CN109694446A - A kind of synthetic method of solid polycarboxylic acid water reducing agent - Google Patents
A kind of synthetic method of solid polycarboxylic acid water reducing agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- 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
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Abstract
The invention belongs to technical field of concrete additives, are related to a kind of synthetic method of solid polycarboxylic acid water reducing agent, mainly comprise the steps that and liquid pfpe A and phthalic anhydride are added into the first reaction vessel, and phthalic acid list polyether ester is made；First part's phthalic acid list polyether ester and unsaturated polyether polymeric monomer are added into the second reaction vessel；It is parallel to prepare solution B and solution C；Solution B and solution C is at the uniform velocity added dropwise into second reaction vessel, after completion of dropwise addition, adds p-methyl benzenesulfonic acid, carries out esterification；Inorganic strong alkali is added to adjust pH, up to product after cooling.Above-mentioned synthetic method is easy to operate, and low raw-material cost, reaction condition is mild, and technique is environmentally protective, therefore is very suitable for large-scale industrial production；Also, according to solid polycarboxylic acid water reducing agent made from the synthetic method there is excellent diminishing dispersion performance therefore to have a extensive future.
Description
Technical field
The invention belongs to technical field of concrete additives more particularly to a kind of synthesis sides of solid polycarboxylic acid water reducing agent
Method.
Background technique
In recent years, polycarboxylate water-reducer is one of key foundation and motive force of modern concrete technological progress.It is existing
Polycarboxylate water-reducer mainly pass through unsaturated polyether monomer and carry out free radical polymerization in aqueous solution with carboxylic monomer and form.
However, polycarboxylate water-reducer currently on the market largely exists in liquid form, therefore show transportation cost
It is high, the special engineerings field such as be not easy to a series of disadvantages such as storage, and dry powder and mortar, grouting material cannot be applied to；And solid
The appearance of (powder) polycarboxylate water-reducer just compensates for above-mentioned deficiency.
Solid polycarboxylic acid water reducing agent mainly passes through the spray drying of liquid polycarboxylate water-reducer and is made, and still, this process is not
Only energy consumption is high, but also polycarboxylate water-reducer can be made to be prone to crosslinking, oxidation under high temperature environment, so as to cause doing by spraying
The comprehensive performance of solid product after dry can also decline, and ultimately cause it and liquid polycarboxylate water-reducer is not achieved in practical applications
Performance level.
The preparation process of many solid polycarboxylic acid water reducing agents is provided in the prior art.For example, Chinese patent CN1919772
Disclose a kind of preparation method of powder poly carboxylic acid series water reducer, by the way that water-reducing agent to be sprayed, heated-air drying is realized, as above
It is described, it is clear that the production energy consumption of this method is excessively high.For example, Chinese patent Shen CN106749967A and CN106749968A are reported
The organic solvent of polymeric monomer 20-50% mass parts is added, in polymerization system with the early strong or collapse protection type water-reducing agent of synthesis；However,
Removing solvent is required to after polymerization reaction is complete, not only energy consumption is higher for this, but also the use of a large amount of organic solvents can also be led
Cause serious environmental pollution and treatment cost.For another example, Chinese patent application CN106986970A discloses a kind of high-performance solid
The water of electrolyte and 8-21% is added in polymerization system to reduce viscosity in the preparation method of polycarboxylate water-reducer, this method, but
It is that this method also needs further high temperature, high pressure dehydrating operations after completion of the polymerization reaction, it is seen that it, which consumes energy, still occupies height not
Under, and whole preparation process is complicated.
In the prior art, it is generally solid for synthesizing the polyether macromonomer of polycarboxylate water-reducer, it is poly- is directly used in ontology
Credit union causes system viscosity excessive, and causes polymerization conversion lower.In view of this, prior art mainly pass through be added water or
Organic solvent reduces system viscosity, however, this generic operation will lead to higher energy consumption cost.In addition, Chinese patent application
CN108084362A discloses a kind of solid polycarboxylic acid water reducing agent and its preparation method and application, wherein it is poly- to use a kind of liquid
Ether polymeric monomer is with synthesis of solid polycarboxylate water-reducer, to reduce system viscosity；However, the preparation manipulation of the liquid monomer itself
Cumbersome, higher cost is not suitable for large-scale industrial production.
Summary of the invention
The present invention is directed to overcome above-mentioned technological deficiency existing in the prior art, and provide a kind of suitable for heavy industrialization
The synthesis technology of the solid polycarboxylic acid water reducing agent of production.
