Summary of the invention:
The technical problem to be solved in the present invention is at some engineerings higher to life requirement, especially the engineering that total alkali content is had relatively high expectations, protect on the basis of advantages such as collapsing at the big diminishing of maintenance sulfamate series high-efficiency water-reducing agent, height, the subtracting property conditioning agent that does not contain sodium, potassium ion by application or certain applications, reduce or remove alkali in the prepared amino water reducer of prior art, for people provide a kind of amino sulfonic acid water reducing agent with very low alkali content and preparation method thereof.
The present invention is formed by following prepared:
(1) methylolation: aminoaryl sulphonating agent, phenolic monomers and water are added in the reactor, after stirring, the pH value of reaction system is transferred to 7-9.5, in 0.5-3.0h, drip condensing agent with alkaline conditioner, heat temperature raising reacts 0.5-2h after 50-100 ℃;
(2) alkaline condensation: utilize alkaline conditioner that the pH value of above-mentioned system is transferred to 8-11, and add the compound of an amount of phosphinylidyne-containing amine group, react 2-10h down at 70-100 ℃;
(3) alkalescence is reformed: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 8.5-13, cooling discharge behind reaction 0.5-3.0h under 85-100 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal;
In above-mentioned three steps, the quality consumption of each raw material is:
Aminoaryl sulphonating agent: 10.5~32%, phenolic monomers: 3.2~16%, compound 0~10.5%, the condensing agent of phosphinylidyne-containing amine group: 9.5~61.0%, alkaline conditioner: 0.7-11.5%, water: 17.5-65%.
Wherein, the aminoaryl sulphonating agent is Sulphanilic Acid, 4-kharophen Phenylsulfonic acid, 4-amino-1, and one or more in the 3-phenyl disulfonic acid are pressed arbitrary proportion blended mixture.
Phenolic monomers is that in the nucleophilic substitution derivative of phenol, Resorcinol, Resorcinol, cresols, diethylstilbestrol, dihydroxyphenyl propane, bisphenol S or above compound one or more are by arbitrary proportion blended mixture.
In condensing agent be formaldehyde, acetaldehyde, furfural, trioxymethylene in one or more by arbitrary proportion blended mixture; The compound of phosphinylidyne-containing amine group is that in urea, Dyhard RU 100, trimeric cyanamide, acrylamide and the toluol sulfonamide one or more are by arbitrary proportion blended mixture.
Alkaline conditioner is that in sodium hydroxide, calcium hydroxide, calcium oxide, lime carbonate, ammoniacal liquor, thanomin, diethanolamine, the trolamine one or more are by arbitrary proportion blended mixture, the summation of three add-ons is the 0.7-11.5% of reaction mass total amount, and wherein sodium hydroxide concentration is no more than 6% of subtracting property conditioning agent total amount.
More than the massfraction summation of raw material of each step be 100%.
Beyond every advantages such as the present invention is except having the big diminishing of sulfamate series high-efficiency water-reducing agent, and high guarantor collapsed, and cement adaptability is strong, outstanding characteristics are: total alkali content is less than 1.0%, even is zero.
Embodiment
Embodiment 1
1. the raw material of present embodiment and prescription (unit-Kg)
Sulphanilic Acid: 225 kilograms;
Phenol: 84 kilograms;
The compound of phosphinylidyne-containing amine group (Dyhard RU 100 and urea admixture, mass ratio are 1:3): 28 kilograms
Cresols: 12 kilograms;
Formaldehyde (37% content): 252 kilograms;
Alkaline conditioner: calcium hydroxide: 14.8 kilograms; Ammoniacal liquor: 34 kilograms
Water: 350.2 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 225 kilograms of Sulphanilic Acid, 84 kilograms and 12 kilograms cresols of phenol and 350.2 kg water are added in the reactor, after stirring, with 14.8 kilograms in calcium hydroxide, the pH value of reaction system is transferred to 8.0, in 1.5h, drip 252 kilograms of formaldehyde, behind the heat temperature raising to 65 ℃, reaction 0.5h.
(2) alkaline condensation: the mixture that utilizes 23 kilograms of ammoniacal liquor transfers to 9.5 with the pH value of above-mentioned system, and adds 28.0 kilograms of Dyhard RU 100s and urea admixture, at 90 ℃ of reaction 7.5h down.
