CN110256638A - A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed - Google Patents
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed Download PDFInfo
- Publication number
- CN110256638A CN110256638A CN201910540541.6A CN201910540541A CN110256638A CN 110256638 A CN110256638 A CN 110256638A CN 201910540541 A CN201910540541 A CN 201910540541A CN 110256638 A CN110256638 A CN 110256638A
- Authority
- CN
- China
- Prior art keywords
- unsaturated
- monomer
- preparation
- acid
- reducer
- 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.)
- Pending
Links
Classifications
-
- 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to building material technical field, especially a kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed.Preparation method of the invention, comprising the following steps: (1) unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated halogen monomer, chain-transferring agent, initiator are uniformly mixed, 70-90 DEG C reaction 2-3 hours；(2) unsaturated phosphate ester monomer is added into reaction system, is reacted 4-6 hours at 80-110 DEG C；It obtains containing the polycarboxylate water-reducer that anti-mud structure is complexed；The unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated phosphate ester monomer, unsaturated halogen monomer, chain-transferring agent, initiator weight ratio be 28-36:1.3-4:2.5-6:1.5-4:0.2-0.5:0.1-0.6.Preparation method of the invention provide it is a kind of with good water-reducing rate, slump retaining, anti-mud polycarboxylate water-reducer.
Description
Technical field
The present invention relates to building material technical field, especially a kind of system containing the polycarboxylate water-reducer that anti-mud structure is complexed
Preparation Method.
Background technique
Poly carboxylic acid series water reducer (PCE) because have water-reducing rate is high, slump retaining is good, volume is low, molecular structure adjustability by force with
And environmentally protective equal excellent performances, it is applied in concrete works more and more widely.But with naphthalene system, sulfamate system etc.
Water-reducing agent is compared, and water-reducing rate, the slump retaining of polycarboxylate water-reducer are more sensitive for sandstone clay content.It is fast with building trade
Speed development and national environmental protection policy requirements, good sand and stone resources gradually use up totally, and the sand and stone resources of various regions tend to deteriorate, and contain
Mud amount is higher, and the volume for improving poly carboxylic acid series water reducer not can effectively solve concrete water-reducing ratio, slump retaining decline etc.
Problem.In addition, the excessive volume of polycarboxylic acids will lead to increased costs, it is serious also to will cause concrete initial isolation, setting time
The problems such as too long.
The main reason for problem above is due to negatively charged clay particle and poly carboxylic acid series water reducer molecule and band
The cement granules of positive charge interact, and reduce cement granules to the adsorption capacity of poly carboxylic acid series water reducer, reduce poly- carboxylic
Effective adsorbance of the sour based water reducer in cement particle surface.Therefore, it is necessary to from poly carboxylic acid series water reducer molecular structure and absorption
Mechanism is set out, and exploitation can effectively solve the polycarboxylate water-reducer of concrete water-reducing ratio, slump retaining decline.
Chinese patent literature CN104261719A discloses a kind of polycarboxylate water-reducer, the knot of polycarboxylate water-reducer molecule
Structure general formula consists of three parts: unsaturated carboxylic acid monomer, unsaturated phosphate ester monomer and polyether macromonomer, disclosed unsaturated
There is no carboxyl on two carbon atoms of phosphate ester monomer, therefore content of the carboxyl in water-reducing agent is lower, the guarantor in cement is collapsed
Ability cannot reach optimum efficiency.
Chinese patent literature CN 106008593A discloses a kind of for producing high collapse protection type poly carboxylic acid series water reducer not
It is saturated the preparation method of phosphate: phosphorylation being carried out by unsaturated acid ester and phosphorus pentoxide and prepares unsaturated phosphate ester, finally
Copolyreaction is carried out by unsaturated polyether polymeric monomer, unsaturated acids, unsaturated phosphate ester, the polycarboxylic acids for obtaining phosphoric acid ester group subtracts
Aqua.However it is undesirable due to target product unsaturated phosphate ester structure, unsaturated phosphate monoester output capacity is low, and with double
The generation of ester and three esters；The phosphate group in unsaturated phosphate ester monomer has certain chain transfer simultaneously, directly participates in
Water-reducing agent copolyreaction influences the structure of water-reducing agent, causes molecular weight that can not accurately control.
