CN103694400B - 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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- CN103694400B CN103694400B CN201310601266.7A CN201310601266A CN103694400B CN 103694400 B CN103694400 B CN 103694400B CN 201310601266 A CN201310601266 A CN 201310601266A CN 103694400 B CN103694400 B CN 103694400B
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Abstract
The present invention relates to Carboxylic acid vinyl copolymer retarder and preparation method thereof, molecular weight is 1500～3000, and molecular formula is following formula I such as, in formula: m=4～10；N=10～20.The present invention adopts acrylic acid and two kinds of monomers of Hydroxyethyl Acrylate, they polymerizations are formed Carboxylic acid vinyl copolymer, compared with existing major part retarder, the present invention at least has techniques below advantage: this method is aqueous solution polymerization, compared with the production technology of existing general retarder more simply, rationally, easily operate；This retarder contains carboxylic acid group and ether, increase along with retarder volume, the setting time of cement mortar and concrete slump can both accord with national standard, and there are good linear relationship its volume and thickening time, this just can in the thickening time that can effectively regulate cement mortar according to different construction requirements, therefore product combination property is fine.
Description
Technical field
The present invention relates to Carboxylic acid vinyl copolymer retarder and preparation method thereof.
Technical background
It is known that retarder is that one can postpone hydrated reaction of cement, thus extending concrete setting time, the fresh concrete long period is made to keep plasticity, convenient cast, improve efficiency of construction, later concrete properties is not resulted in dysgenic additive simultaneously.Current China lignin sulfur salt is yield retarder bigger, widely used.In addition, molasses class, hydroxycarboxylic acid and minority inorganic salts retarder have also been obtained and commonly use.
But these retarder major parts of China are inorganic or small organic molecule at present, and volume is very sensitive.Polymer class retarder is a class retarder of recent domestic most study.Multiple different functional monomer can be combined by polymerization technique, and the length of strand, the size of molecular weight and distribution can be controlled.Therefore this kind of retarder can instruct it to synthesize by MOLECULE DESIGN thought, obtains the retarder that combination property is ideal.
Analyzing from its mechanism of action aspect, Carboxylic acid vinyl copolymer retarder complex theoretical explanation is more particularly suitable.Because hydroxy carboxylic acid can form stable complex with transition metal ions, and can only form kinetically unstable complex in alkaline medium with alkaline-earth metal ions.Just because of this, the calcium ion in hydroxy carboxylic acid and cement forms kinetically unstable complex, controls the concentration of calcium ion in liquid phase at the aquation initial stage, produce deferred action, with the carrying out of hydration process, the complexation of this instability will destroy, and such aquation is normally carried out continuing.
Summary of the invention
The technical problem to be solved is to provide a kind of Carboxylic acid vinyl copolymer retarder and preparation method thereof, this retarder stable performance, easy control of reaction conditions, it is easy to industrialized production for above-mentioned prior art.
This invention address that the technical scheme is that Carboxylic acid vinyl copolymer retarder of above-mentioned technical problem, it is characterized in that molecular weight is 1500～3000, molecular formula is:
In formula: m=4～10；N=10～20.
The preparation method of Carboxylic acid vinyl copolymer retarder, it is characterised in that include following steps:
(1): preparation A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for (1:0.5)～(1:0.15), it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs；
(2): preparation B material: take the initiator solution of 100 weight portion mass percent concentration 1-2%；
(3): in there-necked flask, add 70 weight parts waters, add A material, and regulate solution ph=6～7 in reactor with the NaOH of 50% mass body volume concentrations；
(4) step (3) gained solution is carried out water bath with thermostatic control, be warming up to 40-60 DEG C；
(5) step (2) gained B gob is added in step (4) gained solution, and continuously stirred reaction 4～5h simultaneously, obtain end product.
By such scheme, in described step (1), acrylic acid is preferably 1:0.3 with the mol ratio of Hydroxyethyl Acrylate.
By such scheme, in described step (2), initiator solution solubility is preferably 2%.
