CN104277142A - Production method of narrow-distribution low-molecular-weight polymers - Google Patents
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Abstract
The invention discloses a method for producing narrow-distribution low-molecular-weight high-solid-content polymers by using a steam jet reactor. The reactants (comprising monomer, initiator, chain-transfer agent and water) are instantaneously cut by high-speed steam, dispersed, mixed and heated to the reaction temperature when passing through the steam jet reactor; since the materials are highly dispersed and finely mixed, the reaction speed is very high; the materials flow through a shorter pipeline with larger diameter; and the retention time is controlled at about 30 minutes to complete the reaction. The molecular weight distribution coefficient of the product is less than 1.7, the solid content is greater than 45%, and the product is colorless and transparent. The production technique has the advantages of simple equipment, low investment, high safety, high reaction speed, finely controllable molecular weight (better than tubular reactor) and stable quality, is convenient to operate and control, and can implement continuous production. The production method is suitable for producing all water-soluble narrow-distribution low-molecular-weight polymers.
Description
Technical field
The invention belongs to polymer production field, be specially the production field of narrow distribution low-molecular-weight polymeric thing.Described polymkeric substance comprises water miscible polymkeric substance, such as: polyacrylic acid homopolymer and salt thereof, and the binary of vinylformic acid and more than two or two monomers and multiple copolymer and salt thereof; Methacrylamide homopolymer, the binary of acrylamide and other monomer copolymerizations or multiple copolymer; Also the polymkeric substance of non-water soluble monomers is included, the polymkeric substance of such as esters of acrylic acid.This base polymer is widely used in fields such as circulating water cooling treatment, papermaking, cement, pottery, articles for washing, catalyzer, oil fields as dispersion agent, Scale inhibitors, anti-dehydration agent, anti redeposition agent etc.
Technical background
Low-molecular weight polymer molecular weight is on the impact of use properties
The molecular weight of well-known low-molecular weight polymer has a great impact use properties, and numerous scholar has done large quantity research to this for many years, and typical result is exemplified below:
Yan Binglin, Liu Jixiang (Treatment of Industrial Water 1987, Vol.7) determine polyacrylic acid for 1987 as the impact of water conditioner molecular weight on scale inhibition performance:
| M w | 9755 | 7076 | 5051 | 2952 | 2076 | 1620 | 1507 | 613 |
| Scale inhibition performance, % | 39.2 | 56.2 | 92.2 | 100 | 99 | 92.4 | 80.1 | 47.5 |
2011, model Bao'an (synthetic resins and plastics, 2011, Vol.28): determine polyacrylic acid as dispersant molecule amount to CaCO
3the impact (the lower explanation dispersiveness of viscosity is better) of slurry viscosity:
| M w | 700 | 1100 | 1700 | 2200 | 3150 | 4100 | 5200 | 6700 | 7400 |
| Slurry viscosity (PaS) | 0.69 | 0.53 | 0.42 | 0.31 | 0.28 | 0.35 | 0.55 | 0.73 | 0.86 |
Chang Xiaoxin etc. (petrochemical technology and application, 2000, Vol18) determine vinylformic acid-kalimeris acid copolymer and are used as detergent additives molecular weight to the impact of chelating ability:
| M w | 1700 | 3000 | 4000 | 7600 | 10000 | 23000 | 30000 | 80700 | 100000 |
| Chelating value mg/g | 520 | 706 | 674 | 662 | 646 | 603 | 446 | 328 | 250 |
In molecular weight 1000 ~ 10000 scope, above-mentioned first case is used as Scale inhibitors because the different efficiency difference of molecular weight is up to 2.55 times; Second case reaches 1.89 times as dispersant efficiency difference; 3rd example differs from 1.36 times as detergent additives efficiency.If poor not just larger in the scope of 0 ~ 100000.
Polyacrylic acid product molecular weight distribution is all very wide in the market, distribution coefficient is up to 3 ~ 7.8 (Wu Wei etc., applied chemistry, 2007, Vol.24) if the product of narrow ditribution specified molecular weight can be produced for certain specific area as seen, usage quantity can save 10 ~ 20% or more, will produce huge economic benefit.
