CN104609770A - Micro-spherical hydration heat regulating agent as well as preparation method and application of micro-spherical hydration heat regulating agent - Google Patents
Micro-spherical hydration heat regulating agent as well as preparation method and application of micro-spherical hydration heat regulating agent Download PDFInfo
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- CN104609770A CN104609770A CN201510062213.1A CN201510062213A CN104609770A CN 104609770 A CN104609770 A CN 104609770A CN 201510062213 A CN201510062213 A CN 201510062213A CN 104609770 A CN104609770 A CN 104609770A
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- hydration heat
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Abstract
The invention provides a micro-spherical hydration heat regulating agent which is prepared by carrying out polymerization and crosslinking reaction on dextrin, a crosslinking agent and a dispersing agent in the existence of a redox initiator, wherein the mass of the crosslinking agent accounts for 1-5% of the mass of the dextrin, the mass of the redox initiator accounts for 1-3% of the mass of the dextrin, and the mass of the dispersing agent accounts for 1-3% of the mass of the dextrin. The invention also provides a preparation method and an application of the micro-spherical hydration heat regulating agent. The regulating agent is prepared by carrying out crosslinking modification on the dextrin, is of a spatial net structure and is high in acid, alkaline and shear resistance and capable of effectively reducing the peak value of the hydration heat release rate and improving the compressive strength of concrete.
Description
Technical field
The invention belongs to technical field of concrete additives, particularly a kind of microspheroidal hydration heat adjusting control agent and preparation method thereof and application.
Background technology
Mass concrete has little time to shed because hydrated cementitious liberated heat is gathered in inside concrete, concrete internal temperature is increased, even can reach 70 DEG C in summer.Huge internal-external temperature difference can produce great thermal stress, finally causes concrete to produce crack, causes serious consequence.So need regulation and control hydrated cementitious rate of heat release and thermal discharge, thus control concrete temperature rise rate and gradient better, prevent concrete cracking.
Hydration heat adjusting control agent can regulate and control cement hydration process, reduces hydrated cementitious rate of heat release, avoids concrete heat accumulation.EP1233008A1 discloses a kind of cement additive and cement composition, and the method with the addition of dextrin to suppress hydration heat, but unmodified dextrin can only reduce adiabatic temperature 5 DEG C, can not meet the service requirements of mass concrete.JP3729340B2 discloses a kind of blended material by slag and dextrin compound, although unmodified dextrin can reduce concrete core temperature, concrete strength also decreases, and brings certain counter productive.CN102101759B discloses a kind of composite additive for concrete and its preparation method and application, result display has certain meaning to Concrete Temperature Control anticracking, but its Sunmorl N 60S adopted can be adsorbed on cement concrete surface makes it mutually disperse, thus extend concrete coagulating time, be unfavorable for practice of construction, and patent is not carried out to its preparation method yet open.
Summary of the invention
Goal of the invention: in order to overcome above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of microspheroidal hydration heat adjusting control agent.
Applicant finds: hydration heat controlled material is easy to alkalization and dissolves under the alkaline condition of cement, can not give full play to hydration heat regulating and controlling effect, therefore need to carry out cross-linking modified to dextrin.The cross-link bond of different crosslinked dextrin has different antiacid alkali and shear stability.Although but the crosslinked antiacid alkali resistant stability of the ester bond such as common Trisodium trimetaphosphate and hexanodioic acid is low, the ehter bond such as formaldehyde and epoxy chloropropane is cross-linked and is still partly dissolved under concrete high-strength degree is sheared, and the linking agent toxicity such as formaldehyde used is comparatively large, does not meet modern social development's needs.
Technical scheme: a kind of microspheroidal hydration heat adjusting control agent provided by the invention, under redox initiator exists, reacts obtained by dextrin, linking agent and dispersion agent polymerization crosslinking; Wherein, the quality of described linking agent is 1 ~ 5% of dextrin quality, and the quality of described redox initiator is 1 ~ 3% of dextrin quality, and described dispersion agent quality is 1 ~ 3% of dextrin quality.
Present invention also offers the preparation method of above-mentioned microspheroidal hydration heat adjusting control agent, comprise the following steps:
(1) by dextrin and water mixing, the dextrin solution of obtained 10 ~ 50wt%, adds linking agent and redox initiator successively, obtains aqueous phase; By hexanaphthene and dispersion agent mixing, obtain oil phase;
(2) aqueous phase initiated polymerization crosslinking reaction is dripped after oil phase being heated to 40 ~ 60 DEG C;
(3) product is through washing, dry and screening, to obtain final product.
