CN109824834B - High slump loss resistant and viscosity reduction type polycarboxylate superplasticizer and preparation method and application thereof - Google Patents
High slump loss resistant and viscosity reduction type polycarboxylate superplasticizer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer and a preparation method and application thereof. The water reducing agent comprises a structural unit A, a structural unit B and a structural unit C; the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, and the structural unit C is a structural unit shown as a formula III;
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer as well as a preparation method and application thereof.
Background
The polycarboxylate superplasticizer is used as a fifth component of modern concrete, and has been widely applied to the technical field of concrete engineering by virtue of the advantages of excellent low dosage, high slump loss resistance, large degree of freedom of molecular design and the like. At present, the polycarboxylate superplasticizer widely applied to commercial concrete causes frequent pipe blockage of mixed concrete during field pumping due to the deterioration of sandstone materials, thereby bringing great problems to construction; in addition, a plurality of construction problems caused by high concrete viscosity exist in other building construction fields, for example, workers in the sleeper field need soft concrete for construction, but the requirements of customers cannot be met only by viscosity reduction performance, and certain concrete retention capacity is still needed to be provided for the workers for enough construction time. Therefore, the development of the viscosity-reducing polycarboxylate superplasticizer with high retention performance has extremely important significance for perfecting the defects of polycarboxylate superplasticizer products and popularizing the application of functional polycarboxylate superplasticizers.
Taiwan patent TW200424145 adopts methyl allyl polyether, maleic acid and hydroxyethyl acrylate to copolymerize to achieve the purposes of rapid dispersion and viscosity reduction, but the effect is not sufficient; japanese patent JP-A-2004-43280 discloses that short-side-chain reactive polyether macromonomer is adopted to improve slurry viscosity, but because of poor water reducing performance, higher mixing amount is needed to exert the effect; the Chinese patent CN201010139081.5 synthesizes ester polycarboxylate superplasticizer by introducing a viscosity-reducing functional component (sodium methallyl sulfonate) in conventional polymerization, and has certain viscosity-reducing performance but poorer slump-retaining performance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high slump-retaining viscosity-reducing type polycarboxylate superplasticizer and a preparation method and application thereof.
The invention provides a high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer, which comprises a structural unit A, a structural unit B and a structural unit C;
the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, and the structural unit C is a structural unit shown as a formula III;
wherein "+" indicates a connection site;
R1and R5Identical or different, independently of one another, represent hydrogen, unsubstituted or optionally substituted by one, two or more Rs1Substituted C1-20An alkyl group;
R2and R3Identical or different, independently of one another, represent unsubstituted or optionally substituted by one, two or more Rs2Substituted C1-20An alkylene group;
wherein m + n is a number of 10 to 250;
p is a number from 0 to 20;
R4is unsubstituted or optionally substituted by one, two or more Rs3Substituted C1-20Alkyl radical, C5-20Aryl radical, C1-20Alkyl radical C5-20Aryl radical, C1-20Alkyl 5-20 membered heteroaryl;
Rs1、Rs2、Rs3identical or different, independently of one another, from halogen, C1-20Alkyl or C1-20An alkoxy group;
m is selected from H, Na, K or NH4One, two or more of;
M1selected from Na or K.
According to an embodiment of the invention, R1And R5Identical or different, independently of one another, represent hydrogen or C1-4An alkyl group; illustratively, R1And R5Identical or different, independently of one another, represent hydrogen or methyl;
R2and R3Identical or different, independently of one another, represent a linear or branched C1-10An alkylene group; illustratively, R2Represents ethylene, propylene or butylene; r3Represents ethylene or-CH2-CH(CH3)-；
m + n is a number of 20 to 200; illustratively, m + n is a number from 40 to 150;
p is a number from 0 to 10; illustratively, p is 0 or 1;
R4is unsubstituted or optionally substituted by one, two or more Rs3Substituted C1-12Alkyl radical, C6-14Aryl or C1-12Alkyl radical C6-14An aryl group; illustratively, R4Selected from methyl, ethyl, propyl, butyl or phenyl;
Rs3selected from halogen, C1-12Alkyl or C1-12An alkoxy group;
m is selected from H, Na and K;
M1selected from Na or K.