The R & D and manufacture present situation of narrow distribution low-molecular-weight polymeric thing
In view of molecular weight is to the great effect of use properties, in recent years low-molecular weight water-soluble polymer, particularly low-molecular-weight polypropylene acid field research concentrate in a large number how to produce narrow ditribution this problem of low-molecular weight polymer on.
Research most up to now is all carried out in reaction flask.The patent of the domestic acid of low-molecular-weight polypropylene in recent years field application: as CN201110392809.X, CN200610098170.3, CN201210223831.6, CN92111424.9, CN200810040947.X, CN201210405876.5, reaction is all carried out in reaction flask.Monomer, initiator, chain-transfer agent slowly drip simultaneously in reaction flask, and temperature of reaction controls at 60 ~ 80 DEG C usually, reaction times 3 ~ 6h.Research reaction conditions (such as: the factors such as the kind of the kind consumption of initiator and proportioning, chain-transfer agent and consumption, temperature of reaction, monomer concentration, stirring velocity, addition programs, the feed rate) impact on molecular weight distribution.These are operated in the molecular weight distribution improving product in varying degrees, but the complete mixed characteristic being limited to tank reactor can not obtain the very narrow product of molecular weight distribution, so result is well imagined.
Product commercially available is at present produced with reactor substantially, and the molecular weight distribution of product is very wide.In addition adopt the production method of tank reactor to be gap reaction, criticize and be difficult to ensure that equilibrium is consistent with the quality criticized, this point is also often for use producer denounces.Because monomer polymerization heat is large in tank reactor production, be again confined reaction, safety is also a very important problem.
In order to eliminate the back-mixing of material, (East China University of Science's journal such as Gao Fengqin, 2006, Vol32) attempt in a stacked rectangular capsules, take Dodecyl Mercaptan as chain-transfer agent, Potassium Persulphate is initiator, achieves polyreaction with Static Water solution polymerization process, obtains the product that molecular weight distribution is narrow.Monomer concentration 30%, polymerization temperature 60 DEG C, reaction times 3h.
But dull and stereotyped static reaction not only long reaction time, key is troublesome poeration, and is difficult to amplification and realizes suitability for industrialized production.
(the applied chemistry such as Wu Wei, 2007, Vol.24) employing reversible addion-fragmentation chain transfer (RAFT) method that then looks for another way has synthesized the narrower product of molecular weight distribution, EP2182011A1 and U.S.P2004/0097674 is also existing open before this.But RAFT agent consumption is large, and reach about 6% of monomer, price is expensive again, so cost can rise, the RAFT of sulfur-bearing can participate in reaction chain and receives on molecule in addition, affects product color, discolor, need subsequent reactions as with amine reaction, or and hydroperoxidation, this all can increase cost.So method can not accept for industry.
Still reaction can't resolve problem, so just contemplate pipe reaction.Within 2013, Chinese patent CN103497267A discloses the preparation method of low molecular weight sodium polyacrylate in a kind of narrow ditribution, adopts tubular reactor reaction.Pipe reactor diameter 12mm, long 540m, be placed in the water-bath of 60 DEG C, and the reaction mass (aqueous solution of vinylformic acid, n-dodecyl mereaptan or Virahol, Potassium Persulphate) mixed squeezes into pipeline with volume pump, and material circulates reaction 6h in the duct.Pipeline reactor preferably resolves the problem of material back-mixing, can obtain the product that molecular weight distribution is narrower, product molecular weight distribution coefficient <2.
2012 before U.S.P20120214941 are also disclosed similar employing tubular reactor and prepare the polyacrylic method of narrow distribution low-molecular-weight.The method leading portion adopts secondary static mixer by meticulous for reactant mixing, and two reactors in series of what back segment adopted the is long 10m of internal diameter 3mm form, and the molecular weight of product distribution coefficient obtained is about 2.0.
Tubular reactor is a kind of piston flow reactor in theory, but in fact because polymkeric substance has viscosity, the retention layer of tube wall drags shoots a retrievable arrow function influence very greatly, particularly above-mentioned reactor.In the pipeline of and length like this little at diameter, retention layer drags to shoot a retrievable arrow and acts on the back-mixing caused and can not despise.In addition the operation of pipeline reactor controls also cumbersome.Especially large to this kind of reaction heat effect of vinylformic acid reaction, if temperature of reaction is high, speed of response is fast, and have one section of reaction high-temperature zone, the existence of high-temperature zone can make product variable color, if temperature of reaction is low, the reaction times is very long.Thus the industrialization amplification of this reactor also can be met difficulty.
