CN109574534A - A kind of cement concrete retardation water reducing agent and preparation method thereof - Google Patents
A kind of cement concrete retardation water reducing agent and preparation method thereof Download PDFInfo
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- CN109574534A CN109574534A CN201811508213.XA CN201811508213A CN109574534A CN 109574534 A CN109574534 A CN 109574534A CN 201811508213 A CN201811508213 A CN 201811508213A CN 109574534 A CN109574534 A CN 109574534A
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- reducing agent
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention belongs to technical field of concrete additives, disclose a kind of cement concrete retardation water reducing agent, be made of the raw material of following weight fraction: the polycarboxylate water-reducer 50-60% of phosphoric acid ester group, hydroxycarboxylate 3-5%, Di-phosphorus pentonide 3-8%, rhodanate 1-5%, surplus are water.The various component coordinateds of this present invention retardation water reducing agent, with good slow setting water-reducing effect, concrete coagulating time can extend 3-6h, 20% or more diminishing after mixing retardation water reducing agent of the present invention, and the workability of concrete can be improved, improve concrete seven d, 28d intensity.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to a kind of cement concrete retardation water reducing agent and its
Preparation method.
Background technique
Cement water reducing agent is one of most common concrete admixture, early in the early 1930s, the U.S. just Asia
Sulfate paper pulp waste liquid is added in concrete, to improve the workability, intensity and durability of concrete.China's polycarboxylic acids in recent years
High efficiency water reducing agent is even more to have obtained swift and violent development, and the research and application of high efficiency water reducing agent have pushed concrete to high strengthening, stream
State and high-performance direction are developed.In concrete construction in summar and mass concrete construction, need to be added retarder to prolong
The setting time of slow concrete makes concrete because putting thermogenetic temperature stress to be perfused, slow down hydration heat and then to reduce
Generate crack.Retardation water reducing agent used in hot weather construction at present and mass concrete construction is mostly by water-reducing agent and slow setting
Agent compounding reaches required technical effect, and the water-reducing agent and retarder property of different manufacturers be different, and when use needs repeatedly more
Secondary debugging, low efficiency.
Summary of the invention
The present invention has good slow in view of the above-mentioned problems, providing a kind of concrete retarding water-reducing agent while diminishing
Solidifying effect.In order to achieve the above objectives, the present invention uses following technical scheme.
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 50-60%, hydroxycarboxylate 3-5%, Di-phosphorus pentonide 3-8%, rhodanate 1-5%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.2-0.7mol phosphorus pentoxide is added after mixing, is warming up to 65-100 DEG C for a small amount of catalyst and a certain amount of water entrainer
After back flow reaction 2-4h, it is cooled to not higher than 50 DEG C, adds the methacrylic acid of 0.3-0.6mol, be warming up to 65-100 DEG C,
The reaction was continued 2-4h removes water entrainer, and the chain-transferring agent for accounting for reactant total weight 1-2% is added, is adjusted to sodium hydroxide solution
Then the first of the initiator solution and 0.3-0.6mol that account for reactant total weight 2-4% is added dropwise between 9.5-11 in pH value respectively
Base acrylic monomers solution after being added dropwise to complete, after continuing insulation reaction 0.5-1.5h, is down to room temperature to get the phosphate ester-containing
The polycarboxylate water-reducer of base.
Preferably, the catalyst is the mixture of one or both of phosphoric acid, nitrilotriacetic acid.
It is furthermore preferred that the catalyst is made of phosphoric acid and nitrilotriacetic acid by weight 0.5-2:1.
Preferably, the catalyst accounts for the 1-3% of polyethylene glycol and phosphorus pentoxide total weight.
Preferably, the water entrainer is hexamethylene or tetrahydrofuran.
Preferably, the chain-transferring agent is methylpropene sodium sulfonate or 2,4- diphenyl -4-methyl-1-pentene.
Preferably, initiator solution will be added dropwise prior to methacrylic acid solution 5min, and be added dropwise in methacrylic acid solution
After 5min be added dropwise.
Preferably, the initiator is sodium peroxydisulfate.
Preferably, last gained polycarboxylate water-reducer solid content is 20-40%.
