CN104356314A - Normal-temperature synthetizing method for slow release type polycarboxylate water-reducer and product produced by same - Google Patents
Normal-temperature synthetizing method for slow release type polycarboxylate water-reducer and product produced by same Download PDFInfo
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- CN104356314A CN104356314A CN201410561461.6A CN201410561461A CN104356314A CN 104356314 A CN104356314 A CN 104356314A CN 201410561461 A CN201410561461 A CN 201410561461A CN 104356314 A CN104356314 A CN 104356314A
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Abstract
The invention provides a normal-temperature synthetizing method for a slow release type polycarboxylate water-reducer and a product produced by the same. The method comprises the following steps: bottom materials of unsaturated polyoxyethylene ether, fumaric acid and water are put in a reaction kettle to be stirred until the bottom materials are dissolved, after the bottom materials are completely dissolved, an oxidizer solution is put, materials A and materials B, which are compounded in advance, are dripped at the same time, the dripping time of the materials A is 2-3 hours, the dripping time of the materials B is 2.5-3.5 hours, after the materials B are dripped, the reaction is continued for 1-2 hours, and liquid alkali is used for neutralizing until the pH is 6-7; the materials A comprise a comonomer, a slow release monomer and water; the materials B comprise a chain transfer agent, a reducing agent and water. The product disclosed by the invention has the advantages of strong adaptability, stable performance, high long-term storage quality and definite water reducing rate, can be singly used, and can be compounded with an ordinary polycarboxylate water-reducer for use. The method selects normal-temperature synthesis, the synthesis operation is simple and easy, energy resources are saved, the water is used as a solvent for performing the synthesis, and an organic solvent is not used, so that the method is environmental-friendly.
Description
[technical field]
The present invention relates to the synthesis preparation field of the reinforcement of concrete poly carboxylic acid series water reducer, particularly a kind of normal temperature synthesis method and products thereof of sustained-release polycarboxylic water reducer.
[background technology]
The admixture applied in concrete mainly contains naphthalene water reducer, aliphatic water reducing agent, sulfamate water reducer, melamine class water reducer and polycarboxylate dehydragent.According to present case, polycarboxylate dehydragent has the advantages such as volume is low, water-reducing rate is high, and slump retaining is good, and the application in concrete is more and more wider, is the important directions of following water reducer research.
When running into the materials such as cement complicated and changeable, sand, stone, the phenomenon that polycarboxylic acids dehydragent loses its high-performance benefits can often occur, as there is the problems such as concrete slump loss is fast, concrete workability is poor.Especially, in ready mixed concrete industry, concrete often there will be the too fast phenomenon of slump-loss through long-time transport, affects engineering construction and quality.Concrete can be made to recover good workability by increasing polycarboxylate water-reducer volume, but the performance index such as the weather resistance of maturing can be reduced undoubtedly.By the method that the slow setting components such as composite glucose, sucrose are also conventional control concrete slumps, but cause concrete coagulating time long sometimes, the requirement of engineering construction cannot be met.
The production technique of current polycarboxylate water-reducer is all generally carry out Raolical polymerizable synthesis at 50-85 DEG C, and temperature of reaction is high, needs to heat up and cooling, and the time is long.
The deficiency that polyethers polycarboxylate water-reducer is very large is, responsive to volume, improves volume a little and just easily occurs the workability problems such as segregation bleeding.
[summary of the invention]
One of the technical problem to be solved in the present invention, is the normal temperature synthesis method providing a kind of sustained-release polycarboxylic water reducer, and present method is normal temperature synthesis, synthetic operation is easy, save energy, and is that solvent synthesizes with water, not with an organic solvent, cost-saving further, environmental protection.
