CN109824836A - Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof - Google Patents
Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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Abstract
A kind of workability of the present invention is good, wide adaptability polycarboxylate water-reducer, contains ethylene glycol mono-vinyl polyglycol ether, unsaturated acyl amido comonomer, unsaturated ester group comonomer, unsaturated carboxylic acid comonomer, initiator, reducing agent, chain-transferring agent, liquid alkaline and water in synthesis material；By introducing ethylene glycol mono-vinyl polyglycol ether (2+2 novel active polymeric monomer), high performance water reducing agent of polyocarboxy acid has been synthesized by Raolical polymerizable in room temperature, finally obtained polymerization activity is higher, simple production process, diminishing function of slump protection are excellent, and workability well can adapt to the novel high workability high performance water reducing agent of polyocarboxy acid of different materials actual use demand.
Description
Technical field
The invention belongs to technical field of concrete additives, good, wide adaptability the poly- carboxylic more particularly to a kind of workability
Sour water-reducing agent and preparation method thereof.
Background technique
Concrete workability refers to that concrete mix is easy to constructing operation and can obtain uniform quality, form closely knit property
Energy.Workability is a comprehensive technological property, the meaning including three aspect such as mobility, cohesiveness and water-retaining property.In recent years
With the development of modern science and technology, increasingly complicated and new concrete the appearance of engineering type, concrete structures court
Overlength, superelevation, ultra-large type development, such as it is high-rise pumping, self-compacting concrete, one side they to concrete and easy
Property proposes tightened up requirement；On the other hand, in actual application due to the domestic much particularity of engineerings and season
Variation it is obvious and the sand of different zones, stone material quality are irregular, all give concrete containing mud, powder containing quantity difference are big etc.
Workability brings certain influence.Polycarboxylate high performance water-reducing agent is applied more and more extensive currently on the market, with polyoxy
Ethylene polymeric monomer (APEG, HPEG, TPEG) releasing one after another and applying, polycarboxylate water-reducer product obtained in water-reducing rate and
Embody bigger advantage on function of slump protection, however these polymeric monomers are there is also polymerization activity is low compared with acrylic monomer,
It is more demanding to synthesis technology and formula technique, particularly when aggregate containing mud containing powder content is higher, cement material variation situations such as
Under, polycarboxylate water-reducer occur in practical applications volume is very high, function of slump protection is insufficient, loss is too fast, sandstone sedimentation, bleeding from
The defects of analysis.Therefore develop that a kind of novel polymerization activity is higher, diminishing function of slump protection is excellent, workability can well fit
The high performance water reducing agent of polyocarboxy acid for answering different materials actual use demand, has a very important significance.
Patent CN108752537A discloses the insensitive polycarboxylate water-reducer and preparation method thereof of a kind of pair of environment temperature.
Using six carbon unsaturation polyoxyethylene ether, unsaturated carboxylic acid, function monomer auxiliary agent, oxidant, reducing agent, chain-transferring agent is original
Material carries out aqueous free radical copolyreaction under normal temperature conditions and is prepared.The invention products application is in concrete to ring
Border temperature change is insensitive, and can solve causes concrete to be easy to appear the workability such as bleeding, isolation because of variation of ambient temperature
Problem significantly facilitates concrete production control and guarantees the quality of concrete.Although the invention can solve to a certain extent because
Concrete workability problem caused by variation of ambient temperature, but it is directed to the variation of different concrete materials, sandstone quality variation situation,
But effect cannot be played very well, using with certain limitation.
Patent CN108947314A disclose it is a kind of with water-retaining property, pumping, workability, adaptability concrete and its
Preparation method adds workability of concrete modifying agent into concrete, can effectively promote the water conservation of high performance concrete, mortar
Property, workability, pumping, adaptability.The modifying agent selects the epoxy glue of water-soluble welan gum, natural plant gum, cellulose ether composition
Body can play the cohesiveness and water-retaining property for promoting concrete as water-keeping thickening component, but since complex colloid and polycarboxylic acids subtract
The difference of aqua molecular structure, it is understood that there may be consistency problem causes the unstable phenomenon of the solution such as layering precipitation to occur.
Patent CN108192044A discloses the preparation side of the low responsive type polycarboxylate water-reducer of a kind of pair of concrete clay content
Method.By introducing silane group in polycarboxylic acids molecular structure, it can be formed and be chemically bonded with cement granules, while be conducive to increase
Macromolecular size avoids polycarboxylic acids from being adsorbed by the mud with intercalation configuration, improve with the adaptability problem of cement, can reduce pair
The sensibility of cement content variation；Simultaneously by introducing the structure of polynary ether-ether in polycarboxylic acids molecular structure, poly- carboxylic can be improved
Shape and branched structure of the long side chain of acid in concrete heterogeneous system improve concrete so that side chain more unfolds absent-mindedness
Working performance.But the raw material of the invention reaction step and needs are complicated, can not utilize existing polycarboxylate water-reducer production equipment,
By free radical polymerization One-step production, subsequent industrialized mass production has certain limitation.
