CN105801773B - A kind of comb-shaped polymer, preparation method and the purposes as water-reducing agent - Google Patents
A kind of comb-shaped polymer, preparation method and the purposes as water-reducing agent Download PDFInfo
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Abstract
The present invention provides a kind of comb-shaped polymers, it is the copolymer that the weight average molecular weight formed by monomer A, B, C is 20000~50000, wherein, monomer A is two or more unsaturated end alkenyl polyether polymeric monomer, monomer B is 2 acrylamide, 2 methyl propane sulfonic acid, and monomer C is unsaturated carboxylic acid or derivatives thereof minor comonomer.The present invention also provides the preparation method of the comb-shaped polymer as well as the purposes of polycarboxylate water-reducer.In comb-shaped polymer provided by the invention, three kinds of monomers can organically combine, and obtained comb-shaped polymer polymerize more thorough, monomer conversion higher, and the water-reducing property as polycarboxylate water-reducer is also obviously improved.
Description
Technical field
The present invention relates to polycarboxylate water-reducer fields, and in particular to a kind of comb-shaped polymer, preparation method and its work
For the purposes of water-reducing agent.
Background technology
The comb-shaped polymer of water-soluble is applied in concrete there is excellent cement mortar to disperse as polycarboxylate water-reducer
Performance.The polycarboxylate water-reducer of latest generation is by undersaturated end alkenyl polyoxyethylene ether and undersaturated small molecular organic acid
(acid anhydride), such as (methyl) acrylic acid, itaconic acid, maleic anhydride monomer copolymerizable are prepared, the type of polymerized monomer, structure and
Reactivity ratio between polymerized monomer all directly affects the performance of polycarboxylate water-reducer.
End alkenyl polyoxyethylene ether accounts for 85% or more of entire polycarboxylate water-reducer molecule mass fraction, structure and molecule
It is even more to play the role of vital to measure to the performance of the polycarboxylate water-reducer after synthesis, but is limited by end alkenyl in industry at present
Polyoxyethylene ether structure is single (mainly to have methylallyl alcohol polyoxyethylene ether and 3- methyl-3-butene-1-alcohols polyoxyethylene ether two
Kind of structure), the single limitation (weight average molecular weight is concentrated mainly on 2400 or so) of molecular weight, the performance of polycarboxylate water-reducer fails
It is substantially improved.
Invention content
To overcome the defect that water-reducing property is difficult to improve existing for existing polycarboxylate water-reducer field, the purpose of the present invention it
One is to provide a kind of comb-shaped polymer can be used as polycarboxylate water-reducer.
The second object of the present invention is to provide the preparation method of the comb-shaped polymer.
The third object of the present invention is to provide purposes of the comb-shaped polymer as polycarboxylate water-reducer.
Comb-shaped polymer provided by the invention is by mass percentage by 85%~95% monomer A, 1%~5%
The copolymer that the weight average molecular weight that the monomer C of monomer B and 1%~10% is formed is 20000~50000；
Wherein, the monomer A is selected from the unsaturated end alkenyl polyether that two or more formula (I) indicates,
In formula (I), R1、R2Each independently represent H or CH3, X expressions CH2O、CH2CH2O、OCH2CH2O or
OCH2CH2CH2CH2O, EO indicate CH2CH2O, n indicate 24~90 integer；
The monomer B is selected from 2- acrylamide-2-methyl propane sulfonics (AMPS)；Monomer B structure formula is as follows：
CH2=CH-C (O)-NH-C (CH3)2—CH2—SO3H
The monomer C is one or more in carboxylic acid that formula (II) indicates or derivatives thereof,
In formula (II), R3、R4And R5Each independently represent H, CH3Or (CH2)yCOOM2, M1And M2It each independently represents
H, alkali metal ion, ammonium, organic amine or the alkyl containing 1~3 carbon atom, m and y each independently represent 0~3 it is whole
Number；
Work as R3、R4And R5One or more of indicate (CH2)yCOOM2When, (CH2)yCOOM2It can be with (CH2)mCOOM1Or its
Its (CH2)yCOOM2Form acid anhydrides.
Preferably, comb-shaped polymer of the invention is by mass percentage by 88%~92% monomer A, 1%~2%
The copolymer that the monomer C of monomer B and 6%~10% is formed.
