CN109824834A - A kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducer and its preparation method and application - Google Patents
A kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducer and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducers and its preparation method and application.The water-reducing agent contains structural unit A, structural unit B and structural unit C；Wherein, the structural unit A is structural unit shown in formula I, and the structural unit B is structural unit shown in formula II, and the structural unit C is structural unit shown in formula III；
Description
Technical field
The invention belongs to the technical fields of concrete admixture, and in particular to a kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
And its preparation method and application.
Background technique
Fifth component of the polycarboxylate water-reducer as modern concrete is set by its excellent low-dosage, high-thin arch dam, molecule
The advantages that freedom degree is big is counted, is widely used in concrete works technical field.It is now widely used for commerical ready-mixed concrete
Polycarboxylate water-reducer because of the deterioration of sandstone material, lead to the concrete mixed and stirred frequent plugging when pumping at the scene, to construction band
Carry out very big problem；In addition there is also the big caused constructions of many concrete viscosities to ask in many other the realm of building construction
Topic, for example the worker operation of sleeper field needs soft easy construction of concrete etc., but only viscosity-reducing performance is not able to satisfy client's need
It asks, it is still necessary to there is certain concrete holding capacity, leave worker's enough construction times for.Therefore high retention property has been issued
Viscosity reduction type polycarboxylate water-reducer, for improve polycarboxylate water-reducer product defect, promote Functional polycarboxylate superplasticizer answer
With there is extremely important meaning.
TaiWan, China patent TW200424145 uses methacrylic polyethers, allyl polyether, maleic acid, acrylic acid hydroxyl
Ethyl ester is copolymerized to achieve the purpose that rapid dispersion and viscosity reduction, but effect is abundant not enough；Japan Patent JP Tetsukai 2004-43280
Number bulletin improves slurry viscosity using short-side chain reactive polyether polymeric monomer, but since its water-reducing property is poor, needs compared with high additive
Competence exertion effect；Chinese invention patent CN201010139081.5 then passes through the functional group of the introducing viscosity reduction in conventional polymerization
Divide (methylpropene sodium sulfonate) synthesizing ester polycarboxylate water-reducer, there is certain viscosity-reducing performance, but function of slump protection is poor.
Summary of the invention
In order to improve the deficiencies in the prior art, the present invention provides a kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducer and its preparation
Methods and applications.
The first aspect of the present invention provides a kind of high-thin arch dam viscosity reduction type polycarboxylate water-reducer, the high-thin arch dam viscosity reduction type
Polycarboxylate water-reducer contains structural unit A, structural unit B and structural unit C；
Wherein, the structural unit A is structural unit shown in formula I, and the structural unit B is structure list shown in formula II
Member, the structural unit C are structural unit shown in formula III；
It wherein, is connection site at " * "；
R1And R5It is identical or different, hydrogen, unsubstituted or optionally by one, two or more Rs is represented independently of one another1Replace
C1-20Alkyl；
R2And R3It is identical or different, it represents independently of one another unsubstituted or optionally by one, two or more Rs2Replace
C1-20Alkylidene；
Wherein, the number that m+n is 10~250；
P is the number of 0-20；
R4It is unsubstituted or optionally by one, two or more Rs3Substituted C1-20Alkyl, C5-20Aryl, C1-20Alkyl
C5-20Aryl, C1-20Alkyl 5-20 unit's heteroaryl；
Rs1、Rs2、Rs3It is identical or different, it is independently from each other halogen, C1-20Alkyl or C1-20Alkoxy；
M is selected from H, Na, K or NH4One of, two or more；
M1Selected from Na or K.
According to an embodiment of the invention, R1And R5It is identical or different, hydrogen or C are represented independently of one another1-4Alkyl；Example
Property, R1And R5It is identical or different, hydrogen or methyl are represented independently of one another；
R2And R3It is identical or different, the C of linear chain or branched chain is represented independently of one another1-10Alkylidene；Illustratively, R2It represents
Ethylidene, propylidene or butylidene；R3Represent ethylidene or-CH2-CH(CH3)-；
The number that m+n is 20~200；Illustratively, the number that m+n is 40~150；
P is the number of 0-10；Illustratively, p is 0 or 1；
R4It is unsubstituted or optionally by one, two or more Rs3Substituted C1-12Alkyl, C6-14Aryl or C1-12Alkyl
C6-14Aryl；Illustratively, R4Selected from methyl, ethyl, propyl, butyl or phenyl；
Rs3Selected from halogen, C1-12Alkyl or C1-12Alkoxy；
M is selected from H, Na, K；
M1Selected from Na or K.
