CN104944827B - A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent - Google Patents
A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent Download PDFInfo
- Publication number
- CN104944827B CN104944827B CN201510296715.0A CN201510296715A CN104944827B CN 104944827 B CN104944827 B CN 104944827B CN 201510296715 A CN201510296715 A CN 201510296715A CN 104944827 B CN104944827 B CN 104944827B
- Authority
- CN
- China
- Prior art keywords
- preparation
- reducing agent
- glycol monomethyl
- monomethyl ether
- poly glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of slump-retaining polycarboxylic acid type water reducing agent, are prepared using following steps：1) hydroxyl unsaturation minor comonomer, amine unsaturation minor comonomer, initiator, reducing agent, chain-transferring agent carry out redox Raolical polymerizable and obtain amino-contained copolymerization product；2) excessive sodium hydride is added in poly glycol monomethyl ether, epoxychloropropane is added in after reaction, desalination after reacting is stirred for and obtains epoxy group poly glycol monomethyl ether；3) after obtained amino-contained copolymerization product being added in the reaction of epoxy group poly glycol monomethyl ether, slump-retaining polycarboxylic acid type water reducing agent is obtained with alkali neutralization adjustment pH value；The present invention adjusts properties of product by controlling molecular structure/molecular weight of amino-contained copolymerization product and the molecular weight of poly glycol monomethyl ether, is swift in response efficient and does not use organic solvent, nontoxic and pollution-free, easy to operate.Prepared poly carboxylic acid series water reducer is a kind of polycarboxylic acid series high efficiency water reducing agent of collapse protection type, and properties of product are stablized, and especially protects effect of collapsing with preferable to containing silt particle building stones.
Description
Technical field
The present invention relates to a kind of technical fields of cement concrete poly carboxylic acid series water reducer, are related specifically to a kind of use
The preparation method of amido-epoxy reaction and the slump-retaining polycarboxylic acid type water reducing agent of oxidationreduction free radical polymerization.
Background technology
The world today, social economy flourish, and urban construction is advanced by leaps and bounds, and the thing followed is and traffic, water power, city
The rapid rising of the related constructions such as political affairs, the emergence of high-rise and the raising of construction material construction requirement, to mixed
The aid pumpability requirement for coagulating soil is also higher and higher, and high efficiency water reducing agent is then the required part for preparing pumping, and polycarboxylic acid
Water-reducing agent becomes wherein part and parcel.However, for a long time, how the use of concrete is but effectively controlled slump always
Degree loses this problem and is perplexed.From concrete mixing plant produce pump concrete generally require long range transport and
Construction environment (higher temperature etc.) is different, inevitably leads to the slump-loss of concrete, so as to influence concrete
Construction.At present be mainly used to reduce mix water-reducing agent the method for concrete slump mainly includes, water-reducing agent repeatedly repeatedly addition,
Water-reducing agent latter admixing method, compound retarder and sustained release method etc..But the effect acquired by these methods is not apparent, environment friend
Good property difference or cost are higher.
Polycarboxylate water-reducer prepared by traditional polymerization, the performance influence that sour ether compares product is very big, if it is desired to
Sour ether is reduced than will necessarily reduce the performance of polycarboxylate water-reducer to improve space steric effect.There is presently no a kind of methods
Ensure electrostatic repulsion in fixed acid mole and improve steric hindrance to increase side chain density.CN103613308B reports a kind of poly-
The preparation method of carboxylic acid high-thin arch dam agent：The itaconic acid introduced in molecular structure delays hydrated cementitious, phenyl ring is introduced in molecular structure
Space steric effect is generated, enhances water-reducing agent dispersion stabilization, but the conversion ratio of the invention is not high, and the inadequate ring of preparation process
It protects, is unfavorable for producing and applying on a large scale.CN102153711A reports a kind of by allyl sulphonic acid salt monomer, acrylic acid
Class monomer, Methylacrylic acid polyethylene glycol single armor ether ester polymeric monomer and maleic anhydride graft beta-cyclodextrin polymeric monomer pass through free radical
Copolyreaction obtains a kind of slow-setting polycarboxylic acid water reducing agent, make gained polycarboxylate dehydragent have preferable retarding performance,
Micro- bleed performance and better mobile performance, but the maleic anhydride graft beta-cyclodextrin polymeric monomer grafting rate of the invention is not high,
And its be influenced by temperature it is larger, it is impossible to fundamentally solve the problems, such as the concrete slump loss under different condition, be unfavorable for
Large-scale production and application.
