CN100398481C - Method for batch polymerization preparation of sulphamate composite high-efficiency water reducing agent and its acid and alkali - Google Patents
Method for batch polymerization preparation of sulphamate composite high-efficiency water reducing agent and its acid and alkali Download PDFInfo
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Abstract
The present invention discloses a high-efficiency composite-type sulfamate water-reducing agent and an acid base step polymerized preparation method thereof. The water-reducing agent has the following technological preparation steps: the pH value of a reaction system is adjusted to 3.0 to 5.5 after 9.5 to 26.6% of aminobenzenesulfonic acid (salt)), 1.5 to 15.5% of phenol, 0.2 to 5.5% of compound containing amide groups and 0.5 to 8.0% of phenol derivative and water are firstly added in a reactor according to mass ratio to be uniformly stirred, 8.0 to 45.0% of condensing agent is dripped in 1.0 to 3.0 hours after the materials are heated to 75 to 100 DEG C, and the pH value in the system is adjusted to 8.0 to 9.0 after the materials continuously react for 0.5 to 3.0 hours; then the pH value in the reaction system is adjusted to 9.5 to 12.5 after a proper amount of compound containing the amide groups is added to react for 2 to 6 hours at the temperature of 75 to 100 DEG C, and the materials are cooled and discharged after reacting for 1.0 to 5.0 hours at the temperature of 85 to 100 DEG C. The water-reducing agent is in umber liquid or powder, the weight average molecular weight Mw of the water-reducing agent is from 6000 to 45000, the number average molecular weight Mn is from 1000 to 10000, the integral characteristic indexes of the water-reducing agent are obviously superior to that of other products in the marks of China, and the whole production process is without discharge of three wastes of discharge gas, waste water and waste slag; therefore, the preparation technology is a clean and environmental-friendly technology.
Description
Technical field
The invention belongs to field of fine chemical, specially refer to a kind of sulfamate composite efficient water reducer and soda acid step-by-step polymerization preparation method thereof that cement, concrete (concrete) and mortar are used that be used for.
Background technology
With cement is the concrete that gelling material is produced, become the various Structural Engineering in the whole world today and built first-selected material of construction, this is determined by its economy: starting material wide material sources, cheap, construction is cheaper with maintenance cost, and two large driving forces that concrete technology is pushed ahead are to accelerate its speed of application and improve concrete durability.
At the beginning of China's concrete mixing plant is established in 80 (Shanghai, Changzhou).At present, China continue to enlarge because of construction scale, the high speed development built of Southeastern Coastal Cities especially, and construction at different levels competent authorities have taked a series of policies and measures of fostering, and the commerical ready-mixed concrete every year that makes the city, the amplitude with 15% increased progressively.The increase of commerical ready-mixed concrete output, greatly promoted the development of concrete admixture (particularly various water reducer), because the application of admixture in concrete, produced fairly obvious effect to improving concrete intensity, workability, weather resistance and reducing production costs, become one of requisite component of modern concrete, and water reducer is a kind of admixture that application surface is the widest, usage quantity is maximum.
The developing history of high efficiency water reducing agent and present situation were as far back as 1938, a kind of is that the cement dispersants of composition has been obtained patent in the U.S. with the naphthalenesulfonate, but up to the beginning of the sixties, Japan and Germany develop the concrete high efficiency water reducing agent of naphthalene sulfonic acidformaldehyde condensation product and two series of melamine sulfonate for further improving concrete strength and increasing workability to reduce to build the demand of workload.What the strong doctor of clothes portion of Japanese Kao crystal soda company developed is the water reducer of main component with the beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, commodity are called " mighty ", be a kind of representative water reducer, and progressively develop into series product, very competitive in the international market.The sulfonated melamine compound resin water reducer of Germany SKW company development, commodity be called melment ", become the representative water reducer of more European countries.After the seventies, these water reducers enter other country and obtain increasingly extensive application.Other is also necessarily used as a kind of water-soluble epoxy resin admixture that is polymerized by propylene oxide and tolylene diamine that USSR (Union of Soviet Socialist Republics) works out.