According to an embodiment of the invention, on the basis of the total weight of the polycarboxylate water-reducer, the structural unit A's
Weight content is 80~95%, such as 82~90%, 84~88%.
According to an embodiment of the invention, on the basis of the total weight of the polycarboxylate water-reducer, the structural unit B's
Weight content is 1~10%, such as 2~9%, 4~7%.
According to an embodiment of the invention, on the basis of the total weight of the polycarboxylate water-reducer, the structural unit C's
Weight content is 1~10%, such as 2~9%, 4~7%.
Polycarboxylate water-reducer according to the present invention, the number-average molecular weight of the water-reducing agent is 10000-50000g/mol, excellent
It is selected as 10000-40000g/mol, also preferably 15000-30000g/mol.
According to an embodiment of the invention, the solid content of the polycarboxylate water-reducer is 36~53%, such as 40~50%.
The present invention also provides the preparation method of above-mentioned high-thin arch dam viscosity reduction type polycarboxylate water-reducer, the preparation method include with
Lower step:
The monomer F of structure shown in the monomer E and formula VI of structure shown in monomer D, formula V containing structure shown in formula IV is through poly-
It closes reaction and obtains the high-thin arch dam viscosity reduction type polycarboxylate water-reducer；
Wherein, R1' and R5' there is above-mentioned R1And R5Identical definition, R2' and R3' there is above-mentioned R2And R3Identical definition,
M, n has the identical definition of above-mentioned m, n, R4' the same R of definition4, M ' and M1' there is above-mentioned M and M1Identical definition, p have upper
The text definition.
Preparation method according to the present invention, the preparation method is specifically includes the following steps: the list containing structure shown in formula IV
The monomer F of structure shown in the monomer E and formula VI of structure shown in body D, formula V carries out alkene in the presence of initiator in water
Solution polymerization obtains the polycarboxylate water-reducer.
Illustratively, the aqueous solution of the monomer D can be first prepared, then is prepared containing monomer E, monomer F and initiator
The mixed liquor is added dropwise into the aqueous solution of the monomer D, is added dropwise to complete post curing, is cooled to room temperature, obtain institute by mixed liquor
State polycarboxylate water-reducer.
The weight ratio of preparation method according to the present invention, the monomer D, monomer E and monomer F can for 1:(0.01~
0.2): (0.01~0.2)；Such as weight ratio can be 1:(0.01~0.117): (0.01~0.117), 1:(0.02~0.1):
(0.02~0.1).
Preparation method according to the present invention, wherein monomer D can refer to disclosed in Chinese invention patent CN 105778079A
Method synthesis.
Preparation method according to the present invention, the monomer D can be 4- hydroxyl butyl vinyl polyoxyethylene polyethers or 2- second
Alkenyloxy group ethyl alcohol polyoxyethylene polyethers is reacted with butyl isocyanate or toluene diisocyanate to be prepared.
Preferably, the monomer D is the 4- hydroxyl butyl vinyl that the molecular weight of toluene diisocyanate sealing end is 2000-5000
The 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that the molecular weight of polyoxyethylene polyethers or butyl isocyanate sealing end is 2000-5000
At least one of.
Preparation method according to the present invention, the monomer F according to document S.Gou, S.Luo, T.Liu, H.Xia, D.Jing,
Synthetic method preparation in Q.Zhang, S.Li, Z.Li and Q.Guo, RSC Adv., 2015,5,85165-85173.
Monomer E is added in the above-mentioned polymerization reaction of the present invention be conducive to increase prepared guarantor collapse viscosity reduction type water-reducing agent
Space protection ability, monomer E and monomer F is cooperateed in proportion be added to guarantor collapse be conducive to complex optimum in viscosity reduction type water-reducing agent should
The guarantor for protecting the viscosity reduction type water-reducing agent that collapses is collapsed viscosity-reducing performance.
Preparation method according to the present invention, reaction temperature can be 5~70 DEG C, for example, 10~40 DEG C, illustratively, institute
Stating temperature is 10 DEG C, 20 DEG C, 40 DEG C.Reaction time can be 1~10h, for example, 2~4h.
