CN100509897C - Synthesis for resorcin-containing coarse-pore sphere type adsorption resin and application method thereof - Google Patents
Synthesis for resorcin-containing coarse-pore sphere type adsorption resin and application method thereof Download PDFInfo
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- CN100509897C CN100509897C CNB2006101345442A CN200610134544A CN100509897C CN 100509897 C CN100509897 C CN 100509897C CN B2006101345442 A CNB2006101345442 A CN B2006101345442A CN 200610134544 A CN200610134544 A CN 200610134544A CN 100509897 C CN100509897 C CN 100509897C
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Abstract
A synthesis and application method of resorcinol spherical macroporous adsorbing resin relates to the method of extracting caffeine, theophylline, VB12 from their natural product solution. Its synthesis takes PFA (or formal), resorcinol, phenol as raw materials, in the presence of particular holing agent ethylene glycol, and uses inverse suspension polycondensation to synthesize with the presence of acid catalyst.
Description
Technical field
The present invention relates to a kind of synthetic and application method of polymeric adsorbent, particularly relate to and contain the synthetic method that the Resorcinol pore sphere is given the build polymeric adsorbent, and utilize this pore sphere to give the build polymeric adsorbent from natural product caffeine, theophylline, VB
12The aqueous solution in extraction separation caffeine, theophylline, VB
12Method.
Background technology
Caffeine also claims trimethyl-xanthine (1,3,7-trimethyl xanthine) is alkaloid in tealeaves, coffee, cocoa and other certain plants, content is higher in the tealeaves, be about 1%～5%, caffeine as the central nervous excitation agent, is used for central respiratory failure medically, neurasthenic treatment and eliminate tiredly etc., the method for extracting medicinal caffeine from tealeaves comprises subliming method, solvent method, absorption method and supercritical CO
2Extraction process (the Huang cross board at the rear of an ancient carriage that continues, herbal medicine, 1999,30 (6): 473～475), with the existing report of charcoal absorption caffeine (Kaz SaulNorman, EP, 0,076,620A2,1982), document (HeBing Lin, the Huang Wenqiang chief editor, ion-exchange and polymeric adsorbent, Shanghai: Science and Technology of Shanghai education publishing house, spoken of patent XAD-4 1995:436), Duolite S-761 resin absorption is separated caffeine, therefore, also is an important method with adsorption resin method extraction separation caffeine from the aqueous solution.
Theophylline is the representative medicine of methyl xanthine, is used for obstructive pulmonary disease (COPD) patient's treatment more and more.It is reported (Hu Xien, white and moist life, Wang Xuejun, Tsing-Hua University's journal (natural science edition), 1996,36 (12): 13～17) quantity discharged of factory's theophylline mother liquor of annual output 1000t caffeine is 12kt, will cause serious waste as not reclaiming.
VB
12In human body to playing crucial effect in life such as transmission, storage and activation, electron transport and the enzyme catalysis of oxygen and the chemical process.Medically, VB
12Be anti-anemic, be used for megaloblastic anemia and neuritic assisting therapy.Vitamin V B
12The preparation Wisk plays an important role to the wound healing that promotes burn, radioactive rays to cause, with vitamin V B
12Be used for prevention and treatment oral mucositis, equally also obtained good prevention effect, the existing VB that discovers
12Shortage relevant with diabetes.Because VB
12Structure more complicated, chemosynthesis are very difficult, present medicinal VB
12Be still and from fermented liquid, extract.From fermented liquid, separate VB
12Continue to use solvent method, this method expends a large amount of solvents always, and is difficult to remove multiple proteins wherein.Resin adsorption method was applied to fractionation by adsorption VB from fermented liquid afterwards
12, quality product is improved in (HeBing Lin, Huang Wenqiang chief editor, ion-exchange and polymeric adsorbent, Shanghai: Science and Technology of Shanghai education publishing house, 1995), but effect is unsatisfactory.
