CN101284890A - High molecular compound, method for preparing same and use - Google Patents
High molecular compound, method for preparing same and use Download PDFInfo
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- CN101284890A CN101284890A CNA2008100477918A CN200810047791A CN101284890A CN 101284890 A CN101284890 A CN 101284890A CN A2008100477918 A CNA2008100477918 A CN A2008100477918A CN 200810047791 A CN200810047791 A CN 200810047791A CN 101284890 A CN101284890 A CN 101284890A
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- sodium sulfonate
- methacrylic
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Abstract
The invention relates to a macromolecular compound made by the method which is as follows: at a temperature between 70 and 75 DEG C, a macromolecular monomer prepared in advance, a methacrylic acid water solution, an evocating agent and a sodium methallyl sulfonate water solution are added into solvent water drop by drop within 3 to 4 hours; at a temperature between 75 and 80 DEG C, the mixture is cooled to be neutralize and the pH value is between 7 and 8 to obtain the macromolecular compound. The synthetic technology is simple, the reaction condition is easy to control, the environment is not polluted, the cost is low, the synthetic condensing time can ensure that the polycarboxylic acid type water-reducer has high slushing rate, good liquidity and good liquidity retentivity with the low mixing amount and can effectively avoid the loss of the slump constant; on the other hand, the method defers the cement hydration, delays the time of the hydration and the temperature rise, reduces the hydration and the temperature rise, and can effectively avoid the cracks generated by the hydration and the temperature rise of the large-volume cement. The macromolecular compound can be widely applied to large-scale the high intensity high performance cement building with high ageing resistance such as various dams, bridges and railways.
Description
Technical field
The present invention relates to a kind of macromolecular compound and its production and use.Belong to Polymer Synthesizing and applied technical field.
Background technology
China has entered the high-speed development period of building traffic industry, demand to cement concrete increases day by day, also more and more higher to its performance requriements simultaneously, particularly in the heavy construction of mass concretes such as railway, bridge, dam and stadium, aspect weather resistance, what have requires 50 years even longer.And in fact, many heavy constructions are not reaching the expection time limit or more just crack occurrence occurring in morning.Many Hydraulic and Hydro-Power Engineerings in the world all suffer the puzzlement of crack problem, have many serious discarded fully.China has entered the regulation maintenance interval of concrete dam at present, and power stations such as sieve gulf in the Xinanjiang River in Zhejiang, Jiangxi are because the serious deterioration of concrete durability has entered half running condition, and the Three Gorges Projects of 185m have run into crack problem.Trace it to its cause, just be that greatly the temperature rise of mass concrete aquation produces due to the crack.Because concrete is the poor conductor of heat, it is slower to dispel the heat, so in mass concrete, because hydrated cementitious heat release, the temperature of inside concrete will raise, and can reach 50～70 ℃ sometimes, and this will cause inside concrete to produce significant volumetric expansion and produce cracking.This shows that on engineering, it is a quite severe problem that the temperature rise of mass concrete aquation produces crack problem.
Temperature rise produces fissured research to the mass concrete aquation, generally all be at proportioning design and aggregate selection, mix in the suitable processing of admixture and site operation.Proportioning design and the selection of aggregate and the suitable processing of site operation have certain prophylactic effect, but are radical solving method on solution aquation temperature rise generation problem of cracks.Have only mixing of admixture, temperature rise is unusual effective means to aquation.To the mixing on the method that all rests on additive complex of admixture, promptly added an amount of water reducer, retardant, air entrapment agent and swelling agent etc. in the past.These researchs are had plenty of by composite and have studied the influence of water reducer to mortar and concrete strength, have studied wooden calcium, naphthalene water reducer and carbohydrate retardant as the Sun Zhen equality of university of Tongji University and have mixed influence to cement concrete performance again; Have plenty of by the composite water reducer of having studied hydrated cementitious is influenced rule, studied naphthalene system, sulfamate system and 3 kinds of high efficiency water reducing agents of polycarboxylate system and tripoly phosphate sodium STPP and 2 kinds of compound uses of retardant of sugared calcium rule that influences as the He Yanshu of Xi'an University of Architecture and Technology to hydration heat of cement, aquation Wen Feng, warm peak time of occurrence, also have the Hu Shuguang of Wuhan University of Technology studied naphthalene series high-efficiency water-reducing agent compound the influence rule of phosphoric acid salt retardant to hydrated cementitious temperature rise and rate of heat release.