Preparation method according to the present invention, the reaction carry out in the presence of initiator, and the initiator is that oxidation is gone back
Substance series initiators.For example, the dosage of the oxidant in the redox system initiator can be the monomer mixture
The 0.05~2% of total weight, for example, 0.1~1.0%；It illustratively, is 0.099%, 0.45%, 0.99%.Wherein, described
Oxidant can be bis- (hydrogen peroxide) selected from benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5
At least one of hexane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
Preparation method according to the present invention, the reaction carry out in the presence of a reducing agent, and the dosage of the reducing agent can
Think the 0.01~2% of the monomer mixture total weight, for example, 0.02~1%；Illustratively, for 0.02%, 0.3%,
1.0%.Wherein, the reducing agent can selected from L-AA, L-AA salt, L-AA ester, arabo-ascorbic acid,
Erythorbate, arabo-ascorbic acid ester, ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, sulfurous
At least one of sour hydrogen ammonium, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite.
Preparation method according to the present invention, the reaction carry out in the presence of molecular weight regulators, the molecular weight tune
Saving agent can be mercaptoethanol, thioglycerin, thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid, thiomalic acid, thioacetic acid
Monooctyl ester, 3- mercaptopropionic acid monooctyl ester, mistabrom, n-dodecyl mercaptan, octyl mercaptan, thioacetic acid butyl ester, isopropanol,
One of sodium hypophosphite and potassium hypophosphite, two or more.The dosage of the molecular weight regulator can be the monomer
The 0.1~1.0% of total weight of the mixture, such as 0.5~1.0%；It illustratively, is 0.8%, 1.0%.
Application the present invention also provides above-mentioned high-thin arch dam viscosity reduction type polycarboxylate water-reducer in fields such as cement, concrete.
Beneficial effects of the present invention:
It is provided by the invention to protect the viscosity reduction type polycarboxylate water-reducer that collapses, pass through the conjunction for selecting suitable functional form monomer and monomer
It is adapted to ratio, is collapsed viscosity-reducing performance with improving the guarantor of polycarboxylic acids water reducing ability.It is provided by the invention to protect the viscosity reduction type water-reducing agent that collapses, molecular backbone
It is upper to have cyclic structure, enhance the suction-operated with cement, while contain simultaneously on functional monomer tertiary amine groups, hydroxyl,
It is preferably acted on relatively after sulfonic acid group is introduced into diminishing agent molecule with alkaline cement System forming, enhances water-reducing agent in water
Wetting, infiltration and the absorption on mud surface, and water film thickness can be effectively increased, repulsion is made between enhancing cement granules
With keeping discrete particles smaller, destroy the flocculent structure of cement granules, Cement-water System is made to be in metastable suspension
State, to make water-reducing agent that there is outstanding guarantor to collapse and viscosity-reducing performance.
Term definition and explanation
Unless otherwise indicated, the numberical range that present specification and claims are recorded, when the numberical range is defined as
When " number ", it should be understood that describe two endpoints of the range, each integer within the scope of this and every within the scope of this
One decimal.For example, " 0~10 number " should be understood as not only describing each of 0,1,2,3,4,5,6,7,8,9 and 10
Integer, also at least describe wherein each integer respectively with 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 and.
Term " halogen " indicates fluorine, chlorine, bromine and iodine.
Term " C1-20Alkyl " is interpreted as the preferred linear chain or branched chain saturated hydrocarbyl for indicating to have 1~20 carbon atom,
Preferably C1-12Alkyl."C1-12Alkyl " is interpreted as preferred indicate with 1,2,3,4,5,6,7,8,9,10,11 or 12 carbon original
The linear chain or branched chain saturated hydrocarbyl of son.The alkyl is such as methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, different
Butyl, sec-butyl, tert-butyl, isopentyl.Particularly, the group has 1,2,3,4,5,6 carbon atom (" C1-6Alkyl "),
Such as methyl, ethyl, propyl, butyl, amyl, hexyl, isopropyl, isobutyl group, sec-butyl, tert-butyl.
Term " C1-20The definition of alkyl " is also applied for other containing C1-20The group of alkyl, such as C1-20Alkoxy, C1-20Alkane
Base C5-20Aryl, C1-20Alkyl 5-20 unit's heteroaryl.
Term " C1-20Alkylidene " is above-mentioned C1-20Alkyl further replaces the group in site containing one.
