CN108440720A - A kind of preparation method of four arms block polycarboxylate water-reducer - Google Patents
A kind of preparation method of four arms block polycarboxylate water-reducer Download PDFInfo
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- CN108440720A CN108440720A CN201810369734.5A CN201810369734A CN108440720A CN 108440720 A CN108440720 A CN 108440720A CN 201810369734 A CN201810369734 A CN 201810369734A CN 108440720 A CN108440720 A CN 108440720A
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a kind of preparation methods of four arms block polycarboxylate water-reducer, which is characterized in that this method has following processing step：Tetrahydroxylic alcohol, alkali, CS2, cylite molar ratio be 1：4‑6：2‑7：Four arm chain-transferring agents are made in 39 times reactions；Under four arm chain-transferring agents, initiator effect, causes the RAFT polymerizations of prenol polyoxyethylene ether, acrylic acid successively, four arm block copolymers are obtained, after processing to get four arm block polycarboxylate water-reducers.Water-reducing agent of the present invention has the characteristics that chemical constitution is controllable, molecular weight is controllable, molecular weight distribution is relatively narrow and simple for process, and water-reducing rate is high, slump retaining is good, can obviously improve concrete flowability, and low to mud sensitivity.Higher construction requirement can be met, had a extensive future.
Description
Technical field
The invention belongs to technical field of concrete additives, more particularly to a kind of preparation of novel high-efficiency water-reducing agent of poly-carboxylic acid
Method.
Background technology
Traditional polycarboxylate water-reducer be it is a kind of by the unsaturated monomer containing carboxyl with contain other functional groups
Unsaturated monomer be copolymerized by Raolical polymerizable made of polymer, be a kind of random copolymer, molecular structure is in
Comb shape has the characteristics that water-reducing rate compared with high, slump ongoing change is small and different types of well adapting to property of cement.
Water-reducing agent is a kind of important concrete admixture, is one of the staple product of building material pillar industry.Diminishing
Agent not only substantially increases the mechanical property of high-strength concrete, and provides easy-to-use construction technology.Rely on diminishing
The development and application of agent, various concrete materials and and modernization construction technology rapidly developed.
With the high speed development of building trade, the polycarboxylate water-reducer of traditional structure also gradually expose it is a series of not
Foot, is mainly shown as：（1）Fresh concrete require water-reducing agent have higher water-reducing rate, and comb shape poly carboxylic acid series water reducer by
Its requirement cannot gradually be met；（2）Comb shape polycarboxylate water-reducer is more sensitive to clay, and anti-mud is poor.
Patent CN103012693A（Publication date 2013.04.03）Report a kind of preparation side of high-efficiency water-reducing agent of poly-carboxylic acid
Method.This method prepares water-reducing agent with acrylic acid Raolical polymerizable.The invention still falls within traditional comb shaped structure polycarboxylic acids
Product does not have some unique advantages of star structure polymer on structural level, can not inherently realize polycarboxylic acids
Leap in Series Dispersant structure and breakthrough.
Patent CN102887979A（Publication date 2013.01.23）Report a kind of preparation side of star polycarboxylate water-reducer
Method.This method first prepares the polymerizable active end of star by esterification, then passes through Raolical polymerizable with unsaturated monomer
Prepare product.Although this method has the characteristics that the polycarboxylic acids that preparation method is simple and easy to control, at low cost, pollution-free, obtains
Water-reducing agent molecular structure is simultaneously indefinite, can not fundamentally disclose the relationship of the molecular structure and its performance of polycarboxylate water-reducer.
Patent CN106146859A（Publication date 2016.11.23）Report four arm high efficiency water reducing agents of one kind and its preparation side
Method.This method polymerize step by step using three step atom transition free radical polymerization reaction steps to be obtained the double blocks of AB types of four arm configurations and is total to
Polymers.Because the initiation system used in ATRP polymerization is sensitive to polar monomer, so acrylic monomer cannot be used for ATRP polymerization.
And the synthetic route in patent is to carry out ATRP polymerization using tert-butyl acrylate, it is super to obtain carboxylic polycarboxylic acids for then hydrolysis
Plasticiser, this increases process costs to a certain extent.