The present invention realizes one of above-mentioned technical problem like this:
A normal temperature synthesis method for sustained-release polycarboxylic water reducer, described method steps is as follows:
Unsaturated for bed material Soxylat A 25-7, fumaric acid and water are dropped in reactor, be stirred to dissolving, bed material has dissolved rear input oxidizing agent solution, drip pre-configured A material and B expects afterwards simultaneously, A expects time for adding 2 ~ 3h, B expects time for adding 2.5 ~ 3.5h, and B gob adds rear continuation reaction 1 ~ 2h, and being neutralized to pH with liquid caustic soda is 6-7;
Described A material comprises comonomer, slowly-releasing monomer and water; Described B material comprises chain-transfer agent, reductive agent and water;
Described unsaturated Soxylat A 25-7, its outward appearance is white extremely yellow sheet, degree of unsaturation >=0.30, double bond retention rate >=85%, and hydroxyl value is 24.5 ± 2.5mgKOH/g, and pH value is 5 ~ 8, and its structural formula is shown in general formula (1):
Wherein, R in described general formula (1)
1, R
2and R
3independently represent hydrogen atom or methyl separately, X represents that carbonatoms is the divalent alkyl of 1 ~ 5, R
4represent that carbonatoms is the alkyl of 0 ~ 4, m, n are the average addition mole number of oxidation of alkyl respectively, m=20 ~ 140, n=0 ~ 60;
Described comonomer, its general structure is shown in general formula (2):
Wherein, R in described general formula (2)
5, R
7represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, R
6represent hydrogen atom or
m
1represent hydrogen atom, monovalent metal, ammonium or organic amine;
The general structure of described slowly-releasing monomer is shown in general formula (3):
Wherein, R in described general formula (3)
8, R
9, R
10represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, M
2represent alkyl or the hydroxyalkyl of 1 ~ 3 carbon atom.
Further, the described unsaturated Soxylat A 25-7 of general formula (1) is methyl allyl alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether.
Further, general formula (2) described comonomer is at least one in vinylformic acid, methacrylic acid, maleic acid or fumaric acid.
Further, the described slowly-releasing monomer of general formula (3) is at least one in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
Further, described each raw material dosage is closed and is:
Described unsaturated Soxylat A 25-7: mol ratio=1:2 ~ 6 of (comonomer+slowly-releasing monomer);
Mol ratio=1:0.5 ~ 2 of described comonomer and slowly-releasing monomer;
Described oxygenant accounts for 0.5 ~ 5% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer;
Described reductive agent and oxygenant mol ratio=1:2 ~ 5;
Described chain-transfer agent accounts for 0.3 ~ 3% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer.
Further, described oxidizing agent solution is aqueous oxidizing agent solution, and described oxygenant is the one in hydrogen peroxide, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, potassium permanganate.
Further, described chain-transfer agent is the one in sulfydryl propylene, Thiovanic acid, methacrylic sulfonic acids sodium.
Further, described reductive agent is at least one in sodium bisulfite, ferrous sulfate, Sulfothiorine, vitamins C, rongalite.
Further, described liquid caustic soda is 30wt% sodium hydroxide solution.
The technical problem to be solved in the present invention two, is to provide a kind of sustained-release polycarboxylic water reducer, its strong adaptability, stable performance, and long storage periods quality is good, and has certain water-reducing rate, can be used alone, also can use with common polycarboxylic acids water reducing agent compositional.
The present invention realizes above-mentioned technical problem two like this:
A kind of sustained-release polycarboxylic water reducer, the synthesis material of described sustained-release polycarboxylic water reducer is as follows: unsaturated Soxylat A 25-7, fumaric acid, oxidizing agent solution, alkali lye, comonomer, slowly-releasing monomer, chain-transfer agent, reductive agent and water; It is 6-7 that described sustained-release polycarboxylic water reducer alkali lye is neutralized to pH;
Described unsaturated Soxylat A 25-7, its outward appearance is white extremely yellow sheet, degree of unsaturation >=0.30, double bond retention rate >=85%, and hydroxyl value is 24.5 ± 2.5mgKOH/g, and pH value is 5 ~ 8, and its structural formula is shown in general formula (1):
Wherein, R in described general formula (1)
1, R
2and R
3independently represent hydrogen atom or methyl separately, X represents that carbonatoms is the divalent alkyl of 1 ~ 5, R
4represent that carbonatoms is the alkyl of 0 ~ 4, m, n are the average addition mole number of oxidation of alkyl respectively, m=20 ~ 140, n=0 ~ 60;
Described comonomer, its general structure is shown in general formula (2):
Wherein, R in described general formula (2)
5, R
7represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, R
6represent hydrogen atom or
m
1represent hydrogen atom, monovalent metal, ammonium or organic amine;
The general structure of described slowly-releasing monomer is shown in general formula (3):
Wherein, R in described general formula (3)
8, R
9, R
10represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, M
2represent alkyl or the hydroxyalkyl of 1 ~ 3 carbon atom.