Term " C5-20Aryl " is interpreted as the preferred monovalence armaticity or partial aromatic for indicating to have 5~20 carbon atoms
The monocyclic, bicyclic or tricyclic hydrocarbon ring of property, preferably " C6-14Aryl ".Term " C6-14Aryl " be interpreted as it is preferred indicate to have 6,7,
8,9,10,11,12, the 13 or 14 monovalence armaticity of carbon atom or monocyclic, bicyclic or tricyclic hydrocarbon rings of partial aromatic
(“C6-14Aryl "), especially with the ring (" C of 6 carbon atoms6Aryl "), such as phenyl；Or xenyl, or there are 9
The ring (" C of carbon atom9Aryl "), such as indanyl or indenyl, or the ring (" C with 10 carbon atoms10Aryl "), such as
Tetrahydro naphthyl, ihydro naphthyl or naphthalene, or the ring (" C with 13 carbon atoms13Aryl "), such as fluorenyl, either
Ring (" C with 14 carbon atoms14Aryl "), such as anthryl.
Term " 5-20 unit's heteroaryl " is interpreted as former containing 5-20 annular atom, 5-14 annular atom or 5-12 ring
The monocycle of son or 5-10 annular atom or 5-6 annular atom, bicyclic and three-ring system, wherein at least one ring system are fragrance
Race, and at least one ring system includes one or more hetero atoms (such as N, O, S, Se etc.), wherein each ring system packet
Containing 5-7 former molecular ring, and there are one or more tie points to be connected with molecule rest part.The heteroaryl groups are optional
Ground is replaced one or more substituent groups described in the invention.In some embodiments, 5-10 original is molecular miscellaneous
Aryl includes 1,2,3 or 4 hetero atoms for being independently selected from O, S, Se and N.In other embodiments, 5-6 atom composition
Heteroaryl include 1,2,3 or 4 hetero atoms for being independently selected from O, S, Se and N.
The Monocyclic examples of heteroaryl groups include, but is not limited to, thienyl, furyl, pyrrole radicals, oxazolyl, thiazole
Base, imidazole radicals, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazoles base, triazolyl, thiadiazolyl group, thiophene -4H- pyrazolyl etc. with
And their benzo derivative, such as benzofuranyl, benzothienyl, benzoxazolyl, benzo isoxazolyl, benzimidazole
Base, benzotriazole base, indazolyl, indyl, isoindolyl etc.；Or pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical
Deng and their benzo derivative, such as quinolyl, quinazolyl, isoquinolyl etc.；Or azocine base, indolizine base, purine
Base etc. and their benzo derivative；Or cinnoline base, phthalazinyl, quinazolyl, quinoxalinyl, naphthyridines base, pteridyl, carbazole
Base, acridinyl, phenazinyl, phenothiazinyl, phenoxazine base etc..
When M or M ' is H in this paper structure formula (II) and formula (V), indicate that formula (II) and (V) are carboxylic acid structure, when M or M ' are
Na, K or NH4When, it indicates formula (II) and (V) is carboxylate structure.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
In the embodiment of the present invention, the number-average molecular weight M of polymernUsing Agilent technologies HPLC instrument
Device measurement, chromatographic column are 120 3 pillars of ultrahydrogel 500+ultrahydrogel 250+ultrahydrogel
Series connection, mobile phase are 0.1mol/L sodium nitrate aqueous solution, and flow velocity 1.0ml/min, molecular weight is respectively 202g/mol, 430g/
The PEG of mol, 960g/mol, 4290g/mol, 12600g/mol, 44000g/mol, 152000g/mol are standard sample.
Embodiment 1
Under the conditions of 20 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 87g toluene diisocyanate blocks, (molecular weight is
3000) be placed in kettle and dissolved in 60g water, be added 0.8g thioacetic acid (by thioacetic acid replace with mercaptoethanol, thioglycerin,
2 mercaptopropionic acid, 3- mercaptopropionic acid, thiomalic acid, thioacetic acid monooctyl ester, 3- mercaptopropionic acid monooctyl ester, mistabrom, just
At least one of lauryl mercaptan, octyl mercaptan, thioacetic acid butyl ester, isopropanol, sodium hypophosphite and potassium hypophosphite can also
To obtain target product), L-AA (is replaced with L-AA salt, L-AA ester, different by 0.3gL- ascorbic acid
Ascorbic acid, erythorbate, arabo-ascorbic acid ester, ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sulfurous
At least one in sour sodium, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite
Plant also available target product), it then begins to that 6g acrylic acid, 7g 3- (diallyl amino) -2- hydroxypropyl sulfonic acid is added dropwise
Hydrogen peroxide (is replaced with other oxidants such as Benzoyl Oxide, tert-butyl by sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution)
At least one in bis- (hydrogen peroxide) hexanes of hydrogen peroxide, 2,5- dimethyl -2,5, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate
Kind also available target product), the mixed liquor of 40g water, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature,
Obtain high-thin arch dam viscosity reduction type polycarboxylate water-reducer product S1.Product is through infrared spectrum characterization, in infrared spectrum spectrogram
3440.28cm-1For the stretching vibration of O-H；2871.32cm-1And 2873.25cm-1Strong absworption peak be-CH2Stretching vibration
With-CH3Bending vibration；1731.25cm-1Strong absworption peak be C=O in acrylic acid units vibration peak, 1715.26cm-1For ammonia
The vibration peak of C=O, 1185.18cm in carbamate-1For-SO3The stretching vibration of Na, 1105.50cm-1And 1259.62cm-1Place
Strong absworption peak be-C-O-C- stretching vibration；It is tested through GPC, Mn 25150g/mol.