Specifically, the present invention provides a kind of synthetic methods of solid polycarboxylic acid water reducing agent comprising following steps:
S1: liquid pfpe A and phthalic anhydride being added into the first reaction vessel, and carry out instead at 50~80 DEG C
It answers, phthalic acid list polyether ester is made；
Wherein, the weight average molecular weight of the liquid pfpe A is 200~1200, and the structural formula of the liquid pfpe A
Are as follows:
Wherein, R is selected from the alkyl of C1~C4；M is selected from 0~25 integer；N is selected from 1~25 integer；
S2: first part's phthalic acid list polyether ester and unsaturated polyether polymeric monomer are added into the second reaction vessel；
S3: parallel to prepare solution B and solution C；
Wherein, the solution B is made by the way that initiator is dissolved in second part phthalic acid list polyether ester；
Wherein, the solution C is by being dissolved in Part III phthalic acid list polyether ester system for carboxylic acid monomer, chain-transferring agent
?；
S4: at 70~90 DEG C, being at the uniform velocity added dropwise solution B and solution C in the second reaction vessel of Xiang Suoshu, after completion of dropwise addition,
P-methyl benzenesulfonic acid is added, and is warming up to 90~120 DEG C of progress esterifications；
S5: after esterification is complete, inorganic strong alkali is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer.
Preferably, in above-mentioned synthetic method, in step sl, the liquid pfpe A and the phthalic anhydride
Molar ratio is 1:1~1:1.5.
Preferably, in above-mentioned synthetic method, in step s 2, the unsaturated polyether polymeric monomer is isopentene group polyoxy
Vinethene (TPEG) or/and methyl allyl alcohol polyoxyethylene ether (HPEG).
Preferably, in above-mentioned synthetic method, in step s 2, the weight average molecular weight of the unsaturated polyether polymeric monomer is
600~3000.
Preferably, in above-mentioned synthetic method, in step s 2, first part's phthalic acid list polyether ester and institute
The molar ratio for stating unsaturated polyether polymeric monomer is 1:1~1:3.
Preferably, in above-mentioned synthetic method, in step s3, the initiator be benzoyl peroxide (BPO) or/and
Azodiisobutyronitrile；Also, the quality of the initiator is the 0.5%~2% of the gross mass of the reactant in step S2~S4.
Preferably, in above-mentioned synthetic method, in step s3, the carboxylic acid monomer is selected from following any one or more
Combination: acrylic acid, methacrylic acid, maleic acid, fumaric acid and its monovalence alkali metal salt, divalent alkali metal salt, ammonium salt.
Preferably, the institute in the unsaturated polyether polymeric monomer and step S3 in above-mentioned synthetic method, in step S2
The molar ratio for stating carboxylic acid monomer is 1:1.5~1:6.
Preferably, in above-mentioned synthetic method, in step s3, the chain-transferring agent is selected from following any one or more
Combination: thioacetic acid, mercaptopropionic acid, isopropanol, sodium hypophosphite, tertiary sodium phosphate, mercaptoethanol；Also, the chain-transferring agent
Quality is the 0.05%~0.1% of the gross mass of the reactant in step S2~S4.
Preferably, in above-mentioned synthetic method, in step s 4, the quality of the p-methyl benzenesulfonic acid is in step S2~S4
Reactant gross mass 1%~3%.It is worth supplementary explanation, the p-methyl benzenesulfonic acid is used as the catalysis of esterification
Agent.
Preferably, in above-mentioned synthetic method, in step s 5, the inorganic strong alkali is selected from following any: hydroxide
Lithium, sodium hydroxide, potassium hydroxide.
Therefore, compared with prior art, technical solution provided by the present invention has technical effect beneficial below:
1. the synthetic method of solid polycarboxylic acid water reducing agent provided by the invention introduces a kind of adjacent benzene two in the reaction system
Formic acid list polyether ester is not only used as one of reactant, but also is used as polymerization solvent, can be effectively reduced reaction system viscosity,
Monomer conversion is improved, the performance for improving solid polycarboxylic acid water reducing agent product is conducive to；
2. the synthetic method of the solid polycarboxylic acid water reducing agent only can be gathered phthalic acid list by simple step
Ether-ether is grafted on polymer lateral chain, eliminates the solvent processing step in Conventional solid polycarboxylate water-reducer synthesis process, work
Skill is environmentally protective, hence it is evident that is conducive to large-scale industrial production；
3. being grafted with adjacent benzene on the molecular side chain of solid polycarboxylic acid water reducing agent made from the synthetic method according to the present invention
Diformate mono polyether ester, this is conducive to the steric hindrance effect for improving solid polycarboxylic acid water reducing agent molecule, so that it is poly- to improve solid
The diminishing dispersion performance of carboxylic acid water reducer；Meanwhile can also shorten the length of original polycarboxylate water-reducer molecule side chain relatively, with more
Reaction system viscosity is further decreased, monomer conversion is improved.
