CN105271887B - A kind of collapse protection type modified naphthalene series water-reducing agent and preparation method thereof - Google Patents
A kind of collapse protection type modified naphthalene series water-reducing agent and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of collapse protection type modified naphthalene series water-reducing agent and preparation method thereof, and phosphate group is included in its own molecular structure of the collapse protection type modified naphthalene series water-reducing agent；The phosphate group refers to phosphoric acid, hydrogen phosphate and the phosphate radical of substitution.The present invention solves the fast performance deficiency of existing naphthalene water reducer Slump Time losing of Large, during applied in concrete, and the slump keeps excellent, water-reducing property high and do not influence early age strength of concrete.
Description
Technical field
The present invention relates to concrete admixture field, and in particular to a kind of collapse protection type naphthalene water reducer and preparation method thereof.
Background technology
Concrete has turned into the maximum construction material of consumption in the world, is widely used among all kinds of engineerings.Modern times are mixed
Solidifying soil is generally mixed by sand, stone, cement, mineral admixture (flyash, miberal powder etc.) and additive, and added water stirring, and hardening is formed.
Water reducer is maximum, the most widely used concrete admixture of consumption.The effect of water reducer is can to significantly reduce to mix and stir concrete
When the water that is added, while mobile performance when concrete is newly mixed and the intensity after hardening are increased substantially, so as to improve work
The quality of journey.
Naphthalene series high-efficiency water-reducing agent has the spies such as diminishing high, performance stabilization good from the adaptability of different cement, moderate cost
Point, is current domestic production amount maximum, using most wide water reducer.But, the Slump Time losing of Large of its concrete batching system
Hurry up (i.e. after concrete stirring, after certain time, the gradually retrogradation of stirring material, mobility gradually step-down), waited to pumping, pouring
Journey brings very big difficulty, or causes concrete vibrating unreal, voids and pits occurs, influences component quality.
Most of producers suppress cement early stage using a certain amount of retarder (such as sucrose, sodium gluconate) is compounded at present
The method of aquation controls the slump-loss of fresh concrete, concrete slump loss is made moderate progress, but using process
In easily there is fresh concrete early stage bleeding, later stage mobility and still lose fast phenomenon, also result in early age strength of concrete
It is affected.Therefore, it is necessary to start with from naphthalene water reducer configuration aspects, the Slump Time losing of Large for improving naphthalene water reducer is fast
Performance deficiency, to meet requirement of the market to properties of product.
CN101759393B discloses a kind of preparation method of the modified naphthalene series water-reducing agent of low slump loss, its essence is
Add guarantor to collapse component oxidation-etherification starch to reduce slump-loss, do not change naphthalene water reducer structure.
The preparation method of collapse protection type naphthalene water reducer disclosed in CN103864332A not only needs to introduce other condensed ring in sulfonation stage
Aromatic hydrocarbons, and other sulfonate are added in the condensation stage, finally also neutralized with sodium metasilicate, technique is considerably complicated.
CN103804620A discloses a kind of naphthalene system polycarboxylic acids collapse-preventing type water reducer, and carboxyl is introduced in water reducer structure and hydroxyl comes
Guarantor is played to collapse function, but carboxyl and hydroxyl are much weaker than the sulfonic group in naphthalene water reducer to the adsorption capacity of cement granules,
Therefore its water-reducing property may be a greater impact.Neat Asia and Africa et al. (New Building Materials, 2003, the 3rd phase, the 28th~
Page 30), a kind of method that bisgallic acid method synthesizes naphthalene water reducer is disclosed, it adds a certain amount of phosphoric acid water in condensation step
Solution so that contain phosphate retarder in product, phosphate group is not connected on naphthalene water reducer strand, and it is only
It is being simply mixed for phosphate and naphthalene water reducer.
The content of the invention
There is provided a kind of slump to solve the fast performance deficiency of existing naphthalene water reducer Slump Time losing of Large by the present invention
Keep excellent, water-reducing property high and do not influence the modified naphthalene series water-reducing agent of early age strength of concrete.