The method of above-mentioned several improvement concrete workabilities by polymerized at normal temperature technique, compounding water-retaining admixture, introduces
The methods of silane and ester ether structure all substantially improve on the basis of traditional HPEG, TPEG, VPEG type polyether macromonomer, institute
With there is workability improvement to have the problems such as limitation, combination solution are unstable, production technology is complicated.Therefore one kind is developed
The synthesis of novel polyether monomer, polymerization activity is higher, simple production process, diminishing function of slump protection are excellent, workability well can
The workability for adapting to different materials actual use demand is good, polycarboxylate water-reducer of wide adaptability, has a very important significance.
Therefore, in view of the shortcomings of the prior art, providing a kind of good workability, polycarboxylate water-reducer of wide adaptability and its preparation
Method has the advantages that workability is good, wide adaptability.
Summary of the invention
A kind of polycarboxylate water-reducer and its preparation are provided it is an object of the invention to avoid in place of the deficiencies in the prior art
Method has higher good workability, wide adaptability, polymerization activity, simple production process, diminishing function of slump protection excellent, Neng Goushi
The advantages of answering different materials to actually use demand.
Above-mentioned purpose of the invention is realized by following technological means.
A kind of workability is good, wide adaptability polycarboxylate water-reducer, contains the poly- second of ethylene glycol mono-vinyl in synthesis material
Glycol ethers, unsaturated acyl amido comonomer, unsaturated ester group comonomer, unsaturated carboxylic acid comonomer, initiator, reduction
Agent, chain-transferring agent, liquid alkaline and water.
Preferably, in terms of mass parts, the proportion of synthesis material are as follows:
Ethylene glycol mono-vinyl polyglycol ether polymeric monomer: 360~420 parts；
Unsaturated acyl amido comonomer: 5~10 parts；
Unsaturated ester group comonomer: 10~15 parts；
Unsaturated carboxylic acid comonomer: 20~25 parts；
Initiator: 2.0~3.0 parts；
Reducing agent: 1.2~1.7 parts；
Chain-transferring agent: 0.7~1.5 part；
Liquid alkaline: 35~45 parts；
Water: 450~500 parts.
Preferably, the molecular weight of the ethylene glycol mono-vinyl polyglycol ether polymeric monomer is 1200~3000.
Preferably, the unsaturated acyl amido comonomer be N, N'- methylene-bisacrylamide, Methacrylamide,
At least one of Diacetone Acrylamide, 2- acrylamide -2- methyl propanamide.
Preferably, the unsaturated ester group comonomer is vinylacetate, cyanacrylate, hydroxyethyl methacrylate
At least one of ethyl ester, ethylene glycol dimethacrylate.
Preferably, the unsaturated carboxylic acid comonomer is methacrylic acid, maleic anhydride, at least one in acrylic acid
Kind.
Preferably, the initiator is at least one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide；
Preferably, the reducing agent is ferrous sulfate, in sodium hydrogensulfite, sodium sulfite, sodium formaldehyde sulphoxylate
It is at least one；
Preferably, the chain-transferring agent is isopropanol, in sodium hypophosphite, mercaptoethanol, 3- mercaptopropionic acid, thioacetic acid
It is at least one.
Preferably, the concentration of the liquid alkaline is 32%.
Preferably, in terms of mass parts, the proportion of synthesis material are as follows:
Ethylene glycol mono-vinyl polyglycol ether polymeric monomer: 380 parts；
Unsaturated acyl amido comonomer: 8 parts；
Unsaturated ester group comonomer: 12 parts；
Unsaturated carboxylic acid comonomer: 23 parts；
Initiator: 2.4 parts；
Reducing agent: 1.4 parts；
Chain-transferring agent: 1.0 parts；
Liquid alkaline: 37 parts；
Water: 470 parts.
A kind of preparation method of good, wide adaptability the polycarboxylate water-reducer of workability of the present invention, comprising the following steps:
S1, into reactor, investment ethylene glycol mono-vinyl polyglycol ether polymeric monomer, unsaturated acyl amido copolymerization are single
Body, adding water and stirring and controlling reaction temperature is 20 DEG C~25 DEG C；
S2, after monomer is completely dissolved in reactor, put into initiator, stir 5min~10min after simultaneously be added dropwise I material it is molten
Liquid and II expect that solution, I expect that solution is added dropwise 1h~1.5h, II material solution and 1.5h~2h is added dropwise；
The I material solution is to stir evenly preparation by unsaturated ester group comonomer, unsaturated carboxylic acid comonomer and water
At solution；
The II material solution is to stir evenly the solution being configured to by polymerized at normal temperature reducing agent, chain-transferring agent and water.
S3, continue after dripping off in 20 DEG C~25 DEG C heat preservation 1h~2h；
Polycarboxylate water-reducer is finally made to pH value 6~7 or so in S4, after reaction annex solution alkali neutralization.