According to the embodiment of the invention, the weight content of the structural unit A is 80-95%, such as 82-90% and 84-88% based on the total weight of the polycarboxylate superplasticizer.
According to an embodiment of the present invention, the weight content of the structural unit B is 1 to 10%, for example, 2 to 9%, 4 to 7%, based on the total weight of the polycarboxylate superplasticizer.
According to an embodiment of the present invention, the weight content of the structural unit C is 1 to 10%, for example, 2 to 9%, 4 to 7%, based on the total weight of the polycarboxylate superplasticizer.
According to the polycarboxylic acid water reducing agent, the number average molecular weight of the water reducing agent is 10000-40000g/mol, preferably 10000-40000g/mol and more preferably 15000-30000 g/mol.
According to an embodiment of the invention, the solid content of the polycarboxylate superplasticizer is 36-53%, for example 40-50%.
The invention also provides a preparation method of the high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer, which comprises the following steps:
carrying out polymerization reaction on a monomer D with a structure shown in a formula IV, a monomer E with a structure shown in a formula V and a monomer F with a structure shown in a formula VI to obtain the high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer;
wherein R is1' and R5' having the above-mentioned R1And R5Same definition of R2' and R3' having the above-mentioned R2And R3The same definition, m and n have the same definition as m and n, R4' is as defined for R4M' and M1' having the above M and M1The same definition, p has the definition described above.
According to the preparation method of the invention, the preparation method specifically comprises the following steps: the polycarboxylic acid water reducer is prepared by carrying out solution polymerization reaction on olefin in water in the presence of an initiator by using a monomer D with a structure shown in a formula IV, a monomer E with a structure shown in a formula V and a monomer F with a structure shown in a formula VI.
For example, the polycarboxylic acid water reducing agent can be obtained by preparing an aqueous solution of the monomer D, then preparing a mixed solution containing the monomer E, the monomer F and an initiator, dropwise adding the mixed solution into the aqueous solution of the monomer D, curing after the dropwise adding is completed, and cooling to room temperature.
According to the preparation method, the weight ratio of the monomer D, the monomer E and the monomer F can be 1 (0.01-0.2) to 0.01-0.2; for example, the weight ratio may be 1 (0.01-0.117): (0.01-0.117), 1 (0.02-0.1): 0.02-0.1).
According to the preparation method of the invention, the monomer D can be synthesized by referring to the method disclosed in the Chinese patent CN 105778079A.
According to the preparation method of the invention, the monomer D can be prepared by reacting 4-hydroxybutyl vinyl polyoxyethylene polyether or 2-ethyleneoxy ethanol polyoxyethylene polyether with butyl isocyanate or toluene isocyanate.
Preferably, the monomer D is at least one of toluene isocyanate terminated 4-hydroxybutyl vinyl polyoxyethylene polyether with molecular weight of 2000-5000-glass-fiber or butyl isocyanate terminated 2-ethyleneoxy ethanol polyoxyethylene polyether with molecular weight of 2000-5000-glass-fiber.
According to the preparation process of the present invention, the monomer F is prepared according to the synthesis method described in the documents S.Gou, S.Luo, T.Liu, H.Xia, D.Jing, Q.Zhang, S.Li, Z.Li and Q.Guo, RSC adv, 2015,5, 85173.
The addition of the monomer E in the polymerization reaction is beneficial to increasing the space protection capability of the prepared slump-retaining and viscosity-reducing water reducer, and the synergistic addition of the monomer E and the monomer F into the slump-retaining and viscosity-reducing water reducer according to the proportion is beneficial to comprehensively optimizing the slump-retaining and viscosity-reducing performance of the slump-retaining and viscosity-reducing water reducer.
According to the preparation method of the invention, the reaction temperature can be 5-70 ℃, for example 10-40 ℃, exemplarily 10 ℃,20 ℃ and 40 ℃. The reaction time may be 1 to 10 hours, for example, 2 to 4 hours.