Embodiment 2
Under the conditions of 10 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 90g toluene diisocyanate blocks, (molecular weight is
2000) it is placed in kettle and is dissolved in 60g water, 0.1g thioacetic acid is added, 1.0gL- ascorbic acid then begins to that 2g propylene is added dropwise
Acid, 8g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 3.3g hydrogen peroxide (30 mass % aqueous solution), 40g water it is mixed
Liquid is closed, time for adding 2h is added dropwise to complete post curing 2h, is cooled to room temperature, obtains the production of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S2.Product is through infrared spectrum characterization, 3440.48cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.56cm-1With
2873.67cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.35cm-1Strong absworption peak be third
The vibration peak of C=O, 1715.12cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.16cm-1For-
SO3The stretching vibration of Na, 1105.55cm-1And 1259.62cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 18150g/mol.
Embodiment 3
Under the conditions of 40 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 82g toluene diisocyanate blocks, (molecular weight is
5000) it is placed in kettle and is dissolved in 60g water, 1.0g thioacetic acid is added, 0.02gL- ascorbic acid then begins to that 9g third is added dropwise
Olefin(e) acid sodium, 9g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 0.33g hydrogen peroxide (30 mass % aqueous solution), 40g water
Mixed liquor, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains high-thin arch dam viscosity reduction type polycarboxylic acids diminishing
Agent product S3.Product is through infrared spectrum characterization, 3441.58cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.65cm-1And 2873.45cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1560.47cm-1's
Strong absworption peak is the vibration peak of C=O in sodium acrylate unit, 1715.46cm-1For the vibration peak of C=O in carbamate,
1185.36cm-1For-SO3The stretching vibration of Na, 1104.08cm-1And 1257.86cm-1The strong absworption peak at place is flexible for-C-O-C-
Vibration；It is tested through GPC, Mn 28850g/mol.
Embodiment 4
Under the conditions of 20 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 87g butyl isocyanate blocks, (molecular weight is
3500) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 6g propylene is added dropwise
Acid, 7g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water it is mixed
Liquid is closed, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains the production of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S4.Product is through infrared spectrum characterization, 3440.58cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.86cm-1With
2873.75cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.55cm-1Strong absworption peak be third
The vibration peak of C=O, 1715.20cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.32cm-1For-
SO3The stretching vibration of Na, 1105.49cm-1And 1259.58cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 25860g/mol.
Embodiment 5
Under the conditions of 10 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 90g butyl isocyanate blocks, (molecular weight is
2000) it is placed in kettle and is dissolved in 60g water, 0.1g thioacetic acid is added, 1.0gL- ascorbic acid then begins to that 2g propylene is added dropwise
Acid, 8g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 3.3g hydrogen peroxide (30 mass % aqueous solution), 40g water it is mixed
Liquid is closed, time for adding 2h is added dropwise to complete post curing 2h, is cooled to room temperature, obtains the production of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S5.Product is through infrared spectrum characterization, 3441.12cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.15cm-1With
2873.14cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1730.85cm-1Strong absworption peak be third
The vibration peak of C=O, 1715.03cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.12cm-1For-
SO3The stretching vibration of Na, 1105.20cm-1And 1259.38cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 19060g/mol.
Embodiment 6
Under the conditions of 40 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 82g butyl isocyanate blocks, (molecular weight is
5000) it is placed in kettle and is dissolved in 60g water, 1.0g thioacetic acid is added, 0.02gL- ascorbic acid then begins to that 9g third is added dropwise
Olefin(e) acid, 9g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 0.33g hydrogen peroxide (30 mass % aqueous solution), 40g water
Mixed liquor, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature, obtain high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S6.Product is through infrared spectrum characterization, 3440.50cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.68cm-1
And 2873.55cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.35cm-1Strong absworption peak be
The vibration peak of C=O, 1715.18cm in acrylic acid units-1For the vibration peak of C=O in carbamate, 1185.21cm-1For-
SO3The stretching vibration of Na, 1105.16cm-1And 1259.37cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 29600g/mol.
