CN109796565A - A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application - Google Patents
A kind of Early-strength polycarboxylate superplasticizer and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of concrete admixture, a kind of Early-strength polycarboxylate superplasticizer and its preparation method and application is disclosed.The Early-strength polycarboxylate superplasticizer contains structural unit C shown in structural unit B shown in structural unit A, formula II shown in formula I and formula III；And on the basis of the total weight of the Early-strength polycarboxylate superplasticizer, the weight content of the structural unit A is 76~96%, and the weight content of the structural unit B is 0.8~12%, and the weight content of the structural unit C is 0.8~12%.The polycarboxylate water-reducer has good early epistasis energy, is suitable for early strong concrete field；
Description
Technical field
The invention belongs to the technical fields of concrete admixture, and in particular to a kind of Early-strength polycarboxylate superplasticizer and its system
Preparation Method and application.
Background technique
Polycarboxylate water-reducer is the novel water-reducing agent to grow up in recent years, with conventional wooden element sulfonate, naphthalene sulfonate
System, melamine series compared with sulfamate system, have low-dosage, high water reducing rate, high-collapse-retentivity, low alkali, it is environmentally protective, point
The advantages that sub- design freedom is big, has been widely used in concrete works.But while having excellent properties, polycarboxylic acids
Water-reducing agent has also significantly delayed hydrated cementitious, affects the development of early strength, and especially in prefabricated components, deferred action makes
Production cycle is elongated, and maintenance cost increases, and reduces production efficiency.
There is early powerful polycarboxylate water-reducer can shorten setting time for exploitation, improve production efficiency, accelerate template
Surrounding rate has significant technical benefits.Currently, improve polycarboxylate water-reducer early strength there are mainly two types of way
Diameter: one is certain inorganic, organic accelerating component is compounded in common polycarboxylate water-reducer, another is to pass through molecule
Structural modification, introducing has early powerful characteristic group, synthesizes Early-strength polycarboxylate superplasticizer.
For Compositional type early strength water-reducing agent, used in patent CN1312324A 30~100 parts of sulfonic acid group content for
The modified waste old polystyrene water-reducing agent of 20mol%~98mol%, with 5~20 parts of sodium sulphate, 40~70 parts of sulfomethylated lignin
Hydrochlorate compounds.When rolling over solid volume and being about 6%, water-reducing rate be 20~28%, 1d compression strength about rise to 41%~
48%, but it is bad to play a role to intensity after concrete seven d.CN101024565A disclose it is a kind of by compounding anhydrous calcium chloride,
The morning that the accelerating components such as triethanolamine, sodium benzoate obtain strong composite water-reducing agent, can be improved compression strength to a certain extent, but
Containing villaumite, there is corrosion to armored concrete.
European patent EP 1980541 discloses polyamide-polyethylene glycol branch novel high-performance polycarboxylic acids diminishing
Agent introduces polyamine groups in diminishing agent molecule, when concrete water-cement ratio is down to 0.15, still have preferable mobility and
Retentivity is flowed, the early strength of superelevation is shown in ready-mixed concrete, but the structure polymeric monomer synthesis step is complicated, preparation
Difficulty, higher cost can not industrialized production.CN105199032A discloses a kind of ultra high early strength poly-carboxylic water-reducing agent, the technology
Scheme introduces cation using polyethers polymeric monomer as Material synthesis in the molecule, so that absorption of the soil to additive is reduced, it can
Accelerate the hydration of cement, there is super hardening effect, but polymerization temperature is 85~95 DEG C, temperature is higher, it is more difficult to control, and protect
It is poor to hold ability.
Summary of the invention
In order to improve the deficiencies in the prior art, the present invention provides a kind of Early-strength polycarboxylate superplasticizers and preparation method thereof
And application.