Chinese patent literature CN 106008853A discloses a kind of anti-mud collapse protection type phosphate ester-containing based polycarboxylic acid water-reducing agent
Preparation method, the invention is by the unsaturated monomer containing halogen, unsaturated acids minor comonomer, unsaturated polyether polymeric monomer or insatiable hunger
With esters polymeric monomer under the action of initiator, reducing agent and chain-transferring agent, the polycarboxylate water-reducer pre-polymerization containing halogen is made
Body, performed polymer react at 80-150 DEG C with alkyl phosphate again, obtain the polycarboxylate water-reducer of phosphoric acid ester group, but it is used
Alkyl phosphoric acid dibasic acid esters and three esters may result in copolyreaction and crosslinking implode occur and influence the structure of water-reducing agent, it is used
Alkyl phosphate monoester is not as purity is high and leads to above situation, and the redox initiation system that the invention uses may
It can react with the unsaturated halogen monomer with oxidisability, influence the structure of copolyreaction and generate a large amount of by-product.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of containing the polycarboxylic acids diminishing that anti-mud structure is complexed
The preparation method of agent.The present invention on unsaturated carbon by introducing bound phosphate groups, using polyoxometallate as catalyst, synthesis
The unsaturated phosphate monoester of high-purity.Controllable polycarboxylic acids molecular structure is obtained by reaction, to provide a kind of with good
Water-reducing rate, slump retaining, anti-mud polycarboxylate water-reducer.
The invention adopts the following technical scheme:
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated halogen monomer, chain-transferring agent, initiator are mixed
Close uniformly, 70-90 DEG C reaction 2-3 hours；
(2) unsaturated phosphate ester monomer is added into reaction system, is reacted 4-6 hours at 80-110 DEG C；Contained
The polycarboxylate water-reducer of anti-mud structure is complexed；
The unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated phosphate ester monomer, unsaturated halogen monomer,
Chain-transferring agent, initiator weight ratio be 28-36:1.3-4:2.5-6:1.5-4:0.2-0.5:0.1-0.6.
In the present invention, phosplate group can be with Ca in cement2+Complex compound is formed, delays hydrated cementitious, and can be with
Carboxyl forms competitive Adsorption, reduces the absorption to carboxyl such as clay, is a kind of anti-mud structure of complexing.In step (2), utilize
Arbuzov reaction introduces phosplate group, avoids phosphate minor comonomer and directly participates in copolyreaction bring chain tra nsfer work
With to avoid the occurrence of the structure of water-reducing agent and the problem of molecular weight is unable to control.
Preferably, step (2) is after reaction 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust
The solid content of polycarboxylate water-reducer is 40-60%.
It is further preferred that the lye is by one of sodium hydroxide, potassium hydroxide and calcium hydroxide or a variety of matches
The solution set.
Preferably, the molecular weight of the unsaturated polyether polymeric monomer be 4000-5000, selected from allyl polyethenoxy ether,
One of methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether and vinyl polyoxyethylene ether are a variety of.
It is further preferred that the unsaturated polyether polymeric monomer be molecular weight 4000 methyl allyl polyoxyethylene ether and
One or both of isoamyl alcohol polyoxyethylene ether.
Preferably, the unsaturated acrylic monomer is in acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid
It is one or more.
Preferably, the unsaturated phosphate ester monomer is prepared by the following method: by phosphoric acid agent and unsaturated esters list
Body reacts 1-1.5 hours at 70-90 DEG C, and polyoxometallate is then added, and the reaction was continued 0.5-3 hours, and deionized water is added
At 90-120 DEG C, the reaction was continued 1-3 hours, obtains unsaturated phosphate ester monomer.
Preferably, the weight ratio of the phosphoric acid agent, unsaturated esters monomer, polyoxometallate and deionized water is 2-
7:6-13:0.15-1.5:10-25.
Preferably, the phosphoric acid agent is one in phosphorus oxychloride, phosphorus trichloride, phosphoric acid, pyrophosphoric acid and phosphorus pentoxide
Kind is a variety of；
The unsaturation esters monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and methyl
One of hydroxypropyl acrylate is a variety of；
The polyoxometallate is one or both of phosphotungstic acid and molybdenum silicic acid.
In the present invention, the catalyst reacted as phosphoric acid agent with unsaturated esters monomer esterification using more metal acid-salts,
The unsaturated phosphate ester monomer for preparing high-purity, reduces the generation of dibasic acid esters and three esters, avoids subsequent copolyreaction and occurs
Crosslinking, caused by product structure it is undesirable.
Preferably, the unsaturated halogen monomer is 4- bromobutene, 3- bromobutene, the bromo- 2- butylene of 1-, the bromo- 3- methyl-of 1-
The bromo- 1- amylene of 2- butylene, 5-, the bromo- 2- methyl pentene of 5-, 3- propargyl chloride, the chloro- 3- methyl-1-butine of 3-, 3- iodopropylene and 4-
One of iodine butylene is a variety of.
Preferably, the chain-transferring agent is sodium tripolyphosphate, calgon, mercaptoethanol, thioacetic acid, mercaptopropionic acid
With one of lauryl mercaptan or a variety of.
Preferably, the initiator is azo diisobutyl amidine hydrochloride, two isobutyl imidazoline hydrochloride of azo, azo two
One of cyanopentanoic acid and azo dicyclohexyl formonitrile HCN are a variety of.
The copolymerization rate of unsaturated halogen monomer can be improved in the initiator that the present invention uses, and both by the change of temperature
Molecular weight can be accurately controlled, is avoided due to using redox initiation system by the unsaturated halogen monomer shadow with oxidisability
Ring, and lead to problems such as each monomer be easy autohemagglutination, molecular weight it is uncontrollable, copolymerization efficiency decline appearance.
Contain bound phosphate groups, adsorption energy in the molecular structure of polycarboxylate water-reducer prepared by above-mentioned preparation method
Power is better than carboxylic acid group, the earth surfaces that can be preferentially adsorbed in aggregate, and solvable with the cation generation in cement and soil
Property complex compound, so that Na+Ion enters the adsorption layer of particle, and hydration shell thickens, and Zeta potential becomes larger, and reduces soil to carboxylic acid group
The absorption of group, to reduce polycarboxylate water-reducer to the sensibility of aggregate clay content；On the other hand, phosphate group passes through chemistry
Key is grafted on polycarboxylic acids skeleton, for the phosphate of free state, not only has stronger electrostatic repulsion, while also shape
At very large space steric hindrance, improve the dispersibility of cement granules while extending hydration time, thus make concrete through when collapse damage
It reduces, improves workability.
Beneficial effects of the present invention
(1) preparation method of the invention is reacted as phosphoric acid agent with unsaturated esters monomer esterification using more metal acid-salts
Catalyst, the unsaturated phosphate ester product structure of preparation is single, and yield is high；It is single that introducing structure is reacted by Arbuzov
The water-reducing agent molecular structure of phosplate group, preparation is ideal, can be precisely controlled its molecular weight, while avoiding generating a large amount of pairs
Product；Preparation method simple and efficient of the invention, it is low in cost；
(2) proportion and preparation method of each component of the invention have great influence for synthesis water-reducing agent performance；Institute
The polycarboxylate water-reducer of preparation has good anti-mud under the premise of diminishing guarantor is collapsed again, is able to solve engineered building materials and contains
Mud problem, and its slump-loss can also be reduced under low-dosage.
Specific embodiment
Below by specific embodiment, the present invention will be described in detail.
Embodiment 1
The preparation of unsaturated phosphate ester monomer: by the hydroxy-ethyl acrylate of the phosphorus pentoxide of 6 parts by weight and 7.7 parts by weight
Reacted 1.5 hours at 90 DEG C, the phosphotungstic acids of 1.2 parts by weight is then added, and the reaction was continued 2 hours, be added 20 parts by weight go from
The reaction was continued 1 hour at 120 DEG C for sub- water, obtains unsaturated phosphate ester monomer；
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) by the isoamyl alcohol polyoxyethylene ether of 31.6 parts by weight, the acrylic acid of 1.8 parts by weight, 1.5 parts by weight 4- bromine
Butylene, the mercaptopropionic acid of 0.25 parts by weight, the azo diisobutyl amidine hydrochloride of 0.2 parts by weight are uniformly mixed, react 2 at 70 DEG C
Hour；
(2) the unsaturated phosphate ester monomer of 4.1 parts by weight is added into reaction system, reacted at 90 DEG C 5 hours to get
To containing the polycarboxylate water-reducer that anti-mud structure is complexed；It is 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust poly-
The solid content of carboxylic acid water reducer is 40-60%.
Embodiment 2
The preparation of unsaturated phosphate ester monomer: by the hydroxyethyl methacrylate of the phosphorus oxychloride of 7.1 parts by weight and 8.4 parts by weight
Ethyl ester reaction time 1.5 hours at 90 DEG C, the molybdenum silicic acids of 0.8 parts by weight is then added, and the reaction was continued 2 hours, and 20 weight are added
The reaction was continued 1 hour at 120 DEG C for the deionized water of part, obtains unsaturated phosphate ester monomer；
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) by the methyl allyl polyoxyethylene ether of 31 parts by weight, the methacrylic acid of 2.3 parts by weight, 1.5 parts by weight
3- bromobutene, the thioacetic acid of 0.3 parts by weight, the two isobutyl imidazoline hydrochloride of azo of 0.3 parts by weight are uniformly mixed, at 70 DEG C
Reaction 2.5 hours；
(2) the unsaturated phosphate ester monomer of 4.9 parts by weight is added into reaction system, reacted at 90 DEG C 4 hours to get
To containing the polycarboxylate water-reducer that anti-mud structure is complexed；It is 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust poly-
The solid content of carboxylic acid water reducer is 40-60%.
Embodiment 3
The preparation of unsaturated phosphate ester monomer: the phosphorus trichloride of 5.6 parts by weight and the hydroxypropyl acrylate of 9.2 parts by weight exist
It is reacted 1.5 hours at 90 DEG C, the reaction was continued 1 hour for phosphotungstic acid, the 0.2 parts by weight molybdenum silicic acid that 0.7 parts by weight are then added, and is added
The reaction was continued 2 hours at 95 DEG C for the deionized water of 10 parts by weight, obtains unsaturated phosphate ester monomer；
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) by the allyl polyethenoxy ether of 34 parts by weight, the fumaric acid of 3.5 parts by weight, 2 parts by weight the bromo- 1- penta of 5-
Alkene, the thioacetic acid of 0.4 parts by weight, the azo dicyano valeric acid of 0.4 parts by weight are uniformly mixed, react 2.5 hours at 70 DEG C；
(2) the unsaturated phosphate ester monomer of 3.8 parts by weight is added into reaction system, reacted at 90 DEG C 5 hours to get
To containing the polycarboxylate water-reducer that anti-mud structure is complexed；It is 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust poly-
The solid content of carboxylic acid water reducer is 40-60%.
Embodiment 4
The preparation of unsaturated phosphate ester monomer: the hydroxy propyl methacrylate of the phosphoric acid of 4.5 parts by weight and 10.2 parts by weight
It is reacted 1 hour at 90 DEG C, that the reaction was continued is 3 small for the phosphotungstic acid and the molybdenum silicic acids of 0.6 parts by weight for then adding 0.5 parts by weight
When, the reaction was continued 2 hours at 95 DEG C for the deionized water of 18 parts by weight of addition, obtains unsaturated phosphate ester monomer；
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) by the vinyl polyoxyethylene ether of 35 parts by weight, the maleic acid of 1.2 parts by weight, 3 parts by weight 3- propargyl chloride,
The lauryl mercaptan of 0.22 parts by weight, the azo dicyclohexyl formonitrile HCN of 0.2 parts by weight are uniformly mixed, react 2.5 hours at 70 DEG C；
(2) the unsaturated phosphate ester monomer of 2.8 parts by weight is added into reaction system, reacted at 90 DEG C 5 hours to get
To containing the polycarboxylate water-reducer that anti-mud structure is complexed；It is 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust poly-
The solid content of carboxylic acid water reducer is 40-60%.
Embodiment 5
The preparation of unsaturated phosphate ester monomer: the pyrophosphoric acid of 5.3 parts by weight and the hydroxypropyl acrylate of 5 parts by weight, 7 weight
The hydroxy-ethyl acrylate of part reacts 1 hour at 80 DEG C, then adds the phosphotungstic acid of 0.8 parts by weight and the molybdenum of 0.1 parts by weight
The reaction was continued 0.5 hour for silicic acid, and the reaction was continued 2 hours at 90 DEG C for the deionized water of 25 parts by weight of addition, obtains unsaturated phosphoric acid
Ester monomer；
A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, comprising the following steps:
(1) by the vinyl polyoxyethylene ether of 12 parts by weight, the methyl allyl polyoxyethylene ether of 22 parts by weight, 2.2 weights
Measure the itaconic acid of part, the 3- bromobutene of 4 parts by weight, the thioacetic acid of 0.1 parts by weight, the mercaptopropionic acid of 0.1 parts by weight, 0.5 weight
The azo diisobutyl amidine hydrochloride for measuring part is uniformly mixed, and is reacted 3 hours at 70 DEG C；
(2) the unsaturated phosphate ester monomer of 2.8 parts by weight is added into reaction system, reacted at 90 DEG C 6 hours to get
To containing the polycarboxylate water-reducer that anti-mud structure is complexed；It is 6-7 using the pH value that lye adjusts polycarboxylate water-reducer；Water is added to adjust poly-
The solid content of carboxylic acid water reducer is 40-60%.
Experimental example
Paste flowing degree test: using the resulting polycarboxylate water-reducer of embodiment 1-5 as additive, it is added in swelled ground
To be labeled as sample 1-5.Referring to GB8077-2000 " Methods for testing uniformity of concrete admixture ", net slurry flowing is carried out to it
Degree test.It is the 0.12% of bentonite consumption that additive, which rolls over solid volume, bentonite 5g used, and blank sample is additional to be added without
Agent.Test result is as shown in table 1.
The paste flowing degree of 1 sample 1-5 of table
As shown in Table 1, compared with blank sample, the paste flowing degree for being added to the sample 1-5 of additive has significant change,
Illustrate that polycarboxylate water-reducer confrontation mud of the invention has positive effect, and almost unchanged in paste flowing degree 2h, shows anti-mud
It is functional, slump retaining is excellent.
Testing concrete performance:, the resulting polycarboxylate water-reducer of embodiment 1-5 is added in swelled ground as additive
To be labeled as sample 1-5.Slump-loss, concrete strength inspection are carried out referring to GB8076-2008 " concrete admixture ".Outside
Adding agent to roll over solid volume is the 1.8% of bentonite consumption, and bentonite 5g used, blank sample is to be added without additive.Test result
As shown in table 2.
The performance test of 2 sample 1-5 of table
As shown in Table 2, compared with blank sample, the sample 1-5 slump keeps more preferable, and damage of not collapsing substantially for one hour, two is small
When the slump and divergence do not lose substantially, show that the concrete for adding polycarboxylate water-reducer of the invention has good apply
Work performance；The compression strength of concrete is significantly improved, and enhances with the time, this shows that anti-mud is complexed in of the invention containing
While the polycarboxylate water-reducer of structure has anti-mud, be also significantly improved to concrete strength effect.
Claims (10)
1. a kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed, which comprises the following steps:
(1) unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated halogen monomer, chain-transferring agent, initiator are mixed equal
It is even, 70-90 DEG C reaction 2-3 hours；
(2) unsaturated phosphate ester monomer is added into reaction system, is reacted 4-6 hours at 80-110 DEG C；It obtains containing complexing
The polycarboxylate water-reducer of anti-mud structure；
The unsaturated polyether polymeric monomer, unsaturated acrylic monomer, unsaturated phosphate ester monomer, unsaturated halogen monomer, chain turn
Move agent, the weight ratio of initiator is 28-36:1.3-4:2.5-6:1.5-4:0.2-0.5:0.1-0.6.
2. preparation method according to claim 1, which is characterized in that the molecular weight of the unsaturated polyether polymeric monomer is
4000-5000 is selected from allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether and ethylene
One of base polyoxyethylene ether is a variety of.
3. preparation method according to claim 1, which is characterized in that the unsaturation acrylic monomer is acrylic acid, methyl
One of acrylic acid, fumaric acid, maleic acid and itaconic acid are a variety of.
4. preparation method according to claim 1, which is characterized in that the unsaturated phosphate ester monomer is by the following method
Preparation: phosphoric acid agent is reacted 1-1.5 hours with unsaturated esters monomer at 70-90 DEG C, polyoxometallate is then added
The reaction was continued 0.5-3 hours, and deionized water is added, and at 90-120 DEG C, the reaction was continued 1-3 hours, obtains unsaturated phosphate ester monomer.
5. the preparation method according to claim 4, which is characterized in that the phosphoric acid agent, unsaturated esters monomer, mostly gold
The weight ratio for belonging to oxygen hydrochlorate and deionized water is 2-7:6-13:0.15-1.5:10-25.
6. the preparation method according to claim 4, which is characterized in that the phosphoric acid agent be phosphorus oxychloride, phosphorus trichloride,
One of phosphoric acid, pyrophosphoric acid and phosphorus pentoxide are a variety of；
The unsaturation esters monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and metering system
One of sour hydroxypropyl acrylate is a variety of；
The polyoxometallate is one or both of phosphotungstic acid and molybdenum silicic acid.
7. preparation method according to claim 1, which is characterized in that the unsaturation halogen monomer is 4- bromobutene, 3-
The bromo- 2- butylene of bromobutene, 1-, the bromo- 3- methyl-2-butene of 1-, the bromo- 1- amylene of 5-, the bromo- 2- methyl pentene of 5-, 3- propargyl chloride,
One of the chloro- 3- methyl-1-butine of 3-, 3- iodopropylene and 4- iodine butylene are a variety of.
8. preparation method according to claim 1, which is characterized in that the chain-transferring agent is sodium tripolyphosphate, six inclined phosphorus
One of sour sodium, mercaptoethanol, thioacetic acid, mercaptopropionic acid and lauryl mercaptan are a variety of.
9. preparation method according to claim 1, which is characterized in that the initiator is azo diisobutyl amidine hydrochloric acid
One of salt, two isobutyl imidazoline hydrochloride of azo, azo dicyano valeric acid and azo dicyclohexyl formonitrile HCN are a variety of.
10. containing the polycarboxylate water-reducer that anti-mud structure is complexed prepared by preparation method of any of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910540541.6A CN110256638A (en) | 2019-06-21 | 2019-06-21 | A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910540541.6A CN110256638A (en) | 2019-06-21 | 2019-06-21 | A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110256638A true CN110256638A (en) | 2019-09-20 |
Family
ID=67920095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910540541.6A Pending CN110256638A (en) | 2019-06-21 | 2019-06-21 | A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110256638A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912786A (en) * | 2021-10-21 | 2022-01-11 | 杭州构建新型材料有限公司 | Vinyl glycol ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN114075316A (en) * | 2020-08-21 | 2022-02-22 | 博特新材料泰州有限公司 | Superplasticizer for ultrahigh-performance concrete and preparation method thereof |
| CN114195949A (en) * | 2021-11-26 | 2022-03-18 | 厦门路桥翔通建材科技有限公司 | Early-strength water reducing agent containing phosphate ester monomer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190468A (en) * | 2014-08-04 | 2014-12-10 | 南京师范大学 | Catalyst for synthesizing high-monoester-content methacrylate hydroxyethyl phosphate, preparation method of catalyst and catalytic synthesis process thereof |
| CN105713150A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Method for preparing sulfate-resistant polycarboxylate water-reducing agents and application thereof |
| CN106008853A (en) * | 2016-06-27 | 2016-10-12 | 江苏中铁奥莱特新材料股份有限公司 | Preparation method of mud resisting and slump retaining type phosphate group containing polycarboxylate superplasticizer |
| CN106008593A (en) * | 2016-05-26 | 2016-10-12 | 广东复特新型材料科技有限公司 | Unsaturated phosphate ester for producing high-slump-retaining type polycarboxylic acid water reducing agent |
| CN106519138A (en) * | 2016-10-31 | 2017-03-22 | 科之杰新材料集团有限公司 | Preparation method for ester polycarboxylic acid slump retaining agent |
-
2019
- 2019-06-21 CN CN201910540541.6A patent/CN110256638A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190468A (en) * | 2014-08-04 | 2014-12-10 | 南京师范大学 | Catalyst for synthesizing high-monoester-content methacrylate hydroxyethyl phosphate, preparation method of catalyst and catalytic synthesis process thereof |
| CN105713150A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Method for preparing sulfate-resistant polycarboxylate water-reducing agents and application thereof |
| CN106008593A (en) * | 2016-05-26 | 2016-10-12 | 广东复特新型材料科技有限公司 | Unsaturated phosphate ester for producing high-slump-retaining type polycarboxylic acid water reducing agent |
