CN105418946A - Preparation method of secondarily-crosslinked adsorption resin - Google Patents
Preparation method of secondarily-crosslinked adsorption resin Download PDFInfo
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Abstract
The invention relates to a preparation method of secondarily-crosslinked adsorption resin. The preparation method includes a secondary crosslinking step in which polystyrene resin chloromethylated bead is subjected to a secondary crosslinking reaction to obtain the secondarily-crosslinked adsorption resin. The secondary crosslinking step includes a still-standing and swelling process, in which 1 part by weight of the polystyrene resin chloromethylated bead, 0.5-4 parts by weight of an alcohol substance and 4-6 parts by weight of 1,2-dichloroethane are added to perform the still-standing and swelling process. The secondarily-crosslinked adsorption resin is used for blood purification. Through the preparation method, residual chloromethyl groups in ultrahigh-crosslinked polystyrene-divinylbenzene resin, thereby increasing chemical stability and blood compatability of the adsorption resin.
Description
Technical field
The present invention relates to a kind of preparation method of the secondary crosslinking polymeric adsorbent for blood purification, specifically, relate to a kind of preparation method to the secondary crosslinking polymeric adsorbent that secondary crosslinking step is improved.
Background technology
Blood perfusion is, by power, the blood of patient is caused extracorporeal circulation, by there is the sorbent material of special adsorption function and the endogenous removed in blood samples of patients or exogenous poisonous substance or morbid substance in blood perfusion device, thus reach a kind for the treatment of technology of blood purification.At present, blood perfusion technique be widely used in renal failure, severe liver diseases, poisoning, infect and critical illness field.
Sorbent material in blood perfusion device can be resin sorbent, acticarbon, carbide resin sorbent material, natural macromolecule adsorbent etc.What comparatively commonly use in resin sorbent is neutral macroporous adsorbent resin, and it is by styrene-divinylbenzene microballoon (being commonly called as Archon) polymerization, chloromethylation, then the superhigh cross-linking high-specific surface area resin obtained through Friedel-Crafts reaction (Friedel-Crafts).Such as, be disclose a kind of such preparation method in the Chinese invention patent application of CN201410013169.0 at application number, it adopts 1,2-ethylene dichloride to carry out standing swelling in rear crosslinked (secondary crosslinking) step.
But, because the post-crosslinking reaction in above-mentioned preparation process is thorough not, cause the residual quantity of chloromethyl in final product large, generally can account for 2% to 4% of resin quality.This reduces the chemical stability of resin sorbent, change resin hydrophilicity and hydrophobicity, make the blood compatibility of resin be deteriorated, and its hydrolysate easily corrodes follow-up production unit simultaneously.
In publication, application number is disclose a kind of ethanol that adopts in the Chinese invention patent application of CN200910143423.8 to replace ethylene dichloride etc. as the swelling agent of the post-crosslinking reaction of chloromethylation products.But, adopt the method carry out rear crosslinked time, the swelling effect of ethanol is limited, the degree causing post-crosslinking reaction to carry out is extremely low, after gained, the specific surface area of cross-linking products (absorbent resin) is little, chlorine residual content is high, and its to blood exogenous or endogenous toxic substance Scavenging activity very low, blood compatibility is poor.
Summary of the invention
Main purpose of the present invention is to provide a kind of preparation method reducing residual secondary crosslinking (the being cross-linked afterwards) polymeric adsorbent of chlorine.
To achieve these goals, the preparation method of secondary crosslinking polymeric adsorbent provided by the invention comprises secondary crosslinking step: cross secondary crosslinking by polystyrene resins chlorine ball warp and be obtained by reacting secondary crosslinking polymeric adsorbent; Comprise standing swelling process in secondary crosslinking step, by weight, add 1 part of polystyrene resins chlorine ball, 0.5 part to 4 parts alcohols material and 4 parts to 6 part 1,2-ethylene dichloride, carry out standing swelling process, this secondary crosslinking polymeric adsorbent is used for blood purification.
