CN105174775B

CN105174775B - A kind of efficient slump retaining agent of polycarboxylate concrete and preparation method thereof

Info

Publication number: CN105174775B
Application number: CN201510522352.8A
Authority: CN
Inventors: 关紫星; 关子君; 关未然
Original assignee: Harbin Qiangshi Concrete Technology Development Co Ltd
Current assignee: Harbin Qiangshi Concrete Technology Development Co Ltd
Priority date: 2015-08-25
Filing date: 2015-08-25
Publication date: 2018-03-20
Anticipated expiration: 2035-08-25
Also published as: CN105174775A

Abstract

The invention provides efficient slump retaining agent of a kind of polycarboxylate concrete and preparation method thereof, the slump retaining agent is good to the adaptability of cement, high protect is moulded, and height keeps workability, the pumpability of cement, reduces slump-loss；All steps are completed in a reactor, are had the advantages of simple and quick, process, are easy to industrialized production.

Description

A kind of efficient slump retaining agent of polycarboxylate concrete and preparation method thereof

Technical field

The present invention relates to a kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof.

Background technology

The world today, social economy are flourished, and urban construction is advanced by leaps and bounds, and the thing followed is and traffic, water power, city The rapid rising of the related constructions such as political affairs, high standard, high quality and low-carbon, the market orientation of environmental protection determine for building mixed Solidifying soil must be kept on improving, its performance of constantly improve, to meet the new demand of urban change with rapid changepl. never-ending changes and improvements.Add into concrete It is to meet a kind of necessary means that people require to add additive, and especially slump retaining agent becomes an essential part.

The content of the invention

It is an object of the present invention to provide a kind of concrete slump retaining agent and its simple and quick preparation method, to reach to concrete The holding effect of mixture workability, pumpability and the slump.

A kind of efficient slump retaining agent of polycarboxylate concrete of the present invention, has following structure：

Wherein, R1 represents H, methyl, ethyl, monovalence alkali metal, ammonium ion, divalent alkaline-earth metal；R3 represents H, monoacidic base Metal, ammonium ion, divalent alkaline-earth metal；R2 represents H or hydroxyl；M=5~12, q=10, k=5~20.

The efficient slump retaining agent of polycarboxylate concrete, its weight average molecular weight between 20000~45000, n1=20~ 60, n2=5~23.

The R1 represents H, methyl, ethyl, monovalence alkali metal, ammonium ion, divalent alkaline-earth metal；It is furthermore preferred that R1 is represented Sodium, potassium ion.

The R3 represents H, monovalence alkali metal, ammonium ion, divalent alkaline-earth metal, it is furthermore preferred that R3 represents sodium, potassium ion.

The R2 represents H or hydroxyl.

To prepare the slump retaining agent, the technical solution adopted by the present invention is：By hydroxyl butyl vinyl APEO, water, third Olefin(e) acid ester, SSS, maleic anhydride and polyethylene glycol are major ingredient in catalyst, oxidant initiation and reducing agent and chain Transfer agent control is lower to be completed to prepare, and is specifically comprised the following steps：

1) catalyst A, maleic anhydride and polyethylene glycol are added in the reactor, are warming up to 50~70 DEG C of 1~1.5h of reaction After cool down；

2) suitable quantity of water dissolution system is put into the reactor, and then temperature control is added into catalyst at 30~40 DEG C B, hydroxyl butyl vinyl APEO and SSS, stir；

3) aqueous oxidizing agent solution and acrylate are added dropwise at the temperature disclosed above, while.Dripped in aqueous oxidizing agent solution half an hour Complete, acrylate drips off in 2~3h；Drip off and the water-soluble of reducing agent and chain-transferring agent is added dropwise in oxidant half an hour after Liquid；Finish, be warming up to 50~60 DEG C and be incubated and stir 0.5~1h, PH=6~6.5 are adjusted with alkali after cooling, obtain efficiently protecting and collapse Agent.

In the method, all steps are completed in same reactor, and simple and quick.

The amount ratio of the polyethylene glycol and maleic anhydride is mol ratio 1: 3.1~4.7.

The catalyst A is methanesulfonic acid or sulfamic acid, maleic anhydride and catalyst A amount ratios be mass ratio 1: 0.11~ 0.19.In the presence of the catalyst, the reaction of maleic anhydride and polyethylene glycol can be completed faster at a lower temperature.