Further, the described unsaturated Soxylat A 25-7 of general formula (1) is methyl allyl alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether;
General formula (2) described comonomer is at least one in vinylformic acid, methacrylic acid, maleic acid or fumaric acid;
The described slowly-releasing monomer of general formula (3) is at least one in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
Further, described each raw material dosage is closed and is:
Described unsaturated Soxylat A 25-7: mol ratio=1:2 ~ 6 of (comonomer+slowly-releasing monomer);
Mol ratio=1:0.5 ~ 2 of described comonomer and slowly-releasing monomer;
Described oxygenant accounts for 0.5 ~ 5% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer; Described reductive agent and oxygenant mol ratio=1:2 ~ 5;
Described chain-transfer agent accounts for 0.3 ~ 3% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer.
Further, described oxidizing agent solution is aqueous oxidizing agent solution, described oxygenant be hydrogen peroxide,
One in tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, potassium permanganate;
Described chain-transfer agent is the one in sulfydryl propylene, Thiovanic acid, methacrylic sulfonic acids sodium;
Described reductive agent is at least one in sodium bisulfite, ferrous sulfate, Sulfothiorine, vitamins C, rongalite.
Further, described liquid caustic soda is 30wt% sodium hydroxide solution.
Tool of the present invention has the following advantages:
The present invention has unique advantage compared with product in the past, this sustained-release polycarboxylic water reducer can in specified time the activated water reducer molecule of slow releasing tool, continue to play the dissemination to cement granules, keep concrete slump.Sustained-release polycarboxylic water reducer strong adaptability of the present invention, stable performance, long storage periods quality is good, and it has certain water-reducing rate, can be used alone, and also can use with common polycarboxylic acids water reducing agent compositional.When being used alone, improving volume and there will not be segregation excreting water phenomenon, there is obvious negative growth in 1h concrete slump.When composite use, the common polycarboxylate water-reducer of sustained-release polycarboxylic water reducer equivalent replace, substitution amount is more, and concrete slump loss also diminishes.Product of the present invention adopts normal temperature synthesis, and synthetic operation is easy, save energy, and is that solvent synthesizes with water, not with an organic solvent, cost-saving further, environmental protection.
[embodiment]
The present invention relates to a kind of sustained-release polycarboxylic water reducer and normal temperature synthesis method thereof, the synthesis material of described sustained-release polycarboxylic water reducer is as follows: unsaturated Soxylat A 25-7, fumaric acid, oxidizing agent solution, alkali lye, comonomer, slowly-releasing monomer, chain-transfer agent, reductive agent and water; It is 6-7 that described sustained-release polycarboxylic water reducer alkali lye is neutralized to pH;
Described method steps is as follows:
Unsaturated for bed material Soxylat A 25-7, fumaric acid and water are dropped in reactor, be stirred to dissolving, bed material has dissolved rear input oxidizing agent solution, drip pre-configured A material and B expects afterwards simultaneously, A expects time for adding 2 ~ 3h, B expects time for adding 2.5 ~ 3.5h, and B gob adds rear continuation reaction 1 ~ 2h, and being neutralized to pH with liquid caustic soda is 6-7;
Described A material comprises comonomer, slowly-releasing monomer and water; Described B material comprises chain-transfer agent, reductive agent and water;
Described unsaturated Soxylat A 25-7, its outward appearance is white extremely yellow sheet, degree of unsaturation >=0.30, double bond retention rate >=85%, and hydroxyl value is 24.5 ± 2.5mgKOH/g, and pH value is 5 ~ 8, and its structural formula is shown in general formula (1):
Wherein, R in described general formula (1)
1, R
2and R
3independently represent hydrogen atom or methyl separately, X represents that carbonatoms is the divalent alkyl of 1 ~ 5, R
4represent that carbonatoms is the alkyl of 0 ~ 4, m, n are the average addition mole number of oxidation of alkyl respectively, m=20 ~ 140, n=0 ~ 60;
Described comonomer, its general structure is shown in general formula (2):
Wherein, R in described general formula (2)
5, R
7represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, R
6represent hydrogen atom or
m
1represent hydrogen atom, monovalent metal, ammonium or organic amine;
The general structure of described slowly-releasing monomer is shown in general formula (3):
Wherein, R in described general formula (3)
8, R
9, R
10represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, M
2represent alkyl or the hydroxyalkyl of 1 ~ 3 carbon atom.
Preferably, the described unsaturated Soxylat A 25-7 of general formula (1) is methyl allyl alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether.
Preferably, general formula (2) described comonomer is at least one in vinylformic acid, methacrylic acid, maleic acid or fumaric acid.