Therefore, by adding a certain proportion of alcohols material in secondary crosslinking reaction, utilize the chemical reaction between alcoholic extract hydroxyl group and chloromethyl, consume the residual chlorine in cross-linked resin, thus reduce the residual chloromethyl of crosslinked polystyrene-divinylbenzene resins (one of polystyrene resins), reach the object improving polymeric adsorbent chemical stability and blood compatibility.Meanwhile, by increasing the hydrophilic radical content on polymeric adsorbent surface, improve resin wetting ability, reduction resin as erythrocytic destruction, improves the blood compatibility of resin to blood formed element further; Pass through hemolytic test, find that the resin-phase prepared according to the inventive method is for the resin obtained before improvement, its hemolysis rate obviously reduces, and resin is to albumin, adsorption rate and the thrombocyte retention rate of total protein also obviously reduce compared with before-improvement, thus further increase the security of resin as blood perfusion sorbent material, the data of specifically vide infra middle table 1, table 2 and table 3 and relevant analysis conclusion.In addition, visible by the data of Fourier's infared spectrum in Fig. 1, compared to the resin (A) of other type, carbonyl peak (1708cm in the resin (B, C, D, E) that preparation method of the present invention obtains
-1) and the raising of deriveding group characteristic peak area; And the display of analyses result, in the resin that method provided by the invention obtains, the content of oxygen element adds 20% to 50%.
A preferred scheme is, the specific surface area of secondary crosslinking polymeric adsorbent is 500m
2/ g to 1200m
2/ g, mean pore size is 2nm to 15nm.
Therefore, by preferably limiting the specific surface area of secondary crosslinking polymeric adsorbent and mean pore size, obtain the resin that character is more excellent.
A preferred scheme is, the massfraction that in secondary crosslinking polymeric adsorbent, the residual quantity of chlorine accounts for resin total mass is less than 1.5%.
Therefore, the residual quantity of the polymeric adsorbent chlorine that the residual quantity of chlorine obtains lower than existing preparation method.
A preferred scheme is, in standing swelling process: the amount of the alcohols material added is 1 part to 2 parts, and time remaining 3 is little of 5 hours.
From such scheme, optimize oxygen introduction volume and the swelling time of alcohols material in polymeric adsorbent.
A preferred scheme is, alcohols material is at least one in methyl alcohol, ethanol, propyl alcohol.
Therefore alcohols material can also be the alcohol of other type existing, but three kinds of alcohol are preferred alcohol above, not only with low cost, and are easy to the carrying out controlling swelling process.
A preferred scheme is, controlling chlorine content ranges in polystyrene resins chlorine ball is 8% to 18%.
Therefore, being conducive to follow-up secondary crosslinking step like this, avoiding the impact of the too high secondary crosslinking polymeric adsorbent character on finally obtaining of chlorinity.
A preferred scheme is, after standing swelling process, adds zinc chloride or the iron trichloride of 0.2 part to 0.5 part, after being warming up to 80 DEG C to 90 DEG C under stirring, reaction 10 is little of 20 hours, leach mother liquor after being cooled to room temperature, wash rear acetone extraction, wash removing acetone with water; Suction filtration, drying obtain secondary crosslinking polymeric adsorbent.
A preferred scheme is, the step performed successively below obtains polystyrene resins chlorine ball:
Suspension polymerization step: first, at room temperature configure aqueous phase and oil phase respectively, oil phase and aqueous phase volume ratio are 1:1.5 to 1:3, oil phase comprises the organic mixture that styrene monomer, Vinylstyrene class monomer, initiator and pore-creating agent are formed, the mass ratio of styrene monomer and Vinylstyrene class monomer is 5:1 to 12:1, aqueous phase comprises the aqueous solution of dispersion agent and water formation, and the consumption of dispersion agent is 0.8% to 2% of aqueous phase weight; Initiator amount is 0.5% to 2% of monomer total amount massfraction, and the consumption of pore-creating agent is 60% to 200% of total monomer weight massfraction; Then, oil phase is poured into dispersed with stirring in aqueous phase; Then, be warming up to 50 DEG C to 90 DEG C, the reaction times is little of 20 hours 6, and after reaction system solidification, stopped reaction obtains polystyrene resins Archon, and the particle size range of polystyrene resins Archon is 0.4mm to 2mm.
