CN106883354A - A kind of powdery polycarboxylic-acid slump retaining agent and preparation method thereof - Google Patents
A kind of powdery polycarboxylic-acid slump retaining agent and preparation method thereof Download PDFInfo
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- CN106883354A CN106883354A CN201710127466.1A CN201710127466A CN106883354A CN 106883354 A CN106883354 A CN 106883354A CN 201710127466 A CN201710127466 A CN 201710127466A CN 106883354 A CN106883354 A CN 106883354A
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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
- C08F2/02—Polymerisation in bulk
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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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Abstract
A kind of powdery polycarboxylic-acid slump retaining agent of the invention and preparation method thereof, preparation method is comprised the following steps：Acrylic or methacrylic acid is prepared into a kind of esters monomer with polyalcohol under catalyst action, then with acrylate or methacrylate, unsaturated carboxylic acid and/or acid anhydrides and polyether monomer, bulk copolymerization is carried out under composite initiator and hydrophobic chain transfer agent effect, obtain molten state polycarboxylic-acid slump retaining agent, delivering to freezing crusher finally by utilidor carries out low-temperature grinding, that is, powdery polycarboxylic-acid slump retaining agent is obtained.The present invention, by the combination of oil-soluble and Water Soluble Compound initiator, is prepared for a kind of powdery polycarboxylic-acid slump retaining agent by adjusting the sour ether ratio of poly carboxylic acid series water reducer, introducing acrylate or methacrylate and self-control esters monomer.Slump retaining agent of the invention has slump-retaining energy high, reduces preparation cost, and safe preparation process is environmentally friendly, solvent-free murder by poisoning.
Description
Technical field
The invention belongs to the technical field of concrete additives in construction material, and in particular to a kind of powdery polycarboxylic-acid
Slump retaining agent and preparation method thereof.
Background technology
With the rise of the Large Infrastructure Projects such as China's nuclear power, water conservancy, bridge, tunnel, especially state-owned railroads passenger traffic is special
The extensive implementation of gauze engineering, the market demand sustainable growth to poly carboxylic acid series water reducer.With traditional high efficiency water reducing agent phase
Than poly carboxylic acid series water reducer has turned into concrete property high with premium properties such as its high water reducing rate, low slump loss, Lower alrali contents
The critical material of energyization.
Poly carboxylic acid series water reducer in the market is generally 10~50% fluid product, due to its superior performance, more
It is used in various key projects come more.But often due to engineering construction place farther out, job site place it is limited, cause to deposit
Storage, cost of transportation constantly increase, so development high concentration or solid polycarboxylic acids product are to reduce cost of transportation and the poly- carboxylic of popularization
The sour widely used essential condition of based water reducer.The wide popularization and application of dry powder and mortar, also to solid poly carboxylic acid series water reducer
Production application proposes active demand.Powder poly carboxylic acid series water reducer in the market is generally to be obtained by spray drying process
Arrive, but be diluted to liquid, performance has declined compared with the liquid poly carboxylic acid series water reducer with concentration, and this is mainly poly-
There is partial cross-linked causing after being heated in carboxylic acid water reducing agent.If expecting that the poly carboxylic acid series water reducer powder of excellent performance is produced
Product, can not only destroy operation under conditions of poly carboxylic acid series water reducer structure by the way of low temperature.
CN102372458A reports a kind of preparation method of solid poly carboxylic acid series water reducer, by unsaturated acids with other not
Saturation monomer carries out copolymerization in organic solvent, is prepared after separated precipitation and low temperature drying.The solid water reducer is molten
In aqueous solvent, compared with the liquid poly carboxylic acid series water reducer product of commercially available same concentration, combination property does not have difference.But this is special
Profit needs to use organic solvent such as alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester etc., obtains also needing to dry separation solvent after polymerizate,
The inadequate greenization of production process.
CN103554382A reports a kind of method of synthesis in solid state poly carboxylic acid series water reducer, by polyether monomer, initiator
In ball mill or colloid mill being added to a small amount of water, mixing 10 minutes of machining, then divide small molecule monomer, reduction several times
The mixture equal portions of the water composition of agent, chain-transferring agent and small molecule monomer quality 10% are added in ball mill or colloid mill, all
After adding, it is further continued for reacting 1h, it is possible to obtain solid or paste poly carboxylic acid series water reducer.