Beneficial effect
The present invention passes through first introduces ethylene glycol mono-vinyl polyglycol ether (2+2 novel active polymeric monomer), in room temperature
25 DEG C have synthesized high performance water reducing agent of polyocarboxy acid below by way of Raolical polymerizable.2+2 novel active polymeric monomer molecule knot
The unsaturated double-bond of structure is directly connected with oxygen atom, pushing away electronic action by force and make the big list of 2+2 novel active due to oxygen atom
Body has the reactivity closer to acrylic acid, while the group on polymeric monomer molecule double bond periphery is less, so that polyether lateral chain
It swings and rotary freedom increases, side chain more unfolds freedom, and the wrapped and prehensile of polyether lateral chain is improved, improves
The comprehensive performance of polycarboxylate water-reducer.Unsaturated acyl amido, unsaturation are also introduced in polycarboxylate water-reducer polymerization process simultaneously
The minor comonomers such as ester group carry out free radicals copolymerization reaction, using the strong negative electrical charge of amide groups, the slow release characteristic of electronegativity and ester group, continue
Enhance adaptability and stability of the polycarboxylate water-reducer under varying environment, different materials, is finally made poly- by above method
It is excellent to close higher activity, simple production process, diminishing function of slump protection, workability, which well can adapt to different materials actual use, to be needed
The novel high performance water reducing agent of polyocarboxy acid asked.
Specific embodiment
The specific embodiment of form by the following examples is described in further detail the above content of invention.
But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
Embodiment 1
A kind of workability of the present invention is good, wide adaptability polycarboxylate water-reducer, containing containing ethylene glycol list in synthesis material
Vinyl polyglycol ether (2+2 novel active polymeric monomer), unsaturated acyl amido comonomer, unsaturated ester group comonomer,
Unsaturated carboxylic acid comonomer, initiator, reducing agent, chain-transferring agent, liquid alkaline (32%) and water.
In terms of mass parts, the proportion of synthesis material are as follows:
Ethylene glycol mono-vinyl polyglycol ether polymeric monomer: 360~420 parts；
Unsaturated acyl amido comonomer: 5~10 parts；
Unsaturated ester group comonomer: 10~15 parts；
Unsaturated carboxylic acid comonomer: 20~25 parts；
Initiator: 2.0~3.0 parts；
Reducing agent: 1.2~1.7 parts；
Chain-transferring agent: 0.7~1.5 part；
Liquid alkaline (32%): 35~45 parts；
Water: 450~500 parts.
The molecular weight of ethylene glycol mono-vinyl polyglycol ether polymeric monomer is 1200~3000.
The unsaturated acyl amido comonomer is N, N'- methylene-bisacrylamide, Methacrylamide, diacetone third
At least one of acrylamide, 2- acrylamide -2- methyl propanamide.
Unsaturated ester group comonomer is vinylacetate, cyanacrylate, hydroxyethyl methacrylate, dimethyl
At least one of acrylic acid glycol ester.
Unsaturated carboxylic acid comonomer is at least one of methacrylic acid, maleic anhydride, acrylic acid.
Initiator is at least one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide；
Reducing agent is ferrous sulfate, the sodium hydrogensulfite, Asia suitable for polymerized at normal temperature technique (20~25 DEG C of reaction temperature)
At least one of sodium sulphate, sodium formaldehyde sulphoxylate；
Chain-transferring agent is at least one of isopropanol, sodium hypophosphite, mercaptoethanol, 3- mercaptopropionic acid, thioacetic acid.
A kind of preparation method of polycarboxylate water-reducer of the present invention, comprising the following steps:
S1, into reactor, investment ethylene glycol mono-vinyl polyglycol ether polymeric monomer, unsaturated acyl amido copolymerization are single
Body, adding water and stirring and controlling reaction temperature is 20 DEG C~25 DEG C；
S2, after monomer is completely dissolved in reactor, put into initiator, stir 5min~10min after simultaneously be added dropwise I material it is molten
Liquid and II expect that solution, I expect that solution is added dropwise 1h~1.5h, II material solution and 1.5h~2h is added dropwise；
S3, continue after dripping off in 20 DEG C~25 DEG C heat preservation 1h~2h；
Polycarboxylate water-reducer is finally made to pH value 6~7 or so in S4, after reaction annex solution alkali neutralization.
Specifically, I material solution is stirred evenly and is matched by unsaturated ester group comonomer, unsaturated carboxylic acid comonomer and water
Manufactured solution, II expect that solution is to stir evenly the solution being configured to by polymerized at normal temperature reducing agent, chain-transferring agent and water.
The present invention passes through first introduces ethylene glycol mono-vinyl polyglycol ether (2+2 novel active polymeric monomer), in room temperature
25 DEG C have synthesized high performance water reducing agent of polyocarboxy acid, 2+2 novel active polymeric monomer molecule knot below by way of Raolical polymerizable
The unsaturated double-bond of structure is directly connected with oxygen atom, pushing away electronic action by force and make the big list of 2+2 novel active due to oxygen atom
Body has the reactivity closer to acrylic acid, while the group on polymeric monomer molecule double bond periphery is less, so that polyether lateral chain
It swings and rotary freedom increases, side chain more unfolds freedom, and the wrapped and prehensile of polyether lateral chain is improved, improves
The comprehensive performance of polycarboxylate water-reducer；Unsaturated acyl amido, unsaturation are also introduced in polycarboxylate water-reducer polymerization process simultaneously
The minor comonomers such as ester group carry out free radicals copolymerization reaction, using the strong negative electrical charge of amide groups, the slow release characteristic of electronegativity and ester group, continue
Enhance adaptability and stability of the polycarboxylate water-reducer under varying environment, different materials, is finally made poly- by above method
It is excellent to close higher activity, simple production process, diminishing function of slump protection, workability, which well can adapt to different materials actual use, to be needed
The novel high performance water reducing agent of polyocarboxy acid asked.
