CN103694400A - Carboxylic acid vinyl copolymer retarder and preparation method thereof - Google Patents
Carboxylic acid vinyl copolymer retarder and preparation method thereof Download PDFInfo
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- CN103694400A CN103694400A CN201310601266.7A CN201310601266A CN103694400A CN 103694400 A CN103694400 A CN 103694400A CN 201310601266 A CN201310601266 A CN 201310601266A CN 103694400 A CN103694400 A CN 103694400A
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Abstract
The invention relates to a carboxylic acid vinyl copolymer retarder and a preparation method thereof. The carboxylic acid vinyl copolymer retarder has molecular weight of 1500-3000 and has a molecular formula I, and in the molecular formula I, m is in a range of 4-10 and n is in a range of 10-20. According to the preparation method, acrylic acid and hydroxyethyl acrylate monomers are polymerized into the carboxylic acid vinyl copolymer. Compared with most existing retarders, the carboxylic acid vinyl copolymer retarder has the advantages that compared with the existing common retarder production technologies, the preparation method of the carboxylic acid vinyl copolymer retarder adopts an aqueous solution polymerization technology, is simpler and more reasonable and can be operated easier; and the carboxylic acid vinyl copolymer retarder contains carboxylic and ether groups, curing time and collapsed slump of cement paste with the carboxylic acid vinyl copolymer retarder satisfy national standards with increasing of a retarder doping amount, and the doping amount is in a good linear relationship with thickening time so that cement paste thickening time can be effectively adjusted according to different construction requirements and thus product comprehensive properties are good.
Description
Technical field
The present invention relates to generating vinyl carboxylate based high molecular multipolymer retardant and preparation method thereof.
Technical background
Well-known retardant is a kind of deferrable hydrated reaction of cement, thereby extend concrete time of coagulation, make the fresh concrete long period keep plasticity, convenient cast, improve operating efficiency, to later concrete properties, can not cause dysgenic admixture simultaneously.China's xylogen sulphur salt is larger, the widely used retardant of output at present.In addition, molasses class, hydroxycarboxylic acid and minority inorganic salts retardant have also obtained generally using.
But these retardant of China are most of at present, be inorganic or small organic molecule, very sensitive to volume.Polymer class retardant is a class retardant of recent domestic most study.By polymerization technique, multiple different functional monomer can be combined, and can control the length of molecular chain, the size of molecular weight and distribution.Therefore this class retardant can instruct it synthetic by molecular designing thought, obtains the comparatively desirable retardant of over-all properties.
From its mechanism of action aspect, analyze, generating vinyl carboxylate based high molecular multipolymer retardant is more suitable with complex compound theoretical explanation.Because hydroxycarboxylic acid can form stable complex compound with transition metal ion, and can only form kinetically unstable complex with alkaline-earth metal ions in alkaline medium.Just because of this, calcium ion in hydroxycarboxylic acid and cement forms kinetically unstable complex, at the aquation initial stage, has controlled the concentration of the calcium ion in liquid phase, produce delayed coagulation, with the carrying out of hydration process, this unsettled complexing will destroy, and aquation is normally carried out continuation like this.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of generating vinyl carboxylate based high molecular multipolymer retardant and preparation method thereof for above-mentioned prior art, and this retardant stable performance, easy control of reaction conditions, be easy to suitability for industrialized production.
The present invention solves the problems of the technologies described above adopted technical scheme: generating vinyl carboxylate based high molecular multipolymer retardant, it is characterized in that molecular weight is 1500～3000, and molecular formula is:
In formula: m=4～10; N=10～20.
The preparation method of generating vinyl carboxylate based high molecular multipolymer retardant, is characterized in that including following steps:
(1): preparation A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, in molar ratio for (1:0.5)～(1:0.15) gets respectively vinylformic acid and Hydroxyethyl Acrylate, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir;
(2): preparation B material: the initiator solution of getting 100 weight part mass percent concentration 1-2%;
(3): in there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6～7 in reactor with the NaOH of 50% mass body volume concentrations;
(4) step (3) gained solution is carried out to water bath with thermostatic control, be warming up to 40-60 ℃;
(5) step (2) gained B gob is added in step (4) gained solution, and continue stirring reaction 4～5h simultaneously, obtain final product.