In conclusion the synthetic method of solid polycarboxylic acid water reducing agent of the present invention is easy to operate, low raw-material cost,
Reaction condition is mild, and technique is environmentally protective, therefore is very suitable for large-scale industrial production；Also, according to the synthesis side
There is solid polycarboxylic acid water reducing agent made from method excellent diminishing dispersion performance therefore to have a extensive future.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiment party
Formula.
A kind of synthetic method of solid polycarboxylic acid water reducing agent according to a preferred embodiment of the present invention, including following step
It is rapid:
S1: liquid pfpe A and phthalic anhydride being added into the first reaction vessel, and 1~3 is reacted at 50~80 DEG C
Hour, phthalic acid list polyether ester is made；
Wherein, the weight average molecular weight of the liquid pfpe A is 200~1200, and the structural formula of the liquid pfpe A
Are as follows:
Wherein, R is selected from the alkyl of C1~C4；M is selected from 0~25 integer；N is selected from 1~25 integer；
S2: first part's phthalic acid list polyether ester and unsaturated polyether polymeric monomer are added into the second reaction vessel；
S3: parallel to prepare solution B and solution C；
Wherein, the solution B is made by the way that initiator is dissolved in second part phthalic acid list polyether ester；
Wherein, the solution C is by being dissolved in Part III phthalic acid list polyether ester system for carboxylic acid monomer, chain-transferring agent
?；
S4: at 70~90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu, both solution are each
From time for adding be 2~5 hours, after completion of dropwise addition, add p-methyl benzenesulfonic acid, and be warming up to 90~120 DEG C be esterified it is anti-
It answers；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer.
In a preferred embodiment, in step sl, the molar ratio of the liquid pfpe A and the phthalic anhydride
For 1:1~1:1.5.
In a preferred embodiment, in step s 2, the unsaturated polyether polymeric monomer is isopentene group polyoxyethylene
Ether or/and methyl allyl alcohol polyoxyethylene ether.
In a preferred embodiment, in step s 2, the weight average molecular weight of the unsaturated polyether polymeric monomer be 600~
3000。
In a preferred embodiment, in step s 2, first part's phthalic acid list polyether ester and it is described not
The molar ratio for being saturated polyether macromonomer is 1:1~1:3.
In a preferred embodiment, in step s3, the initiator is two isobutyl of benzoyl peroxide or/and azo
Nitrile；Also, the quality of the initiator is the 0.5%~2% of the gross mass of the reactant in step S2~S4.
In a preferred embodiment, in step s3, the carboxylic acid monomer is selected from following any one or more combination:
Acrylic acid, methacrylic acid, maleic acid, fumaric acid and its monovalence alkali metal salt, divalent alkali metal salt, ammonium salt.
In a preferred embodiment, the unsaturated polyether polymeric monomer in step S2 and the carboxylic acid in step S3
The molar ratio of monomer is 1:1.5~1:6.
In a preferred embodiment, in step s3, the chain-transferring agent is selected from following any one or more combination:
Thioacetic acid, mercaptopropionic acid, isopropanol, sodium hypophosphite, tertiary sodium phosphate, mercaptoethanol；Also, the quality of the chain-transferring agent is
The 0.05%~0.1% of the gross mass of reactant in step S2~S4.
In a preferred embodiment, in step s 4, the quality of the p-methyl benzenesulfonic acid is anti-in step S2~S4
Answer the 1%~3% of the gross mass of object.
Operation in following embodiments is routine operation unless otherwise instructed, and described device, reagent etc. are especially said such as nothing
It is bright equal to be bought from public commercial source.