A kind of Early-strength polycarboxylate superplasticizer, the Early-strength polycarboxylate superplasticizer contain 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；
Wherein, R1With R3It is identical or different, R1With R3Represent hydrogen or C1-12Alkyl；Preferably, R1With R3Represent hydrogen or
C1-4Alkyl；Illustratively, R1With R3Represent hydrogen or methyl；
R2Represent C1-12Alkylidene, preferably R2Represent C1-8Alkylidene, C1-4Alkylidene, for example, R2Represent ethylidene
M is the natural number in 10~250, for example, m is the natural number in 43~112；
N is the natural number of 1-10, such as n=2,3,4, preferably n=2.
Wherein, formula II can represent carboxylic acid or carboxylate；When formula II is carboxylic acid, M H；When formula II is carboxylate, M
Na, K, NH can be selected from4One of, two or more.
Wherein, M described in formula III1Na or K can be selected from.
Polycarboxylate water-reducer according to the present invention, on the basis of the total weight of the polycarboxylate water-reducer, the structure list
The weight content of first A is 76~96%, such as 80~95%, 81~93%, 82~90%, 83~89%, 84~88%.
Polycarboxylate water-reducer according to the present invention, on the basis of the total weight of the polycarboxylate water-reducer, the structure list
The weight content of first B is 0.8~12%；Such as 0.85~11.5%, 0.95~11.1%, 1~10%, 2~9%, 4~7%.
Polycarboxylate water-reducer according to the present invention, on the basis of the total weight of the polycarboxylate water-reducer, the structure list
The weight content of first C is 0.8~12%；Such as 0.85~11.5%, 0.95~11.1%, 1~10%, 2~9%, 4~7%.
Polycarboxylate water-reducer according to the present invention, the number-average molecular weight of the water-reducing agent can be 10000~50000g/
mol；Such as molecular weight can be 12000~45000g/mol, 15000~35000g/mol, 18000~30000g/mol.
Polycarboxylate water-reducer according to the present 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 Early-strength polycarboxylate superplasticizer, which includes following step
It is rapid: the monomer mixing of 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
Object, aggregated reaction obtain the polycarboxylate water-reducer；
Wherein, R1' and R3' identical or different, R1' and R3' represent hydrogen or C1-12Alkyl；Preferably, R1' and R3' represent
Hydrogen or C1-4Alkyl；Illustratively, R1' and R3' represent hydrogen or methyl；
R2' represent C1-12Alkylidene, preferably R2' represent C1-8Alkylidene, C1-4Alkylidene, for example, R2' represent Asia
Ethyl
M is the natural number in 10~250, for example, m is the natural number in 43~112；N is the natural number of 1-10, such as n
=2,3,4, preferably n=2.
Wherein, formula V can represent carboxylic acid or carboxylate；When formula V is carboxylic acid, M ' is H；When formula V is carboxylate,
M ' can be selected from Na, K, NH4One of, two or more.
Wherein, M described in formula VI1' Na or K can be selected from.
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 mixture of the monomer F of structure shown in the monomer E and formula VI of structure shown in body D, formula V makes institute in the presence of initiator
The solution polymerization that monomer mixture carries out alkene in water is stated, the polycarboxylate water-reducer is obtained.Illustratively, Ke Yixian
The aqueous solution of the monomer D is prepared, then prepares the mixed liquor containing monomer E, monomer F and initiator, by the mixed liquor to institute
It states and is added dropwise in the aqueous solution of monomer D, be added dropwise to complete post curing, be cooled to room temperature, obtain the polycarboxylate water-reducer.
The weight ratio of preparation method according to the present invention, the monomer D, monomer E and monomer F can be 1: (0.01~
0.125): (0.01~0.125)；Such as weight ratio can be 1: (0.01~0.117): (0.01~0.117), 1: (0.02~
0.1): (0.02~0.1)；Illustratively, the weight ratio can be 1: 0.07: 0.08,1: 0.02: 0.08,1: 0.1: 0.1.