Those skilled in the art have found, in the condensation step that naphthalene water reducer is synthesized, by phosphorous acid groups (herein
Substituted phosphoric acid, hydrogen phosphate and phosphate radical are referred to as phosphate group) polycondensation monomer and naphthalene sulfonic acids copolycondensation, so as to change
The structure of traditional naphthalene water reducer, not only water-reducing property has been lifted obtained modified naphthalene series water-reducing agent, and with excellent
Slump-retaining energy.
Those skilled in the art also found, obtained after the cocondensation polycondensation monomer of the phosphorous acid groups of above-mentioned introducing
Water reducer product only slightly extends concrete coagulating time, and does not interfere with the early strength of concrete.
Collapse protection type modified naphthalene series water-reducing agent of the present invention, its core technology point is, is wrapped in its own molecular structure
Phosphorous acid groups.
The phosphate group refers to phosphoric acid, hydrogen phosphate and the phosphate radical of substitution.
Used different from the phosphate as retarder is simply mixed with naphthalene water reducer in the prior art；It is of the invention straight
It is connected in naphthalene water reducer molecular structure and introduces phosphate group, there is modified naphthalene water reducer molecule and slow down cement water
The effect of change, makes diminishing agent molecule only be covered and fail by hydrolysis product of cement soon, can effectively control newly to mix coagulation
The slump-loss of soil, keep its mobility, and avoid the defect that directly compounding retarder is brought.
The preparation method of collapse protection type modified naphthalene series water-reducing agent of the present invention, is comprised the following steps that：
(1) sulfonation：Naphthalene heating is melted to 130 DEG C~160 DEG C, 98%~100% concentrated sulfuric acid is added, the concentrated sulfuric acid and naphthalene
Mol ratio is (1~1.6)：1, in 145 DEG C~175 DEG C sulfonating reactions 1.5~3.5 hours；Obtain sulfonation material；
The naphthalene is refined naphthalene or crude naphthalene；
(2) hydrolyze：105 DEG C~135 DEG C are cooled to, the water of sulfonation material gross mass 10%~40%, hydrolysis 0.5 is added
~2 hours；
(3) it is condensed：Material through hydrolysing step is cooled to 85 DEG C~105 DEG C, adds the cocondensation polycondensation monomer of phosphorous acid groups,
Add 37% formalin, the mol ratio of cocondensation polycondensation monomer and naphthalene is (0.1~0.5)：1；Formalin：(naphthalene+copolycondensation list
Body) mol ratio be (0.9~1.3)：1；Condensation reaction 4~6 hours is carried out at 95 DEG C~125 DEG C；
(4) neutralize：Sodium hydroxide is added in the foregoing material through condensation step, it is 7~8 that reactant is neutralized into pH value,
Obtain the collapse protection type modified naphthalene series water-reducing agent.
The cocondensation polycondensation monomer of the phosphorous acid groups includes appointing in the compound with following structure formula (I)~(VIII)
Any combination of meaning ratio：
Wherein, n is 1~4 integer.
Not only water-reducing property has been lifted modified naphthalene series water-reducing agent of the present invention, and is protected with the excellent slump
Hold performance；Concrete coagulating time is only slightly extended, and does not interfere with the early strength of concrete.
Embodiment
Naphthalene used, sulfuric acid, formalin, sodium hydroxide solution, sodium tripolyphosphate in comparative example and embodiment of the present invention
It is general technical grade product with sodium gluconate, the phosphorous acid groups copolycondensation monomer is purchased from Sigma-Aldrich
(Shanghai) trade Co., Ltd, uncommon love (Shanghai) the chemical conversion industry Development Co., Ltd of ladder, Shanghai Aladdin biochemical technology share have
The suppliers such as limit company, Chemical Reagent Co., Ltd., Sinopharm Group.