These researchs, all be to be based upon on the composite basis, because retardant and water reducer kind are many, have any problem in the composite selection on the one hand, on the other hand again because the cement type variation, also have an adaptive problem on composite, also there is certain complicacy in compounded technology in technology and construction in addition.
Summary of the invention:
The objective of the invention is to overcome retardant and water reducer compounded technology difficulty in the past, composite back and inferior suitability and composite back produce problems such as unfavorable factor to cement concrete later stage property development, the synthetic a kind of macromolecular compound of exploitation, this macromolecular compound can be used as controllable polycarboxylic acids water reducing agents time of coagulation, this poly carboxylic acid series water reducer has controllability time of coagulation, existing delayed coagulation also has water-reduction, and to the not influence of cement concrete later stage property development.Simultaneously synthesis technique equipment is simple, reaction conditions is simple and easy to control, do not pollute, the low suitability for industrialized production that is easy to of cost.
The present invention realizes by the following technical solutions:
A kind of macromolecular compound, its structural formula is:
In the formula: M represents Na
+Perhaps NH
4 +, a=15～50, b=5～30, c=10～40, m=9～45.
Described high molecular molecular weight is between 5000～20000.
The present invention also provides the preparation method of above-mentioned macromolecular compound: under 70～75 ℃ of conditions, with big monomer and methacrylic aqueous acid, initiator and the methylpropene sodium sulfonate aqueous solution for preparing in advance, be added drop-wise in the aqueous solvent simultaneously, in 3～4h, drip off, 75～80 ℃ of insulation 3～4h, naturally cool to room temperature, be neutralized to pH=7～8, obtain required macromolecular compound with diluted alkaline (alkali lye of sodium or ammonium) solution; Consumption weight percent raw materials used in the preparation process is:
Methacrylic acid: 2～6%
Big monomer Methylacrylic acid polyethylene glycol single armor ether (350～2000) ester: 10～15%
Methylpropene sodium sulfonate: 1～4%
Initiator: 1～2%
Water: 75～85%.
Preferably, raw materials used consumption weight percent is in the above-mentioned preparation process:
Methacrylic acid: 3%
Methylacrylic acid polyethylene glycol single armor ether (400) ester: 14%
Methylpropene sodium sulfonate: 2%
Initiator: 1%
Water: 80%.
The consumption of water in the consumption of water and initiator and the methylpropene sodium sulfonate aqueous solution in above-mentioned big monomer and the methacrylic aqueous acid, suggestion is controlled at being equal in weight of the weight that makes big monomer and methacrylic aqueous acid and the initiator and the methylpropene sodium sulfonate aqueous solution.
Above-mentioned initiator is the mixture of S-WAT and Diisopropyl azodicarboxylate, and its mass ratio is 1: 10～20.
Macromolecular compound of the present invention is as the application of water reducer in the preparation cement concrete.
Method of the present invention is compared with the past, direct carboxyl grafting, sulfonic group and polyoxyethylene base side chain, by regulating side chain lengths (polyoxyethylene base side chain molecular weight), adjust methacrylic acid and methylpropene sodium sulfonate consumption, thereby realize the poly carboxylic acid series water reducer controllability of time of coagulation.
The present invention compares with polycarboxylate water-reducer in the past, have on the one hand that synthesis technique equipment is simple, reaction conditions is simple and easy to control, do not pollute, the low suitability for industrialized production that is easy to of cost, synthetic controllable polycarboxylic acids water reducing agents time of coagulation is under lower volume, has the water-reducing rate height, mobile and mobile retentivity is good, effectively inhibition of slump-loss; Delay hydrated cementitious on the other hand, postpone the time that the aquation temperature rise occurs, also reduced the aquation temperature rise simultaneously, can effectively suppress the crack that the temperature rise of mass concrete aquation produces.