Chloromethylation step: employing chloromethyl ether is reaction solvent, zinc chloride or iron trichloride are catalyzer, and the proportioning of reaction system is: the polystyrene resins Archon often adding 1g, then add the catalyzer of 2ml to 7mL chloromethyl ether and 0.2g to 0.5g; First the polystyrene resins Archon of drying is added reaction vessel; Then chloromethyl ether is added swelling 1 little of 5 hours; Then add catalyzer temperature-elevating to 45 DEG C to react 20 hours 24 hours after 50 DEG C; Then be cooled to room temperature, use methyl alcohol extracting 12 hours after leaching mother liquor, washing removing methyl alcohol, suction filtration, screening, chooses the resin of particle diameter at 0.4mm to 2mm, obtains polystyrene resins chlorine ball.
Preferred scheme is that initiator is peralcohol initiator and/or azo-initiator further; Pore-creating agent is good solvent or poor solvent;
Preferred scheme is that peralcohol initiator comprises benzoyl peroxide and/or peroxidized t-butyl perbenzoate further again, and azo-initiator comprises Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile); Good solvent is toluene and/or dimethylbenzene, and poor solvent is higher alcohols, alkanes or ketone; Higher alcohols is hexanol, hexalin, and alkanes is at least one in normal heptane, hexanaphthene, gasoline, kerosene, whiteruss, and ketone is hexone; Dispersion agent is at least one in gelatin, polyvinyl alcohol, polyvinyl alcohol-Sodium dodecylbenzene sulfonate.
Accompanying drawing explanation
Fig. 1 is Fourier's infared spectrum of the polymeric adsorbent that preparation method's embodiment 1 to 4 of secondary crosslinking polymeric adsorbent of the present invention and reference examples 1 obtain.
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment
In some embodiments of the present invention, according to the methods below for the preparation of the secondary crosslinking polymeric adsorbent of blood purification.
Step 1: prepare polystyrene resins Archon by suspension polymerization step, polystyrene resins Archon can be understood as (once) crosslinked polystyrene resinoid Archon for the first time.
First, at room temperature configure aqueous phase and oil phase respectively, oil phase and aqueous phase volume ratio are 1:1.5 to 1:3.Oil phase comprises the organic mixture that styrene monomer, Vinylstyrene class monomer (linking agent), initiator and pore-creating agent are formed, and the mass ratio of styrene monomer and Vinylstyrene class monomer is 5:1 to 12:1.Aqueous phase comprises the aqueous solution of dispersion agent and water formation, and the consumption of dispersion agent is 0.8% to 2% of aqueous phase weight.Initiator amount is 0.5% to 2% of monomer total amount massfraction.The consumption of pore-creating agent is 60% to 200% of total monomer weight massfraction.Then, oil phase being poured into dispersed with stirring in aqueous phase, the liquid pearl of appropriate particle size can be obtained by controlling stirring velocity.Then, be warming up to 50 DEG C to 90 DEG C, the reaction times is little of 20 hours 6, and after reaction system solidification, stopped reaction obtains polystyrene resins Archon, and the particle size range of polystyrene resins Archon is 0.4mm to 2mm.Reaction process is above preferred scheme, and in other embodiments, can also carry out independent adjustment to above-mentioned multiple reaction parameter, can obtain polystyrene resins Archon equally.
Wherein, initiator is peralcohol initiator and/or azo-initiator; Pore-creating agent is good solvent or poor solvent.Peralcohol initiator comprises benzoyl peroxide and/or peroxidized t-butyl perbenzoate, and azo-initiator comprises Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile).Good solvent is toluene and/or dimethylbenzene.Poor solvent is higher alcohols, alkanes or ketone, and higher alcohols is hexanol, hexalin, and alkanes is at least one in normal heptane, hexanaphthene, gasoline, kerosene, whiteruss, and ketone is hexone.Dispersion agent is at least one in gelatin, polyvinyl alcohol, polyvinyl alcohol-Sodium dodecylbenzene sulfonate.
Step 2: obtain polystyrene resins chlorine ball by chloromethylation step.