Embodiment 1
The synthesis of solid polycarboxylic acid water reducing agent (S2-1)
S1: liquid pfpe A (the polyethyleneglycol ether CH of 300g is added into the first reaction vessel3CH2(OCH2CH2O)
NH, molecular weight 300) and 148g phthalic anhydride, and reacted 3 hours at 60 DEG C, it is poly- that 448g phthalic acid list is made
Ether-ether (S1-1)；
S2: 600g TPEG-600 and 300g phthalic acid list polyether ester (S1-1) is added into the second reaction vessel；
S3: parallel to prepare solution B and solution C:
1) the 6g initiator B PO phthalic acid list polyether ester (S1-1) for being dissolved in 30g is obtained into solution B；
2) by 144g acrylic acid, 0.8g mercaptopropionic acid, 60g phthalic acid list polyether ester (S1-1) be uniformly mixed obtain it is molten
Liquid C；
S4: at 80 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 30g, and it is small to be warming up to 90 DEG C of esterifications 5
When, then keep the temperature 2 hours；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-1).
Embodiment 2
The synthesis of solid polycarboxylic acid water reducing agent (S2-2)
S1: liquid pfpe A (the polyethyleneglycol ether CH of 300g is added into the first reaction vessel3CH2(OCH2CH2O)
NH, molecular weight 300) and 162.8g phthalic anhydride, and reacted 3 hours at 50 DEG C, 462.8g phthalic acid is made
Single polyether ester (S1-2)；
S2: 800g TPEG-800 and 400g phthalic acid list polyether ester (S1-2) is added into the second reaction vessel；
S3: parallel to prepare solution B and solution C:
1) the 8g initiator B PO phthalic acid list polyether ester (S1-2) for being dissolved in 30g is obtained into solution B；
2) 108.1g acrylic acid, 1.0g mercaptopropionic acid, 32.8g phthalic acid list polyether ester (S1-2) are uniformly mixed
To solution C；
S4: at 90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 30g, and be warming up to 100 DEG C of esterifications 5
Hour, then keep the temperature 2 hours；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-2).
Embodiment 3
The synthesis of solid polycarboxylic acid water reducing agent (S2-3)
S1: liquid pfpe A (the polyethylene glycol mono-n-butyl ether CH of 500g is added into the first reaction vessel3CH2CH2CH2
(OCH2CH2O) nH, molecular weight 500) and 177.6g phthalic anhydride, and reacted 3 hours at 50 DEG C, it is adjacent that 677.6g is made
Phthalic acid list polyether ester (S1-3)；
S2: 800g TPEG-800 and 250g phthalic acid list polyether ester (S1-3) is added into the second reaction vessel；
S3: parallel to prepare solution B and solution C:
1) the 10g initiator B PO phthalic acid list polyether ester (S1-3) for being dissolved in 40g is obtained into solution B；
2) 288.24g acrylic acid, 1.2g mercaptopropionic acid, 48.8g phthalic acid list polyether ester (S1-3) are uniformly mixed
Obtain solution C；
S4: at 90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 30g, and be warming up to 100 DEG C of esterifications 5
Hour, then keep the temperature 2 hours；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-3).
Embodiment 4
The synthesis of solid polycarboxylic acid water reducing agent (S2-4)
S1: liquid pfpe A (the polyethylene glycol propylene glycol block monomethyl ether CH of 1000g is added into the first reaction vessel3
(OCH2CH2CH2)m(OCH2CH2O) nH, molecular weight 1000) and 148g phthalic anhydride, and reacted 3 hours at 70 DEG C,
1148g phthalic acid list polyether ester (S1-4) is made；
S2: 800g TPEG-800 and 800g phthalic acid list polyether ester (S1-4) is added into the second reaction vessel；
S3: parallel to prepare solution B and solution C:
1) the 15g initiator B PO phthalic acid list polyether ester (S1-4) for being dissolved in 100g is obtained into solution B；
2) 288.24g acrylic acid, 1.3g mercaptopropionic acid, 50g phthalic acid list polyether ester (S1-4) are uniformly mixed
To solution C；
S4: at 90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 40g, and be warming up to 100 DEG C of esterifications 5
Hour, then keep the temperature 2 hours；
S5: after esterification is complete, potassium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-4).