Preferably, the described slowly-releasing monomer of general formula (3) is at least one in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
Described each raw material dosage is closed and is:
Described unsaturated Soxylat A 25-7: mol ratio=1:2 ~ 6 of (comonomer+slowly-releasing monomer);
Mol ratio=1:0.5 ~ 2 of described comonomer and slowly-releasing monomer;
Described oxygenant accounts for 0.5 ~ 5% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer;
Described reductive agent and oxygenant mol ratio=1:2 ~ 5;
Described chain-transfer agent accounts for 0.3 ~ 3% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer.
Preferably, described oxidizing agent solution is aqueous oxidizing agent solution, and described oxygenant is the one in hydrogen peroxide, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, potassium permanganate.
Preferably, described chain-transfer agent is the one in sulfydryl propylene, Thiovanic acid, methacrylic sulfonic acids sodium.
Preferably, described reductive agent is at least one in sodium bisulfite, ferrous sulfate, Sulfothiorine, vitamins C, rongalite.
Described liquid caustic soda is 30wt% sodium hydroxide solution.
Below in conjunction with specific embodiment, the inventive method is described in detail, but therefore do not limited the present invention among described scope of embodiments.
Embodiment 1
240g isopentenol polyoxyethylene ether and 5.8g fumaric acid are dropped in reactor, adds 278g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 15g tap water of 1.5g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 21.6g vinylformic acid, 11.6g Hydroxyethyl acrylate and 50g tap water composition.B expects the solution be made up of 0.68g vitamins C, 1.18g thiohydracrylic acid and 80g water.A expects that 2.5h drips, and B expects that 3h drips.A material, after B gob adds, continue reaction 1.5h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Embodiment 2
240g isopentenol polyoxyethylene ether and 5.8g fumaric acid are dropped in reactor, adds 290g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 15g tap water of 1.5g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 14.4g vinylformic acid, 23.2g Hydroxyethyl acrylate and 45g tap water composition.B expects the solution be made up of 0.68g vitamins C, 1.18g thiohydracrylic acid and 80g water.A expects that 3h drips, and B expects that 3.5h drips.A material, after B gob adds, continue reaction 1.5h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Embodiment 3
240g isopentenol polyoxyethylene ether and 5.8g fumaric acid are dropped in reactor, adds 290g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 16g tap water of 1.8g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 10.8g vinylformic acid, 17.4g Hydroxyethyl acrylate, 13g Propylene glycol monoacrylate and 50g tap water composition.B expects the solution be made up of 0.86g vitamins C, 1.42g thiohydracrylic acid and 80g water.A expects that 3h drips, and B expects that 3.5h drips.A material, after B gob adds, continue reaction 1.5h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Embodiment 4
80g methyl allyl alcohol polyoxyethylene ether, 160g isopentenol polyoxyethylene ether are dropped in reactor, adds 300g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 16g tap water of 1.8g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 21.6g vinylformic acid, 17.4g Hydroxyethyl acrylate, 19.5g Propylene glycol monoacrylate and 46g tap water composition.B expects the solution be made up of 0.94g vitamins C, 1.55g thiohydracrylic acid and 92g water.A expects that 3h drips, and B expects that 3.5h drips.A material, after B gob adds, continue reaction 2h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Embodiment 5
240g isopentenol polyoxyethylene ether is dropped in reactor, adds 277g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 15g tap water of 1.35g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 18g vinylformic acid, 23.2g Hydroxyethyl acrylate and 52g tap water composition.B expects the solution be made up of 0.61g vitamins C, 1.06g Thiovanic acid and 82g water.A expects that 2.5h drips, and B expects that 3h drips.A material, after B gob adds, continue reaction 1.5h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Embodiment 6
240g isopentenol polyoxyethylene ether is dropped in reactor, adds 285g tap water, be stirred to bed material and dissolve completely.Bed material dissolves and drops into the solution be made up of hydrogen peroxide and the 15g tap water of 1.5g35% afterwards.After stirring, first drip the B material that configured in advance is good, B gob drips the good A material of configured in advance again after adding 2 minutes.A material is the solution of 18g vinylformic acid, 17.4g Hydroxyethyl acrylate, 13g hydroxyethyl methylacrylate and 52g tap water composition.B expects the solution be made up of 0.68g vitamins C, 1.18g Thiovanic acid and 85g water.A expects that 2.5h drips, and B expects that 3h drips.A material, after B gob adds, continue reaction 1.5h, then adding liquid caustic soda, to be neutralized to pH be 6 ~ 7, obtains product.
Respectively following test is carried out to the sustained-release polycarboxylic water reducer of above 6 embodiments synthesis:
Contrast product 1 is the common polyether polycarboxylate water-reducer that Fujian Construction Building Materials Science and Technology Development Co., Ltd. produces.