Employing chloromethyl ether is reaction solvent, and zinc chloride or iron trichloride are catalyzer, and the proportioning of reaction system is: the polystyrene resins Archon often adding 1g, then add the catalyzer of 2mL to 7mL chloromethyl ether and 0.2g to 0.5g.First the polystyrene resins Archon of drying is added reaction vessel; Then chloromethyl ether is added swelling 1 little of 5 hours; Then add catalyzer temperature-elevating to 45 DEG C to react 20 hours 24 hours after 50 DEG C; Then be cooled to room temperature, leach with methyl alcohol extracting 12 hours after mother liquor, washing removing methyl alcohol, concrete operations are up to without methyl alcohol taste, and suction filtration, sieves, choose the resin of particle diameter at 0.4mm to 2mm, obtain chlorine ball.In a preferred embodiment, controlling chlorine content ranges in polystyrene resins chlorine ball is 8% to 18%.Reaction process is above preferred scheme, and in other embodiments, can also carry out independent adjustment to above-mentioned multiple reaction parameter, can obtain polystyrene resins chlorine ball equally.
Step 3: prepare secondary crosslinking polymeric adsorbent by secondary crosslinking step.
Cross secondary crosslinking by polystyrene resins chlorine ball warp and be obtained by reacting secondary crosslinking polymeric adsorbent.Comprise standing swelling process in secondary crosslinking step, by weight, add 1 part of polystyrene resins chlorine ball, 0.5 part to 4 parts alcohols material and 4 parts to 6 part 1,2-ethylene dichloride, carry out standing swelling process.In some preferred embodiments, after standing swelling process, add zinc chloride or the iron trichloride of 0.2 part to 0.5 part, after being warming up to 80 DEG C to 90 DEG C under stirring, reaction 10 is little of 20 hours, mother liquor is leached after being cooled to room temperature, wash rear acetone extraction, wash removing acetone with water, be washed to without acetone taste during concrete operations; Suction filtration, drying obtain secondary crosslinking polymeric adsorbent.In other preferred embodiment, in standing swelling process: the amount of the alcohols material added is 1 part to 2 parts, and time remaining 3 is little of 5 hours, and alcohols material is at least one in methyl alcohol, ethanol, propyl alcohol.
In some preferred embodiments, the specific surface area of the secondary crosslinking polymeric adsorbent that above-mentioned preparation method obtains is 500m
2/ g to 1200m
2/ g, mean pore size is 2nm to 15nm.The massfraction that in secondary crosslinking polymeric adsorbent, the residual quantity of chlorine accounts for resin total mass is less than 1.5%.
In other embodiments, styrene monomer is at least one of vinylbenzene, vinyl toluene, ethyl styrene or Vinylstyrene, and the mode that polystyrene resins is also bought by business obtains, or is obtained by the polyreaction of other type.
According to the preparation method of the secondary crosslinking polymeric adsorbent provided, obtain multiple specific embodiments below above, and, in order to the beneficial effect of preparation method provided by the invention is described, also show in particular two reference examples.
embodiment 1:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 1.5wt% gelatin is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 6.94g Vinylstyrene, the 200# gasoline of 76.92g vinylbenzene, 83.86g toluene, 50.32g, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 7 hours, then be warming up to 85 DEG C of reactions 13 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (one of polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 17%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 10g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 5g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 1252m
2/ g, mean pore size is 6.42nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 8.9%.It is 1.2% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.Its infrared spectrum is as shown in C curve in Fig. 1.
embodiment 2:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 6.94g Vinylstyrene, the 200# gasoline of 76.92g vinylbenzene, 55g toluene, 45g, 1.0g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 7 hours, then be warming up to 85 DEG C of reactions 13 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 18%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 80g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 5g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 564m
2/ g, mean pore size is 8.72nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 13.1%.It is 0.67% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.Its infrared spectrum is as shown in E curve in Fig. 1.
embodiment 3:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 18.52g Vinylstyrene, 74.08g vinylbenzene, 87.97g dimethylbenzene, 69.45g hexanaphthene, 0.5g Diisopropyl azodicarboxylate, mix rear formation oil phase, join in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 7 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 11.6%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 20g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 5g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 754m
2/ g, mean pore size is 7.62nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 10.3%.It is 0.85% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.Its infrared spectrum is as shown in B curve in Fig. 1.