In a word, the production of current domestic low-molecular weight polymer is all adopt reactor, gap operating substantially.The molecular weight distribution of product is all wider, because operating parameters is not easy strictly to control product performance poor reproducibility.Cause that product weak effect, consumption are large, cost is high.Can not meet the need of market.
From reaction engineering Perspective Analysis, product molecular weight distribution wide mainly material back-mixing causes, and tank reactor is continuous stir reactor, and back-mixing is inevitable; Tubular reactor is due to caliber small pipeline length, Matter Transfer long reaction time, material toughness, and the back-mixing that tube wall retention layer drags the effect of shooting a retrievable arrow to produce also can not be ignored, and amplification also can be met difficulty.Therefore find more simple, efficient, the safety of one, environmental protection, low cost, product molecular weight distribution be narrower, the easy production method of industrialization amplification, be the active demand of industry.
Summary of the invention
The present invention devises a kind of vapo(u)r blasting reactor, the reaction of monomer rapid polymerization can be realized by means of this reactor, the auxiliary tubular reactor control residence time shorter with one section of diameter greater depth, thus make reaction to the full extent close to desirable piston flow reactor, can obtain that molecular weight distribution is very narrow, distribution coefficient <1.7, the product of solid content >45%.Device is shown in accompanying drawing.
Implementing process program of the present invention is:
The mixture volume pump of reactant monomer, chain-transfer agent and water etc. pumps into middle runner 1, and the steam of certain pressure sprays via runner 2, and the aqueous solution of initiator pumps into runner 3 by volume pump.
Under the jetting action of steam, material moment to be heated by steam atomizing, the pressure and the flow that control steam make aerosol temperature control at 60 ~ 100 DEG C, the reaction of the overwhelming majority in seconds completes, then flow in a pipeline and continued reaction, control material and stop 30 minutes in the duct, be greater than 99.5% with bonding transformation rate, then flow into storage tank.Also can control to stop 10 minutes in the duct, then flow into storage tank thermal insulation slaking.The product obtained is as polyacrylic acid, and polyacrylamide etc. are water white transparency all.
Wherein:
The feature of described vapo(u)r blasting reactor utilizes the jetting action of high velocity vapor to be cut instantaneously by reactant, disperse, mix, be heated to temperature of reaction, be exceedingly fast because material is highly dispersed meticulous hybrid reaction speed, overwhelming majority reaction can in seconds complete.Vapo(u)r blasting reactor can have two runners, also can have the runner of more than three or three, but usual three runners are enough.
The vapor pressure of described vapo(u)r blasting reactor is 0 ~ 10MPa, normally 0.2 ~ 0.6MPa
Described aerosol temperature controls at 60 ~ 100 DEG C.
Described reactant monomer comprises: vinylformic acid and salt thereof; The multicomponent mixture more than binary of vinylformic acid and other monomer or binary and salt thereof; Acrylamide; The multicomponent mixture more than binary of acrylamide and other monomer or binary.
Also can be non-water soluble monomers, as esters of acrylic acid etc.
Described chain-transfer agent comprises: the conventional chain-transfer agents such as n-dodecyl mereaptan, inferior sodium phosphate, sodium formiate, Sodium Pyrosulfite, sodium bisulfite, mercaptoethanol, Virahol, propyl alcohol.The consumption of chain-transfer agent is determined by the molecular weight of object product, and non-alcohols is 1 ~ 30% of monomer, is generally 1 ~ 10%.
Described initiator is oxygenant, oxidation ~ reduction initiator: comprise Potassium Persulphate, ammonium persulphate, Sodium Persulfate, hydrogen peroxide, potassium permanganate; And oxidation ~ reduction initiator that the reductive agent such as above-mentioned superoxide and ferrous sulfate, sodium bisulfite, Sulfothiorine forms.Initiator amount is 1 ~ 20% of monomer weight, normally 2 ~ 5%
The pipeline reactor connect under described vapo(u)r blasting reactor is more much bigger than the diameter of common pipeline reactor, length shortens greatly, difference is the order of magnitude, the impact of tube wall retention layer on back-mixing can be reduced thus, closer to desirable piston flow reactor, the narrower product of molecular weight distribution thus can be obtained.
