CN101864019B - Preparation method of sodium polystyrene sulfonate ion exchange resin - Google Patents
Preparation method of sodium polystyrene sulfonate ion exchange resin Download PDFInfo
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Abstract
The invention provides a preparation method of a sodium polystyrene sulfonate ion exchange resin, which comprises the following steps: (1) taking styrene as a monomer, divinylbenzene as a cross-linking agent, benzoyl peroxide as an initiator, polyvinyl alcohol as a suspending agent, methylene blue as an aqueous phase polymerization inhibitor and water as a reaction medium, and carrying out suspension polymerization reaction at 78-97 DEG C; and (2) adding copolymer in the step (1) in chloroform for swelling, adding sulfuric acid at 60-95 DEG C for sulfonation reaction to obtain a sulfonate hydrogen type resin, reacting the sulfonated hydrogen type resin and NaOH to convert into sodium type, then purifying and drying to obtain the spherical sodium polystyrene sulfonate ion exchange resin. The invention adopts chloroform to replace the traditional dichloroethane as a sweller, and has less damage to human health and environment and obviously lowered temperature of sulfonation reaction, and the prepared pharmaceutical bead ion exchange resin has small grain diameter, light color, high purity and less impurities and conforms to the requirements of United States and European pharmacopeia.
Description
Skill wood field
The present invention relates to a kind of preparation method of sodium polystyrene sulfonate ion exchange resin.
Technical background
Sodium polystyrene sulfonate ion exchange resin has been widely used in multiple fields such as separation and purification and the pharmaceutical prepn of water purification, compound.Wherein, as the auxiliary material of oral slow controlled release suspensoid, the existing abroad medicinal specification auxiliary material of sodium polystyrene sulfonate ion exchange resin provides, like ROHM AND HAAS (Rohm & Haas) and all production pharmaceutical grade of DOW Chemical (Dow Chemical) resin.
Yet; The production of sodium polystyrene sulfonate ion exchange resin both at home and abroad at present; After all need using ethylene dichloride as swelling agent p-poly-phenyl ethene cross-linking copolymer swelling; Carry out sulfonation reaction, and ethylene dichloride is the first kind solvent in the pharmacy, the health of environment and production operator is all constituted bigger threat.Secondly, the resin particle diameter of producing at present is many at 400～2000 mu m ranges, need can reach the needed particle diameter of preparations carrier through pulverizing, and pulverizing can partly destroy the structure of resin, and produce new surface, is unfavorable for the stable of preparation.Once more, normal residual more styrene monomer and other impurity in the resin of this big particle diameter.
Patent CN1331607 discloses under a kind of condition that does not have organic swelling agent, through the sulfonation of wet cross-linking copolymer, prepares the method for strong-acid cation-exchange resin.But this sulfonation reaction requires under 105～140 ℃ of temperature, to carry out, and uses a large amount of 96～100% sulfuric acid (4～8 times of copolymerization weight).Sulfonation under this high temperature and the high-concentration sulfuric acid condition can make resin that the aging and oxidation of part takes place inevitably.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of sodium polystyrene sulfonate ion exchange resin to overcome the above-mentioned defective that prior art exists, satisfies the needs of pharmaceutical prepn auxiliary material.