Preferably, the weight average molecular weight of comb-shaped polymer of the invention is 30000~40000.
Preferably, in the formula (I), n indicates 35~80 integer.
Preferably, the insatiable hunger that the monomer A is indicated by the formula (I) that two kinds of weight average molecular weight are different and/or substituent X is different
With end alkenyl polyether P and Q composition.Specifically, unsaturated end alkenyl polyether P and Q can be two kinds of different polyethers of molecular weight,
Or two kinds of polyethers of structure different (i.e. X group is different), or exist simultaneously two kinds of difference for molecular weight and structure and gather
Ether.
In monomer A, the ratio of polyethers P or Q are unsuitable too small, and otherwise corresponding structural unit is very few in polymer, it is difficult to rise
To the effect for improving polymer performance.Preferably, the monomer A by mass percentage by 30%~70% unsaturated end alkene
The unsaturated end alkenyl polyether Q of base polyethers P and 30%~70% is formed.
In monomer A, when the weight average molecular weight difference of polyethers P or Q, mass difference is unsuitable too small, otherwise two kinds of polyethers
End alkenyl double-bond polymerization activity difference it is smaller, it is difficult to play the purpose that polyethers polymerization activity is adjusted by molecular weight difference.It is excellent
Selection of land, the weight average molecular weight difference are that weight average molecular weight differs 500 or more.
Preferably, one kind in acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid of the monomer C or
A variety of carboxylic acids, or the salt selected from the carboxylic acid or acid anhydrides.
The preparation method of comb-shaped polymer provided by the invention is：In the presence of initiator and chain-transferring agent, make monomer A,
B, C carries out random copolymerization up to the comb-shaped polymer in aqueous solution.
The aqueous solution polymerization method in existing combed polycarboxylate water-reducer can be used in above-mentioned preparation method.Reaction examination therein
The reagent used in any number of existing method, the technological parameters such as reaction time, temperature can be used in agent such as initiator, chain-transferring agent
Existing method is can refer to be readily determined.
In above-mentioned preparation method, the addition of monomer can be disposable input reactor, or it is added dropwise respectively, it can be by
Those skilled in the art determine.According to the mode of dropwise addition, the time of dropwise addition was preferably controlled within 1~5 hour.
Preferably, the initiator includes but not limited to ammonium persulfate, azo-compound or anti-bad by hydrogen peroxide and L-
The dosage of the redox type initiator of hematic acid composition, initiator can be the 0.4~9% of total monomer molal quantity；The chain turns
It includes but not limited to one or more in thioacetic acid, mercaptopropionic acid, mercaptoethanol and methylpropene sodium sulfonate to move agent, and chain turns
The dosage for moving agent can be the 0.1~5% of total monomer molal quantity.
Preferably, at 20~70 DEG C, the reaction time controlled within about 1~5 hour the control of copolyreaction temperature, reaction knot
Constant temperature aging about 0.5~1.5 hour after beam.
Purposes provided by the invention is any one of the above technical scheme comb-shaped polymer as polycarboxylate water-reducer
Purposes.
The inventors discovered that the alkenyl activity one of the unsaturated end alkenyl polyether polymeric monomer for synthesizing polycarboxylate water-reducer
Aspect and the structure of its initiator unsaturated alcohol are closely bound up, and on the other hand the molecular weight with end alkenyl polyether itself also has directly
Relationship, specifically, alkenyl activity are gradually reduced with the increase of molecular weight.Therefore, in polycarboxylate water-reducer building-up process
In can carry out control terminal alkenyl polyether activity by adjusting polyether structure, molecular weight etc., and then reach itself and unsaturated minor comonomer
(such as carboxylic acid or acid anhydrides) optimal reactivity ratio, and then synthesize the polycarboxylate water-reducer of performance brilliance.The present inventor goes back simultaneously
It was found that introduce sulfonic group in polycarboxylate water-reducer building-up process, can effectively promote water-reducing rate and meanwhile improve concrete and it is easy
Property, and contain sulfonic group in 2- acrylamide-2-methylpro panesulfonic acids (AMPS), simultaneously as amides of the AMPS close to double bond
Influence of the group for double bond so that AMPS double bond activity is higher, has good copolymerizable with other monomers, can be in polycarboxylic acids point
It introduces sulfonic while as the copolymerization of other monomers " bridge " in minor structure, and then comb-shaped polymer polymerization can be made more thorough
Bottom, monomer conversion higher.In addition, two or more different polyether macromonomers and AMPS monomers are in synthesis polycarboxylate water-reducer
When, can generate synergistic effect, the performance of gained polycarboxylate water-reducer, which has, to be significantly improved, individually add polyether macromonomer and
AMPS monomers can not all obtain the excellent effect.The present inventor has obtained the comb-shaped polymer of the present invention as a result,.