Embodiment 2
A kind of preparation method of polycarboxylate water-reducer is provided, comprising the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, put into 360 parts of ethylene glycol mono-vinyl polyglycol ethers
Polymeric monomer (molecular weight 1200), 6 parts of N, N'- methylene-bisacrylamide add 240 parts of water to open and stir and control its reaction temperature
It is 20 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.0 parts of hydrogen peroxide, I material solution be added dropwise simultaneously after stirring 10min
Expect that solution, I expect that solution is added dropwise 1h, II material solution and 1.5h is added dropwise with II；
S3, continue after dripping off in 22 DEG C of heat preservation 1h；
S4 plus 36 parts of liquid alkaline are neutralized to pH value 6~7 or so, and polycarboxylate water-reducer is finally made.
Specifically, I material solution is stirred evenly and is configured to by 11 parts of vinylacetates, 22 parts of acrylic acid and 120 parts of water
Solution；II expects that solution is to stir evenly the solution being configured to by 1.3 parts of ferrous sulfate, 0.97 part of mercaptoethanol and 100 parts of water.
The present invention is by being added 360 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers and 6 parts of N, N'- di-2-ethylhexylphosphine oxide third
Acrylamide has synthesized high performance water reducing agent of polyocarboxy acid, the big list of 2+2 novel active by Raolical polymerizable at 20 DEG C of temperature
The unsaturated double-bond of body molecular structure is directly connected with oxygen atom, pushing away electronic action by force and make 2+2 novel due to oxygen atom
Surface-active macromonomer has the reactivity closer to acrylic acid, while the group on polymeric monomer molecule double bond periphery is less, so that poly-
The swing of ether side chain and rotary freedom increase, and side chain more unfolds freedom, and the wrapped and prehensile of polyether lateral chain is mentioned
Height improves the comprehensive performance of polycarboxylate water-reducer；6 parts of N are additionally added in polycarboxylate water-reducer polymerization process simultaneously, N'- is sub-
The minor comonomers such as bisacrylamide, 11 parts of vinylacetates and 22 parts of acrylic acid carry out free radicals copolymerization reaction, utilize amide
The slow release characteristic of the strong negative electrical charge of base, electronegativity and ester group continues to enhance polycarboxylate water-reducer under varying environment, different materials
It is excellent that higher polymerization activity, simple production process, diminishing function of slump protection are finally made by above method for adaptability and stability
Different, workability well can adapt to the novel high performance water reducing agent of polyocarboxy acid of different materials actual use demand.
Embodiment 3
A kind of preparation method of polycarboxylate water-reducer is provided, comprising the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, put into 370 parts of ethylene glycol mono-vinyl polyglycol ethers
Polymeric monomer (molecular weight 2000), 8 parts of Methacrylamides, adding 260 parts of water to open stirring and controlling reaction temperature is 20 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.8 parts of hydrogen peroxide, I material solution be added dropwise simultaneously after stirring 10min
Expect that solution, I expect that solution is added dropwise 1.2h, II material solution and 1.5h is added dropwise with II；
S3, continue after dripping off in 20 DEG C of heat preservation 1.5h；
S4 plus 39 parts of liquid alkaline are neutralized to pH value 6~7 or so, and polycarboxylate water-reducer is finally made.
I expects that solution is stirred evenly and is configured to by 13 parts of cyanacrylates, 21 parts of methacrylic acids and 120 parts of water
Solution；II material solution be stirred evenly by 1.1 parts of sodium hydrogensulfites, 0.8 part of 3- mercaptopropionic acid and 100 parts of water be configured to it is molten
Liquid.
The present invention is by being added 370 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers (molecular weight 1800) and 8 parts of first
Base acrylamide has synthesized high performance water reducing agent of polyocarboxy acid, 2+2 novel active by Raolical polymerizable at 20 DEG C of temperature
The unsaturated double-bond of polymeric monomer molecular structure is directly connected with oxygen atom, pushing away electronic action by force and make 2+2 due to oxygen atom
Novel active polymeric monomer has the reactivity closer to acrylic acid, while the group on polymeric monomer molecule double bond periphery is less, makes
The swing and rotary freedom for obtaining polyether lateral chain increase, and side chain more unfolds freedom, and the wrapped and prehensile of polyether lateral chain obtains
To raising, the comprehensive performance of polycarboxylate water-reducer is improved；I material solution and II material solution are added simultaneously, I expects that solution is by 13 parts
Cyanacrylate, 21 parts of methacrylic acids and 120 parts of water stir evenly the solution being configured to；II expects that solution is by 1.1 parts
Sodium hydrogensulfite, 0.8 part of 3- mercaptopropionic acid and 100 parts of water stir evenly the solution being configured to, and utilize the strong negative electrical charge of amide groups, electricity
The slow release characteristic of negativity and ester group continues to enhance adaptability and stabilization of the polycarboxylate water-reducer under varying environment, different materials
Property, finally it is made that polymerization activity is higher, simple production process, diminishing function of slump protection are excellent by above method, workability is good
It can adapt to the novel high performance water reducing agent of polyocarboxy acid of different materials actual use demand.