The catalyst B is copper p-toluenesulfonate, p-methyl benzenesulfonic acid iron and paratoluenesulfonic acid sodium salt three's mixture, three's Amount ratio is mass ratio 1: 0.27~0.38: 0.55~0.80, and hydroxyl butyl vinyl APEO and copper p-toluenesulfonate Mass ratio be 1: 0.01~0.03.In the presence of the catalyst, the reaction between monomer can be in the short period and compared with low temperature Degree is lower to be completed.

The main material hydroxyl butyl vinyl APEO: water: maleic anhydride: SSS: oxidant: third Olefin(e) acid ester: reducing agent: the amount ratio of chain-transferring agent is mass ratio 1: 1.3~1.8: 0.041~0.053: 0.022~0.033: 0.002~0.007: 0.029~0.047: 0.004~0.007: 0.003~0.006.

The oxidant, acrylate, reducing agent and chain-transferring agent the aqueous solution concentration be mass fraction 20~30%, 50~60%, 15~22% and 17~27%.

The molecular weight of the polyethylene glycol is 200,300,600 or 800.

The acrylate is any one in acrylic acid, methyl acrylate, ethyl acrylate or acrylic acid hydroxyl ester.

The oxidant is any one in potassium permanganate, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide.

The chain-transferring agent is TGA, β-mercaptopropionic acid, mercaptopropionic acid, lauryl mercaptan, Stearyl mercaptan With any one in isopropanol.

The reducing agent is any one in ferrous sulfate, sodium hypophosphite, sodium hydrogensulfite, sodium formaldehyde sulfoxylate and stannous sulfate.

The slump retaining agent prepared using the inventive method has the characteristics that guarantor to collapse, and ability is higher, adaptability is stronger, and 2h can be achieved Interior slump free of losses.

Embodiment

Embodiment 1

4.52g catalyst methanesulfonic acids, 41g maleic anhydrides and 26g polyethylene glycol 200s are added in the reactor, are warming up to 50 DEG C reaction 1.5h after cool down；The water-soluble enzymatic hydrolysis systems of 1300g are put into the reactor, and by temperature control at 30 DEG C, are then added and urged Agent (30g copper p-toluenesulfonates, 8.1g p-methyl benzenesulfonic acid iron and 15g paratoluenesulfonic acid sodium salts), 1000g hydroxyl butyl vinyl polyoxies Vinethene and 22g SSSs, stir；At this temperature, at the same be added dropwise the ammonium persulfate containing 2g 20% aqueous solution, 50% aqueous solution of the acrylic acid containing 29g.Ammonium sulfate solution drips off in half an hour, and acrylate drips off in 2h；Drip off sulfuric acid 17% aqueous solution and chain tra nsfer of 15% aqueous solution TGA containing 3g of the ferrous sulfate containing 4g are added dropwise in ammonium half an hour after The aqueous solution of agent；Finish, be warming up to 50 DEG C and be incubated and stir 0.5h, adjust PH=6~6.5 with alkali after cooling, obtain product.

Embodiment 2

Catalyst 10g sulfamic acids, 53g maleic anhydrides 92g and polyethylene glycol-800 are added in the reactor, are warming up to 70 DEG C reaction 1h after cool down；The water-soluble enzymatic hydrolysis systems of 1800g are put into the reactor, and by temperature control at 40 DEG C, then add catalysis Agent (10g copper p-toluenesulfonates, 3.8g p-methyl benzenesulfonic acid iron and 8g paratoluenesulfonic acid sodium salts), 1000g hydroxyl butyl vinyl polyoxy second Alkene ether and 33g SSSs, stir；At this temperature, while 30% aqueous solution of the sodium peroxydisulfate containing 7g is added dropwise, contains 60% aqueous solution of 47g acrylic acid hydroxyl esters.Aqueous sodium persulfate solution drips off in half an hour, and acrylic acid hydroxyl ester drips off in 3h；Drip off Be added dropwise in ammonium sulfate half an hour after 27% aqueous solution of 22% aqueous solution lauryl mercaptan containing 6g of the sodium formaldehyde sulfoxylate containing 7g with The aqueous solution of chain-transferring agent；Finish, be warming up to 60 DEG C and be incubated and stir 1h, adjust PH=6~6.5 with alkali after cooling, produced Thing.

Embodiment 3

Compliance test result：

Polycarboxylate slump retaining agent of the present invention is according to GB/T8977-2000《Concrete admixture homogeneity test method》To net Slurry fluidity is measured, cement on the basis of cement.Result of the test is as shown in the table：

The flowing degree of net paste of cement test result of table 1

The concrete slump test result of table 2

From solid parameter 0.2%, the comparing result that Application No. 201110337164.X patent of invention provides is as follows：

The Application No. 201110337164.X of table 3 patent of invention concrete slump test result

	Embodiment one	Embodiment two	Embodiment three
				Initial slump	200	200	200
The slump after 1h	170	180	190

Contrast table 2 and table 3 can go out, and the present invention protects the invention that positive effect of collapsing is better than Application No. 201110337164.X Patent.