Comb-shaped polymer provided by the invention uses two or more different molecular weights and/or the unsaturated end alkene of structure
Base polyethers is added to as polymeric monomer and contains sulfonic AMPS monomers, unsaturated end alkenyl polyether polymeric monomer, AMPS on a small quantity
It is organically combined with the unsaturated carboxylic acid of small molecule or derivatives thereof monomer, obtained comb-shaped polymer polymerization is more thorough, and monomer turns
Rate higher, water-reducing property are also obviously improved, and can be used as a kind of very polycarboxylate water-reducer with application value.
Specific implementation mode
For a better understanding of the present invention, hereinafter, the present invention will be further illustrated with reference to latter embodiments.It removes
Non- to make separate stipulations herein, scientific and technical terminology used herein is usual with general technical staff of the technical field of the invention institute
The meaning of understanding is identical.Material, method and latter embodiments mentioned in it are merely to illustrate, rather than to the present invention's
The limitation of range.
Material involved by following embodiment is commercial product unless otherwise instructed.
The monomer A that embodiment uses is as described in Table 1, can synthesize or can be purchased from according to the preparation method of existing polyoxyethylene ether
Liaoning AoKe Chemical Co., Ltd.
Table 1
Embodiment 1
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
I, 3 part of AMPS of TPEG of I, 85 part of HPEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, be added 1.50 parts it is a concentration of
30% hydrogen peroxide solution stirs 3min, and acrylic acid, the monomer that is configured to of 5 parts of deionized waters by 16 parts are then added dropwise simultaneously
Aqueous solution and the initiator being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water
3h is added dropwise in aqueous solution, monomer solution, and initiator solution is added dropwise 3.2h, after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, is added
It is 6 that 30wt% sodium hydrate aqueous solutions, which are neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (I ＆ of 50HPEG
50TPEG I), weight average molecular weight is about 35300.
Embodiment 2
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
I, 2.5 part of AMPS of TPEG of II, 85 part of HPEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, 1.50 parts of concentration are added
For 30% hydrogen peroxide solution, 3min is stirred, acrylic acid, the list that is configured to of 5 parts of deionized waters by 16 parts are then added dropwise simultaneously
Body aqueous solution and the initiation being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water
3h is added dropwise in agent aqueous solution, monomer solution, and initiator solution is added dropwise 3.2h, after completion of dropwise addition, is down to room temperature after constant temperature aging 1h, adds
It is 6 to enter 30% sodium hydrate aqueous solution to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (II ＆ of 50HPEG
50TPEG I), weight average molecular weight is about 38800.
Embodiment 3
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 119 is added
II, 3 part of AMPS of TPEG of II, 51 part of the VPEG of part, which is stirred and evenly mixed, is warming up to 60 DEG C, until completely dissolved, 1.50 parts of concentration is added
For 30% hydrogen peroxide solution, 3min is stirred, acrylic acid, the list that is configured to of 5 parts of deionized waters by 16 parts are then added dropwise simultaneously
Body aqueous solution and the initiation being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water
3h is added dropwise in agent aqueous solution, monomer solution, and initiator solution is added dropwise 3.2h, after completion of dropwise addition, is down to room temperature after constant temperature aging 1h, adds
It is 6 to enter 30% sodium hydrate aqueous solution to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (II ＆ of 70VPEG
30TPEG II), weight average molecular weight is about 33500.