Conventional resin is limited to the middle pharmaceutically active ingredient adsorptive power that contains hydrogen bond receptor, and phenolic hydroxyl group to be a good hydrogen-bond donor easily form hydrogen bond with the middle pharmaceutically active ingredient that contains hydrogen bond receptor.Because caffeine, theophylline molecule all are good hydrogen bond receptors, and phenolic hydroxyl group is good hydrogen-bond donor, can form hydrogen bond between them, in addition, VB
12Contain a large amount of amide functional groups in the molecule, wherein carbonyl energy and phenolic hydroxyl group form hydrogen bond action, and according to this fact, we wish to synthesize the polymeric adsorbent of phenolic hydroxy group.That adopts that copolymerization method prepares phenolic hydroxy group gives the build polymeric adsorbent, reactions steps is many, and the comparatively small amt of resin phenolic hydroxy group is to containing the limited (Li Aimin of organism adsorptive power of hydrogen bond receptor, Zhang Quanxing, Liu Fuqiang, Fei Zhenghao, Wang Xuejiang, Chen Jinlong, ion-exchange and absorption, 2001,17 (6): 515～525; Xu Mingcheng, Liu Juxiang, Fan Yunge, Shi Zuoqing, Shi Rongfu, Jin Xiaonong, HeBing Lin, Xu Mancai, ion-exchange and absorption, 2001,16 (1): 16～21) containing the Resorcinol pore sphere by the preparation of anti-phase suspension polycondensation method gives the build polymeric adsorbent, and method is simple, and the quantity of phenolic hydroxy group is more, stronger to the organic adsorptive power of hydrogen bond receptor, will contain the Resorcinol pore sphere and be used for aqueous systems to theophylline, caffeine, VB for the build polymeric adsorbent
12The extraction separation of medicine is to theophylline, caffeine, VB
12The extraction separation of medicine has been opened up a new approach.
The relevant both at home and abroad at present Resorcinol pore sphere that contains does not appear in the newspapers to the build polymeric adsorbent is synthetic.Contain the Resorcinol pore sphere and give the build polymeric adsorbent, cause its absorption caffeine, theophylline, VB owing to contain more strong polar group phenolic hydroxyl group-OH
12Middle pharmaceutically active ingredient dominant mechanism be adsorption by hydrogen bond mechanism.
Containing the Resorcinol pore sphere gives the build polymeric adsorbent not only to theophylline, caffeine, VB
12Medicine has absorption property preferably, but also can cooperate certain density hydrochloric acid soln to carry out effective wash-out with methyl alcohol or its aqueous solution or its, and is reusable behind the wash-out.
Summary of the invention
The object of the present invention is to provide a kind of contain that the Resorcinol pore sphere is given the synthetic method of build polymeric adsorbent and in the aqueous solution to caffeine, theophylline, VB
12Application method during extract drugs is separated.Contain the Resorcinol pore sphere by the preparation of anti-phase suspension polycondensation method and give the build polymeric adsorbent, water content is higher, and the quantity of phenolic hydroxy group is also more, and technology is simple, and a step finishes.
The objective of the invention is to be achieved through the following technical solutions:
Contain the synthetic of Resorcinol pore sphere type adsorption resin, give the build polymeric adsorbent, comprise following compositions with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96:
Oil phase: liquid wax;
Reaction monomers: Paraformaldehyde 96, Resorcinol, phenol;
Pore-creating agent: ethylene glycol;
Dispersion agent: Span80; (anhydrosorbitol acid anhydride monoleate)
Catalyzer: the concentrated hydrochloric acid that contains (HCl) 36～38%.
Contain the synthetic of Resorcinol pore sphere type adsorption resin, comprise following compositions for the build polymeric adsorbent with the synthetic Resorcinol pore sphere that contains of formalin:
Oil phase: liquid wax;
Reaction monomers: formalin (content of HCHO is 36～38%), Resorcinol, phenol;
Pore-creating agent: ethylene glycol;
Dispersion agent: Span80;
Catalyzer: the concentrated hydrochloric acid that contains (HCl) 36～38%.
Aforesaidly contain the synthetic of Resorcinol pore sphere type adsorption resin, the outward appearance of this resin is a spheroid, be brown, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 30～120nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 60～100m
2/ g, water content 30～50%, content of phenolic hydroxyl groups 2～3.72mmol/g.
Aforesaidly contain the synthetic of Resorcinol pore sphere type adsorption resin, the outward appearance of this resin is a spheroid, be faint yellow or yellow, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 50～300nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 100～200m
2/ g, water content 40～65%, content of phenolic hydroxyl groups 1.5～2.5mmol/g.