Adopt macromolecular compound of the present invention as controllable polycarboxylic acids water reducing agents time of coagulation, the adaptation of product is strong, is adapted to the cement of multiple model.When this water reducer with 20wt% concentration, volume is 1.0% o'clock of cement weight, and water-reducing rate can reach 30%, the concrete 3d of preparation, and 28d, 90d ultimate compression strength can improve 60%, 50% respectively, more than 30%.Alkali content is low in addition, and chloride ion-containing not is to the reinforcing bar non-corrosiveness; Effectively delay the time that the concrete hydrating temperature rise occurs, reduced hydration heat.Can be widely used in various dams, bridge is during the large-scale high-strength high-performance concrete that weather resistance is had higher requirements such as railway is built.Product does not contain formaldehyde, environment do not polluted, and stable performance.
Description of drawings
The infrared spectrum of the macromolecular compound that accompanying drawing makes for the present invention.
Embodiment:
Embodiment 1:
The water that in reactor, adds 70.00g, when being preheated to 70～75 ℃, drip on one side by the 4.00g methacrylic acid, 30.00g the mixing solutions that Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight is 350) and 31.00g water are formed (mixes the three to shake up and gets final product, down together), the other side drips the mixing solutions be made up of 4.00g methylpropene sodium sulfonate and 2.00g initiator (being mixed by 0.18g S-WAT and 1.82g Diisopropyl azodicarboxylate) and 59.00g water (to be mixed the three to shake up and gets final product, down together), drip off at 3～4h, reacted back insulation 3～4h, be cooled to room temperature, regulate pH=7～8 with sodium hydroxide, obtain the macromolecular compound (molecular weight is 20000) of 20wt% concentration of the present invention.Its INFRARED SPECTRUM is seen accompanying drawing; In infared spectrum, can see the characteristic peaks of the main group of this polymer: polyoxy alkyl (2500cm
-1～3300cm
-1), sulfonic acid group (1039cm
-1, 619cm
-1), carboxyl (1577cm
-1, 1248cm
-1) etc.
Embodiment 2:
The water that in reactor, adds 70.00g, when being preheated to 70～75 ℃, drip on one side by the 8.00g methacrylic acid, 20.00g the solution that Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight is 1000) and 37.00g water are formed, the other side drips the mixing solutions of being made up of 8.00g methylpropene sodium sulfonate and 4.00g initiator (being mixed by 0.36g S-WAT and 3.64g Diisopropyl azodicarboxylate) and 53.00g water, drip off at 3～4h, reacted back insulation 3～4h, be cooled to room temperature, regulate pH=7～8 with sodium hydroxide, obtain the macromolecular compound (molecular weight is 10000) of 20wt% concentration of the present invention.Infrared spectrum such as accompanying drawing.
Embodiment 3:
The water that in reactor, adds 70.00g, when being preheated to 70～75 ℃, drip on one side by the 12.00g methacrylic acid, 24.00g the solution that Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight is 2000) and 29.00g water are formed, the other side drips the mixing solutions of being made up of 2.00g methylpropene sodium sulfonate and 2.00g initiator (being mixed by 0.10g S-WAT and 1.90g Diisopropyl azodicarboxylate) and 61.00g water, drip off at 3～4h, reacted back insulation 3～4h, be cooled to room temperature, regulate pH=7～8 with sodium hydroxide, obtain the macromolecular compound (molecular weight is 5000) of 20wt% concentration of the present invention.Infrared spectrum such as accompanying drawing.
Embodiment 4:
The water that in reactor, adds 70.00g, when being preheated to 70～75 ℃, drip on one side by the 6.00g methacrylic acid, 28.00g the solution that Methylacrylic acid polyethylene glycol single armor ether ester (molecular weight is that 400 poly glycol monomethyl ether and methacrylic acid are polymerized) and 31.00g water are formed, the other side drips the mixing solutions of being made up of 4.00g methylpropene sodium sulfonate and 2.00g (being mixed by 0.18g S-WAT and 1.82g Diisopropyl azodicarboxylate) initiator and 59.00g water, drip off at 3～4h, reacted back insulation 3～4h, be cooled to room temperature, regulate pH=7～8 with sodium hydroxide, obtain the macromolecular compound (molecular weight is 15000) of 20wt% concentration of the present invention.Infrared spectrum such as accompanying drawing.