Invention content
A kind of slump-retaining polycarboxylic acid type water reducing agent is provided the purpose of the invention is to improve the deficiencies in the prior art
Preparation method can assign water-reducing agent new function in this way.
The technical scheme is that：A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent, is as follows：
1) preparation of amino-contained copolymerization product：Hydroxyl unsaturation minor comonomer and the unsaturated minor comonomer containing amine are existed
Under initiator, reducing agent and chain-transferring agent effect, 25~45 DEG C of conditions carry out oxidationreduction Raolical polymerizables 30~
90min obtains amino-contained copolymerization product；Wherein described hydroxyl unsaturation minor comonomer, draws the unsaturated minor comonomer containing amine
The molar ratio for sending out agent, reducing agent and chain-transferring agent is 1：(0.1~1)：(0.01~0.1)：(0.03~0.2)：(0.001~
0.01)；
2) preparation of epoxy group poly glycol monomethyl ether：At 0~25 DEG C, excessive hydrogen is added in poly glycol monomethyl ether
Change sodium, add in epoxychloropropane after reacting 10~40min, after being stirred for 30~90min of reaction, desalination obtains the poly- second two of epoxy group
Alcohol monomethyl ether；Wherein the molar ratio of poly glycol monomethyl ether, sodium hydride and epoxychloropropane is 1：(1.01~1.05)：(1.01
~1.1)；
3) preparation of slump-retaining polycarboxylic acid type water reducing agent：Step 2) system will be added in amino-contained copolymerization product made from step 1)
The epoxy group poly glycol monomethyl ether obtained, after reacting 10~50min, it is 6~7 to add alkali neutralization adjustment pH value, obtains collapse protection type
Poly carboxylic acid series water reducer；Wherein the molar ratio of amino-contained copolymerization product and epoxy group poly glycol monomethyl ether is 1：(0.5~1).
It is preferred that above-mentioned steps 1) in the molecular weight of obtained amino-contained copolymerization product be 3000~5000.
Preferred steps 1) described in initiator be persulfuric acid object or peroxide；More preferable tert-butyl hydroperoxide, mistake
Hydrogen oxide, ammonium persulfate, benzoyl peroxide, isopropyl benzene hydroperoxide, potassium peroxydisulfate or sodium peroxydisulfate it is one or two kinds of with
Upper combination.
Preferred steps 1) described in reducing agent for rongalite, sodium pyrosulfite, n,N-Dimethylaniline, bisulfite
One kind of sodium, rongalite, ferrous sulfate, N, N- diethylanilines, ferrous pyrophosphate, four aziridines etc. or sodium ascorbate or
Two or more combinations.
Preferred steps 1) described in chain-transferring agent for thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acids, methylpropenyl
One or more kinds of combinations of sodium sulfonate or lauryl mercaptan.
Preferred steps 1) described in hydroxyl unsaturation minor comonomer general formula：R1OH expressions, wherein R1For 4~14 carbon
Atom ethylenic unsaturation alkyl or phenyl and its derivative；More preferably the hydroxyl unsaturation minor comonomer is 2- methallyls
Alcohol, propenyl, acrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, 4- ethylene
Base phenol, 2- methoxyl-4-vinyl phenols, hydroxyethyl methacrylate N-butyl, hydroxypropyl acrylate or acrylic acid hydroxyl N-butyl
One or more kinds of combinations.
Preferred steps 1) described in amine unsaturation minor comonomer general formula：R2NHR3It represents, wherein R2For 3~8 carbon atoms
Ethylenic unsaturation alkyl, R3For H or the alkyl of 2-5 carbon atom；More preferably the amine unsaturation minor comonomer is acryloyl
Amine, allylamine, Methacrylamide, N- ethyl acrylamides, n-isopropyl acrylamide or N- propyl Methacrylamides one
Kind or two or more combinations.