Embodiment 5
The synthesis of solid polycarboxylic acid water reducing agent (S2-5)
S1: liquid pfpe A (the polyethylene glycol propylene glycol block monomethyl ether CH of 1000g is added into the first reaction vessel3
(OCH2CH2CH2)m(OCH2CH2O) nH, molecular weight 1000) and 148g phthalic anhydride, and reacted 3 hours at 70 DEG C,
1148g phthalic acid list polyether ester (S1-4) is made；
S2: 1200g TPEG-1200 and 900g phthalic acid list polyether ester (S1-4) is added into the second reaction vessel；
S3: parallel to prepare solution B and solution C:
1) the 17g initiator B PO phthalic acid list polyether ester (S1-4) for being dissolved in 100g is obtained into solution B；
2) 288.24g acrylic acid, 1.5g mercaptopropionic acid, 50g phthalic acid list polyether ester (S1-4) are uniformly mixed
To solution C；
S4: at 90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 40g, and be warming up to 100 DEG C of esterifications 5
Hour, then keep the temperature 2 hours；
S5: after esterification is complete, potassium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-5).
Embodiment 6
The synthesis of solid polycarboxylic acid water reducing agent (S2-6)
S1: liquid pfpe A (the polyethylene glycol propylene glycol block monomethyl ether CH of 1000g is added into the first reaction vessel3
(OCH2CH2CH2)m(OCH2CH2O) nH, molecular weight 1000) and 148g phthalic anhydride, and reacted 3 hours at 70 DEG C,
1148g phthalic acid list polyether ester (S1-4) is made；
S2: 1200g TPEG-1200 and 1000g phthalic acid list polyether ester (S1- are added into the second reaction vessel
4)；
S3: parallel to prepare solution B and solution C:
1) the 17g initiator B PO phthalic acid list polyether ester (S1-4) for being dissolved in 100g is obtained into solution B；
2) by 360.3g acrylic acid, 2g thioacetic acid, 50g phthalic acid list polyether ester (S1-4) be uniformly mixed obtain it is molten
Liquid C；
S4: at 90 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B drop
Add 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 40g, and be warming up to 100 DEG C of esterifications 5
Hour, then keep the temperature 2 hours；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-6).
Embodiment 7
The synthesis of solid polycarboxylic acid water reducing agent (S2-7)
S1: liquid pfpe A (the polyethylene glycol propylene glycol block monomethyl ether CH of 800g is added into the first reaction vessel3
(OCH2CH2CH2)m(OCH2CH2O) nH, molecular weight 800) and 222g phthalic anhydride, and reacted 3 hours at 70 DEG C, it makes
Obtain 1022g phthalic acid list polyether ester (S1-7)；
S2: 1200g TPEG-1200 and 1000g phthalic acid list polyether ester (S1- are added into the second reaction vessel
7)；
S3: parallel to prepare solution B and solution C:
1) the 20g initiator B PO phthalic acid list polyether ester (S1-7) for being dissolved in 100g is obtained into solution B；
2) by 360.3g acrylic acid, 2g thioacetic acid, 50g phthalic acid list polyether ester (S1-7) be uniformly mixed obtain it is molten
Liquid C；
S4: at 100 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B
It is added dropwise 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 40g, and be warming up to 120 DEG C of esterifications
4 hours, then keep the temperature 1 hour；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-7).
Embodiment 8
The synthesis of solid polycarboxylic acid water reducing agent (S2-8)
S1: liquid pfpe A (the polyethylene glycol propylene glycol block monomethyl ether CH of 800g is added into the first reaction vessel3
(OCH2CH2CH2)m(OCH2CH2O) nH, molecular weight 800) and 222g phthalic anhydride, and reacted 3 hours at 70 DEG C, it makes
Obtain 1022g phthalic acid list polyether ester (S1-7)；
S2: 1200g HPEG-1200 and 1000g phthalic acid list polyether ester (S1- are added into the second reaction vessel
7)；
S3: parallel to prepare solution B and solution C:
1) the 20g initiator B PO phthalic acid list polyether ester (S1-7) for being dissolved in 100g is obtained into solution B；
2) by 360.3g acrylic acid, 2g thioacetic acid, 50g phthalic acid list polyether ester (S1-7) be uniformly mixed obtain it is molten
Liquid C；
S4: at 100 DEG C, solution B and solution C is at the uniform velocity added dropwise in the second reaction vessel of Xiang Suoshu simultaneously, wherein solution B
It is added dropwise 2 hours, solution C is added dropwise 3 hours, after completion of dropwise addition, adds the p-methyl benzenesulfonic acid of 40g, and be warming up to 120 DEG C of esterifications
4 hours, then keep the temperature 1 hour；
S5: after esterification is complete, sodium hydroxide is added to adjust pH value to 4.0~6.5, up to the solid after cooling
Polycarboxylate water-reducer (S2-8).
