CN106279666B - A kind of polyhydroxy PEG polymeric monomer and preparation method thereof - Google Patents
A kind of polyhydroxy PEG polymeric monomer and preparation method thereof Download PDFInfo
- Publication number
- CN106279666B CN106279666B CN201610742389.6A CN201610742389A CN106279666B CN 106279666 B CN106279666 B CN 106279666B CN 201610742389 A CN201610742389 A CN 201610742389A CN 106279666 B CN106279666 B CN 106279666B
- Authority
- CN
- China
- Prior art keywords
- polyhydroxy
- water
- concrete
- added dropwise
- polymeric monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3318—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group heterocyclic
-
- 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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 present invention provides a kind of polyhydroxy PEG polymeric monomers, the water-retaining property shrinkage type polycarboxylate water-reducer synthesized by polyhydroxy PEG polymeric monomer of the present invention, due to the micro- cross-linked structure formed between the hydrogen bond and hydrogen bond between the hydrophily of hydroxyl, hydroxyl and between hydrone, increase the viscosity of pore aqueous solution and cement slurry with can dramatically, moisture evaporation rate is reduced, there is superior water-retaining property.Concrete reducing test result shows it with preferable Reduce shrinkage effect, compared with the common ethers polycarboxylic acid water reducing agent of our company, the 28d decrement of concrete is than significantly reducing, when for concrete, the workability of concrete and intensity are not influenced, sexual valence is relatively high.The present invention provides a kind of preparation methods of polyhydroxy PEG polymeric monomer, and this method is simple, and raw material is easy to get and low in cost, and cost performance is high, polymeric monomer (according to actual needs, with different number of) can be made with multiple hydroxyls by this method.
Description
Technical field
The present invention relates to a kind of PEG polymeric monomers, and in particular to a kind of polyhydroxy PEG polymeric monomer and preparation method thereof.
Background technique
Appearance, development and its extensive use of concrete admixture impart the new vitality of concrete, water-reducing agent incorporation
In fresh concrete, the flocculent structure of cement granules can be destroyed, plays the role of disperse cement particles and hydrated cementitious particle,
To release the Free water in flocculent structure, increase the mobility of concrete mix.Polycarboxylic acids (PCEs) water-reducing agent belongs to
Anionic surfactant mixes in cement slurry, is adsorbed on the cement particle surface with cation, and be dissociated into hydrophilic
With the organic anionic groups of oleophilic function.
PCEs water-reducing agent molecular skeleton is made of main chain and more branch.Contain more active group on main chain, and
Polarity is stronger, and by these active groups, main chain " can be anchored " on cement particle surface, and side chain has hydrophily, can
To stretch in the liquid phase, to form biggish three-dimensional adsorption structure in cement particle surface, space steric effect is generated, thus
Cement granules are made to disperse and stablize.Carboxylic acid ion makes the negative electrical charge on cement granules band generate electrostatic row between cement granules
Reprimand effect, and disperse cement granules, increase contact of the cement granules with water, makes the abundant aquation of cement.In disperse cement particles
During, the Free water that condensate is included is released, workability is improved, reduces and mix water.
The cracking of concrete is a big technical problem of concrete application, mixes economization agent, reduces concrete shrinkage, is wherein
One of solution controls and is reduced with economization agent the drying shrinkage of concrete, the plastic shrinkage of early stage and own vol and shrinks.1982
Year Japanese Nissan cement company and chemical company, Sanyo take the lead in developing economization agent, and 1985, U.S. Goto et al. achieved the
One economization agent patent.
Concrete shrinkage is the phenomenon that concrete generates volume-diminished after pouring and hardening.If contraction is excessive, produced
Raw shrinkage stress can make concrete generate cracking, can not only reduce structural strength, crack is also that air and water enter concrete
One channel is provided, concrete is made to be easy to happen graphitic corrosion, steel bar corrosion, in cold district it also occur that Frozen-thawed cycled, this
The durability for all greatly reducing concrete a bit, shortens the service life of building.Thus, shrinkage cracking is puzzlement concrete
One problem of engineering.
The approach for usually solving the problems, such as concrete shrinkage is incorporation swelling agent, and main principle is by swelling agent in coagulation
A possibility that expansile hydrated product is generated in soil to compensate and shrink, reduce concrete cracking.But use swelling agent special
Do not need concrete in the maintenance for having water in early days, condition is harsh, and there is serious cement adaptability and delay calcium alum in itself
In addition, having difficulties on adjusting its additive amount if volume is very few, effect is not achieved, if volume mistake in the problems such as stone generates
Greatly, excessive part may lead to expanded crack due to expansion, thus be had to final result using swelling agent certain
It is uncertain.
Another is to mix fiber, but adding of fiber can only be the anti-crack ability for improving concrete, not can be reduced mixed
The contraction of soil is coagulated, while fiber price is high, exists and concrete consistency problem.Also its popularization is greatly limited.
Last century the eighties, Japan and the U.S. conduct a research for problem, and that develops the first generation can reduce concrete
The new additive of contraction, referred to as economization agent, it is a kind of based on the concrete admixture for reducing aqueous solution surface tension.China is nine
The ten's ends just had scientific research institutions to start developmental research to economization agent successively.
The decrement mechanism of economization agent is that the surface tension of water is reduced from the microstructure in concrete pore, reduces water
Divide the convergent force of evaporation process, to reduce the contraction of concrete, achievees the purpose that reduce distress in concrete.
Concrete shrinkage mechanism:
The contraction of concrete can be divided into chemical shrinkage, plastic shrinkage, temperature shrinkage, self-constriction, dry contraction and carbonization and receive
Contract six big types, wherein the most universal with dry contraction, mechanism is more complicated, and existing theory mainly has capillary tensiometry
It says, adsorption theory, dismantle stress theory etc., most convincing with capillary tension theory among these, which thinks,
When ambient humidity is less than 100%, the water surface inside capillary declines and forms meniscus, according to Laplas formula, in the table of water
Under the tension force effect of face, the additonal pressure that is generated in capillary: △ P=2 σ COS θ/R
In formula, △ P is the additonal pressure being bent under the page, and σ is the surface tension of water, and θ is water concave meniscus and capillary hole wall
Contact angle, R is capillary radius.
In the case where σ is constant, capillary is thinner, and the radius of curvature of meniscus is smaller, and the capillary pressure of generation is bigger；
When R is constant, P is directly proportional to the surface tension σ of water.
With scattering and disappearing for pore water, R becomes smaller, and △ P increases, and capillary tension acts on hole wall, generates pulling force, in turn
Lead to concrete shrinkage macroscopically.
In formula, P is the additonal pressure under curved liquid surface, and σ is the surface tension of water, and R is water concave meniscus and capillary radius.
In the case where σ is constant, capillary is thinner, and the radius of curvature of meniscus is smaller, and the capillary pressure of generation is bigger,
When R is constant, P is directly proportional to the surface tension of water.With the evaporation of pore water, R becomes smaller, and P increases, capillary tension effect
On hole wall, pulling force is generated, and then lead to concrete shrinkage macroscopically.
The decrement principle of economization agent:
It is analyzed according to contractile mechanism above, the dry of concrete is shunk, and is due to the meniscus that water is formed in pore
And caused by the additonal pressure △ P generated, and determine △ P is three variables: σ, θ and R, R is by component materials of concrete
What ingredient and match ratio determined, σ and θ are related with liquid of the infiltration in pore, and the surface tension of pure water is 72N/m, very
Height, if it can be reduced to 35N/m, corresponding stress is reduced by half, and economization agent is exactly therefore to be born.It is this
The surface tension of water can be greatly lowered in a kind of substance of sample in the environment of highly basic, on the other hand, be made of water and economization agent
Solution viscosity increases, so that contact angle θ increases, to also further decrease the shrinkage stress of concrete, reduces opening for concrete
It splits.
Japan and the U.S. are more for the research of economization agent for concrete, from the point of view of its research and development distance, one-component before this
Small molecule compound, due to readily volatilized, and then develop to macromolecular compound, while multiple groups are also developed to by one-component
The compound product of compound divided, can not only reduce the cracking shrinkage value of concrete in this way, and also overcome single group in the past
Divide many disadvantages of product, the long-term Reduce shrinkage effect such as one-component economization agent is not ideal enough, higher cost and concrete strength
Easily reduce etc., another rule of development is exactly gradually to be developed from the product of simple function to multifunctional product, such as have simultaneously
Decrement and diminishing function.
The country starts late to the research and development of economization agent, and general economization agent price is again relatively high, therefore pushes away so far there has been no more
Wide application.But constantly increase with economical, the durability and quality appearance of marine engineering concrete and infrastructure building object
It is required that can step up, the problem of concrete cracking, can also be incrementally increased, and solving this problem is still concrete research scholar
A challenge.
Economization agent can substantially reduce concrete early-age shrinkage, main function mechanism be reduce pore water surface tension and
The shrinkage stress generated when pore dehydration is reduced, is on the other hand the viscosity for increasing concrete pore water, enhancing water is mixed
Suction-operated in solidifying soil colloid and the shrinkage value for reducing concrete.The main component of economization agent is polyethers or polyalcohols and its derivative
Object, such as glycerine, POLYPROPYLENE GLYCOL, the polycarboxylic acids containing ethylene glycol.
Drying shrinkage can make concrete structure or component generate cracking, shrink as caused by many reasons, but moisture loss is main
Want reason:
First stage: the water in pore is lost；
Second stage: C-H-S surface adsorption water is lost；
Phase III: the water in C-H-S structure is lost；
When the water in these apertures loses, hole wall is furthered and makes volume contraction by the surface tension that water is remained in hole.
Though the use of these economization agents reduces the contraction of concrete to a certain extent, engineering cost increases greatly, and
Synthesis technology is complicated.
Summary of the invention
A kind of polyhydroxy PEG polymeric monomer is provided it is an object of the invention to overcome the shortcomings of the prior art place
And preparation method thereof, the water-retaining property shrinkage type polycarboxylate water-reducer synthesized by polyhydroxy PEG polymeric monomer of the present invention, due in side chain
In introduce a large amount of hydroxyl group, form hydrogen bond between hydroxyl and between hydrone, at the same itself also due to form hydrogen bond and
Micro- cross-linked structure is formed, solution viscosity is increased, improves water-retaining property, it is main to play decrement work by improving its water-retaining property
With being water-retaining property shrinkage type polycarboxylate water-reducer, decrement principle is that economization agent is by introducing the hydrogen bond that is formed of polyhydroxy
With micro- cross-linked structure, increase the viscosity of concrete pore water, enhances suction-operated of the water in concrete colloid and reduce mixed
Coagulate the shrinkage value of soil.
To achieve the above object, the technical solution taken: a kind of polyhydroxy PEG polymeric monomer, the big list of polyhydroxy PEG
Body be reacted as formula (I) compound represented with containing epoxy and hydroxyl bifunctional compound prepared by, formula (I) institute
The structural formula of the compound shown is as follows:
The wherein integer that m is 0~30；
R is H2C=CH-CH2-、
And H2C=CH-O-CH2CH2CH2CH2One of.
Preferably, the integer that the m is 1~30.
Preferably, described to be containing epoxy and hydroxyl bifunctional compoundIn
It is at least one.
The present invention provides the preparation method of polyhydroxy PEG polymeric monomer described above, the preparation method includes following step
It is rapid:
(1) enol and catalyst are mixed in a nitrogen atmosphere, is warming up to 70~115 DEG C, epoxy second is then slowly added dropwise
Alkane, by reaction temperature control within the scope of 70~130 DEG C, reaction pressure is controlled in 0.2~0.6MPa, when ethylene oxide drips
Bi Hou controls reaction temperature at 80~120 DEG C, and the reaction was continued 0.5~5h obtains intermediate product；
(2) temperature for the intermediate product that step (1) obtains is reduced to 80 DEG C, be then slowly added dropwise containing epoxy and hydroxyl
Bifunctional compound, after being added dropwise, the reaction was continued 4~6h obtains the polyhydroxy PEG polymeric monomer.
Preferably, the molar ratio of enol and ethylene oxide is 1:0~1:80 in the step (1).
It is highly preferred that the molar ratio of enol and ethylene oxide is 1:1~1:80 in the step (1).
Preferably, enol is propenyl, allyl alcohol, prenol, isobutene alcohol and 4- ethylene in the step (1)
At least one of oxygroup butanol.
Preferably, catalyst is one of sodium hydroxide, potassium hydroxide, potassium carbonate in the step (1).
Preferably, in the step (1) dosage of catalyst be the sum of weight of the enol and ethylene oxide 0.1-
0.5%.
Preferably, ethylene oxide is added dropwise using Subtraction method in the step (1).
Preferably, it is containing epoxy and hydroxyl bifunctional compound in the step (2) At least one of.
Preferably, intermediate product and the molar ratio containing epoxy and hydroxyl bifunctional compound are small in the step (2)
In equal to 1.
Preferably, it is 1.5~2h that the time containing epoxy and hydroxyl bifunctional compound is added dropwise in the step (2).
Shown in the structural formula such as formula (I) for the intermediate product that reaction obtains in above-mentioned steps (1),
The wherein integer that m is 0~30；
R is H2C=CH-CH2-、And H2C=
CH-O-CH2CH2CH2CH2One of.
Reaction equation in above-mentioned steps (1) is as follows:
The molar ratio of intermediate product and glycidol in above-mentioned steps (2) are as follows: 1:(x-1), x is the sealing end of surface-active macromonomer
Hydroxyl value works as x=2, reacts resulting product structure formula as shown in Formula II；Work as x=4, reacts resulting product structure formula such as formula
III；Work as x=8, react resulting product structure formula such as formula IV ... etc..
The structural formula of formula (II) compound represented is as follows:
Corresponding reaction equation is as follows:
The structural formula of formula (III) compound represented is as follows:
Corresponding reaction equation is as follows:
The structural formula of formula (IV) compound represented is as follows:
Corresponding reaction equation is as follows:
Economization agent is a kind of nonionic surfactant, can reduce the surface tension of water, and the concrete for mixing economization agent is received
Compression deformation is reduced, and improves the anti-crack ability of concrete, underbead crack is relatively fewer, is beneficial to the raising of concrete durability.
Substance as economization agent for concrete should have the property that 1, liquid-vapor interface tension is greatly reduced；2, increase solution
Viscosity, delay the volatilization 3 of hydrone, anomalous effects do not generated to hydrated cementitious process；4, high temperature low volatility；5, low entraining
Property.Polycarboxylate water-reducer can reduce the surface tension of liquid, therefore have the performance of certain reduction Shrinkage Cracking of Concrete,
But still it is not able to satisfy engine request.The water-retaining property shrinkage type polycarboxylate water-reducer synthesized by polyhydroxy PEG polymeric monomer of the present invention, by
Largely reduce group hydroxy in introducing in the molecule, forms hydrogen bond between hydroxyl or between hydroxyl and hydrone, it is micro- to form hydrogen bond
Cross-linked structure changes HLB value, increased hydrophilicity compared with common polycarboxylate water-reducer, and lipophilicity slightly declines, incrementss
Solution viscosity delays the evaporation rate of hydrone, significantly improves the water-retaining property of solution, receives to reach and significantly reduce concrete
The purpose of contracting.Concrete reducing test result shows its common ethers polycarboxylic acids with preferable Reduce shrinkage effect, with our company
Water-reducing agent is compared, and the 28d shrinkage ratio of concrete significantly reduces, and does not influence on the workability of concrete and intensity, sexual valence
It is relatively high.
The water conservation water-retaining property shrinkage type polycarboxylate water-reducer synthesized by polyhydroxy PEG polymeric monomer of the present invention, in molecular side chain
Middle to introduce a large amount of hydroxyl, hydroxyl hydrophilic is good, and forms hydrogen bond with hydrone, itself forms micro- crosslinking due to forming hydrogen bond
Structure improves hydrophily, significantly improves water-retaining property, and main function mechanism is to reduce coagulation and significantly improving water-retaining property
The contraction of soil and cracking.
The surface-active macromonomer with polyhydroxy decrement group that the present invention synthesizes, can be according to the need of actual product performance
It wants, controls the additional proportion of reactant glycidol and its derivative and make surface-active macromonomer that there are 2,4,8......n hydroxyl
Base.
The beneficial effects of the present invention are: the present invention provides a kind of polyhydroxy PEG polymeric monomers, by polyhydroxy of the present invention
The water-retaining property shrinkage type polycarboxylate water-reducer of PEG polymeric monomer synthesis, due to forming hydrogen bond between hydroxyl or between hydrone, parent
Aqueous increase, lipophilicity are declined slightly, and are increased the viscosity of concrete capillary hole solution and cement slurry, are improved water-retaining property,
Moisture evaporation rate is delayed, it is that water-retaining property subtracts that the water-retaining property by improving solution, which achievees the purpose that reduce concrete shrinkage,
Miniature polycarboxylate water-reducer.Concrete reducing test result shows its common ether with preferable Reduce shrinkage effect, with our company
Class polycarboxylate water-reducer is compared, and the 28d shrinkage ratio of concrete significantly reduces, when being used for concrete, to the workability of concrete
It is not influenced with intensity, sexual valence is relatively high.The present invention provides a kind of preparation method of polyhydroxy PEG polymeric monomer, this method letters
Single, raw material is easy to get and low in cost, and cost performance is high, polymeric monomer can be made to have multiple hydroxyls by this method.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the preparation method of polyhydroxy PEG polymeric monomer of the present invention, comprising the following steps:
(1) in closed autoclave, with air 2 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol propylene is injected
Pure and mild 0.2g catalyst n aOH, is warming up to 70-85 DEG C for reaction kettle, starts that 1mol ethylene oxide is slowly added dropwise, makes reaction temperature
Control is within the scope of 70 DEG C, and pressure control is added dropwise required amount of ethylene oxide with Subtraction method control, works as epoxy in 0.2MPa in kettle
After ethane is added dropwise, temperature is controlled at 80 DEG C, the reaction was continued 5h obtains the intermediate products of required molecular weight.
(2) 80 DEG C of temperature are kept, the glycidol that 1mol is slowly added dropwise is started, is added dropwise and controls in 1.5h, after being added dropwise,
The reaction was continued 4h, cooling, blowing is to get the polyhydroxy PEG polymeric monomer.
Embodiment 2
A kind of embodiment of the preparation method of polyhydroxy PEG polymeric monomer of the present invention, comprising the following steps:
(1) in closed autoclave, with air 3 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol isoamyl is injected
Reaction kettle is warming up to 110 DEG C by the catalyst potassium hydroxide of enol and 0.5g, starts that 4mol ethylene oxide is slowly added dropwise, and is made anti-
Answer temperature control within the scope of 115 DEG C, ethylene oxide of the pressure control in 0.4MPa, needed for being added dropwise with Subtraction method control in kettle
Amount controls temperature at 110 DEG C, the reaction was continued 2h after ethylene oxide is added dropwise, and obtains the intermediate of required molecular weight and produces
Product.
(2) temperature is reduced to 80 DEG C, starts the glycidol that 2mol is slowly added dropwise, control is added dropwise in 2h, is added dropwise
Afterwards, the reaction was continued 5h, cooling, blowing is to get the polyhydroxy PEG polymeric monomer.
Embodiment 3
A kind of embodiment of the preparation method of polyhydroxy PEG polymeric monomer of the present invention, comprising the following steps:
(1) in closed autoclave, with air 2 times in high pure nitrogen repeatedly replacement reaction kettle, 1mol isobutyl is injected
Reaction kettle is warming up to 115 DEG C by the catalyst potassium carbonate of enol and 2g, starts that 80mol ethylene oxide is slowly added dropwise, and makes reaction temperature
Degree control is within the scope of 130 DEG C, and pressure control controls the amount of ethylene oxide needed for being added dropwise with Subtraction method in 0.6MPa in kettle, when
After ethylene oxide is added dropwise, temperature is controlled at 120 DEG C, the reaction was continued 0.5h obtains the intermediate products of required molecular weight.
(2) temperature is reduced to 80 DEG C, starts the glycidol that 3mol is slowly added dropwise, control is added dropwise in 2h, is added dropwise
Afterwards, the reaction was continued 6h, cooling, blowing is to get the polyhydroxy PEG polymeric monomer.
Embodiment 4
A kind of embodiment of the preparation method of polyhydroxy PEG polymeric monomer of the present invention, comprising the following steps:
1mol isobutene alcohol, 1g catalyst KOH are added in the reactor, and temperature is adjusted to 80 DEG C, starts slowly drop
Add the glycidol of 5mol, control is added dropwise in 2h, after being added dropwise, the reaction was continued 6h cools down big to get the polyhydroxy PEG
Monomer.
Embodiment 5
The synthesis of water-retaining property shrinkage type polycarboxylate water-reducer:
Equipped with blender, thermometer and reflux condensing tube 2000ml glass four-hole boiling flask in, be added 1500ml go from
Sub- water, 0.009mol thioacetic acid molecular weight regulator, polyhydroxy PEG polymeric monomer, 0.05mol made from 0.3mol embodiment 1
APEG, 2mol acrylic acid, 0.5mol maleic anhydride are warming up to 85 DEG C, and the aqueous solution containing potassium peroxydisulfate initiator is added dropwise, described
The mole of initiator is 0.0045mol, time for adding 2h, and after being added dropwise, insulation reaction 4h is cooled to 45 DEG C, uses matter
Measuring the NaOH solution that score is 30% and adjusting pH is 7.0 to get water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 6
The synthesis of water-retaining property shrinkage type polycarboxylate water-reducer:
In the glass four-hole boiling flask equipped with blender, thermometer and reflux condensing tube, deionized water, 0.12mol is added
Polyhydroxy PEG polymeric monomer made from isopropanol molecular weight regulator, 2mol embodiment 2,1molHPEG, 15mol methacrylic acid,
0.5mol itaconic acid is warming up to 90 DEG C, and the aqueous solution containing 0.12mol ammonium persulfate initiator is added dropwise, and the initiator rubs
Your amount is 0.12mol, time for adding 3h, and after being added dropwise, insulation reaction 2h is cooled to 50 DEG C, is 30% with mass fraction
NaOH solution to adjust pH be 6.0 to get water-retaining property shrinkage type polycarboxylate water-reducer.
Embodiment 7
The synthesis of water-retaining property shrinkage type polycarboxylate water-reducer:
In the glass four-hole boiling flask equipped with blender, thermometer and reflux condensing tube, deionized water, 0.045mol is added
Polyhydroxy PEG polymeric monomer made from isopropanol molecular weight regulator, 3mol embodiment 3,0.5molVPEG, 10mol acrylic acid,
0.1mol Sodium Allyl Sulfonate is warming up to 95 DEG C, and the aqueous solution containing 0.05mol potassium peroxydisulfate initiator, the initiation is added dropwise
The mole of agent is 0.05mol, time for adding 2h, and after being added dropwise, insulation reaction 3h is cooled to 45 DEG C, uses mass fraction
It is 6.5 to get water-retaining property shrinkage type polycarboxylate water-reducer for 30% NaOH solution adjusting pH.
Embodiment 8
The synthesis of water-retaining property shrinkage type polycarboxylate water-reducer:
In the glass four-hole boiling flask equipped with blender, thermometer and reflux condensing tube, deionized water, 0.03mol is added
Polyhydroxy PEG polymeric monomer, 0.5mol TPEG, 15mol the third made from sulfhydryl compound molecular weight regulator, 1.5mol embodiment 4
Olefin(e) acid, 0.3mol Sodium Allyl Sulfonate are warming up to 95 DEG C, and the aqueous solution containing 0.04mo ammonium persulfate initiator is added dropwise, described
The mole of initiator is 0.04mol, time for adding 2h, and after being added dropwise, insulation reaction 3h is cooled to 45 DEG C, uses quality
It is 6.5 to get water-retaining property shrinkage type polycarboxylate water-reducer that the NaOH solution that score is 30%, which adjusts pH,.
Embodiment 9: application of the water-retaining property shrinkage type polycarboxylate water-reducer of the present invention in concrete
Water-retaining property shrinkage type polycarboxylate water-reducer PCE-S and common polyether polycarboxylic acids prepared by 5-8 of the embodiment of the present invention
Water-reducing agent PCE prepares concrete, detection examination coagulation by additive is used as after the weight proportion mixing in table 2, by the match ratio of table 1
The performance of soil.
1 C30 concrete mix of table
| C (cement) | FA (flyash) | K (miberal powder) | SRiver sand(sand) | G1-2(stone) | W (water) | Additive |
| 220 parts by weight | 80 parts by weight | 50 parts by weight | 800 parts by weight | 1100 parts by weight | 168 parts by weight | 7.0 parts by weight (folding is solid) |
The performance test results of 2 concrete of table
The water-retaining property shrinkage type polycarboxylate water-reducer that the present invention synthesizes, can be with common polyether or polyester polycarboxylate water-reducer
It is used in compounding or is used alone, compared with common polyether or polyester polycarboxylate water-reducer, there is more superior Reduce shrinkage effect, subtract
Contracting mechanism mainly due to introducing polyhydroxy base side chain, increased hydrophilicity, shape between hydroxyl and water or hydroxyl in the molecular structure
At hydrogen bond, the viscosity of concrete pore water is increased, improves the water-retaining property of concrete mortar.
Test in table 2 the result shows that: compared with common polyether polycarboxylate water-reducer PCE, water-retaining property shrinkage type of the present invention is poly-
Carboxylic acid water reducer PCE-S has more superior water conservation and Reduce shrinkage effect, when being used in compounding, with the increase of PCE-S ratio,
28d shrinkage ratio significantly reduces.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (7)
1. a kind of polyhydroxy PEG polymeric monomer, which is characterized in that the polyhydroxy PEG polymeric monomer is by formula (I) compound represented
Prepared by reacting with containing epoxy and hydroxyl bifunctional compound, the structural formula of formula (I) compound represented is as follows:
Wherein m is 0；
R is One of；
It is described to be containing epoxy and hydroxyl bifunctional compoundAt least one of；
The polyhydroxy PEG polymeric monomer is prepared using following methods:
(1) enol and catalyst are mixed in a nitrogen atmosphere, is warming up to 70~115 DEG C, ethylene oxide is then slowly added dropwise, it will
Reaction temperature controls within the scope of 70~130 DEG C, and reaction pressure is controlled in 0.2~0.6MPa, after ethylene oxide is added dropwise,
Reaction temperature is controlled at 80~120 DEG C, the reaction was continued 0.5~5h obtains intermediate product；
(2) temperature for the intermediate product that step (1) obtains is reduced to 80 DEG C, be then slowly added dropwise containing epoxy and the double officials of hydroxyl
Compound can be rolled into a ball, after being added dropwise, the reaction was continued 4~6h obtains the polyhydroxy PEG polymeric monomer.
2. a kind of preparation method of polyhydroxy PEG polymeric monomer as described in claim 1, which is characterized in that the preparation method
The following steps are included:
(1) enol and catalyst are mixed in a nitrogen atmosphere, is warming up to 70~115 DEG C, ethylene oxide is then slowly added dropwise, it will
Reaction temperature controls within the scope of 70~130 DEG C, and reaction pressure is controlled in 0.2~0.6MPa, after ethylene oxide is added dropwise,
Reaction temperature is controlled at 80~120 DEG C, the reaction was continued 0.5~5h obtains intermediate product；
(2) temperature for the intermediate product that step (1) obtains is reduced to 80 DEG C, be then slowly added dropwise containing epoxy and the double officials of hydroxyl
Compound can be rolled into a ball, after being added dropwise, the reaction was continued 4~6h obtains the polyhydroxy PEG polymeric monomer.
3. preparation method according to claim 2, which is characterized in that enol is propenyl, iso-amylene in the step (1)
At least one of alcohol, isobutene alcohol and 4- ethyleneoxy butanol.
4. preparation method according to claim 2, which is characterized in that catalyst is sodium hydroxide, hydrogen in the step (1)
One of potassium oxide, potassium carbonate, the dosage of the catalyst are the 0.1-0.5% of the enol weight.
5. preparation method according to claim 2, which is characterized in that contain epoxy and the double officials of hydroxyl in the step (1)
Compound, which can be rolled into a ball, isAt least one of.
6. preparation method according to claim 2, which is characterized in that in the step (1) enol with contain epoxy and hydroxyl
The molar ratio of base bifunctional compound is less than or equal to 1.
7. preparation method according to claim 2, which is characterized in that be added dropwise in the step (1) and contain epoxy and hydroxyl
The time of bifunctional compound is 1.5~2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742389.6A CN106279666B (en) | 2016-08-27 | 2016-08-27 | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610742389.6A CN106279666B (en) | 2016-08-27 | 2016-08-27 | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106279666A CN106279666A (en) | 2017-01-04 |
| CN106279666B true CN106279666B (en) | 2019-08-23 |
Family
ID=57677906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610742389.6A Active CN106279666B (en) | 2016-08-27 | 2016-08-27 | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106279666B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251273B (en) * | 2018-09-30 | 2022-04-26 | 山东理工大学 | Method for synthesizing polyhydroxy polybutadiene through butadiene-hydroxyl-rubber graft modification |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999507A (en) * | 2006-12-28 | 2007-07-18 | 樊福定 | Process of industrialized preparing allyl glycidol ether |
| CN102993432A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN103145648A (en) * | 2013-03-13 | 2013-06-12 | 安徽新远化工有限公司 | Synthetic method of allyl glycidyl ether |
-
2016
- 2016-08-27 CN CN201610742389.6A patent/CN106279666B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999507A (en) * | 2006-12-28 | 2007-07-18 | 樊福定 | Process of industrialized preparing allyl glycidol ether |
| CN102993432A (en) * | 2012-10-19 | 2013-03-27 | 江苏博特新材料有限公司 | Water reducer midbody, preparation method thereof and water reducer prepared by using preparation method |
| CN103145648A (en) * | 2013-03-13 | 2013-06-12 | 安徽新远化工有限公司 | Synthetic method of allyl glycidyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106279666A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106279566A (en) | A kind of water-retaining property shrinkage type polycarboxylate water-reducer and preparation method thereof | |
| CN106380550B (en) | A kind of surface tension adjustment shrinkage type polycarboxylate water-reducer and preparation method thereof | |
| JP6761443B2 (en) | Cement Additives, Cement Compositions, and Raw Materials for Cement Additives | |
| CN109399999B (en) | Green high-early-strength low-alkali liquid accelerator and preparation method thereof | |
| CN107867807A (en) | A kind of alkali-free quick-coagulant with reducing function and preparation method thereof | |
| CN104496253B (en) | Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer | |
| CN103965460A (en) | Polycarboxylate-type water reducing agent | |
| JP2007153652A (en) | Method of producing ae concrete and ae concrete | |
| CN112028580A (en) | Water seepage-proof grouting material for repairing sandstone grotto rock cracks and preparation method thereof | |
| JP2018140920A (en) | Additive for cement, and cement composition | |
| CN109704619B (en) | Sulfamate high-efficiency water reducing agent and preparation process thereof | |
| CN106279666B (en) | A kind of polyhydroxy PEG polymeric monomer and preparation method thereof | |
| CN103613307A (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN109021179B (en) | Phosphonic acid-based polymer, preparation method thereof and phosphate mother liquor | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| CN109320714A (en) | A kind of dedicated small molecule super plasticizer of middle low-slump concrete and preparation method thereof | |
| CN108003302A (en) | A kind of amidogen ether class ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof | |
| CN113831057A (en) | Concrete compaction reinforcing agent | |
| CN110963739B (en) | Aqueous concrete hydration temperature rise inhibitor and preparation method thereof | |
| CN106365534B (en) | Purposes of the water-retaining property shrinkage type polycarboxylate water-reducer in high performance concrete is prepared | |
| CN113929836B (en) | High-dispersion viscosity-reducing water reducer and preparation method thereof | |
| JP6739291B2 (en) | Cement additive and cement composition | |
| US5595596A (en) | Cement composition and its use for the preparation of lightweight concretes | |
| CN106380132B (en) | Surface tension adjusts purposes of the shrinkage type polycarboxylate water-reducer in high performance concrete is prepared | |
| CN112745055B (en) | Graphene suspension, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |