CN104292396A - Preparation method of dual-control polycarboxylic acid slump retaining agent - Google Patents
Preparation method of dual-control polycarboxylic acid slump retaining agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a dual-control polycarboxylic acid slump retaining agent, which comprises the following steps: adding a monomer A and deionized water into a substrate, heating to reaction temperature, adding an oxidizer, stirring uniformly, simultaneously and dropwisely adding a solution A composed of a monomer B, a monomer C, a monomer D and deionized water and a solution B composed of a chain-transfer agent, a reducer and deionized water, reacting for some time, regulating the pH value of the copolymerization product to 6.5-7 with an alkali solution, and adding water to obtain the polycarboxylic acid water reducing agent of which the mass concentration is 15-60%. Under the dual-control actions, the dual-control polycarboxylic acid slump retaining agent can obviously improve the slump loss of the concrete within the range of very low doping amount, satisfies the demand for long slump retaining time, does not prolong the setting time of the concrete, and has favorable adaptability with polycarboxylic acid water reducing agents.
Description
Technical field
The present invention relates to a kind of preparation method of polycarboxylic acid slump retaining agent of dual regulation and control, belong to technical field of concrete additives.
Background technology
The outstanding advantages such as volume is low, water-reducing rate is high because having, function of slump protection is good, concrete contraction percentage is low for the high performance water reducing agent of polyocarboxy acid containing polyether lateral chain, slow setting, alkali content be not low, is used widely in the engineerings such as high-speed railway, water conservancy and hydropower, Longspan Bridge, subway tunnel, Highrise buildings.
But along with the not short minimizing of sand material qualified on market, the sand that some silt contents are high, stone material makes polycarboxylate water-reducer often occur the problem that slump-loss is too fast in actual applications, summer high temperature season in addition, hydrated cementitious speed is accelerated, run into ready mixed concrete shipment distance far away time, the slump is often comparatively hard to keep, and require on higher special engineering at some to slump retention, although polycarboxylate water-reducer function of slump protection is good, but still be not well positioned to meet construction requirement, for these problems, engineering technical personnel adopt and Sunmorl N 60S usually, caster sugar, the composite function of slump protection improving water reducer of the slow setting components such as sucrose, but the interpolation of slow setting component, concrete time of coagulation can be made elongated, affect construction speed, the most effective means of current alleviation concrete slump loss is admixture slump retaining agent component, many sections of patents have disclosed the relevant preparation method with the polycarboxylate polymer protecting function of collapsing.
Patent 201010185721.6 describes a kind of collapse protective poly-carboxylic acid water reducing agent and preparation method thereof; the polymerization single polymerization monomer that this technique adopts is maleic anhydride, molecular weight is 2400 allyl polyglycol, methallylsulfonic acid sodium; preparation technology is that bed material throws maleic anhydride and allyl polyglycol ether; under nitrogen protection; be warming up to 90 DEG C; drip ammonium persulfate solution; holding-zone 2.5 hours; be cooled to 45 DEG C; add alkali neutralization; this technique is higher to equipment requirements, and needs higher temperature of reaction, and energy consumption is large.
Patent 201210047415 reports a kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof, methacrylic Soxylat A 25-7, sodium p styrene sulfonate and oxygenant drop in reactor by concrete preparation technology, add water mix and blend, control temperature is at 30 ~ 60 DEG C, drip the solution A be made up of acrylate and vinylformic acid and the B solution be made up of reductive agent and chain-transfer agent simultaneously, the time for adding of solution A controls at 3 ~ 4h, and the time for adding of B solution controls at 3.5 ~ 4.5h; Insulation 1 ~ 1.5h, then adjust ph to 7, discharging described ethers polycarboxylic acid slump retaining agent.This technique adopts a kind of esters monomer as eluting group, has very large effect to the slump-loss making up ready mixed concrete, but run into sandstone material poor or shipment distance is far away time, still have certain limitation.