At present, naphthalene system, trimeric cyanamide system, modified lignin sulfonate high efficiency water reducing agent are to use the most general high efficiency water reducing agent, and their water-reducing rates are higher, but slump-loss is bigger.Development along with science and technology and production, various overlength, superelevation, ultra-large type concrete structures and the concrete structure that uses under harsh and unforgiving environments constantly propose higher requirement to concrete quality, impel concrete technology the serviceability high volume stability be good to possessing, the high performance concrete development of characteristics such as high strength and high-durability, these characteristics also become concrete developing direction of 21 century
[1]The appearance of high performance concrete is had higher requirement to concrete admixture, have high water reducing rate,, concrete slump good in the low water-cement ratio current downflow is big and through the time loss little high-performance water reducing agent become the target that scientific research and engineering technical personnel research and develop
[2,5]The high-performance water reducing agent that is at present among the research and development mainly contains amido sulfoacid series and polycarboxylic acid series high efficiency water reducing agent etc.The amido sulfoacid series high-efficiency water reducer production technique is simple, is one of domestic and international the most rising current high efficiency water reducing agent
[3-5]
At the end of the eighties, amido sulfoacid series high-efficiency water reducer obtains development and application in states such as Japan.This series products can be controlled the slump loss with himself performance.At present, this high efficiency water reducing agent has been widely used in manufacturing high strength, high performance concrete.In recent years, the research of external water reducer was mainly the super high strength concrete service, can make the high-strength concrete of 140MPa.Obtain flowing concrete simultaneously, pumping highly reaches 432m.The Papalos of the U.S. etc.
[6]Utilize styryl phenol sulfonic acid and formaldehyde generation polycondensation, the product of developing is used as cement water reducing agent, and then has drawn back the prelude of amido sulfoacid series high-efficiency water reducer.The Furuhashi of Japan etc.
[7]Introduce amino-aryl sulfonic acid-P-F condenses as cement dispersants, this kind cement dispersants can improve the concrete slump greatly, and the while can be transported in longer for some time and do not lost the slump, is particularly suitable for pump concrete.Kawamura
[8]As high efficiency water reducing agent, water-reducing rate can reach 35%～55% when this high efficiency water reducing agent was used in mortar with the condenses of bisphenol compound and alkylamino Phenylsulfonic acid and formaldehyde, kept good fluidity to surpass 1h.Dispersion agent.Tsuji
[9]As high efficiency water reducing agent, can improve concrete flowability with the condenses of phenol, aniline sulfonic acid, trimeric cyanamide and formaldehyde, and quicken to condense, and not influence the stability of bubble.These water reducers all have high water reducing rate and high workability, and can control concrete slump loss.China just began amido sulfoacid series high-efficiency water reducer is studied in late 1990s, was in the starting stage at present.What early carry out this class work is Beijing urban construction project research institute and Tsing-Hua University.Feng of Tsing-Hua University is modest
[4]Make sulfamate high-effective water-reducing agent AS and carry out composite with Sulphanilic Acid, phenol and formaldehyde reaction with naphthalene series high-efficiency water-reducing agent, cement paste and concrete test have been carried out, the result shows that amido sulfoacid series high-efficiency water reducer all has excellent adaptability to different cement, the degree of mobilization and the slump are big, and it is very little through time loss, the concrete slump of mixing amido sulfoacid series high-efficiency water reducer remains unchanged in 90min substantially, and the slump-loss of naphthalene system and trimeric cyanamide series high-efficiency water-reducing agent is very fast, can not flow basically behind the 60min.The Qiu Xue of South China Science ﹠ Engineering University green grass or young crops etc.
[10]Utilizing amino-aryl sulfonic acid, aryl phenol, terephthalyl alcohol (or methyl alcohol) and Sulfite lignin is the high efficiency water reducing agent that feedstock production goes out a kind of high water reducing rate.The Chen Yingxin of Guangdong Province building materials industry institute etc.
[11]With sodium sulfanilate, aniline sulfonic acid, phenol, formaldehyde etc. is that starting material are developed aniline sulfonic acid formaldehyde condensation products water reducer.