Aforesaidly contain the synthetic of Resorcinol pore sphere type adsorption resin, give the preparation method of build polymeric adsorbent, comprise following steps with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96:
(1) ethylene glycol, Paraformaldehyde 96, Resorcinol, phenol are pressed 10.9:3.7:0.7:1 (mol ratio) mixing, added 1～2% dispersion agent Span80 in above-mentioned system, continue to be stirred to evenly.Oil phase: the liquid wax of getting 4～6 times of volumes;
(2) mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
(3) add the concentrated hydrochloric acid that 2mL contains (HCl) 36～38%, continued stirring and constant temperature 2 hours, regulate stirring velocity, make oil droplet size to fit (giving body polymeric adsorbent sphere diameter size to fit) with the pore sphere that contains Resorcinol that guarantees to generate, slowly be warming up to 82 ℃ of isothermal reaction 1h, be warming up to 100 ℃ of reactions 1.5 hours, be warming up to 130～140 ℃ of reaction 5h;
(4) discharging after polyreaction is finished leaches resin, and repeatedly washs with the aqueous solution of tensio-active agent preparation, and acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
Aforesaidly contain the synthetic of Resorcinol pore sphere type adsorption resin, give the preparation method of build polymeric adsorbent, comprise following steps with the synthetic pore sphere that contains Resorcinol of formalin:
(1) with the content of ethylene glycol, formalin HCHO be 36～38%, Resorcinol, phenol be by 10.9:3.7:0.7:1 (mol ratio) mixing, adds 1～2% dispersion agent Span80 in above-mentioned system, continue to be stirred to evenly.Oil phase: the liquid wax of getting 4～6 times of volumes;
(2) mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
(3) add the concentrated hydrochloric acid that 2mL contains (HCl) 36～38%, continued stirring and constant temperature 2 hours, regulate stirring velocity, make oil droplet size to fit (giving body polymeric adsorbent sphere diameter size to fit) with the pore sphere that contains Resorcinol that guarantees to generate, slowly be warming up to 82 ℃ of isothermal reaction 1h, be warming up to 100 ℃ of reactions 1.5 hours, water trap is told the water of generation, when the water yield to be told no longer increases, be warming up to 130～140 ℃ of reaction 5h;
(4) discharging after polyreaction is finished leaches resin, and with the solution washing of tensio-active agent preparation, and acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
The application method that contains the Resorcinol pore sphere type adsorption resin, caffeine, theophylline, the VB of this resin to containing hydrogen bond receptor
12Reusable behind absorption, desorb, the wash-out.
The aforesaid application method that contains the Resorcinol pore sphere type adsorption resin, the method from caffeine extraction with aqueous solution caffeine may further comprise the steps:
(1) polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, the resin volume is in the post of 5mL～2.5L, device resin post;
(2) with the caffeine water solution flow in above-mentioned resin column, caffeine is attracted in the resin, after washing with 1MHCl and 40% methanol solution wash-out;
The flow velocity of (3) absorption, washing, desorb be 1.5～2.5 bed volumes/hour, stripping liquid promptly gets pulverous whitening coffee because of product through vacuum-drying, the caffeine rate of recovery is 90～95%, the polymeric adsorbent behind the wash-out can be reused.
The aforesaid application method that contains the Resorcinol pore sphere type adsorption resin, the method from theophylline extraction with aqueous solution theophylline may further comprise the steps:
(1) polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, the resin volume is in the post of 5mL～2.5L, device resin post;
(2) with the theophylline water solution flow in above-mentioned resin column, theophylline is attracted in the resin, after washing with 1MHCl and 80% methanol solution wash-out;
The flow velocity of (3) absorption, washing, desorb be 1.5～3 bed volumes/hour, stripping liquid promptly gets the theophylline product of white powder through vacuum-drying, the theophylline rate of recovery is 85～90%, the polymeric adsorbent behind the wash-out can be reused.
The aforesaid application method that contains the Resorcinol pore sphere type adsorption resin is from VB
12Extraction with aqueous solution VB
12Method, may further comprise the steps:
(1) polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, the resin volume is in the post of 5mL～2.5L, device resin post;
(2) with VB
12Water solution flow in above-mentioned resin column, VB
12Be attracted in the resin, after washing with 80% methanol solution wash-out;
The flow velocity of (3) absorption, washing, desorb be 1.1～1.5 bed volumes/hour, stripping liquid promptly gets the VB of red powder shape through vacuum-drying
12Product, VB
12The rate of recovery is 60～85%, and the polymeric adsorbent behind the wash-out can be reused.
Advantage of the present invention and effect are:
Contain the Resorcinol pore sphere by anti-phase suspension polycondensation method preparation and give the build polymeric adsorbent, water content is higher, and the quantity of phenolic hydroxy group is also more, and technology is simple, and a step finishes, and the one-time investment cost is low, be easy to industrialized production.
Give the build polymeric adsorbent from caffeine, theophylline, VB with the pore sphere that contains Resorcinol
12Extraction with aqueous solution caffeine, theophylline, VB
12Medicine is compared with traditional solvent extration, and technology is simple, do not use toxicity and volatile organic solvent in the technical process, and safe and reliable, production cost is lower.
The caffeine that the present invention extracts can be used for central respiratory failure, neurasthenic treatment and eliminate tired etc.The theophylline that extracts can be used for obstructive pulmonary disease (COPD) patient's treatment.The VB that extracts
12Can be used for megaloblastic anemia and neuritic assisting therapy, also can be used for prevention and treatment oral mucositis, the wound healing that its preparation Wisk can promote to burn, radioactive rays cause.
Description of drawings
Fig. 1 is for giving build polymeric adsorbent SEM photo figure (* 80) with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96;
Fig. 2 is for giving build polymeric adsorbent SEM photo figure (* 80) with the synthetic pore sphere that contains Resorcinol of formalin;
Fig. 3 is for giving build polymeric adsorbent SEM photo figure (* 10 with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96
4);
Fig. 4 is for giving build polymeric adsorbent SEM photo figure (* 10 with the synthetic pore sphere that contains Resorcinol of formalin
4);
Fig. 5 is for giving build polymeric adsorbent SEM photo figure (* 2 * 10 with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96
4);
Fig. 6 is for giving build polymeric adsorbent SEM photo figure (* 2 * 10 with the synthetic pore sphere that contains Resorcinol of formalin
4).
Embodiment
The present invention is described in detail in conjunction with the embodiments with reference to the accompanying drawings.
Embodiment 1
Step 1: ethylene glycol 60mL, Paraformaldehyde 96 11.0g, Resorcinol 7.3g, phenol 9.4g are pressed 10.9:3.7:0.7:1 (mol ratio) mixing, add 1.5g dispersion agent Span80 (anhydrosorbitol acid anhydride monoleate) in above-mentioned system, continue to be stirred to evenly.Oil phase: get 400mL liquid wax;
Step 2: the mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
Step 3: add the concentrated hydrochloric acid that 2mL contains (HCl) 36～38%, continued stirring and constant temperature 2 hours, regulate stirring velocity, make oil droplet size to fit (giving body polymeric adsorbent sphere diameter size to fit) with the pore sphere that contains Resorcinol that guarantees to generate, slowly be warming up to 82 ℃ of isothermal reaction 1h, be warming up to 100 ℃ of reactions 1.5 hours, be warming up to 130～140 ℃ of reaction 5h;
Step 4: discharging after polyreaction is finished, leach resin, and with repeatedly (so that dispersion agent, the pore-creating agent major part be removed) washing of the aqueous solution of tensio-active agent preparation, acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
Embodiment 2
Step 1: ethylene glycol 60mL, formalin 27mL, Resorcinol 7.3g, phenol 9.4g are pressed 10.9:3.7:0.7:1 (mol ratio) mixing, add 1.5g dispersion agent Span80 in above-mentioned system, continue to be stirred to evenly.Oil phase: get 400mL liquid wax;
Step 2: the mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
Step 3: add the concentrated hydrochloric acid that 2mL contains (HCl) 36～38%, continued stirring and constant temperature 2 hours, regulate stirring velocity, make oil droplet size (giving body polymeric adsorbent sphere diameter size to fit) suitable with the pore sphere that contains Resorcinol that guarantees to generate, slowly be warming up to 82 ℃ of isothermal reaction 1h, be warming up to 100 ℃ of reactions 1.5 hours, water trap is told the water of generation, when the water yield to be told no longer increases, be warming up to 130～140 ℃ of reaction 5h;
Step 4: discharging after polyreaction is finished, leach resin, and with repeatedly (so that dispersion agent, the pore-creating agent major part be removed) washing of the aqueous solution of tensio-active agent preparation, acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
Embodiment 3
Step 1: polymeric adsorbent is contained in post directly in the glass adsorption column of 10mm, and the resin volume is in the post of 5mL, device resin post;
Step 2: the caffeine solution of 3000mg/L is flowed through in the above-mentioned resin column, and caffeine is attracted in the resin, after washing with the methanol solution wash-out of 1MHCl and 40%;
Step 3: the flow velocity of absorption, washing, desorb be 1.5～2.5 bed volumes/hour, stripping liquid promptly gets pulverous whitening coffee because of product through vacuum-drying, the caffeine rate of recovery is 90～95%, the polymeric adsorbent behind the wash-out can be reused.
Embodiment 4
Step 1: polymeric adsorbent is contained in post directly in the glass adsorption column of 10mm, and the resin volume is in the post of 5mL, device resin post;
Step 2: in above-mentioned resin column, theophylline is attracted in the resin with 3000mg/L theophylline water solution flow, uses the methanol solution wash-out of 1MHCl and 80% after washing;
Step 3: the flow velocity of absorption, washing, desorb be 1.5～3 bed volumes/hour, stripping liquid promptly gets the theophylline product of white powder through vacuum-drying, the theophylline rate of recovery is 85～90%, the polymeric adsorbent behind the wash-out can be reused.
Embodiment 5
Step 1: polymeric adsorbent is contained in post directly in the glass adsorption column of 10mm, and the resin volume is in the post of 5mL, device resin post;
Step 2: with 1000mg/L VB
12Water solution flow in above-mentioned resin column, VB
12Be attracted in the resin, after washing with 80% methanol solution wash-out;
Step 3: the flow velocity of absorption, washing, desorb be 1.1～1.5 bed volumes/hour, stripping liquid promptly gets the VB of red powder shape through vacuum-drying
12Product, VB
12The rate of recovery is 60～85%, and the polymeric adsorbent behind the wash-out can be reused.
Because of accompanying drawing is a photo, small character wherein is unintelligible, but does not influence the understanding to the technical program.
Fig. 1, Fig. 3, Fig. 5 are for giving build polymeric adsorbent SEM photo figure with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96, the outward appearance of this resin is a spheroid, be brown, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 30～120nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 60～100m
2/ g.
Fig. 2, Fig. 4, Fig. 6 are for giving build polymeric adsorbent SEM photo figure with the synthetic pore sphere that contains Resorcinol of formalin, the outward appearance of this resin is a spheroid, be faint yellow or yellow, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 50～300nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 100～200m
2/ g.
Claims (5)
1. the synthetic method that contains the Resorcinol pore sphere type adsorption resin is characterized in that giving the build polymeric adsorbent with the synthetic pore sphere that contains Resorcinol of Paraformaldehyde 96, and step is as follows:
(1) with pore-creating agent: ethylene glycol, reaction monomers: Paraformaldehyde 96, Resorcinol, phenol 10.9: 3.7: 0.7 in molar ratio: 1 mixing, add 1～2% dispersion agent Span80, continue to be stirred to evenly; Oil phase: the liquid wax of getting 4～6 times of volumes;
(2) mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
(3) add the 2mL catalyzer: HCl content is 36～38% concentrated hydrochloric acid, continued stirring and constant temperature 2 hours, regulate stirring velocity, make the oil droplet size to fit, give body polymeric adsorbent sphere diameter size to fit with the pore sphere that contains Resorcinol that guarantees to generate, slowly be warming up to 82 ℃ of isothermal reaction 1h, be warming up to 100 ℃ of reactions 1.5 hours, be warming up to 130～140 ℃ of reaction 5h;
(4) discharging after polyreaction is finished leaches resin, and repeatedly washs with the aqueous solution of tensio-active agent preparation, and acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
2. the synthetic method that contains the Resorcinol pore sphere type adsorption resin as claimed in claim 1, the outward appearance that it is characterized in that this resin is a spheroid, be brown, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 30～120nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 60～100m
2/ g, water content 30～50%, content of phenolic hydroxyl groups 2～3.72mmol/g.
3. the synthetic method that contains the Resorcinol pore sphere type adsorption resin is characterized in that giving the build polymeric adsorbent with the synthetic pore sphere that contains Resorcinol of formalin, and step is as follows:
(1) with pore-creating agent: ethylene glycol, reaction monomers: HCHO content is 36～38% formalin, Resorcinol, phenol 10.9: 3.7: 0.7 in molar ratio: 1 mixing, add 1～2% dispersion agent Span80, continue to be stirred to evenly; Oil phase: the liquid wax of getting 4～6 times of volumes;
(2) mixture in (1) is added in the liquid wax, begin to stir, 100～150 rev/mins, heat up 70～75 ℃ constant temperature 1～2 hour;
(3) add the 2mL catalyzer: HCl content is 36～38% concentrated hydrochloric acid, continued stirring and constant temperature 2 hours, regulate stirring velocity, make the oil droplet size to fit, give body polymeric adsorbent sphere diameter size to fit, slowly be warming up to 82 ℃ of isothermal reaction 1h with the pore sphere that contains Resorcinol that guarantees to generate, be warming up to 100 ℃ of reactions 1.5 hours, water trap is told the water of generation, when the water yield to be told no longer increases, is warming up to 130～140 ℃ of reaction 5h;
(4) discharging after polyreaction is finished leaches resin, and with the solution washing of tensio-active agent preparation, and acetone extracting, vacuum-drying, screening are prepared particle diameter and are the pore sphere that contains Resorcinol of 0.2～1mm and give the build polymeric adsorbent.
4. the synthetic method that contains the Resorcinol pore sphere type adsorption resin as claimed in claim 3, the outward appearance that it is characterized in that this resin is a spheroid, be faint yellow or yellow, the sphere diameter size is at 0.2～1mm, the surface has spongy or cellular structure, the surface has porousness, and mean pore size is 50～300nm, and skeletal density is 1.08～1.32g/cm
3, specific surface area 100200m
2/ g, water content 40～65%, content of phenolic hydroxyl groups 1.5～2.5mmol/g.
5. the application method that contains the Resorcinol pore sphere type adsorption resin is characterized in that extracting the caffeine, theophylline, the VB that contain hydrogen bond receptor in the aqueous solution
12Method be respectively:
(1) method from caffeine extraction with aqueous solution caffeine is: polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, and the resin volume is in the post of 5mL～2.5L, device resin post; In above-mentioned resin column, caffeine is attracted in the resin with the caffeine water solution flow, uses the methanol solution wash-out of 1M HCl and 40% after washing; The flow velocity of absorption, washing, desorb be 1.5～2.5 bed volumes/hour, stripping liquid promptly gets pulverous whitening coffee because of product through vacuum-drying, the caffeine rate of recovery is 90～95%, the polymeric adsorbent behind the wash-out can be reused;
(2) method from theophylline extraction with aqueous solution theophylline is: polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, and the resin volume is in the post of 5mL～2.5L, device resin post; In above-mentioned resin column, theophylline is attracted in the resin with the theophylline water solution flow, uses the methanol solution wash-out of 1MHCl and 80% after washing; The flow velocity of absorption, washing, desorb be 1.5～3 bed volumes/hour, stripping liquid promptly gets the theophylline product of white powder through vacuum-drying, the theophylline rate of recovery is 85～90%, the polymeric adsorbent behind the wash-out can be reused;
(3) from VB
12Extraction with aqueous solution VB
12Method be: polymeric adsorbent is contained in the glass adsorption column that post directly is 10～50mm, and the resin volume is in the post of 5mL-2.5L, device resin post; With VB
12Water solution flow in above-mentioned resin column, VB
12Be attracted in the resin, after washing with 80% methanol solution wash-out; The flow velocity of absorption, washing, desorb be 1.1～1.5 bed volumes/hour, stripping liquid promptly gets the VB of red powder shape through vacuum-drying
12Product, VB
12The rate of recovery is 60～85%, and the polymeric adsorbent behind the wash-out can be reused.
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| CN1046533A (en) * | 1989-03-15 | 1990-10-31 | 陶氏化学公司 | The method for preparing adsorptive porous resin beads |
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| 酚醛型吸附树脂吸附VB12的热力学研究. 王重等.功能高分子学报，第16卷第1期. 2003 * |
| 酚醛型吸附树脂吸附咖啡因的热力学研究. 王重等.离子交换与吸附，第19卷第1期. 2003 |
| 酚醛型吸附树脂吸附咖啡因的热力学研究. 王重等.离子交换与吸附，第19卷第1期. 2003 * |
| 酚醛型吸附树脂对VB12的吸附性能研究. 王重等.高分子学报，第1期. 2004 |
| 酚醛型吸附树脂对VB12的吸附性能研究. 王重等.高分子学报，第1期. 2004 * |
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| 酚醛型吸附树脂对咖啡因和茶碱吸附性能的研究. 王重等.高等学校化学学报，第24卷第10期. 2003 * |
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