The code name of table 1 is used in embodiment：
The code name and structure of phosphorous acid groups copolycondensation monomer in the synthetic example of table 1
Comparative example
A kind of conventional naphthalene water reducer, it does not add any modified cocondensation polycondensation monomer in the condensation step of building-up process, bag
Include following steps：
(1) sulfonation：95% naphthalene 162kg (1.2kmol) heating is melted to 140 DEG C, 98% concentrated sulfuric acid 180kg is added
(1.8kmol), in 165 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：120 DEG C are cooled to, 50kg water is added, hydrolyzed 1 hour；
(3) it is condensed：95 DEG C are cooled to, 37% formalin 97kg (1.2kmol) is added, carries out being condensed instead at 100 ± 3 DEG C
Answer 5 hours；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 1
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：95% naphthalene 162kg (1.2kmol) heating is melted to 140 DEG C, 98% concentrated sulfuric acid 180kg is added
(1.8kmol), in 165 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：120 DEG C are cooled to, 50kg water is added, hydrolyzed 1 hour；
(3) it is condensed：95 DEG C are cooled to, cocondensation polycondensation monomer A 26.9kg (0.12kmol) is added, then adds 37% formaldehyde
Solution 97kg (1.2kmol), condensation reaction 5 hours is carried out at 100 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 2
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：96% naphthalene 187kg (1.4kmol) heating is melted to 150 DEG C, 99% concentrated sulfuric acid 178kg is added
(1.8kmol), in 150 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：115 DEG C are cooled to, 140kg water is added, hydrolyzed 1 hour；
(3) it is condensed：100 DEG C are cooled to, cocondensation polycondensation monomer B 52.2kg (0.3kmol) is added, then adds 37% formaldehyde
Solution 162kg (2.0kmol), condensation reaction 6 hours is carried out at 98 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 3
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：95% naphthalene 162kg (1.2kmol) heating is melted to 130 DEG C, 98% concentrated sulfuric acid 190kg is added
(1.9kmol), in 150 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：105 DEG C are cooled to, 70kg water is added, hydrolyzed 1.5 hours；
(3) it is condensed：105 DEG C are cooled to, cocondensation polycondensation monomer C 47.6kg (0.2kmol) is added, then adds 37% formaldehyde
Solution 130kg (1.6kmol), condensation reaction 5 hours is carried out at 105 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 4
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：95% naphthalene 162kg (1.2kmol) heating is melted to 160 DEG C, 98% concentrated sulfuric acid 190kg is added
(1.9kmol), in 170 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：125 DEG C are cooled to, 70kg water is added, hydrolyzed 1.5 hours；
(3) it is condensed：85 DEG C are cooled to, cocondensation polycondensation monomer D 138kg (0.6kmol) is added, then adds 37% formaldehyde molten
Liquid 178kg (2.2kmol), condensation reaction 5.5 hours is carried out at 100 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 5
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：96% naphthalene 187kg (1.4kmol) heating is melted to 140 DEG C, 99% concentrated sulfuric acid 178kg is added
(1.8kmol), in 170 ± 3 DEG C of sulfonating reactions 3.5 hours；
(2) hydrolyze：115 DEG C are cooled to, 90kg water is added, hydrolyzed 1 hour；
(3) it is condensed：90 DEG C are cooled to, cocondensation polycondensation monomer E 187.2kg (0.6kmol) is added, then adds 37% formaldehyde
Solution 211kg (2.6kmol), condensation reaction 5 hours is carried out at 110 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 6
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：96% naphthalene 187kg (1.4kmol) heating is melted to 130 DEG C, 99% concentrated sulfuric acid 178kg is added
(1.8kmol), in 155 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：125 DEG C are cooled to, 80kg water is added, hydrolyzed 0.5 hour；
(3) it is condensed：95 DEG C are cooled to, cocondensation polycondensation monomer F 183.6kg (0.6kmol) is added, then adds 37% formaldehyde
Solution 162kg (2.0kmol), condensation reaction 4 hours is carried out at 120 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 7
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：97% naphthalene 158kg (1.2kmol) heating is melted to 140 DEG C, 98% concentrated sulfuric acid 170kg is added
(1.7kmol), in 155 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：130 DEG C are cooled to, 40kg water is added, hydrolyzed 1 hour；
