CN110003406A - A kind of Abietyl modified polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of Abietyl modified polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN110003406A CN110003406A CN201910444069.6A CN201910444069A CN110003406A CN 110003406 A CN110003406 A CN 110003406A CN 201910444069 A CN201910444069 A CN 201910444069A CN 110003406 A CN110003406 A CN 110003406A
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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
- 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
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of Abietyl modified polycarboxylate water-reducers and preparation method thereof.Abietyl modified vinyl acetate containing double bonds is obtained as monomer and other polycarboxylate water-reducer monomers with vinylacetate progress transesterification by the carboxyl to rosin derivative to polymerize in aqueous solution, obtains the Abietyl modified polycarboxylate water-reducer.It is preferred that ratio of the Abietyl modified vinyl acetate in mix monomer, polycarboxylate water-reducer obtained has excellent performance, when as additive and cement, concrete mixing, has high water reducing rate under 0.12% low-dosage.Meanwhile Abietyl modified polycarboxylate water-reducer provided by the invention, to the mobility of cement, concrete, compression strength also has a distinct increment.In above-mentioned technical proposal provided by the invention, rosin derivative is from a wealth of sources, at low cost, environmentally protective and renewable, has good market popularization value.
Description
Technical field
The present invention relates to water-reducing agent technical fields, and in particular to a kind of Abietyl modified polycarboxylate water-reducer and its preparation side
Method.
Background technique
After cement and water stirring, hydration reaction being generated, some flocculence structures occurs, it is wrapped in many mixing waters, from
And reduce the workability of fresh concrete.Required workability is kept in construction, must just be increase accordingly and be mixed and stirred water,
Since the increase of water can make to form excessive hole in water mudrock structure, to seriously affect the physical mechanics of maturing
Performance, if can come out the water release of these packages, the water consumption of concrete can greatly reduce.In the mistake for preparing concrete
Cheng Zhong mixes appropriate water-reducing agent, can function well as such effect.Water-reduction is surfactant to hydrated cementitious mistake
A kind of important function of Cheng Suoqi.It can guaranteed by the way that water-reducing agent is added to reinforce the peptizaiton between cement particle
The dosage that mixing water is reduced in the case where fluidity, improves the intensity of concrete.
Polycarboxylate high performance water-reducing agent has many advantages, such as that occupation rate of market rises year by year, and gradually replaces tradition contracting
Poly- type water-reducing agent becomes the mainstream product in the market.The main chain of polycarboxylate water-reducer molecule is firmly adsorbed on the surface of cement granules, energy
Effectively hydration reaction is prevented to improve its plastic property, branch is then enclosed in cement granules surrounding, plays steric hindrance and electrostatic repulsion
Double action, this is different from the mechanism that conventional water reducing agents are dispersed by electrostatic repulsion, have better dispersibility and diminishing
Effect finally makes the comprehensive performance of concrete product get a promotion.It, can be with since polycarboxylate water-reducer molecule structure is easy to modify
It is related to effective molecular structure according to cement peptizaiton mechanism, it is long by the backbone repeat unit quantity, the side chain that design molecule
Degree and density.Due to this molecular structure of high-efficiency water-reducing agent of poly-carboxylic acid itself and the designability of performance, to further perfect
Seriation, functionalization water-reducing agent be following developing direction.It is poly- that a kind of low entraining viscosity reduction type is disclosed in CN106883355A
Carboxylic acid water reducer and preparation method thereof, by being introduced on main chain containing there are two the three rouge structures of alkyl phosphoric acid of double bond to increase
Water-reducing agent adsorbent layer thickness to achieve the purpose that reduce concrete plastic viscosity, while also improving antifoam performance, reduces bleed
Property, but preparation process is complex, and fluidity retention property is general.CN107245130B discloses a kind of ginkgo graft modification
Polycarboxylate water-reducer and preparation method thereof.The method is ginkgoic acid and unsaturated polyether is soluble in water, addition unsaturation
Carboxylic acid is copolymerized, and the polycarboxylate water-reducer of ginkgoic acid graft modification is obtained.But its function of slump protection is poor, anti-mud performance is also
Have to be hoisted.
Rosin is a kind of renewable resource with good characteristic, the mixture being made of various kinds of resin acid, fatty acid.Tree
Resin acid is the chief component of rosin, and there are monoacid and tricyclic phenanthrene skeleton that one has 2 double bonds.Rosin and its derivative
Object is widely used in the industries such as adhesive, coating, ink due to their distinctive properties.China is rosin production big country, is produced per year
500000 tons or more, how this renewable natural resources of rosin is utilized, novel fine chemical product is developed, to meet every profession and trade
It needs, is the research topic to become more and more important.
Patent CN108503254A, CN108409189A, CN108623768A disclose a kind of one system of useless rosin preparation
The method of column water-reducing agent.But on the one hand these methods need not accomplishing green using formaldehyde in large quantities during the preparation process
Environmental protection；On the other hand, these methods are directly using useless rosin, and there is no analysis is made to its ingredient, it is anti-that wherein generation is not illustrated
What the ingredient answered is, also the product determining you can't get composition, repeatability may be unable to reach industrial demand.
Importantly, this non-modified rosin is due to space steric effect, directly as raw material, reactivity causes anxiety.And
This non-modified CRYSTALLIZATION OF ROSIN tendency is big, oxidizable, softening point is low.In order to improve so that eliminating these defects, it is necessary to
Rosin structure is modified.
Summary of the invention
The present invention provides a kind of Abietyl modified polycarboxylate water-reducer and its system to solve the defect of the above-mentioned prior art
Preparation Method.The present invention introduces double bond in rosin molecular structure by being modified to rosin, by ester exchange reaction, as thin
Water modified monomer and other monomers copolymerization, the polycarboxylate water-reducer being had excellent performance.Rosin structure introducing polycarboxylic acids is subtracted
In the molecular structure of aqua, have not been reported.
The technical problem to be solved in the present invention solves by the following technical programs:
It is by including following molar part the first purpose of the invention is to provide a kind of Abietyl modified polycarboxylate water-reducer
Raw material is prepared:
Salt, 15~30 parts of unsaturated polyethers of 20~50 parts of small molecule unsaturated carboxylic acids, 3~10 parts of small molecule unsaturated acids
Class polymeric monomer, 5~20 parts of Abietyl modified vinyl acetates, 0.2~2 part of initiator, 0.2~2 part of chain-transferring agent.
In the preferred technical solution of the present invention, the Abietyl modified polycarboxylate water-reducer is by including following mole
Part raw material is prepared:
Salt, 20~25 parts of unsaturated polyethers of 35~50 parts of small molecule unsaturated carboxylic acids, 5~8 parts of small molecule unsaturated acids
Class polymeric monomer, 8~12 parts of Abietyl modified vinyl acetates, 0.5~1 part of initiator, 0.5~0.8 part of chain-transferring agent.
Further, the small molecule unsaturated carboxylic acid is selected from at least one of acrylic acid, methacrylic acid.At described small point
A certain proportion of ester can also be contained in sub- unsaturated carboxylic acid, at least one that ester group is methyl esters, ethyl ester, propyl ester and butyl ester
Kind, the amount of the ester substance of unsaturated carboxylic acid is no more than the 10% of its unsaturated carboxylic acid.
Further, the salt of the small molecule unsaturated acids is the salt or acrylic sulfonate of unsaturated carboxylic acid, the salt
For sodium salt or sylvite；It preferably is selected from sodium acrylate, potassium acrylate, Sodium methacrylate, methacrylic acid potassium, sodium allylsulfonate, third
At least one of alkene potassium sulfonate, methylpropene sodium sulfonate and methacrylic sulfonic acid potassium.
Further, the unsaturated polyether class polymeric monomer is selected from allyl polyethenoxy ether (APEG), isoamyl dilute alcohol polyoxy
At least one of vinethene (TPEG) and methyl allyl alcohol polyoxyethylene ether (HPEG)；The number of the unsaturated polyether class polymeric monomer
Average molecular weight is 500-4000, preferably 1500-3000.
