CN104031217B - A kind of loose anti-stick type high-performance polycarboxylic admixture and its preparation method and application - Google Patents
A kind of loose anti-stick type high-performance polycarboxylic admixture and its preparation method and application Download PDFInfo
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- CN104031217B CN104031217B CN201410246733.3A CN201410246733A CN104031217B CN 104031217 B CN104031217 B CN 104031217B CN 201410246733 A CN201410246733 A CN 201410246733A CN 104031217 B CN104031217 B CN 104031217B
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Abstract
The invention discloses a kind of high performance concrete water reducer having loose pick resistance.It is a kind of polycarboxylate high performance water-reducing agent that can reduce concrete viscosity and the loose performance of regulation, by screening PCE synthesis material and proportioning adjustment, introduces non-traditional PCE synthesis material；Modified lignin resin and acrylic acid pre-monomer, can change the organic phosphonate compound of viscous temperature resistance, novel loose anti-stick type high performance water reducing agent of polyocarboxy acid prepared by rheological property regulator etc..During to reach to prepare high strength concrete, reduce viscosity, do not take off the end, improve the requirement such as workability and divergence, receive preferable effect in actual applications.
Description
Technical field
The present invention relates to a kind of loose anti-stick type high performance concrete admixture, be specifically related to one and there is tune
Joint reduces fresh concrete viscosity and the polycarboxylate high performance water-reducing agent having loose performance and preparation method thereof.
Background technology
Polycarboxylate high performance water-reducing agent is current third generation Concrete superplastizer, it have water-reducing rate high,
Volume is low, workability good and favorable working performance, and the advantage such as pollution-free.For vast scientific research institution and production
Enterprise falls over each other research and development.Along with C60～C100Deng strong concrete day by day by building trade and capital construction facility
Extensively application, in being widely applied field how the requirement to concrete admixture also improves constantly, especially
Adapt to the requirement of strong concrete, the new problem also facing for vast engineers and technicians and exploring.
For as C60～C100Strong concrete and self-compacting concrete, prefabricated components and large diameter concrete pipe
Road, they often use high intensity rating cement, increase folk prescription concrete when improving concrete strength
The methods such as cement consumption, increases the total amount of Binder Materials, reduces the ratio of mud, the volume of raising additive carry
High concrete comprcssive strength.But it is incident: concrete viscosity increases, and mobility divergence drops therewith
Low, concrete is substantially taken off at the end, have impact on workability and workability, and this makes the technical staff couple of application
How to reduce and regulate control viscosity and be one in newly mixing strong concrete and feel stubborn problem deeply.
Wu Zengli et al.*Propose to use viscosity modifier functional agent (VMA) to join in PCE (polycarboxylic acids),
Affect the rheological property of cement concrete system.The last month of spring is big*Develop one (POS 01) workability to adjust
Joint agent joins in PCE, and purpose, for increasing water holding capacity, reduces concrete surface tension force, do not affects coagulation
The viscosity of soil and mobility.But it is actually used that above-mentioned research and development achievement can not solve newly to mix strong concrete
In viscosity big, take off the end and problem that mobile performance is deteriorated.Have no other patents domestic and science and technology report at present.
Summary of the invention
The purpose of the present invention solve exactly polycarboxylic-acid in prior art (PCE) additive apply mix newly high-strength
Viscosity during degree concrete increases, takes off the end and the problem of mobile performance variation, it is provided that a kind of novel loosening resists
Viscous type high-performance polycarboxylic admixture and preparation method thereof.
Present inventor by the synthesis material of high-performance poly carboxylic acid (PCE) water reducer is carried out screening and
Adjust, introduce some non-traditional PCE synthesis particular monomers raw material and auxiliary agent, by modified lignin resin through and
Acrylic acid polymerization monomer, organic phospho acid salt compounds, participate in the copolyreaction with hydroxy-acid group, preparation
Going out substantially to have makes fresh concrete loose and viscosity reduction, does not produce the high-performance polycarboxylic acids water reducing agent taking off end phenomenon.
It can be used alone and can also fill compounding in ester group class PCE and ether class PCE use.