| CN106008853A (en) * | 2016-06-27 | 2016-10-12 | 江苏中铁奥莱特新材料股份有限公司 | Preparation method of mud resisting and slump retaining type phosphate group containing polycarboxylate superplasticizer |
| CN106519138A (en) * | 2016-10-31 | 2017-03-22 | 科之杰新材料集团有限公司 | Preparation method for ester polycarboxylic acid slump retaining agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075316A (en) * | 2020-08-21 | 2022-02-22 | 博特新材料泰州有限公司 | Superplasticizer for ultrahigh-performance concrete and preparation method thereof |
| CN114075316B (en) * | 2020-08-21 | 2024-05-03 | 博特新材料泰州有限公司 | Super plasticizer for ultra-high performance concrete and preparation method thereof |
| CN113912786A (en) * | 2021-10-21 | 2022-01-11 | 杭州构建新型材料有限公司 | Vinyl glycol ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN113912786B (en) * | 2021-10-21 | 2023-12-22 | 杭州构建新型材料有限公司 | Vinyl glycol ether polycarboxylate superplasticizer and preparation method thereof |
| CN114195949A (en) * | 2021-11-26 | 2022-03-18 | 厦门路桥翔通建材科技有限公司 | Early-strength water reducing agent containing phosphate ester monomer and preparation method thereof |
| CN114195949B (en) * | 2021-11-26 | 2023-07-21 | 厦门路桥翔通建材科技有限公司 | Early-strength water reducer containing phosphate monomer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008853B (en) | A kind of preparation method of anti-mud collapse protection type phosphate ester-containing based polycarboxylic acid water-reducing agent | |
| CN105110687B (en) | A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN107337765B (en) | Phosphonic acid-based polymer with strong adaptability and slump retaining performance as well as preparation method and application thereof | |
| CN107325234B (en) | Anti-mud phosphate modified polycarboxylate superplasticizer and preparation method thereof | |
| CN104788629B (en) | A kind of polycarboxylate water-reducer and its normal temperature preparation method | |
| CN112694574B (en) | Polycarboxylate superplasticizer with high mud resistance and high slump loss resistance and preparation method thereof | |
| CN106832147B (en) | A kind of preparation method of the polycarboxylate water-reducer containing phosphonyl group | |
| CN104177562B (en) | Slow-release high-adaptability polyester polycarboxylic acid water-reducing agent and preparation method and application thereof | |
| CN105713151A (en) | Application and preparation method of concrete superplasticizer with phosphorous acid group | |
| CN110256638A (en) | A kind of preparation method containing the polycarboxylate water-reducer that anti-mud structure is complexed | |
| CN106220791A (en) | The polycarboxylate water-reducer of a kind of phosphorous acidic group and preparation method | |
| CN105293970A (en) | Anti-montmorillonoid high-efficiency amphiprotic polycarboxylate superplasticizer and preparation method thereof | |
| CN106366257A (en) | Low-sensitivity anti-mud crossed branched chain type polycarboxylate superplasticizer and preparation method thereof | |
| CN109400825A (en) | A kind of low responsive type polycarboxylate water-reducer and preparation method thereof with anti-mud effect | |
| CN114349914B (en) | Ferrocene modified anti-mud polycarboxylate water reducer and preparation method thereof | |
| CN108975746B (en) | Synthesis method of polycarboxylate superplasticizer containing siloxy | |
| CN105294949B (en) | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof | |
| CN110643003B (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| CN107603110B (en) | Branched chain type mud-inhibiting polycarboxylate superplasticizer, and preparation method and application thereof | |
| CN109956696B (en) | Synthesis method of side chain adsorption type concrete superplasticizer | |
| CN111378117B (en) | Low-molecular-weight phosphate water reducing agent and preparation method and application thereof | |
| CN111087552A (en) | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance | |
| CN114685730B (en) | Preparation method and application of phosphate group-containing water reducer | |
| CN110204240B (en) | Organic amphoteric high-molecular activity excitant, preparation method thereof and application thereof in high-admixture cement-based material | |
| CN116040975A (en) | Mud-resistant polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190920 |