Patent 201210116963 describes a kind of cross-linking type polycarboxylate water-reducer and preparation method thereof, concrete preparation method is: in the reactor of good leak tightness, methyl allyl alcohol polyoxyethylene ether, polyethylene glycol dimethacrylate, methylpropene sodium sulfonate, deionized water, be warming up to 60 ~ 62 DEG C, add hydrogen peroxide, then slowly acrylic acid solution and chain-transfer agent is dripped, drip off in 3 ~ 3.5 hours, be incubated 1 ~ 1.5 hour, 50 DEG C are cooled to after reaction terminates, moisturizing, add liquid caustic soda and be neutralized to pH=6.5 ~ 7, obtain the cross-linking type polycarboxylate water-reducer that solid content is 40%.This technique introduces linking agent in the molecular structure, in the alkaline environment that hydrated cementitious is formed, linking agent is hydrolyzed, and discharges the effective water reducer molecule of part, and then reach the effect controlling concrete slump loss, because the group be connected with ester group in linking agent is sterically hindered comparatively large, hydrolysis rate is slow, is not well positioned to meet the slump-loss that concrete causes in earlier stage, like this, reach good serviceability, volume wants high, considers uneconomical from the angle of cost.
Patent 201210104355 describes the preparation method that a kind of ester ether is cross-linked class polycarboxylate water-reducer, preparation technology is in airtight reactor, drop into methoxy poly (ethylene glycol) and catalyzer, 30min is stirred when being then heated to 80 ~ 90 DEG C, abundant dissolving slowly adds the mixed solution of methacrylic acid and hydroxyethyl methylacrylate afterwards, and heat temperature raising, logical rare gas element pressurization, be incubated 4 ~ 8 hours, obtain polycarboxylic acid water reducer intermediate, throw at bed material and have methacrylic Soxylat A 25-7, in the reactor of methylpropene sodium sulfonate and water, drip the mixed solution having Thiovanic acid and water reducer midbody, time for adding 3.5h, drip ammonium persulphate, time for adding 4h, insulation, neutralization obtains.This technique adopts first synthesizing ester polymeric monomer and then polymerization of carboxylic acid and esters monomer, and when such product is applied in concrete, workability is better, but synthesizing ester polymeric monomer complex process, and also have room for improvement when esterification is used for industrialization.
Known in sum, existing slump retaining agent products characteristics differs, or synthesis technique is complicated, or yield also has room for promotion, or early stage discharges release of fast later stage deficiency, or release in early stage is slow waits not enough, therefore, develop that a kind of technique is simple, to take into account the polycarboxylic acid slump retaining agent that release in early stage and later stage discharge very meaningful.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, and the preparation method that a kind of synthesis technique is simple, take into account the polycarboxylic acid slump retaining agent of a kind of dual regulation and control of release in early stage and later stage release is provided, this slump retaining agent adopts to regulate and control the design of molecular structure, by the mode that release in early stage and later stage discharge, effectively solve the problem of the slump-loss that the too fast or long-distance transportation of slump-loss in the ready mixed concrete short period of time causes.
The mechanism that the present invention adopts hydrolytic action can occur based on Ester in cement alkaline environment, and generates hydroxy-acid group gradually, the electron donating group that the speed of hydrolysis of ester group is connected with ester group, electron-withdrawing group and sterically hindered relevant.The present invention adopts the ester groups simultaneously having two kinds of release rate in a part of molecule, makes it in concrete system, keep having Double regulating control ability to concrete slump.
Technical scheme of the present invention is: a kind of preparation method of polycarboxylic acid slump retaining agent of dual regulation and control, and its concrete steps are as follows:
(1) preparation of material first solution is dripped: take monomers B, C, D respectively, add water and fully dissolve and mix stand-by;
(2) preparation of material second solution is dripped: take chain-transfer agent and reductive agent, add water and fully dissolve and mix stand-by;
(3) taking monomer A pours in vessel, is dissolved in water, is warming up to temperature of reaction, adds oxygenant and stirs; Drip first solution and second solution simultaneously; After held for some time, with liquid caustic soda, the pH value of above-mentioned copolymerization product is adjusted to 6.5 ~ 7, adds water and obtain the polycarboxylic acid slump retaining agent of massfraction 5 ~ 60%; The molar ratio of wherein said monomer A, monomers B, monomer C, monomer D is 1:(3 ~ 7): (3 ~ 8): (0.03 ~ 0.06); The general formula of described monomer A represents:
r1 is H or CH
3, X is CH
2person or C
2h
4, n
1for the integer of 30-60; The general formula of described monomers B represents:
r
2for H or CH
3, R
3for hydroxyethyl, hydroxypropyl or hydroxyl butyl; The general formula of monomer C represents:
r
4for H or CH3, M are H, Na or K; The general formula of monomer D represents:
r5 is H or CH3, n
2for the integer of 5-20.
Preferred monomers A is the mixture of one or more arbitrary proportions in allyl polyglycol ether, methacrylic polyglycol ether, 3-butene-1-ol base polyglycol ether, 3-methyl-3-butene-1-alcohol base polyglycol ether or vinyl polyglycol ether; Preferred monomers B is Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, hydroxyethyl methylacrylate, Rocryl 410 or methacrylate; Preferred monomers C is vinylformic acid, methacrylic acid, sodium acrylate, potassium acrylate, sodium methacrylate or methacrylic acid potassium.
The general formula of preferred monomers D represents:
r5 is H or CH3, n
2for the integer of 9-16.
Preferably described oxygenant be in hydrogen peroxide, Potassium Persulphate, ammonium persulphate or Sodium Persulfate any one; Described reductive agent be selected from L-AA, rongalite, sodium bisulfite or Sodium Pyrosulfite any one; The mixture of one or more arbitrary proportions in chain-transfer agent selected from mercapto acetic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid or mercaptoethanol.
The mole dosage of preferred oxidant accounts for 1.9% ~ 9% of monomer A, monomers B, monomer C and monomer D total mole number; The mole dosage of reductive agent accounts for 0.4% ~ 5% of monomer A, monomers B, monomer C and monomer D total mole number; The mole dosage of chain-transfer agent accounts for monomer A, monomers B, monomer C and monomer D total mole number 1 ~ 5%.
The temperature of the reaction in preferred steps (3) is 30 ~ 80 DEG C; It is 2 ~ 3 hours that first solution drips reagent; Second solution time for adding is 3 ~ 4 hours; Soaking time is 1 ~ 4 hour.
The esters monomer that polymer monomer B of the present invention adopts for the first readjustment control slump-loss, ester group is hydrolyzed in the basic conditions, forms carboxyl.
Inventive polymers monomer D is the second readjustment control slump-loss esters monomer used, the space structure of hydrolysis of ester group speed and ester group and the electrophilic be connected or electron donating group relevant, the group be connected with ester group in monomer C is sterically hindered larger, hydrolysis rate will be slower than monomers B, by the difference of hydrolysis rate, reach the difference of the speed of release water reducer, thus realize concrete dual regulation and control.
Beneficial effect:
1. this slump retaining agent product is by dual regulating and controlling effect, within the scope of very low volume, can obviously improve concrete slump-loss, meets and protects the demand of collapsing for a long time.
2. do not extend concrete coagulating time.
3. good with polycarboxylic acids dehydragent adaptability.
4. the inventive method is safe and reliable in the whole preparation process of polycarboxylate water-reducer product of preparation, operation steps is simple and convenient, not with an organic solvent, and nontoxic pollution-free, the advantage such as environmentally safe.
Embodiment
Below in conjunction with chart and embodiment, the present invention will be described further, but content of the present invention is not only confined to the following examples.