embodiment 4:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol-Sodium dodecylbenzene sulfonate is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 7.14g Vinylstyrene, 82.14g vinylbenzene, 89.29g toluene, 71.43g hexone, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 12 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 18.5%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 20g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 7g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 982m
2/ g, mean pore size is 6.92nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 10.4%.It is 0.98% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.Its infrared spectrum is as shown in D curve in Fig. 1.
embodiment 5:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 7.14g Vinylstyrene, 64.26g vinylbenzene, 89.29g dimethylbenzene, 71.43g hexanaphthene, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 12 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 17.5%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 30g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 7g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 972m
2/ g, mean pore size is 6.97nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 11.2%.It is 0.90% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.
embodiment 6:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 1.0wt% gelatin is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 8.25g Vinylstyrene, 66g vinylbenzene, 70.53g dimethylbenzene, 59.40g hexone, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 20 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 16.8%.
Step 3: the process that secondary crosslinking (being cross-linked afterwards) reacts is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 36g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 7g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 940m
2/ g, mean pore size is 7.82nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 11.6%.It is 0.85% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.
embodiment 7:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 1.5wt% gelatin is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 8.24g Vinylstyrene, 82.40g vinylbenzene, 81.58g toluene, 77.04g hexone, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 16 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 17.92%.
Step 3: the process that secondary crosslinking (being cross-linked afterwards) reacts is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 40g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 7g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 870m
2/ g, mean pore size is 7.32nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 12.4%.It is 0.85% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.
embodiment 8:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% gelatin is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 6.94 Vinylstyrenes, the 200# gasoline of 76.92g vinylbenzene, 55g toluene, 45g, 1.0g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 7 hours, then be warming up to 85 DEG C of reactions 13 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 17.8%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 60g dehydrated alcohol and 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 7g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of the present embodiment is 664m
2/ g, mean pore size is 8.52nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 13.1%.It is 0.70% that polymeric adsorbent after purification measures its residual chlorine through Fo Erhadefa.
reference examples 1:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol-Sodium dodecylbenzene sulfonate is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 7.14g Vinylstyrene, 82.14g vinylbenzene, 89.29g toluene, 71.43g hexone, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 12 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 18.4%.
Step 3: the process of secondary crosslinking reaction is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add 1, the 2-ethylene dichloride of 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 5g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of this reference examples is 1244m
2/ g, mean pore size is 5.32nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 7.92%.It is 4.2% that Fo Erhadefa measures its residual chlorine.Its infrared spectrum is as shown in A curve in Fig. 1.
reference examples 2:
Step 1: the building-up process of polystyrene resins Archon is as follows.
The aqueous solution 500mL containing 2.0wt% polyvinyl alcohol-Sodium dodecylbenzene sulfonate is added, as aqueous phase after stirring and dissolving in 1000mL there-necked flask.
Get 500mL beaker, toward wherein adding 7.14g Vinylstyrene, 82.14g vinylbenzene, 89.29g toluene, 71.43g hexone, 0.5g benzoyl peroxide, mixing rear formation oil phase, joining in there-necked flask.Then be warming up to 75 DEG C under mechanical stirring, react 5 hours, then be warming up to 85 DEG C of reactions 12 hours.After reaction terminates, steam pore-creating agent, be washed to water lotion clarification, then through suction filtration, drying, screening, choose the resin of particle diameter at 0.4mm to 2mm, obtain required polystyrene-divinylbenzene Archon (polystyrene resins Archon).
Step 2: the process of chloromethylation is as follows.
First in the there-necked flask of 500mL, add the above-mentioned polystyrene-divinylbenzene Archon of 30g, and add the chloromethyl ether of 210mL, room temperature leaves standstill 1.5 hours; Then start agitator, add 15g Zinc Chloride Anhydrous at twice, react 24 hours after being warming up to 50 DEG C; Be cooled to room temperature after reaction terminates, leach mother liquor, with methyl alcohol extracting 12 hours, wash with water to without methyl alcohol taste; Then suction filtration, dry faint yellow chlorine ball.Finally, the cl content that chlorine ball warp Fo Erhadefa tests is 18.3%.