Further, the Abietyl modified vinyl acetate is vinyl tetrahydroabietate (VTA), dehydroabietic acid vinyl acetate
(VDA) and at least one of maleopimaric acid vinyl acetate (VMPA).
Further, the initiator be selected from dibenzoyl peroxide (BPO), azodiisobutyronitrile (AIBN), ammonium persulfate,
At least one of potassium peroxydisulfate.
Further, the chain-transferring agent is selected from mercaptopropionic acid, thioacetic acid, at least one of mercaptoethanol and isopropanol.
Abietyl modified vinyl acetate of the present invention refer to using in rosin molecule carboxyl carry out and vinyl acetate
The ester exchange reaction of ester is prepared.Specific example has vinyl tetrahydroabietate (VTA), dehydroabietic acid vinyl acetate (VDA)
With maleopimaric acid vinyl acetate (VMPA).
Vinyl tetrahydroabietate (VTA) is to carry out transesterification with vinylacetate by perhydrogenated rosin to obtain.Specifically
Method refers to Lierpin R, et al.J.Polym.Sci.A, 1966,4 (8): 2003.Dehydroabietic acid vinyl acetate (VDA) be with
Dehydroabietic acid is raw material, and mercuric sulfate is initiator, is prepared with vinylacetate through ester exchange reaction.Specific method reference
Fukuda W, et al.J polym.Sci A.1968,6 (4): 1050.Maleopimaric acid vinyl acetate (VMPA) is Malaysia Korean pine
Sour (MPA) and vinylacetate are prepared through ester exchange reaction, and acid anhydrides is contained in structure, and specific method refers to Lewis
JB, et al.J.Org.Chem.1960,25 (7): 1206.
It is specific to wrap a second object of the present invention is to provide a kind of preparation method of Abietyl modified polycarboxylate water-reducer
Include following steps:
(S1), each reactant is formulated as aqueous solution according to the proportion；
(S2), unsaturated polyether class polymeric monomer is added in the reaction vessel, after being warming up to 40~80 DEG C, slowly adds thereto
Enter small molecule unsaturated carboxylic acid, the salt of small molecule unsaturated carboxylic acid, Abietyl modified vinyl acetate, initiator and chain-transferring agent
Aqueous solution reacts 2~6h at 40~80 DEG C after addition；
(S3) cooling, will to pH be 6~7 in system with liquid alkaline, both the Abietyl modified polycarboxylate water-reducer.
Further, described to be slowly added to small molecule unsaturated carboxylic acid, the salt of small molecule unsaturated carboxylic acid, Abietyl modified second
The aqueous solution of enester, initiator and chain-transferring agent is by the way of being added dropwise.
Further, the aqueous solution that each raw material can be added dropwise into reaction vessel simultaneously respectively is added dropwise, can also hold to reaction
The mixed liquor of each aqueous solution of raw material is added dropwise in device.
Further, time for adding is 2~4h.
Third object of the present invention is application of the above-mentioned Abietyl modified polycarboxylate water-reducer in cement works construction.
Abietyl modified polycarboxylate water-reducer provided by the invention is as the additive in cement, concrete construction, effectively
Improve the workability of cement, while compression strength also has and largely promoted.Confirm that water-reducing agent provided by the invention is comprehensive
It has excellent performance, and easily manufactured, it is low in cost, it is a kind of environmentally protective novel water-reducing agent, there is good marketing
Value.
The present invention carry out simple ester exchange reaction from rosin derivative both and must contain it is active it is double build it is Abietyl modified
Vinyl esters monomer, by with other monomers combined polymerization, the polycarboxylate water-reducer containing rosin molecular structure has been prepared.Pine
Tricyclic phenanthrene skeleton has carried out hydrophobically modified to diminishing agent molecule in fragrant molecular structure, hydrophobic segment enhancing attachment diminishing agent molecule
The interparticle resistance of concrete, strengthens the space steric effect of diminishing agent molecule, strengthens adaptation of the polycarboxylic acids to concrete
Property, reach the mobility for improving slurry thus the comprehensive performance for improving water-reducing agent.Common polycarboxylate water-reducer is in cement point
In granular media system, by polarity electronegative on main chain group, such as carboxyl, sulfonic group, it is adsorbed on cement particle surface, while parent
The side chain polyethylene oxide stretching, extension of water in aqueous solution, plays the role of certain space steric hindrance.It is provided by the invention Abietyl modified
Polycarboxylate water-reducer introduces the molecular structure of rosin in molecular backbone structure.Due to the hydrophobic effect of rosin, not with hydrone
It can interact, generate hydrogen bond, gas-water interface can not be moved to, solid-liquid circle of cement granules and water can only be adsorbed onto
Face, therefore adsorption capacity is greater than common polycarboxylate water-reducer.