Amido sulfoacid series high-efficiency water reducer exists the problem aspect 3 in producing and using at present, and then influences its production and apply
[5]: the one, cost of material is expensive partially, and production cost is higher; The 2nd, responsive in the application process to addition ratio, if volume is low excessively, the cement particle can not fully disperse, concrete slump is less, if the water reducer volume is excessive, the cement particle is too disperseed, the concrete water-retentivity is bad, the segregation excreting water phenomenon is serious, even slurry hardens and water sepn, is difficult to grasp in construction; The 3rd, the raw material of producing amido sulfoacid series high-efficiency water reducer at present is phenol and formaldehyde, is volatile toxic substance, and the bad meeting of controlling of production process causes bigger pollution to environment.
Reference:
1.Sspiratos?N，Jolicoeur?G.Trends?in?concrete?chemical?admixture?for?the?21st?century[C].6thCANMET/AC?I?International?Conference.Nice，2000
2. Wuzhong is big. high performance concrete and fine mineral admixture thereof [J], Building technology, 1999,30 (3): 160～163
3. Li Chong intelligence, the present Research of contour performance water reducer and prospect [J], concrete and mud product, 2001, (2): 3～6
4. Feng is modest. the development of amido sulfoacid series high-efficiency water reducer and concrete characteristic [J] thereof. and concrete and cement products, 2000, (2): 5-8
5. Qiu Xue green grass or young crops, Jiang Xinyuan, Ou Yangxinping. the present Research of amido sulfoacid series high-efficiency water reducer and developing direction [J]. chemical industry progress, 2003,22 (4): 336-340
6.Papalos?J?G，Savoly?A.Condensation?products?of?substituted?phenol?sulfonicacid?and?formaldehyde[P].US?4479826，1984
7.Furuhashi?T，Kawada?K，Tahara?S，et?al.Aminoacrylsulfonic?acid-phenol-formaldehyde?and?concrete?admixture?comprising?the?same[P].US?5245001，1993
8.Kawamura?M，Hamada?S，Date?T，et?al.Production?of?novel?condensatecomprising?biphenols?and?aromatic?aminosulfonic?acids，condensates?anddispersant，additive?and?water-reducing?agent?based?thereon[P].US?5233012，1993
9.Tsuji?A，Yamato?F，Tamaoki?R，et?al.Water-reducing?agents?for?Gypsumslurries[P].JP?04254452，1992
10. Qiu Xue green grass or young crops, Ou Yangxinping, Yang Dongjie. amido sulfoacid series high-efficiency water reducer and preparation method thereof [P]. application number: 01129711.5,2001; Publication number CN 1341571A, 2002
11. old should be glad, old Xiao grass, Yang Zhengmei etc. aniline sulfonic acid formaldehyde condensation products water reducer and preparation method thereof [P]. application number: 03126609.6,2003; Publication number CN 1458108A, 2003
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of production cost is lower, the over-all properties performance is good sulfamate composite efficient water reducer and soda acid step-by-step polymerization preparation method thereof are provided.
A kind of sulfamate composite efficient water reducer provided by the present invention and soda acid step-by-step polymerization preparation method thereof, the weight-average molecular weight Mw of product is 6000～45000, and number-average molecular weight Mn is 1000～10000, and chemical general formula is:
In the formula, m, n, o, p, x are the polymerization degree (15≤m≤160; 12≤n≤115; 5≤o≤25; 2≤p≤15; G is a phosphinylidyne-containing amine group
Compound, i.e. urea, Dyhard RU 100, trimeric cyanamide, acrylamide or toluol sulfonamide; D is for containing phenols
Compound, i.e. dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or 2-Naphthol.