Preferred steps 2) described in poly glycol monomethyl ether molecular weight be 400~5000.
Preferred steps 3) described in alkali be sodium hydroxide, potassium hydroxide or calcium hydroxide.
Amido-epoxy addition grafting method that this patent uses effectively reduces the difficulty on long side chain branch knot to main chain,
It is swift in response efficient and does not use organic solvent, it is nontoxic and pollution-free, it is easy to operate.The polycarboxylic-acid prepared with the method for the present invention
Water-reducing agent is a kind of functional polycarboxylic acid series high efficiency water reducing agent, since a primary amine groups can be therefore same with two epoxy reactions
Polycarboxylate water-reducer its side chain quantity that sample side chain positions are prepared using amido-epoxy addition grafting method is that traditional polycarboxylic acids subtracts
2 times of aqua, considerably increase steric hindrance, make the more excellent stabilization of properties of product, especially have preferably to containing silt particle building stones
Guarantor collapse effect.
Advantageous effect：
Compared with prior art, the present invention it has the following advantages：
1. the raw material sources that the method for the present invention is utilized enrich, each step has all industrialized, and method is ripe.
2. the method for the present invention amido-epoxy reaction, substantially reduces the reaction time, steric hindrance is increased, is improved anti-
Efficiency is answered, especially protects effect of collapsing with preferable to containing silt particle building stones.
3. polycarboxylate water-reducer prepared by the method for the present invention simplifies it to assign new function, makes properties of product more
Excellent stabilization.
4. collapse protective poly-carboxylic acid water reducing agent product adaptation prepared by the method for the present invention is wide, performance is stablized after aqueous solution, storage
It is not stratified when depositing, do not precipitate.
5. the method for the present invention is safe and reliable in the collapse protective poly-carboxylic acid water reducing agent product whole preparation process of preparation, operation
Step is simple and convenient, nontoxic and pollution-free without using organic solvent, it is environmentally safe the advantages that.
Specific embodiment
Technical solution of the present invention is described in further detail below by embodiment.
Embodiment 1
1) preparation of amine-containing copolymerization product：10mol 2- methallyl alcohols are with 25 DEG C of 10mol acrylamides in uncle 0.1mol
Butylhydroperoxide, 0.3mol rongalites, the effect of 0.01mol methallylsulfonic acids sodium is lower to carry out oxidationreduction radical polymerization
It closes reaction 30min and obtains the copolymerization product that molecular weight is 3000；
2) preparation of epoxy group poly glycol monomethyl ether：The poly glycol monomethyl ether that 10mol molecular weight is 5000 at 0 DEG C adds
Enter 10.1mol sodium hydrides, reaction 40min adds in 10.1mol epoxychloropropane, after being stirred to react 90min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 10mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 2
1) preparation of amine-containing copolymerization product：10mol propenyls are with 30 DEG C of 9mol allylamines in 0.2mol tert-butyl hydroperoxides
Hydrogen, 0.4mol sodium pyrosulfites, the lower progress oxidationreduction Raolical polymerizable 35min of 0.02mol thioacetic acid effect are obtained
Molecular weight is 3500 copolymerization product；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 400 poly glycol monomethyl ethers at 25 DEG C
10.2mol sodium hydrides, reaction 10min add in 11mol epoxychloropropane, after being stirred to react 90min desalination obtain the poly- second of epoxy group
Glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in calcium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
Embodiment 3：
1) preparation of amine-containing copolymerization product：10mol acrylates are with 35 DEG C of 8mol Methacrylamides in 0.3mol
Benzoyl peroxide, 0.6mol n,N-Dimethylaniline, the effect of 0.03mol 2 mercaptopropionic acids is lower to carry out oxidationreduction freedom
Base polymerisation 40min obtains the copolymerization product that molecular weight is 5000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 2000 poly glycol monomethyl ethers at 20 DEG C
Enter 10.5mol sodium hydrides, reaction 10min adds in 10.2mol epoxychloropropane, after being stirred to react 40min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 9mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.5.