It is that the present invention obtains compared with the existing technology the utility model has the advantages that
One, the polycarboxylate water-reducer that the present invention is prepared, can reach 32% or more high water reducing rate in low-dosage,
To provide more intensity marginal spaces when actual production, while making it possible to produce the high-strength concrete easily pumped.
Two, the special construction of rosin introduce certain amount in concrete small, the bubble of homogeneous, extra free water shape
At " ball ", the mobility of coagulation degree is improved, while reducing the brittleness of coagulation degree.
Three, in the case where meeting high water reducing rate, raw material proportioning is carried out preferably, in the case where cement consumption is constant,
So that mixing concrete has Gao Zengqiang.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but should not be understood as limitation of the present invention.
Embodiment 1
(S1) by the raw material of following molar part: 38 parts of methacrylic acids, 5 parts of methylpropene sodium sulfonates, 9 parts of VTA, 0.5 part
Ammonium persulfate and 0.6 part of mercaptopropionic acid are configured to aqueous solution；
(S2), 21 molar part TPEG (number-average molecular weight 2200) are added in the reaction vessel, after being warming up to 60 DEG C, thereto
The aqueous solution of above-mentioned raw materials is added dropwise simultaneously respectively, time for adding 3h reacts 5h at 60~80 DEG C after being added dropwise；
(S3) cooling, will to pH be 6~7 in system with liquid alkaline, both the Abietyl modified polycarboxylate water-reducer.
Embodiment 2
(S1) by the raw material of following molar part: 42 parts of methacrylic acids, 7 parts of methylpropene sodium sulfonates, 10 parts of VTA, 0.8 part
Potassium peroxydisulfate and 0.7 part of mercaptopropionic acid are configured to aqueous solution；
(S2), 25 molar part HPEG (number-average molecular weight 2400) are added in the reaction vessel, after being warming up to 70 DEG C, thereto
The mixed liquor of the aqueous solution of above-mentioned raw materials is added dropwise, time for adding 2h reacts 4h at 60~80 DEG C after being added dropwise；
(S3) cooling, will to pH be 6~7 in system with liquid alkaline, both the Abietyl modified polycarboxylate water-reducer.
The general preparative methods of Abietyl modified polycarboxylate water-reducer
(S1), each reactant is formulated as aqueous solution according to the proportion；
(S2), unsaturated polyether class polymeric monomer is added in the reaction vessel to delay thereto respectively after being warming up to 40~80 DEG C
It is slow that small molecule unsaturated carboxylic acid, the salt of small molecule unsaturated acids, Abietyl modified vinyl acetate, initiator and chain-transferring agent is added
Aqueous solution, after addition at 40~80 DEG C react 2~6h；
(S3) cooling, will to pH be 6~7 in system with liquid alkaline, both the Abietyl modified polycarboxylate water-reducer.
According to above-mentioned general preparative methods, different raw material and proportion are selected, has been prepared a series of Abietyl modified
Polycarboxylate water-reducer (is added without Abietyl modified vinyl acetate monomer) in comparative example.Those skilled in the art according to actual needs may be used
To select suitable reaction condition, such as reaction temperature and reaction time etc..The mode being slowly added to is to be added dropwise, and be can choose point
The mixture of each aqueous solution of raw material is not added dropwise or is directly added dropwise not simultaneously, and time for adding is 2~4h.According to raw material shown in table 1 and
The polycarboxylate water-reducer of embodiment 3-8 and comparative example 1 and 2 is prepared in proportion.