Press such scheme, in described step (1), the mol ratio of vinylformic acid and Hydroxyethyl Acrylate is preferably 1:0.3.
Press such scheme, in described step (2), initiator solution solubility is preferably 2%.
Press such scheme, in described step (5), step (4) gained solution is continued to drip B material after stirring 30min again, continuing the stirring reaction time is 5h.
Press such scheme, described initiator is selected Potassium Persulphate, ammonium persulphate and Sodium Persulfate.
Reaction equation involved in the present invention is as follows:
In formula: m=4～10; N=10～20.
The present invention adopts vinylformic acid and two kinds of monomers of Hydroxyethyl Acrylate, and their polymerizations are formed to generating vinyl carboxylate based high molecular multipolymer, compares with existing most of retardant, and the present invention at least has following technical superiority:
(1) present method is aqueous solution polymerization, compares simpler, reasonable, easy to operate with the production technique of existing general retardant;
(2) this retardant contains carboxylic acid group and ether, increase along with retardant volume, the time of coagulation of grout and concrete slump can both accord with national standard, and there are good linear relationship its volume and thickening time, this just can effectively regulate the thickening time of grout according to different construction requirements, therefore product over-all properties is fine.
Accompanying drawing explanation
The time of coagulation of Fig. 1 during by the handy generating vinyl carboxylate based high molecular of embodiment 1-6 multipolymer retardant and the linear relationship chart of its volume.
Embodiment
For illustrating further content of the present invention, exemplify especially following examples the present invention is described in further detail.Embodiment provides in the mode of explanation, but is never only confined to content of the present invention.Protection scope of the present invention is as the criterion with claims.
Generating vinyl carboxylate based high molecular multipolymer retardant, is characterized in that molecular weight is 1500～3000, and molecular formula is:
In formula: m=4～10; N=10～20.
Embodiment 1: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.5, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B material: get the potassium persulfate solution of 100 weight part mass percent concentrations 1% as initiator.In there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 40 ℃.Question response device solution adds reactor by B gob after continuing to stir 10min again, and continues stirred reactor 4h simultaneously, obtains final product, is numbered No. 1.
Table one: the performance test of lower No. 1 product of different addition quantity
Embodiment 2: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.3, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B: get the Sodium Persulfate solution of 100 weight part mass percent concentrations 1% as initiator.In there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 40 ℃.Question response device solution adds reactor by B gob after continuing to stir 20min again, and continues stirred reactor 5h simultaneously, obtains final product, is numbered No. 2.
Table two: the performance test of lower No. 2 products of different addition quantity
Embodiment 3: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.3, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B material: get the ammonium persulphate of 100 weight part mass percent concentrations 1% as initiator solution.In there-necked flask, add 70 parts of water, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 50 ℃.Question response device solution adds reactor by B gob after continuing to stir 10min again, and continues stirred reactor 4h simultaneously, obtains final product, is numbered No. 3.
Table three: the performance test of lower No. 3 products of different addition quantity
Embodiment 4: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.3, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B material: get the Potassium Persulphate of 100 weight part mass percent concentrations 2% as initiator solution.In there-necked flask, add 70 parts of water, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 50 ℃.Question response device solution adds reactor by B gob after continuing to stir 10min again, and continues stirred reactor 5h simultaneously, obtains final product, is numbered No. 4.
Table four: the performance test of lower No. 4 products of different addition quantity
Embodiment 5: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.15, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B material: get the Sodium Persulfate of 100 weight part mass percent concentrations 2% as initiator solution.In there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 60 ℃.Question response device solution adds reactor by B gob after continuing to stir 20min again, and continues stirred reactor 4h simultaneously, obtains final product, is numbered No. 5.