(3) alkalescence is reformed: utilize 11 kilograms of ammoniacal liquor that the pH value of above-mentioned system is transferred to 12.5, cooling discharge behind reaction 1.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 2
1. the raw material of embodiment and prescription (unit-Kg)
Sulphanilic Acid: 242 kilograms;
Phenol: 125 kilograms;
Trimeric cyanamide: 5.0 kilograms
Trioxymethylene: 85 kilograms;
Alkaline conditioner: 9.5 kilograms in calcium hydroxide; Thanomin: 45 kilograms
Water: 488.5 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 242 kilograms of Sulphanilic Acid, 125 kilograms of phenol and 488.5 kg water are added in the reactor, after stirring, with 15 kilograms of 9.5 kilograms in calcium hydroxide and thanomins, the pH value of reaction system is transferred to 8.5, in 0.5h, drip 85 kilograms of trioxymethylenes, behind the heat temperature raising to 50 ℃, reaction 3.0h.
(2) alkaline condensation: utilize 18 kilograms of thanomins that the pH value of above-mentioned system is transferred to 9.5, and add 5.0 kilograms of trimeric cyanamides, react 5.5h down at 85 ℃.
(3) alkalescence is reformed: utilize 12 kilograms of thanomins that the pH value of above-mentioned system is transferred to 11.5, cooling discharge behind reaction 2.0h under 95 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 3
1. the raw material of embodiment and prescription (unit-Kg)
4-amino-1,3-phenyl disulfonic acid: 18 kilograms;
Sulphanilic Acid: 224 kilograms;
Phenol: 83 kilograms;
Urea: 16.5 kilograms
Dihydroxyphenyl propane: 12 kilograms;
Formaldehyde (37% content): 210 kilograms;
Alkaline conditioner: ammoniacal liquor: 19.5 kilograms; Diethanolamine: 48 kilograms
Water: 369 kilograms.
1. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: with the 4-amino-1 of 224 kilograms of Sulphanilic Acid and 18 kilograms, 3-phenyl disulfonic acid, 83 kilograms and 12 kilograms dihydroxyphenyl propanes of phenol and 369 kg water add in the reactor, after stirring, with 16.5 kilograms of ammoniacal liquor, the pH value of reaction system is transferred to 7.5, in 1.5h, drip 210 kilograms of formaldehyde, behind the heat temperature raising to 75 ℃, reaction 1.5h.
(2) alkaline condensation: the mixture that utilizes 3 kilograms of ammoniacal liquor and 27 kilograms of diethanolamine transfers to 8.5 with the pH value of above-mentioned system, and adds 16.5 kg urea mixtures, at 90 ℃ of reaction 7.5h down.
(3) alkalescence is reformed: utilize 21 kilograms of diethanolamine that the pH value of above-mentioned system is transferred to 12.5, cooling discharge behind reaction 1.0h under 95 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 4
1. the raw material of present embodiment and prescription (unit-Kg)
Sulphanilic Acid: 174 kilograms;
Phenol: 68 kilograms;
Acrylamide: 21.5 kilograms
Resorcinol: 22 kilograms;
Field aldehyde (37% content): 235 kilograms;
Alkaline conditioner: calcium hydroxide: 9.5 kilograms; Trolamine: 56 kilograms;
Water: 414 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 174 kilograms of Sulphanilic Acid, 68 kilograms and 22 kilograms Resorcinols of phenol and 414 kg water are added in the reactor, after stirring, with 8.5 kilograms in calcium hydroxide, the pH value of reaction system is transferred to 8.0, in 1.5h, drip 235 kilograms of formaldehyde, behind the heat temperature raising to 85 ℃, reaction 0.5h.
(2) alkaline condensation: the mixture that utilizes 1 kg of hydrogen calcium oxide and 32 kilograms of trolamines transfers to 10.5 with the pH value of above-mentioned system, and adds 21.5 kilograms of acrylamides, at 95 ℃ of reaction 10h down.
(3) alkalescence is reformed: utilize 24 kilograms of trolamines that the pH value of above-mentioned system is transferred to 12.5, cooling discharge behind reaction 2.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 5
1. raw material and prescription (unit-Kg)
4-acetaminobenzenesulfonic acid: 150 kilograms;
Phenol: 30 kilograms;
The compound of phosphinylidyne-containing amine group (mixture of Dyhard RU 100 and trimeric cyanamide, mass ratio are 1:4): 11 kilograms
Bisphenol S: 58 kilograms;
Formaldehyde (37% content): 150 kilograms;
Acetaldehyde: 30 kilograms;
Alkaline conditioner: ammoniacal liquor: 9.5 kilograms; Trolamine: 33 kilograms;
Water: 528.5 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 150 kilograms of 4-kharophen Phenylsulfonic acids, 30 kilograms and 58 kilograms bisphenol Ss of phenol and 528.5 kg water are added in the reactor, after stirring, with 9.5 kilograms in the mixture of ammoniacal liquor, the pH value of reaction system is transferred to 7.5, in 1.0h, drip 150 kilograms of formaldehyde, 0.5 drip 30 kilograms in acetaldehyde in hour, behind the heat temperature raising to 75 ℃, reaction 0.5h.