CN103755885A proposes a kind of method of microwave-assisted Solid-state synthesizing polycarboxylic acid dehydragent, by polyethers list
The pasty mixture of the water composition of body, initiator, small molecule monomer, reducing agent, chain-transferring agent and small molecule monomer quality 50%
It is placed in the micro-wave oven of power adjustable, reacts certain hour, obtains solid or paste poly carboxylic acid series water reducer.In above-mentioned patent
Method is not suitable for large-scale industrial production.
CN102993387B reports a kind of preparation method that pure solid poly carboxylic acid series water reducer is directly synthesized by a step,
Unsaturated APEO is heated to 50~70 DEG C of fusings, successively to addition molecular weight regulator, (methyl) third in reactor
Olefin(e) acid or its mixture monomer, initiator with unsaturated carboxylic acid, and feeding interval mixing time 5~20 minutes every time, after
Continue and carry out 1.5~8h of bulk polymerization at being warming up to 75~95 DEG C, be cooled to room temperature and obtain pure solid polycarboxylic-acid diminishing
Agent.There is the defect of temperature drift or complex process in above two method.
The content of the invention
Regarding to the issue above, the present invention discloses a kind of powdery polycarboxylic-acid slump retaining agent and preparation method thereof, by copolymerization
The introducing of the functional groups such as ester group of carboxyl density, the adjustment of side chain lengths and slow release in thing molecule, preparation is collapsed with height
Degree of falling keeps the concrete slump retaining agent of performance, has good compatibility and excellent slump holding with poly carboxylic acid series water reducer
Ability.
The present invention relates to a kind of preparation method of powdery polycarboxylic-acid slump retaining agent, it is characterised in that by weight percentage
Meter, including following raw materials composition：
The polyalcohol is in ethylene glycol, diethylene glycol, 1,2-PD, 1,3-PD, dipropylene glycol
Kind.
The catalyst is p-methyl benzenesulfonic acid or sulfamic acid, and the polymerization inhibitor is in hydroquinones, phenthazine, diphenylamines
One kind.
The polyether monomer is methyl allyl alcohol polyoxyethylene ether, the methallyl alcohol polyoxy second of molecular weight 600~4000
One kind in alkene polyethenoxy ether, isopentenol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether.
The unsaturated carboxylic acid be acid anhydrides be acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride in extremely
Few one kind, or the unsaturated carboxylic acid is that unsaturated carboxylic acid and acid anhydrides are acrylic acid, methacrylic acid, fumaric acid, maleic acid, horse
At least one mixing come in acid anhydrides.
The acrylate includes methyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, propylene
One kind in sour hydroxypropyl acrylate；The methacrylate includes methyl methacrylate, EMA, methacrylic acid
One kind in different monooctyl ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate.
The oil-soluble initiator is azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, peroxidating
One kind in benzoyl, the benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, the water soluble starter is ammonium persulfate, mistake
One kind in sodium sulphate and potassium peroxydisulfate.
The chain-transferring agent is hydrophobic chain transfer agent, including butyl mercaptan, spicy thioalcohol, decyl mercaptan, lauryl mercaptan, 16
Alkyl hydrosulfide, Stearyl mercaptan, 2 mercaptopropionic acid monooctyl ester, 3- mercaptopropionic acids monooctyl ester, thio glycolic monooctyl ester, TGA-
2- Octyl Nitrites, may be used singly or in combin two kinds or more.
The preparation method of above-mentioned powdery polycarboxylic-acid slump retaining agent, comprises the following steps：
Acrylic or methacrylic acid is prepared into a kind of esters monomer with polyalcohol under catalyst action, then with propylene
Acid esters or methacrylate, unsaturated carboxylic acid and/or acid anhydrides and polyether monomer, shift in composite initiator and hydrophobic chain
Bulk copolymerization is carried out under agent effect, molten state polycarboxylic-acid slump retaining agent is obtained, freezing crusher is delivered to finally by utilidor
Low-temperature grinding is carried out, that is, powdery polycarboxylic-acid slump retaining agent is obtained.The present invention by adjust poly carboxylic acid series water reducer sour ether ratio,
Acrylate or methacrylate and self-control esters monomer are introduced, and by oil-soluble and the group of Water Soluble Compound initiator
Close, be prepared for a kind of powdery polycarboxylic-acid slump retaining agent.