Embodiment 1:
120 grams of n are added in four-hole boiling flask
1it is the methacrylic polyglycol ether (0.05mol) of 53,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 35 degree, add the hydrogen peroxide solution (0.007mol) that 0.81 gram of concentration is 30%, after continuing stirring 10 minutes, start evenly to drip first solution and second solution, wherein first solution is by 10.8g vinylformic acid (0.15mol), 17.5 grams of Hydroxyethyl acrylates (0.15mol) and 0.935 gram of n
2be polyethylene glycol dimethacrylate (0.0017mol) 15 grams of deionized water compositions of 9; Second solution is by 0.32 gram of xitix (0.002mol), and 0.89 gram of 3-thiohydracrylic acid (0.008mol) and 40 grams of deionized waters form.First solution 3h drips off, and second solution 3.5h drips off, and after second solution drips off, insulation 1h, adds 32% sodium hydroxide solution 13.1 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 40% with deionized water, and get product PC-1.
Embodiment 2:
120 grams of n are added in four-hole boiling flask
1it is 3-methyl-3-butene-1-alcohol base polyglycol ether (0.05mol) of 53,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 35 degree, add 11 grams of Potassium Persulphates after (0.041mol) continuous stirring 5 ~ 10 minutes, start evenly to drip first solution and second solution, wherein first solution is by 24.14 grams of vinylformic acid (0.335mol), 36.4 grams of Propylene glycol monoacrylates (0.28mol) and 2.3 grams of n
2be 16 polyethylene glycol dimethacrylates (0.0027mol), 15 grams of deionized water compositions; Second solution is by 2.5 grams of xitix (0.014mol), and 1.64 grams of mercaptoethanols (0.021mol) and 40 grams of deionized waters form.First solution 2.5h drips off, and second solution 3h drips off, and after second solution drips off, insulation 1.5h, adds 32% sodium hydroxide solution 29.3 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 20% with deionized water, and get product PC-2.
Embodiment 3:
120 grams of n are added in four-hole boiling flask
1it is the methacrylic polyglycol ether (0.05mol) of 44,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 35 degree, add after 7.61 grams of ammonium persulphates (0.033mol) continue stirring 5 ~ 10 minutes, start evenly to drip first solution and second solution, wherein first solution is by 17.2 grams of methacrylic acids (0.2mol), 18.5 grams of Hydroxyethyl acrylates (0.16mol) and 1.32 grams of n
2be 9 polyethylene glycol dimethacrylates (0.0024mol), 15 grams of deionized water compositions; Second solution is by 1.44 grams of sodium bisulfites (0.014mol), and 1.87 grams of Thiovanic acids (0.02mol) and 40 grams of deionized waters form.First solution 2h drips off, and second solution 3h drips off, and after second solution drips off, insulation 1h, adds 32% sodium hydroxide solution 17.5 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 35% with deionized water, and get product PC-3.
Embodiment 4
50 grams of n are added in four-hole boiling flask
1be the allyl polyglycol ether (0.025mol) of 44,50 grams of n
1it is 3-butene-1-ol base polyglycol ether (0.025mol) of 44,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 65 degree, add the hydrogen peroxide solution (0.027mol) that 3.1 grams of concentration are 30%, after continuing stirring 5 ~ 10 minutes, start evenly to drip first solution and second solution, wherein first solution is by 33.79 grams of methacrylic acids (0.39mol), 37.4 grams of Propylene glycol monoacrylates (0.29mol) and 1.93 grams of n
2be polyethylene glycol dimethacrylate (0.0022mol) 15 grams of deionized water compositions of 16; Second solution is by 3.1 grams of rongalites (0.02mol), and 0.88 gram of 3-thiohydracrylic acid (0.008mol) and 40 grams of deionized waters form.First solution 3h drips off, and second solution 3.5h drips off, and after second solution drips off, insulation 3.5h, adds 32% sodium hydroxide solution 34.4 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 60% with deionized water, and get product PC-4.
Comparative example 1
120 grams of n are added in four-hole boiling flask
1it is the methacrylic polyglycol ether (0.05mol) of 53,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 45 degree, add the hydrogen peroxide solution (0.02mol) that 2.3 grams of concentration are 30%, after continuing stirring 5 ~ 10 minutes, start evenly to drip first solution and second solution, wherein first solution is by 10.8 grams of vinylformic acid (0.15mol), 17.5 grams of Hydroxyethyl acrylates (0.15mol) and 15 grams of deionized water compositions; Second solution is by 3.02 grams of xitix (0.017mol), and 0.88 gram of 3-thiohydracrylic acid (0.008mol) and 40g deionized water form.First solution 3h drips off, and second solution 3.5h drips off, and after second solution drips off, insulation 1h, adds 32% sodium hydroxide solution 13.1 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 15% with deionized water, and get product PC-a.