The soda acid step-by-step polymerization preparation method's of above-mentioned sulfamate composite efficient water reducer concrete technology is as follows:
1, raw material and prescription (massfraction):
The mixture of one or both in Sulphanilic Acid or the Sodium sulfanilate: 9.5～26.6% phenol: 1.5～15.5%
The compound of phosphinylidyne-containing amine group, the i.e. mixture of one or more in urea, Dyhard RU 100, trimeric cyanamide, acrylamide or the toluol sulfonamide: 0.2～5.5%
Phenol derivatives, the i.e. mixture of one or more in dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or the 2-Naphthol: 0.5～8.0%
Condensing agent, the i.e. mixture of a kind of in formaldehyde, the Paraformaldehyde 96 or two kinds: 8.0～45.0%
Acid regulator: 0.1～1.5%
Alkaline conditioner: 0.1～6.5%
Water: 15～68%
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier one or both the compound of mixture, phenol, phosphinylidyne-containing amine group and phenol derivatives and the water in Sulphanilic Acid or the Sodium sulfanilate is added in the reactor, after stirring, with acid regulator the pH value of reaction system is transferred to 3.0～5.5, behind heat temperature raising to 75～100 ℃, in 1.0～3.0h, drip condensing agent, and continue reaction 0.5～3.0h.
(2) alkaline condensation: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 8.0～9.0, and add the compound of phosphinylidyne-containing amine group, react 2～6h down at 75～100 ℃.
(3) alkalescence is reformed: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 9.5～12.5, and cooling discharge behind reaction 1.0～5.0h under 85～100 ℃, product of the present invention is a reddish-brown liquid, promptly gets powder-like product by spraying drying.
In this technology, acid regulator is one or more the mixture in thionamic acid, sulfuric acid, phosphoric acid, nitric acid, Whitfield's ointment, citric acid, tartrate, oxysuccinic acid, toxilic acid, phenylformic acid, the succsinic acid: alkaline conditioner is one or more the mixture in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate, the water glass.
The present invention has the following advantages and positively effect:
1, the present invention utilizes the phenol derivatives of nontoxic or low toxicity to replace or the part fortified phenol, and the compound that utilizes phosphinylidyne-containing amine group removes the residual formaldehyde in the product, adopt a totally enclosed feed way and a bath synthesis method and soda acid distribution polymerization method to prepare amido sulfoacid series green high-efficient water reducer, to reduce or eliminate in production and the use to the environment produced pollution, and whole process of production do not have " three wastes " (waste gas, waste water, waste residue) discharging, thus this preparation technology be one clean, environmentally friendly technology.
2, in order further to improve the performance of product of the present invention, as water-reducing rate height, the slump the big and slump through the time advantages such as loss is little, in preparation technology, add an amount of phenol derivatives to improve the molecular weight of product, its weight-average molecular weight Mw is controlled in 6000～45000 scopes.
3, keep product water-reducing rate height, the slump is big and the slump through the time advantages such as loss is little the basis on, the present invention also adds other different additive in preparation technology, wait as compound, acid regulator and the alkaline conditioner of phosphinylidyne-containing amine group and to reduce production costs, overcome simultaneously to volume sensitivity, bleeding rate height, the easy isolating shortcoming of concrete, so that the present invention can obtain wide popularization and application in engineering.
4, the present invention utilizes first and cleans the soda acid step polymerization and prepare sulfamate composite efficient water reducer, the thionamic acid based water reducer of this method preparation has advantages such as molecular weight comprehensive characteristic index higher and water reducer is good, and this method is not seen relevant report as yet at present.
5, production technique is simple, and raw materials for production are easy to get, and is with short production cycle, reaction temperature and, required equipment is a conventional equipment, is convenient to existing chemical plant and practices midwifery.
Description of drawings
Now the present invention is further elaborated in conjunction with the accompanying drawings:
Fig. 1 is a kind of process flow sheet of the present invention.
Embodiment
As shown in Figure 1, concrete performance of the present invention is as follows:
Embodiment 1 concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: 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
Dihydroxyphenyl propane: 22 kilograms
Formaldehyde (37% content): 180 kilograms
Thionamic acid: 3.5 kilograms
Alkaline conditioner (sodium hydroxide and sodium phosphate mixture, mass ratio are 19: 1): 9.5 kilograms
Water: 525 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier 180 kilograms of Sodium sulfanilates, 68 kilograms of phenol, 8.0 kilograms of Dyhard RU 100s and urea admixture and 22 kilograms of dihydroxyphenyl propanes and 483.5 kg water are added in the reactor, after stirring, add 7.0 kilogram of 50% thionamic acid aqueous solution the pH value of reaction system is transferred to 4.5, behind the heat temperature raising to 75 ℃, in 2.0h, drip 180 kilogram of 37% formaldehyde solution, and continue reaction 1.5h.