In the pipeline reactor connect under vapo(u)r blasting reactor, residence time of material controls at 0 ~ 6h, general 30 minutes, then flows into storage tank; Also can control 10 minutes residence time, then flow into storage tank, in storage tank, continue slaking.
The present invention compares with existing production technology: have the following advantages:
(1) cut instantaneously by high velocity vapor by during vapo(u)r blasting reactor by reactant of the present invention, disperse, mix, be heated to temperature of reaction, be exceedingly fast because material is highly dispersed meticulous hybrid reaction speed, major part reaction completed in a few second, then a segment pipe is flowed through, continue reaction in the duct, within about 30 minutes, can complete.With the polymerization of traditional reactor, or tubular reactor is compared speed of response and is significantly improved.
(2) traditional mode of production adopts reactor, and the complete mixed characteristic of tank reactor can not obtain the product of molecular weight narrow ditribution; Tubular reactor is piston flow reactor in theory, the product that molecular weight distribution is very narrow can be obtained, but drag due to tube wall retention layer the effect of shooting a retrievable arrow, especially for the larger fluid of viscosity and pipeline, very long (or material is at pipe internal recycle, the residence time is very long) reactor, sizable back-mixing can be produced thus the distribution affecting molecular weight broadens.React at a terrific speed by during vapo(u)r blasting reactor by reactant of the present invention, then comparatively large by a diameter, the pipeline that length is very short, that effectively can reduce tube wall retention layer drags the effect of shooting a retrievable arrow, reactive mode is closer to piston flow reactor, and molecular weight of product distribution is narrower.
(3) traditional reactor mode of production system interval type is produced, and quality product is difficult to keep uniformity between batches.Production technique reaction of the present invention is continuous print, and quality product is all permanent, and molecular weight also easily accurately controls.
(4) simply compact, the less investment of processing unit provided by the invention, convenient operation and control, safety, reaction times short, molecular weight can accurately control.
(5) the present invention is particularly suitable for amplifying suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing is vapo(u)r blasting reaction unit schematic diagram of the present invention.
Embodiment
Method provided by the invention is through lot of experiment validation, and the following examples give a detailed description technique of the present invention more specifically.
Polyacrylic production (the viscosity-average molecular weight M of embodiment 1.
w11194)
The ratio of water, vinylformic acid, sodium hypophosphite is 25/50/1.Vapo(u)r blasting reactor intermediate flow channel 1 is squeezed into the speed pump of 4.95kg/h, the ratio of ammonium persulphate, water is 1/13, with the speed pump people runner 3 of 1.37kg/h, steam enters through runner 2, control vapor pressure 0.2mPa, spray temperature 90 DEG C, spray flow ipe reactor continues reaction, reaction product flows out from lower end of duct, controls 30 minutes residence time.Product viscosity-average molecular weight M
w11194, number-average molecular weight M
n6909, distribution coefficient 1.62, solid content 47%, monomeric acrylic residual quantity <0.5%,
Polyacrylic production (the viscosity-average molecular weight M of embodiment 2.
w6031)
Change water, vinylformic acid, sodium hypophosphite, ratio be 12/25/1.Other condition is with embodiment 1
The polyacrylic viscosity-average molecular weight M of products therefrom
w6031, number-average molecular weight M
n3950, distribution coefficient 1.53.Solid content 47%.
Polyacrylic production (the viscosity-average molecular weight M of embodiment 3.
w4342)
Change water, vinylformic acid, sodium hypophosphite, ratio be 8/16.7/1.Other condition is with the polyacrylic M of embodiment 1. products therefrom
w4642, M
n2817, distribution coefficient 1.54, solid content 47%.
Polyacrylic production (the viscosity-average molecular weight M of embodiment 4.
w3234)
Change water, vinylformic acid, sodium hypophosphite, ratio be 6/12.5/1.Other condition is with the polyacrylic M of embodiment 1. products therefrom
w3234, M
n2204, distribution coefficient 1.47, solid content 47%.