More specifically, the step of preparation method is：(1) preparation of esters monomer：To equipped with thermometer, stirring slurry, constant current
In the reactor of pump, condenser and water knockout drum, acrylic or methacrylic acid, polyalcohol, catalyst and the inhibition of metering are added
Agent, is warming up to 90~120 DEG C under agitation, is stirred at reflux 2~7h, separates water layer with water knockout drum and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：The polyether monomer of metering is added in reactor, stirring melts, then
Add oil-soluble initiator stirring and dissolving；Then water soluble starter, chain-transferring agent and acrylic acid are made into mixed solution, and
The interior constant flow pumps of 2~4h are dripped off；Follow-up continuation of insurance 2~4h of temperature is dripped off, adds a certain amount of powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：Molten product delivers to freezing crusher by utilidor ,-
Low-temperature grinding is carried out at 20~-40 DEG C, that is, the powdery polycarboxylic-acid slump retaining agent that fineness is 100~200 mesh is obtained.
The initiator is while the composite initiator comprising oil-soluble and water soluble starter, its feed postition is oil soluble
Property initiator disposably puts into reactor as bed material, and water soluble starter is dissolved in unsaturated carboxylic acid and is slowly dropped to reactor
In.
The inventive method has the advantages that compared with prior art：
(1) the powdery polycarboxylic-acid slump retaining agent prepared using the present invention, can avoid spray drying treatment causedization
Learn the problems such as side reaction or wall built-up calcination, the abundant method for preparing polycarboxylic-acid slump retaining agent.
(2) safe preparation process is environmentally friendly, solvent-free murder by poisoning, cleanliness without any pollution, reaction raw materials used are simply common, synthesize
Cheng Wuxu nitrogen is protected, and greatly reduces production cost.
(3) present invention is according to molecular design theory, the esters monomer for introducing in the polymer and acrylate or methyl-prop
Olefin(e) acid ester moiety substitutional crylic acid or methacrylic acid, reduce the carboxyl density in molecular backbone, adjust adsorption equilibrium, realize
Polymer dispersity can and function of slump protection regulation and control, and because the speed of each monomer hydrolysis is different, guarantor is collapsed effect duration
Can be adjusted according to actual conditions, better adaptability.
(4) present invention prepares gained slump retaining agent and remains to show preferable mobility holding capacity under compared with low-dosage, and
And the cement to different cultivars shows very strong adaptability.Additionally, slump retaining agent Product Status stabilization, deposits under low temperature and does not tie
Performance is unaffected after crystalline substance, and low-temperature storage, is conducive to industrial application, is imitated with good economic benefit and society
Benefit.
(5) powdery polycarboxylic-acid slump retaining agent of the invention, can Ying Yu commodity mortars, grout filler and various extensively
Extraordinary mortar, compensate in conventional dry powder and mortar retarder can only being used to protect the deficiency of modeling or due to using liquid slump retaining agent band
The application inconvenience for coming, can effectively promote the development of dry powder and mortar technology.
Specific embodiment
Describe embodiments of the present invention in detail with specific embodiment below, whereby to the present invention how application technology hand
Section solves technical problem, and reaches the implementation process of technique effect and can fully understand and implement according to this.
The embodiment of the present invention when introduces self-control esters monomer by adjusting the sour ether of poly carboxylic acid series water reducer, and by oil
The combination of dissolubility and Water Soluble Compound initiator, is prepared for a kind of solid polycarboxylic-acid slump retaining agent in the molten state.Due to not
There is substantial amounts of water, store, transport more convenient, and greatly reduce cost of transportation.
Embodiment 1：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
312.8kg methacrylic acids, 94.0kg ethylene glycol, 8.1kg sulfamic acids and 2.0kg hydroquinones are added, is heated up under agitation
To 110~120 DEG C, 3~3.5h is stirred at reflux, separates water layer with water knockout drum and be cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 4168kg isopentenol polyoxyethylene ether (molecular weight
2400), stirring melts, and adds 29.2kg benzoyl peroxide stirring and dissolvings；Then by 19.5kg sodium peroxydisulfates, 38.9kg sulphur
Mixed solution is made into for glycolic monooctyl ester, 86.8kg ethyl acrylates and 187.6kg acrylic acid, and constant current is used in 3.5~4h
Pump is dripped off；Follow-up continuation of insurance 2~2.5h of temperature is dripped off, adds 53.1kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：Molten product delivers to freezing crusher low temperature by utilidor
Crush, that is, white powder polycarboxylic-acid slump retaining agent is obtained.