(2) alkaline condensation: add 17.5 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 8.0, and add 4.0 kilograms of Dyhard RU 100s and urea admixture, react 6h down at 85 ℃.
(3) alkalescence is reformed: add 30.0 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 10.5, cooling discharge behind reaction 5h under 85 ℃, product of the present invention is a reddish-brown liquid, weight-average molecular weight Mw is 35000, number-average molecular weight Mn is 5600, promptly gets powder-like product by spraying drying.
Embodiment 2
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: 260 kilograms
Phenol: 125 kilograms
Toluol sulfonamide: 5.0 kilograms
Acid regulator (Whitfield's ointment and phenylformic acid mixture, mass ratio are 3: 1): 7.0 kilograms
Paraformaldehyde 96: 85 kilograms
Alkaline conditioner (sodium hydroxide, tripoly phosphate sodium STPP and sodium phosphate mixture, mass ratio are 5: 3: 2): 20 kilograms
Water: 498 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier 260 kilograms of Sodium sulfanilates, 125 kilograms of phenol, 3.0 kilograms of toluol sulfonamides and 7.0 kilograms of acid regulators and 398 kg water are added in the reactor, after stirring, add 15 kilogram of 20% alkaline conditioner solution the pH value of reaction system is transferred to 3.5, behind the heat temperature raising to 75 ℃, in 1.0h, slowly add 85 kilograms of Paraformaldehyde 96s, and continue reaction 1.0h.
(2) alkaline condensation: add 25 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to about 8.1, and add 2.0 kilograms of toluol sulfonamides, react 4.0h down at 80 ℃.
(3) alkalescence is reformed: add 60 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 11.0, cooling discharge behind reaction 3h under 95 ℃, product of the present invention is a reddish-brown liquid, its weight-average molecular weight Mw is 10000, number-average molecular weight Mn is 2000, promptly gets powder-like product by spraying drying.
Embodiment 3
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
4-amino-1,3-phenyl disulfonic acid: 18 kilograms
Sodium sulfanilate: 172 kilograms
Phenol: 83 kilograms
Urea: 16.5 kilograms
Dihydroxyphenyl propane: 12 kilograms
Formaldehyde (36% content): 210 kilograms
Alkaline conditioner (sodium hydroxide and tripoly phosphate sodium STPP mixture, mass ratio are 19: 1): 15 kilograms
Water: 473.5 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier with 18 kilograms of 4-amino-1,3-phenyl disulfonic acid, 172 kilograms of Sodium sulfanilates, 83 kilograms of phenol, 7.5 kg urea and 12 kilograms of dihydroxyphenyl propanes and 451 kg water add in the reactor, after stirring, the alkaline conditioner solution that adds 10 kilogram 40% transfers to 5.5 with the pH value of reaction system, behind the heat temperature raising to 85 ℃, in 1.5h, drip 210 kilogram of 37% formaldehyde solution, and continue reaction 0.5h.
(2) alkaline condensation: the alkaline conditioner solution that adds 7.5 kilogram 40% transfers to 8.5 with the pH value in the above-mentioned system, and adds 9.0 in gram urea, reacts 4.5h down at 98 ℃.
(3) alkalescence is reformed: the alkaline conditioner solution that adds 20 kilogram 40% transfers to 11.0 with the pH value in the above-mentioned system, cooling discharge behind reaction 3h under 98 ℃, product of the present invention is a reddish-brown liquid, its weight-average molecular weight Mw is 30870, number-average molecular weight Mn is 5000, promptly gets powder-like product by spraying drying.
Embodiment 4
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sulphanilic Acid: 195 kilograms
Phenol: 98 kilograms
Trimeric cyanamide: 21.5 kilograms
Catechol: 11.5 kilograms
Formaldehyde (35% content): 235 kilograms
Alkaline conditioner (sodium hydroxide): 55 kilograms
Water: 384 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier 195 kilograms of aniline sulfonic acids, 98 kilograms of phenol, 13 kilograms of trimeric cyanamides and 11.5 kilograms of catechols and 329 kg water are added in the reactor, after stirring, add 92 kilogram of 50% sodium hydroxide solution the pH value of reaction system is transferred to 5.0, behind the heat temperature raising to 90 ℃, in 2.0h, drip 235 kilogram of 35% formaldehyde solution, and continue reaction 1.5h.