Preferably, the hydroxycarboxylate is sodium glucoheptonate, Calcium Glucoheptonate, natrium malicum, one in sodium tartrate
Kind.
It is furthermore preferred that the hydroxycarboxylate is sodium glucoheptonate.
Preferably, the ratio of monoesters and dibasic acid esters is 1-3:1 in the Di-phosphorus pentonide.
It is furthermore preferred that the ratio of monoesters and dibasic acid esters is 2.5:1 in the Di-phosphorus pentonide.
Preferably, the rhodanate is guanidine thiocyanate.
A kind of preparation method of retardation setting type cement water reducing agent, it is characterised in that the following steps are included:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.2-0.7mol phosphorus pentoxide is added after mixing, is warming up to 65-100 DEG C of back flow reaction 2-
After 4h, it is cooled to not higher than 50 DEG C, adds the methacrylic acid of 0.3-0.6mol, be warming up to 65-100 DEG C, the reaction was continued 2-
4h removes water entrainer, and the chain-transferring agent for accounting for reactant total weight 1-2% is added, is adjusted to pH value in 9.5- with sodium hydroxide solution
Between 11, the methacrylic acid list of the initiator solution and 0.3-0.6mol that account for reactant total weight 2-4% is then added dropwise respectively
Liquid solution after being added dropwise to complete, after continuing insulation reaction 0.5-1.5h, is down to room temperature to get the polycarboxylic acids of the phosphoric acid ester group
Water-reducing agent.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Phosphate can be with the Ca in cement in the present invention2+Insoluble calcium phosphate is formed, cement particle surface is covered on, is prolonged
Slow hydrated cementitious；Hydroxyl in hydroxycarboxylate can be with Ca at the initial stage of cement slurry aquation2+The effects of generate unstable network
Object is closed, has inhibiting effect to cement initial stage aquation, with the progress of aquation, kinetically unstable complex is voluntarily decomposed, after having no effect on
Phase aquation.Unexpectedly, inventors have found that rhodanate it is strong can to improve cement, the 3d of concrete under conditions of not influencing slow setting
Degree, especially guanidine thiocyanate, effect are best.
Beneficial effects of the present invention
(1) the various component coordinateds of retardation water reducing agent of the present invention have good slow setting water-reducing effect, the incorporation present invention
Concrete coagulating time can extend 3-6h, 20% or more diminishing after retardation water reducing agent, and can improve the workability of concrete, mention
High concrete 7d, 28d intensity.
(2) concrete for mixing retardation water reducing agent of the present invention is slack-off since early water compound is grown, thus has obtained more evenly
Distribution and adequately growth, make hyrate overlapped more complete and closely knit, be not only advantageous to the increasing of maturing intensity
It is long, it is additionally favorable for the raising of concrete permeability resistance and freezing and thawing performance.
Specific embodiment
Son illustrates the present invention with reference to embodiments.
Embodiment 1
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 50%, hydroxycarboxylate 5%, Di-phosphorus pentonide 3%, rhodanate 5%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
1% phosphoric acid and a certain amount of hexamethylene of polyethylene glycol and phosphorus pentoxide total weight are accounted for, 0.7mol five is added after mixing
Two phosphorus are aoxidized, after being warming up to 65 DEG C of back flow reaction 4h, 50 DEG C is cooled to, adds the methacrylic acid of 0.3mol, be warming up to
100 DEG C, the reaction was continued 2h, hexamethylene is removed, the methylpropene sodium sulfonate for accounting for reactant total weight 2% is added, uses sodium hydroxide
Solution is adjusted to pH value 9.5, and the metering system of the sodium peroxydisulfate solution and 0.3mol that account for reactant total weight 4% is then added dropwise respectively
Acid monomers solution after being added dropwise to complete, after continuing insulation reaction 1.5h, is down to room temperature to get the polycarboxylic acids of the phosphoric acid ester group
Water-reducing agent.
The hydroxycarboxylate is sodium glucoheptonate.
The ratio of monoesters and dibasic acid esters is 1:1 in the Di-phosphorus pentonide.