Embodiment 2：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
417.8kg methacrylic acids, 125.5kg ethylene glycol, 10.9kg sulfamic acids and 2.7kg hydroquinones are added, is risen under agitation
Temperature is stirred at reflux 3~3.5h to 110~120 DEG C, separates water layer with water knockout drum and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：3712kg prenols polyoxyethylene poly-oxygen propylene aether is added (to divide
1600), stirring melts son amount, adds 29.0kg ABVN stirring and dissolvings；Then by 19.2kg ammonium persulfates,
33.9kg butyl mercaptan, 269.1kg hydroxy-ethyl acrylates and 299.2kg methacrylic acids are made into mixed solution, and in 2.5~3h
Dripped off with constant flow pump；Follow-up continuation of insurance temperature 4h is dripped off, adds 80.9kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 3：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
707.0kg methacrylic acids, 212.4kg ethylene glycol, 18.4kg sulfamic acids and 4.6kg hydroquinones are added, is risen under agitation
Temperature is stirred at reflux 4~5h to 100~110 DEG C, separates water layer with water knockout drum and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 3140kg isopentenol polyoxyethylene ether (molecular weight
1200), stirring melts, and adds 384.8kg maleic anhydrides and 33.5kg benzoyl peroxide stirring and dissolvings；Then by 14.4kg
Sodium peroxydisulfate, 38.5kg3- mercaptopropionic acids monooctyl ester and 340.3kg hydroxyethyl methacrylates are made into mixed solution, and are used in 3h
Constant flow pump is dripped off；Follow-up continuation of insurance 3.5~4h of temperature is dripped off, adds 106.1kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 4：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
220.6kg acrylic acid, 146.6kg dipropylene glycols, 5.5kg sulfamic acids and 1.9kg phenthazine are added, is heated up under agitation
To 110~120 DEG C, 3~3.5h is stirred at reflux, separates water layer with water knockout drum and be cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 4280kg isopentenol polyoxyethylene ether (molecular weight
4000), stirring melts, and adds 34.1kg azo-bis-iso-dimethyl stirring and dissolvings；Then by 14.7kg ammonium persulfates,
29.3kg decyl mercaptans, 69.6kg hydroxypropyl acrylates and 154.1kg acrylic acid are made into mixed solution, and with perseverance in 2~2.5h
Stream pump is dripped off；Follow-up continuation of insurance 3.5~4h of temperature is dripped off, adds 43.6kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 5：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
382.1kg acrylic acid, 254.0kg dipropylene glycols, 9.5kg sulfamic acids and 3.2kg phenthazine are added, is heated up under agitation
To 100~110 DEG C, 4~5h is stirred at reflux, separates water layer with water knockout drum and be cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 3708kg isopentenol polyoxyethylene ether (molecular weight
2000), stirring melts, and adds 24.1kg methyl ethyl ketone peroxide stirring and dissolvings；Then by 24.1kg potassium peroxydisulfates, 33.7kg sulphur
Mixed solution is made into for glycolic monooctyl ester, 159.4kg methyl acrylates and 318.8kg methacrylic acids, and constant current is used in 3h
Pump is dripped off；Follow-up continuation of insurance temperature 4h is dripped off, adds 83.1kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 6：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
693.2kg acrylic acid, 460.7kg dipropylene glycols, 17.3kg sulfamic acids and 5.8kg phenthazine are added, is risen under agitation
Temperature is stirred at reflux 3~3.5h to 110~120 DEG C, separates water layer with water knockout drum and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 2690kg isopentenol polyoxyethylene ether (molecular weight
800), stirring melts, and adds 23.9kg methyl ethyl ketone peroxide stirring and dissolvings；Then it is 23.9kg potassium peroxydisulfates, 28.6kg is pungent
Mercaptan, 437.2kg hydroxypropyl acrylates and 484.3kg acrylic acid are made into mixed solution, and are dripped with constant flow pump in 2~2.5h
It is complete；Follow-up continuation of insurance 3~3.5h of temperature is dripped off, adds 135.1kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 7：
(1) preparation of esters monomer：To in the reactor equipped with thermometer, stirring slurry, constant flow pump, condenser and water knockout drum
307.7kg acrylic acid, 141.6kg diethylene glycols, 8.1kg p-methyl benzenesulfonic acid and 2.2kg diphenylamines are added, is warming up under agitation
100~110 DEG C, 4~4.5h is stirred at reflux, separates water layer with water knockout drum and be cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 3804kg methyl allyl alcohol polyoxyethylene ether (molecular weight