(2) alkaline condensation: add 3 kilogram of 50% sodium hydroxide solution the pH value in the above-mentioned system is transferred to 8.0, and add 8.5 kilograms of trimeric cyanamides, react 6h down at 85 ℃.
(3) alkalescence is reformed: add 15 kilogram of 50% sodium hydroxide solution the pH value in the above-mentioned system is transferred to 11.5, cooling discharge behind reaction 4h under 95 ℃, product of the present invention is a reddish-brown liquid, its weight-average molecular weight Mw is 22320, number-average molecular weight Mn is 3700, promptly gets powder-like product by spraying drying.
Embodiment 5
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: 150 kilograms
Phenol: 30 kilograms
Dyhard RU 100: 21 kilograms
Dihydroxyphenyl propane: 58 kilograms
Formaldehyde (37% content): 180 kilograms
Tartrate: 2.5 kilograms
Alkaline conditioner (sodium hydroxide and trisodium phosphate mixture, mass ratio 9: 1): 8.5 kilograms
Water: 550 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier 150 kilograms of Sodium sulfanilates, 30 kilograms of phenol, 9 kilograms of Dyhard RU 100s and 58 kilograms of dihydroxyphenyl propanes and 507.5 kg water are added in the reactor, after stirring, add 2.5 kilograms of tartrate the pH value of reaction system is transferred to 3.5, behind the heat temperature raising to 75 ℃, in 1.0, drip 180 kilogram of 37% formaldehyde solution, and continue reaction 0.5h.
(2) alkaline condensation: add 10.5 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 8.5, and add 12 kilograms of Dyhard RU 100s, react 5.0h down at 90 ℃.
(3) alkalescence is reformed: add 32 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 11.0, cooling discharge behind reaction 3.0h under 96 ℃, product of the present invention is a reddish-brown liquid, its weight-average molecular weight Mw is 43210, number-average molecular weight Mn is 9600, promptly gets powder-like product by spraying drying.
Embodiment 6
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: 120 kilograms
Phenol: 55 kilograms
The compound of phosphinylidyne-containing amine group (urea and acrylamide mixture, mass ratio are 19: 1): 12 kilograms
Phenol derivatives (dihydroxyphenyl propane and naphthyl alcohol mixture, mass ratio are 3: 2): 15 kilograms
Formaldehyde (37% content): 150 kilograms
Oxysuccinic acid: 1.0 kilograms
Sodium hydroxide: 6.0 kilograms
Water: 641 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier the compound of 120 kilograms of sodium sulfanilates, 55 kilograms of phenol, 12 kilograms of phosphinylidyne-containing amine groups and 15 kilograms of phenol derivatives and 617 kg water are added in the reactor, after stirring, adding 1.0 kilograms of oxysuccinic acid transfers to the pH value of reaction system about 4.0, behind the heat temperature raising to 80 ℃, in 1.5h, drip 150 kilogram of 37% formaldehyde solution, and continue reaction 1.0h.
(2) alkaline condensation: add 5 kilogram of 20% sodium hydroxide solution the pH value in the above-mentioned system is transferred to about 8.0, react 5.0h down at 90 ℃.
(3) alkalescence is reformed: add 25 kilogram of 20% sodium hydroxide solution the pH value in the above-mentioned system is transferred to 11.5, and cooling discharge behind reaction 3.0h under 97 ℃, product of the present invention is a reddish-brown liquid, and its weight-average molecular weight Mw is 26750, and number-average molecular weight Mn is 5560.