Embodiment 4
A kind of preparation method of polycarboxylate water-reducer is provided, comprising the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, 380 parts of big lists of ethylene glycol mono-vinyl polyglycol ether
Body (molecular weight 1600), 7 parts of Diacetone Acrylamide, adding 250 parts of water to open stirring and controlling its reaction temperature is 25 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.5 parts of ammonium persulfates, stir that I material is added dropwise simultaneously after 10min is molten
Liquid and II expect that solution, I expect that solution is added dropwise 1.5h, II material solution and 1.8h is added dropwise,；
S3, continue after dripping off in 25 DEG C of heat preservation 2h；
S4 plus 40 parts of liquid alkaline are neutralized to pH value 6~7 or so, and high performance water reducing agent of polyocarboxy acid is finally made.
Specifically, I material solution is by 12 parts of ethylene glycol dimethacrylate, 24 parts of maleic anhydrides and 120 parts of water stirrings
The solution being uniformly configured to；II expects that solution is to stir evenly preparation by 1.5 parts of sodium sulfites, 1.2 parts of sodium hypophosphites and 110 parts of water
At solution.
The present invention, which passes through, is added 380 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers and 7 parts of Diacetone Acrylamide,
High performance water reducing agent of polyocarboxy acid, 2+2 novel active polymeric monomer molecule have been synthesized by Raolical polymerizable at 25 DEG C of temperature
The unsaturated double-bond of structure is directly connected with oxygen atom, pushing away electronic action by force and make 2+2 novel active big due to oxygen atom
Monomer has the reactivity closer to acrylic acid, while the group on polymeric monomer molecule double bond periphery is less, so that polyether lateral chain
Swing and rotary freedom increase, side chain more unfolds freedom, and the wrapped and prehensile of polyether lateral chain is improved, promotion
The comprehensive performance of polycarboxylate water-reducer；I material solution and II material solution are added simultaneously, I expects that solution is by 12 parts of dimethyl allenes
Sour glycol ester, 24 parts of maleic anhydrides and 120 parts of water stir evenly the solution being configured to；II expects that solution is by 1.5 parts of sulfurous acid
Sodium, 1.2 parts of sodium hypophosphites and 110 parts of water stir evenly the solution being configured to, and utilize the strong negative electrical charge of amide groups, electronegativity and ester group
Slow release characteristic, continue to enhance adaptability and stability of the polycarboxylate water-reducer under varying environment, different materials, by above
Method is finally made that polymerization activity is higher, simple production process, diminishing function of slump protection are excellent, and workability well can adapt to difference
The novel high performance water reducing agent of polyocarboxy acid of material actual use demand.
Embodiment 5
A kind of preparation method of polycarboxylate water-reducer is provided, comprising the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, put into 410 parts of ethylene glycol mono-vinyl polyglycol ethers
Polymeric monomer (molecular weight 3000), 9 parts of 2- acrylamide-2-methyl propane sulfonics add 240 parts of water to open and stir and control reaction temperature
It is 23 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.8 parts of potassium peroxydisulfates, stir that I material is added dropwise simultaneously after 10min is molten
Liquid and II expect that solution, I expect that solution is added dropwise 1.2h, II material solution and 2.0h is added dropwise；
S3, continue after dripping off in 23 DEG C of heat preservation 1.5h,；
S4 plus 42 parts of liquid alkaline are neutralized to pH value 6~7 or so, and polycarboxylate water-reducer is finally made.
Specifically, I material solution is stirred evenly by 13 parts of hydroxyethyl methacrylates, 25 parts of maleic anhydrides and 120 parts of water
The solution being configured to.II expects that solution is stirred evenly and matched by 1.2 parts of sodium formaldehyde sulphoxylates, 1.2 parts of isopropanols and 110 parts of water
Manufactured solution.
The present invention is by being added 410 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers (molecular weight 3000) and 9 parts of 2-
Acrylamide-2-methyl propane sulfonic has synthesized high performance water reducing agent of polyocarboxy acid by Raolical polymerizable at 23 DEG C of temperature,
The unsaturated double-bond of 2+2 novel active polymeric monomer molecular structure is directly connected with oxygen atom, pushes away electronics by force due to oxygen atom
Effect is so that 2+2 novel active polymeric monomer has the reactivity closer to acrylic acid, while polymeric monomer molecule double bond periphery
Group is less, so that the swing of polyether lateral chain and rotary freedom increase, side chain more unfolds freedom, polyether lateral chain it is wrapped
It is improved with prehensile, improves the comprehensive performance of polycarboxylate water-reducer；I material solution and II material solution are added simultaneously, I material is molten
Liquid is to stir evenly the solution being configured to by 13 parts of hydroxyethyl methacrylates, 25 parts of maleic anhydrides and 120 parts of water.II expects solution
It is to stir evenly the solution being configured to by 1.2 parts of sodium formaldehyde sulphoxylates, 1.2 parts of isopropanols and 110 parts of water, utilizes amide groups
The slow release characteristic of strong negative electrical charge, electronegativity and ester group continues to enhance polycarboxylate water-reducer fitting under varying environment, different materials
Answering property and stability, are finally made that polymerization activity is higher, simple production process, diminishing function of slump protection are excellent by above method,
Workability well can adapt to the novel high performance water reducing agent of polyocarboxy acid of different materials actual use demand.
Embodiment 6
A kind of preparation method of polycarboxylate water-reducer is provided, comprising the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, put into 400 parts of ethylene glycol mono-vinyl polyglycol ethers
Polymeric monomer (molecular weight 2000), 8 parts of 2- acrylamide-2-methyl propane sulfonics add 250 parts of water to open and stir and control reaction temperature
It is 22 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.7 parts of ammonium persulfates, stir that I material is added dropwise simultaneously after 10min is molten
Liquid and II expect that solution, I expect that solution is added dropwise 1.0h, II material solution and 1.5h is added dropwise,
S3, continue after dripping off in 22 DEG C of heat preservation 1.5h；
S4 plus 39 parts of liquid alkaline are neutralized to pH value 6~7 or so, and polycarboxylate water-reducer is finally made.
Specifically, I material solution is stirred evenly and is configured to by 14 parts of vinylacetates, 20 parts of acrylic acid and 120 parts of water
Solution.II expects that solution is to stir evenly the solution being configured to by 1.7 parts of ferrous sulfate, 1.1 parts of thioacetic acid and 120 parts of water.
The present invention is by being added 400 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers (molecular weight 2400) and 8 parts of 2-
Acrylamide-2-methyl propane sulfonic has synthesized high performance water reducing agent of polyocarboxy acid by Raolical polymerizable at 22 DEG C of temperature,
The unsaturated double-bond of 2+2 novel active polymeric monomer molecular structure is directly connected with oxygen atom, pushes away electronics by force due to oxygen atom
Effect is so that 2+2 novel active polymeric monomer has the reactivity closer to acrylic acid, while polymeric monomer molecule double bond periphery
Group is less, so that the swing of polyether lateral chain and rotary freedom increase, side chain more unfolds freedom, polyether lateral chain it is wrapped
It is improved with prehensile, improves the comprehensive performance of polycarboxylate water-reducer；It is added simultaneously plus I expects that solution and II expect solution, I material
Solution is to stir evenly the solution being configured to by 14 parts of vinylacetates, 20 parts of acrylic acid and 120 parts of water.II material solution be by
1.7 parts of ferrous sulfate, 1.1 parts of thioacetic acid and 120 parts of water stir evenly the solution being configured to, using the strong negative electrical charge of amide groups,
The slow release characteristic of electronegativity and ester group continues to enhance adaptability of the polycarboxylate water-reducer under varying environment, different materials and steady
It is qualitative, finally it is made that polymerization activity is higher, simple production process, diminishing function of slump protection are excellent by above method, workability is good
It can adapt to the novel high workability high performance water reducing agent of polyocarboxy acid of different materials actual use demand well.
Embodiment 7
A kind of preparation method of polycarboxylate water-reducer is provided, is included the following steps:
S1, to equipped with blender, thermometer four-hole boiling flask in, put into 380 parts of ethylene glycol mono-vinyl polyglycol ethers
Polymeric monomer (molecular weight 2400), 10 parts of N, N'- methylene-bisacrylamide add 240 parts of water to open and stir and control reaction temperature
It is 21 DEG C；
S2, after monomer is completely dissolved in flask, put into 2.1 parts of hydrogen peroxide, I material solution be added dropwise simultaneously after stirring 10min
Expect that solution, I expect that solution is added dropwise 1.5h, II material solution and 1.8h is added dropwise with II；
S3, continue after dripping off in 21 DEG C of heat preservation 2.0h；
S4 plus 37 parts of liquid alkaline are neutralized to pH value 6~7 or so, and a kind of polycarboxylate water-reducer is finally made.
Specifically, I material solution is equal by 11 parts of hydroxyethyl methacrylates, 21 parts of methacrylic acids and 120 parts of water stirrings
The even solution being configured to.II expects that solution is to stir evenly preparation by 1.6 parts of sodium hydrogensulfites, 1.1 parts of sodium hypophosphites and 110 parts of water
At solution.
The present invention, which passes through, is added 380 parts of ethylene glycol mono-vinyl polyglycol ether polymeric monomers (molecular weight 2400) and 10 parts of N,
N'- methylene-bisacrylamide has synthesized high performance water reducing agent of polyocarboxy acid, 2+ by Raolical polymerizable at 21 DEG C of temperature
The unsaturated double-bond of 2 novel active polymeric monomer molecular structures is directly connected with oxygen atom, since the electronics that pushes away by force of oxygen atom is made
With making 2+2 novel active polymeric monomer that there is the reactivity closer to acrylic acid, while the base on polymeric monomer molecule double bond periphery
Group is less, so that the swing of polyether lateral chain and rotary freedom increase, side chain more unfolds freedom, polyether lateral chain wrapped and
Prehensile is improved, and improves the comprehensive performance of polycarboxylate water-reducer；It is added simultaneously plus I expects that solution and II expect that solution, I material are molten
Liquid is to stir evenly the solution being configured to by 11 parts of hydroxyethyl methacrylates, 21 parts of methacrylic acids and 120 parts of water.II material is molten
Liquid is to stir evenly the solution being configured to by 1.6 parts of sodium hydrogensulfites, 1.1 parts of sodium hypophosphites and 110 parts of water, strong using amide groups
The slow release characteristic of negative electrical charge, electronegativity and ester group continues to enhance adaptation of the polycarboxylate water-reducer under varying environment, different materials
Property and stability, be finally made that polymerization activity is higher, simple production process, diminishing function of slump protection are excellent by above method, and
Easy property well can adapt to the novel high workability high performance water reducing agent of polyocarboxy acid of different materials actual use demand.
Comparative example 1
In order to compare effect of the invention, following comparative example is provided, the preparation method is as follows: to blender, thermometer is equipped with
Four-hole boiling flask in, put into 360 parts of polyisobutenyl polyoxyethylene ether (molecular weight 2400), 240 parts of water added to open agitating and heatings
60 DEG C are warming up to, after monomer is completely dissolved in flask, puts into 2.5 parts of hydrogen peroxide, I material and II are added dropwise simultaneously after stirring 10min
Expect that solution, I expect that 2.5h, II material is added dropwise (by 1.0 parts in (adding 100 parts of water to stir evenly the solution being formulated by 35 parts of acrylic acid)
L-AA, 1.2 parts of 3- mercaptopropionic acids and 100 parts of water stir evenly the solution being configured to) 3h is added dropwise, continue after dripping off 60
DEG C heat preservation 1.5h, mends 50 parts after reaction and is water-cooled to 30 DEG C or so, liquid feeding alkali neutralization to pH value 6~7 or so is made common
Type polycarboxylate water-reducer.
Comparative example 2
In order to compare effect of the invention, following comparative example is provided, the preparation method is as follows: to blender, thermometer is equipped with
Four-hole boiling flask in, put into 360 parts of polyisoamylene base polyoxyethylene ether (molecular weight 2400), 240 parts of water added to open agitating and heatings
50 DEG C are warming up to, after monomer is completely dissolved in flask, puts into 2.0 parts of hydrogen peroxide, I material and II are added dropwise simultaneously after stirring 10min
Expect that solution, I expect that 3h, II material is added dropwise (by 1.0 parts of L- in (adding 100 parts of water to stir evenly the solution being formulated by 32 parts of acrylic acid)
Ascorbic acid, 1.2 parts of mercaptoethanols and 110 parts of water stir evenly the solution being configured to) 3.5h is added dropwise, continue after dripping off at 50 DEG C
1h is kept the temperature, 50 parts is mended after reaction and is water-cooled to 30 DEG C or so, it is poly- that plain edition is made in liquid feeding alkali neutralization to pH value 6~7 or so
Carboxylic acid water reducer.
Application Example
The embodiment of the present invention 2~7 is prepared into polycarboxylate water-reducer and comparative example 1~2 carries out fresh concrete application performance
Comparison, referring to standard GB/T 8076-2018 " concrete admixture " relevant regulations, test use water-cement ratio to mix for 0.45
Solidifying soil match ratio, specific as shown in table 1, test uses China Resources P.O.42.5 cement, the rubble of 5mm~20mm continuous grading, Buddhist
The sensible I grades of flyash in the mountain South Sea, the sensible S95 miberal powder in Foshan South Sea, at the same in order to evaluate polycarboxylate water-reducer to sandstone quality compared with
Workability in poor situation improves situation, and the higher middle sand (fine powder content 7%, fineness modulus 2.4) of fine powder content is selected to carry out
Adaptability for materials test.Concrete crushing strength is tested according to " standard for test methods of mechanical properties of ordinary concrete " GB/T
50081-2002 is carried out.
1 concrete mix of table (kg/m3)
The comparison of 2 concrete performance of table
By the result of table 2 it can be concluded that, control concrete initial slump degree (divergence) it is almost the same under conditions of, with
The plain edition polycarboxylate water-reducer of comparative example 1~2 is compared, polycarboxylate water-reducer needed for adding present invention preparation embodiment 2~7
Volume be significantly lower than comparative example 1~2, show good concrete water-reducing ratio and excellent guarantor collapsed performance, while in sandstone product
In the poor situation of matter, the concrete workability of embodiment 2~7 is good, hence it is evident that better than the concrete state of comparative example 1~2.Finally
The concrete strength of embodiment 2~7 and comparative example 1~2 increases preferably, and 7d can reach 50% or more, 28d and substantially exceed
30MPa is demonstrated by good comprehensive performance.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of workability is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that contain ethylene glycol list second in synthesis material
Alkenyl polyglycol ether, unsaturated ester group comonomer, unsaturated carboxylic acid comonomer, draws unsaturated acyl amido comonomer
Send out agent, reducing agent, chain-transferring agent, liquid alkaline and water.
2. a kind of workability according to claim 1 is good, wide adaptability polycarboxylate water-reducer, which is characterized in that with matter
Measure part meter, the proportion of synthesis material are as follows:
Ethylene glycol mono-vinyl polyglycol ether polymeric monomer: 360~420 parts；
Unsaturated acyl amido comonomer: 5~10 parts；
Unsaturated ester group comonomer: 10~15 parts；
Unsaturated carboxylic acid comonomer: 20~25 parts；
Initiator: 2.0~3.0 parts；
Reducing agent: 1.2~1.7 parts；
Chain-transferring agent: 0.7~1.5 part；
Liquid alkaline: 35~45 parts；
Water: 450~500 parts.
3. workability according to claim 2 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the second two
The molecular weight of alcohol mono-vinyl polyglycol ether polymeric monomer is 1200~3000.
4. workability according to claim 3 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the insatiable hunger
It is N, N'- methylene-bisacrylamide, Methacrylamide, Diacetone Acrylamide, 2- acryloyl with amide groups comonomer
At least one of amine -2- methyl propanamide.
5. workability according to claim 4 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the insatiable hunger
It is vinylacetate, cyanacrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate with ester group comonomer
At least one of ester.
6. workability according to claim 5 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the insatiable hunger
It is at least one of methacrylic acid, maleic anhydride, acrylic acid with carboxylic acid comonomers.
7. workability according to claim 6 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the initiation
Agent is at least one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide；
The reducing agent is at least one of ferrous sulfate, sodium hydrogensulfite, sodium sulfite, sodium formaldehyde sulphoxylate；
The chain-transferring agent is at least one of isopropanol, sodium hypophosphite, mercaptoethanol, 3- mercaptopropionic acid, thioacetic acid.
8. workability as claimed in claim 2 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that the liquid alkaline
Concentration is 32%.
9. workability according to claim 2 is good, the polycarboxylate water-reducer of wide adaptability, which is characterized in that with mass parts
Meter, the proportion of synthesis material are as follows:
Ethylene glycol mono-vinyl polyglycol ether polymeric monomer: 380 parts；
Unsaturated acyl amido comonomer: 8 parts；
Unsaturated ester group comonomer: 12 parts；
Unsaturated carboxylic acid comonomer: 23 parts；
Initiator: 2.4 parts；
Reducing agent: 1.4 parts；
Chain-transferring agent: 1.0 parts；
Liquid alkaline: 37 parts；
9. water: 470 parts.
10. a kind of preparation method of the polycarboxylate water-reducer as described in claim 1~9 is any, which is characterized in that including following
Step:
S1, into reactor, put into ethylene glycol mono-vinyl polyglycol ether polymeric monomer, unsaturated acyl amido comonomer, add
It is 20 DEG C~25 DEG C that water, which stirs and controls reaction temperature,；
S2, after monomer is completely dissolved in reactor, put into initiator, stir 5min~10min after simultaneously be added dropwise I material solution and
II expects that solution, I expect that solution is added dropwise 1h~1.5h, II material solution and 1.5h~2h is added dropwise；
The I material solution is stirred evenly and is configured to by unsaturated ester group comonomer, unsaturated carboxylic acid comonomer and water
Solution；
The II material solution is to stir evenly the solution being configured to by polymerized at normal temperature reducing agent, chain-transferring agent and water.
S3, continue after dripping off in 20 DEG C~25 DEG C heat preservation 1h~2h；
Polycarboxylate water-reducer is finally made to pH value 6~7 or so in S4, after reaction annex solution alkali neutralization.
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| CN112126022A (en) * | 2020-09-11 | 2020-12-25 | 浙江玖龙新材料有限公司 | Formula and preparation method of polycarboxylate superplasticizer |
| WO2022056975A1 (en) * | 2020-09-17 | 2022-03-24 | 江苏尼高科技有限公司 | Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete |
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| CN114031728A (en) * | 2021-11-11 | 2022-02-11 | 科之杰新材料集团有限公司 | High-water-reduction-type EPEG polycarboxylic acid water reducer and preparation method thereof |
| CN116265494A (en) * | 2021-12-17 | 2023-06-20 | 江苏苏博特新材料股份有限公司 | Side chain macromonomer, preparation method thereof and low-sensitivity high-adaptability polycarboxylate superplasticizer prepared by using side chain macromonomer |
| CN114478940A (en) * | 2022-01-25 | 2022-05-13 | 重庆彼目加科技有限公司 | Special dispersant for light cement base and preparation method thereof |
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