CN108329435A - A method of preparing poly carboxylic acid series water reducer - Google Patents
A method of preparing poly carboxylic acid series water reducer Download PDFInfo
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- CN108329435A CN108329435A CN201810157121.5A CN201810157121A CN108329435A CN 108329435 A CN108329435 A CN 108329435A CN 201810157121 A CN201810157121 A CN 201810157121A CN 108329435 A CN108329435 A CN 108329435A
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- acid
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- carboxylic acid
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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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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 discloses a kind of synthetic methods of high performance water reducing agent of polyocarboxy acid, belong to water reducer of cement concrete field.The present invention carries out mechanical ball mill after mixing unsaturated polyoxyethylene ether or unsaturated polyester (UP) polymeric monomer, unsaturated carboxylic acid or unsaturated acid anhydride minor comonomer, chain-transferring agent and initiator, bring it about mechanico-chemical reaction, then obtained product is removed, is dissolved in water, is adjusted with lyepHIt is worth to 6 ~ 8 obtained high performance water reducing agent of polyocarboxy acid.Preparation process of the present invention is simple, is operated at room temperature, and the time is short, at low cost, product solid content is high, can substantially reduce energy expenditure, convenience in transport and use, there is high performance water reducing agent of polyocarboxy acid obtained water-reducing rate height, the good feature of function of slump protection to be suitble to industrialization large-scale production.
Description
Technical field
The invention belongs to technical field of concrete additives, are related to a kind of preparation method of water-reducing agent, specifically a kind of system
The method of standby poly carboxylic acid series water reducer.
Background technology
Poly carboxylic acid series water reducer（PCE）It is a kind of well known concrete additive, is mainly used in concrete mix, is
After lignosulfonates system and naphthalene water reducer, third generation high performance concrete water-reducing agent has obtained domestic and international researcher
Extensive concern.Poly carboxylic acid series water reducer（PCE）It is current research and most widely used concrete admixture, can keeps pre-
Under mixed concrete workability permanence condition, mix water consumption is greatly reduced, improves concrete construction performance, improves hardening coagulation
The intensity and durability of soil, while having low volume, cementitious material strong adaptability, low loss late, preparation process environmental-friendly etc.
Advantage.Poly carboxylic acid series water reducer is widely used and quickly grows.In Japan, PCE products account for water-reducing agent product sum
90%, China's poly carboxylic acid series water reducer yield reaches 6,200,000 tons within 2015（It is calculated by 20% concentration）More than, it accounts for all synthesis and subtracts
The 72.9% of aqua total amount is 124 times in 2005.
Poly carboxylic acid series water reducer is mainly copolymerized by unsaturated monomer under the action of initiator, and pendant reactive will be carried
Group is grafted on main polymer chain and obtains, and belongs to free radicals copolymerization reaction.Currently, common polymerization is poly- for solution
It closes, wherein being subdivided into three kinds of concrete technology methods：Activated monomer copolymerization method, polymerization Post functionalization method and in-situ polymerization and grafting
Method.Common poly carboxylic acid series water reducer is prepared with solution polymerization process, and the reaction time needed certain add at 3 hours or more
Heat, obtained polycarboxylate water-reducer product is usually liquid condition, and solid content is low, and volume is big, is not easy to store and transport.China
Unsaturated carboxylic acid, unsaturation is added with a kind of organic solvent system synthesis of solid polycarboxylate water-reducer in patent CN106188422A
Alcohol polyethers, toluene；Thioacetic acid and azodiisobutyronitrile are added, free radicals copolymerization reaction is carried out under mechanical agitation,
Toluene is evaporated under reduced pressure after reaction, through mechanical crushing to get solid poly carboxylic acid series water reducer, has the reaction time short, purity
Height, the advantages of being conducive to storage and transport, but this method cannot be directly used to concrete due to the water-reducing agent that dicyandiamide solution synthesizes
Production process needs to remove organic solvent toluene, and removing process is complicated, of high cost, causes centainly to pollute to environment, be unfavorable for
Production.
Invention content
The purpose of the present invention is overcoming the scarce limit of the prior art, a kind of method preparing poly carboxylic acid series water reducer is provided.This
Invention be in mechanical ball mill synthesizing polycarboxylic acid dehydragent, without heating, synthesising reacting time can be foreshortened to 30 minutes with
It is interior, it is simple for process, it takes less, does not add organic solvent, at low cost, gained polycarboxylate water-reducer yield is high, convenient for storage and fortune
It is defeated.
The present invention proposes a kind of method preparing poly carboxylic acid series water reducer, is as follows：
The first step：Polymeric monomer, minor comonomer, chain-transferring agent, initiator are mixed, the polymeric monomer is selected from unsaturated polyoxyethylene ether
Or unsaturated polyester (UP), the minor comonomer are selected from unsaturated carboxylic acid or unsaturated acid anhydride, then in the ball mill by above-mentioned mixed liquor
Mechanical ball mill is carried out, the reaction time is 5min ~ 30min, brings it about mechanico-chemical reaction；
Specifically, above-mentioned unsaturated polyoxyethylene ether is preferably isopentene group polyoxyethylene ether, allyl polyethenoxy ether, first
One or more of mixing of base allyl polyethenoxy ether.
Above-mentioned unsaturated polyester (UP) polymeric monomer is preferably methoxy polyethylene glycol acrylate, methoxy poly (ethylene glycol) methyl
One or more of mixing of acrylate, methoxy poly (ethylene glycol) maleate.
Above-mentioned unsaturated carboxylic acid monomer is preferably the one of acrylic acid, methacrylic acid, itaconic acid, citraconic acid or fumaric acid
Kind or several mixing.
Above-mentioned unsaturated acid anhydride is selected from maleic anhydride.
Above-mentioned chain-transferring agent is preferably that one or more of methylpropene sodium sulfonate, mercaptopropionic acid or thioacetic acid are mixed
It closes.
Above-mentioned initiator is preferably that one or more of ammonium persulfate, potassium peroxydisulfate, ascorbic acid-hydrogen peroxide are mixed
It closes.
Further, above-mentioned preferred unsaturated polyoxyethylene ether or the weight average molecular weight of unsaturated polyester (UP) polymeric monomer are
400~2400。
Further, above-mentioned insatiable hunger polyoxyethylene ether or unsaturated polyester (UP) polymeric monomer, unsaturated carboxylic acid or unsaturated acids
The molar ratio of anhydride monomer and chain-transferring agent is 1.0:1.0~8.0:0.05~3.0.
Further, the dosage of above-mentioned initiator is the 1.0%~2.0% of unsaturated alcohol polyether quality.
Further, above-mentioned mechanical ball mill reaction can be in planetary, drum-type, stirring-type or oscillatory type ball mill
It carries out.
Second step：After waiting for above-mentioned mechanico-chemical reaction, obtained product is removed, with deionized water dissolving, with alkali
Liquid adjusts solutionpH, finally obtainpHThe high performance water reducing agent of polyocarboxy acid that value is 6 ~ 8.
Specifically, the lye is selected from the mixing of one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide
Solution.
The present invention prepares the simple for process of high performance water reducing agent of polyocarboxy acid, is reacted without heating, and the time is short, cost
Low, product solid content is high, can substantially reduce energy consumption, convenience in transport and use, high performance water reducing agent of polyocarboxy acid tool obtained
There are water-reducing rate height, the good feature of function of slump protection.There are distinguishing feature and substantial advance compared with existing preparation method, therefore has
There is good application prospect.
Specific implementation mode
The invention will be further described With reference to embodiment and description, but does not limit this hair in any way
It is bright.
This method for preparing high performance water reducing agent of polyocarboxy acid of the present invention, includes the following steps：
1）By unsaturated polyoxyethylene ether or unsaturated polyester (UP) polymeric monomer, unsaturated carboxylic acid, such as acrylic acid, chain-transferring agent, such as first
After base sodium allylsulfonate, initiator mixing, mechanical ball mill is carried out in the ball mill, without heating, it is anti-to bring it about mechanochemistry
It answers.
2）By step 1）In obtained product remove, with deionized water dissolving, solution is adjusted with lyepH, make itpHFor 6 ~
8 can be obtained high performance water reducing agent of polyocarboxy acid.
Step in the preparation method of following water-reducing agents is conventional method unless otherwise instructed, and the raw material are such as without spy
Bright equal can be obtained from open commercial sources is not mentionleted alone.
Embodiment one
The isopentene group polyoxyethylene ether for being 2400 by molecular weight：Acrylic acid：Methylpropene sodium sulfonate molar ratio is 1.0:2.5:
0.08 weighs, and weigh that ammonium persulfate dosage is isopentene group polyoxyethylene ether quality 1.0% is placed in beaker and stirs evenly.It will
Monomer mixture is added in ball grinder, screws ball grinder, is installed on planetary ball mill, is set Ball-milling Time 30min, is opened
Beginning ball-milling reaction.Reaction terminates to take out reaction product, with water dissolution, is adjusted with 30% sodium hydroxide solutionpH=6 ~ 8, it finally obtains
Polycarboxylate high performance water-reducing agent is recorded as PC-1.
Embodiment two
The allyl polyethenoxy ether for being 400 by molecular weight：Methacrylic acid：Mercaptopropionic acid molar ratio is 1.0:1.0:0.05 claims
It takes, weigh that potassium peroxydisulfate dosage is allyl polyethenoxy ether quality 1.5% is placed in beaker and stirs evenly.Monomer is mixed
Object is added in ball grinder, screws ball grinder, is installed on tumbling ball mill, and Ball-milling Time 25min is set, and it is anti-to start ball milling
It answers.Reaction terminates to take out reaction product, with water dissolution, is adjusted with 30% potassium hydroxide solutionpH=6 ~ 8, finally obtain polycarboxylic-acid
High-performance water reducing agent is recorded as PC-2.
Embodiment three
It is 1200 methyl allyl polyoxyethylene ethers by molecular weight：Itaconic acid：Methylpropene sodium sulfonate molar ratio is 1.0:3.5:
0.5 weighs, and weigh that ammonium persulfate dosage is methyl allyl polyoxyethylene ether quality 2.0% is placed in beaker and stirs evenly.It will
Monomer mixture is added in ball grinder, screws ball grinder, is installed on stirring ball mill, is set Ball-milling Time 20min, is opened
Beginning ball-milling reaction.Reaction terminates to take out reaction product, with water dissolution, is adjusted with 30% calcium hydroxide solutionpH=6 ~ 8, it finally obtains
Polycarboxylate high performance water-reducing agent is recorded as PC-3.
Example IV
The methoxy polyethylene glycol acrylate for being 1000 by molecular weight：Citraconic acid：Thioacetic acid molar ratio is 1.0:4.5:1.0
It weighs, weigh that ascorbic acid-hydrogen peroxide use is methoxy polyethylene glycol acrylate quality 2.0% is placed in beaker and stirs
It mixes uniformly.Monomer mixture is added in ball grinder, ball grinder is screwed, is installed on oscillatory type ball mill, when setting ball milling
Between 15min, start ball-milling reaction.Reaction terminates to take out reaction product, with water dissolution, is adjusted with 30% sodium hydroxide solutionpH=6~
8, it finally obtains polycarboxylate high performance water-reducing agent and is recorded as PC-4.
Embodiment five
The methoxy polyethylene glycol methacrylate-styrene polymer for being 1500 by molecular weight：Fumaric acid：Methylpropene sodium sulfonate molar ratio is
1.0:6.0:1.5 weigh, and it is that methoxy polyethylene glycol methacrylate-styrene polymer quality 1.0% is placed in burning to weigh ammonium persulfate dosage
It is stirred evenly in cup.Monomer mixture is added in ball grinder, ball grinder is screwed, is installed on planetary ball mill, is set
Ball-milling Time 10min starts ball-milling reaction.Reaction terminates to take out reaction product, with water dissolution, with 30% sodium hydroxide solution tune
SectionpH=6 ~ 8, it finally obtains polycarboxylate high performance water-reducing agent and is recorded as PC-5.
Embodiment six
The methoxy poly (ethylene glycol) maleate for being 2000 by molecular weight：Maleic anhydride：Methylpropene sodium sulfonate molar ratio is
1.0:8:3.0 weigh, and weigh that ammonium persulfate dosage is methoxy poly (ethylene glycol) maleate quality 2.0% is placed in beaker and stirs
It mixes uniformly.Monomer mixture is added in ball grinder, ball grinder is screwed, is installed on stirring ball mill, when setting ball milling
Between 5min, start ball-milling reaction.Reaction terminates to take out reaction product, with water dissolution, is adjusted with 30% sodium hydroxide solutionpH=6~
8, it finally obtains polycarboxylate high performance water-reducing agent and is recorded as PC-6.
Comparative example
The isopentene group polyoxyethylene ether for being 2400 by molecular weight：Acrylic acid：Methylpropene sodium sulfonate molar ratio is 1.0:2,5:
0.08 weighs monomer, weighs 1.0% that ammonium persulfate dosage is isopentene group polyoxyethylene ether quality.It will be different with a certain amount of water
Pentenyl polyoxyethylene ether is dissolved in the four-hole boiling flask equipped with condenser pipe.Prepare initiator solution A simultaneously（Ammonium persulfate+water）
With monomer mixture solution B（Acrylic acid+methylpropene sodium sulfonate+water）.Polymeric monomer is warming up to 60 DEG C, two kinds of lists of A, B are added dropwise
Body, 70min or so are dripped off.75 DEG C are warming up to, insulation reaction 3h.Reaction terminates, and is down to room temperature, is adjusted with 30% sodium hydroxidepH=
6 ~ 8, obtain polycarboxylate water-reducer PC-7.
Water-reducing agent obtained by above-described embodiment and comparative example is tested, the results detailed in Table 1.
Experiment determines the paste flowing degree of each Examples and Comparative Examples under same volume.Experiment is according to GB/T8077-2000
《Methods for testing uniformity of concrete admixture》It carries out, W/C=0.29, volume is the solid volume of folding.Test result is shown in Table 1：
Table 1：Net slurry mobile performance result
With the concrete outcome in upper table 1 as it can be seen that the poly carboxylic acid series water reducer using the present invention with synthesized by mechanochemical reaction
Solid content is apparently higher than the polycarboxylate water-reducer using prior art preparation, and the reaction time is significantly shorter than using prior art preparation
Polycarboxylate water-reducer, paste flowing degree and fluidity retentivity reach the polycarboxylate water-reducer using prior art preparation, demonstrate,proves
The poly carboxylic acid series water reducer that the present invention is illustrated has very good practical value.
The preparation method of the poly carboxylic acid series water reducer of the present invention has the advantages that simple for process, reduction energy consumption, is not added with
Solvent, at low cost, gained polycarboxylate water-reducer yield is high, and product is easily stored and transports.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (7)
1. a kind of method preparing poly carboxylic acid series water reducer, includes the following steps：
The first step：Polymeric monomer, minor comonomer, chain-transferring agent and initiator are mixed, carry out mechanical ball mill in the ball mill, when reaction
Between be 5.0 ~ 30.0 minutes, the polymeric monomer is unsaturated polyoxyethylene ether or unsaturated polyester (UP), and the minor comonomer is unsaturation
Carboxylic acid or unsaturated acid anhydride；
Second step：Wait for it is above-mentioned after reaction, by obtained product remove, be dissolved in water, adjusted with lyepHIt is worth to 6 ~ 8 and is made
High performance water reducing agent of polyocarboxy acid.
2. preparation method according to claim 1, which is characterized in that in the first step：
The unsaturated polyoxyethylene ether is selected from isopentene group polyoxyethylene ether, allyl polyethenoxy ether or methacrylic
One or more of mixing of polyoxyethylene ether；
The unsaturated polyester (UP) is selected from methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate-styrene polymer or first
One or more of mixing of oxygroup PEGMa polyethylene glycol maleate；
The one or more that the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid or fumaric acid are mixed
It closes；
The unsaturated acid anhydride is selected from maleic anhydride；
The chain-transferring agent is selected from the mixing of one or more of methylpropene sodium sulfonate, mercaptopropionic acid or thioacetic acid；
The initiator is selected from the mixing of one or more of ammonium persulfate, potassium peroxydisulfate, ascorbic acid-hydrogen peroxide.
3. according to any preparation method in claims 1 or 2, which is characterized in that the unsaturation in the first step is poly-
The weight average molecular weight of ethylene oxide ether or unsaturated polyester (UP) is 400 ~ 2400.
4. according to any preparation method in claims 1 or 2, which is characterized in that polymeric monomer described in the first step with
The dosage molar ratio of minor comonomer and chain-transferring agent is 1.0: 1~8.0: 0.05~3.0.
5. according to any preparation method in claims 1 or 2, which is characterized in that initiator described in the first step
Dosage is the 1.0%~2.0% of polymeric monomer quality.
6. preparation method according to claim 1, which is characterized in that the mechanical ball mill reaction in the first step is to be expert at
Planetary, drum-type, stirring-type or oscillatory type ball mill in carry out.
7. preparation method according to claim 1, which is characterized in that lye in the second step be selected from sodium hydroxide,
The mixed solution of one or more of potassium hydroxide or calcium hydroxide.
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| CN201810157121.5A CN108329435B (en) | 2018-02-24 | 2018-02-24 | Method for preparing polycarboxylic acid water reducing agent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029049A (en) * | 2020-09-14 | 2020-12-04 | 安徽瑞和新材料有限公司 | Solvent-free low-temperature ball milling preparation method of solid polycarboxylic slump retaining agent |
| CN112645630A (en) * | 2020-12-19 | 2021-04-13 | 厦门宏发先科新型建材有限公司 | Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete |
| CN112679674A (en) * | 2020-12-29 | 2021-04-20 | 江西富创新材料有限公司 | Polycarboxylate superplasticizer and production process thereof |
| CN113278144A (en) * | 2021-05-12 | 2021-08-20 | 北京金隅水泥节能科技有限公司 | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof |
| CN113912842A (en) * | 2021-09-14 | 2022-01-11 | 科之杰新材料集团有限公司 | Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof |
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| CN103554382A (en) * | 2013-09-25 | 2014-02-05 | 沈阳建筑大学 | Method for solid-phase synthesizing polycarboxylic acid water reducer |
| CN107698716A (en) * | 2017-07-06 | 2018-02-16 | 徐州巨龙新材料科技有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554382A (en) * | 2013-09-25 | 2014-02-05 | 沈阳建筑大学 | Method for solid-phase synthesizing polycarboxylic acid water reducer |
| CN107698716A (en) * | 2017-07-06 | 2018-02-16 | 徐州巨龙新材料科技有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029049A (en) * | 2020-09-14 | 2020-12-04 | 安徽瑞和新材料有限公司 | Solvent-free low-temperature ball milling preparation method of solid polycarboxylic slump retaining agent |
| CN112645630A (en) * | 2020-12-19 | 2021-04-13 | 厦门宏发先科新型建材有限公司 | Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete |
| CN112679674A (en) * | 2020-12-29 | 2021-04-20 | 江西富创新材料有限公司 | Polycarboxylate superplasticizer and production process thereof |
| CN113278144A (en) * | 2021-05-12 | 2021-08-20 | 北京金隅水泥节能科技有限公司 | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof |
| CN113912842A (en) * | 2021-09-14 | 2022-01-11 | 科之杰新材料集团有限公司 | Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof |
| CN113912842B (en) * | 2021-09-14 | 2023-10-24 | 科之杰新材料集团有限公司 | Ligand, conductive early-strength polycarboxylate superplasticizer, conductive early-strength graphene dispersion slurry and preparation method thereof |
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