Preparing method of the present invention comprises the steps:
(1) preparation of multipolymer
With vinylbenzene (St) is that monomer, divinylbenzene (DVB) are that linking agent, Lucidol (BPO) are that initiator, Z 150PH (PVA) are that suspending agent, Socryl Blue BRL are that water stopper, water are reaction medium; Carry out suspension polymerization; Reaction times is 4～12h hour; Temperature of reaction is 78～97 ℃, from reaction product, collects multipolymer then, and this multipolymer is spherical in shape;
The weight consumption of each component is following:
The linking agent divinylbenzene is 4～18% of a monomer weight; BP0 is 0.3～3% of a monomer weight;
The weight ratio of monomer and water is: monomer: water=1: 2～1: 5;
The weight concentration of Z 150PH in water is 0.3～2%; Socryl Blue BRL is 5～50ppm in the concentration of aqueous phase;
Preferably, adopt the method for temperature programming, carry out polymerization, comprise the steps:
Under 400～700 rev/mins stirring velocity, 78～82 ℃ kept 2～4 hours with each component, were warming up to 88～92 ℃ and kept 2～3 hours then, were warming up to 93～97 ℃ and kept 2～3 hours again; Stir down, be cooled to 40～50 ℃, from reaction product, collect multipolymer then;
(2) sulfonation of multipolymer
The multipolymer of step (1) is placed chloroform, and swelling is 10～60 minutes under the room temperature, adds sulfuric acid then and carries out sulfonation reaction; Temperature of reaction is 60～95 ℃, and the reaction times is 4～12 hours, from reaction product, collects sulfonated bodies then; Be h type resin, with h type resin and NaOH reaction, change the sodium type into then; Through washing, drying, obtain said sodium polystyrene sulfonate ion exchange resin again;
The weight ratio of multipolymer and chloroform is 1: 0.5～1: 2;
Multipolymer and vitriolic weight ratio are 1: 3～1: 5;
Method of the present invention, adopting suspension polymerization to prepare particle diameter is the spherical multipolymers of 20～100 μ m crosslinked polystyrenes; Multipolymer drying-free process directly with the chloroform give swelling agent, carries out being sulfonation reaction and transition sodium type sulfate resin under 60～95 ℃ of temperature; Adopt water and ethanol to carry out the purifying of resin, make sodium polystyrene sulfonate ion exchange resin as solvent.Adopt chloroform to replace ethylene dichloride to make the resins process of swelling agent, little to environment and operator's healthy effect, temperature of reaction is low, and the particle diameter of gained resin is little, of light color, purity is high, impurity is few, meet the requirement of US and European pharmacopeia.
Embodiment
Embodiment 1
Get 100g vinylbenzene (99.4wt%) and 18g Vinylstyrene (80.2wt%) is put in the separating funnel; Use weight concentration to be 2%NaOH solution extraction 2～3 times, about at every turn 100g, washing is to neutral; Get purified vinylbenzene and Vinylstyrene, add 1.2g BPO stirring and dissolving.
In three mouthfuls of reaction flasks of 1L, add 500g water and 5g PVA, start stirring, treat the PVA swelling after, be heated to 50 ± 2 ℃, PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make fully and dissolve.Add above-mentioned vinylbenzene and the divinylbenzene made from extra care and being dissolved with BPO then, it is 100 μ m that the adjustment stirring velocity makes the emulsion droplet particle diameter.Heat temperature raising to 80 ± 2 ℃ also kept 3 hours, were warming up to 90 ± 2 ℃ and kept 2 hours then, were warming up to 95 ℃ and kept 2 hours again.Stop heating, continue to be stirred to temperature and be reduced to about 40 ℃.The gained resin filters with B, and the degradation production of PVA and BPO is removed in 85 ℃ of hot water drip washing, the B suction filtration, and the weight water cut of control resin is in 8%.
Get the above-mentioned crosslinked polystyrene copolymerization thing 100g that makes and put in the there-necked flask, add the 100g chloroform, swelling is 20 minutes under the room temperature, adds 300g sulfuric acid, heat temperature raising to 60 under stirring ± 2 ℃, and be incubated 3 hours, be warming up to backflow (63～65 ℃) again and be incubated 9 hours.After boiling off chloroform, stop heating.After cold slightly, under agitation, above-mentioned sulfonation reaction product is slowly joined in about 1000ml pure water, leave standstill, the layer that anhydrates that inclines, the resin water is washed till nearly neutrality, gets h type resin.
In the gained resin, adding weight concentration is 10%NaOH solution, and the pH that makes the system water is greater than 12, stirring reaction 60 minutes.Filter, the resin pure water is washed till neutrality, gets sodium polystyrene sulfonate ion exchange resin.