For reaching above-mentioned purpose, the technical scheme that the present invention takes is as follows:
A kind of preparation method of loose anti-stick type polycarboxylic admixture, the method be by following monomer initiator,
Carry out aqueous solution polymerization under the effect of chain-transferring agent and auxiliary rheological agents to form:
Monomer (I): one or both in ester group class polymeric monomer A or ether class polymeric monomer B are by proper proportion
Mixture；
Monomer (II): acrylic acid (AA), methacrylic acid (MAA), maleic anhydride (MAn) and clothing
A kind of in health acid or any two are by the mixture of proper proportion；
Monomer (III): organic phospho acid salt compounds HEDP, PBTC or EDTMP；
Monomer (IV): the polymer of acrylic acid-lignin: AA-LS；
Initiator: free radical aqueous solution initiator；
The auxiliary agent of regulation rheological property: acrylic amide and/or carbamide.
Described ester group class polymeric monomer A is MPEGMAA, MPEGAA or MPEGMAn.Described
Ether class polymeric monomer B is HPEG, VPEG, SPEG or TPEG.Monomer (I): by A or B, also
Can both mix by proper proportion, when being used in mixed way, the weight ratio of A Yu B is 1:5～1:10.
Preferably, monomer (I) accounts for the 45～65% of total monomer weight；Monomer (II) accounts for total monomer weight
10～30%；Monomer (III) accounts for the 0.1～5% of total monomer weight；Monomer (IV) accounts for the 3～10% of total monomer weight.
Above-mentioned free radical aqueous solution initiator, including persulfate and oxidoreduction class composite initiator, adds
Enter in reactant mixture that initiator is total monomer weight 0.5～4%, uses acrylic in aqueous solution glycerol polymerization
Sulphonic acids, as chain-transferring agent, accounts for the 0.2～5% of total monomer weight.
Described regulated fluid rheological property the regulation auxiliary agent that can participate in reaction are acrylamide, polyacrylamide
Or carbamide；Being preferably two kinds of agent mixture, acrylic amide is 10:1～15:1 with the weight ratio of carbamide.
The addition of auxiliary agent is the 0.1～0.5% of total monomer weight.
The preparation method of above-mentioned loose anti-stick type polycarboxylic admixture, further, step is as follows:
1) in reactor, the aqueous solution of monomer (IV), chain-transferring agent, monomer (I), initiator solution are added；
2) adding monomer (II) and the mixed liquor of monomer (III), stirring is warming up to 50～90 DEG C simultaneously；
3) adding auxiliary rheological agents after having fed, and add initiator, initiator added in 0.5 hour；Always
Feed time control in 2～3 hours；
4) insulation reaction 0.5～be cooled to 40～45 DEG C after 1 hour, adds alkali and adjusts PH6～7.
The preparation method of above-mentioned loose anti-stick type polycarboxylic admixture, further, step 1) little in 2～3
Time fed.
Beneficial effects of the present invention: the present invention is except selecting conventional polymerization monomeric ester ether type monomer and unsaturation organic
Outside acid monomers, also use organic phosphate compounds and novel two kinds of monomers of AA-LS and resist as temperature resistance
Viscous component, specifically:
1) present invention selects the lignin through commercially available chemical modification, improves the activity of lignin, with acrylic acid
Class unsaturated organic acid carries out graft reaction, obtains being polymerized monomer (IV), and present patent application claims AA-LS,
This Type of Collective monomer warp carries out atactic polymerization reaction together with unsaturated alcohol ethers polyoxyethylene compound,
Obtain the polymer that a kind of molecular structure space is big.It can strengthen adsorbed water molecule and increase water conservation sky
Between.Actually used through in certain high ferro building site, the high-strength concrete viscosity newly mixed substantially reduces, and does not sends out
The end and stifled pump phenomenon are taken off in life.
2) the present patent application uses AA-LS polymerization monomer (IV), reduces polycarboxylate high performance water-reducing agent
Cost of material about 5～8%, achieves the effect killed two birds with one stone.
3) the organic phospho acid salt compounds selected and acrylamides, it has the change of uniqueness and glues anti-height
Temperature and the poly-function of resistance, the anti-stick guarantor further increasing PCE after polyreaction moulds loose function.
4) the loose anti-stick type polycarboxylate high performance water-reducing agent of the present invention can be used alone, it is also possible to as tune
Joint volume adds in the polycarboxylate high performance water-reducing agent of other standard type, retardation setting type and early-strength, with
Control the viscosity of fresh concrete, loose and workability, hence it is evident that sensation workability is good.