Embodiment 7
Under the conditions of 20 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 87g butyl isocyanate blocks, (molecular weight is
3500) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 6g methyl is added dropwise
Acrylic acid, 7g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water
Mixed liquor, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains high-thin arch dam viscosity reduction type polycarboxylic acids diminishing
Agent product S7.Product is through infrared spectrum characterization, 3440.45cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.38cm-1And 2873.55cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.49cm-1's
Strong absworption peak is the vibration peak of C=O in acrylic acid units, 1715.58cm-1For the vibration peak of C=O in carbamate,
1185.37cm-1For-SO3The stretching vibration of Na, 1105.61cm-1And 1259.86cm-1The strong absworption peak at place is flexible for-C-O-C-
Vibration；It is tested through GPC, Mn 24230g/mol.
Embodiment 8
Under the conditions of 20 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 87g toluene diisocyanate blocks, (molecular weight is
3000) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 6g methyl is added dropwise
Acrylic acid, 7g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water
Mixed liquor, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains high-thin arch dam viscosity reduction type polycarboxylic acids diminishing
Agent product S8.Product is through infrared spectrum characterization, 3441.56cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.87cm-1And 2873.67cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.68cm-1's
Strong absworption peak is the vibration peak of C=O in acrylic acid units, 1715.65cm-1For the vibration peak of C=O in carbamate,
1185.64cm-1For-SO3The stretching vibration of Na, 1105.86cm-1And 1259.88cm-1The strong absworption peak at place is flexible for-C-O-C-
Vibration；It is tested through GPC, Mn 26210g/mol.
Embodiment 9
Under the conditions of 20 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 87g toluene diisocyanate blocks, (molecular weight is
1000) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 6g propylene is added dropwise
Acid, 7g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water it is mixed
Liquid is closed, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains the production of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S9.Product is through infrared spectrum characterization, 3441.66cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.76cm-1With
2873.62cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.57cm-1Strong absworption peak be third
The vibration peak of C=O, 1715.54cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.45cm-1For-
SO3The stretching vibration of Na, 1105.65cm-1And 1259.53cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 16500g/mol.
Embodiment 10
Under the conditions of 20 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 87g butyl isocyanate blocks, (molecular weight is
8000) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 6g propylene is added dropwise
Acid, 7g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water it is mixed
Liquid is closed, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains the production of high-thin arch dam viscosity reduction type polycarboxylate water-reducer
Product S10.Product is through infrared spectrum characterization, 3440.23cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.25cm-1
And 2873.46cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.32cm-1Strong absworption peak be
The vibration peak of C=O, 1715.18cm in acrylic acid units-1For the vibration peak of C=O in carbamate, 1185.26cm-1For-
SO3The stretching vibration of Na, 1105.12cm-1And 1259.33cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 38560g/mol.
Comparative example 1
Under the conditions of 20 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 87g butyl isocyanate blocks, (molecular weight is
3500) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 13g third is added dropwise
Olefin(e) acid, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h is added dropwise to complete post curing
1h is cooled to room temperature, obtains polycarboxylate water-reducer product P1.Product is through infrared spectrum characterization, in infrared spectrum spectrogram
3440.55cm-1For the stretching vibration of O-H；2871.65cm-1And 2873.75cm-1Strong absworption peak be-CH2Stretching vibration
With-CH3Bending vibration；1731.43cm-1Strong absworption peak be C=O in acrylic acid units vibration peak, 1715.46cm-1For ammonia
The vibration peak of C=O, 1105.37cm in carbamate-1And 1259.56cm-1The strong absworption peak at place is-C-O-C- stretching vibration；
It is tested through GPC, Mn 26760g/mol.
Comparative example 2
Under the conditions of 20 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 87g toluene diisocyanate blocks, (molecular weight is
3000) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 13g third is added dropwise
Olefin(e) acid, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h is added dropwise to complete post curing
1h is cooled to room temperature, obtains polycarboxylate water-reducer product P2.Product is through infrared spectrum characterization, in infrared spectrum spectrogram
3440.26cm-1For the stretching vibration of O-H；2871.36cm-1And 2873.53cm-1Strong absworption peak be-CH2Stretching vibration
With-CH3Bending vibration；1731.18cm-1Strong absworption peak be C=O in acrylic acid units vibration peak, 1715.20cm-1For ammonia
The vibration peak of C=O, 1105.25cm in carbamate-1And 1259.32cm-1The strong absworption peak at place is-C-O-C- stretching vibration；
It is tested through GPC, Mn 25420g/mol.