Embodiment 7
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: double centner
Phenol: 25 kilograms
The compound of phosphinylidyne-containing amine group (acrylamide, trimeric cyanamide and tolylsulfonyl amine mixt, mass ratio are 1: 8: 1): 11.5 kilograms
Cresols: 31 kilograms
Formaldehyde (35% content): 150 kilograms
Thionamic acid: 1.5 kilograms
Alkaline conditioner (sodium hydroxide and dimerization sodium phosphate mixture, mass ratio are 4: 1): 9.0 kilograms
Water: 672 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier the compound of double centner Sodium sulfanilate, 25 kilograms of phenol, 11.5 kilograms of phosphinylidyne-containing amine groups and 32 kilograms of cresolss and 636 kg water are added in the reactor, after stirring, with 1.5 kilograms of thionamic acids the pH value of reaction system is transferred to 4.5, behind the heat temperature raising to 80 ℃, in 1.0, drip 150 kilogram of 37% formaldehyde solution, and continue reaction 3.0h.
(2) alkaline condensation: add 15 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 9.0, react 5.0h down at 90 ℃.
(3) alkalescence is reformed: add 30 kilogram of 20% alkaline conditioner solution the pH value in the above-mentioned system is transferred to 12.0, cooling discharge behind reaction 1.5h under 99 ℃, product of the present invention is a reddish-brown liquid, and its weight-average molecular weight Mw is 12500, and number-average molecular weight Mn is 1108.
Embodiment 8
Concrete steps are as follows:
1, the raw material of present embodiment and prescription (unit-kilogram):
Sodium sulfanilate: 200 kilograms
4-sodium acetylsulfanilate: 35 kilograms
Phenol: 95 kilograms
The compound of phosphinylidyne-containing amine group (urea and trimeric cyanamide mixture, mass ratio are 9: 1): 35 kilograms
Dihydroxyphenyl propane: 35 kilograms
Formaldehyde (37% content): 360 kilograms
Citric acid: 1.5 kilograms
Sodium hydroxide: 9.5 kilograms
Water: 229 kilograms
2, processing step and processing parameter
Preparation technology of the present invention comprises three steps: acid condensation, alkaline condensation and alkaline reforming step, and each processing step all carries out under normal pressure:
(1) acid condensation: promptly earlier the compound of 200 kilograms of Sodium sulfanilates, 35 kilograms of 4-sodium acetylsulfanilates, 95 kilograms of phenol, 20 kilograms of phosphinylidyne-containing amine groups and 35 kilograms of dihydroxyphenyl propanes and 191 kg water are added in the reactor, after stirring, add 1.5 kilograms of citric acids the pH value of reaction system is transferred to 3.0, behind the heat temperature raising to 75 ℃, in 2.5h, drip condensing agent, and continue reaction 0.5h.
(2) alkaline condensation: add 17.5 kilogram of 20% sodium hydroxide solution the pH value in the above-mentioned system is transferred to about 8.2, and add the compound of 15 kilograms of phosphinylidyne-containing amine groups, react 6h down at 90 ℃.
(3) alkalescence is reformed: add 30 kilogram of 20% sodium hydroxide solution the pH value in the above-mentioned system is transferred to 12.5, cooling discharge behind reaction 1.5h under 98 ℃, product of the present invention is a reddish-brown liquid, its weight-average molecular weight Mw is 11890, number-average molecular weight Mn is 1020, promptly gets powder-like product by spraying drying.
The performance of water reducer compares:
The viscosity of table 1 liquid product of the present invention and water-reducing rate thereof
Annotate: product of the present invention has two kinds in aqua and pulvis, and this table is research object with the aqua product.
The flowing degree of net paste of cement of table 2 water reducer and through the time change relatively
Annotate: utilize National Standard Method G8B 8077-87 to detect the clean slurry degree of mobilization of cement, with Refining stone 425 cement (Fujian Refining stone), W/C=0.29 should deduct the water yield in the aqua water reducer, 24.1 ℃ of room temps in clean slurry amount of water.
Table 3 compares with the flowing degree of net paste of cement of other water reducer product
Annotate: utilize National Standard Method G8B 8077-87 to detect the clean slurry degree of mobilization of cement, W/C=0.29 should deduct the water yield in the aqua water reducer, 25.8 ℃ of room temps in clean slurry amount of water.
The content of free formaldehyde and release ammonia in table 4 product
Table 5 concrete test proportioning
Table 6 concrete slump through the time change
Annotate: 29.8 ℃ of room temps are subjects with the concrete proportioning in the table 5, should deduct the water yield in the aqua water reducer in the concrete amount of water.