Step 3: the process that secondary crosslinking (being cross-linked afterwards) reacts is as follows.
First in the there-necked flask of 500mL, add the chlorine ball of the above-mentioned gained of 20g, and add the dehydrated alcohol of 120g, leave standstill swelling 4 hours; Then start mechanical stirring, add 5g FERRIC CHLORIDE ANHYDROUS, be warming up to 80 DEG C, insulation reaction 20 hours.Be cooled to room temperature after reaction terminates, leach mother liquor, use acetone extraction after washing 3 times with water 12 hours, be finally washed to without acetone taste, suction filtration, dryly must be cross-linked ball (secondary crosslinking polymeric adsorbent).
The specific surface area of the secondary crosslinking polymeric adsorbent of this reference examples is 82m
2/ g, mean pore size is 35.72nm.Recording its oxygen element content through elemental microanalysis method, to account for massfraction ratio be 3.4%.After purification, Fo Erhadefa measures its residual chlorine is 14.7%.
For the corresponding secondary crosslinking polymeric adsorbent that multiple embodiment and reference examples above obtain, also carried out safety evaluation test, absorption property evaluation test, concrete evaluation procedure and result as follows.
The safety evaluation process of the test of secondary crosslinking polymeric adsorbent is as follows.
Get human normal plasma to thaw at 37 DEG C, get the secondary crosslinking polymeric adsorbent (being called for short sorbent material or resin below) that 2ml sterile saline soaks half an hour more than, blot physiological saline, according to sorbent material: blood plasma=1:10(v/v) ratio, add each 20mL of the blood plasma after thawing.Sample is placed in the gas bath constant temperature oscillation groove of 37 DEG C, adsorbs 2 hours with the speed oscillation of 160rpm.After absorption terminates, take out the upper plasma of about 1.5ml, measure the adsorption rate of albumin and total protein.The results are shown in Table 1.
Hemolysis rate and thrombocyte retention rate is measured according to GB/T16886.4-2003 and GB/T16175-1996.Test result is in table 2.
Resin absorption benchmark test process is as follows.
Get 105 DEG C of dryings resin 1g of 2 hours, physiological saline soaks half an hour more than, blots physiological saline, and toward the 35mg/L creatinine solution 25ml wherein adding deionized water preparation, be placed in the gas bath vibration case of 37 DEG C, the speed oscillation of 160rpm adsorbs 2 hours.After absorption terminates, get supernatant liquor and detect absorbancy at 232nm, make typical curve, according to typical curve conversion creatinine adsorption rate with the creatinine solution of preparation simultaneously.
Get nephropathy patient's blood plasma to thaw at 37 DEG C, get 2ml sterile saline and soak more than half an hour sorbent material, blot physiological saline, according to sorbent material: blood plasma=1:10(v/v) ratio, add each 20mL of the blood plasma after thawing.Sample is placed in the gas bath constant temperature oscillation groove of 37 DEG C, adsorbs 2 hours with the speed oscillation of 160rpm.After absorption terminates, take out about 1.5ml upper plasma, measure the content of interleukin-6 (IL-6), B2M (β 2-MG) and Rat parathyroid hormone 1-34 (PTH) in blood plasma, according to the content in initial plasma, calculate adsorption rate.The results are shown in Table 3.
The resin of table 1 embodiment and reference examples is to albumin and total protein adsorpting data
| Resin is numbered | Albumin (%) | Total protein (%) |
| Embodiment 1 | 4.2% | 8.5% |
| Embodiment 2 | 3.4% | 6.3% |
| Embodiment 3 | 6.7% | 7.2% |
| Embodiment 4 | 6.1% | 7.6% |
| Embodiment 5 | 6.6% | 8.4% |
| Embodiment 6 | 6.0% | 7.0% |
| Embodiment 7 | 3.1% | 6.6% |
| Embodiment 8 | 5.1% | 7.0% |
| Reference examples 1 | 17.2% | 14.1% |
| Reference examples 2 | 5.0% | 8.9% |
From the data of table 1, for reference examples 1, namely do not use alcohols material carry out standing swelling time, it significantly improves the absorption of albumin and total protein.
The hemolysis rate of the resin of table 2 embodiment and reference examples and thrombocyte retention rate data
| Resin is numbered | Hemolysis rate (%) | Thrombocyte retention rate (%) |
| Embodiment 1 | 2.1% | 19.1% |
| Embodiment 2 | 1.1% | 18.3% |
| Embodiment 3 | 1.3% | 18.2% |
| Embodiment 4 | 1.2% | 17.6% |
| Embodiment 5 | 3.2% | 20.6% |
| Embodiment 6 | 2.2% | 19.6% |
| Embodiment 7 | 1.0% | 21.4% |
| Embodiment 8 | 0.8% | 15.6% |
| Reference examples 1 | 13.2% | 35.4% |
| Reference examples 2 | 25.2% | 15.4% |
From the data of table 2, the hemolysis rate of the resin of embodiment 1-8 is significantly lower than the hemolysis rate of the resin of reference examples 1,2.
The resin absorption performance data of table 3 embodiment and reference examples
| Resin is numbered | IL-6 | β2-MG | iPTH | Creatinine |
| Embodiment 1 | 54.54% | 84.80% | 97.70% | 82.11% |
| Embodiment 2 | 73.90% | 93.14% | 99.20% | 45.72% |
| Embodiment 3 | 75.22% | 90.66% | 99.50% | 55.78% |
| Embodiment 4 | 64.20% | 90.86% | 98.50% | 76.64% |
| Embodiment 5 | 64.58% | 91.77% | 99.06% | 77.42% |
| Embodiment 6 | 74.92% | 92.14% | 99.80% | 76.49% |
| Embodiment 7 | 72.85% | 89.82.% | 98.70% | 75.78% |
| Embodiment 8 | 70.90% | 90.14% | 98.20% | 42.72% |
| Reference examples 1 | 36.20% | 66.02% | 85.42% | 32.14% |
| Reference examples 2 | 5.30% | 10.21% | 35.52% | 0 |
As can be seen from Table 3, the resin of embodiment 1-8 to the absorption property of IL-6, β 2-MG, iPTH, creatinine all higher than the absorption property of the resin of reference examples 1,2.
In general, the present invention by adding a certain proportion of alcohols material in secondary crosslinking reaction, utilize the chemical reaction between alcoholic extract hydroxyl group and chloromethyl, consume the residual chlorine in hypercrosslinked polymeric resin, thus reduce the residual chloromethyl of Hypercrosslinked polystyrene divinylbenzene resins, reach the object improving polymeric adsorbent chemical stability and blood compatibility.Meanwhile, by increasing the hydrophilic radical content of resin surface, improving resin wetting ability, reducing resin and blood formed element is detained as erythrocytic destruction and to the absorption of albumen and thrombocyte, improving the blood compatibility of resin further.
Claims (10)
1. the preparation method of secondary crosslinking polymeric adsorbent, this secondary crosslinking polymeric adsorbent is used for blood purification, and this preparation method comprises secondary crosslinking step: cross secondary crosslinking by polystyrene resins chlorine ball warp and be obtained by reacting secondary crosslinking polymeric adsorbent;
It is characterized in that: comprise standing swelling process in described secondary crosslinking step, by weight, add 1 part of polystyrene resins chlorine ball, 0.5 part to 4 parts alcohols material and 4 parts to 6 part 1,2-ethylene dichloride, carry out described standing swelling process.
2. the preparation method of secondary crosslinking polymeric adsorbent according to claim 1, is characterized in that:
The specific surface area of described secondary crosslinking polymeric adsorbent is 500m
2/ g to 1200m
2/ g, mean pore size is 2nm to 15nm.
3. the preparation method of secondary crosslinking polymeric adsorbent according to claim 1, is characterized in that:
The massfraction that in described secondary crosslinking polymeric adsorbent, the residual quantity of chlorine accounts for resin total mass is less than 1.5%.
4. the preparation method of the secondary crosslinking polymeric adsorbent according to any one of claims 1 to 3, is characterized in that:
In described standing swelling process, the amount of the described alcohols material added is 1 part to 2 parts, and time remaining 3 is little of 5 hours.
5. the preparation method of the secondary crosslinking polymeric adsorbent according to any one of claims 1 to 3, is characterized in that:
Described alcohols material is at least one in methyl alcohol, ethanol, propyl alcohol.
6. the preparation method of the secondary crosslinking polymeric adsorbent according to any one of claims 1 to 3, is characterized in that:
Controlling chlorine content ranges in described polystyrene resins chlorine ball is 8% to 18%.
7. the preparation method of the secondary crosslinking polymeric adsorbent according to any one of claims 1 to 3, is characterized in that:
After described standing swelling process, add zinc chloride or the iron trichloride of 0.2 part to 0.5 part, after being warming up to 80 DEG C to 90 DEG C under stirring, reaction 10 is little of 20 hours, leaches mother liquor, wash rear acetone extraction, wash removing acetone with water after being cooled to room temperature; Suction filtration, drying obtain described secondary crosslinking polymeric adsorbent.
8. the preparation method of the secondary crosslinking polymeric adsorbent according to any one of claims 1 to 3, is characterized in that: the step performed successively below obtains described polystyrene resins chlorine ball:
Suspension polymerization step: first, at room temperature configure aqueous phase and oil phase respectively, oil phase and aqueous phase volume ratio are 1:1.5 to 1:3, described oil phase comprises styrene monomer, Vinylstyrene class monomer, the organic mixture that initiator and pore-creating agent are formed, the mass ratio of described styrene monomer and described Vinylstyrene class monomer is 5:1 to 12:1, described aqueous phase comprises the aqueous solution of dispersion agent and water formation, the consumption of described dispersion agent is 0.8% to 2% of aqueous phase weight, initiator amount is 0.5% to 2% of monomer total amount massfraction, the consumption of described pore-creating agent is 60% to 200% of total monomer weight massfraction, then, oil phase is poured into dispersed with stirring in aqueous phase, then, be warming up to 50 DEG C to 90 DEG C, the reaction times is little of 20 hours 6, and after reaction system solidification, stopped reaction obtains polystyrene resins Archon, and the particle size range of described polystyrene resins Archon is 0.4mm to 2mm,
Chloromethylation step: employing chloromethyl ether is reaction solvent, zinc chloride or iron trichloride are catalyzer, the proportioning of reaction system is: the described polystyrene resins Archon often adding 1g, then add the described catalyzer of chloromethyl ether described in 2ml to 7mL and 0.2g to 0.5g; First the described polystyrene resins Archon of drying is added reaction vessel; Then chloromethyl ether is added swelling 1 little of 5 hours; Then add catalyzer temperature-elevating to 45 DEG C to react 20 hours 24 hours after 50 DEG C; Then be cooled to room temperature, use methyl alcohol extracting 12 hours after leaching mother liquor, washing removing methyl alcohol, suction filtration, screening, filters out the described polystyrene resins chlorine ball of particle diameter at 0.4mm to 2mm.
9. the preparation method of secondary crosslinking polymeric adsorbent according to claim 8, is characterized in that:
Described initiator is peralcohol initiator and/or azo-initiator;
Described pore-creating agent is good solvent or poor solvent.
10. the preparation method of secondary crosslinking polymeric adsorbent according to claim 9, is characterized in that:
Described peralcohol initiator comprises benzoyl peroxide and/or peroxidized t-butyl perbenzoate, and described azo-initiator comprises Diisopropyl azodicarboxylate and/or 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described good solvent is toluene and/or dimethylbenzene, and described poor solvent is higher alcohols, alkanes or ketone; Described higher alcohols is hexanol, hexalin, and described alkanes is at least one in normal heptane, hexanaphthene, gasoline, kerosene, whiteruss, and described ketone is hexone;
Described dispersion agent is at least one in gelatin, polyvinyl alcohol, polyvinyl alcohol-Sodium dodecylbenzene sulfonate.
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