Above-mentioned resin is put in three mouthfuls of reaction flasks, added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours.After cold slightly, filter.Resin after the washing is put in three mouthfuls of reaction flasks, adds the ethanol (95%) of 3 times of weight, and reflux is 2 hours under stirring, and cold slightly back filters.Resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, is heated to 85 ± 5 ℃ under stirring, and keeps 2 hours.After cold slightly, filter.Resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture about 5%.
Adopt the European Pharmacopoeia standard to detect, main result such as table 1:
The character of table 1 sodium polystyrene sulfonate ion exchange resin
| Project | Outward appearance | Median size (μ m) | Sodium content (%) | Potassium exchange capacity (mmol/g) | Vinylbenzene residual quantity (ppm) |
| Character | Pale yellow powder | 70 | 9.8 | 3.0 | ＜1 |
Embodiment 2
Get 100g vinylbenzene (99.4wt%) and 5.5g Vinylstyrene (80.2wt%) is put in the separating funnel, make with extra care with method same among the embodiment 1, purified vinylbenzene and Vinylstyrene, add 0.5g BPO stirring and dissolving.
In three mouthfuls of reaction flasks of 1L, add 300g pure water and 3g PVA, start stirring, treat the PVA swelling after, be heated to 50 ± 2 ℃, PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make fully and dissolve.Add above-mentioned purified vinylbenzene and divinylbenzene then, it is 50 μ m that the adjustment stirring velocity makes the emulsion droplet median size.Heat temperature raising to 80 ± 2 ℃ and keeping 2 hours slowly are warming up to 90 ± 2 ℃ and kept 3 hours then, are warming up to 95 ℃ and kept 2 hours again.Stop heating, continue to be stirred to temperature and drop to about 40 ℃.The gained resin filters with B, 85 ℃ of hot water drip washing, and B filters, and the weight water cut of control resin is in 8%.
Get the above-mentioned styron 100g that makes and put in the there-necked flask, add the 70g chloroform, swelling is 40 minutes under the room temperature, adds 400g sulfuric acid under stirring, heat temperature raising to 60 ± 2 ℃ slowly, and be incubated 3 hours, be warming up to backflow (63-65 ℃) again and be incubated 3 hours.After boiling off chloroform, be warming up to 85 ℃ of insulation reaction 4 hours.After cold slightly, under agitation, above-mentioned sulfonation reaction product is slowly joined in about 1000ml pure water, leave standstill, the layer that anhydrates that inclines, the resin water is washed till nearly neutrality, gets h type resin.In the gained resin, adding weight concentration is 10%NaOH solution, and the pH that makes the system water is greater than 12, stirring reaction 60 minutes.Filter, the resin pure water is washed till neutrality, gets sodium polystyrene sulfonate ion exchange resin.
Above-mentioned resin is put in three mouthfuls of reaction flasks, added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours.After cold slightly, filter.Resin after the washing is put in three mouthfuls of reaction flasks, adds the ethanol (95%) of 4 times of weight, and reflux is 2 hours under stirring, and filters.Resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, is heated to 85 ± 5 ℃ under stirring, and keeps 2 hours.After cold slightly, filter.Resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture about 5%.
Adopt the European Pharmacopoeia standard to detect, main result such as table 2:
The character of table 2 sodium polystyrene sulfonate ion exchange resin
| Project | Outward appearance | Median size (μ m) | Sodium content (%) | Potassium exchange capacity (mmol/g) | Vinylbenzene residual quantity (ppm) |
| Character | Pale yellow powder | 40 | 10.6 | 3.1 | ＜1 |
Embodiment 3
Get 100g vinylbenzene (99.4wt%) and 25g Vinylstyrene (80.2wt%) is put in the separating funnel, make with extra care with method same among the embodiment 1, purified vinylbenzene and Vinylstyrene, add 2.5g BPO stirring and dissolving after, subsequent use.