2400), stirring melts, and adds 459.6kg fumaric acid and 33.8kg benzoyl peroxide stirring and dissolvings；Then by 14.4kg mistakes
Potassium sulfate, 38.7kg thioglycollic acid-2-ethyl hexyl esters and 103.0kg hydroxyethyl methacrylates are made into mixed solution, and 2~
The interior constant flow pumps of 2.5h are dripped off；Follow-up continuation of insurance 3.5~4h of temperature is dripped off, adds 86.9kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 8：
(1) preparation of esters monomer：(1) preparation of esters monomer：To equipped with thermometer, stirring slurry, constant flow pump, condenser
And 255.8kg acrylic acid, 117.8kg diethylene glycols, 6.7kg p-methyl benzenesulfonic acid and 1.9kg bis- are added in the reactor of water knockout drum
Aniline, is warming up to 110~120 DEG C under agitation, is stirred at reflux 3~3.5h, separates water layer with water knockout drum and is cooled to 60~70
℃；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 3953kg isopentenol polyoxyethylene ether (molecular weight
3000), stirring melts, and adds 29.1kg benzoyl peroxide tert-butyl ester stirring and dissolvings；Then by 19.4kg sodium peroxydisulfates,
24.2kg 2 mercaptopropionic acids monooctyl ester, 242.5kg Isooctyl acrylate monomers and 283.3kg methacrylic acids are made into mixed solution, and
The interior constant flow pumps of 2~2.5h are dripped off；Follow-up continuation of insurance 3.5~4h of temperature is dripped off, adds 66.3kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Embodiment 9：
(1) preparation of esters monomer：(1) preparation of esters monomer：To equipped with thermometer, stirring slurry, constant flow pump, condenser
And 446.8kg acrylic acid, 205.5kg diethylene glycols, 11.8kg p-methyl benzenesulfonic acid and 3.2kg bis- are added in the reactor of water knockout drum
Aniline, is warming up to 90~95 DEG C under agitation, is stirred at reflux 5.5~6h, separates water layer with water knockout drum and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：Add 3680kg methallyl alcohol polyoxyethylene poly-oxygen propylene aethers
(molecular weight 2400), stirring melts, and adds 29.2kg azodiisobutyronitrile stirring and dissolvings；Then by 19.3kg ammonium persulfates,
29.2kg lauryl mercaptans, 220.9kg hydroxy propyl methacrylates and 276.1kg acrylic acid are made into mixed solution, and 2h~
The interior constant flow pumps of 2.5h are dripped off；Follow-up continuation of insurance 3~3.5h of temperature is dripped off, adds 78.0kg powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：With embodiment 1.
Application Example 1：
Flowing degree of net paste of cement is with reference to standard GB/T/T 8077-2012《Methods for testing uniformity of concrete admixture》,
Three kinds of cement is respectively that reference cement, conch PO42.5 grades of Chinese cement Co., Ltd., Factory and Nanjing-small wild water in field mud have
Peaceful PII52.5 grades of the sheep of gold of limit company；The liquid polycarboxylic-acid slump retaining agent of contrast selects the auspicious limited public affairs of enlightening new and high technology in Nanjing
The TX-209 of the department and ST-412 of Jiangsu factory, the volume of slump retaining agent is 0.2% (being counted on the basis of the weight of cement after rolling over admittedly),
Result of the test is shown in Table 1.
The paste flowing degree of the different slump retaining agents of table 1 and loss contrast
From the result of table 1, initial cement paste stream of the solid polycarboxylic-acid slump retaining agent of the invention in different cement
Dynamic degree aspect performance differs greatly, but is respectively provided with good fluidity holding capacity, generally with through when increase, the liquid with contrast
Body polycarboxylic-acid slump retaining agent TX-209 similar natures, better than commercially available liquid polycarboxylic-acid slump retaining agent ST-412.
Application Example 2：
With reference to standard GB/T 8076-2008《Concrete admixture》Relevant regulations are performed.Testing cement uses reference water
Mud, additive is mixes 0.2% admittedly, and concrete mix is shown in Table 2, and result of the test see the table below 3.
Concrete mix (the kg/m of table 23)
| Cement | Sand | Middle stone | Gravelstone | Water | Additive |
| 360 | 820 | 600 | 400 | 178 | 0.72 |
The concrete performance contrast of the different polycarboxylic-acid slump retaining agents of table 3
Result shows that solid polycarboxylic-acid slump retaining agent of the invention has preferable concrete slump holding capacity, 2h
Concrete still has good mobility afterwards, and the liquid polycarboxylic-acid slump retaining agent TX-209 performances with contrast are approached, better than commercially available
Liquid polycarboxylic-acid slump retaining agent ST-412.