The rhodanate is sodium sulfocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the polycarboxylate water-reducer preparation of phosphoric acid ester group: the poly- diethanol of 1mol is added in the reactor, accounts for polyethylene glycol
With 1% phosphoric acid and a certain amount of hexamethylene of phosphorus pentoxide total weight, 0.7mol phosphorus pentoxide is added after mixing,
After being warming up to 65 DEG C of back flow reaction 4h, 50 DEG C are cooled to, adds the methacrylic acid of 0.3mol, is warming up to 100 DEG C, is continued
2h is reacted, hexamethylene is removed, the methylpropene sodium sulfonate for accounting for reactant total weight 2% is added, is adjusted to pH with sodium hydroxide solution
Value 9.5, the methacrylic acid monomer that the sodium peroxydisulfate solution and 0.3mol that account for reactant total weight 4% are then added dropwise respectively are molten
Liquid after being added dropwise to complete, after continuing insulation reaction 1.5h, is down to room temperature to get the polycarboxylate water-reducer of the phosphoric acid ester group.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 2
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 60%, hydroxycarboxylate 3%, Di-phosphorus pentonide 8%, rhodanate 1%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
3% nitrilotriacetic acid and a certain amount of tetrahydrofuran for accounting for polyethylene glycol and phosphorus pentoxide total weight, are added after mixing
0.2mol phosphorus pentoxide is cooled to 45 DEG C after being warming up to 100 DEG C of back flow reaction 2h, adds the methacrylic acid of 0.6mol,
65 DEG C are warming up to, the reaction was continued 4h removes tetrahydrofuran, and 2, the 4- diphenyl -4- methyl-for accounting for reactant total weight 1% is added
1- amylene is adjusted to pH value 11 with 30% sodium hydroxide solution, and the persulfuric acid for accounting for reactant total weight 2% is then added dropwise respectively
Ammonium salt solution and 0.6mol methacrylic acid monomer solution (initiator solution will be added dropwise prior to methacrylic acid solution 5min, and
5min is added dropwise after methacrylic acid solution is added dropwise), after being added dropwise to complete, after continuing insulation reaction 0.5h, it is down to room
Temperature to get the phosphoric acid ester group polycarboxylate water-reducer.
The hydroxycarboxylate is Calcium Glucoheptonate.
The ratio of monoesters and dibasic acid esters is 3:1 in the Di-phosphorus pentonide.
The rhodanate is potassium rhodanide.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the polycarboxylate water-reducer preparation of phosphoric acid ester group: the poly- diethanol of 1mol is added in the reactor, accounts for polyethylene glycol
With 3% nitrilotriacetic acid and a certain amount of tetrahydrofuran of phosphorus pentoxide total weight, 0.2mol five is added after mixing and aoxidizes
Two phosphorus are cooled to 45 DEG C after being warming up to 100 DEG C of back flow reaction 2h, add the methacrylic acid of 0.6mol, are warming up to 65 DEG C,
The reaction was continued 4h removes tetrahydrofuran, and 2, the 4- diphenyl -4-methyl-1-pentene for accounting for reactant total weight 1% is added, and uses
30% sodium hydroxide solution is adjusted to pH value 11, then respectively be added dropwise account for reactant total weight 2% ammonium persulfate solution and
(initiator solution will be added dropwise the methacrylic acid monomer solution of 0.6mol prior to methacrylic acid solution 5min, and in methyl-prop
Olefin(e) acid solution is added dropwise rear 5min and is added dropwise), after being added dropwise to complete, after continuing insulation reaction 0.5h, room temperature is down to get institute
State the polycarboxylate water-reducer of phosphoric acid ester group.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 3
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 55%, hydroxycarboxylate 4%, Di-phosphorus pentonide 5%, rhodanate 3%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.5mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 3h, 40 DEG C are cooled to, adds the methacrylic acid of 0.5mol, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, adds
The chain-transferring agent for entering to account for reactant total weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant
The initiator solution of total weight 3% and the methacrylic acid monomer solution of 0.5mol after being added dropwise to complete, continue insulation reaction 1h
Afterwards, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst by phosphoric acid and nitrilotriacetic acid by weight
It is formed than 1:1, accounts for the 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent
For 2,4- diphenyl -4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Finally gained polycarboxylate water-reducer solid content is
20-40%.