Comparative example 2
100 grams of n are added in four-hole boiling flask
1it is the methacrylic polyglycol ether (0.05mol) of 44,80 grams of deionized waters, stirring treats that material dissolves completely, temperature controls at 35 degree, add 2.5 grams of concentration be 30% hydrogen peroxide solution (0.022mol) continue stirring 5 ~ 10 minutes after, start evenly to drip first solution and second solution, wherein first solution is by 12.6 grams of vinylformic acid (0.175mol), 2.3 grams of n
2be polyethylene glycol dimethacrylate (0.0027mol) and 15 grams of deionized water compositions of 16; Second solution is by 0.16 gram of xitix (0.001mol), and 1.2 grams of 2 mercaptopropionic acids (0.011mol) and 40 grams of deionized waters form.First solution 3h drips off, and second solution 3.5h drips off.After second solution drips off, insulation 1h, adds 32% sodium hydroxide solution 15.3 grams, adjust ph to 6.5 ~ 7, and regulates concentration to 50% with deionized water, and get product PC-b.
Be understandable that, unsaturated polyether molecular weight, cross-linker molecules amount, acrylic ester monomer to be not limited in above embodiment cited several.
Evaluation to the product of above 4 embodiments:
Above 4 embodiment products are carried out respectively flowing degree of net paste of cement and concrete serviceability of collapsing with comparative sample PC-a, PC-b and carry out simultaneous test.
Paste flowing degree is tested: with reference to GB8077-2000 " Methods for testing uniformity of concrete admixture ", carry out paste flowing degree test to gained sample.W/C is 0.29, and the solid volume of admixture folding is 0.12% of cement consumption.
Testing concrete performance: slump-loss, concrete strength inspection are carried out to experiment gained sample with reference to GB8076-2008 " concrete admixture ".Choose C30 graduation two concrete optimum proportioning: C:F:S:G
little: G
in=280:70:754:434:652, W/C=0.49, the solid volume 0.14% of admixture folding, wherein cement (C) joins cement P.O42.5 cement in adopting, flyash (F) is first level flour coal ash, fineness 80 μm tails over 3%, and sand (S) is medium coarse sand, fineness modulus 2.6 ~ 2.9 stone (G
little) for particle diameter be 5 ~ 10mm, G
infor particle diameter is the rubble of 10 ~ 20mm.
Table 1 flowing degree of net paste of cement is tested you
The paste flowing degree of the different sample of table 1 and gradual loss
Table 2 concrete work performance simultaneous test
Admixture dosage 1.2% (it is 14% that sample concentration all dilutes), each sample tests 0h respectively, slump when 1h, 2h and divergence, and 3d, 7d, 28d intensity, and concrete numerical value sees the following form:
The concrete slump retaining performance of the different sample of table 2 and mechanical property
Can find out that use two kinds of esters monomers are as sustained release component from paste flowing degree test, than not using esters monomer or using a kind of esters monomer good as the mobility hold facility of sustained release component, also can find out in concrete slump retaining performance test, two kinds of esters monomers are adopted to carry out the sample of dual regulation and control, the mixed concrete slump and divergence are not almost lost in 1h, during 2h, degree of mobilization only has a small amount of loss, the sample do not introduced esters monomer or use a kind of esters monomer to synthesize, its mixed concrete divergence just has very large loss when 1h, more obvious during 2h.And adopt the sample of two kinds of esters monomer synthesis, to concrete strength without negative impact
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (8)
1. a preparation method for the polycarboxylic acid slump retaining agent of dual regulation and control, its concrete steps are as follows:
(1) preparation of material first solution is dripped: take monomers B, C, D respectively, add water dissolution and mix stand-by;