Embodiment 4
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
II, 3.5 part of AMPS of HPEG of I, 85 part of HPEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, 1.50 parts of concentration are added
For 30% hydrogen peroxide solution, 3min is stirred, acrylic acid, the list that is configured to of 5 parts of deionized waters by 16 parts are then added dropwise simultaneously
Body aqueous solution and the initiation being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water
3h is added dropwise in agent aqueous solution, monomer solution, and initiator solution is added dropwise 3.2h, after completion of dropwise addition, is down to room temperature after constant temperature aging 1h, adds
It is 6 to enter 30% sodium hydrate aqueous solution to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (I ＆ of 50HPEG
50HPEG II), weight average molecular weight is about 35800.
Embodiment 5
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
II, 3 part of AMPS of TPEG of I, 85 part of APEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, be added 1.50 parts it is a concentration of
30% hydrogen peroxide solution stirs 3min, and acrylic acid, the monomer that is configured to of 5 parts of deionized waters by 16 parts are then added dropwise simultaneously
Aqueous solution and the initiator being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water
3h is added dropwise in aqueous solution, monomer solution, and initiator solution is added dropwise 3.2h, after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, is added
It is 6 that 30% sodium hydrate aqueous solution, which is neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (I ＆ of 50APEG
50TPEG II), weight average molecular weight is about 37600.
Comparative example 1
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
The APEG I of part, stirs and evenly mixs and is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide solution is added, stirs
3min is mixed, is then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and mercapto by 1.65 parts
The initiator solution that guanidine-acetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, monomer solution are added dropwise
3h, 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30% sodium hydrate aqueous solution is added
It is 6 to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (100APEG I), weight average molecular weight is about 25400.
Comparative example 2
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
The HPEG I of part, stirs and evenly mixs and is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide solution is added, stirs
3min is mixed, is then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and mercapto by 1.65 parts
The initiator solution that guanidine-acetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, monomer solution are added dropwise
3h, 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30% sodium hydrate aqueous solution is added
It is 6 to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (100HPEG I), weight average molecular weight is about 35200.
Comparative example 3
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
The TPEG II of part, stirs and evenly mixs and is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide solution is added,
3min is stirred, is then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and by 1.65 parts
The initiator solution that thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, monomer solution drop
Add 3h, 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, it is water-soluble that 30% sodium hydroxide is added
It is 6 that liquid, which is neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (100TPEG II), weight average molecular weight is about
39300。
Comparative example 4
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
The VPEG I of part, stirs and evenly mixs and is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide solution is added, stirs
3min is mixed, is then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and mercapto by 1.65 parts
The initiator solution that guanidine-acetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, monomer solution are added dropwise
3h, 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30% sodium hydrate aqueous solution is added
It is 6 to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs (100VPEG I), weight average molecular weight is about 36500.
Comparative example 5
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
The TPEG I of I, 85 part of HPEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of dioxygen is added
Aqueous solution stirs 3min, be then added dropwise simultaneously by 19 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and by
The initiator solution that 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, it is single
3h is added dropwise in liquid solution, and 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30wt% hydrogen is added
It is 6 that aqueous solution of sodium oxide, which is neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs-1 (50HPEG Ⅰs ＆50TPEG
I), weight average molecular weight is about 39000.
Comparative example 6
Equipped with thermometer, blender, drop tube 1L four round flask in be added 100 parts deionized water and 85 parts
The TPEG I of II, 85 part of HPEG stir and evenly mix and be warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% double are added
Oxygen aqueous solution stirs 3min, be then added dropwise simultaneously by 19 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and
The initiator solution being formulated by 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water,
3h is added dropwise in monomer solution, and 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30% hydrogen is added
It is 6 that aqueous solution of sodium oxide, which is neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs-2 (50HPEG Ⅱs ＆50TPEG
I), weight average molecular weight is about 32200.
Comparative example 7
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
I, 3 part of AMPS of HPEG of part, which is stirred and evenly mixed, is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide is added
Solution stirs 3min, be then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and by
The initiator solution that 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, it is single
3h is added dropwise in liquid solution, and 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30wt% hydrogen is added
It is 6 that aqueous solution of sodium oxide, which is neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs-3 (50HPEG Ⅰs ＆50TPEG
I), weight average molecular weight is about 37600.