The hydroxycarboxylate is sodium glucoheptonate.
The ratio of monoesters and dibasic acid esters is 2.5:1 in the Di-phosphorus pentonide.
The rhodanate is guanidine thiocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.5mol phosphorus pentoxide is added after mixing and is cooled to after being warming up to 85 DEG C of back flow reaction 3h
40 DEG C, the methacrylic acid of 0.5mol is added, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, and it is total that addition accounts for reactant
The chain-transferring agent of weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant total weight 3%
The methacrylic acid monomer solution of initiator solution and 0.5mol after being added dropwise to complete, after continuing insulation reaction 1h, is down to room temperature,
Up to the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst is made of phosphoric acid and nitrilotriacetic acid by weight 1:1, is accounted for
The 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent is 2,4- diphenyl-
4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Last gained polycarboxylate water-reducer solid content is 20-40%.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 4
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 56%, hydroxycarboxylate 4.5%, Di-phosphorus pentonide 4%, rhodanate 4%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.6mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 2.5h, 42 DEG C are cooled to, adds the methacrylic acid of 0.45mol, is warming up to 80 DEG C, the reaction was continued 3h removes water entrainer,
The chain-transferring agent for accounting for reactant total weight 1.8% is added, is adjusted to pH value 10.5 with the sodium hydroxide solution of 20% concentration, then
The methacrylic acid monomer solution of the initiator solution and 0.35mol that account for reactant total weight 3.5% is added dropwise respectively, is added dropwise to complete
Afterwards, after continuing insulation reaction 1.2h, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group.
The hydroxycarboxylate is natrium malicum.
The ratio of monoesters and dibasic acid esters is 2:1 in the Di-phosphorus pentonide.
The rhodanate is ammonium thiocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.6mol phosphorus pentoxide is added after mixing, after being warming up to 85 DEG C of back flow reaction 2.5h, cooling
To 42 DEG C, the methacrylic acid of 0.45mol is added, is warming up to 80 DEG C, the reaction was continued 3h removes water entrainer, and addition accounts for reaction
The chain-transferring agent of object total weight 1.8% is adjusted to pH value 10.5 with the sodium hydroxide solution of 20% concentration, is then added dropwise and is accounted for instead respectively
Answer the initiator solution of object total weight 3.5% and the methacrylic acid monomer solution of 0.35mol, after being added dropwise to complete, continue to keep the temperature
After reacting 1.2h, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 5
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 58%, hydroxycarboxylate 3.5%, Di-phosphorus pentonide 7%, rhodanate 2%, surplus are water.
(1) polycarboxylate water-reducer of phosphoric acid ester group is prepared.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 6
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 55%, hydroxycarboxylate 4%, Di-phosphorus pentonide 5%, rhodanate 3%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.5mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 3h, 40 DEG C are cooled to, adds the methacrylic acid of 0.5mol, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, adds
The chain-transferring agent for entering to account for reactant total weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant
The initiator solution of total weight 3% and the methacrylic acid monomer solution of 0.5mol after being added dropwise to complete, continue insulation reaction 1h
Afterwards, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst by phosphoric acid and nitrilotriacetic acid by weight
It is formed than 1:1, accounts for the 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent
For 2,4- diphenyl -4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Finally gained polycarboxylate water-reducer solid content is
20-40%.
The hydroxycarboxylate is natrium malicum.
The ratio of monoesters and dibasic acid esters is 2.5:1 in the Di-phosphorus pentonide.