According to the preparation method of the invention, the reaction is carried out in the presence of an initiator, and the initiator is a redox system initiator. For example, the amount of the oxidant in the redox initiator may be 0.05 to 2%, for example 0.1 to 1.0% by weight of the total weight of the monomer mixture; illustratively, 0.099%, 0.45%, 0.99%. Wherein the oxidizing agent may be at least one selected from the group consisting of benzoyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2, 5 bis (hydroperoxy) hexane, ammonium persulfate, sodium persulfate, and potassium persulfate.
According to the preparation method of the invention, the reaction is carried out in the presence of a reducing agent, and the amount of the reducing agent can be 0.01-2% of the total weight of the monomer mixture, such as 0.02-1%; exemplary, 0.02%, 0.3%, 1.0%. Wherein the reducing agent can be selected from at least one of L-ascorbic acid, L-ascorbate, isoascorbic acid, isoascorbate, ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite, and sodium bisulfite.
According to the preparation method of the present invention, the reaction is carried out in the presence of a molecular weight modifier, which may be one, two or more of mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecylmercaptan, octylmercaptan, butyl thioglycolate, isopropanol, sodium hypophosphite and potassium hypophosphite. The molecular weight regulator can be used in an amount of 0.1 to 1.0% by weight, for example 0.5 to 1.0% by weight, based on the total weight of the monomer mixture; illustratively, 0.8%, 1.0%.
The invention also provides application of the high slump loss resistant and viscosity reduction type polycarboxylate superplasticizer in the fields of cement, concrete and the like.
The invention has the beneficial effects that:
the slump-retaining and viscosity-reducing type polycarboxylate superplasticizer provided by the invention has the advantage that the slump-retaining and viscosity-reducing performance of polycarboxylate water reducing property is improved by selecting a proper ratio of a proper functional monomer to a proper monomer. The main chain of the molecule of the slump-retaining and viscosity-reducing water reducer provided by the invention is provided with an annular structure, so that the adsorption effect with cement is enhanced, and after tertiary amino, hydroxyl and sulfonic acid groups simultaneously contained on a functional monomer are introduced into the water reducer molecule, the functional monomer and an alkaline cement system form a better relative action, so that the wetting, permeation and adsorption of the water reducer on the cement surface are enhanced, the thickness of a water film layer can be effectively increased, the repulsion effect among cement particles is enhanced, dispersed particles are smaller, the flocculation structure of the cement particles is destroyed, and the cement-water system is in a relatively stable suspension state, so that the water reducer has excellent slump-retaining and viscosity-reducing performances.
Definition and description of terms
Unless otherwise indicated, the description and claims reciting numerical ranges, when defined as "numbers," are to be understood as reciting both endpoints of the range, each integer within the range, and each decimal within the range. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2,3, 4, 5, 6, 7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
The term "halogen" denotes fluorine, chlorine, bromine and iodine.
The term "C1-20Alkyl is understood to preferably mean straight-chain or branched saturated having from 1 to 20 carbon atomsAnd a hydrocarbon group, preferably C1-12An alkyl group. "C1-12Alkyl "is understood to preferably mean a straight-chain or branched saturated hydrocarbon radical having 1,2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl. In particular, the radicals have 1,2,3, 4, 5, 6 carbon atoms ("C)1-6Alkyl groups) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl.
The term "C1-20The definition of alkyl also applies to other C-containing groups1-20Radicals of alkyl radicals, e.g. C1-20Alkoxy radical, C1-20Alkyl radical C5-20Aryl radical, C1-20Alkyl 5-20 membered heteroaryl.
The term "C1-20Alkylene "is as defined above for C1-20Alkyl groups further contain a substituent group.