Detailed description of the invention
Below in conjunction with example, the specific implementation method of the present invention is elaborated.
Embodiment 1-2
1) in the four-hole boiling flask of 1000ml, 380g deionized water is added as bottom water, addition polymerization monomer
(IV) 95g, chain-transferring agent sodium allylsulfonate SAS5.2g, dissolve while stirring and be warming up to
60～65 DEG C.
2) add the mixed liquor of hydrogen peroxide (30%) 2.1g and 10.5g pure water under nitrogen protection, stir 5
Minute.
3) start what dropping was made up of ester group class polymeric monomer MPEGMAA<I>148g and deionized water 210g
Compound.
4) it is simultaneously added dropwise by methacrylic acid<II>50g and<III>EDTMP (embodiment 2 is PBTC) 5.5g
The compound of composition.
5) and be simultaneously added dropwise the initiator being made up of APS6.3g and deionized water 105g.
6) charging control time for adding is to add for 2～3 hours.
7) rheology-modifying auxiliary agent acrylamide 0.5g is the most disposably added.
8) then insulation reaction 1 hour, temperature controls at 80～90 DEG C.
9) detection double bond the most all open, then at a temperature of be down to 45～50 DEG C, adjust with liquid caustic soda
PH6.0～6.5.
Embodiment 3
1) in the four-hole boiling flask of 1000ml, add the HPEG of 600g60% concentration, and add SAS3.0g,
Dissolve while stirring and be warming up to 50～55 DEG C.
2) add APS1.2g, stir 10 minutes.
3) mixed liquor of dropping acrylic acid 38g and HEDP5g and deionized water 8.75g composition.
4) mixed liquor of AA-LS polymer 95g and deionized water 150g composition it is simultaneously added dropwise.
5) after dropping, second time adds APS0.5g, and is warming up to 60 DEG C.
6) add carbamide 3g, be incubated 1 hour, be subsequently cooled to 40～45 DEG C, adjust P with liquid caustic sodaH6～6.5
?.
7) survey solid content and moisturizing regulation solid content is 40% ± 0.5%.
Embodiment 4
1) in the four-hole boiling flask of 1000ml, the polyethylene glycol methacrylate-styrene polymer of 600g60% concentration is added
The MPEGAA of MPEGMAA and 100g60% concentration, and add SAS3.0g, dissolve liter while stirring
Temperature is to 50～55 DEG C.
2) add APS1.2g, stir 10 minutes.
3) mixed liquor of dropping acrylic acid<II>38g and HEDP5g and deionized water 8.75g composition.
4) mixed liquor of AA-LS polymer 95g and deionized water 150g composition it is simultaneously added dropwise.
5) after dropping, second time adds APS0.5g, and is warming up to 60 DEG C.
6) add carbamide 3g, be incubated 1 hour, be subsequently cooled to 40～45 DEG C, adjust P with liquid caustic sodaH6～6.5
?.
Survey solid content and moisturizing regulation solid content is 40% ± 0.5%.
Detection and application:
1) concrete performance after admixture example 1, example 2 and GJ-80G compares
GJ-80G selects from the market product mechanism after testing detection of Shanghai Gujia Chemical Technology Co., Ltd.
After report data.
Example 1, embodiment 3 are and the self-inspection data of GJ-80G contrast, all reach GB8076-2008
Standard, cement uses little wild field P.O52.5
2) concrete viscosity detection, uses little wild field P.O52.5 cement, and its grating is as follows:
| C | S | G | W | W/C | Slump mm |
| 500 | 670 | 1100 | 130 | 0.26 | 200 |
It is upside down on flat board with slump cone, floating after adding concrete, then pump flat board, concrete is complete
Portion flows down, and compares elapsed time.
| GJ-80G | Example 1 | Example 3 |
| 70S | 62S | 57S |
The relatively concrete viscosity of example 1 and example 3 is little compared with GJ-80G.