The rhodanate is guanidine thiocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.5mol phosphorus pentoxide is added after mixing and is cooled to after being warming up to 85 DEG C of back flow reaction 3h
40 DEG C, the methacrylic acid of 0.5mol is added, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, and it is total that addition accounts for reactant
The chain-transferring agent of weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant total weight 3%
The methacrylic acid monomer solution of initiator solution and 0.5mol after being added dropwise to complete, after continuing insulation reaction 1h, is down to room temperature,
Up to the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst is made of phosphoric acid and nitrilotriacetic acid by weight 1:1, is accounted for
The 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent is 2,4- diphenyl-
4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Last gained polycarboxylate water-reducer solid content is 20-40%.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Embodiment 7
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 55%, hydroxycarboxylate 4%, Di-phosphorus pentonide 5%, rhodanate 3%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.5mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 3h, 40 DEG C are cooled to, adds the methacrylic acid of 0.5mol, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, adds
The chain-transferring agent for entering to account for reactant total weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant
The initiator solution of total weight 3% and the methacrylic acid monomer solution of 0.5mol after being added dropwise to complete, continue insulation reaction 1h
Afterwards, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst by phosphoric acid and nitrilotriacetic acid by weight
It is formed than 1:1, accounts for the 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent
For 2,4- diphenyl -4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Finally gained polycarboxylate water-reducer solid content is
20-40%.
The hydroxycarboxylate is sodium glucoheptonate.
The ratio of monoesters and dibasic acid esters is 2.5:1 in the Di-phosphorus pentonide.
The rhodanate is sodium sulfocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.5mol phosphorus pentoxide is added after mixing and is cooled to after being warming up to 85 DEG C of back flow reaction 3h
40 DEG C, the methacrylic acid of 0.5mol is added, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, and it is total that addition accounts for reactant
The chain-transferring agent of weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant total weight 3%
The methacrylic acid monomer solution of initiator solution and 0.5mol after being added dropwise to complete, after continuing insulation reaction 1h, is down to room temperature,
Up to the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst is made of phosphoric acid and nitrilotriacetic acid by weight 1:1, is accounted for
The 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent is 2,4- diphenyl-
4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Last gained polycarboxylate water-reducer solid content is 20-40%.
(2) hydroxycarboxylate, Di-phosphorus pentonide, sulphur are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Cyanate and water, stir evenly, and obtain mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Comparative example 1
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: polycarboxylate water-reducer 55%, hydroxyl carboxylic
Hydrochlorate 4%, Di-phosphorus pentonide 5%, rhodanate 3%, surplus are water.
The polycarboxylate water-reducer solid content is 40%, water-reducing rate >=20%.
The hydroxycarboxylate is sodium glucoheptonate.
The ratio of monoesters and dibasic acid esters is 2.5:1 in the Di-phosphorus pentonide.
The rhodanate is guanidine thiocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) it by polycarboxylate water-reducer, hydroxycarboxylate, Di-phosphorus pentonide, rhodanate and water, stirs evenly, obtains mixed
Close object.
(2) packaging is after the mixture of step (1) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Comparative example 2
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 55%, hydroxycarboxylate 4%, rhodanate 3%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.5mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 3h, 40 DEG C are cooled to, adds the methacrylic acid of 0.5mol, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, adds
The chain-transferring agent for entering to account for reactant total weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant
The initiator solution of total weight 3% and the methacrylic acid monomer solution of 0.5mol after being added dropwise to complete, continue insulation reaction 1h
Afterwards, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst by phosphoric acid and nitrilotriacetic acid by weight
It is formed than 1:1, accounts for the 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent
For 2,4- diphenyl -4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Finally gained polycarboxylate water-reducer solid content is
20-40%.
The hydroxycarboxylate is sodium glucoheptonate.
The rhodanate is guanidine thiocyanate.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.5mol phosphorus pentoxide is added after mixing and is cooled to after being warming up to 85 DEG C of back flow reaction 3h
40 DEG C, the methacrylic acid of 0.5mol is added, is warming up to 85 DEG C, the reaction was continued 3h removes water entrainer, and it is total that addition accounts for reactant
The chain-transferring agent of weight 1.2% is adjusted to pH value 10 with sodium hydroxide solution, is then added dropwise respectively and accounts for reactant total weight 3%
The methacrylic acid monomer solution of initiator solution and 0.5mol after being added dropwise to complete, after continuing insulation reaction 1h, is down to room temperature,
Up to the polycarboxylate water-reducer of the phosphoric acid ester group；The catalyst is made of phosphoric acid and nitrilotriacetic acid by weight 1:1, is accounted for
The 2% of polyethylene glycol and phosphorus pentoxide total weight；The water entrainer is hexamethylene；The chain-transferring agent is 2,4- diphenyl-
4-methyl-1-pentene；The initiator is sodium peroxydisulfate；Last gained polycarboxylate water-reducer solid content is 20-40%.