By such scheme, dripping B material again in described step (5) after the continuously stirred 30min of step (4) gained solution, the continuously stirred response time is 5h.
By such scheme, described initiator selects potassium peroxydisulfate, Ammonium persulfate. and sodium peroxydisulfate.
Reaction equation involved in the present invention is as follows:
In formula: m=4～10；N=10～20.
The present invention adopts acrylic acid and two kinds of monomers of Hydroxyethyl Acrylate, and they polymerizations are formed Carboxylic acid vinyl copolymer, and compared with existing major part retarder, the present invention at least has techniques below advantage:
(1) this method is aqueous solution polymerization, compared with the production technology of existing general retarder more simply, rationally, easily operate；
(2) this retarder contains carboxylic acid group and ether, increase along with retarder volume, the setting time of cement mortar and concrete slump can both accord with national standard, and there are good linear relationship its volume and thickening time, this just can in the thickening time that can effectively regulate cement mortar according to different construction requirements, therefore product combination property is fine.
Accompanying drawing explanation
The linear relationship chart of setting time during Fig. 1 Carboxylic acid vinyl copolymer retarder handy by embodiment 1-6 and its volume.
Detailed description of the invention
For illustrating further present disclosure, enumerate following example especially and the present invention is described in further detail.Embodiment provides by way of illustration, but is in no way restricted to present disclosure.Protection scope of the present invention is as the criterion with claims.
Carboxylic acid vinyl copolymer retarder, 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: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.5, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B material: take the potassium persulfate solution of 100 weight portion mass percent concentrations 1% as initiator.There-necked flask adds 70 weight parts waters, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 10min of question response device solution reactor continuously stirred reactor 4h simultaneously again, obtains end product, be numbered No. 1.
Table one: the performance test of lower No. 1 product of different addition quantity
Embodiment 2: configuration A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.3, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B: take the sodium peroxydisulfate solution of 100 weight portion mass percent concentrations 1% as initiator.There-necked flask adds 70 weight parts waters, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 20min of question response device solution reactor continuously stirred reactor 5h simultaneously again, obtains end product, be numbered No. 2.
Table two: the performance test of lower No. 2 products of different addition quantity
Embodiment 3: configuration A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.3, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B material: take the Ammonium persulfate. of 100 weight portion mass percent concentrations 1% as initiator solution.There-necked flask adds 70 parts of water, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 10min of question response device solution reactor continuously stirred reactor 4h simultaneously again, obtains end product, be numbered No. 3.
Table three: the performance test of lower No. 3 products of different addition quantity
Embodiment 4: configuration A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.3, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B material: take the potassium peroxydisulfate of 100 weight portion mass percent concentrations 2% as initiator solution.There-necked flask adds 70 parts of water, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 10min of question response device solution reactor continuously stirred reactor 5h simultaneously again, obtains end product, be numbered No. 4.
Table four: the performance test of lower No. 4 products of different addition quantity
Embodiment 5: configuration A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.15, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B material: take the sodium peroxydisulfate of 100 weight portion mass percent concentrations 2% as initiator solution.There-necked flask adds 70 weight parts waters, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 20min of question response device solution reactor continuously stirred reactor 4h simultaneously again, obtains end product, be numbered No. 5.
Table five: the performance test of lower No. 5 products of different addition quantity
Embodiment 6: configuration A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for 1:0.3, it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs.Preparation B material: take the ammonium persulfate solution of 100 weight portion mass percent concentrations 1% as initiator.There-necked flask adds 70 weight parts waters, adds A material, and regulate solution 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 DEG C.B gob is added after the continuously stirred 30min of question response device solution reactor continuously stirred reactor 5h simultaneously again, obtains end product, be numbered No. 6.
Table six: the performance test of lower No. 6 products of different addition quantity
The thickening time of six kinds of above-mentioned table one to table and product volume are depicted as figure below, obtain Fig. 1:
The effect of above-mentioned six embodiments is: this retarder can imitate control cement slurry thickening time by the change of volume.For Hua Xinpu silicon 42.5R cement, cement mortar by the GB/T19139-2003 standard configuration ratio of mud 0.44, by GB/JGJ52-2006 standard configuration concrete, the above-mentioned retarder sample of different addition quantity is added in cement mortar and in concrete, measure thickening time and the setting time of cement mortar, measuring concrete slump, result is in Table 1-6.