Illustrative preparation method according to the present invention, the monomer D can be allyl polyethenoxy polyethers, methallyl
At least one of base polyoxyethylene polyethers and prenol polyoxyethylene ether；Preferably molecular weight be 1000-5000 (such as
At least one of methacrylic polyoxyethylene polyethers and prenol polyoxyethylene ether 2000-5000).The monomer
E can be acrylic monomer；Preferably, R in the formula V3' it is H or methyl, M ' is Na or NH4.The monomer F according to
S.Gou,S.Luo,T.Liu,H.Xia,D.Jing,Q.Zhang,S.Li,Z.Li and Q.Guo,RSC Adv.,2015,5,
Synthetic method preparation in 85165-85173 document.Monomer E is added in the above-mentioned polymerization reaction of the present invention to be conducive to increase institute
Monomer E and monomer F are cooperateed in proportion and are added in early-strength water-reducing agent by the space protection ability of the early-strength water-reducing agent of preparation
Be conducive to the early epistasis energy of the complex optimum early-strength water-reducing agent.
Preparation method according to the present invention, the solution polymerization condition of the alkene include: reaction temperature can for 5~
70 DEG C, for example, 10~40 DEG C, illustratively, the temperature are 10 DEG C, 20 DEG C, 40 DEG C.Reaction time can be 1~10h, example
For example 2~4h.
Preparation method according to the present invention, the initiator are redox system initiator.For example, the redox
The dosage of oxidant in system initiator can for the monomer mixture total weight 0.05~2%, for example, 0.1~
1.0%；It illustratively, is 0.099%, 0.45%, 0.99%.Wherein, the oxidant can be selected from benzoyl peroxide, mistake
Bis- (hydrogen peroxide) hexanes of hydrogen oxide, tert-butyl hydroperoxide, 2,5- dimethyl -2,5, ammonium persulfate, sodium peroxydisulfate and over cure
At least one of sour potassium.
For example, the dosage of the reducing agent can be the 0.01~2.0% of the monomer mixture total weight, for example,
0.02~1.0%；It illustratively, is 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 and arabo-ascorbic acid ester, ferrous sulfate, sulfuric acid
Ferrous ammonium, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, thiosulfuric acid
At least one of potassium, rongalite and sodium hydrogensulfite.
Preparation method according to the present invention, the olefin solution polymerization further include molecular weight regulator in reacting.For example,
The molecular weight regulator 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
One of butyl ester, isopropanol, sodium hypophosphite and potassium hypophosphite, two or more.For example, the use of the molecular weight regulator
Amount can be the 0.1~1.0% of the monomer mixture total weight, such as 0.5~1.0%；Be illustratively, 0.8%,
1.0%.
Application the present invention also provides above-mentioned Early-strength polycarboxylate superplasticizer in fields such as cement, concrete.
Beneficial effects of the present invention:
Early-strength polycarboxylate superplasticizer provided by the invention, by selecting suitable functional form monomer to subtract to improve polycarboxylic acids
Aqueous early epistasis energy.Early-strength polycarboxylate superplasticizer provided by the invention has cyclic structure on molecular backbone, enhance with
The suction-operated of cement, while after hydroxyl, the sulfonic acid group contained simultaneously on functional monomer is introduced into diminishing agent molecule and alkali
Property cement system form preferable opposite effect, enhance water-reducing agent in the wetting, infiltration and absorption of cement surface, and can
Water film thickness is effectively increased, repulsive interaction between cement granules is enhanced, keeps discrete particles smaller, destroys cement granules
Flocculent structure makes Cement-water System be in metastable suspended state, so that making water-reducing agent not only has outstanding mobility
Early powerful also has outstanding early epistasis energy.
Term definition:
Unless otherwise indicated, group and the term definition recorded in present specification and claims, including its work
For definition etc. of particular compound in the definition of example, illustrative definition, preferred definition, embodiment, can between
Any combination and combination.Group definition and compound structure after such combination and combination, should belong to present specification
In the range of record.