Claims

A kind of 1. efficient slump retaining agent of polycarboxylate concrete, it is characterised in that：With following structure：

Wherein, R1 represents H, methyl, ethyl, monovalence alkali metal, ammonium ion, divalent alkaline-earth metal；R3 represent H, monovalence alkali metal, Ammonium ion, divalent alkaline-earth metal；R2 represents H or hydroxyl；M=5~12, q=10, k=5~20.
2. the efficient slump retaining agent of polycarboxylate concrete as claimed in claim 1, it is characterised in that：Its weight average molecular weight is 20000 Between~45000, n1=20~60, n2=5~23.
3. the efficient slump retaining agent of polycarboxylate concrete as claimed in claim 1, it is characterised in that：R1 represents sodium, potassium ion.
4. the efficient slump retaining agent of polycarboxylate concrete as claimed in claim 1, it is characterised in that：R3 represents sodium, potassium ion.
A kind of 5. preparation method of the efficient slump retaining agent of polycarboxylate concrete as claimed in claim 1, it is characterised in that：Be by Hydroxyl butyl vinyl APEO, water, acrylate, SSS, maleic anhydride and polyethylene glycol are that major ingredient is being urged Agent, oxidant initiation and reducing agent and chain-transferring agent control are lower completing preparation, comprise the following steps that：

1) catalyst A, maleic anhydride and polyethylene glycol are added in the reactor, are warming up to cold after 50~70 DEG C of 1~1.5h of reaction But；

2) suitable quantity of water dissolution system is put into the reactor, and by temperature control at 30~40 DEG C, then adds catalyst B, hydroxyl Butyl vinyl APEO and SSS, it is to be mixed uniform；

3) at the temperature disclosed above, while aqueous oxidizing agent solution and acrylate being added dropwise, aqueous oxidizing agent solution drips off in half an hour, and third Olefin(e) acid ester drips off in 2~3h, drips off the aqueous solution that reducing agent and chain-transferring agent are added dropwise in oxidant half an hour after, adds Finish, be warming up to 50~60 DEG C and be incubated and stir 0.5~1h, adjust pH=5~6.5 with alkali after cooling, obtain efficient slump retaining agent.
6. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described poly- The amount ratio of ethylene glycol and maleic anhydride is mol ratio 1: 3.1~4.7.
7. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described to urge Agent A is methanesulfonic acid or sulfamic acid, and maleic anhydride and catalyst A amount ratios are mass ratio 1: 0.11~0.19.
8. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described to urge Agent B is copper p-toluenesulfonate, p-methyl benzenesulfonic acid iron and paratoluenesulfonic acid sodium salt three's mixture, and the amount ratio of three is mass ratio 1: 0.27~0.38: 0.55~0.80, and the mass ratio of hydroxyl butyl vinyl APEO and copper p-toluenesulfonate is 1: 0.01~0.03.
9. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：The thing Expect hydroxyl butyl vinyl APEO: water: maleic anhydride: SSS: oxidant: acrylate: reducing agent: chain turns Move agent amount ratio for mass ratio 1: 1.3~1.8: 0.041~0.053: 0.022~0.033: 0.002~0.007: 0.029~ 0.047: 0.004~0.007: 0.003~0.006.
10. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described Oxidant, acrylate, the concentration of the aqueous solution of reducing agent and chain-transferring agent are mass fraction 20~30%, 50~60%, 15 ~22% and 17~27%.
11. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described The molecular weight of polyethylene glycol is 200,300,600 or 800.
12. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described Acrylate is any one in methyl acrylate, ethyl acrylate or acrylic acid hydroxyl ester.
13. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described Oxidant is any one in potassium permanganate, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide.
14. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described Chain-transferring agent is to appoint in TGA, β-mercaptopropionic acid, mercaptopropionic acid, lauryl mercaptan, Stearyl mercaptan and isopropanol Meaning is a kind of.
15. the preparation method of the efficient slump retaining agent of polycarboxylate concrete according to claim 5, it is characterised in that：It is described Reducing agent is any one in ferrous sulfate, sodium hypophosphite, sodium hydrogensulfite, sodium formaldehyde sulfoxylate and stannous sulfate.