Polyacrylic production (the viscosity-average molecular weight M of embodiment 5.
w1510)
Change water, vinylformic acid, sodium hypophosphite, ratio be 5/10/1.Other condition is with the polyacrylic M of embodiment 1. products therefrom
w1510, M
n1100, distribution coefficient 1.37, solid content 47%.
The production of embodiment 6. acrylic acid-maleic acid copolymer
The ratio of water, vinylformic acid, toxilic acid, Sodium Pyrosulfite is 8/12.45/4.15/1, and during preparation, toxilic acid is first dissolved in hot water, then add Sodium Pyrosulfite and dissolve, then add vinylformic acid and mix.Vapo(u)r blasting reactor intermediate flow channel 1 is squeezed into the speed pump of 4.95kg/h, the ratio of ammonium persulphate, water is 1/13, with the speed pump people runner 3 of 1.37kg/h, steam enters through runner 2, control vapor pressure 0.2mPa, spray temperature 90 DEG C, spray flow ipe reactor continues reaction, reaction product flows out from lower end of duct, controls 30 minutes residence time.Product limit viscosity 0.0964. solid content 47%.
The production of embodiment 7. acrylic acid-acrylamide copolymer
Acrylamide is first dissolved in hot water, and then adds sodium bisulfite and vinylformic acid.The ratio of water, vinylformic acid, acrylamide and sodium bisulfite is for being 6/6.25/6.25/2.Vapo(u)r blasting reactor intermediate flow channel 1 is squeezed into the speed pump of 4.95kg/h, the ratio of Potassium Persulphate, water is 1/13, with the speed pump people runner 3 of 1.37kg/h, steam enters through runner 2, control vapor pressure 0.2mPa, spray temperature 90 DEG C, spray flow ipe reactor continues reaction, reaction product flows out from lower end of duct, controls 30 minutes residence time.Product limit viscosity 0.0864.
The production of embodiment 8. polyacrylamide
Acrylamide, sodium formiate are successively soluble in water, and water, acrylamide, sodium formiate proportioning are 6/12.5/1.Other condition is with embodiment 1.
The limiting viscosity of products therefrom is 0.0722.
The production of embodiment 9. acrylamide-maleic acid copolymer
The ratio of the acid of water, acrylamide, kalimeris, sodium hypophosphite is 8/12.45/4.15/1.Other condition is with embodiment 1
The limiting viscosity of products therefrom is 0.0932
The production of embodiment 10. acrylic acid-acrylamides-maleic acid terpolymer
The ratio of the acid of water, vinylformic acid, acrylamide, kalimeris, sodium formiate is 6/5/5/2/1.Kalimeris acid is first dissolved in hot water, then adds acrylamide and the lower dissolving of sodium formiate stirring respectively.Other condition is with embodiment 1.
Products therefrom limiting viscosity is 0.0883
The production of embodiment 11. acrylicstyrene sodium sulfonate-Hydroxyethyl acrylate terpolymer
The ratio of water, vinylformic acid, Hydroxyethyl acrylate, Sodium styrene sulfonate, sodium hypophosphite is 8/12/4.1/0.5/1.Other condition is with embodiment 1.Product limiting viscosity 0.0926.
Claims (9)
1. the production method of narrow distribution low-molecular-weight polymeric thing, is characterized in that:
Reactant (monomer, initiator, chain-transfer agent, water etc.) realizes the rapid polymerization reaction of monomer by a vapo(u)r blasting reactor, the auxiliary tubular reactor shorter with one section of diameter greater depth controls the residence time and completes reaction, molecular weight distribution index <1.7 can be obtained, the product of solid content >45%.Device is shown in accompanying drawing.
2. vapo(u)r blasting reactor according to claim 1 utilizes the jetting action of high velocity vapor to be cut instantaneously by reactant, disperse, mix, be heated to temperature of reaction, sprays in spray.Be exceedingly fast because material is highly dispersed meticulous hybrid reaction speed, overwhelming majority reaction in seconds completes.Vapo(u)r blasting reactor can have two runners, also can have the runner of more than three or three.But usual three runners are enough.