The term "C5-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 5 to 20 carbon atoms, preferably" C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The term "5-20 membered heteroaryl" is understood to mean monocyclic, bicyclic, and tricyclic ring systems containing 5-20 ring atoms, 5-14 ring atoms, or 5-12 ring atoms, or 5-10 ring atoms, or 5-6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms (e.g., N, O, S, Se, etc.), wherein each ring system contains a ring of 5-7 atoms with one or more attachment points to the rest of the molecule. The heteroaryl group is optionally substituted with one or more substituents described herein. In some embodiments, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, Se and N. In other embodiments, a 5-6 atom heteroaryl group contains 1,2,3, or 4 heteroatoms independently selected from O, S, Se and N.
Examples of monocyclic rings of heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
When M or M 'is H in the structural formula (II) and the formula (V), the structural formula (II) and the formula (V) are carboxylic acid structures, and when M or M' is Na, K or NH4When the formula (II) and the formula (V) are carboxylate structures.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In the examples of the present invention, the number average molecular weight M of the polymernThe method is characterized in that an Agilent technologies HPLC instrument is adopted for measurement, three columns of a chromatographic column, namely, ultra hydrogel 500+ ultra hydrogel 250+ ultra hydrogel 120, are connected in series, a mobile phase is 0.1mol/L sodium nitrate aqueous solution, the flow rate is 1.0ml/min, PEG with molecular weights of 202g/mol, 430g/mol, 960g/mol, 4290g/mol, 12600g/mol, 44000g/mol and 152000g/mol is taken as a standard sample.
Example 1
87g of tolylene isocyanate terminated 4-hydroxybutyl vinyl polyoxyethylene polyether (molecular weight 3000) was dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid (the thioglycolic acid was replaced with at least one of mercaptoethanol, thioglycerol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecylmercaptan, octylmercaptan, butyl thioglycolate, isopropanol, sodium hypophosphite and potassium hypophosphite to obtain the target product), 0.3g of L-ascorbic acid (the L-ascorbic acid was replaced with L-ascorbate, isoascorbate, ferrous sulfate, ammonium sulfate, cuprous chloride, At least one of potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium bisulfite can also obtain the target product), then mixed solution of 6g of acrylic acid, 7g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass% aqueous solution) (the target product can also be obtained by replacing the hydrogen peroxide with other oxidants such as benzoyl oxide, tert-butyl hydroperoxide, 2, 5-dimethyl-2, 5-di (hydrogen peroxide) hexane, at least one of ammonium persulfate, sodium persulfate and potassium persulfate) and 40g of water is started to be dripped, the dripping time is 2h, the mixed solution is aged for 1h after the dripping is completed, and the mixed solution is cooled to room temperature, thus obtaining the high slump loss reduction type polycarboxylic acid water reducer product S1. The product is characterized by infrared spectrum, and 3440.28cm in the infrared spectrum-1Is an oxygen atom of O-HPerforming contraction vibration; 2871.32cm-1And 2873.25cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.25cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.26cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.18cm-1is-SO3Stretching vibration of Na, 1105.50cm-1And 1259.62cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 25150 g/mol.
Example 2
90g of 4-hydroxybutyl vinyl polyoxyethylene polyether (molecular weight is 2000) blocked by toluene isocyanate is placed in a kettle and dissolved in 60g of water at 10 ℃, 0.1g of thioglycolic acid and 1.0g of L-ascorbic acid are added, then a mixed solution of 2g of acrylic acid, 8g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 3.3g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, and after the dropwise addition is completed, the mixture is aged for 2 hours and cooled to room temperature, so that a high slump-retaining and viscosity-reducing polycarboxylic acid water reducer product S2 is obtained. The product is characterized by infrared spectrum, and 3440.48cm in the infrared spectrum-1Stretching vibration of O-H; 2871.56cm-1And 2873.67cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.35cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.12cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.16cm-1is-SO3Stretching vibration of Na, 1105.55cm-1And 1259.62cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 18150 g/mol.