Although the present invention is described by embodiment, embodiment is not used for limiting the present invention.Art technology
Personnel can make various modifications and improvement in the scope of spirit of the invention, the adjustment of such as component ratio or time range,
Effect after this adjustment is predictable, so it is same within protection scope of the present invention.Therefore protection of the invention
The protection domain that scope should be defined by the identical or equivalent technical characteristic of claims hereof is defined.
Claims (10)
1. a kind of powdery polycarboxylic-acid slump retaining agent, it is characterised in that by weight percentage, including the following raw material：
2. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The polyalcohol be ethylene glycol,
One kind in diethylene glycol, 1,2-PD, 1,3-PD, dipropylene glycol.
3. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The catalyst is to toluene sulphur
Acid or sulfamic acid, the polymerization inhibitor are the one kind in hydroquinones, phenthazine, diphenylamines.
4. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The polyether monomer is molecular weight
600~4000 methyl allyl alcohol polyoxyethylene ether, methallyl alcohol polyoxyethylene poly-oxygen propylene aether, prenol polyoxyethylene
One kind in ether, prenol polyoxyethylene poly-oxygen propylene aether.
5. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The unsaturated carboxylic acid is acid anhydrides
Be at least one in acrylic acid, methacrylic acid, fumaric acid, maleic acid, or the unsaturated carboxylic acid be unsaturated carboxylic acid with
Acid anhydrides is at least one mixing in acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride.
6. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The acrylate includes propylene
Sour methyl esters, ethyl acrylate, Isooctyl acrylate monomer, hydroxy-ethyl acrylate, hydroxypropyl acrylate；The methacrylate includes
Methyl methacrylate, EMA, EHMA, hydroxyethyl methacrylate, hydroxyethyl methacrylate
Propyl ester.
7. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The oil-soluble initiator is even
Nitrogen bis-isobutyronitrile, ABVN, azo-bis-iso-dimethyl, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, mistake
One kind in MEKP, the water soluble starter is the one kind in ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
8. powdery polycarboxylic-acid slump retaining agent according to claim 1, it is characterised in that：The chain-transferring agent is hydrophobicity
Chain-transferring agent, including butyl mercaptan, spicy thioalcohol, decyl mercaptan, lauryl mercaptan, hexadecyl mercaptan, Stearyl mercaptan, 2- sulfydryls
One or more in octyl propionate, 3- mercaptopropionic acids monooctyl ester, thio glycolic monooctyl ester, thioglycollic acid-2-ethyl hexyl ester.
9. in a kind of claim 1-8 any described powdery polycarboxylic-acid slump retaining agent preparation method, it is characterised in that bag
Include following steps：
Acrylic or methacrylic acid is prepared into a kind of esters monomer with polyalcohol under catalyst action, then with acrylate
Or methacrylate, unsaturated carboxylic acid and/or acid anhydrides and polyether monomer, make in composite initiator and hydrophobic chain transfer agent
Bulk copolymerization is carried out under, molten state polycarboxylic-acid slump retaining agent is obtained, finally delivering to freezing crusher carries out low-temperature grinding, that is, make
Obtain powdery polycarboxylic-acid slump retaining agent.
10. the preparation method of powdery polycarboxylic-acid slump retaining agent according to claim 9, it is characterised in that specifically include
Following steps：
(1) preparation of esters monomer：To added in reactor the acrylic or methacrylic acid of metering, polyalcohol, catalyst and
Polymerization inhibitor, is warming up to 90~120 DEG C under agitation, is stirred at reflux 2~7h, separates water layer and is cooled to 60~70 DEG C；
(2) preparation of molten state polycarboxylic-acid slump retaining agent：The polyether monomer of metering is added in reactor, stirring melts, adds
Oil-soluble initiator stirring and dissolving；Then water soluble starter, chain-transferring agent and acrylic acid are made into mixed solution, and 2~
Dripped off in 4h；Follow-up continuation of insurance 2~4h of temperature is dripped off, adds a certain amount of powder alkali to stir；
(3) preparation of powdery polycarboxylic-acid slump retaining agent：Molten product delivers to freezing crusher by utilidor, -20~-
Low-temperature grinding is carried out at 40 DEG C, that is, the powdery polycarboxylic-acid slump retaining agent that fineness is 100~200 mesh is obtained.
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Application publication date: 20170623 |