invention by by the modified side chain of polycarboxylate water-reducer into the phosphate group containing two phenyl ring, phosphonic functional groups enter polycarboxylate water-reducer pectination molecule, improve the sulfur resistive acid group ability and anti-mud ability of polycarboxylate water-reducer, the introducing of phenyl ring considerably increases the physical size of polycarboxylate water-reducer side chain, it is set to be difficult to insert in the layer structure of clay, so as to reach the effect of anti-mud and not influence its inherent function.
Description
Technical field
The present invention relates to a kind of technical field of cement concrete polycarboxylate water-reducer, a kind of anti-chamotte mould is related specifically to
Polycarboxylate water-reducer and preparation method thereof.
Background technology
Poly carboxylic acid series water reducer is because with water-reducing rate is high, slump retaining is good, volume is low, molecular structure adjustability is strong and green
The premium properties such as environmental protection, are applied in concrete works more and more widely.However, substantial amounts of case history and research table
Bright, compared with the water reducers such as traditional naphthalene system, melamine series and amido sulfoacid series, poly carboxylic acid series water reducer contains mud to aggregate
Amount is more sensitive, and the mud in aggregate can adsorb polycarboxylate water-reducer, with the increase of clay content, the diminishing of poly carboxylic acid series water reducer
Dispersibility degradation, guarantor's effect of collapsing are poor, cause the workability of fresh concrete to decline to a great extent.It is quick with building trade
Development, the sand and stone resources of high-quality are gradually used up totally, and the sand and stone resources of various regions tend to deterioration, particularly big and medium-sized cities, use
Sandstone clay content is higher.In the case that aggregate clay content is high, even if improving the volume of poly carboxylic acid series water reducer, though initial flow degree
The problems such as making moderate progress, but can not solve water-reducing rate, slump retaining, super mix of polycarboxylic acids increases cost, on the other hand can also make
Serious, the problems such as setting time is long into concrete initial isolation.Therefore, from polycarboxylate water-reducer molecule structure in itself,
The functional group of adsorption by clay can be reduced by introducing some, a kind of anti-chamotte mould polycarboxylate water-reducer is developed, can be significantly
The applicability in China of polycarboxylate water-reducer is improved, the development to building trade is significant.
Existing research shows at present, can be with the Ca in cement using small molecule phosphate2+Complex compound is formed, delays water
Muddy water, while the absorption to carboxyl such as clay can be reduced with the carboxyl competitive Adsorption in polycarboxylate water-reducer, so that
Ensure polycarboxylate water-reducer performance (and just etc. gathers materials influence of the middle clay content to polycarboxylate water-reducer performance and correspondingly [J],
5th national special concrete technology seminar, 2014, Chengdu).
Patent WO2010/040611A1 discloses a kind of preparation side that phosphate group is introduced into straight chain condensed type water reducer
Method.Which employs ethylene glycol phenyl ether and the esterification products of phosphoric acid, polyoxyethylene monophenyl ether and formaldehyde are contracted under the conditions of 105 DEG C
Reaction is closed to prepare.The polycarboxylic acids diminishing of condensation water reducing agent of the method for straight chain type, its water-reducing rate and retentivity compared with pectination
It is relatively poor for agent.
The A of Chinese patent literature CN 105418857 report a kind of preparation method of phosphate ester-containing based polycarboxylic acid water reducer,
It is that unsaturated polyether polymeric monomer, esters of unsaturated carboxylic acids, unsaturated alcohol are first carried out to copolyreaction in organic solvent to be gathered
Carboxylic acid water reducer performed polymer, then carries out phosphorylation modification by polycarboxylate water-reducer performed polymer, then in the presence of acidic aqueous solution,
The carboxylate group on the modified product of phosphorylation is hydrolyzed, and removes organic solvent, finally neutralizes, obtains the phosphoric acid
The polycarboxylate water-reducer of ester group, but this invention complex manufacturing, and conversion ratio is not high, production cost is higher, and largely uses
Organic solvent, is unfavorable for large-scale production and application.