Example 3
Dissolving 82g of 4-hydroxybutyl vinyl polyoxyethylene polyether (molecular weight is 5000) blocked by toluene isocyanate in 60g of water at 40 ℃, adding 1.0g of thioglycolic acid and 0.02g of L-ascorbic acid, then starting to dropwise add a mixed solution of 9g of sodium acrylate, 9g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 0.33g of hydrogen peroxide (30 mass% aqueous solution) and 40g of water for 2 hours, curing for 1 hour after the dropwise addition is finished, and cooling to room temperature to obtain the high slump retaining and viscosity reducing type poly (ethylene glycol terephthalate)Carboxylic acid water reducing agent product S3. The product is characterized by infrared spectrum, and 3441.58cm in the infrared spectrum-1Stretching vibration of O-H; 2871.65cm-1And 2873.45cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1560.47cm-1The strong absorption peak of (A) is the vibration peak of C ═ O in the sodium acrylate unit, 1715.46cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.36cm-1is-SO3Stretching vibration of Na, 1104.08cm-1And 1257.86cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 28850 g/mol.
Example 4
87g of butyl isocyanate terminated 2-ethyleneoxy ethanol polyoxyethylene polyether (molecular weight is 3500) is placed in a kettle to be dissolved in 60g of water at the temperature of 20 ℃, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, and then a mixed solution of 6g of acrylic acid, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that a high slump loss and viscosity reduction type polycarboxylate water reducer product S4 is obtained. The product is characterized by infrared spectrum, and 3440.58cm in the infrared spectrum-1Stretching vibration of O-H; 2871.86cm-1And 2873.75cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.55cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.20cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.32cm-1is-SO3Stretching vibration of Na, 1105.49cm-1And 1259.58cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 25860 g/mol.
Example 5
90g of butyl isocyanate terminated 2-ethyleneoxyethanol polyoxyethylene polyether (molecular weight: 2000) was dissolved in 60g of water at 10 ℃ in a kettle, 0.1g of thioglycolic acid and 1.0g of L-ascorbic acid were added, and then 2g of acrylic acid, 8g of sodium 3- (diallylamino) -2-hydroxypropylsulfonate, 3.3g of hydrogen peroxide (30% by mass aqueous solution) and 40g of sodium hydroxide were added dropwiseAnd (3) dropwise adding the mixed solution of water for 2h, curing for 2h after dropwise adding, and cooling to room temperature to obtain a high slump loss resistant polycarboxylic acid water reducing agent product S5. The product is characterized by infrared spectrum, and 3441.12cm in the infrared spectrum-1Stretching vibration of O-H; 2871.15cm-1And 2873.14cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1730.85cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.03cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.12cm-1is-SO3Stretching vibration of Na, 1105.20cm-1And 1259.38cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 19060 g/mol.
Example 6
82g of butyl isocyanate terminated 2-ethyleneoxy ethanol polyoxyethylene polyether (molecular weight is 5000) is placed in a kettle to be dissolved in 60g of water at the temperature of 40 ℃, 1.0g of thioglycolic acid and 0.02g of L-ascorbic acid are added, then a mixed solution of 9g of acrylic acid, 9g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 0.33g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is finished, the mixture is aged for 1 hour and cooled to room temperature, and the high slump retaining and viscosity reducing type polycarboxylate superplasticizer product S6 is obtained. The product is characterized by infrared spectrum, and 3440.50cm in the infrared spectrum-1Stretching vibration of O-H; 2871.68cm-1And 2873.55cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.35cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.18cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.21cm-1is-SO3Stretching vibration of Na, 1105.16cm-1And 1259.37cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 29600 g/mol.
Example 7
87g of butyl isocyanate-terminated 2-ethyleneoxyethanol polyoxyethylene polyether (molecular weight is 3500) was dissolved in 60g of water at 20 ℃ in a kettle, 0.8g of thioglycolic acid and 0.3g of ascorbic acid were added, and dropwise addition was started6g of methacrylic acid, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass% aqueous solution) and 40g of water, wherein the dropping time is 2 hours, the mixture is cured for 1 hour after the dropping is finished, and the mixture is cooled to room temperature to obtain a high slump loss resistant and viscosity reducing type polycarboxylate superplasticizer product S7. The product is characterized by infrared spectrum, and 3440.45cm in the infrared spectrum-1Stretching vibration of O-H; 2871.38cm-1And 2873.55cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.49cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.58cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.37cm-1is-SO3Stretching vibration of Na, 1105.61cm-1And 1259.86cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 24230 g/mol.