In step (1), described dextrin is maltodextrin, cyclodextrine or thermo-cracking dextrin; Described linking agent is N, N '-methylene-bisacrylamide, neopentylglycol diacrylate or polyethyleneglycol diacrylate; The wherein preferred 200-1000 of the molecular weight of polyethyleneglycol diacrylate; Described dispersion agent is Span 60 or Tween 60.
In step (2), aqueous phase time for adding is 5 ~ 30min.
In step (2), described redox initiator comprises the Oxidizing and Reducing Agents of mol ratio 2 ~ 5:1; Wherein, oxygenant is one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate and hydrogen peroxide; Described reductive agent is one or more of sodium bisulfite, tetraethylene pentamine, sodium hyposulfate and L-AA.
In step (2), the quality of described linking agent is 1 ~ 5% of dextrin quality, and the quality of described redox initiator is 1 ~ 3% of dextrin quality.
In step (2), the reaction times is 2 ~ 12h.
In step (3), drying temperature is 50 ~ 60 DEG C, and time of drying is 20 ~ 40h.
In step (3), sieve size is 80 ~ 140 orders.
Present invention also offers the application of above-mentioned microspheroidal hydration heat adjusting control agent in hydration heat regulation and control, it is characterized in that: its volume is 0.5 ~ 2wt% of concrete gel material.
Beneficial effect: microspheroidal hydration heat adjusting control agent provided by the invention is cross-linking modified obtained by dextrin, has space net structure, antiacid alkali and anti-shear ability high, effectively can reduce hydration heat speed peak value, improve concrete ultimate compression strength.
The linking agent that the preparation method of microspheroidal hydration heat adjusting control agent provided by the invention introduces participates in reaction with the form of short chain free radical, improves the Structure and form of dextrin, and technique is simple, be easy to realize industrialization.
Embodiment
In order to understand the present invention better, below in conjunction with embodiment, content of the present invention is further described, but content of the present invention is not limited to the scope of embodiment statement.
Embodiment 1
The preparation of hydration heat adjusting control agent, comprise the following steps: being added to the water by 100g maltodextrin stirs, be modulated into the dextrin solution of 10wt%, N is added successively under whipped state, N '-methylene-bisacrylamide 1g, 2.229g ammonium persulphate and 0.771g sodium bisulfite, add interval and be no more than 10 minutes; 1g Span 60 and 200g hexanaphthene are joined in four-hole boiling flask and is warming up to 40 DEG C; Be added drop-wise to by aqueous phase in oil phase, 5min drips off, and initiated polymerization is cross-linked 5h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 50 DEG C of dry 40h of baking oven, screening obtains 80 ~ 100 object solid granular hydration heat adjusting control agent products.
Embodiment 2
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g cyclodextrine stirs, and is modulated into the dextrin solution of 25wt%; Under whipped state, add N successively, N '-methylene-bisacrylamide 1g, 1.486g ammonium persulphate and 0.514g sodium bisulfite, add interval and be no more than 10 minutes; 1g Span 60 and 400g hexanaphthene are joined in four-hole boiling flask and is warming up to 40 DEG C; Be added drop-wise to by aqueous phase in oil phase, 15min drips off, and initiated polymerization is cross-linked 2h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 60 DEG C of dry 20h of baking oven, screening obtains 80 ~ 100 object solid granular hydration heat adjusting control agent products.
Embodiment 3
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g thermo-cracking dextrin stirs, and is modulated into the dextrin solution of 50wt%; Under whipped state, add N successively, N '-methylene-bisacrylamide 1g, 0.743g ammonium persulphate and 0.257g sodium bisulfite, add interval and be no more than 10 minutes; 3g Span 60 and 600g hexanaphthene are joined in four-hole boiling flask and is warming up to 60 DEG C; Be added drop-wise to by aqueous phase in oil phase, 30min drips off, and initiated polymerization is cross-linked 12h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 55 DEG C of dry 30h of baking oven, screening obtains 80 ~ 100 object solid granular hydration heat adjusting control agent products.
Embodiment 4
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g thermo-cracking dextrin stirs, and is modulated into the dextrin solution of 25wt%; Under whipped state, add neopentylglycol diacrylate 2.5g, 1.55g Potassium Persulphate and 0.45g tetraethylene pentamine successively, add interval and be no more than 10 minutes; 2g Span 60 and 400g hexanaphthene are joined in four-hole boiling flask and is warming up to 50 DEG C; Be added drop-wise to by aqueous phase in oil phase, 15min drips off, and initiated polymerization is cross-linked 5h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 60 DEG C of dry 20h of baking oven, screening obtains 100 ~ 120 object solid granular hydration heat adjusting control agent products.