(3) it is condensed：90 DEG C are cooled to, cocondensation polycondensation monomer G 112.8kg (0.4kmol) is added, then adds 37% formaldehyde
Solution 122kg (1.5kmol), condensation reaction 4 hours is carried out at 122 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 8
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：97% naphthalene 158kg (1.2kmol) heating is melted to 140 DEG C, 98% concentrated sulfuric acid 170kg is added
(1.7kmol), in 160 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：120 DEG C are cooled to, 50kg water is added, hydrolyzed 1.5 hours；
(3) it is condensed：105 DEG C are cooled to, cocondensation polycondensation monomer H 145kg (0.5kmol) is added, then adds 37% formaldehyde molten
Liquid 146kg (1.8kmol), condensation reaction 5 hours is carried out at 110 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 9
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：95% naphthalene 162kg (1.2kmol) heating is melted to 160 DEG C, 98% concentrated sulfuric acid 190kg is added
(1.9kmol), in 170 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：125 DEG C are cooled to, 70kg water is added, hydrolyzed 1.5 hours；
(3) it is condensed：85 DEG C are cooled to, cocondensation polycondensation monomer D 19.3kg (0.084kmol) is added, then adds 37% formaldehyde
Solution 114kg (1.4kmol), condensation reaction 5.5 hours is carried out at 100 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 10
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：96% naphthalene 187kg (1.4kmol) heating is melted to 140 DEG C, 99% concentrated sulfuric acid 178kg is added
(1.8kmol), in 170 ± 3 DEG C of sulfonating reactions 3.5 hours；
(2) hydrolyze：115 DEG C are cooled to, 90kg water is added, hydrolyzed 1 hour；
(3) it is condensed：90 DEG C are cooled to, cocondensation polycondensation monomer E 280.8kg (0.9kmol) is added, then adds 37% formaldehyde
Solution 219kg (2.7kmol), condensation reaction 5 hours is carried out at 110 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 11
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：96% naphthalene 187kg (1.4kmol) heating is melted to 130 DEG C, 99% concentrated sulfuric acid 178kg is added
(1.8kmol), in 155 ± 3 DEG C of sulfonating reactions 2.5 hours；
(2) hydrolyze：125 DEG C are cooled to, 80kg water is added, hydrolyzed 0.5 hour；
(3) it is condensed：95 DEG C are cooled to, cocondensation polycondensation monomer F 122.4kg (0.4kmol) is added, then adds 37% formaldehyde
Solution 113kg (1.4kmol), condensation reaction 4 hours is carried out at 120 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 12
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：97% naphthalene 158kg (1.2kmol) heating is melted to 140 DEG C, 98% concentrated sulfuric acid 170kg is added
(1.7kmol), in 155 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：130 DEG C are cooled to, 40kg water is added, hydrolyzed 1 hour；
(3) it is condensed：90 DEG C are cooled to, cocondensation polycondensation monomer G 84.6kg (0.3kmol) is added, then adds 37% formaldehyde molten
Liquid 186kg (2.3kmol), condensation reaction 4 hours is carried out at 122 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 13
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：98% naphthalene 196kg (1.5kmol) heating is melted to 150 DEG C, 98% concentrated sulfuric acid 150kg is added
(1.5kmol), in 160 ± 3 DEG C of sulfonating reactions 2 hours；
(2) hydrolyze：125 DEG C are cooled to, 35kg water is added, hydrolyzed 0.5 hour；
(3) it is condensed：90 DEG C are cooled to, cocondensation polycondensation monomer A 67.2kg (0.3kmol) and cocondensation polycondensation monomer C are added
71.4kg (0.3kmol), then adds 37% formalin 211kg (2.6kmol), and it is small to carry out condensation reaction 5 at 105 ± 3 DEG C
When；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Embodiment 14
A kind of collapse protection type naphthalene water reducer, its preparation process is as follows：
(1) sulfonation：98% naphthalene 196kg (1.5kmol) heating is melted to 150 DEG C, 98% concentrated sulfuric acid 150kg is added
(1.5kmol), in 165 ± 3 DEG C of sulfonating reactions 3 hours；
(2) hydrolyze：110 DEG C are cooled to, 40kg water is added, hydrolyzed 1 hour；
(3) it is condensed：95 DEG C are cooled to, cocondensation polycondensation monomer D 23kg (0.1kmol) and cocondensation polycondensation monomer G 56.4kg are added
(0.2kmol), then adds 37% formalin 186kg (2.3kmol), and condensation reaction 5.5 hours is carried out at 100 ± 3 DEG C；
(4) neutralize：32% sodium hydroxide solution is added, it is 7~8 that reactant is neutralized into pH value, that is, obtains product.