Example 8
87g of 4-hydroxybutyl vinyl polyoxyethylene polyether (molecular weight is 3000) blocked by toluene isocyanate is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, then a mixed solution of 6g of methacrylic acid, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, and after the dropwise addition is finished, the mixture is aged for 1 hour and cooled to room temperature, so that a high slump retaining and viscosity reducing type polycarboxylate water reducer product S8 is obtained. The product is characterized by infrared spectrum, and 3441.56cm in the infrared spectrum-1Stretching vibration of O-H; 2871.87cm-1And 2873.67cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.68cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.65cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.64cm-1is-SO3Stretching vibration of Na, 1105.86cm-1And 1259.88cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 26210 g/mol.
Example 9
87g of 4-hydroxybutyl vinyl polyoxyethylene poly (oxyethylene) blocked with toluene isocyanate at 20 deg.CDissolving ether (molecular weight is 1000) in 60g of water in a kettle, adding 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid, then starting to dropwise add a mixed solution of 6g of acrylic acid, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water for 2 hours, curing for 1 hour after dropwise addition is finished, and cooling to room temperature to obtain the high slump loss resistant and viscosity reducing type polycarboxylate superplasticizer product S9. The product is characterized by infrared spectrum, and 3441.66cm in the infrared spectrum-1Stretching vibration of O-H; 2871.76cm-1And 2873.62cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.57cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.54cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.45cm-1is-SO3Stretching vibration of Na, 1105.65cm-1And 1259.53cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 16500 g/mol.
Example 10
87g of butyl isocyanate terminated 2-ethyleneoxy ethanol polyoxyethylene polyether (molecular weight is 8000) is placed in a kettle to be dissolved in 60g of water at the temperature of 20 ℃, 0.8g of thioglycolic acid and 0.3g of ascorbic acid are added, then a mixed solution of 6g of acrylic acid, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, and the high slump retaining and viscosity reducing type polycarboxylate water reducer product S10 is obtained. The product is characterized by infrared spectrum, and 3440.23cm in the infrared spectrum-1Stretching vibration of O-H; 2871.25cm-1And 2873.46cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.32cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.18cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.26cm-1is-SO3Stretching vibration of Na, 1105.12cm-1And 1259.33cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 38560 g/mol.
Comparative example 1
87g of butyl isocyanate terminated 2-ethyleneoxyethanol polyoxyethylene polyether (molecular weight is 3500) is placed in a kettle to be dissolved in 60g of water at the temperature of 20 ℃, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, then a mixed solution of 13g of acrylic acid, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, and after the dropwise addition is completed, the mixture is cured for 1 hour and cooled to room temperature, and the polycarboxylate water reducer product P1 is obtained. The product is characterized by infrared spectrum, and 3440.55cm in the infrared spectrum-1Stretching vibration of O-H; 2871.65cm-1And 2873.75cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.43cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.46cm-1Is the oscillation peak of C ═ O in the carbamate, 1105.37cm-1And 1259.56cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 26760 g/mol.
Comparative example 2
87g of toluene isocyanate terminated 4-hydroxybutyl vinyl polyoxyethylene polyether (molecular weight is 3000) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, then a mixed solution of 13g of acrylic acid, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is cured for 1 hour, and the mixture is cooled to room temperature, so that a polycarboxylic acid water reducing agent product P2 is obtained. The product is characterized by infrared spectrum, and 3440.26cm in the infrared spectrum-1Stretching vibration of O-H; 2871.36cm-1And 2873.53cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.18cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.20cm-1Is the oscillation peak of C ═ O in the carbamate, 1105.25cm-1And 1259.32cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 25420 g/mol.