3. the vapor pressure of vapo(u)r blasting reactor according to claim 2 is 0 ~ 10MPa, normally 0.1 ~ 0.6MPa.
4. spray temperature according to claim 2 controls at 60 ~ 100 DEG C.
5. reactant monomer according to claim 1 comprises: vinylformic acid and salt thereof; The mixture more than binary of vinylformic acid and other monomer or binary and salt thereof; Acrylamide; The mixture more than binary of acrylamide and other monomer or binary; Kalimeris acid; Also non-water-soluble monomer is comprised, as esters of acrylic acid etc.
6. chain-transfer agent according to claim 1 comprises: the chain-transfer agent that n-dodecyl mereaptan, inferior sodium phosphate, sodium formiate, Sodium Pyrosulfite, sodium bisulfite, Virahol, propyl alcohol etc. are conventional.
The consumption of chain-transfer agent is determined by the molecular weight of object product, and non-alcohols is 1 ~ 30% of monomer, is generally 2 ~ 10%.
7. initiator according to claim 1 comprises oxygenant and oxidation ~ reduction initiator, such as: Potassium Persulphate, ammonium persulphate, Sodium Persulfate, hydrogen peroxide, potassium permanganate etc.; And the oxidation ~ reduction initiator of the reductive agent such as these oxygenants and ferrous sulfate, sodium bisulfite, Sulfothiorine composition.
Initiator amount is 1 ~ 20% of monomer weight, normally 2 ~ 5%.
8. the pipeline reactor connect under vapo(u)r blasting reactor according to claim 1 is more much bigger than the diameter of common pipeline reactor, length shortens greatly, difference is the order of magnitude, the impact of tube wall retention layer on back-mixing can be reduced thus, like this closer to desirable piston flow reactor, thus the narrower product of molecular weight distribution can be obtained.
9. in the pipeline reactor connect under vapo(u)r blasting reactor according to claim 1, residence time of material controls at 0 ~ 6h, within usual 30 minutes, enough, then flows into storage tank; Also can control 10 minutes residence time, then flow into storage tank, in storage tank, continue slaking.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672401A (en) * | 2015-03-13 | 2015-06-03 | 武汉理工大学 | Preparation method for slump retaining agent for polycarboxylate superplasticizer |
| CN107473456A (en) * | 2017-10-09 | 2017-12-15 | 江苏开磷瑞阳化工股份有限公司 | A kind of integrated conduct method of acrylate industrial wastewater |
| CN111848847A (en) * | 2020-07-28 | 2020-10-30 | 山东泰和水处理科技股份有限公司 | Production method of polyacrylic acid and salt thereof |
| CN112028527A (en) * | 2020-08-12 | 2020-12-04 | 河北合众建材有限公司 | High-adaptability polycarboxylic acid high-performance water reducing agent and preparation method thereof |
| CN112625179A (en) * | 2021-01-25 | 2021-04-09 | 河南省科学院高新技术研究中心 | Narrow-distribution low-molecular-weight cationic polyacrylamide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672401A (en) * | 2015-03-13 | 2015-06-03 | 武汉理工大学 | Preparation method for slump retaining agent for polycarboxylate superplasticizer |
| CN107473456A (en) * | 2017-10-09 | 2017-12-15 | 江苏开磷瑞阳化工股份有限公司 | A kind of integrated conduct method of acrylate industrial wastewater |
| CN111848847A (en) * | 2020-07-28 | 2020-10-30 | 山东泰和水处理科技股份有限公司 | Production method of polyacrylic acid and salt thereof |
| CN111848847B (en) * | 2020-07-28 | 2022-03-04 | 山东泰和水处理科技股份有限公司 | Production method of polyacrylic acid and salt thereof |
| CN112028527A (en) * | 2020-08-12 | 2020-12-04 | 河北合众建材有限公司 | High-adaptability polycarboxylic acid high-performance water reducing agent and preparation method thereof |
| CN112625179A (en) * | 2021-01-25 | 2021-04-09 | 河南省科学院高新技术研究中心 | Narrow-distribution low-molecular-weight cationic polyacrylamide and preparation method thereof |
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