By the trend of the data of the experimental procedure of the present invention and table one to table six and Fig. 1, the present invention is aqueous solution polymerization, compared with the production technology of existing general retarder more simply, rationally, easily operate；And carboxylic acid group and ether is contained due to this retarder, increase along with retarder volume, there is good linear relationship the thickening time of its volume and cement mortar, this just can in the thickening time that can effectively regulate cement mortar according to different construction requirements, known by table one to table six again and only need to mix this retarder 0.02% namely up to reaching construction requirement with concrete slump the setting time being cement mortar, therefore known product combination property is fine.
Claims (6)
1. the preparation method of Carboxylic acid vinyl copolymer retarder, described Carboxylic acid vinyl copolymer retarder molecular weight is 1500～3000, and molecular formula is:
In formula: m=4～10；N=10～20, include following steps:
(1): preparation A material: take acrylic acid and the Hydroxyethyl Acrylate solution of 320 weight portion mass percent concentrations 60%, acrylic acid and Hydroxyethyl Acrylate is taken respectively in molar ratio for (1:0.5)～(1:0.15), it is simultaneously introduced the phenol of 1 weight portion as molecular weight regulator, stirs；
(2): preparation B material: take the initiator solution of 100 weight portion mass percent concentration 1-2%；
(3): in there-necked flask, add 70 weight parts waters, add A material, and regulate solution ph=6～7 in reactor with the NaOH of 50% mass body volume concentrations；
(4) step (3) gained solution is carried out water bath with thermostatic control, be warming up to 40-60 DEG C；
(5) step (2) gained B gob is added in step (4) gained solution, and continuously stirred reaction 4～5h simultaneously, obtain end product.
2. the preparation method of Carboxylic acid vinyl copolymer retarder according to claim 1, it is characterised in that: in described step (1), acrylic acid is 1:0.3 with the mol ratio of Hydroxyethyl Acrylate.
3. the preparation method of Carboxylic acid vinyl copolymer retarder according to claim 1, it is characterised in that: in described step (3), pH value is 6.
4. the preparation method of Carboxylic acid vinyl copolymer retarder according to claim 1, it is characterised in that: in described step (4), the temperature of intensification is 50 DEG C.
5. the preparation method of Carboxylic acid vinyl copolymer retarder according to claim 1, it is characterized in that: dripping B material after the continuously stirred 30min of step (4) gained solution again in described step (5), the continuously stirred response time is 5h.
6. the preparation method of Carboxylic acid vinyl copolymer retarder according to claim 1, it is characterised in that: described initiator selects potassium peroxydisulfate, Ammonium persulfate. or sodium peroxydisulfate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN102603996A (en) * | 2012-02-28 | 2012-07-25 | 武汉理工大学 | Ether type polycarboxylic acid slump retaining agent and preparation method thereof |
| CN102951865A (en) * | 2012-11-01 | 2013-03-06 | 重庆健杰科技有限公司 | Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077361A (en) * | 1989-06-26 | 1991-12-31 | Rohm And Haas Company | Low molecular weight water soluble phosphinate and phosphonate containing polymers |
| CN101492518B (en) * | 2009-02-27 | 2010-12-08 | 上海市建筑科学研究院(集团)有限公司 | Ethers polycarboxylic acid water reducing agent and preparation |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN102603996A (en) * | 2012-02-28 | 2012-07-25 | 武汉理工大学 | Ether type polycarboxylic acid slump retaining agent and preparation method thereof |
| CN102951865A (en) * | 2012-11-01 | 2013-03-06 | 重庆健杰科技有限公司 | Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 羟基羧酸盐对水泥水化历程的影响;白建飞;《建材世界》;20090415;第30卷(第2期);第163-166页 * |
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