Embodiment 4：
1) preparation of amine-containing copolymerization product：40 DEG C of 10mol hydroxy-ethyl acrylates and 7mol N- ethyl acrylamides exist
0.4mol ammonium persulfates, 0.8mol sodium hydrogensulfites, the effect of 0.04mol 3- mercaptopropionic acids is lower to carry out oxidationreduction radical polymerization
It closes reaction 45min and obtains the copolymerization product that molecular weight is 5000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 1000 poly glycol monomethyl ethers at 25 DEG C
Enter 10.1mol sodium hydrides, reaction 40min adds in 10.2mol epoxychloropropane, after being stirred to react 30min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 8mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 5：
1) preparation of amine-containing copolymerization product：45 DEG C of 10mol hydroxyethyl methacrylates and 6mol n-isopropyl acrylamide
In 0.5mol hydrogen peroxide, 1mol sodium ascorbates, the effect of 0.05mol methylpropenyls sodium sulfonate is lower to carry out oxidationreduction certainly
The copolymerization product that molecular weight is 4000 is obtained by base polymerisation 50min；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 2000 poly glycol monomethyl ethers at 25 DEG C
Enter 10.5mol sodium hydrides, reaction 40min adds in 10.5mol epoxychloropropane, after being stirred to react 50min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 8mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
Embodiment 6：
1) preparation of amine-containing copolymerization product：25 DEG C of 10mol hydroxy propyl methacrylates and 5mol N- propyl Methacrylamides
In 0.6mol hydrogen peroxide, 1.2mol rongalites, the effect of 0.1mol lauryl mercaptans is lower to carry out oxidationreduction Raolical polymerizable
55min obtains the copolymerization product that molecular weight is 4500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 800 poly glycol monomethyl ethers at 25 DEG C
10.4mol sodium hydrides, reaction 40min add in 10.3mol epoxychloropropane, are stirred to react desalination after 60min and obtain epoxy group and gather
Glycol monoethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 9mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 7：
1) preparation of amine-containing copolymerization product：10mol 4-Vinyl phenols are with 45 DEG C of 4mol acrylamides in 0.7mol over cures
Sour ammonium, 1.4mol ferrous sulfate, the lower progress oxidationreduction Raolical polymerizable 60min of 0.05mol thioacetic acid effect are obtained
Molecular weight is 3000 copolymerization product；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 5000 poly glycol monomethyl ethers at 15 DEG C
Enter 10.3mol sodium hydrides, reaction 10min adds in 10.1mol epoxychloropropane, after being stirred to react 30min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 10min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.5.
Embodiment 8：
1) preparation of amine-containing copolymerization product：25 DEG C of 10mol 2- methoxyl-4-vinyl phenols and 4mol allylamines exist
0.8mol hydrogen peroxide, 1.6mol ferrous sulfate, the effect of 0.03mol 2 mercaptopropionic acids is lower to carry out oxidationreduction free radical polymerization
Reaction 65min obtains the copolymerization product that molecular weight is 3500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 500 poly glycol monomethyl ethers at 0 DEG C
10.1mol sodium hydrides, reaction 40min add in 11mol epoxychloropropane, after being stirred to react 90min desalination obtain the poly- second of epoxy group
Glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 6mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in calcium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 9：
1) preparation of amine-containing copolymerization product：45 DEG C of 10mol hydroxyethyl methacrylates N-butyl and 3mol Methacrylamides exist
0.9mol benzoyl peroxides, 1.8molN, N- diethylanilines, the effect of 0.04mol 3- mercaptopropionic acids is lower to carry out oxidationreduction
Raolical polymerizable 70min obtains the copolymerization product that molecular weight is 4000；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight adds for 1200 poly glycol monomethyl ethers at 25 DEG C
Enter 10.4mol sodium hydrides, reaction 30min adds in 10.6mol epoxychloropropane, after being stirred to react 80min desalination obtain epoxy group
Poly glycol monomethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 5mol epoxy group polyethyleneglycol first
Ether reaction 20min adds in potassium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 6.