(2) alkaline condensation: utilize 23 kilograms of trolamines that the pH value of above-mentioned system is transferred to 10.5, and add the mixture of 11 kilograms of Dyhard RU 100s and trimeric cyanamide, react 10.5h down at 90 ℃.
(3) alkalescence is reformed: utilize 10 kilograms of trolamines that the pH value of above-mentioned system is transferred to 11.5, cooling discharge behind reaction 3.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 6
1. raw material and prescription (unit-Kg)
Sulphanilic Acid: 180 kilograms;
Sodium sulfanilate: 30 kilograms;
Phenol: 68 kilograms;
The compound of phosphinylidyne-containing amine group (Dyhard RU 100 and urea admixture, mass ratio are 1:4): 26 kilograms
Dihydroxyphenyl propane: 22 kilograms;
Formaldehyde (37% content): 180 kilograms;
Alkaline conditioner: calcium hydroxide: 9.5 kilograms; Ammoniacal liquor: 17 kilograms;
Water: 467.5 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 180 kilograms of Sulphanilic Acid and 30 kilograms of Sodium sulfanilates, 68 kilograms and 22 kilograms dihydroxyphenyl propanes of phenol and 467.5 kg water are added in the reactor, after stirring, with 4.5 kilograms in calcium hydroxide, the pH value of reaction system is transferred to 8.0, in 1.5h, drip 180 kilograms of formaldehyde, behind the heat temperature raising to 75 ℃, reaction 1.5h.
(2) alkaline condensation: the mixture that utilizes 5 kg of hydrogen calcium oxide and 6 kilograms of ammoniacal liquor transfers to 9.5 with the pH value of above-mentioned system, and adds 26.0 kilograms of Dyhard RU 100s and urea admixture, at 90 ℃ of reaction 7.5h down.
(3) alkalescence is reformed: utilize 11 kilograms of ammoniacal liquor that the pH value of above-mentioned system is transferred to 12.5, cooling discharge behind reaction 1.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 7
1. raw material and prescription (unit-Kg)
Sulphanilic Acid: 160 kilograms;
Phenol: 58 kilograms;
The compound of phosphinylidyne-containing amine group (Dyhard RU 100 and urea admixture, mass ratio are 1:4): 8 kilograms
Dihydroxyphenyl propane: 15 kilograms;
Bisphenol S: 12 kilograms;
Formaldehyde (37% content): 160 kilograms;
Alkaline conditioner: (ammoniacal liquor: 37 kilograms; Sodium hydroxide: 2 kilograms; )
Water: 548 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 160 kilograms of Sulphanilic Acid, 58 kilograms, 15 kilograms dihydroxyphenyl propanes of phenol, 12 kilograms of bisphenol Ss and 548 kg water are added in the reactor, after stirring, with 21.5 kilograms of ammoniacal liquor, the pH value of reaction system is transferred to 9.0, in 1.0h, drip 160 kilograms of formaldehyde, behind the heat temperature raising to 85 ℃, reaction 0.5h.
(2) alkaline condensation: the mixture that utilizes 15.5 kilograms of ammoniacal liquor transfers to 10.5 with the pH value of above-mentioned system, and adds 8.0 kilograms of Dyhard RU 100s and urea admixture, at 90 ℃ of reaction 4.5h down.
(3) alkalescence is reformed: utilize 2 kg of hydrogen sodium oxides that the pH value of above-mentioned system is transferred to 12.5, cooling discharge behind reaction 3.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Embodiment 8
1. raw material and prescription (unit-Kg)
Sulphanilic Acid: 180 kilograms;
Phenol: 68 kilograms;
The compound of phosphinylidyne-containing amine group (Dyhard RU 100 and urea admixture, mass ratio are 1:3): 12 kilograms
Formaldehyde (37% content): 180 kilograms;
Alkaline conditioner: trolamine: 29.5 kilograms; Sodium hydroxide: 1 kilogram;
Water: 529.5 kilograms.
2. processing step and processing parameter:
Preparation technology of the present invention comprises three steps: the methylolation under the alkaline condition, alkaline condensation and alkaline reforming step, each processing step all carries out under normal pressure.
(1) methylolation: 180 kilograms of Sulphanilic Acid, 68 kilograms of phenol and 529.5 kg water are added in the reactor, after stirring, with 18.5 kilograms of trolamines, the pH value of reaction system is transferred to 7.5, in 1.0h, drip 180 kilograms of formaldehyde, behind the heat temperature raising to 90 ℃, reaction 0.5h.
(2) alkaline condensation: utilize 11 kilograms of trolamines that the pH value of above-mentioned system is transferred to 9.5, and add 12.0 kilograms of Dyhard RU 100s and urea admixture, react 3.5h down at 90 ℃.