The numberical range that present specification and claims are recorded, when the numberical range is defined as " integer ",
Two endpoints and each integer within the scope of this that should be understood as describing the range.For example, " 0~10 integer " is answered
When each integer for being interpreted as describing 0,1,2,3,4,5,6,7,8,9 and 10.When the numberical range is defined as " counting ",
It should be understood as that two endpoints, each integer within the scope of this and each within the scope of this that describe the range are small
Number.For example, " 0~10 number " should be understood as not only describing 0,1,2,3,4,5,6,7,8,9 and 10 each 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 " C1-12Alkyl " is interpreted as the preferred direct-connected or branch saturation monovalent hydrocarbon for indicating to have 1~12 carbon atom
Base, preferably C1-8Alkyl."C1-8Alkyl " be interpreted as it is preferred indicate to have the direct-connected of 1,2,3,4,5,6,7,8 carbon atom or
Branch is saturated monovalent hydrocarbon.The alkyl is such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth
Base, more particularly, the group have 1,2,3 or 4 carbon atom (" C1-4Alkyl "), such as methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl or isobutyl group.
Term " C1-12Alkylidene " is interpreted as the preferred direct-connected or branch saturation divalent for indicating to have 1~12 carbon atom
Alkyl, preferably C1-8Alkylidene."C1-8Alkylidene ", which is interpreted as preferred expression, has 1,2,3,4,5,6,7,8 carbon atom
Direct-connected or branch saturated divalent hydrocarbon radical.The alkyl is such as methylene, ethylidene, propylidene, butylidene, isopropylidene, Asia
Isobutyl group, more particularly, the group have 1,2,3 or 4 carbon atom (" C1-4Alkylidene "), for example, methylene, ethylidene,
Sub- n-propyl or isopropylidene.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
In the embodiment of the present invention, the number-average molecular weight M of early-strength water-reducing agent productnUsing Agilent
Technologies HPLC apparatus measures, chromatographic column are ultrahydrogel 500+ultrahydrogel 250+
Ultrahydrogel 120 is connected in series, and mobile phase is 0.1mol/L sodium nitrate aqueous solution, flow velocity 1.0mL/min.Molecular weight
Respectively 202g/mol, 430g/mol, 960g/mol, 4290g/mol, 12600g/mol, 44000g/mol, 152000g/mol
PEG be standard sample.
Embodiment 1
Under the conditions of 20 DEG C, 87g methacrylic polyoxyethylene polyethers (molecular weight 2400) is placed in kettle in 60g water
Dissolution, is added 0.8g thioacetic acid, and 0.3g L-AA then begins to that 6g acrylic acid, 7g 3- (diallyl ammonia is added dropwise
Base) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h, drop
Post curing 1h is added into, room temperature is cooled to, obtains early-strength water-reducing agent product S1.
Product S1 is through infrared spectrum characterization, 3440.22cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.21cm-1And 2873.44cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.25cm-1's
Strong absworption peak is the vibration peak of C=O, 1185.15cm-1For-SO3The stretching vibration of Na, 1105.45cm-1And 1259.68cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S1 is tested through GPC, MnFor 24345g/mol.
Embodiment 2
Under the conditions of 10 DEG C, 90g methacrylic polyoxyethylene polyethers (molecular weight 2000) is placed in kettle in 60g water
Dissolution, is added 0.1g thioacetic acid, and 1.0g L-AA then begins to that 2g acrylic acid, 8g 3- (diallyl ammonia is added dropwise
Base) -2- hydroxypropyl azochlorosulfonate acid sodium, 3.3g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h, drop
Post curing 2h is added into, room temperature is cooled to, obtains early-strength water-reducing agent product S2.
Product S2 is through infrared spectrum characterization, 3441.86cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.88cm-1And 2873.64cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.75cm-1's
Strong absworption peak is the vibration peak of C=O, 1185.60cm-1For-SO3The stretching vibration of Na, 1104.15cm-1And 1258.03cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S2 is tested through GPC, MnFor 20650g/mol.
Embodiment 3
Under the conditions of 40 DEG C, 82g methacrylic polyoxyethylene polyethers (molecular weight 5000) is placed in kettle in 60g water
Dissolution, is added 1.0g thioacetic acid, and 0.02g L-AA then begins to that 9g sodium acrylate, 9g 3- (diallyl is added dropwise
Amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 0.33g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding is
2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains early-strength water-reducing agent product S3.