Comparative example 3
Under the conditions of 20 DEG C, by 4- hydroxyl butyl vinyl polyoxyethylene polyethers that 87g toluene diisocyanate blocks, (molecular weight is
3000) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 12.2g is added dropwise
Acrylic acid, 0.8g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g
The mixed liquor of water, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature, obtain polycarboxylate water-reducer product P3.It produces
Object is through infrared spectrum characterization, 3440.46cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.50cm-1With
2873.66cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.18cm-1Strong absworption peak be third
The vibration peak of C=O, 1715.35cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.43cm-1For-
SO3The stretching vibration of Na, 1105.25cm-1And 1259.58cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 28350g/mol.
Comparative example 4
Under the conditions of 20 DEG C, by 2- ethyleneoxy ethyl alcohol polyoxyethylene polyethers that 87g butyl isocyanate blocks, (molecular weight is
3500) it is placed in kettle and is dissolved in 60g water, 0.8g thioacetic acid is added, 0.3gL- ascorbic acid then begins to that 12.2g is added dropwise
Acrylic acid, 0.8g 3- (diallyl amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g
The mixed liquor of water, time for adding 2h are added dropwise to complete post curing 1h, are cooled to room temperature, obtain polycarboxylate water-reducer product P4.It produces
Object is through infrared spectrum characterization, 3441.12cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；2871.23cm-1With
2873.13cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1730.86cm-1Strong absworption peak be third
The vibration peak of C=O, 1714.85cm in olefin(e) acid unit-1For the vibration peak of C=O in carbamate, 1185.96cm-1For-
SO3The stretching vibration of Na, 1105.74cm-1And 1259.68cm-1The strong absworption peak at place is-C-O-C- stretching vibration；It is surveyed through GPC
Examination, Mn 28120g/mol.
Test case 1
1. flowing degree of net paste of cement
The mobility of solid P.0 42.5 cement of disk is made to investigate the dam viscosity reduction type polycarboxylate water-reducer of protecting that the present invention synthesizes
With effect, test determines under identical volume each embodiment to the paste flowing degree of different cement types.GB/ is pressed in test
T8077-2012 " Methods for testing uniformity of concrete admixture " is carried out, ratio of mud W/C=0.29, and rolling over solid volume is 0.15%.
Test result is shown in Table 1.
1 pulp flowage results of property of table
From table 1 it follows that the high-thin arch dam viscosity reduction polycarboxylate water-reducer performance of embodiment 1-10 method synthesis is above
The water-reducing agent of comparative example 1-4 method synthesis, such as in solid volume 0.15% with excellent net slurry retention property.
2. testing concrete performance
Test is referring to GB/T50080-2016 " Standard for test methods of properties of ordinary concrete mixture standard ", GB8076-2008
" concrete admixture " carries out concrete NDT to sample obtained by embodiment and comparative example.Sample is in solid P.0 42.5 cement of disk
Solid volume be 0.20%, concrete mix be benchmark cement: sand: stone: water=380:578:848:130.Test result
It is shown in Table 2.
2 concrete slump of table, divergence and compression strength
From Table 2, it can be seen that the high-thin arch dam viscosity reduction type polycarboxylate water-reducer of the method for the present invention preparation, more common high-performance
Poly- carboxylic ester water-reducing agent shows superior workability and concrete mellowness in concrete, with excellent viscosity reduction ability and
Retention property.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of polycarboxylate water-reducer, which is characterized in that the polycarboxylate water-reducer contains structural unit A, structural unit B and knot
Structure unit C；
Wherein, the structural unit A is structural unit shown in formula I, and the structural unit B is structural unit shown in formula II,
The structural unit C is structural unit shown in formula III；
It wherein, is connection site at " * "；
R1And R5It is identical or different, hydrogen, unsubstituted or optionally replaced by one, two or more Rs1 is represented independently of one another
C1-20Alkyl；
R2And R3It is identical or different, C that is unsubstituted or optionally being replaced by one, two or more Rs2 is represented independently of one another1-20
Alkylidene；
Wherein, the number that m+n is 10~250；
P is the number of 0-20；
R4For C that is unsubstituted or optionally being replaced by one, two or more Rs31-20Alkyl, C5-20Aryl, C1-20Alkyl C5-20Virtue
Base, C1-20Alkyl 5-20 unit's heteroaryl；
Rs1, Rs2, Rs3 are identical or different, are independently from each other halogen, C1-20Alkyl or C1-20Alkoxy；
M is selected from H, Na, K or NH4One of, two or more；
M1Selected from Na or K.