(3) alkalescence is reformed: utilize 1 kg of hydrogen sodium oxide that the pH value of above-mentioned system is transferred to 10.5, cooling discharge behind reaction 2.0h under 85 ℃ is reddish-brown liquid, and liquid product through the spraying drying operation, is made meal.
Below be performance situation of the present invention and with every performance comparable situation of like product:
Main raw material(s), concrete mix and test method
Starting material:
Cement: cement mill, the south of the River produces the peaceful sheep 425R.P.II type cement of gold
Sand: fineness modulus is 2.6 medium sand.
Stone: the Nanjing six directions is produced basalt, and crush index is 2.5%, and the grain warp is the rubble of 5-20mm.
Concrete mix:
The big stone handstone of cement sand
1 : 2.15 : 2.1 : 1.425
When concrete batching, cement, sand, stone material carry out weighing by above proportioning, and amount of water is that 8 ± 1cm is a standard with the control slump then.The concrete of admixture admixture preparation is not called normal concrete.
Test method:
Concrete performance test mainly comprises water-reducing rate, bleeding rate, air content, time of coagulation, ultimate compression strength, static pressure Young's modulus, concrete contraction, concrete anti-freezing property, concrete anti-carbonation properties and concrete impermeability etc.
Water-reducing rate, bleeding rate, air content, time of coagulation, test method was carried out with reference to the relevant regulations of GB8076-97 " concrete admixture ".
Concrete crushing strength, static pressure elasticity modulus test method are carried out with reference to the relevant regulations of GBJ81-85 " normal concrete mechanical test method ".
Concrete anti-freezing property, anti-carbonation properties and anti-permeability performance test method are carried out with reference to the relevant regulations of GBJ82-85 " Standard for test methods of longterm performance and durability of ordinary concrete ".
The solid content of table 1 liquid product of the present invention and water-reducing rate
Embodiment |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
Solid content (%) |
38.2 |
46.6 |
40.5 |
35.5 |
28.8 |
32.6 |
22.4 |
26.5 |
Water-reducing rate (%) |
26.3 |
20.4 |
23.8 |
27.8 |
27.5 |
25.6 |
28.5 |
28.8 |
Annotate: volume is: solid part 0.5%, flowing degree of net paste of cement test amount of water for 87mL. cement is: cement mill, the south of the River produces the peaceful sheep 42.5R.P.II type cement of gold
The amino high efficiency water reducing agent of table 2 the present invention compares with the total alkali content of domestic and international other high efficiency water reducing agent
The water reducer kind |
Total alkali content (Na
2O+0.658K
2O),%
|
Embodiment 1 |
0 |
Embodiment 2 |
0 |
Embodiment 3 |
0 |
Embodiment 4 |
0 |
Embodiment 5 |
0 |
Embodiment 6 |
0.52 |
Embodiment 7 |
0.88 |
Embodiment 8 |
0.36 |
AS-1 |
6.58 |
AS-2 |
7.05 |
AS-3 |
7.63 |
AS-4 |
6.59 |
AS-5 |
6.71 |
AS-6 |
7.83 |
Melment |
9.24 |
SPP-II |
9.02 |
Might-100 |
8.06 |
Annotate: amido sulfoacid series high-efficiency water reducer AS-1. Tianjin, Beijing amido sulfoacid series high-efficiency water reducer AS-2, Shandong amido sulfoacid series high-efficiency water reducer AS-3, Shaanxi amido sulfoacid series high-efficiency water reducer AS-4, Zhejiang sulfamate AS-5, Jiangsu thionamic acid sulfonate AS-6, domestic certain the high sulfonated melamine high efficiency water reducing agent SPP-II of Melment. of Germany and the naphthalene series high-efficiency water-reducing agent Might-100 of Japanese Kao, total alkali content press the calculating of solid part.
Table 3 embodiment 7 concrete performances
Annotate: volume is: solid part 0.45%, cement is: cement mill, the south of the River produces the peaceful sheep 42.5R.P.II type cement of gold.
The homogeneity index of table 4 embodiment 7
Test subject |
Detected result |
Solid content, % |
26.14 |
Density, g/cm |
1.114 |
Chloride ion content, % |
0.0003 |
Flowing degree of net paste of cement
*,mm
|
245 |
PH value |
8.27 |
Surface tension, mN/m |
64.8 |
Total alkali content (Na
2O+0.658K
2O),%
|
0.23 |
The ammonia burst size, % |
Do not measure |
Sodium sulfate, % |
0.08 |
Annotate: volume is: solid part 0.45%, flowing degree of net paste of cement test amount of water is 87mL
Table 5 the present invention and other high efficiency water reducing agent concrete performance simultaneous test