Patent US2014/0039098 is disclosed with the preparation of middle bis phosphoric acid group water reducer, and it is provided with certain sulfur resistive
The characteristic of acid ion and anti-mud.Using polyacrylic acid, poly glycol monomethyl ether, 1-hydroxy ethylidene-1,1-diphosphonic acid is in 175 DEG C and vacuum
Under the conditions of spending 20mBar prepared by reaction.The method reaction time is long, and industrialized condition is harsh, and esterification yield is not high, early stage industry
Investment of production equipment is high.
The content of the invention
A kind of anti-chamotte mould phosphate modified polycarboxylic acid is provided the invention aims to improve the deficiencies in the prior art
The preparation method of water reducer, it improves anti-mud again on the premise of diminishing.
The technical scheme is that：A kind of anti-chamotte mould phosphate modified polycarboxylic acid water reducer and preparation method thereof, it is special
Levy and be that its molecular structural formula is as follows：
Wherein, R1、R3It is each independently hydrogen atom, methyl or COOM, M and represents monovalent metal atom；R2For H or containing 1~
4 carbon atom alkyls, phenyl or phenyl derivatives；R4For H or 1~5 carbon atom alkyl, phenyl or phenyl derivatives；A is 1
Or 2；B is 5~200；C is 0~100；X, y are each independently as 500~1000；Z is 250~500.
Present invention also offers the preparation method of above-mentioned anti-chamotte mould phosphate modified polycarboxylic acid water reducer, specific steps are such as
Under：
1) by unsaturated carboxylic acid class minor comonomer, unsaturated polyether polymeric monomer initiator, reducing agent and chain-transferring agent work
Under, it is maintained at 20~60 DEG C of progress 3~5h of Raolical polymerizable and obtains the polycarboxylate water-reducer performed polymer containing carboxyl, its
Molecular structural formula is as follows：
Wherein, w is 1000~2000.
2) preparation of anti-chamotte mould phosphate modified polycarboxylic acid water reducer：Using diphenyl phosphoryl chloride to the poly- carboxylic containing carboxyl
Sour water reducer performed polymer carries out the partially modified copolymerization product for obtaining phosphorous acidic group, is adjusted to the pH value of copolymerization product with alkali lye
6~7, add water the poly carboxylic acid series water reducer for obtaining that mass concentration is 5~60%, wherein the polycarboxylate water-reducer pre-polymerization containing carboxyl
The mol ratio of body and diphenyl phosphoryl chloride is 1：(0.1~0.9).
Preferably, step 1) described in unsaturated carboxylic acid class minor comonomer molecular structural formula be：
Wherein, R1、R3H or monovalent metal atom are represented to hydrogen atom, methyl or COOM, M independently is certainly；R2For H or contain
1~4 carbon atom alkyl, phenyl or phenyl derivatives.
Step 1) described in unsaturated polyether polymeric monomer molecular structural formula be：
Wherein, R4For H or 1~5 carbon atom alkyl, phenyl or phenyl derivatives；A is 1 or 2；B is 5~200；C is 0
~100.
Preferably, step 1) described in unsaturated carboxylic acid class minor comonomer be acrylic acid, methacrylic acid, fumaric acid, horse
Come sour, 2- methyl-2-butenoic acids, the one or more of 3- methyl-2-butenoic acids.
Preferably, step 1) described in unsaturated polyether polymeric monomer be methyl allyl polyoxyethylene ether, methallyl
One or more in base polyoxyethylenepropylene ether, prenyl APEO, prenyl polyoxyethylenepropylene ether.
Preferably, step 1) in initiator be hydrogen peroxide, potassium peroxydisulfate, one kind of ammonium persulfate or sodium peroxydisulfate or
Two or more combinations；Reducing agent is sodium formaldehyde sulfoxylate, sodium sulfite, sodium pyrosulfite, sodium hydrogensulfite, ferrous pyrophosphate, sulfuric acid Asia
Any one or two or more combinations of iron, sodium hypophosphite or sodium ascorbate；Chain-transferring agent is mercaptoethanol, sulfydryl second
Acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, one or more kinds of combinations of methylpropenyl sodium sulfonate or lauryl mercaptan.