The concrete test result of table 7 product of the present invention
Annotate: the room temp scope is 24.1～31.2 ℃, is subjects with the concrete proportioning in the table 5, should deduct the water yield in the aqua water reducer in the concrete amount of water.
Claims (4)
1. the preparation method of sulfamate composite efficient water reducer, it is characterized in that: these starting material comprise the composition of following massfraction proportioning:
The mixture of one or both in Sulphanilic Acid or the Sodium sulfanilate: 9.5～26.6%
Phenol: 1.5～15.5%
The compound of phosphinylidyne-containing amine group, the i.e. mixture of one or more in urea, Dyhard RU 100, trimeric cyanamide, acrylamide or the toluol sulfonamide: 0.2～5.5%
Phenol derivatives, the i.e. mixture of one or more in dihydroxyphenyl propane, bisphenol S, p-cresol, meta-cresol, cresols, Resorcinol, quinhydrones, catechol, naphthyl alcohol or the 2-Naphthol: 0.5～8.0%
Condensing agent, the i.e. mixture of a kind of in formaldehyde, the Paraformaldehyde 96 or two kinds: 8.0～45.0%
Acid regulator: 0.1～1.5%
Alkaline conditioner: 0.1～6.5%
Water: 15～68%
Its preparation technology comprises the steps: (1) acid condensation in regular turn: promptly earlier one or both the compound of mixture, phenol, phosphinylidyne-containing amine group and phenol derivatives and the water in Sulphanilic Acid or the Sodium sulfanilate is added in the reactor, after stirring, with acid regulator the pH value of reaction system is transferred to 3.0～5.5, behind heat temperature raising to 75～100 ℃, in 1.0～3.0h, drip condensing agent, and continue reaction 0.5～3.0h; (2) alkaline condensation: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 8.0～9.0, and add the compound of phosphinylidyne-containing amine group, react 2～6h down at 75～100 ℃; (3) alkalescence is reformed: utilize alkaline conditioner that the pH value in the above-mentioned system is transferred to 9.5～12.5, cooling discharge behind reaction 1.0～5.0h under 85～100 ℃ promptly gets powder-like product by spraying drying.
2. sulfamate composite efficient water reducer according to claim 1 is characterized in that: this product is a reddish-brown liquid, or with the spray-dried again powder-like product that makes of reddish-brown liquid.
3. soda acid step-by-step polymerization preparation method according to claim 1 is characterized in that: the acid regulator that uses is one or more the mixture in thionamic acid, sulfuric acid, phosphoric acid, nitric acid, Whitfield's ointment, citric acid, tartrate, oxysuccinic acid, toxilic acid, phenylformic acid, the succsinic acid.
4. soda acid step-by-step polymerization preparation method according to claim 1 is characterized in that: the alkaline conditioner that uses is one or more the mixture in sodium hydroxide, potassium hydroxide, sodium phosphate, trisodium phosphate, two sodium polyphosphates, tripoly phosphate sodium STPP, sodium polyphosphate or the water glass.
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| CN105060757B (en) * | 2015-07-23 | 2017-09-12 | 云南森博混凝土外加剂有限公司 | A kind of preparation method of sulfamate formaldehyde condensation products |
| CN107722207B (en) * | 2017-09-21 | 2020-06-19 | 广东科隆智谷新材料股份有限公司 | Preparation method of sulfamate water reducer |
| CN109704619B (en) * | 2019-01-19 | 2021-04-30 | 浙江吉盛化学建材有限公司 | Sulfamate high-efficiency water reducing agent and preparation process thereof |
| CN112028538B (en) * | 2020-08-28 | 2022-04-22 | 南通市展成商品混凝土有限公司 | Green and environment-friendly water reducing agent and recycled concrete using same |
| CN113336465B (en) * | 2021-06-24 | 2023-12-26 | 山东业安建材有限公司 | CF90 high-strength high-performance steel fiber concrete composite additive and preparation method thereof |
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| CN1341571A (en) * | 2001-09-29 | 2002-03-27 | 华南理工大学 | Aminosulfonic acid series high-effective water-reducing agent and its preparation method |
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