Table five: the performance test of lower No. 5 products of different addition quantity
Embodiment 6: configuration A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, for 1:0.3, get respectively vinylformic acid and Hydroxyethyl Acrylate in molar ratio, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir.Preparation B material: get the ammonium persulfate solution of 100 weight part mass percent concentrations 1% as initiator.In there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6 in reactor with the NaOH of 50% mass body volume concentrations.Carry out water bath with thermostatic control, be warming up to 50 ℃.Question response device solution adds reactor by B gob after continuing to stir 30min again, and continues stirred reactor 5h simultaneously, obtains final product, is numbered No. 6.
Table six: the performance test of lower No. 6 products of different addition quantity
Above-mentioned table one to thickening time and the product volume of table six kind is depicted as to figure below, obtains Fig. 1:
The effect of above-mentioned six embodiment is: this retardant can be imitated control cement slurry thickening time by the variation of volume.The Hua Xinpu silicon 42.5R cement of take is example, press the grout of GB/T19139-2003 standard configuration water cement ratio 0.44, press GB/JGJ52-2006 standard configuration concrete, the above-mentioned retardant sample that adds different addition quantity in grout and in concrete, measure thickening time and the time of coagulation of grout, measure concrete slump, the results are shown in Table 1-6.
By experimental procedure of the present invention and table one, to the data of table six and the trend of Fig. 1, the present invention is aqueous solution polymerization, compares simpler, reasonable, easy to operate with the production technique of existing general retardant; And because this retardant contains carboxylic acid group and ether, increase along with retardant volume, there is good linear relationship the thickening time of its volume and grout, this just can effectively regulate the thickening time of grout according to different construction requirements, by table one to table six, know that only need mix that this retardant 0.02% can reach is that time of coagulation and the concrete slump of grout reaches construction requirement again, therefore known product over-all properties is fine.
Claims (8)
1. generating vinyl carboxylate based high molecular multipolymer retardant, is characterized in that molecular weight is 1500～3000, and molecular formula is:
In formula: m=4～10; N=10～20.
2. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant claimed in claim 1, is characterized in that including following steps:
(1): preparation A material: vinylformic acid and the Hydroxyethyl Acrylate solution of getting 320 weight part mass percent concentrations 60%, in molar ratio for (1:0.5)～(1:0.15) gets respectively vinylformic acid and Hydroxyethyl Acrylate, add the phenol of 1 weight part as molecular weight regulator simultaneously, stir;
(2): preparation B material: the initiator solution of getting 100 weight part mass percent concentration 1-2%;
(3): in there-necked flask, add 70 weight parts waters, add A material, and regulate pH=6～7 in reactor with the NaOH of 50% mass body volume concentrations;
(4) step (3) gained solution is carried out to water bath with thermostatic control, be warming up to 40-60 ℃;
(5) step (2) gained B gob is added in step (4) gained solution, and continue stirring reaction 4～5h simultaneously, obtain final product.
3. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: in described step (1), the mol ratio of vinylformic acid and Hydroxyethyl Acrylate is 1:0.3.
4. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: in described step (2), initiator solution solubility is 2%.
5. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: in described step (3), pH value is 6.
6. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: in described step (4), the temperature of intensification is 50 ℃.
7. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: after step (4) gained solution being continued to stir 30min in described step (5), drip B material, continuing the stirring reaction time is 5h again.
8. the preparation method of generating vinyl carboxylate based high molecular multipolymer retardant according to claim 2, is characterized in that: described initiator is selected Potassium Persulphate, ammonium persulphate and Sodium Persulfate.
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| US5087648A (en) * | 1988-03-04 | 1992-02-11 | Takemoto Yushi Kabushiki Kaisha | Method of providing fluidizing property to hydraulic cement compositions using cement dispersion agents comprising water soluble vinyl copolymer |
| US5077361A (en) * | 1989-06-26 | 1991-12-31 | Rohm And Haas Company | Low molecular weight water soluble phosphinate and phosphonate containing polymers |
| CN101225148A (en) * | 2007-12-21 | 2008-07-23 | 北京工业大学 | Method for synthesizing allyl polyether-type high-performance water reducing agent |
| CN101239793A (en) * | 2007-12-21 | 2008-08-13 | 王伟松 | Synthetic method of polycarboxylic acid series high-efficiency water reducing agent |
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