Comparative example 8
Equipped with thermometer, blender, drop tube 1L four round flask in 100 parts of deionized water and 170 is added
I, 3 part of AMPS of TPEG of part, which is stirred and evenly mixed, is warming up to 60 DEG C, until completely dissolved, 1.50 parts a concentration of 30% of hydrogen peroxide is added
Solution stirs 3min, be then added dropwise simultaneously by 16 parts of acrylic acid, the monomer solution that is configured to of 5 parts of deionized waters and by
The initiator solution that 1.65 parts of thioacetic acid, 0.47 part of L-AA, 113 parts of deionized water are formulated, it is single
3h is added dropwise in liquid solution, and 3.2h is added dropwise in initiator solution, and after completion of dropwise addition, room temperature is down to after constant temperature aging 1h, 30% hydrogen-oxygen is added
It is 6 to change sodium water solution to be neutralized to pH, and discharging, as polycarboxylate superplasticizer mother liquor are denoted as PCEs-4 (50HPEG Ⅱs ＆50TPEG I),
Weight average molecular weight is about 33400.
Polycarboxylate water-reducer performance evaluation
Characteristics and advantages for a better understanding of the present invention, using the polymer of the present invention as polycarboxylate water-reducer application
In actual concrete and evaluate its performance.
First, it would be desirable to sample blended by JGJ55 with certain proportioning with cement, sand, stone, water.Material and
Specification is shown in Table 2, and concrete mix is shown in Table 3.
2 material of table and specification
| Material | Specification |
| Sand | Middle sand (river sand) |
| Stone | 16~31.5mm of grain size |
| Reference cement | Concrete admixture examines special PI 42.5 |
3 concrete mix of table
" ratio of mud " in table 3 refers to the mass ratio of cement and water in concrete；" sand coarse aggregate ratio " refer in concrete sand with
The mass ratio of sand and stone summation；" water-reducing agent volume " refers to that cement quality 0.2% is added after polycarboxylate water-reducer folding is solid
Dosage.Various concrete test materials and environment temperature should all be maintained at (20 ± 3) DEG C.Using the nominal for meeting JG3036 requirements
The single horizontal shaft type forced stirrer that capacity is 60 liters, once puts into blender by cement, sand, stone, adds mixed with additive
Mixing water stir together 2 minutes, after discharging, manually turned on iron plate to uniform, tested.Each concrete takes one
A sample, initial extension degree and divergence is indicated with the average value of test result three times after 1 hour." divergence " refers to newly mixing
Concrete voluntarily flows into subcircular after the outflow of slump bucket, the average value of maximum gauge and minimum diameter, size to
Characterize the diminishing function of slump protection of polycarboxylate water-reducer.Concrete divergence is measured according to GB/T50080, two layers of dress of slump bucket point
Material, it is the high half of cylinder that every layer, which is packed into height, and every layer is plugged and pounded 15 times with stick is plugged and pounded, and cylinder is vertically lifted, and it is in nature to make concrete
Flow regime measures divergence.In the test specimen tube that loading gauze nuzzles up after measurement, container capping is stood to 1 hour (from adding
Water stir when start to calculate), then pour out, on iron plate with spade turn to uniformly after, measure divergence again.Evaluation result
As shown in table 4.
4 polycarboxylate water-reducer performance evaluation of table
From table 4, it can be seen that in polycarboxylate water-reducer prepared by embodiment and comparative example, relative to it is conventional only
For adding a kind of polycarboxylate water-reducer (comparative example 1-4) of polyoxyethylene ether monomer, while being added to two kinds of differences point
Water-reducing agent (embodiment 1-5) water-reducing effect obtained by monomer A and the AMPS monomer of son amount and/or structure has clearly
Improvement, the initial divergence with early stage all has clear improvement, and workability is also significantly better than comparative example 1-4, illustrates this hair
Bright comb-shaped polymer has good water-reducing agent performance.
In addition, with individually adding the monomer A (comparative example 5,6) of two kinds of different molecular weights and/or structure or individually adding
The water-reducing agent obtained by AMPS monomers (comparative example 7,8) is added to compare, polycarboxylate water-reducer performance of the invention, which also has, obviously to be changed
Kind, especially early stage (1 hour) performance, workability illustrate also superior to comparative example 5-8 in comb-shaped polymer of the invention,
Both monomer A and monomer AMPS produce synergistic effect.