Embodiment 10：
1) preparation of amine-containing copolymerization product：9mol acrylic acid hydroxyls, 1mol propyl ester acrylic acid hydroxyl N-butyl and 1mol N- ethyls
In 1mol benzoyl peroxides, 2mol ferrous pyrophosphates under the effect of 0.1mol lauryl mercaptans aoxidize-go back 25 DEG C of acrylamide
Former Raolical polymerizable 90min obtains the copolymerization product that molecular weight is 4500；
2) preparation of epoxy group poly glycol monomethyl ether：10mol molecular weight is added in for 800 poly glycol monomethyl ethers at 5 DEG C
10.4mol sodium hydrides, reaction 40min add in 10.6mol epoxychloropropane, are stirred to react desalination after 90min and obtain epoxy group and gather
Glycol monoethyl ether；
3) preparation of collapse protection type water-reducing agent：10mol amino-containeds copolymerization product is added in into 10mol epoxy group polyethyleneglycol first
Ether reaction 50min adds in sodium hydroxide and adjustment pH value obtains a kind of collapse protective poly-carboxylic acid water reducing agent for 7.
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 10 gained sample of embodiment.W/C is 0.29, and the solid volume of additive folding is cement consumption
0.15%, 5h loss are hardly lost；
The paste flowing degree and gradual loss of the different samples of table 1
Testing concrete performance：With reference to GB8076-2008《Concrete admixture》10 gained sample of embodiment is arrived to embodiment 1
Product carry out slump-loss, concrete strength inspection.(relative to cement consumption) when the solid volume of additive folding is 1.8wt%, 3 days
Compression strength raising is all higher than 85%, and compression strength raising in 7 days is all higher than 70%, and compression strength raising in 28 days is all higher than 75%.
The concrete slump retaining performance and mechanical property of the different samples of table 2
Claims (8)
1. a kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent, is as follows：
1) preparation of amino-contained copolymerization product：Hydroxyl unsaturation minor comonomer and the unsaturated minor comonomer containing amine are being caused
Under agent, reducing agent and chain-transferring agent effect, oxidationreduction 30~90min of Raolical polymerizable is carried out in 25~45 DEG C of conditions,
Obtain amino-contained copolymerization product；Wherein described hydroxyl unsaturation minor comonomer, the unsaturated minor comonomer containing amine, initiator,
The molar ratio of reducing agent and chain-transferring agent is 1：(0.1~1)：(0.01~0.1)：(0.03~0.2)：(0.001~0.01)；Its
Described in hydroxyl unsaturation minor comonomer general formula R1OH expressions, wherein R1For 4~14 carbon atom ethylenic unsaturation alkyl or not
Saturation phenyl derivatives；The general formula of the unsaturated minor comonomer containing amine is with R2NHR3It represents, wherein R2For 3~8 carbon
The ethylenic unsaturation alkyl of atom, R3For H or the alkyl of 2-5 carbon atom；
2) preparation of epoxy group poly glycol monomethyl ether：At 0~25 DEG C, excessive hydrogenation is added in poly glycol monomethyl ether
Sodium adds in epoxychloropropane after reacting 10~40min, and after being stirred for 30~90min of reaction, desalination obtains epoxy group polyethylene glycol
Monomethyl ether；Wherein the molar ratio of poly glycol monomethyl ether, sodium hydride and epoxychloropropane is 1：(1.01~1.05)：(1.01~
1.1)；
3) preparation of slump-retaining polycarboxylic acid type water reducing agent：It will be in amino-contained copolymerization product made from step 1) plus made from step 2)
Epoxy group poly glycol monomethyl ether, after reacting 10~50min, it is 6~7 to add alkali neutralization adjustment pH value, obtains the poly- carboxylic of collapse protection type
Sour based water reducer；Wherein the molar ratio of amino-contained copolymerization product and epoxy group poly glycol monomethyl ether is 1：(0.5~1).