Product S3 is through infrared spectrum characterization, 3441.16cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.28cm-1And 2873.34cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1556.25cm-1's
Strong absworption peak is the vibration peak of C=O, 1186.45cm-1For-SO3The stretching vibration of Na, 1104.85cm-1And 1258.54cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S3 is tested through GPC, MnFor 29876g/mol.
Embodiment 4
Under the conditions of 20 DEG C, 87g methacrylic polyoxyethylene polyethers (molecular weight 2400) is placed in kettle in 60g water
Dissolution, is added 0.8g thioacetic acid, and 0.3g L-AA then begins to that 6g methacrylic acid, 7g 3- (diallyl is added dropwise
Amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h,
It is added dropwise to complete post curing 1h, is cooled to room temperature, obtains early-strength water-reducing agent product S4.
Product S4 is through infrared spectrum characterization, 3442.08cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.98cm-1And 2874.45cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1732.87cm-1's
Strong absworption peak is the vibration peak of C=O, 1187.56cm-1For-SO3The stretching vibration of Na, 1104.65cm-1And 1257.86cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S4 is tested through GPC, MnFor 23870g/mol.
Embodiment 5
Under the conditions of 20 DEG C, 87g prenol polyoxyethylene ether (molecular weight 2400) is placed in kettle molten in 60g water
Solution, is added 0.8g thioacetic acid, and 0.3g L-AA then begins to that 6g methacrylic acid, 7g 3- (diallyl ammonia is added dropwise
Base) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h, drop
Post curing 1h is added into, room temperature is cooled to, obtains early-strength water-reducing agent product S5.
Product S5 is through infrared spectrum characterization, 3441.68cm in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.58cm-1And 2874.32cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.34cm-1's
Strong absworption peak is the vibration peak of C=O, 1186.26cm-1For-SO3The stretching vibration of Na, 1104.45cm-1And 1256.16cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S5 is tested through GPC, Mn 22468g/mol.
Embodiment 6
Under the conditions of 20 DEG C, 87g prenol polyoxyethylene ether (molecular weight 1000) is placed in kettle molten in 60g water
Solution, is added 0.8g thioacetic acid, and 0.3gL- ascorbic acid then begins to that 6g acrylic acid, 7g 3- (diallyl amino)-is added dropwise
2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding 2h drips
At post curing 1h, it is cooled to room temperature, obtains early-strength water-reducing agent product S6.
Product S6 is through infrared spectrum characterization, 3442.65m in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2871.53cm-1And 2874.78cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1732.87cm-1's
Strong absworption peak is the vibration peak of C=O, 1187.66cm-1For-SO3The stretching vibration of Na, 1104.41cm-1And 1257.65cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product S6 is tested through GPC, MnFor 18670g/mol.
Comparative example 1
Under the conditions of 20 DEG C, 87g prenol polyoxyethylene ether (molecular weight 1000) is placed in kettle molten in 60g water
Solution, is added 0.8g thioacetic acid, and 0.3gL- ascorbic acid then begins to that 13g acrylic acid, 1.5g hydrogen peroxide (30 matter is added dropwise
Measure % aqueous solution), the mixed liquor of 40g water, time for adding 2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtain early-strength
Water-reducing agent product P1.
Product P1 is through infrared spectrum characterization, 3441.26m in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2872.46cm-1And 2874.92cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1732.56cm-1's
Strong absworption peak is the vibration peak of C=O, 1104.87cm-1And 1257.45cm-1The strong absworption peak at place is-C-O-C- stretching vibration.
Product P1 is tested through GPC, MnFor 21063g/mol.
Comparative example 2
Under the conditions of 20 DEG C, 87g methacrylic polyoxyethylene polyethers (molecular weight 2400) is placed in kettle in 60g water
Dissolution, is added 0.8g thioacetic acid, and 0.3g L-AA then begins to that 12.2g acrylic acid, 0.8g 3- (two allyls is added dropwise
Base amino) -2- hydroxypropyl azochlorosulfonate acid sodium, 1.5g hydrogen peroxide (30 mass % aqueous solution), 40g water mixed liquor, time for adding is
2h is added dropwise to complete post curing 1h, is cooled to room temperature, obtains early-strength water-reducing agent product P2.