Contrast product 2 is domestic similar-type products.
Test 1: cement paste is tested
This experiment cement is refining stone P.O42.5.According to flowing degree of net paste of cement test (GB/T8077-2012).
Table 1 cement paste experimental result
As can be seen from Table 1, polycarboxylate water-reducer of the present invention has excellent flowing degree of net paste of cement hold facility, and product performance are slightly better than domestic similar-type products.
Test 2: the concrete test of product of the present invention and contrast product contrasts
This experiment cement is refining stone P.O42.5, and grain fineness number modulus is 2.6, ballast grain sizes 5 ~ 25mm.Proportioning is C:S:G:W=360:777:1073:185 (GB8076-2008).
Table 2 concrete performance experimental result
As can be seen from Table 2, polycarboxylate water-reducer of the present invention has longer slump retention ability, and initial slump/divergence is not substantially lost compared with 1h, 2h, and concrete strength is high, and product performance are better than domestic similar-type products.
In summary, the present invention has unique advantage compared with product in the past, this sustained-release polycarboxylic water reducer can in specified time the activated water reducer molecule of slow releasing tool, continue to play the dissemination to cement granules, keep concrete slump.Sustained-release polycarboxylic water reducer strong adaptability of the present invention, stable performance, long storage periods quality is good, and it has certain water-reducing rate, can be used alone, and also can use with common polycarboxylic acids water reducing agent compositional.When being used alone, improving volume and there will not be segregation excreting water phenomenon, there is obvious negative growth in 1h concrete slump.When composite use, the common polycarboxylate water-reducer of sustained-release polycarboxylic water reducer equivalent replace, substitution amount is more, and concrete slump loss also diminishes.Product of the present invention adopts normal temperature synthesis, and synthetic operation is easy, save energy, and is that solvent synthesizes with water, not with an organic solvent, cost-saving further, environmental protection.
Although the foregoing describe the specific embodiment of the present invention; but be familiar with those skilled in the art to be to be understood that; specific embodiment described by us is illustrative; instead of for the restriction to scope of the present invention; those of ordinary skill in the art, in the modification of the equivalence done according to spirit of the present invention and change, should be encompassed in scope that claim of the present invention protects.
Claims (14)
1. a normal temperature synthesis method for sustained-release polycarboxylic water reducer, is characterized in that: described method steps is as follows:
Unsaturated for bed material Soxylat A 25-7, fumaric acid and water are dropped in reactor, be stirred to dissolving, bed material has dissolved rear input oxidizing agent solution, drip pre-configured A material and B expects afterwards simultaneously, A expects time for adding 2 ~ 3h, B expects time for adding 2.5 ~ 3.5h, and B gob adds rear continuation reaction 1 ~ 2h, and being neutralized to pH with liquid caustic soda is 6-7;
Described A material comprises comonomer, slowly-releasing monomer and water; Described B material comprises chain-transfer agent, reductive agent and water;
Described unsaturated Soxylat A 25-7, its outward appearance is white extremely yellow sheet, degree of unsaturation >=0.30, double bond retention rate >=85%, and hydroxyl value is 24.5 ± 2.5mgKOH/g, and pH value is 5 ~ 8, and its structural formula is shown in general formula (1):
Wherein, R in described general formula (1)
1, R
2and R
3independently represent hydrogen atom or methyl separately, X represents that carbonatoms is the divalent alkyl of 1 ~ 5, R
4represent that carbonatoms is the alkyl of 0 ~ 4, m, n are the average addition mole number of oxidation of alkyl respectively, m=20 ~ 140, n=0 ~ 60;
Described comonomer, its general structure is shown in general formula (2):
Wherein, R in described general formula (2)
5, R
7represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, R
6represent hydrogen atom or
m
1represent hydrogen atom, monovalent metal, ammonium or organic amine;
The general structure of described slowly-releasing monomer is shown in general formula (3):
Wherein, R in described general formula (3)
8, R
9, R
10represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, M
2represent alkyl or the hydroxyalkyl of 1 ~ 3 carbon atom.
2. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: the described unsaturated Soxylat A 25-7 of general formula (1) is methyl allyl alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether.
3. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: general formula (2) described comonomer is at least one in vinylformic acid, methacrylic acid, maleic acid or fumaric acid.
4. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: the described slowly-releasing monomer of general formula (3) is at least one in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
5. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: described each raw material dosage is closed and is:
Described unsaturated Soxylat A 25-7: mol ratio=1:2 ~ 6 of (comonomer+slowly-releasing monomer);
Mol ratio=1:0.5 ~ 2 of described comonomer and slowly-releasing monomer;
Described oxygenant accounts for 0.5 ~ 5% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer;
Described reductive agent and oxygenant mol ratio=1:2 ~ 5;
Described chain-transfer agent accounts for 0.3 ~ 3% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer.
6. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, it is characterized in that: described oxidizing agent solution is aqueous oxidizing agent solution, described oxygenant is the one in hydrogen peroxide, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, potassium permanganate.
7. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: described chain-transfer agent is the one in sulfydryl propylene, Thiovanic acid, methacrylic sulfonic acids sodium.
8. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: described reductive agent is at least one in sodium bisulfite, ferrous sulfate, Sulfothiorine, vitamins C, rongalite.
9. the normal temperature synthesis method of a kind of sustained-release polycarboxylic water reducer as claimed in claim 1, is characterized in that: described liquid caustic soda is 30wt% sodium hydroxide solution.
10. a sustained-release polycarboxylic water reducer, its synthetic method as claimed in claim 1, is characterized in that: the synthesis material of described sustained-release polycarboxylic water reducer is as follows: unsaturated Soxylat A 25-7, fumaric acid, oxidizing agent solution, alkali lye, comonomer, slowly-releasing monomer, chain-transfer agent, reductive agent and water; It is 6-7 that described sustained-release polycarboxylic water reducer alkali lye is neutralized to pH;
Described unsaturated Soxylat A 25-7, its outward appearance is white extremely yellow sheet, degree of unsaturation >=0.30, double bond retention rate >=85%, and hydroxyl value is 24.5 ± 2.5mgKOH/g, and pH value is 5 ~ 8, and its structural formula is shown in general formula (1):
Wherein, R in described general formula (1)
1, R
2and R
3independently represent hydrogen atom or methyl separately, X represents that carbonatoms is the divalent alkyl of 1 ~ 5, R
4represent that carbonatoms is the alkyl of 0 ~ 4, m, n are the average addition mole number of oxidation of alkyl respectively, m=20 ~ 140, n=0 ~ 60;
Described comonomer, its general structure is shown in general formula (2):
Wherein, R in described general formula (2)
5, R
7represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, R
6represent hydrogen atom or
m
1represent hydrogen atom, monovalent metal, ammonium or organic amine;
The general structure of described slowly-releasing monomer is shown in general formula (3):
Wherein, R in described general formula (3)
8, R
9, R
10represent the alkyl of hydrogen atom or 1 ~ 5 carbon atom, M
2represent alkyl or the hydroxyalkyl of 1 ~ 3 carbon atom.
11. a kind of sustained-release polycarboxylic water reducers as claimed in claim 10, is characterized in that: the described unsaturated Soxylat A 25-7 of general formula (1) is methyl allyl alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether;
General formula (2) described comonomer is at least one in vinylformic acid, methacrylic acid, maleic acid or fumaric acid;
The described slowly-releasing monomer of general formula (3) is at least one in methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate or Propylene glycol monoacrylate.
12. a kind of sustained-release polycarboxylic water reducers as claimed in claim 10, is characterized in that: described each raw material dosage is closed and is:
Described unsaturated Soxylat A 25-7: mol ratio=1:2 ~ 6 of (comonomer+slowly-releasing monomer);
Mol ratio=1:0.5 ~ 2 of described comonomer and slowly-releasing monomer;
Described oxygenant accounts for 0.5 ~ 5% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer; Described reductive agent and oxygenant mol ratio=1:2 ~ 5;
Described chain-transfer agent accounts for 0.3 ~ 3% of unsaturated Soxylat A 25-7, comonomer and slowly-releasing total moles monomer.
13. a kind of sustained-release polycarboxylic water reducers as claimed in claim 10, it is characterized in that: described oxidizing agent solution is aqueous oxidizing agent solution, described oxygenant is the one in hydrogen peroxide, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, potassium permanganate;
Described chain-transfer agent is the one in sulfydryl propylene, Thiovanic acid, methacrylic sulfonic acids sodium;
Described reductive agent is at least one in sodium bisulfite, ferrous sulfate, Sulfothiorine, vitamins C, rongalite.
14. a kind of sustained-release polycarboxylic water reducers as claimed in claim 10, is characterized in that: described liquid caustic soda is 30wt% sodium hydroxide solution.
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