Preferably, alkali lye in for potassium hydroxide, sodium hydroxide or calcium hydroxide any one or two or more groups
Close.
Preferably, described unsaturated carboxylic acid class minor comonomer, unsaturated polyether polymeric monomer, initiator, reducing agent and chain turn
The mol ratio for moving agent is 1：(1.2~10)：(0.01~0.1)：(0.03~0.2)：(0.005~0.1)；Wherein containing carboxyl
The mol ratio of polycarboxylate water-reducer performed polymer and diphenyl phosphoryl chloride is 1：(0.1~0.9).
The inventive method introduces the phosphate group containing two phenyl ring, the suction of phosphate group due to water reducer molecular structure
Attached ability is better than hydroxy-acid group, can be preferentially adsorbed to the surface of clay in aggregate, reduces absorption of the clay to hydroxy-acid group, so that
Reduce sensitiveness of the polycarboxylate water-reducer to aggregate clay content；And the introducing of phosphate group makes it than traditional polycarboxylic acids diminishing
Agent has stronger adsorption capacity, it is sufficient to resist the competitive Adsorption to polycarboxylate water-reducer such as sulfate in cement so that poly- carboxylic
Sour water reducer performance is not influenceed by sulfate etc., substantially increases the dispersibility of the polycarboxylate water-reducer.In addition, phenyl ring knot
The introducing of structure considerably increases the physical size of polycarboxylate water-reducer side chain, adds steric hindrance, reduces molecule to clay
The interspersed suction-operated of mineral, make its be difficult insert clay layer structure in, solve clay content it is higher when, anti-chamotte mould diminishing
The phenomenon that agent volume is big, concrete gradual loss is too fast.
Beneficial effect：Compared with prior art, the invention has the advantages that：
(1) modified side chain of polycarboxylate water-reducer has been synthesized anti-chamotte mould by the present invention into the phosphate group containing two phenyl ring
Polycarboxylate water-reducer, technique is simple, improves the problem of polycarboxylate water-reducer is larger to sandstone clay content sensitiveness, effectively improves
The anti-mud function of polycarboxylate water-reducer.
(2) the inventive method is modified introducing phosphate group using diphenyl phosphoryl chloride to diminishing agent molecule, it is to avoid
Unsaturated phosphate ester monomer containing phosphate group directly participates in the chain transfer that water reducer copolyreaction is brought, and causes diminishing
The shortcoming that the structure and molecular weight of agent can not be controlled accurately.
(3) phosphate modified polycarboxylic acid water reducer product prepared by the inventive method, has again on the premise of diminishing is protected and collapsed
There is anti-mud.
(4) to be made into performance after the aqueous solution steady for anti-chamotte mould phosphate modified polycarboxylic acid water reducer product prepared by the inventive method
It is fixed, it is not stratified during storage, do not precipitate, convenient transportation.
(5) anti-chamotte mould phosphate modified polycarboxylic acid water reducer product prepared by the inventive method, solves engineered building materials
Slump-loss is can also ensure that under problem containing mud, and low-dosage.
Embodiment
Technical solution of the present invention is described in further detail below by embodiment.
Embodiment 1
By 1mol acrylic acid, 5mol methyl allyl polyoxyethylene ethers in 0.05mol hydrogen peroxide, 0.1mol sodium formaldehyde sulfoxylates and
In the presence of 0.05mol TGAs, it is maintained at 20 DEG C and carries out Raolical polymerizable 5h and obtain the polycarboxylic acids containing carboxyl and subtract
Aqua performed polymer；The polycarboxylate water-reducer performed polymer for containing carboxyl to 1mol with 0.1mol diphenyl phosphoryl chlorides is modified and obtained
The copolymerization product of phosphorous acidic group, 6.5 are adjusted to sodium hydroxide by the pH value of copolymerization product, and it is 40% to add water and obtain mass concentration
Poly carboxylic acid series water reducer.