In three mouthfuls of reaction flasks of 1L, add 500g pure water and 5g PVA, start stirring, treat the PVA swelling after, be heated to 50 ± 2 ℃, PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make fully and dissolve.Add above-mentioned purified vinylbenzene and divinylbenzene (being dissolved with BPO) then, it is 120 μ m that the adjustment stirring velocity makes the emulsion droplet median size.Heat temperature raising to 80 ± 2 ℃ also kept 3 hours, were warming up to 90 ± 2 ℃ and kept 2 hours then, were warming up to 95 ℃ and kept 2 hours again.Stop heating, continue to be stirred to temperature and drop to about 40 ℃.The gained resin filters with B, 85 ℃ of hot water drip washing, and B filters, and control resin water cut is in 8%.
Get the above-mentioned styron 100g that makes and put in the there-necked flask, add the 200g chloroform, swelling is 60 minutes under the room temperature, adds 500g sulfuric acid under stirring, heat temperature raising to 60 ± 2 ℃ slowly, and be incubated 3 hours, be warming up to backflow (63-65 ℃) again and be incubated 3 hours.After boiling off chloroform, be warming up to 90 ℃ of insulation reaction 4 hours.After cold slightly, under agitation, above-mentioned sulfonation reaction product is slowly joined in about 1000ml pure water, leave standstill, the layer that anhydrates that inclines, the resin water is washed till nearly neutrality, filters.In the gained resin, add 10%NaOH liquid, the pH that makes the system water is greater than 12, stirring reaction 60 minutes.Filter, the resin pure water is washed till neutrality.
Above-mentioned resin is put in three mouthfuls of reaction flasks, added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours.After cold slightly, filter.Resin after the washing is put in three mouthfuls of reaction flasks, adds the ethanol (95%) of 4 times of weight, and reflux is 2 hours under stirring, and filters.Resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, stirs down and is heated to 85 ± 5 ℃, and kept 2 hours, cold slightly after, filtration.Resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture about 5%.
Adopt the European Pharmacopoeia standard to detect, main result such as table 3:
The character of table 3 sodium polystyrene sulfonate ion exchange resin
| Project | Outward appearance | Median size (μ m) | Sodium content (%) | Potassium exchange capacity (mmol/g) | Vinylbenzene residual quantity (ppm) |
| Character | Pale yellow powder | 95 | 10.3 | 2.9 | ＜1 |
Claims (3)
1. the preparation method of sodium polystyrene sulfonate ion exchange resin is characterized in that, step is following:
Get the vinylbenzene of 100g 99.4wt% and the Vinylstyrene of 18g 80.2wt%, put in the separating funnel; Use weight concentration to be 2%NaOH solution extraction 2～3 times, each 100g, washing is to neutral; Get purified vinylbenzene and Vinylstyrene, add the 1.2gBPO stirring and dissolving;
In three mouthfuls of reaction flasks of 1L, add 500g water and 5g PVA, start stirring, treat the PVA swelling after; Be heated to 50 ± 2 ℃, PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make dissolving fully; Add above-mentioned refiningly and be dissolved with vinylbenzene and the Vinylstyrene of BPO then, it is 100 μ m that the adjustment stirring velocity makes the emulsion droplet particle diameter, and heat temperature raising to 80 ± 2 ℃ also kept 3 hours; Be warming up to 90 ± 2 ℃ and kept 2 hours then, be warming up to 95 ℃ and kept 2 hours again, stop heating; Continue to be stirred to temperature and be reduced to 40 ℃, the gained resin filters with B, and the degradation production of PVA and BPO is removed in 85 ℃ of hot water drip washing; The B suction filtration, the weight water cut of control resin is in 8%;
Get the above-mentioned crosslinked polystyrene copolymerization thing 100g that makes and put in the there-necked flask, add the 100g chloroform, swelling is 20 minutes under the room temperature, adds 300g sulfuric acid, heat temperature raising to 60 under stirring ± 2 ℃; And be incubated 3 hours, be warming up to 63～65 ℃ of backflows again, and be incubated 9 hours, boil off chloroform after; Stop the heating, cold slightly after, under agitation, above-mentioned sulfonation reaction product is slowly joined in the 1000ml pure water; Leave standstill, the layer that anhydrates that inclines, the resin water is washed till nearly neutrality, gets h type resin;
In the gained resin, adding weight concentration is 10%NaOH solution, and the pH that makes the system water is greater than 12, and stirring reaction 60 minutes filters, and the resin pure water is washed till neutrality, gets sodium polystyrene sulfonate ion exchange resin;
Above-mentioned resin is put in three mouthfuls of reaction flasks, is added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours, cold slightly after; Filter, the resin after the washing is put in three mouthfuls of reaction flasks, adds 95% ethanol of 3 times of weight, stirs down reflux 2 hours; Cold slightly back filters, and the resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, is heated to 85 ± 5 ℃ under stirring; And kept 2 hours, cold slightly after, filter, resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture 5%.
2. the preparation method of sodium polystyrene sulfonate ion exchange resin is characterized in that, step is following:
Get the vinylbenzene of 100g 99.4wt% and the Vinylstyrene of 5.5g 80.2wt%, put in the separating funnel; Use weight concentration to be 2%NaOH solution extraction 2～3 times, each 100g, washing is to neutral; Get purified vinylbenzene and Vinylstyrene, add 0.5g BPO stirring and dissolving;
In three mouthfuls of reaction flasks of 1L, add 300g pure water and 3gPVA, start stirring, treat the PVA swelling after, be heated to 50 ± 2 ℃; PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make dissolving fully, add above-mentioned purified vinylbenzene and Vinylstyrene then, it is 50 μ m that the adjustment stirring velocity makes the emulsion droplet median size; Heat temperature raising to 80 ± 2 ℃ and keeping 2 hours slowly are warming up to 90 ± 2 ℃ and kept 3 hours then, are warming up to 95 ℃ and kept 2 hours again; Stop heating, continue to be stirred to temperature and drop to 40 ℃, the gained resin filters with B; 85 ℃ of hot water drip washing, B filters, and the weight water cut of control resin is in 8%;
Get the above-mentioned styron 100g that makes and put in the there-necked flask, add the 70g chloroform, swelling is 40 minutes under the room temperature, adds 400g sulfuric acid under stirring; Heat temperature raising to 60 ± 2 ℃ slowly, and be incubated 3 hours, be warming up to 63-65 ℃ of backflow again, and be incubated 3 hours; After boiling off chloroform, be warming up to 85 ℃ of insulation reaction 4 hours, cold slightly after, under agitation; Above-mentioned sulfonation reaction product is slowly joined in the 1000ml pure water, leave standstill, the layer that anhydrates that inclines, the resin water is washed till nearly neutrality; H type resin, in the gained resin, adding weight concentration is 10%NaOH solution, the pH that makes the system water is greater than 12, stirring reaction 60 minutes; Filter, the resin pure water is washed till neutrality, gets sodium polystyrene sulfonate ion exchange resin;
Above-mentioned resin is put in three mouthfuls of reaction flasks, is added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours, cold slightly after; Filter, the resin after the washing is put in three mouthfuls of reaction flasks, adds 95% ethanol of 4 times of weight, and reflux is 2 hours under stirring; Filter, the resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, is heated to 85 ± 5 ℃ under stirring; And kept 2 hours, cold slightly after, filter, resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture 5%.
3. the preparation method of sodium polystyrene sulfonate ion exchange resin is characterized in that, step is following:
Get the vinylbenzene of 100g 99.4wt% and the Vinylstyrene of 25g 80.2wt%, put in the separating funnel; Use weight concentration to be 2%NaOH solution extraction 2～3 times, each 100g, washing is to neutral; Purified vinylbenzene and Vinylstyrene, add 2.5g BPO stirring and dissolving after, subsequent use;
In three mouthfuls of reaction flasks of 1L, add 500g pure water and 5g PVA, start stirring, treat the PVA swelling after, be heated to 50 ± 2 ℃; PVA is dissolved fully, add the 5mg Socryl Blue BRL again and make dissolving fully, add above-mentioned purified vinylbenzene and the Vinylstyrene that is dissolved with BPO then, it is 120 μ m that the adjustment stirring velocity makes the emulsion droplet median size; Heat temperature raising to 80 ± 2 ℃ also kept 3 hours, were warming up to 90 ± 2 ℃ and kept 2 hours then, were warming up to 95 ℃ and kept 2 hours again; Stop heating, continue to be stirred to temperature and drop to 40 ℃, the gained resin filters with B; 85 ℃ of hot water drip washing, B filters, and control resin water cut is in 8%;
Get the above-mentioned styron 100g that makes and put in the there-necked flask, add the 200g chloroform, swelling is 60 minutes under the room temperature, adds 500g sulfuric acid under stirring, slowly heat temperature raising to 60 ± 2 ℃; And be incubated 3 hours, be warming up to 63-65 ℃ of backflow again, and be incubated 3 hours, boil off chloroform after, be warming up to 90 ℃ of insulation reaction 4 hours; After cold slightly, under agitation, above-mentioned sulfonation reaction product is slowly joined in the 1000ml pure water, leave standstill; The layer that anhydrates that inclines, the resin water is washed till nearly neutrality, filters, and in the gained resin, adds 10%NaOH liquid; The pH that makes the system water is greater than 12, and stirring reaction 60 minutes filters, and the resin pure water is washed till neutrality;
Above-mentioned resin is put in three mouthfuls of reaction flasks, is added the deionized water of 6 times of weight, be heated to 85 ± 5 ℃ under stirring, and kept 2 hours, cold slightly after; Filter, the resin after the washing is put in three mouthfuls of reaction flasks, adds 95% ethanol of 4 times of weight, and reflux is 2 hours under stirring; Filter, the resin after the washing with alcohol is put in the reactor, adds the pure water of 5 times of weight, is heated to 85 ± 5 ℃ under stirring; And kept 2 hours, cold slightly after, filter, resin is put in 90 ± 5 ℃ the baking oven and is dried to moisture 5%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514492B1 (en) * | 1999-07-14 | 2003-02-04 | Schering-Plough Veterinary Corporation | Taste masking of oral quinolone liquid preparations using ion exchange resins |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthesis of composite functional super high cross-linked adsorbing resin containing sulfo radical |
| CN101036896A (en) * | 2007-02-07 | 2007-09-19 | 江苏工业学院 | Method for purifying sodium polystyrylsulfinate cation exchange resin |
-
2010
- 2010-05-13 CN CN2010101747659A patent/CN101864019B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514492B1 (en) * | 1999-07-14 | 2003-02-04 | Schering-Plough Veterinary Corporation | Taste masking of oral quinolone liquid preparations using ion exchange resins |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthesis of composite functional super high cross-linked adsorbing resin containing sulfo radical |
| CN101036896A (en) * | 2007-02-07 | 2007-09-19 | 江苏工业学院 | Method for purifying sodium polystyrylsulfinate cation exchange resin |
Non-Patent Citations (2)
| Title |
|---|
| B.O.烈赫斯费尔特著，天津大学化工系基本有机合成教研室 译.二氯乙烷的生产.《高等学校教学用书 基本有机合成工艺学（上册）》.化学工业出版社,1959,第117页. * |
| 刘宏飞等.一种新型药用辅料-聚苯乙烯磺酸钠离子交换树脂的合成与表征.《中国新药杂志》.2006,第 15卷(第23期),第2047-2049页. * |
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