Product P2 is through infrared spectrum characterization, 3441.26m in infrared spectrum spectrogram-1For the stretching vibration of O-H；
2872.13cm-1And 2874.78cm-1Strong absworption peak be-CH2Stretching vibration and-CH3Bending vibration；1731.34cm-1's
Strong absworption peak is the vibration peak of C=O, 1186.53cm-1For-SO3The stretching vibration of Na, 1104.76cm-1And 1257.86cm-1Place
Strong absworption peak be-C-O-C- stretching vibration.
Product P2 is tested through GPC, MnFor 36680g/mol.
Test case
1. flowing degree of net paste of cement
To investigate the mobility effect effect that the Early-strength polycarboxylate superplasticizer that the present invention synthesizes consolidates 42.5 cement of P0 to disk
Fruit, test determine under identical volume each embodiment to the paste flowing degree of different cement types.GB/T8077- is pressed in test
2012 " Methods for testing uniformity of concrete admixture " carry out, ratio of mud W/C=0.29, and volume is to roll over solid volume.Test result
It is shown in Table 1.
1 pulp flowage results of property of table
| Number | Roll over solid parameter (%) | Paste flowing degree (mm) |
| S1 | 0.15 | 250 |
| S2 | 0.15 | 242 |
| S3 | 0.15 | 244 |
| S4 | 0.15 | 248 |
| S5 | 0.15 | 247 |
| S6 | 0.15 | 235 |
| P1 | 0.15 | 223 |
| P2 | 0.15 | 228 |
From table 1 it follows that Early-strength polycarboxylate superplasticizer S1~S6 net slurry water-reducing rate of the method for the present invention synthesis is equal
It is higher than comparative sample P1 and P2.
2. concrete slump, divergence and compression strength
Test is referring to GB/T50080-2016 " Standard for test methods of properties of ordinary concrete mixture standard ", GB/T50081-
2016 " standard for test methods of mechanical properties of ordinary concretes " are to poly- carboxylic prepared by sample S1-S6 obtained by embodiment and comparative example
Sour water-reducing agent P1, P2 carry out concrete strength inspection.Concrete quality match ratio is benchmark cement: flyash: miberal powder: sand: stone:
Water=315:58:41:669:1189:138.Wherein cement is middle P.0 52.5, and flyash is II grade of ash, and sand is fineness modulus
For 2.6 middle sand, stone is 5~31.5 continuous grading rubble of partial size, is matched as parts by weight, and the machine slump is 70 ± 20mm out,
Design strength is C50, selects reference cement, and test result is shown in Table 2.
2 concrete experiments result of table
From 2 concrete experiments result of table it is found that the high early strength poly-carboxylic water-reducing agent S1-S6 of embodiment preparation is more below in volume
In the case where P1 and P2, corresponding initial slump and comparative example 1 and 2 initial slump of comparative example at least maintain an equal level, or even also
It is apparently higher than the initial slump of comparative example 1 and comparative example 2；S1-S6 corresponding 1d, 3d and 7d early anti pressured intension value is intended to bright
It is aobvious to be higher than comparative example P1 and comparative example P2, illustrate that polycarboxylate water-reducer prepared by the present invention has promotion hydrated cementitious outstanding anti-
The function of answering can be significantly shorter the setting time of concrete, increase substantially the early strength of concrete.
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 Early-strength polycarboxylate superplasticizer, which is characterized in that the Early-strength polycarboxylate superplasticizer contains structural unit A, knot
Structure 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,
The structural unit C is structural unit shown in formula III；
Preferably, R1With R3It is identical or different, R1With R3Represent hydrogen or C1-12Alkyl；
R2Represent C1-12Alkylidene；
M is the natural number in 10~250；N is the natural number of 1-10；
Wherein, formula II represents carboxylic acid or carboxylate；Preferably, when formula II is carboxylic acid, M H；When formula II is carboxylate, M choosing
From Na, K, NH4One of, two or more；
Wherein, M described in formula III1Selected from Na or K.