Embodiment 5
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g cyclodextrine stirs, and is modulated into the dextrin solution of 35wt%; Under whipped state, add neopentylglycol diacrylate 1g, 2.1g Sodium Persulfate and 0.9g sodium hyposulfate successively, add interval and be no more than 10 minutes; 1g Span 60 and 571g hexanaphthene are joined in four-hole boiling flask and is warming up to 50 DEG C; Be added drop-wise to by aqueous phase in oil phase, 15min drips off, and sends out polymerization crosslinking 8h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 60 DEG C of dry 20h of baking oven, screening obtains 120 ~ 140 object solid granular hydration heat adjusting control agent products.
Embodiment 6
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g maltodextrin stirs, and is modulated into the dextrin solution of 40wt%; Under whipped state, add polyethyleneglycol diacrylate (polyethyleneglycol diacrylate of molecular weight 200-1000 all can realize the present invention) 5g, 0.66g hydrogen peroxide, 0.14g Potassium Persulphate and 0.20gL-xitix successively, add interval and be no more than 10 minutes; 3g Span 60 and 250g hexanaphthene are joined in four-hole boiling flask and is warming up to 60 DEG C; Be added drop-wise to by aqueous phase in oil phase, 30min drips off, and initiated polymerization is cross-linked 5h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 60 DEG C of dry 20h of baking oven, screening obtains 100 ~ 120 object solid granular hydration heat adjusting control agent products.
Embodiment 7
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g maltodextrin stirs, and is modulated into the dextrin solution of 25wt%; Under whipped state, add polyethyleneglycol diacrylate 1g, 1.5g ammonium persulphate, 0.2g sodium bisulfite and 0.1gL-xitix successively, add interval and be no more than 10 minutes; 1g Span 60 and 400g hexanaphthene are joined in four-hole boiling flask and is warming up to 50 DEG C; Be added drop-wise to by aqueous phase in oil phase, 15min drips off, and initiated polymerization is cross-linked 5h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 60 DEG C of dry 20h of baking oven, screening obtains 80 ~ 100 object solid granular hydration heat adjusting control agent products.
Embodiment 8
The preparation of hydration heat adjusting control agent, comprises the following steps: being added to the water by 100g thermo-cracking dextrin stirs, and is modulated into the dextrin solution of 25wt%; Under whipped state, add N successively, N '-methylene-bisacrylamide 1g, 1.0g Sodium Persulfate, 0.3g sodium bisulfite and 0.2g sodium hyposulfate, adds interval and is no more than 10 minutes; 1g Tween 60 and 400g hexanaphthene are joined in four-hole boiling flask and is warming up to 40 DEG C; Be added drop-wise to by aqueous phase in oil phase, 15min drips off, and initiated polymerization is cross-linked 5h; Reacted dextrin solution is used ethyl acetate, ethanol and washing with acetone successively, is placed in 50 DEG C of dry 40h of baking oven, screening obtains 80 ~ 100 object solid granular hydration heat adjusting control agent products.
Comparative example 1
Hydration heat controlled material is prepared with reference to patent CN103739722A embodiment 1.
Comparative example 2
Hydration heat controlled material is prepared with reference to patent CN103739722A embodiment 5.
Comparative example 3
Prepare hydration heat controlled material with reference to patent CN103739722A embodiment 5, linking agent adopts Trisodium trimetaphosphate.
The performance of the microspheroidal hydration heat adjusting control agent that testing example 1 to 8 and comparative example 1 to 3 obtain, the results are shown in Table 1.
Concrete proportioning is water-cement ratio 0.4, water 168kg/m
3, cement 330kg/m
3, flyash 90kg/m
3, fine aggregate 685kg/m
3, coarse aggregate 1128kg/m
3, water reducer 3.36kg/m
3.Wherein, cement uses Hunan Shimen Special Cement Co., Ltd.'s moderate heat cement; Fine aggregate is river sand, apparent density 2.63g/cm3, and fineness modulus is 2.60; Coarse aggregate is 5 ~ 20mm continuous grading rubble; Jiangsu Subotexin Material Co., Ltd SBT selected by water reducer
naphthalene series high-efficiency water-reducing agent.
Alkali resistant degree is tested: take 3g hydration heat adjusting control agent in beaker, add 87g cement slurry hole solution and 10g2mol/L sodium hydroxide solution, sealing, stir at 40 DEG C after 10 hours and filter, be placed in 105 DEG C of baking ovens and be dried to constant weight, take remaining hydration heat adjusting control agent quality m after cooling, calculate alkali resistant degree with formula m*100%/3.
Hydrated cementitious heat testing method is with reference to GB/T 2022-1980.
Concrete coagulating time testing method is with reference to GB/T 50080-2002.