Detect example
Introduced in naphthalene water reducer structure after phosphorous acid groups copolycondensation monomer of the present invention, nuclear-magnetism can be used
Resonance phosphorus spectrum easily, delicately detects the presence of phosphorous polycondensation fragment.The product aqueous solution synthesized by above example is taken,
According to volume ratio 1:1 adds methanol, and the polymer of precipitation is centrifuged out, 40% solution is configured to deionized water dissolving, then
According to volume ratio 1:1 adds methanol, and the polymer of precipitation is centrifuged out, testing sample is then dried in vacuo into.Nuclear-magnetism is total to
Detection of shaking is completed on the AVANCE DPX-400 spectrometers of Bruker companies.The solvent of sample dissolution is heavy water.31P NMR inspection
Measured frequency is 161.98MHz.It is test result below：
Embodiment 1
31P NMR(161.98MHz,D2O):δ=- 5.86, -2.47.
Embodiment 2
31P NMR(161.98MHz,D2O):δ=- 0.98,1.42.
Embodiment 3
31P NMR(161.98MHz,D2O):δ=5.14,7.33.
Embodiment 4
31P NMR(161.98MHz,D2O):δ=5.38,7.67.
Embodiment 5
31P NMR(161.98MHz,D2O):δ=4.39,6.78.
Embodiment 6
31P NMR(161.98MHz,D2O):δ=4.04,6.42.
Embodiment 7
31P NMR(161.98MHz,D2O):δ=4.61,7.10.
Embodiment 8
31P NMR(161.98MHz,D2O):δ=4.56,6.77.
Embodiment 9
31P NMR(161.98MHz,D2O):δ=5.38,7.67.
Embodiment 10
31P NMR(161.98MHz,D2O):δ=4.39,6.78.
Embodiment 11
31P NMR(161.98MHz,D2O):δ=4.04,6.42.
Embodiment 12
31P NMR(161.98MHz,D2O):δ=4.61,7.10.
Embodiment 13
31P NMR(161.98MHz,D2O):δ=- 5.86, -2.46,5.14,7.33.
Embodiment 14
31P NMR(161.98MHz,D2O):δ=4.61,5.38,7.11,7.68.
Water reducer obtained by the embodiment of the present invention, P elements are all detected in its polymer, show phosphorous
Acid groups polycondensation monomer is all successfully introduced among water reducer structure.
Application examples
The application effect of prepared collapse protection type naphthalene water reducer is investigated by concrete test.Cement wherein used is
The cement of south of the River little Ye fields PII 52.5, flyash is II grade flyash, and sand is the middle sand of modulus of fineness 2.7, coarse aggregate for 5~
20mm continuous grading rubbles.Concrete mix：Cement 260kg/m3, flyash 110kg/m3, sand 770kg/m3, rubble
1080kg/m3, water 160kg/m3.Naphthalene water reducer, sodium gluconate, sodium tripolyphosphate volume are on the basis of cement quality, naphthalene system
Water reducer is calculated as 0.5% by the solid amount of folding, and sodium gluconate and sodium tripolyphosphate are calculated as 0.05% by the solid amount of folding.Experiment according to
Condition as defined in GB8076-2008 and method are tested and determination data, and result of the test is as follows.
The embodiment concrete test data comparison of table 2
It is can be seen that from above concrete test correction data using the collapse protection type naphthalene system diminishing obtained by the inventive method
The properties of product of agent are compared with the common naphthalene water reducer of comparative example, and not only water-reducing property increases, and 1 hour slump
Penalty values are substantially reduced.Using conventional guarantor's landslide case, slow setting component (glucose is added by the common naphthalene water reducer of comparative example
Sour sodium or sodium tripolyphosphate), initial water-reducing property is too high to be caused concrete water bleeding serious and isolates, concrete coagulating time extension
Excessively, and early strength is affected.
It can also find out from test data, the amount of cocondensation polycondensation monomer is very few, and function of slump protection is too poor；And cocondensation polycondensation monomer is excessive,
Concrete coagulating time extension is excessive.Formaldehyde amount is very few, and the product degree of polymerization can not enough make product water-reducing property be deteriorated, and formaldehyde amount
Excessively, the product degree of polymerization is too high can also influence properties of product.