3) engineer applied:
The product of example 3 production technology in present patent application is employed in the high ferro engineering of Hebei.Due to ground material
With the reason of cement, employ several proportioning, take passages following grating:
Box beam, C60 grating, cement is P.O52.5
| C | S (fluvial sand) | G | K | F | W | W/C | Additive |
| 335 | 706 | 1060 | 100 | 45 | 158 | 0.33 | 4.8 |
Through building site feedback opinion: properties of product are good, steady quality, and local cement and ground material adaptability are well,
The concrete of mix is of a relatively loose, solves viscosity big, takes off the problems such as the end.
Claims (9)
1. a preparation method for loose anti-stick type polycarboxylic admixture, the method is to be carried out aqueous solution polymerization under the effect of initiator, chain-transferring agent and auxiliary rheological agents by following monomer to form:
Monomer (I): one or both in ester group class polymeric monomer A or ether class polymeric monomer B are by the mixture of proper proportion；Described ester group class polymeric monomer A is MPEGMAA, MPEGAA or MPEGMAn, and described ether class polymeric monomer B is HPEG, VPEG, SPEG or TPEG；
Monomer (II): a kind of in acrylic acid (AA), methacrylic acid (MAA), maleic anhydride (MAn) and itaconic acid or any two are by the mixture of proper proportion；
Monomer (III): organic phospho acid salt compounds HEDP, PBTC or EDTMP；
Monomer (IV): the polymer of acrylic acid-lignin: AA-LS；
Initiator: free radical aqueous solution initiator；
The auxiliary agent of regulation rheological property: acrylic amide and/or carbamide.
2. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 1, it is characterized in that, monomer (I) accounts for the 45～65% of total monomer weight, monomer (II) accounts for the 10～30% of total monomer weight, monomer (III) accounts for the 0.1～5% of total monomer weight, monomer (IV) accounts for the 3～10% of total monomer weight, and monomer (I), monomer (II), monomer (III) and monomer (IV) weight ratio sum are 100%.
3. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 1, it is characterized in that, described free radical aqueous solution initiator includes persulfate and oxidoreduction class composite initiator, join that initiator in reactant mixture is total monomer weight 0.5～4%.
4. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 1, it is characterised in that described chain-transferring agent is acrylic sulphonic acids chain-transferring agent, accounts for the 0.2～5% of total monomer weight.
5. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 1, it is characterised in that regulated fluid rheological characteristic auxiliary agent uses one or both the mixture in acrylamide, polyacrylamide, carbamide.
6. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 5, it is characterised in that regulated fluid rheological characteristic auxiliary agent is the mixture of acrylamide and carbamide, and weight ratio is 10:1～15:1.
7. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 5, it is characterised in that regulated fluid rheological characteristic auxiliary agent is the 0.1～0.5% of total monomer weight.
8. the preparation method of loose anti-stick type polycarboxylic admixture as claimed in claim 1, it is characterised in that the step of this preparation method is as follows:
1) in reactor, the aqueous solution of monomer (IV), chain-transferring agent, monomer (I), initiator solution are added；
2) adding monomer (II) and the mixed liquor of monomer (III), stirring is warming up to 50～90 DEG C simultaneously；
3) adding auxiliary rheological agents after having fed, and add initiator, initiator added in 0.5 hour；Total feed time controlled in 2～3 hours；
4) insulation reaction 0.5～be cooled to 40～45 DEG C after 1 hour, adds alkali and adjusts pH6～7.
9. the loose anti-stick type polycarboxylic admixture that any one preparation method loosening anti-stick type polycarboxylic admixture described in claim 1-8 obtains.
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| CN107501479A (en) * | 2017-08-16 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN114479115B (en) * | 2022-01-12 | 2023-05-09 | 浙江红墙材料科技有限公司 | Phosphorylation modified lignin macromolecule, phosphorylation modified lignin polymer, and preparation methods and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1154953A (en) * | 1995-07-13 | 1997-07-23 | 株式会社日本触媒 | Cement dispersing agent, prepn, method and composition using said cement dispersing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1154953A (en) * | 1995-07-13 | 1997-07-23 | 株式会社日本触媒 | Cement dispersing agent, prepn, method and composition using said cement dispersing agent |
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Address after: 200137, Jiangdong Road 1585, Shanghai, Pudong New Area Patentee after: Shanghai Sinpo special assistant Co., Ltd. Address before: 200137, Jiangdong Road 1585, Shanghai, Pudong New Area Patentee before: Shanghai Sepal Chemical Co., Ltd. |