The cement slurry of mixing macromolecular compound of the present invention (as controllable polycarboxylic acids water reducing agents time of coagulation) that experiment records is as follows time of coagulation:
Claims (8)
1. macromolecular compound, its structural formula is:
In the formula: M represents Na
+Perhaps NH
4 +, a=15～50, b=5～30, c=10～40, m=9～45.
2. macromolecular compound according to claim 1 is characterized in that: the molecular weight of described macromolecular compound is between 5000～20000.
3. the preparation method of the described macromolecular compound of claim 1, it is characterized in that: under 70～75 ℃ of conditions, with big monomer and methacrylic aqueous acid, initiator and the methylpropene sodium sulfonate aqueous solution for preparing in advance, be added drop-wise in the aqueous solvent simultaneously, drip off in 3～4h, 75～80 ℃ of insulation 3～4h naturally cool to room temperature, dilute alkaline soln with sodium or ammonium is neutralized to pH=7～8, obtains the described macromolecular compound of claim 1; Consumption weight percent raw materials used in the building-up process is:
Methacrylic acid: 2～6%
Big monomer Methylacrylic acid polyethylene glycol single armor ether ester: 10～15%
Methylpropene sodium sulfonate: 1～4%
Initiator: 1～2%
Water: 75～85%.
4. preparation method according to claim 3, it is characterized in that: the consumption of water in the consumption of water and the initiator and the methylpropene sodium sulfonate aqueous solution in big monomer and the methacrylic aqueous acid is controlled at being equal in weight of the weight that makes big monomer and methacrylic aqueous acid and the initiator and the methylpropene sodium sulfonate aqueous solution.
5. the molecular weight of big monomer Methylacrylic acid polyethylene glycol single armor ether ester is 350～2000.
6. according to claim 3 or 4 described preparation methods, it is characterized in that: consumption weight percent raw materials used in the building-up process is: methacrylic acid 3%, Methylacrylic acid polyethylene glycol single armor ether ester 14%, methylpropene sodium sulfonate 2%, initiator 1%, water 80% wherein are Methylacrylic acid polyethylene glycol single armor ether (400) ester.
7. claim 3 or 4 described preparation methods, it is characterized in that: initiator is the mixture of S-WAT and Diisopropyl azodicarboxylate, its mass ratio is 1: 10～20.
8. claim 1 or 2 described macromolecular compounds are as the application of water reducer in the preparation cement concrete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100477918A CN101284890A (en) | 2008-05-20 | 2008-05-20 | High molecular compound, method for preparing same and use |
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|---|---|---|---|
| CNA2008100477918A CN101284890A (en) | 2008-05-20 | 2008-05-20 | High molecular compound, method for preparing same and use |
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| Publication Number | Publication Date |
|---|---|
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ID=40057313
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|---|---|---|---|
| CNA2008100477918A Pending CN101284890A (en) | 2008-05-20 | 2008-05-20 | High molecular compound, method for preparing same and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558935A (en) * | 2011-12-15 | 2012-07-11 | 洛阳理工学院 | Stabilizing agent for lime colloid paint |
| CN108047395A (en) * | 2018-01-18 | 2018-05-18 | 安徽省交通控股集团有限公司 | A kind of Machine-made Sand cement concrete Special modifier |
| CN111087541A (en) * | 2019-12-27 | 2020-05-01 | 广东六合新型建材有限公司 | High water-reducing water reducer and preparation method thereof |
-
2008
- 2008-05-20 CN CNA2008100477918A patent/CN101284890A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558935A (en) * | 2011-12-15 | 2012-07-11 | 洛阳理工学院 | Stabilizing agent for lime colloid paint |
| CN102558935B (en) * | 2011-12-15 | 2013-10-09 | 洛阳理工学院 | Stabilizing agent for lime colloid paint |
| CN108047395A (en) * | 2018-01-18 | 2018-05-18 | 安徽省交通控股集团有限公司 | A kind of Machine-made Sand cement concrete Special modifier |
| CN111087541A (en) * | 2019-12-27 | 2020-05-01 | 广东六合新型建材有限公司 | High water-reducing water reducer and preparation method thereof |
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Open date: 20081015 |