Comparative example 3
87g of tolylene isocyanate-terminated 4-hydroxybutyl-vinylpolyoxyethylene polyether (molecular weight 3000) were placed in a kettle at 20 ℃ in a reactor at 60g of water, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, then a mixed solution of 12.2g of acrylic acid, 0.8g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, and a polycarboxylic acid water reducing agent product P3 is obtained. The product is characterized by infrared spectrum, and 3440.46cm in the infrared spectrum-1Stretching vibration of O-H; 2871.50cm-1And 2873.66cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.18cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1715.35cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.43cm-1is-SO3Stretching vibration of Na, 1105.25cm-1And 1259.58cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 28350 g/mol.
Comparative example 4
87g of butyl isocyanate terminated 2-ethyleneoxyethanol polyoxyethylene polyether (molecular weight is 3500) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g of L-ascorbic acid are added, then a mixed solution of 12.2g of acrylic acid, 0.8g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1.5g of hydrogen peroxide (30 mass percent aqueous solution) and 40g of water is added dropwise for 2 hours, and after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, and a polycarboxylic acid water reducing agent product P4 is obtained. The product is characterized by infrared spectrum, and 3441.12cm in the infrared spectrum-1Stretching vibration of O-H; 2871.23cm-1And 2873.13cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1730.86cm-1The strong absorption peak of (A) is a C ═ O oscillation peak in the acrylic acid unit, 1714.85cm-1Is the oscillation peak of C ═ O in the carbamate, 1185.96cm-1is-SO3Stretching vibration of Na, 1105.74cm-1And 1259.68cm-1The strong absorption peak is-C-O-C-stretching vibration; the Mn, determined by GPC, was 28120 g/mol.
Test example 1
1. Fluidity of cement paste
In order to examine the effect of the synthesized dam-protecting viscosity-reducing type polycarboxylate superplasticizer on the fluidity of the disc-fixed P.042.5 cement, the net slurry fluidity of each example on different cement varieties under the same mixing amount is measured in an experiment. The test is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method', the water-cement ratio W/C is 0.29, and the folded solid content is 0.15%. The test results are shown in Table 1.
TABLE 1 Cement paste flow Performance results
As can be seen from Table 1, the high slump loss resistant polycarboxylic acid water reducing agents synthesized by the methods of examples 1-10 all have higher performance than the water reducing agents synthesized by the methods of comparative examples 1-4, for example, have excellent net slurry retention performance at a solid content of 0.15%.
2. Testing of concrete Properties
The concrete test is carried out on the samples obtained in the examples and the comparative examples by referring to GB/T50080-2016 standard of common concrete mixture performance test method and GB8076-2008 concrete admixture. The solid content of the sample in the cement for setting P.042.5 is 0.20%, and the mixing proportion of the concrete is that the basic cement comprises sand, stone and water, 380:578:848: 130. The test results are shown in Table 2.
TABLE 2 slump, extension and compressive strength of concrete
As can be seen from Table 2, the high slump loss resistant and viscosity reduction type polycarboxylate water reducer prepared by the method shows more excellent workability and concrete softness in concrete compared with the common high-performance polycarboxylate water reducer, and has excellent viscosity reduction capability and retention performance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The polycarboxylate superplasticizer is characterized by comprising a structural unit A, a structural unit B and a structural unit C;
the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, and the structural unit C is a structural unit shown as a formula III;
the compound has a structure shown in a formula I,
the compound of the formula II is shown in the specification,
in the formula (III), the reaction is carried out,
wherein "+" indicates a connection site;
R1and R5Identical or different, independently of one another, represents hydrogen, C which is unsubstituted or optionally substituted by one, two or more Rs11-8An alkyl group;
R2and R3Identical or different, independently of one another, represent C which is unsubstituted or optionally substituted by one, two or more Rs21-8An alkylene group;
wherein m + n is a number of 10 to 250;
p is a number from 0 to 10;
R4is unsubstituted or optionally substituted by one, two or more Rs31-20Alkyl radical, C6-10Aryl radical, C1-20Alkyl radical C6-10An aryl group;
Rs1、Rs2 and Rs3, which are identical or different, are independently selected from halogen and C1-8An alkyl group;
m is selected from H, Na, K or NH4One, two or more of;
M1selected from Na or K;
the weight content of the structural unit A is 80-95% by taking the total weight of the polycarboxylate superplasticizer as a reference;
based on the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit B is 1-10%;
and on the basis of the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit C is 1-10%.