Although in order to illustrate the present invention, the preferred embodiments of the invention, those skilled in the art are had been disclosed for
Member can be the present invention it should be appreciated that in the case where not departing from present inventive concept defined by claims and range
Go out various modifications, addition and replacement.
Claims (10)
1. a kind of comb-shaped polymer, for by mass percentage by 85%~95% monomer A, 1%~5% monomer B and
The copolymer that the weight average molecular weight that 1%~10% monomer C is formed is 30000 to less than 40000；
Wherein, the monomer A is selected from the unsaturated end alkenyl polyether that two or more formula (I) indicates,
In formula (I), R1And R2Each independently represent H or CH3, X expressions CH2O、CH2CH2O、OCH2CH2O or
OCH2CH2CH2CH2O, EO indicate CH2CH2O, n indicate 24~90 integer；
The monomer B is selected from 2- acrylamide-2-methyl propane sulfonics；
The monomer C is one or more in carboxylic acid that formula (II) indicates or derivatives thereof,
In formula (II), R3、R4And R5Each independently represent H, CH3Or (CH2)yCOOM2, M1And M2Each independently represent H, alkali
Metal ion, ammonium, organic amine or the alkyl containing 1~3 carbon atom, m and y each independently represent 0~3 integer；
Work as R3、R4And R5One or more of indicate (CH2)yCOOM2When, (CH2)yCOOM2It can be with (CH2)mCOOM1Or it is other
(CH2)yCOOM2Form acid anhydrides.
2. comb-shaped polymer according to claim 1, wherein the comb-shaped polymer be by mass percentage by 88%~
The copolymer of the monomer C formation of 92% monomer A, 1%~2% monomer B and 6%~10%.
3. comb-shaped polymer according to claim 1 or 2, wherein in the formula (I), n indicates 35~80 integer.
4. comb-shaped polymer according to claim 1 or 2, wherein the monomer A by two kinds of weight average molecular weight differences and/
Or unsaturated end alkenyl polyether P and the Q composition that the formula (I) that substituent X is different indicates.
5. comb-shaped polymer according to claim 4, wherein the monomer A is by mass percentage by 30%~70%
Unsaturated end alkenyl polyether P and 30%~70% unsaturated end alkenyl polyether Q composition.
6. comb-shaped polymer according to claim 4, wherein the weight average molecular weight difference differs for weight average molecular weight
500 or more.
7. comb-shaped polymer according to claim 1 or 2, wherein the monomer C is selected from acrylic acid, methacrylic acid, horse
Come one or more carboxylic acids in sour, itaconic acid, citraconic acid, or the salt selected from the carboxylic acid or acid anhydrides.
8. the preparation method of any one of the claim 1-7 comb-shaped polymers makes list in the presence of initiator and chain-transferring agent
Body A, B, C carry out random copolymerization up to the comb-shaped polymer in aqueous solution.
9. preparation method according to claim 8, wherein the initiator be selected from ammonium persulfate, azo-compound or by
The redox type initiator of hydrogen peroxide and L-AA composition；The chain-transferring agent be selected from thioacetic acid, mercaptopropionic acid,
It is one or more in mercaptoethanol and methylpropene sodium sulfonate.
10. purposes of any one of the claim 1-7 comb-shaped polymers as polycarboxylate water-reducer.
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| CN106674440A (en) * | 2017-01-04 | 2017-05-17 | 云南宸磊建材有限公司 | Early strength type polycarboxylate water reducer and preparation method thereof |
| CN110922537A (en) * | 2019-10-22 | 2020-03-27 | 浙江老虎山建材有限公司 | Preparation process of concrete slump retaining agent |
| CN112707694B (en) * | 2019-12-24 | 2022-05-10 | 科之杰新材料集团福建有限公司 | Reinforcing steel bar sleeve grouting material for prefabricated part and preparation method thereof |
| CN112321241A (en) * | 2020-06-08 | 2021-02-05 | 上海艺盛实业有限公司 | Masterbatch for quickly repairing concrete road and concrete road repairing material |
| CN115010875A (en) * | 2021-03-04 | 2022-09-06 | 辽宁奥克化学股份有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN117003960A (en) * | 2023-09-04 | 2023-11-07 | 中南大学 | Preparation and application of comb-type polyoxyethylene ether copolymer |
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