2. polycarboxylate water-reducer according to claim 1, which is characterized in that the total weight with the polycarboxylate water-reducer is
Benchmark, the weight content of the structural unit A are 76~96%；
Preferably, the weight content of the structural unit B is 0.8~12%；
Preferably, the weight content of the structural unit C is 0.8~12%.
3. polycarboxylate water-reducer according to claim 1 or 2, which is characterized in that the molecular weight of the water-reducing agent is 10000
~50000g/mol；
Preferably, the solid content of the polycarboxylate water-reducer is 36~53%.
4. the preparation method of the described in any item Early-strength polycarboxylate superplasticizers of claim 1-3, which is characterized in that the preparation side
Method the following steps are included: structure shown in the monomer E and formula VI of structure shown in monomer D, formula V containing structure shown in formula IV list
The monomer mixture of body F, aggregated reaction obtain the polycarboxylate water-reducer；
Preferably, R1' and R3' identical or different, R1' and R3' represent hydrogen or C1-12Alkyl；
R2' represent C1-12Alkylidene；
M is the natural number in 10~250；N is the natural number of 1-10；
Wherein, formula V represents carboxylic acid or carboxylate；Preferably, when formula V is carboxylic acid, M ' is H；When formula V is carboxylate, M '
Selected from Na, K, NH4One of, two or more；
Wherein, M described in formula VI1' it is selected from Na or K.
5. the preparation method according to claim 4, which is characterized in that the preparation method is specifically includes the following steps: contain
The monomer mixture of the monomer F of structure shown in the monomer E and formula VI of structure shown in the monomer D of structure shown in formula IV, formula V, is drawing
In the presence of sending out agent, so that the monomer mixture is carried out the solution polymerization of alkene in water, obtain the polycarboxylate water-reducer.
6. preparation method according to claim 4 or 5, which is characterized in that the weight of the monomer D, monomer E and monomer F
Than being 1: (0.01~0.12): (0.01~0.12).
7. according to the described in any item preparation methods of claim 4-6, which is characterized in that the monomer D is allyl polyoxy second
At least one of alkene polyethers, methacrylic polyoxyethylene polyethers and prenol polyoxyethylene ether；
Preferably, the monomer E is acrylic monomer.
8. according to the described in any item preparation methods of claim 5-7, which is characterized in that the solution polymerization item of the alkene
Part includes: that reaction temperature is 5~70 DEG C, and the reaction time is 1~10h；
Preferably, the initiator is redox system initiator.
9. according to the described in any item preparation methods of claim 5-8, which is characterized in that in the olefin solution polymerization reaction,
It further include molecular weight regulator.
10. the described in any item Early-strength polycarboxylate superplasticizers of claim 1-3 are in cement, the application of concrete field.
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| CN103965416A (en) * | 2014-04-18 | 2014-08-06 | 北京建筑大学 | Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent |
| CN104371691A (en) * | 2014-10-27 | 2015-02-25 | 西南石油大学 | Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof |
| EP2886580A1 (en) * | 2013-12-20 | 2015-06-24 | Construction Research & Technology GmbH | Additive for rheology improvement of inorganic binders |
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| EP2886580A1 (en) * | 2013-12-20 | 2015-06-24 | Construction Research & Technology GmbH | Additive for rheology improvement of inorganic binders |
| CN103965416A (en) * | 2014-04-18 | 2014-08-06 | 北京建筑大学 | Early-strength polycarboxylate water reducing agent for component and preparation method for early-strength polycarboxylate water reducing agent |
| CN104371691A (en) * | 2014-10-27 | 2015-02-25 | 西南石油大学 | Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof |
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| CN112480332A (en) * | 2020-12-01 | 2021-03-12 | 四川宇砼建材有限公司 | Polycarboxylate superplasticizer and preparation method thereof |
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