Embodiment 2
By 1mol methacrylic acids, 1.2mol prenyls APEO in 0.01mol ammonium persulfates, 0.03mol
In the presence of sodium pyrosulfite and 0.005mol methylpropenyl sodium sulfonates, it is maintained at 50 DEG C of progress Raolical polymerizable 3h and obtains
To the polycarboxylate water-reducer performed polymer containing carboxyl；Contain the polycarboxylic acids diminishing of carboxyl to 1mol with 0.4mol diphenyl phosphoryl chlorides
Agent performed polymer is modified the copolymerization product for obtaining phosphorous acidic group, and the pH value of copolymerization product is adjusted into 7 with potassium hydroxide, added water
Obtain the poly carboxylic acid series water reducer that mass concentration is 10%.
Embodiment 3
By 1mol maleic acids, 8mol methacrylic polyoxyethylenepropylene ethers in 0.1mol sodium peroxydisulfates, 0.2mol is anti-bad
In the presence of hematic acid sodium and 0.1mol 2 mercaptopropionic acids, it is maintained at 25 DEG C of progress Raolical polymerizable 3.5h and obtains containing carboxylic
The polycarboxylate water-reducer performed polymer of base；Contain the polycarboxylate water-reducer performed polymer of carboxyl to 1mol with 0.9mol diphenyl phosphoryl chlorides
The copolymerization product for obtaining phosphorous acidic group is modified, the pH value of copolymerization product is adjusted to 6.5 with sodium hydroxide, adds water and obtains matter
Measure the poly carboxylic acid series water reducer that concentration is 45%.
Embodiment 4
By 1mol fumaric acid, 10mol prenyls APEO in 0.05mol hydrogen peroxide, 0.1mol pyrophosphoric acids
In the presence of ferrous and 0.05mol 3- mercaptopropionic acids, it is maintained at 45 DEG C of progress Raolical polymerizable 3h and obtains containing carboxyl
Polycarboxylate water-reducer performed polymer；The polycarboxylate water-reducer performed polymer for containing carboxyl to 1mol with 0.5mol diphenyl phosphoryl chlorides is carried out
The modified copolymerization product for obtaining phosphorous acidic group, is adjusted to 6 by the pH value of copolymerization product with calcium hydroxide, adds water and obtain mass concentration
For 35% poly carboxylic acid series water reducer.
Embodiment 5
By 1mol2- methyl-2-butenoic acids, 4mol methyl allyl polyoxyethylene ethers in 0.01mol potassium peroxydisulfates,
In the presence of 0.05mol sodium hydrogensulfites and 0.005mol lauryl mercaptans, it is maintained at 30 DEG C of progress Raolical polymerizable 4h and obtains
To the polycarboxylate water-reducer performed polymer containing carboxyl；Contain the polycarboxylic acids diminishing of carboxyl to 1mol with 0.3mol diphenyl phosphoryl chlorides
Agent performed polymer is modified the copolymerization product for obtaining phosphorous acidic group, and the pH value of copolymerization product is adjusted into 7 with potassium hydroxide, added water
Obtain the poly carboxylic acid series water reducer that mass concentration is 60%.
Embodiment 6
By 1mol3- methyl-2-butenoic acids, 2mol prenyl polyoxyethylenepropylene ethers in 0.02mol ammonium persulfates,
In the presence of 0.05mol ferrous sulfate and 0.01mol lauryl mercaptans, it is maintained at 40 DEG C of progress Raolical polymerizable 4.5h and obtains
Polycarboxylate water-reducer performed polymer containing carboxyl；Contain the polycarboxylate water-reducer of carboxyl to 1mol with 0.6mol diphenyl phosphoryl chlorides
Performed polymer is modified the copolymerization product for obtaining phosphorous acidic group, and the pH value of copolymerization product is adjusted into 6 with calcium hydroxide, added water
To the poly carboxylic acid series water reducer that mass concentration is 25%.
Embodiment 7
By 1mol acrylic acid, 4mol methacrylic polyoxyethylenepropylene ethers in 0.05mol sodium peroxydisulfates,
In the presence of 0.2mol sodium sulfites and 0.05mol mercaptoethanols, 35 DEG C of progress Raolical polymerizables are maintained at
3.5h obtains the polycarboxylate water-reducer performed polymer containing carboxyl；Contain the poly- carboxylic of carboxyl to 1mol with 0.8mol diphenyl phosphoryl chlorides
Sour water reducer performed polymer is modified the copolymerization product for obtaining phosphorous acidic group, is adjusted to the pH value of copolymerization product with sodium hydroxide
6.5, add water the poly carboxylic acid series water reducer for obtaining that mass concentration is 50%.
Embodiment 8
By 1mol methacrylic acids, 1.2mol prenyls APEO in 0.01mol potassium peroxydisulfates, 0.03mol
In the presence of sodium formaldehyde sulfoxylate and 0.01mol TGAs, it is maintained at 50 DEG C of progress Raolical polymerizable 5h and obtains containing carboxyl
Polycarboxylate water-reducer performed polymer；The polycarboxylate water-reducer performed polymer for containing carboxyl to 1mol with 0.2mol diphenyl phosphoryl chlorides is carried out
The modified copolymerization product for obtaining phosphorous acidic group, is adjusted to 7 by the pH value of copolymerization product with potassium hydroxide, adds water and obtain mass concentration
For 15% poly carboxylic acid series water reducer.
Implementation result
Paste flowing degree is tested：With reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, to embodiment 1
Paste flowing degree test is carried out to the gained sample of embodiment 8.W/C is 0.29, and the solid volume of additive folding is cement consumption
0.21%, 2% montmorillonite.From following table as can be seen that with commercially available anti-mud agentContrasted, with the addition of additional
The embodiment 1 of agent has a clear superiority to the gained sample paste flowing degree of embodiment 8, illustrates this anti-chamotte mould polycarboxylate water-reducer confrontation
Mud has obvious effect, and paste flowing degree gradual loss is small.
The paste flowing degree and gradual loss of the different samples of table 1
Testing concrete performance：With reference to GB8076-2008《Concrete admixture》The gained sample of embodiment 8 is arrived to embodiment 1
Product carry out slump-loss, concrete strength inspection.Additive is rolled over when solid volume is 1.8% (relative to cement consumption), under
Table can be seen that and commercially available anti-mud agentCompare, the embodiment 1 that with the addition of montmorillonite arrives the gained sample of embodiment 8
The slump-loss of product is significantly improved, and illustrates that the anti-mud effect of this anti-chamotte mould water reducer has than commercially available anti-mud agent and substantially carries
It is high.
The concrete test of the different samples of table 2
Claims (9)
1. a kind of anti-chamotte mould phosphate modified polycarboxylic acid water reducer, it is characterised in that its molecular structural formula is as follows：
Wherein, R1、R3It is each independently hydrogen atom, methyl or COOM, M and represents monovalent metal atom；R2For H or containing 1~4
Carbon atom alkyl, phenyl or phenyl derivatives；R4For H or 1~5 carbon atom alkyl, phenyl or phenyl derivatives；A is 1 or 2；
B is 5~200；C is 0~100；X, y are each independently 500~1000；Z is 250~500.