In addition, inventor is also respectively by solid polycarboxylic acid water reducing agent (S2-1)~(S2-8), the polycarboxylic acids diminishing of comparative example 1
Agent, comparative example 2 polycarboxylate water-reducer be applied to prepare concrete；Wherein, comparative example 1 uses commercial liquid collapse protective poly-carboxylic acid
Water-reducing agent (solid content 40%), comparative example 2 use commercial liquid high water reduction type polycarboxylate water-reducer (solid content 40%).And
And inventor has carried out mechanical property to concrete made above and working performance is tested.
Compression strength: according to pressure resistance in GB/T 50081-2002 " standard for test methods of mechanical properties of ordinary concrete "
Spend test method measurement.
Concrete divergence gradual loss: according to GB/T 50080-2016 " Standard for test methods of properties of ordinary concrete mixture
Standard " in test method measurement.
Concrete foundation component formula are as follows: cement 220kg/m3, flyash 80kg/m3, miberal powder 90kg/m3, sand 780kg/
m3, stone 1080kg/m3, water 170kg/m3, cement is conch cement PO42.5R.
The specific testing result of each concrete sample is as shown in the following table 1 and 2:
The working performance test result of each concrete sample of table 1
The working performance test result of each concrete sample of table 2
By all data in analytical table 1, table 2 it is found that compared to by commercially available conventional liq polycarboxylate water-reducer (such as
Comparative example 1 and comparative example 2) preparation concrete, the concrete of as synthesized by present invention solid polycarboxylic acid water reducing agent preparation
Properties are significantly improved.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it any equivalent modifications to the practical progress and replaces
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all should be contained within the scope of the invention.
Claims (10)
1. a kind of synthetic method of solid polycarboxylic acid water reducing agent, which comprises the following steps:
S1: liquid pfpe A and phthalic anhydride being added into the first reaction vessel, and is reacted at 50~80 DEG C, with
Phthalic acid list polyether ester is made；
Wherein, the weight average molecular weight of the liquid pfpe A is 200~1200, and the structural formula of the liquid pfpe A are as follows:
Wherein, R is selected from the alkyl of C1~C4；M is selected from 0~25 integer；N is selected from 1~25 integer；
S2: first part's phthalic acid list polyether ester and unsaturated polyether polymeric monomer are added into the second reaction vessel；
S3: parallel to prepare solution B and solution C；
Wherein, the solution B is made by the way that initiator is dissolved in second part phthalic acid list polyether ester；
Wherein, the solution C is made by the way that carboxylic acid monomer, chain-transferring agent are dissolved in Part III phthalic acid list polyether ester；
S4: at 70~90 DEG C, being at the uniform velocity added dropwise solution B and solution C in the second reaction vessel of Xiang Suoshu, after completion of dropwise addition, addition
P-methyl benzenesulfonic acid, and it is warming up to 90~120 DEG C of progress esterifications；
S5: after esterification is complete, inorganic strong alkali is added to adjust pH value to 4.0~6.5, up to the poly- carboxylic of the solid after cooling
Sour water-reducing agent.
2. synthetic method according to claim 1, which is characterized in that in step sl, the liquid pfpe A and the neighbour
The molar ratio of phthalate anhydride is 1:1~1:1.5.
3. synthetic method according to claim 1, which is characterized in that in step s 2, the unsaturated polyether polymeric monomer
For isopentene group polyoxyethylene ether or/and methyl allyl alcohol polyoxyethylene ether.
4. synthetic method according to claim 1, which is characterized in that in step s 2, the unsaturated polyether polymeric monomer
Weight average molecular weight be 600~3000.
5. synthetic method according to claim 1, which is characterized in that in step s 2, first part's O-phthalic
The molar ratio of sour list polyether ester and the unsaturated polyether polymeric monomer is 1:1~1:3.
6. synthetic method according to claim 1, which is characterized in that in step s3, the initiator is benzoyl peroxide
Formyl or/and azodiisobutyronitrile；Also, the quality of the initiator is the gross mass of the reactant in step S2~S4
0.5%~2%.
7. synthetic method according to claim 1, which is characterized in that in step s3, the carboxylic acid monomer is selected from following
Any one or more combination: acrylic acid, methacrylic acid, maleic acid, fumaric acid and its monovalence alkali metal salt, divalent alkali metal
Salt, ammonium salt.
8. synthetic method according to claim 1, which is characterized in that the unsaturated polyether polymeric monomer in step S2 with
The molar ratio of the carboxylic acid monomer in step S3 is 1:1.5~1:6.
9. synthetic method according to claim 1, which is characterized in that in step s3, the chain-transferring agent is selected from following
Any one or more combination: thioacetic acid, mercaptopropionic acid, isopropanol, sodium hypophosphite, tertiary sodium phosphate, mercaptoethanol；Also,
The quality of the chain-transferring agent is the 0.05%~0.1% of the gross mass of the reactant in step S2~S4.
10. synthetic method according to claim 1, which is characterized in that in step s 4, the quality of the p-methyl benzenesulfonic acid
It is the 1%~3% of the gross mass of the reactant in step S2~S4.
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| CN111825367A (en) * | 2020-06-24 | 2020-10-27 | 中建西部建设建材科学研究院有限公司 | Viscosity reducer for ultra-high performance concrete and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042147A (en) * | 1988-06-29 | 1990-05-16 | 阿勒根公司 | Have active thiochroman phenolic ester of similar retinoid and terephthalate |
| US20050043419A1 (en) * | 2003-08-18 | 2005-02-24 | Saehn Industries Incorporation | Method for producing foamed products based on aromatic polyester resin with low melting point |
| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
| CN102206060A (en) * | 2011-03-15 | 2011-10-05 | 赵争艳 | Synthetic method for maleic polycarboxylic water reducer |
| JP2014152187A (en) * | 2013-02-05 | 2014-08-25 | Kao Corp | Method for producing polycarboxylic acid-based polymer |
| CN104478279A (en) * | 2014-12-27 | 2015-04-01 | 陕西科技大学 | Multi-sulfonate type cement water reducing agent and preparation method thereof |
| CN105475280A (en) * | 2015-11-30 | 2016-04-13 | 广州世航生物科技有限公司 | Daily chemical product degerming agent and daily chemical product |
| CN106084149A (en) * | 2016-06-08 | 2016-11-09 | 柳州市强威锻造厂 | A kind of phthalic acid class polycarboxylate water-reducer |
| CN107446089A (en) * | 2017-08-09 | 2017-12-08 | 武汉理工大学 | One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer and preparation method thereof |
-
2018
- 2018-12-14 CN CN201811534723.4A patent/CN109694446B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042147A (en) * | 1988-06-29 | 1990-05-16 | 阿勒根公司 | Have active thiochroman phenolic ester of similar retinoid and terephthalate |
| US20050043419A1 (en) * | 2003-08-18 | 2005-02-24 | Saehn Industries Incorporation | Method for producing foamed products based on aromatic polyester resin with low melting point |
| CN101205127A (en) * | 2007-11-21 | 2008-06-25 | 厦门市建筑科学研究院集团股份有限公司 | Formula of sustained release type polycarboxylic acid series high-performance dehydragent and method for manufacturing same |
| CN102206060A (en) * | 2011-03-15 | 2011-10-05 | 赵争艳 | Synthetic method for maleic polycarboxylic water reducer |
| JP2014152187A (en) * | 2013-02-05 | 2014-08-25 | Kao Corp | Method for producing polycarboxylic acid-based polymer |
| CN104478279A (en) * | 2014-12-27 | 2015-04-01 | 陕西科技大学 | Multi-sulfonate type cement water reducing agent and preparation method thereof |
| CN105475280A (en) * | 2015-11-30 | 2016-04-13 | 广州世航生物科技有限公司 | Daily chemical product degerming agent and daily chemical product |
| CN106084149A (en) * | 2016-06-08 | 2016-11-09 | 柳州市强威锻造厂 | A kind of phthalic acid class polycarboxylate water-reducer |
| CN107446089A (en) * | 2017-08-09 | 2017-12-08 | 武汉理工大学 | One kind is drawn money on credit chain end group esterification modification polycarboxylate water-reducer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 朱洪法，等: "《工业助剂手册》", 30 June 2007, 金盾出版社 * |
| 杜勇，等: "丁二酸酐酯化改性聚羧酸长侧链端羟基及减水剂性能", 《新型建筑材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825367A (en) * | 2020-06-24 | 2020-10-27 | 中建西部建设建材科学研究院有限公司 | Viscosity reducer for ultra-high performance concrete and preparation method thereof |
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