2. polycarboxylate water-reducer according to claim 1, which is characterized in that R1And R5It is identical or different, generation independently of one another
Table hydrogen or C1-4Alkyl；
R2And R3It is identical or different, the C of linear chain or branched chain is represented independently of one another1-10Alkylidene；
The number that m+n is 20~200；
P is the number of 0-10；
R4For C that is unsubstituted or optionally being replaced by one, two or more Rs31-12Alkyl, C6-14Aryl or C1-12Alkyl C6-14Virtue
Base；
Rs3 is selected from halogen, C1-12Alkyl or C1-12Alkoxy；
M is selected from H, Na, K；
M1Selected from Na or K.
3. polycarboxylate water-reducer according to claim 1 or 2, which is characterized in that R1And R5It is identical or different, independently of one another
Ground represents hydrogen or methyl；
R2Represent ethylidene, propylidene or butylidene；
R3Represent ethylidene or-CH2-CH(CH3)-；
The number that m+n is 40~150；
P is 0 or 1；
R4Selected from methyl, ethyl, propyl, butyl or phenyl；
M is selected from H, Na, K；
M1Selected from Na or K.
4. polycarboxylate water-reducer according to claim 1-3, which is characterized in that with the polycarboxylate water-reducer
On the basis of total weight, the weight content of the structural unit A is 80~95%；
On the basis of the total weight of the polycarboxylate water-reducer, the weight content of the structural unit B is 1~10%；
On the basis of the total weight of the polycarboxylate water-reducer, the weight content of the structural unit C is 1~10%.
5. polycarboxylate water-reducer according to claim 1-4, which is characterized in that the molecular weight of the water-reducing agent is
10000-50000g/mol。
6. polycarboxylate water-reducer according to claim 1-5, which is characterized in that the polycarboxylate water-reducer contains
Gu amount is 36~53%.
7. the preparation method of polycarboxylate water-reducer described in any one of claims 1-6, which comprises the following steps:
The monomer F of structure shown in the monomer E and formula VI of structure shown in monomer D, formula V containing structure shown in formula IV is aggregated anti-
It should obtain the high-thin arch dam viscosity reduction type polycarboxylate water-reducer；
Wherein, R1' and R5' there is R1And R5Identical definition, R2' and R3' there is R2And R3Identical definition, m, n have m, n phase
Same definition, R4' the same R of definition4, M ' and M1' there is M and M1Identical definition, p definition having the same.
8. preparation method according to claim 7, which is characterized in that the weight ratio of the monomer D, monomer E and monomer F is
1:(0.01~0.2): (0.01~0.2).
9. preparation method according to claim 7 or 8, which is characterized in that the reaction carries out in the presence of initiator,
The initiator is redox system initiator；
Preferably, the dosage of the oxidant in the redox system initiator is the 0.05 of the monomer mixture total weight
~2%；
Preferably, the oxidant is selected from benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5
At least one of bis- (hydrogen peroxide) hexanes, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；
Preferably, the reaction carries out in the presence of a reducing agent, and the dosage of the reducing agent is the monomer mixture gross weight
The 0.01~2% of amount；
Preferably, the reducing agent is selected from L-AA, L-AA salt, L-AA ester, arabo-ascorbic acid, different anti-
Bad hematic acid salt, arabo-ascorbic acid ester, ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, bisulfite
At least one of ammonium, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite；
Preferably, the reaction carries out in the presence of molecular weight regulators, and the molecular weight regulator is mercaptoethanol, sulphur is sweet
Oil, thioacetic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid, thiomalic acid, thioacetic acid monooctyl ester, 3- mercaptopropionic acid monooctyl ester, 2- mercapto
One in base ethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, thioacetic acid butyl ester, isopropanol, sodium hypophosphite and potassium hypophosphite
It plants, two or more；
Preferably, the dosage of the molecular weight regulator is the 0.1~1.0% of the monomer mixture total weight.
10. polycarboxylate water-reducer described in any one of claims 1-6 is in the application in the fields such as cement, concrete.
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