Common naphthalene water reducer product concrete slump is improved using the naphthalene water reducer obtained by the inventive method
The fast defect of gradual loss, realizes the performance optimization to naphthalene water reducer.
Claims (1)
1. a kind of collapse protection type modified naphthalene series water-reducing agent, it is characterised in that the self-molecules present of the collapse protection type modified naphthalene series water-reducing agent
Phosphate group is included in structure；The phosphate group refers to phosphoric acid, hydrogen phosphate and the phosphate radical of substitution；
The preparation method of the collapse protection type modified naphthalene series water-reducing agent, is comprised the following steps that：
(1) sulfonation：Naphthalene heating is melted to 130 DEG C~160 DEG C, mole of 98%~100% concentrated sulfuric acid, the concentrated sulfuric acid and naphthalene is added
Than for (1~1.6)：1, in 145 DEG C~175 DEG C sulfonating reactions 1.5~3.5 hours；Obtain sulfonation material；The naphthalene be refined naphthalene or
Crude naphthalene；
(2) hydrolyze：105 DEG C~135 DEG C are cooled to, the water of sulfonation material gross mass 10%~40% is added, hydrolysis 0.5~2 is small
When；
(3) it is condensed：Material through hydrolysing step is cooled to 85 DEG C~105 DEG C, adds the cocondensation polycondensation monomer of phosphorous acid groups, then add
Enter 37% formalin, the mol ratio of cocondensation polycondensation monomer and naphthalene is (0.1~0.5)：1；Formalin：(naphthalene+cocondensation polycondensation monomer)
Mol ratio be (0.9~1.3)：1；Condensation reaction 4~6 hours is carried out at 95 DEG C~125 DEG C；
(4) neutralize：Sodium hydroxide is added in the foregoing material through condensation step, it is 7~8 that reactant is neutralized into pH value, is produced
To the collapse protection type modified naphthalene series water-reducing agent；
The cocondensation polycondensation monomer of the phosphorous acid groups includes any ratio in the compound with following structure formula (I)~(VIII)
Any combination of example：
Wherein, n is 1~4 integer.
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| CN106186781B (en) * | 2016-06-29 | 2018-10-23 | 南京瑞迪高新技术有限公司 | A kind of preparation method of modified naphthalene series water-reducing agent |
| CN106632930B (en) * | 2016-09-18 | 2019-03-08 | 江苏苏博特新材料股份有限公司 | A kind of modified condensation polymer type water-reducing agent, preparation method and its application |
| CN107337366B (en) * | 2016-12-07 | 2019-12-27 | 江苏苏博特新材料股份有限公司 | Slow-release slump-retaining concrete water reducer and preparation method and application thereof |
| CN107043442B (en) * | 2017-02-24 | 2019-05-17 | 唐山市龙亿科技开发有限公司 | High-thin arch dam, high water reduction, the preparation method of anti-stick soil type modified naphthalene series water-reducing agent |
| CN113121771B (en) * | 2019-12-30 | 2022-12-02 | 江苏苏博特新材料股份有限公司 | Air-entraining modified naphthalene water reducer and preparation method thereof |
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| WO2010040612A1 (en) * | 2008-10-06 | 2010-04-15 | Construction Research & Technology Gmbh | Phosphated polycondensation product, method for production and use thereof |
| RU2554944C2 (en) * | 2008-10-06 | 2015-07-10 | Констракшн Рисерч Энд Текнолоджи Гмбх | Method of preparing phosphated products of polycondensation and application thereof |
| CN102596847B (en) * | 2009-09-02 | 2015-04-01 | 巴斯夫聚合建材有限公司 | Formulation and its use |
| CN102086105B (en) * | 2010-12-10 | 2012-10-10 | 马清浩 | Modified naphthalene water reducer and preparation method thereof |
| CN103159425A (en) * | 2013-03-21 | 2013-06-19 | 安徽淮河化工股份有限公司 | Synthesis method of modified naphthalene water-reducing agent |
| CN103382092B (en) * | 2013-06-17 | 2015-12-02 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of naphthalene water reducer |
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