Patent CN105669912A（Publication date 2016.06.15）It reports and a kind of preparing star-like poly carboxylic acid series water reducer
Method.Under the action of catalyst using the organic molecule and carboxylic chain-transferring agent that will contain polyol hydroxyl, esterification is anti-for this method
It should obtain star-like RAFT agent；Then by star-like RAFT agent, unsaturated acids minor comonomer, unsaturated polymeric monomer and
Initiator obtains a kind of star-like polycarboxylate water-reducer.This method prepares star-like RAFT agent by esterification, and esterification is anti-
Reversible reaction should be belonged to, reaction is not thorough under normal circumstances, and has the generation of by-product water, destroys reaction system.
RAFT polymerizations are the new polymerizations of discovered in recent years, and what is prepared as ATRP polymerization is all that structure is clear
Block polymer, but its cause system it is insensitive to polar monomer, the polymerization of polar monomer can be caused.And added due to reversible
At-fracture chain transfer polymerization (RAFT) molecular structure designability it is strong, pass through the optimum organization control of different function structural unit
The high performance of poly carboxylic acid series water reducer may be implemented in backbone polymerization degree processed, side chain lengths, functional group's type, and being prepared has
High performance polycarboxylate water-reducer, to solve the problems, such as site operation.The present invention changes the preparation method of star-like chain-transferring agent
Into chain-transferring agent synthetic method is simple and efficient, and reversible reaction is not present, yield is high, reduces the manufacturing cost of water-reducing agent.And
We design space steric effect of the polycarboxylate water-reducer with more high energy efficiency of four arm configurations of synthesis, which not only has
There are the various performances of traditional comb polymer, while the also various special natures with star-type polymer, there is prodigious application
Potentiality.
Invention content
In view of the deficiencies of the prior art, the problem to be solved in the present invention is to provide a kind of four arm block polycarboxylate water-reducer preparation sides
Method.
Four arm block polycarboxylate water-reducers described in this patent, it is characterised in that：The water-reducing agent is general structure shown in formula
Compound：
；
Wherein：
；
R1=CH3Or H.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of four arms block polycarboxylate water-reducer, which is characterized in that this method has following processing step：
（1）The preparation of four arm chain-transferring agents：In the reactor, tetrahydroxylic alcohol is added, stirs to it and is dissolved in tetrahydrofuran, then again
Alkali is added, 10-20 h are reacted after being heated to 30-50 DEG C so that is cooled to room temperature after alkali reaction thoroughly；CS is added2After heat up
2-5 h are reacted after to 30-50 DEG C, cylite is then added dropwise, and rate of addition is 5-20 drops/min, and room temperature is in reaction 18-25 h.Instead
Reaction solution is precipitated in water to get four arm chain-transferring agents after answering；
（2）The preparation of four arm block polymers I：In the reactor by four arm chain-transferring agents, initiator and prenol polyoxy second
Alkene ether is dissolved in tetrahydrofuran mixing, after deoxygenation in a nitrogen atmosphere, 50-64 DEG C of reaction 10-24 h.It after reaction will reaction
Liquid is precipitated in petroleum ether to get four arm block polymers I；
（3）The preparation of four arm block polycarboxylate water-reducers：In the reactor by step polymer I, initiator, propylene refined in advance
Acid, after deoxygenation in a nitrogen atmosphere, 50-64 DEG C of reaction 6-14 h.Reaction solution is precipitated in petroleum ether after reaction to get
Four arm block polycarboxylate water-reducers.
Step（1）The tetrahydroxylic alcohol, alkali, CS2, cylite molar ratio be 1：4-6：2-7：3-9；The tetrahydroxylic alcohol is
Pentaerythrite；The alkali is KOH；
Step（2）The four arm chain-transferring agents, initiator, prenol polyoxyethylene ether molar ratio be 1：0.2-5：
10-300；
Step（3）The four arm block polymers I, initiator, acrylic acid molar ratio be 1：0.2-5：19-650；
Initiator is azodiisobutyronitrile, and the molecular weight of prenol polyoxyethylene ether is 600-2400.
Beneficial effects of the present invention：
（1）The present invention prepares the polycarboxylic acids diminishing with four arm block structures using reversible addion-fragmentation chain transfer polymerization technique
Agent.Protic monomer or acid, alkaline monomer can smoothly polymerize, and the polymerization for being advantageous to the vinyl monomer containing specific functional groups is anti-
It answers, and molecule designability is strong, polymer is diblock copolymer, and molecular structure is four arm configurations and molecular structure and divides
Son amount is clear, controllable, can fundamentally disclose the relationship of the molecular structure and its performance of polycarboxylate water-reducer.
（2）The present invention uses the method for four arm chain-transferring agents of synthesis relative to the chain-transferring agent obtained by esterification, tool
Have that reaction condition is simply controllable, and do not generate by-product, four obtained arm chain-transferring agent yields are high, and single step reaction can be made
's.
（3）Four arm block polycarboxylate water-reducers can be effectively increased adsorption capacity of the diminishing agent molecule to cement granules, simultaneously
With stronger affinity, dispersibility is stronger, improves the mobility of concrete.
Specific implementation mode
More to be stated in detail to specific implementation method of the present invention below, it is therefore intended that illustrate the present invention design and
Feature, it is not intended to limit the scope of the present invention.Any equivalent change or modification in accordance with the spirit of the invention,
It should be covered by the protection scope of the present invention.
Embodiment 1
（1）The preparation of four arm chain-transferring agents：In the reactor, 5 mol pentaerythrites are added, 30 mL THF are stirred to its dissolving,
Then 20 mol KOH are added, 12 h are reacted after being heated to 40 DEG C so that are cooled to room temperature after KOH reactions thoroughly；It is added
20 mol CS2After be warming up to 40 DEG C after react 2 h, be then added dropwise 26 mol cylites, rate of addition is 8 drops/min, and room temperature exists
React 24 h.Reaction solution is precipitated in water after reaction to get four arm chain-transferring agents.
（2）The preparation of four arm block polymers I：The four arm chain-transferring agents 1 that step (1) obtains are added in the reactor
Mol, 0.4 mol of initiator and prenol polyoxyethylene ether（Molecular weight is 1200）30 mol are dissolved in 50 ml tetrahydrofurans
(DMF) mixing in, after deoxygenation in a nitrogen atmosphere, 55 DEG C of 20 h of reaction.Reaction solution is precipitated in petroleum ether after reaction,
Up to four arm block polymers I.
（3）The preparation of four arm block polycarboxylate water-reducers：In the reactor be added step 1. obtain I 1 mol of polymer,
0.4 mol of AIBN, 90 mol of acrylic acid refined in advance, after deoxygenation in a nitrogen atmosphere, 50 DEG C of 12 h of reaction.Reaction terminates
Reaction solution is precipitated in petroleum ether afterwards to get four arm block polycarboxylate water-reducers.Labeled as PC1.
Embodiment 2
The present embodiment prepares four arm block polycarboxylate water-reducers (being labeled as PC2) according to 1 identical mode of embodiment, and difference only exists
In step（1）Middle CS2Amount be 37 mol.
Embodiment 3
The present embodiment prepares four arm block polycarboxylate water-reducers (being labeled as PC3) according to 1 identical mode of embodiment, and difference only exists
In step（2）The middle reaction time is 12 h.
Embodiment 4
The present embodiment prepares four arm block polycarboxylate water-reducers (being labeled as PC4) according to 1 identical mode of embodiment, and difference only exists
In step（2）The molecular weight of middle prenol polyoxyethylene ether is 2400.
Comparative example 1
62.4 g TPEG2400 are added into reactor, 90.2 g water are opened and stir and be warming up to 60 DEG C, wait for that polymeric monomer is complete
After dissolving, 1.75 g, 30% hydrogenperoxide steam generators are added, while it is water-soluble that a concentration of 80% acrylic acid of 5.62 g is added dropwise into reactor
The solution of liquid and 0.12 g Vc and 0.234 g thioacetic acid and 15.2 g water composition；3 h are added dropwise in the former, and the latter is added dropwise 3.5
H, the reaction was continued 1 h after band is added dropwise to complete wait adjusting pH to 6-7 at the end of reacting, polycarboxylate water-reducer are made.Labeled as PC5.
Comparative example 2
Commercially available polycarboxylate water-reducer.Labeled as PC6.
Performance test
1. flowing degree of net paste of cement
Measurement results of the 1 polycarboxylate water-reducer PC1-PC6 of table to flowing degree of net paste of cement
From table 1 it follows that in the case of the four arm high performance water reducing agent of polyocarboxy acid and same acids ether ratio of the method for the present invention synthesis
Traditional comb shape polycarboxylate water-reducer and commercially available comb shape polycarboxylate water-reducer compare, show good dispersibility and
Function of slump protection,
2. water-reducing agent hinders mud ability
Experiment is measured reaches identical fluidity in clay presence（260±5 mm）When water-reducing agent volume, and with not
It is compared when mixing clay.Select the water-reducing agent of newly synthesized traditional comb shaped structure and existing commercially available traditional comb shape polycarboxylic-acid
Water-reducing agent（Comparative example）It is as a comparison sample.
Non-clay test：300 g cement, 87 g water, adjusting the dosage of water-reducing agent makes paste flowing degree be reached in 10 min
To 260 ± 5 mm;1% clay is tested：297 g cement, 87 g water, 3 g clays, adjusting the dosage of water-reducing agent makes paste flowing degree
Reach 260 ± 5 mm after 10 min.
Test result is shown in Table 2.
2 water-reducing agent of table hinders mud ability Contrast on effect table
From Table 2, it can be seen that the four arm high performance water reducing agent of polyocarboxy acid confrontation mud of the method for the present invention synthesis has obvious effect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not limited by embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, replacement, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of four arms block polycarboxylate water-reducer, which is characterized in that this method has following processing step：
（1）The preparation of four arm chain-transferring agents：In the reactor, tetrahydroxylic alcohol is added, stirs to it and is dissolved in tetrahydrofuran, then again
Alkali is added, 10-20 h are reacted after being heated to 30-50 DEG C so that is cooled to room temperature after alkali reaction thoroughly；CS is added2After heat up
2-5 h are reacted after to 30-50 DEG C, cylite is then added dropwise, and rate of addition is 5-20 drops/min, and room temperature is in reaction 18-25 h；Instead
Reaction solution is precipitated in water to get four arm chain-transferring agents after answering；
（2）The preparation of four arm block polymers I：In the reactor by four arm chain-transferring agents, initiator and prenol polyoxy second
Alkene ether is dissolved in tetrahydrofuran mixing, after deoxygenation in a nitrogen atmosphere, 50-64 DEG C of reaction 10-24 h；It after reaction will reaction
Liquid is precipitated in petroleum ether to get four arm block polymers I；
（3）The preparation of four arm block polycarboxylate water-reducers：In the reactor by step polymer I, initiator, propylene refined in advance
Acid, after deoxygenation in a nitrogen atmosphere, 50-64 DEG C of reaction 6-14 h；Reaction solution is precipitated in petroleum ether after reaction to get
Four arm block polycarboxylate water-reducers.
2. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that step
（1）The tetrahydroxylic alcohol, alkali, CS2, cylite are 1 in molar ratio：4-6：2-7：3-9；The tetrahydroxylic alcohol is pentaerythrite；Institute
It is KOH to state alkali.
3. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that step
（2）The four arm chain-transferring agents, initiator, prenol polyoxyethylene ether molar ratio be 1：0.2-5：10-300.
4. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that step
（3）The four arms block polymer I, initiator, acrylic acid molar ratio be 1：0.2-5：19-650.
5. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that initiator
Molecular weight for azodiisobutyronitrile, prenol polyoxyethylene ether is 600-2400.
6. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that step
（1）The four arms chain-transferring agent reaction process is as follows：
。
7. a kind of preparation method of four arms block polycarboxylate water-reducer according to claim 1, which is characterized in that its feature
It is that structural formula is as follows：
；
Wherein：
；
R1=CH3Or H.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467654A (en) * | 2018-11-09 | 2019-03-15 | 安徽森普新型材料发展有限公司 | Four arm block polycarboxylate water-reducers of one kind and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN106749958A (en) * | 2016-11-21 | 2017-05-31 | 山东交通学院 | A kind of starblock polycarboxylate water-reducer and preparation method thereof |
-
2018
- 2018-04-24 CN CN201810369734.5A patent/CN108440720A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN106749958A (en) * | 2016-11-21 | 2017-05-31 | 山东交通学院 | A kind of starblock polycarboxylate water-reducer and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| DANIEL BOSCHMANN ET AL: "Poly(vinyl acetate) and Poly(vinyl propionate) Star Polymers via Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization", 《POLYMER BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467654A (en) * | 2018-11-09 | 2019-03-15 | 安徽森普新型材料发展有限公司 | Four arm block polycarboxylate water-reducers of one kind and preparation method thereof |
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