(2) preparation of material second solution is dripped: take chain-transfer agent and reductive agent, add water dissolution and mix stand-by;
(3) taking monomer A pours in vessel, is dissolved in water, is warming up to temperature of reaction, adds oxygenant and stirs; Drip first solution and second solution simultaneously; After dripping off rear held for some time, obtain copolymerization product; Then with liquid caustic soda, the pH value of above-mentioned copolymerization product is adjusted to 6.5 ~ 7, adds water and obtain the polycarboxylic acid slump retaining agent of massfraction 5 ~ 60%; The molar ratio of wherein said monomer A, monomers B, monomer C, monomer D is 1:(3 ~ 7): (3 ~ 8): (0.03 ~ 0.06); The general formula of described monomer A is:
r1 is H or CH
3, X is CH
2person or C
2h
4, n
1for the integer of 30-60; The general formula of described monomers B is:
r
2for H or CH
3, R
3for hydroxyethyl, hydroxypropyl or hydroxyl butyl; The general formula of monomer C is:
r
4for H or CH3, M are H, Na or K; The general formula of monomer D is:
r5 is H or CH3, n
2for the integer of 5-20.
2. preparation method as claimed in claim 1, is characterized in that monomer A is the mixture of one or more arbitrary proportions in allyl polyglycol ether, methacrylic polyglycol ether, 3-butene-1-ol base polyglycol ether, 3-methyl-3-butene-1-alcohol base polyglycol ether or vinyl polyglycol ether.
3. preparation method as claimed in claim 1, is characterized in that monomers B is Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, hydroxyethyl methylacrylate, Rocryl 410 or methacrylate.
4. preparation method as claimed in claim 1, is characterized in that monomer C is vinylformic acid, methacrylic acid, sodium acrylate, potassium acrylate, sodium methacrylate or methacrylic acid potassium.
5. preparation method as claimed in claim 1, is characterized in that the general formula of monomer D represents:
r5 is H or CH3, n
2for the integer of 9-16.
6. preparation method as claimed in claim 1, it is characterized in that described oxygenant be in hydrogen peroxide, Potassium Persulphate, ammonium persulphate or Sodium Persulfate any one; Described reductive agent is any one in L-AA, rongalite, sodium bisulfite or Sodium Pyrosulfite; Described chain-transfer agent is the mixture of one or more arbitrary proportions in Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid or mercaptoethanol.
7. preparation method as claimed in claim 1, is characterized in that oxygenant mole dosage accounts for 1.9% ~ 9% of monomer A, monomers B, monomer C and monomer D total mole number; The mole dosage of reductive agent accounts for 0.4% ~ 5% of monomer A, monomers B, monomer C and monomer D total mole number; The mole dosage of chain-transfer agent accounts for monomer A, monomers B, monomer C and monomer D total mole number 1 ~ 5%.
8. preparation method as claimed in claim 1, is characterized in that the temperature of the reaction in step (3) is 30 ~ 80 DEG C; It is 2 ~ 3 hours that first solution drips reagent; Second solution time for adding is 3 ~ 4 hours; Soaking time is 1 ~ 4 hour.
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| CN106699985A (en) * | 2016-11-15 | 2017-05-24 | 湖北工业大学 | Super-long super slow release type polycarboxylic acid slump-retaining agent master batch |
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| CN108383953A (en) * | 2018-03-30 | 2018-08-10 | 湖北工业大学 | A kind of preparation method of the initially polycarboxylic acid slump retaining agent without anchoring group |
| CN114380957A (en) * | 2022-01-21 | 2022-04-22 | 太原市天鼎恒砼外加剂科技发展有限公司 | High-performance ultra-slow release slump retaining agent and preparation method thereof |
| CN114380957B (en) * | 2022-01-21 | 2023-08-25 | 太原市天鼎恒砼外加剂科技发展有限公司 | High-performance ultra-slow-release slump retaining agent and preparation method thereof |
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