(2) it is separately added into hydroxycarboxylate, rhodanate and water in the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group, stirred
It mixes uniformly, obtains mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Comparative example 3
A kind of concrete retarding water-reducing agent, by the material composition of following parts by weight: the polycarboxylic acids diminishing of phosphoric acid ester group
Agent 56%, hydroxycarboxylate 4.5%, Di-phosphorus pentonide 4%, surplus are water.
The polycarboxylate water-reducer of the phosphoric acid ester group the preparation method is as follows: be added in the reactor the poly- diethanol of 1mol,
0.6mol phosphorus pentoxide is added after mixing, is warming up to 85 DEG C of back flow reactions for a small amount of catalyst and a certain amount of water entrainer
After 2.5h, 42 DEG C are cooled to, adds the methacrylic acid of 0.45mol, is warming up to 80 DEG C, the reaction was continued 3h removes water entrainer,
The chain-transferring agent for accounting for reactant total weight 1.8% is added, is adjusted to pH value 10.5 with the sodium hydroxide solution of 20% concentration, then
The methacrylic acid monomer solution of the initiator solution and 0.35mol that account for reactant total weight 3.5% is added dropwise respectively, is added dropwise to complete
Afterwards, after continuing insulation reaction 1.2h, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group.
The hydroxycarboxylate is natrium malicum.
The ratio of monoesters and dibasic acid esters is 2:1 in the Di-phosphorus pentonide.
The preparation method of above-mentioned concrete retarding water-reducing agent:
(1) the poly- diethanol of 1mol, a small amount of catalyst the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
With a certain amount of water entrainer, 0.6mol phosphorus pentoxide is added after mixing, after being warming up to 85 DEG C of back flow reaction 2.5h, cooling
To 42 DEG C, the methacrylic acid of 0.45mol is added, is warming up to 80 DEG C, the reaction was continued 3h removes water entrainer, and addition accounts for reaction
The chain-transferring agent of object total weight 1.8% is adjusted to pH value 10.5 with the sodium hydroxide solution of 20% concentration, is then added dropwise and is accounted for instead respectively
Answer the initiator solution of object total weight 3.5% and the methacrylic acid monomer solution of 0.35mol, after being added dropwise to complete, continue to keep the temperature
After reacting 1.2h, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group.
(2) be separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group hydroxycarboxylate, Di-phosphorus pentonide and
Water stirs evenly, and obtains mixture.
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
Performance test
Reference standard GB8076-2008 " concrete admixture " is to admixture 1-7's of the embodiment of the present invention and comparative example 1-3
Some main performances of concrete are tested, and retardation water reducing agent volume is 0.5%, as a result see the table below 1.
1 the performance test results of table
Claims (8)
1. a kind of concrete retarding water-reducing agent, which is characterized in that by the material composition of following parts by weight: phosphoric acid ester group gathers
Carboxylic acid water reducer 50-60%, hydroxycarboxylate 3-5%, Di-phosphorus pentonide 3-8%, rhodanate 1-5%, surplus are water.
2. concrete retarding water-reducing agent according to claim 1, which is characterized in that the polycarboxylic acids of the phosphoric acid ester group subtracts
For aqua the preparation method is as follows: the poly- diethanol of 1mol, a small amount of catalyst and a certain amount of water entrainer are added in the reactor, mixing is equal
0.2-0.7mol phosphorus pentoxide is added after even to be cooled to after being warming up to 65-100 DEG C of back flow reaction 2-4h not higher than 50 DEG C, then
The methacrylic acid of 0.3-0.6mol is added, is warming up to 65-100 DEG C, the reaction was continued 2-4h removes water entrainer, and addition accounts for reaction
The chain-transferring agent of object total weight 1-2% is adjusted to pH value between 9.5-11 with sodium hydroxide solution, is then added dropwise respectively and accounts for reaction
The initiator solution of object total weight 2-4% and the methacrylic acid monomer solution of 0.3-0.6mol, after being added dropwise to complete, continue to keep the temperature
After reacting 0.5-1.5h, room temperature is down to get the polycarboxylate water-reducer of the phosphoric acid ester group.