Table 1
The characterization of Abietyl modified polycarboxylate water-reducer
1. gel chromatography is analyzed
Gel aqueous phase chromatography is U.S. Waters gel permeation chromatograph using instrument, and test gained is Abietyl modified poly-
The molecular weight of carboxylic acid water reducer and its distribution.When polycarboxylate water-reducer with 1.0L/min flow velocity pass through chromatographic column, it is different size of
Molecule is separated by pillar at different rates, and chromatogram column temperature control is at 40 DEG C, elutriant 0.1mol/LNa2SO4
Aqueous solution, with the polyethylene glycol calibration standard curve of different molecular weight monodispersity.
2. net slurry experiment and the experiment of coagulation degree
Abietyl modified polycarboxylate water-reducer produced by the present invention is tested for the property.Flowing degree of net paste of cement experiment according to
Relevant criterion specified in GB/T 8077-2010 " concrete admixture homogeneity test method " executes.Polycarboxylate water-reducer folding
Gu volume is 0.12%.The compressive strength test of coagulation degree is according to " the normal concrete mechanical property test side GB/T 50081-2002
Method standard " it carries out, test block size is 100mm × 100mm × 100mm, is converted to reference block intensity by standard requirements.
Test is that concrete admixture examines dedicated fiducial cement with cement in embodiment, is by the silicon of the following index of quality
The P.I type portland cement of 42.5 strength grades made of acid salt cement clinker and dihydrate gypsum intergrinding.Reference cement removes
Meet outside 42.5 strength grade portland cement technical requirements, also compound tricalcium aluminate content 6-8%, tricalcium silicate content 50-
55%, free calcium oxide content is no more than 1.2%, alkali (Na2O+0.658K2O) content is no more than 1.0%, and cement specific surface area is
320±20m2/kg.Operating condition is that the ratio of mud is 0.35, and cement solidification sample curing time is 28 days.
The present invention is made the characterize data of Abietyl modified polycarboxylate water-reducer, performance test results are as shown in table 2 below:
Table 2
Continued 2
As can be seen from Table 2, using Abietyl modified polycarboxylate water-reducer provided by the invention with use conventional method
The polycarboxylic acids of synthesis is compared, MnAnd MwAnd PDI is relatively, illustrates the addition of Abietyl modified vinyl acetate monomer, does not have
Influence polycarboxylic acids molecular structure.But the quiet slurry mobility of Abietyl modified polycarboxylate water-reducer of the invention is obviously improved, and through when
Loss is smaller, has a clear superiority.Under conditions of 0.12% low-dosage, water-reducing agent diminishing with higher provided by the invention
Rate makes it possible to produce the high-strength concrete easily pumped.In addition, also being surveyed to the concrete compression-resistanmodifier performance for mixing water-reducing agent
Examination, after Abietyl modified, compression strength significantly increases polycarboxylate water-reducer of the present invention.It may be hydrophobic rosin molecular structure
The hydration process for affecting cement granules makes its intensity get a promotion.
The above specific embodiment only schematically illustrates the content of present invention, does not represent the limitation of the content of present invention.
It may occur to persons skilled in the art that be that specific structure can have other versions in the present invention.
Claims (10)
1. a kind of Abietyl modified polycarboxylate water-reducer is by including that following molar part raw material is prepared:
20~50 parts of small molecule unsaturated carboxylic acids, the salt of 3~10 parts of small molecule unsaturated acids, 15~30 parts of unsaturated polyether classes are big
Monomer, 5~20 parts of Abietyl modified vinyl acetates, 0.2~2 part of initiator agent and 0.2~2 part of chain-transferring agent.
2. Abietyl modified polycarboxylate water-reducer as described in claim 1, which is characterized in that it is by including that following molar part is former
Material is prepared:
35~50 parts of small molecule unsaturated carboxylic acids, the salt of 5~8 parts of small molecule unsaturated acids, 20~25 parts of unsaturated polyether classes are big
Monomer, 8~12 parts of Abietyl modified vinyl acetates, 0.5~1 part of initiator and 0.5~0.8 part of chain-transferring agent.