2. The polycarboxylate water reducer of claim 1, wherein R1And R5Identical or different, independently of one another, represent hydrogen or C1-4An alkyl group;
R2and R3Identical or different, independently of one another, represent a linear or branched C1-6An alkylene group;
m + n is a number of 40 to 200;
p is a number from 0 to 6;
R4is unsubstituted or optionally substituted by one, two or more Rs31-6Alkyl radical, C6Aryl or C1-6Alkyl radical C6An aryl group;
rs3 is selected from halogen, C1-6An alkyl group;
m is selected from H, Na and K;
M1selected from Na or K;
based on the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit A is 82-90%;
based on the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit B is 2-9%;
and on the basis of the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit C is 2-9%.
3. The polycarboxylic acid of claim 1Aqueous preparation, characterized in that R1And R5Identical or different, independently of one another, represent hydrogen or methyl;
R2represents ethylene, propylene or butylene;
R3represents ethylene or-CH2-CH(CH3)-；
m + n is a number of 40 to 150;
p is 0 or 1;
R4selected from methyl, ethyl, propyl, butyl or phenyl;
m is selected from H, Na and K;
M1selected from Na or K;
based on the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit A is 84-88%;
the weight content of the structural unit B is 4-7% by taking the total weight of the polycarboxylate superplasticizer as a reference;
and taking the total weight of the polycarboxylate superplasticizer as a reference, wherein the weight content of the structural unit C is 4-7%.
4. The polycarboxylic acid water reducer according to claim 1, characterized in that the molecular weight of the water reducer is 10000-50000 g/mol.
5. The polycarboxylate water reducer according to claim 1, characterized in that the polycarboxylate water reducer has a solid content of 36-53%.
6. The method for preparing the polycarboxylic acid water reducing agent according to any one of claims 1 to 5, characterized by comprising the steps of:
carrying out polymerization reaction on a monomer D containing a structure shown in a formula IV, a monomer E containing a structure shown in a formula V and a monomer F containing a structure shown in a formula VI to obtain the polycarboxylate superplasticizer;
formula IV
Formula V
In the formula VI, the reaction mixture is shown in the specification,
wherein R is1' and R5' having R1And R5Same definition of R2' and R3' having R2And R3Same definition of R4' is as defined for R4M' and M1' having M and M1The same definition.
7. The method according to claim 6, wherein the weight ratio of the monomer D, the monomer E and the monomer F is 1 (0.01-0.2) to (0.01-0.2).
8. The method according to claim 7, wherein the reaction is carried out in the presence of an initiator, the initiator being a redox system initiator;
the dosage of the oxidant in the redox system initiator is 0.05-2% of the total weight of the monomer mixture.
9. The method according to claim 8, wherein the oxidizing agent is at least one selected from the group consisting of benzoyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2, 5-bis (hydroperoxide) hexane, ammonium persulfate, sodium persulfate, and potassium persulfate.
10. The method according to claim 7, wherein the reaction is carried out in the presence of a reducing agent in an amount of 0.01 to 2% by weight based on the total weight of the monomer mixture.
11. The method according to claim 10, wherein the reducing agent is at least one selected from the group consisting of L-ascorbic acid, L-ascorbate ester, erythorbic acid, erythorbate salt, erythorbate ester, ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite, and sodium bisulfite.
12. The production method according to claim 7, wherein the reaction is carried out in the presence of a molecular weight modifier which is one, two or more of mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecylmercaptan, octylmercaptan, butyl thioglycolate, isopropanol, sodium hypophosphite and potassium hypophosphite.
13. The method according to claim 12, wherein the molecular weight regulator is used in an amount of 0.1 to 1.0% by weight based on the total weight of the monomer mixture.
14. The use of the polycarboxylic acid water reducing agent according to any one of claims 1 to 5 in the fields of cement and concrete.
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