3. concrete retarding water-reducing agent according to claim 2, which is characterized in that the catalyst is phosphoric acid, three second of ammonia
The mixture of one or both of acid.
4. concrete retarding water-reducing agent according to claim 2, which is characterized in that the chain-transferring agent is metering system sulphur
Sour sodium or 2,4- diphenyl -4-methyl-1-pentene.
5. concrete retarding water-reducing agent according to claim 1, which is characterized in that the hydroxycarboxylate is glucoheptonic acid
One of sodium, Calcium Glucoheptonate, natrium malicum, sodium tartrate.
6. concrete retarding water-reducing agent according to claim 1, which is characterized in that in the Di-phosphorus pentonide monoesters with
The ratio of dibasic acid esters is 1-3:1.
7. concrete retarding water-reducing agent according to claim 1, which is characterized in that the rhodanate is guanidine thiocyanate.
8. the preparation method of retardation setting type cement water reducing agent as claimed in claim 1 to 7, it is characterised in that including following step
It is rapid:
(1) the poly- diethanol of 1mol, a small amount of catalyst and one the polycarboxylate water-reducer preparation of phosphoric acid ester group: are added in the reactor
0.2-0.7mol phosphorus pentoxide is added in quantitative water entrainer after mixing, after being warming up to 65-100 DEG C of back flow reaction 2-4h,
It is cooled to not higher than 50 DEG C, adds the methacrylic acid of 0.3-0.6mol, be warming up to 65-100 DEG C, the reaction was continued 2-4h is removed
Remove water entrainer, the chain-transferring agent for accounting for reactant total weight 1-2% be added, with sodium hydroxide solution be adjusted to pH value 9.5-11 it
Between, the methacrylic acid monomer that the initiator solution and 0.3-0.6mol that account for reactant total weight 2-4% are then added dropwise respectively is molten
Liquid after being added dropwise to complete, after continuing insulation reaction 0.5-1.5h, is down to room temperature to get the polycarboxylic acids diminishing of the phosphoric acid ester group
Agent；
(2) hydroxycarboxylate, Di-phosphorus pentonide, thiocyanic acid are separately added into the polycarboxylate water-reducer of above-mentioned phosphoric acid ester group
Salt and water, stir evenly, and obtain mixture；
(3) packaging is after the mixture of step (2) being crossed 200 mesh filter screens to get the retardation setting type cement water reducing agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563233A (en) * | 2021-08-13 | 2021-10-29 | 石家庄市长安育才建材有限公司 | Anti-carbonization concrete reinforcing agent and preparation method thereof |
| CN114853381A (en) * | 2022-05-24 | 2022-08-05 | 广西龙洋建设工程有限责任公司 | Preparation method of retarder for water reducer |
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| CN104231182A (en) * | 2014-09-22 | 2014-12-24 | 科之杰新材料集团有限公司 | Ester slump retaining type polycarboxylate water reducer and preparation method thereof |
| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
| EP3255026A1 (en) * | 2016-06-10 | 2017-12-13 | Shin-Etsu Chemical Co., Ltd. | Method for preparing hydraulic composition |
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2018
- 2018-12-11 CN CN201811508213.XA patent/CN109574534A/en not_active Withdrawn
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| CN104231182A (en) * | 2014-09-22 | 2014-12-24 | 科之杰新材料集团有限公司 | Ester slump retaining type polycarboxylate water reducer and preparation method thereof |
| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
| EP3255026A1 (en) * | 2016-06-10 | 2017-12-13 | Shin-Etsu Chemical Co., Ltd. | Method for preparing hydraulic composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563233A (en) * | 2021-08-13 | 2021-10-29 | 石家庄市长安育才建材有限公司 | Anti-carbonization concrete reinforcing agent and preparation method thereof |
| CN114853381A (en) * | 2022-05-24 | 2022-08-05 | 广西龙洋建设工程有限责任公司 | Preparation method of retarder for water reducer |
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