3. the Abietyl modified polycarboxylate water-reducer as described in any one of claims 1 or 2, which is characterized in that the small molecule insatiable hunger
At least one of acrylic acid, methacrylic acid is selected from carboxylic acid；Certain ratio can be contained in the small molecule unsaturated carboxylic acid
The ester of example unsaturated carboxylic acid is at least one of methyl esters, ethyl ester, propyl ester and butyl ester, the ester of the unsaturated carboxylic acid at ester group
No more than the 10mol% of unsaturated carboxylic acid.
4. such as the described in any item Abietyl modified polycarboxylate water-reducers of claims 1 or 2, which is characterized in that the small molecule is not
The salt of saturated acid is the salt or acrylic sulfonate of unsaturated carboxylic acid, and the salt is sodium salt or sylvite；Preferably be selected from sodium acrylate,
Potassium acrylate, Sodium methacrylate, methacrylic acid potassium, sodium allylsulfonate, propene sulfonic acid potassium, methylpropene sodium sulfonate and methyl
At least one of propene sulfonic acid potassium.
5. such as the described in any item Abietyl modified polycarboxylate water-reducers of claims 1 or 2, which is characterized in that described unsaturated poly-
Ethers polymeric monomer is selected from allyl polyethenoxy ether (APEG), isoamyl dilute alcohol polyoxyethylene ether (TPEG) and methallyl alcohol polyoxy
At least one of vinethene (HPEG), the number-average molecular weight of the unsaturated polyether class polymeric monomer are 500-4000, preferably
1500-3000。
6. such as the described in any item Abietyl modified polycarboxylate water-reducers of claims 1 or 2, which is characterized in that described Abietyl modified
Vinyl acetate be rosin derivative on carboxyl and vinylacetate carry out transesterification product.
7. Abietyl modified polycarboxylate water-reducer as claimed in claim 6, which is characterized in that the Abietyl modified vinyl acetate is
At least one of vinyl tetrahydroabietate (VTA), dehydroabietic acid vinyl acetate (VDA) and maleopimaric acid vinyl acetate (VMPA).
8. such as the described in any item Abietyl modified polycarboxylate water-reducers of claims 1 or 2, which is characterized in that the initiator choosing
From at least one of dibenzoyl peroxide (BPO), azodiisobutyronitrile (AIBN), ammonium persulfate, potassium peroxydisulfate；The chain turns
It moves agent and is selected from mercaptopropionic acid, thioacetic acid, at least one of mercaptoethanol and isopropanol.
9. such as the preparation method of the described in any item Abietyl modified polycarboxylate water-reducers of claim 1-8, comprising the following steps:
(S1), each reactant is formulated as aqueous solution according to the proportion；
(S2), unsaturated polyether class polymeric monomer is added in the reaction vessel, after being warming up to 40~80 DEG C, is slowly added to thereto small
Molecule unsaturated carboxylic acid, the salt of small molecule unsaturated carboxylic acid, Abietyl modified vinyl acetate, initiator and chain-transferring agent it is water-soluble
Liquid reacts 2~6h at 40~80 DEG C after addition；
(S3) cooling, it will to pH be 6~7 to get the Abietyl modified polycarboxylate water-reducer in system with liquid alkaline.
10. preparation method as claimed in claim 9, which is characterized in that described be slowly added to be added dropwise by the way of being added dropwise
Time is 2~4h；The aqueous solution that each raw material can be added dropwise into reaction vessel simultaneously respectively is added dropwise, it can also be into reaction vessel
The mixed liquor of each aqueous solution of raw material is added dropwise.
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| CN112679675A (en) * | 2020-12-29 | 2021-04-20 | 科之杰新材料集团浙江有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
| CN112939543A (en) * | 2021-03-30 | 2021-06-11 | 刘双燕 | Method for manufacturing self-compacting concrete with high-dispersity water reducing agent |
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| CN112679675A (en) * | 2020-12-29 | 2021-04-20 | 科之杰新材料集团浙江有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
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| CN112939543A (en) * | 2021-03-30 | 2021-06-11 | 刘双燕 | Method for manufacturing self-compacting concrete with high-dispersity water reducing agent |
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