2. preparation method according to claim 1, it is characterised in that obtained amino-contained copolymerization product in step 1)
Molecular weight is 3000~5000.
3. preparation method according to claim 1, it is characterised in that the initiator in step 1) is persulfuric acid object or peroxide
Compound.
4. preparation method according to claim 1, it is characterised in that initiator in step 1) is tert-butyl hydroperoxide,
Hydrogen peroxide, ammonium persulfate, benzoyl peroxide, isopropyl benzene hydroperoxide, potassium peroxydisulfate or sodium peroxydisulfate one or two
Combination of the above.
5. preparation method according to claim 1, it is characterised in that the reducing agent in step 1) is rongalite, pyrosulfurous acid
Sodium, n,N-Dimethylaniline, sodium hydrogensulfite, ferrous sulfate, N, N- diethylanilines, ferrous pyrophosphate, four aziridines or
One or more kinds of combinations of sodium ascorbate；The chain-transferring agent is thioacetic acid, 2 mercaptopropionic acid, 3- sulfydryls third
One or more kinds of combinations of acid, methylpropenyl sodium sulfonate or lauryl mercaptan.
6. preparation method according to claim 1, it is characterised in that the hydroxyl unsaturation described in the step 1) is small
Monomer is 2- methallyl alcohols, propenyl, acrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, metering system
Sour hydroxypropyl acrylate, 4-Vinyl phenol, 2- methoxyl-4-vinyl phenols, hydroxyethyl methacrylate N-butyl, hydroxypropyl acrylate or
One or more kinds of combinations of acrylic acid hydroxyl N-butyl.
7. preparation method according to claim 1, it is characterised in that the insatiable hunger containing amine described in the step 1)
With minor comonomer for acrylamide, allylamine, Methacrylamide, N- ethyl acrylamides, n-isopropyl acrylamide or N- just
One or more kinds of combinations of propylacrylamide.
8. preparation method according to claim 1, it is characterised in that point of the poly glycol monomethyl ether described in step 2)
Son amount is 400~5000；The alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510296715.0A CN104944827B (en) | 2015-06-02 | 2015-06-02 | A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510296715.0A CN104944827B (en) | 2015-06-02 | 2015-06-02 | A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104944827A CN104944827A (en) | 2015-09-30 |
| CN104944827B true CN104944827B (en) | 2018-06-12 |
Family
ID=54159966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510296715.0A Active CN104944827B (en) | 2015-06-02 | 2015-06-02 | A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104944827B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377644B (en) * | 2018-12-31 | 2022-03-18 | 江苏苏博特新材料股份有限公司 | Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof |
| CN112552517B (en) * | 2020-11-23 | 2022-04-01 | 中建西部建设建材科学研究院有限公司 | Hyperbranched polymer viscosity reducer for high-strength concrete and preparation method thereof |
| CN113736034B (en) * | 2021-08-25 | 2022-09-09 | 武汉三源特种建材有限责任公司 | Nanometer type super-long slump retaining polycarboxylate superplasticizer and preparation method thereof |
| CN115784671B (en) * | 2022-12-21 | 2024-01-30 | 安徽海盾建材有限公司 | Method for preparing baking-free bricks from tailings in machine-made sand production process |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136950A (en) * | 1997-09-23 | 2000-10-24 | Mbt Holding Ag | Highly efficient cement dispersants |
| CN102807652A (en) * | 2011-06-02 | 2012-12-05 | 黎思幸 | High-concentration cement concrete dispersing agent suitable for being powdered and powder product production method |
| CN102358763B (en) * | 2011-07-21 | 2013-10-16 | 北京工业大学 | Method for preparing additive for inhibiting side effect of clay |
| CN102993432B (en) * | 2012-10-19 | 2015-05-20 | 江苏苏博特新材料股份有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN102964533B (en) * | 2012-12-11 | 2014-09-17 | 上海三瑞高分子材料有限公司 | Hyperbranched polycarboxylic acid copolymer and preparation method thereof |
| CN103450369B (en) * | 2013-09-18 | 2015-12-09 | 周口师范学院 | The preparation method of poly glycol monomethyl ether-chitosan derivatives |
| CN104327280B (en) * | 2014-10-10 | 2017-06-06 | 华南理工大学 | A kind of preparation method of alkali lignin modified polycarboxylic-acid coal water slurry dispersing agent |
-
2015
- 2015-06-02 CN CN201510296715.0A patent/CN104944827B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104944827A (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102976655B (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN104945633A (en) | Preparation method of novel polycarboxylic acid type water-reducer | |
| CN109021181A (en) | A kind of poly carboxylic acid series water reducer and preparation method thereof for having both viscosity reduction and protecting function of collapsing | |
| CN104944827B (en) | A kind of preparation method of slump-retaining polycarboxylic acid type water reducing agent | |
| CN108794700B (en) | Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent | |
| CN104031216B (en) | A kind of polyether-amide type high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof | |
| CN107586366B (en) | Modified polycarboxylate superplasticizer and preparation method thereof | |
| CN104945634A (en) | Preparation method of amine-ester slow-setting polycarboxylic acid type water-reducer | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN107265907B (en) | Amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent and preparation method thereof | |
| CN103897116A (en) | Mud-resistant polycarboxylic acid water reducer and preparation method thereof | |
| CN113736036B (en) | Multi-arm polycarboxylate superplasticizer and preparation method thereof | |
| CN104231183A (en) | Preparation method for polycarboxylate-type water reducer | |
| CN105175740B (en) | A kind of preparation method of high workability esters polycarboxylate water-reducer | |
| WO2022110356A1 (en) | High-early-strength cement dispersion polymer and preparation method therefor | |
| CN105036596A (en) | Low-temperature synthesis polycarboxylate superplasticizer and preparation method thereof | |
| CN104945632B (en) | A kind of preparation method of microspheric polycarboxylate water-reducer | |
| CN107163191B (en) | Anti-mud polycarboxylic acid high-efficiency water reducing agent and preparation method thereof | |
| CN106397682B (en) | The preparation method of collapse protective poly-carboxylic acid water reducing agent | |
| CN114656600A (en) | Preparation method of high-solid-content early-strength polycarboxylate superplasticizer | |
| CN112194762B (en) | Preparation method of non-crosslinked reticular polycarboxylic acid water reducing agent | |
| CN110845172A (en) | Preparation method of solid polycarboxylic acid slump retaining agent | |
| CN102030872A (en) | Comb copolymer shrinkage reducing agent and preparation method thereof | |
| CN104371075A (en) | Method for preparing polycarboxylate superplasticizer synthesized at room temperature | |
| CN117384327A (en) | Gypsum water reducer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22 Applicant after: JIANGSU ARIT NEW MATERIALS CO., LTD. Address before: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22 Applicant before: Jiangsu Arit New Materials Co., Ltd. |
|
| CB03 | Change of inventor or designer information |
Inventor after: Qian Shanshan Inventor after: Ding Bei Inventor after: Jiang Haidong Inventor after: Wang Yi Inventor after: Wang Gaoming Inventor after: Hu Yangcheng Inventor after: Zheng Chunyang Inventor after: Guo Zhaolai Inventor before: Qian Shanshan Inventor before: Shi Yu Inventor before: Ding Bei Inventor before: Wang Yi Inventor before: Jiang Haidong Inventor before: Zheng Chunyang |
|
| COR | Change of bibliographic data | ||
| CB02 | Change of applicant information |
Address after: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22 Applicant after: JIANGSU ARIT NEW MATERIALS CO., LTD. Address before: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22 Applicant before: JIANGSU ARIT NEW MATERIALS CO., LTD. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 210048 Huixin Road, Zhongshan science and Technology Park, Liuhe District, Nanjing, Jiangsu 22 Patentee after: Jiangsu Olite New Materials Co., Ltd. Address before: 210048 Huixin Road, Zhongshan science and Technology Park, Liuhe District, Nanjing, Jiangsu 22 Patentee before: JIANGSU ARIT NEW MATERIALS CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |