CN106397686A - Modified polycarboxylate superplasticizer master batch and preparation method thereof - Google Patents
Modified polycarboxylate superplasticizer master batch and preparation method thereof Download PDFInfo
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- CN106397686A CN106397686A CN201610863417.XA CN201610863417A CN106397686A CN 106397686 A CN106397686 A CN 106397686A CN 201610863417 A CN201610863417 A CN 201610863417A CN 106397686 A CN106397686 A CN 106397686A
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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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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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
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a modified polycarboxylate superplasticizer master batch. A mother liquor accounts for 40% by mass. The preparation method includes the specific steps of 1), adding polyether macromonomer and water in a specific ratio into a reaction kettle, stirring and making the polyether macromonomer dissolve; 2), adding a 10-30% small monomer solution into the reaction kettle, continuously stirring for 10 minutes and adding an oxidizing agent; 3), starting to dropwise add an initiator 5 minutes after the oxidizing agent is added; 4), starting to dropwise add the residual small monomer solution 0.5 hour after addition of the initiator, wherein the time for dropwise adding the residual small monomer solution is set as a hour(s), and the time for dropwise adding the initiator is (a+0.6) hour(s); 5), curing for 1-2 hours after dropwise adding, adding liquid caustic soda when the solution temperature in the kettle is lower than 30 DEG C, supplementing water, stirring evenly and standing for 10-15 hours. Acrylic autopolymer in the modified mother liquor and byproducts are reduced, molecular weight distribution is centralized, a water-reducing rate is increased while slump-retaining performance is improved, and the air-entraining content of the mother liquor can be lowered through reduction of macromonomer residues.
Description
Technical field
The invention belongs to cement additire field, it is related to a kind of preparation method of modified polycarboxylic acid diminishing masterbatch.
Background technology
In prior art, the addition of minor comonomer solution mostly is dripping method, takes minor comonomer to be once placed in bottom on a small quantity, such
Specifically arranged evenly, the polycarboxylate water-reducer molecule of method uncontrollable unsaturated carboxylic acid polymer main chain and polyether macromonomer side chain
Amount distribution is wider, and main chain is long cannot to be stretched, too short, cannot wrap up cement granules；And the overstocked excessively dilute distribution meeting of side chain
Offset or be not enough to provide sterically hindered effect lasting enough, this feature give polycarboxylate water-reducer performance uncertainty or
Randomness, but this is uncertain or randomness is also misunderstood into the adaptive raising of polycarboxylate water-reducer simultaneously.For regionality
Concrete floor material feature, designs polycarboxylate water-reducer molecule amount integrated distribution within the specific limits, can effectively improve polycarboxylic acids diminishing
The charge distribution state of agent and promote side chain to be evenly distributed so as to being easier to be adsorbed in cement particle surface and providing effectively empty
Between steric hindrance.
CN 104497223 A discloses a kind of polycarboxylate water-reducer, and provides one kind phosphorus-containing compound to make chain-transferring agent
The method that normal temperature synthesizes this water reducer.Water, unsaturated APEO, acrylic acid are added four-hole bottle, stirs to dissolving, put into
Phosphorus compound stirs, and adds after oxidizing agent solution stirs, drip thereto simultaneously the dropping liquid A that oneself configure with
Dropping liquid B, drips off in 4h, is incubated in 1 ~ 2h, plus alkali lye and pH is 6 ~ 7, moisturizing obtains the polycarboxylic acids diminishing containing solids 40%
Agent.Wherein dropping liquid A is acrylic acid, feature minor comonomer and water, and dropping liquid B is reducing agent and chain-transferring agent.
CN 105061692 A discloses a kind of polyether type of poly carboxylic acid and preparation method thereof, using activity relatively
Weak polymeric monomer part substitutes active preferable but expensive polymeric monomer, using the unsaturated acids part substitute valence of lower cost
The higher unsaturated acids of lattice, chooses suitable redox initiation system, by adjusting initiator, molecular weight regulator and being total to
The ratio of poly- monomer, is polymerized at 25 ~ 30 DEG C, and the prepared high-performance poly carboxylic acid that can be applied to low-grade concrete preparation subtracts
Aqua.
A kind of open polycarboxylate water-reducer with high water-reducing property of carboxylic acid integrated distribution of knowing clearly of CN 105037658 A
Preparation method, comprises the following steps：Add low-molecular-weight unsaturated carboxylic acid class compound, and add catalyst, react to obtain insatiable hunger
And carboxylic acid polyalcohol；Add unsaturated carboxylic acid polymer, unsaturated polyether monomer and unsaturated sulfonic acid salt or polyether monomer not
Saturated carboxylic acid ester, and add distilled water, mechanical agitation, fully dissolving form settled solution, add initiator, and constant speed dropping chain turns
Move the agent aqueous solution, continue reaction after completion of dropping, finally stop reaction, obtain the polycarboxylic acids of carboxylic acid integrated distribution；Carboxylic acid is concentrated
Add aqueous slkali in the polycarboxylic acids of distribution, be neutralized to pH=5 ~ 7, be diluted with water, obtain final product product.
Content of the invention
The technical problem to be solved is to provide a kind of preparation method of modified polycarboxylic acid diminishing masterbatch.
Appropriate design polycarboxylate water-reducer molecule amount distribution of the present invention, using the stronger acrylic acid of reactivity, carries
The weaker maleic anhydride of dynamic reactivity, the polycarboxylate water-reducer backbone structure of synthesis builds the short of different length and anchoring ability
Side chain；Additionally, minor comonomer solution first adds, reduce the pH value of solution in kettle, excite initiator efficiency of initiation, intensified response activity；
In technique delayed remaining minor comonomer solution initial time for adding it is ensured that in kettle first plus part minor comonomer solution reaction complete
Entirely；Above-mentioned synthesis technique guarantees that the distribution of polycarboxylate water-reducer molecule amount is concentrated, and accessory substance reduces, and shows water-reducing rate, slump retaining
Can synchronously improve, reduce from amount of air entrainment.
The preparation method of the modified polycarboxylic acid diminishing masterbatch of the present invention, is divided by following each groups and is polymerized, gross mass part
For 1000, comprise the following steps that：
1) 340 ~ 360 parts of polyether macromonomer and 200 ~ 250 parts of water are added in reactor, continuously stirred, until solution is no bright
Aobvious bulk or sheet material；
2) control reactor temperature at 5 ~ 25 DEG C, disposably put into 10 ~ 30% minor comonomer solution, described minor comonomer solution by
30.0 ~ 50.0 parts of acrylic acid, 5 ~ 10 parts of maleic anhydrides and 40 ~ 60 parts of water compositions, are simultaneously introduced 2.0 ~ 3.5 parts of oxidants, continue
Stirring；
3), after the 2 ~ 10min of interval, start to drip initiator；Initiator by 1.50 ~ 2.80 parts of chain-transferring agents, 0.60 ~ 1.00 part also
Former dose and 100 ~ 120 parts of water compositions；
4) after initiator adds, in 30min, start to drip remaining minor comonomer solution, remaining minor comonomer solution time for adding is that a is little
When, initiator time for adding is (a+0.6) hour；
5) after completion of dropwise addition, cure 1 ~ 2h, when question response solution temperature is less than 30 degree, be slowly added to 10 ~ 15 parts of liquid caustic soda, moisturizing
10 ~ 15h is stood after stirring.
Described polyether macromonomer is methyl allyl polyoxyethylene ether, isopentenol polyoxyethylene ether, isobutene alcohol polyoxy
One or more compositions of vinethene；
Described polyether macromonomer from reactivity angle, preferably isopentenol polyoxyethylene ether, isobutene alcohol polyoxyethylene
Ether；
Described polyether macromonomer from slump retaining angle, the isopentenol polyoxyethylene ether of preferably 2400 molecular weight and butenol
One or two compositions of APEO；
Described polyether macromonomer judges from comprehensive angle, and preferably mass ratio is 1：1 2400 isobutene alcohol polyoxyethylene
The composition of the isopentenol polyoxyethylene ether of ether and 2400 molecular weight；
If described polyether macromonomer is chosen as methyl allyl polyoxyethylene ether, quality is preferably 350 ~ 360；
If described polyether macromonomer is chosen as one or two groups of isopentenol polyoxyethylene ether, isobutene alcohol APEO
Become, quality is preferably 340 ~ 350.
The mass percent that the described minor comonomer solution partly first thrown accounts for total minor comonomer solution is preferably 20%.
Described oxidant is 27.5% industrial grade hydrogen peroxide for mass percent.
Described chain-transferring agent be TGA (MSDS), mercaptopropionic acid (MPA) one or two；
When described chain-transferring agent is TGA, slump retaining is stronger, and consumption is 1.50 ~ 2.55；
When described chain-transferring agent is mercaptopropionic acid, water-reducing rate is higher, and consumption is 1.65 ~ 2.80.
Described reducing agent is ascorbic acid, i.e. Vc.
Described liquid caustic soda is the technical grade NaOH solution of mass ratio 30 ~ 32%.
Described partly first throw minor comonomer solution when, temperature in the kettle priority acccess control be 10 ~ 15 DEG C, too low easy impact the later stage cause
Effect, too high to be easily caused acrylic acid autohemagglutination degree in minor comonomer solution excessive.
Described residue minor comonomer solution time for adding a is 1.0 ~ 2.5h, and time for adding is preferably 2h.
The invention has the beneficial effects as follows：
1. maleic anhydride reaction activity is relatively low, and the space steric effect of its cyclic anhydride group reduces double bond reactivity, makes
It is more difficult to carry out self-polymeric reaction；Acrylic acid first adds solution ph in reduction kettle, increases efficiency of initiation, drives maleic anhydride and polyethers
Polymeric monomer copolyreaction；The feature that this polycarboxylate superplasticizer mother liquor shows initial water-reducing rate, slump retaining synchronously improves, maleic acid
The use of acid anhydride improves the adaptability of such water reducer.
2. it is directed to cold area or weather, if manufacturing enterprise does not possess heating condition, minor comonomer solution is first processed skill and led to
Acid-base neutralization and acrylic acid autohemagglutination heat release, solution temperature in reactor can be improved, temperature increases to guarantee polymerisation just
Often cause.This technology controlling and process notes guaranteeing the timely addition of initiator, prevents the chain-transferring agent of initiator from adding and leads to not in time
The main chain of acrylic acid autohemagglutination is long.
Specific embodiment
Below by example, the present invention will be further elaborated, and the description below is not only for explaining the present invention, right
Content is defined.
Embodiment 1
A kind of minor comonomer partly first throws method modified polycarboxylic acid diminishing masterbatch and preparation method thereof, and this water reducer is by by percent mass
Following each groups of ratio are divided and are polymerized, and raw material gross mass is 1000, and each component and technological parameter are as follows：
1) in terms of mass parts, the isopentenol polyoxyethylene ether of 345 part of 2400 molecular weight and 200 parts of water are added to reactor
In, continuously stirred, until agitating solution no obvious bulk or sheet material；To be homogenised completely after；
2) measure temperature in the kettle, control temperature at 12 DEG C, after temperature stabilization, minor comonomer solution (the little list of disposable input 15%
Liquid solution is made up of 43.2 parts of acrylic acid, 5.8 parts of maleic anhydrides and 45 parts of water) disposably add in reactor, disposably simultaneously
Add 2.2 parts of hydrogen peroxide；
3) after adding hydrogen peroxide, keep continuously stirred, after the 3min of interval, start to drip initiator；Initiator is by 1.8 parts of sulfydryls
Acetic acid, 0.75 part of Vc and 110 parts of water compositions；
4), after initiator adds, start to drip remaining 85% minor comonomer solution in 30min, remaining minor comonomer solution time for adding is
2 hours, initiator time for adding was 2.6 hours, and remaining minor comonomer solution drips, and initiator also can drip 10min；
5) after completion of dropwise addition, cure 1h, when question response solution temperature is less than 30 degree, be slowly added to 12 parts of liquid caustic soda, moisturizing 234.25
Part, after standing 10h after stirring, get product.
Embodiment 2
1) in terms of mass parts, the isobutene alcohol APEO of 350 part of 2400 molecular weight and 220 parts of water are added to reactor
In, continuously stirred, until agitating solution no obvious bulk or sheet material；To be homogenised completely after；
2) measure temperature in the kettle, control temperature at 15 DEG C, after temperature stabilization, minor comonomer solution (the little list of disposable input 20%
Liquid solution is made up of 35.5 parts of acrylic acid, 7.0 parts of maleic anhydrides and 50 parts of water) disposably add in reactor, disposably simultaneously
Add 2.5 parts of hydrogen peroxide；
3) after adding hydrogen peroxide, keep continuously stirred, after the 5min of interval, start to drip initiator；Initiator is by 1.92 parts of sulfydryls
Propionic acid, 0.82 part of Vc and 110 parts of water compositions；
4), after initiator adds, start to drip remaining 80% minor comonomer solution in 30min, remaining minor comonomer solution time for adding is
2.5 hours, initiator time for adding was 3.1 hours, and remaining minor comonomer solution drips, and initiator also can drip 10min；
5) after completion of dropwise addition, cure 2h, when question response solution temperature is less than 30 degree, be slowly added to 15 parts of liquid caustic soda, moisturizing 207.26
Part, after standing 12h after stirring, get product.
Embodiment 3
1) in terms of mass parts, by the isoamyl of 173 part of 2400 molecular weight isobutene alcohol APEO and 173 part of 2400 molecular weight
Enol APEO and 250 parts of water are added in reactor, continuously stirred, until agitating solution no obvious bulk or tablet
Material；To be homogenised completely after；
2) measure temperature in the kettle, control temperature at 15 DEG C, after temperature stabilization, minor comonomer solution (the little list of disposable input 20%
Liquid solution is made up of 38.7 parts of acrylic acid, 8.5 parts of maleic anhydrides and 80 parts of water) disposably add in reactor, disposably simultaneously
Add 3.2 parts of hydrogen peroxide；
3) after adding hydrogen peroxide, keep continuously stirred, after the 7min of interval, start to drip initiator；Initiator is by 2.2 parts of sulfydryls
Acetic acid, 0.85 part of Vc and 120 parts of water compositions；
4) after initiator adds, in 30min, start to drip remaining minor comonomer solution, remaining minor comonomer solution time for adding is 2.5
Hour, initiator time for adding is 3.1 hours, and remaining minor comonomer solution drips, and initiator also can drip 10min；
5) after completion of dropwise addition, cure 2h, when question response solution temperature is less than 30 degree, be slowly added to 12 parts of liquid caustic soda, moisturizing 138.55
Part, after standing 15h after stirring, get product.
Embodiment 4
1) in terms of mass parts, the methyl allyl polyoxyethylene ether of 358 part of 2400 molecular weight and 200 parts of water are added to reaction
In kettle, continuously stirred, until agitating solution no obvious bulk or sheet material；To be homogenised completely after；
2) measure temperature in the kettle, control temperature at 22 DEG C, after temperature stabilization, minor comonomer solution (the little list of disposable input 28%
Liquid solution is made up of 30.5 parts of acrylic acid, 5.0 parts of maleic anhydrides and 60 parts of water) disposably add in reactor, disposably simultaneously
Add 2.8 parts of hydrogen peroxide；
3) after adding hydrogen peroxide, keep continuously stirred, after the 8min of interval, start to drip initiator；Initiator is by 2.0 parts of sulfydryls
Propionic acid, 0.90 part of Vc and 120 parts of water compositions；
4), after initiator adds, start to drip remaining 72% minor comonomer solution in 30min, remaining minor comonomer solution time for adding is
2 hours, initiator time for adding was 2.6 hours, and remaining minor comonomer solution drips, and initiator also can drip 10min；
5) after completion of dropwise addition, cure 2h, when question response solution temperature is less than 30 degree, be slowly added to 10 parts of liquid caustic soda, moisturizing 210.8
Part, after standing 14h after stirring, get product.
Modified polycarboxylic acid diminishing masterbatch and the equal consumption of common polycarboxylate superplasticizer mother liquor in test examples detailed above respectively
Under pulp flowage and its through when mobility and concrete 's air-containing.Cement used by experiment is new 42.5 Pu Guishui of China
Mud, with reference to GB/8076-2008《Concrete admixture》、GB/T50080-2002《Normal concrete mix performance test side
Method》Test cement paste initial fluidity, through when mobility, air content.
Different Water-reducing Admixtures To Cements starch flowing and concrete 's air-containing impact only
| Water reducer species | Initial fluidity mm | Through when mobility mm | Air content % |
| Ordinary water-reducing agent | 240 | 220 | 4.2 |
| Embodiment 1 | 250 | 240 | 3.5 |
| Embodiment 2 | 255 | 255 | 3.6 |
| Embodiment 3 | 260 | 275 | 3.2 |
| Embodiment 4 | 250 | 245 | 2.8 |
According to above-mentioned initial and through when net slurry mobility compare, the example 1,2,3,4 of modified polycarboxylic acid diminishing masterbatch initial
Mobility and through when mobility improve compared with the significantly synchronous of ordinary water-reducing agent, show that the modified water-reducing rate of polycarboxylic acids mother liquor and guarantor are collapsed
Performance synchronization improves；The air content of Synchronous concrete mix, because modified polycarboxylic acids mother liquor reduces from amount of air entrainment,
And then lead to the air content of concrete synchronously to decline.
Claims (9)
1. a kind of preparation method of modified polycarboxylic acid diminishing masterbatch, is divided by following each groups and is polymerized, and gross mass part is 1000,
Comprise the following steps that：
1) 340 ~ 360 parts of polyether macromonomer and 200 ~ 250 parts of water are added in reactor, continuously stirred, until solution is no bright
Aobvious bulk or sheet material；
2) control reactor temperature at 5 ~ 25 DEG C, disposably put into 10 ~ 30% minor comonomer solution, described minor comonomer solution by
30.0 ~ 50.0 parts of acrylic acid, 5 ~ 10 parts of maleic anhydrides and 40 ~ 60 parts of water compositions, are simultaneously introduced 2.0 ~ 3.5 parts of oxidants, continue
Stirring；
3), after the 2 ~ 10min of interval, start to drip initiator；Initiator by 1.50 ~ 2.80 parts of chain-transferring agents, 0.60 ~ 1.00 part also
Former dose and 100 ~ 120 parts of water compositions；
4) after initiator adds, in 30min, start to drip remaining minor comonomer solution, remaining minor comonomer solution time for adding is that a is little
When, initiator time for adding is (a+0.6) hour；
5) after completion of dropwise addition, cure 1 ~ 2h, when question response solution temperature is less than 30 degree, be slowly added to 10 ~ 15 parts of liquid caustic soda, moisturizing
10 ~ 15h is stood after stirring.
2. preparation method according to claim 1 is it is characterised in that described polyether macromonomer is methacrylic polyoxy second
Alkene ether, isopentenol polyoxyethylene ether, isobutene alcohol APEO one or more.
3. preparation method according to claim 1 is it is characterised in that described oxidant is 27.5% work for mass percent
Industry grade hydrogen peroxide.
4. preparation method according to claim 1 is it is characterised in that described chain-transferring agent is TGA, mercaptopropionic acid
In one or two.
5. preparation method according to claim 4 is it is characterised in that described chain-transferring agent is TGA, consumption is
1.50~2.55.
6. it is characterised in that described chain-transferring agent is mercaptopropionic acid, consumption is preparation method according to claim 4
1.65~2.80.
7. preparation method according to claim 1 is it is characterised in that described reducing agent is ascorbic acid.
8. preparation method according to claim 1 is it is characterised in that described liquid caustic soda is the technical grade of mass ratio 30 ~ 32%
NaOH solution.
9. preparation method according to claim 1 is it is characterised in that described residue minor comonomer solution time for adding a is
1.0~2.5h.
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| CN109133702A (en) * | 2018-09-12 | 2019-01-04 | 湖北工业大学 | A kind of preparation method of over cure cement water-reducing agent auxiliary material |
| CN110028633A (en) * | 2019-05-10 | 2019-07-19 | 山西黄河新型化工有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
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| CN110028633A (en) * | 2019-05-10 | 2019-07-19 | 山西黄河新型化工有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
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Application publication date: 20170215 |