2. the preparation method of the anti-chamotte mould phosphate modified polycarboxylic acid water reducer described in claim 1, it is characterised in that including such as
Lower step：
1) by unsaturated carboxylic acid class minor comonomer, unsaturated polyether polymeric monomer in the presence of initiator, reducing agent and chain-transferring agent,
It is maintained at 20~60 DEG C of progress 3~5h of Raolical polymerizable and obtains the polycarboxylate water-reducer performed polymer containing carboxyl, its molecule
Structural formula is as follows：
Wherein, w is 1000~2000；
2) preparation of anti-chamotte mould phosphate modified polycarboxylic acid water reducer：The polycarboxylic acids containing carboxyl is subtracted using diphenyl phosphoryl chloride
Aqua performed polymer carries out the partially modified copolymerization product for obtaining phosphorous acidic group, the pH value of copolymerization product is adjusted to 6 with alkali lye~
7, add water the poly carboxylic acid series water reducer for obtaining that mass concentration is 5~60%, wherein the polycarboxylate water-reducer performed polymer containing carboxyl
Mol ratio with diphenyl phosphoryl chloride is 1：(0.1~0.9).
3. preparation method according to claim 2, it is characterised in that step 1) described in unsaturated carboxylic acid class minor comonomer
Molecular structural formula is：
Wherein, R1、R3H or monovalent metal atom are represented to hydrogen atom, methyl or COOM, M independently is certainly；R2For H or containing 1~4
Individual carbon atom alkyl, phenyl or phenyl derivatives.
4. preparation method according to claim 2, it is characterised in that step 1) described in unsaturated polyether polymeric monomer point
Subformula is：
Wherein, R4For H or 1~5 carbon atom alkyl, phenyl or phenyl derivatives；A is 1 or 2；B is 5~200；C is 0~100.
5. preparation method according to claim 2, it is characterised in that step 1) described in unsaturated carboxylic acid class minor comonomer
For acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2- methyl-2-butenoic acids, one kind of 3- methyl-2-butenoic acids or several
Kind.
6. the preparation method according to claim 2 or 4, it is characterised in that step 1) described in the big list of unsaturated polyether
Body is methyl allyl polyoxyethylene ether, methacrylic polyoxyethylenepropylene ether, prenyl APEO, isoamyl two
One or more in alkenyl polyoxyethylenepropylene ether.
7. preparation method according to claim 2, it is characterised in that step 1) in initiator be hydrogen peroxide, over cure
One or more kinds of combinations of sour potassium, ammonium persulfate or sodium peroxydisulfate；Reducing agent is sodium formaldehyde sulfoxylate, sodium sulfite, pyrosulfurous acid
Sodium, sodium hydrogensulfite, ferrous pyrophosphate, ferrous sulfate, sodium hypophosphite or sodium ascorbate any one or it is two or more
Combination；Chain-transferring agent is mercaptoethanol, TGA, 2 mercaptopropionic acid, 3- mercaptopropionic acids, methylpropenyl sodium sulfonate or 12
One or more kinds of combinations of mercaptan.
8. preparation method according to claim 2, it is characterised in that step 2) in alkali lye be potassium hydroxide, hydroxide
Any one or two or more combinations of sodium or calcium hydroxide.
9. preparation method according to claim 2, it is characterised in that wherein described unsaturated carboxylic acid class minor comonomer, no
Saturation polyether macromonomer, initiator, the mol ratio of reducing agent and chain-transferring agent are 1：(1.2~10)：(0.01~0.1)：(0.03
~0.2)：(0.005~0.1)；The mol ratio of polycarboxylate water-reducer performed polymer and diphenyl phosphoryl chloride wherein containing carboxyl is
1：(0.1~0.9).
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| CN108623745A (en) * | 2018-06-08 | 2018-10-09 | 科之杰新材料集团有限公司 | A kind of phosphorous polycarboxylate water-reducer and preparation method thereof |
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| CN116102283A (en) * | 2023-02-27 | 2023-05-12 | 广西云鹰新材料科技有限公司 | Super-temperature-resistant high MB-value-resistant adsorption type polycarboxylate superplasticizer and preparation method thereof |
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| CN117024669A (en) * | 2023-08-21 | 2023-11-10 | 湖北腾辰科技股份有限公司 | Mud-resistant polycarboxylate superplasticizer and preparation method thereof |
| CN117024669B (en) * | 2023-08-21 | 2024-04-09 | 湖北腾辰科技股份有限公司 | Mud-resistant polycarboxylate superplasticizer and preparation method thereof |
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