Concrete crushing strength testing method is with reference to GB/T 50081-2002.
The performance test results of the microspheroidal hydration heat adjusting control agent that table 1 embodiment and comparative example obtain
As shown in Table 1, the present invention carries out modified crosslinking to dextrin, linking agent participates in reaction with short chain radical form, dextrin Structure and form can be changed, antiacid alkali and anti-shear ability high, preparation method is simple, and the hydration heat adjusting control agent obtained can reduce hydration heat speed peak value effectively, and concrete ultimate compression strength can be improved, be conducive to the practical application of hydration heat adjusting control agent.
Claims (10)
1. a microspheroidal hydration heat adjusting control agent, is characterized in that: under redox initiator exists, and reacts obtained by dextrin, linking agent and dispersion agent polymerization crosslinking; Wherein, the quality of described linking agent is 1 ~ 5% of dextrin quality, and the quality of described redox initiator is 1 ~ 3% of dextrin quality, and described dispersion agent quality is 1 ~ 3% of dextrin quality.
2. the preparation method of microspheroidal hydration heat adjusting control agent according to claim 1, it is characterized in that: comprise the following steps: (1) is by dextrin and water mixing, the dextrin solution of obtained 10 ~ 50wt%, adds linking agent and redox initiator successively, obtains aqueous phase; By hexanaphthene and dispersion agent mixing, obtain oil phase;
(2) aqueous phase initiated polymerization crosslinking reaction is dripped after oil phase being heated to 40 ~ 60 DEG C;
(3) product is through washing, dry and screening, to obtain final product.
3. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, is characterized in that: in step (1), and described dextrin is maltodextrin, cyclodextrine or thermo-cracking dextrin; Described linking agent is N, N '-methylene-bisacrylamide, neopentylglycol diacrylate or polyethyleneglycol diacrylate; Described dispersion agent is Span 60 or Tween 60.
4. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, it is characterized in that: in step (2), aqueous phase time for adding is 5 ~ 30min.
5. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, is characterized in that: in step (2), described redox initiator comprises the Oxidizing and Reducing Agents of mol ratio 2 ~ 5:1; Wherein, oxygenant is one or more in ammonium persulphate, Sodium Persulfate, Potassium Persulphate and hydrogen peroxide; Described reductive agent is one or more of sodium bisulfite, tetraethylene pentamine, sodium hyposulfate and L-AA.
6. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, it is characterized in that: in step (2), the quality of described linking agent is 1 ~ 5% of dextrin quality, and the quality of described redox initiator is 1 ~ 3% of dextrin quality.
7. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, it is characterized in that: in step (2), the reaction times is 2 ~ 12h.
8. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, it is characterized in that: in step (3), drying temperature is 50 ~ 60 DEG C, and time of drying is 20 ~ 40h.
9. the preparation method of a kind of microspheroidal hydration heat adjusting control agent according to claim 2, it is characterized in that: in step (3), sieve size is 80 ~ 140 orders.
10. the application of microspheroidal hydration heat adjusting control agent according to claim 1 in hydration heat regulation and control, is characterized in that: its volume is 0.5 ~ 2wt% of concrete gel material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432650A (en) * | 2016-09-19 | 2017-02-22 | 江苏苏博特新材料股份有限公司 | Hydration heat regulation and control emulsion as well as preparation method and application thereof |
| CN109748532A (en) * | 2017-12-13 | 2019-05-14 | 江苏苏博特新材料股份有限公司 | A kind of alkali-free quick-coagulant and the preparation method and application thereof |
| CN109776022A (en) * | 2019-03-07 | 2019-05-21 | 东南大学 | The compound controllable heat of hydration cement-based material of one kind and its application |
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2015
- 2015-02-05 CN CN201510062213.1A patent/CN104609770B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432650A (en) * | 2016-09-19 | 2017-02-22 | 江苏苏博特新材料股份有限公司 | Hydration heat regulation and control emulsion as well as preparation method and application thereof |
| CN109748532A (en) * | 2017-12-13 | 2019-05-14 | 江苏苏博特新材料股份有限公司 | A kind of alkali-free quick-coagulant and the preparation method and application thereof |
| CN109748532B (en) * | 2017-12-13 | 2022-03-18 | 江苏苏博特新材料股份有限公司 | Alkali-free accelerator and preparation method and application thereof |
| CN109776022A (en) * | 2019-03-07 | 2019-05-21 | 东南大学 | The compound controllable heat of hydration cement-based material of one kind and its application |
| CN109776022B (en) * | 2019-03-07 | 2021-06-11 | 东南大学 | Composite controllable hydration cement-based material and application thereof |
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