CN109833854A - A kind of macroporous absorbent resin and preparation method thereof - Google Patents
A kind of macroporous absorbent resin and preparation method thereof Download PDFInfo
- Publication number
- CN109833854A CN109833854A CN201910160753.1A CN201910160753A CN109833854A CN 109833854 A CN109833854 A CN 109833854A CN 201910160753 A CN201910160753 A CN 201910160753A CN 109833854 A CN109833854 A CN 109833854A
- Authority
- CN
- China
- Prior art keywords
- parts
- ball
- archon
- temperature
- warming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of macroporous absorbent resin, is prepared from the following raw materials: water, gelatin, styrene, divinylbenzene, white oil, initiator, pore-foaming agent, solvent naphtha, 1,2- dichloroethanes, zinc chloride, chloromethyl ether composition.By Archon polymerization, Archon drying and screening, mention wax, the drying of wax ball and screening, chlorination, chlorine ball are dried, are prepared after post-crosslinking reaction step.It is prepared that resin specific surface area and porosity is larger, has preferable mechanical strength, high temperature resistant, and preparation process is simple, it is easy to industrialized production.
Description
Technical field
The invention belongs to the field of chemical synthesis more particularly to a kind of macroporous absorbent resin and preparation method thereof.
Background technique
Absorption resin refers to a kind of high molecular polymer, can be used for removing the organic matter in waste water, Sugarcane juice decolorization, day
Separation and purification of right product and biochemistry product etc..It is many to adsorb resin variety, functional group in the variation of monomer and monomer
Variation can assign resin various special performances.There are commonly the macromolecules such as polystyrene resin and polyacrylate resin
Polymer.Absorption resin is the resin sorbent with the characteristics of adsorbing, with porous three dimensional structure.It is high score recent years
A kind of porous resin that new development is got up in subdomains, by monomers such as styrene and divinylbenzenes, in organic solvents such as toluene
In the presence of, the small ball of the roe sample as made from suspension copolymerization method.It is widely used in wastewater treatment, medicament separation and purification, is used
Make the carrier of chemical reaction catalyst, the filler of gas chromatographic analysis and gel permeation chromatography molecular-weight gradation column.Its main feature is that
Regenerating easily, it can be used repeatedly.
Absorption resin at home and abroad has many manufacturing firms and many kinds.As China is to its type and quantity
Demand is increasing, and more and more producers make improvements production.
Chinese patent CN101070400A discloses a kind of preparation side of imidazole modified styrene tyle macroporous adsorption resin
Method provides a kind of preparation method of imidazole modified styrene tyle macroporous adsorption resin.Two steps of preparation method point, first
The functionalization of imidazoles is realized in 1 upper introducing particular functional group by the salt-forming reaction of imidazoles, it is then anti-with chlorination again
The styrene tyle macroporous adsorption resin reaction answered, realizes that styrene tyle macroporous adsorption resin is imidazole modified.The present invention is by functionalization
Imidazol ion be introduced in styrene tyle macroporous adsorption resin, utilize the unique physicochemical properties of imidazol ion and its object
The controllability for changing property, can not only increase the polarity and hydrophily of resin, but also can widen phenylethylene macroporous absorbent resin and eat
The fields such as product, drug isolate and purify range.But the product aperture of the invention application is smaller, it is biggish to certain molecular weight
It isolates and purifies object to be difficult to reach effective absorption, limits the application of the product.
Chinese patent application CN107163176A discloses a kind of preparation method of macroporous absorbent resin, which is characterized in that
Comprise the following steps that the preparation of monomer: by formula the dilute benzene of diethyl, methacrylate, dibenzoyl peroxide investment reaction
It in kettle, is stirred at room temperature 25-30 minutes, puts into pore-foaming agent hexamethylene, be stirred at room temperature 25-30 minutes, the preparation of water phase: reacting
It is put into suitable water in kettle, then puts into powder salt, stirs so that salt water is uniform.Gelatin is put into, methylene blue is stirred and heated
To 55-60 DEG C, turn off stirring in advance, prepared amount of monomer is pumped into reaction kettle, does not heat empty stirring 10-15 minutes, water
It is mutually 55-60 DEG C at the beginning, finishing the temperature in monomer reaction kettle is 40-45 DEG C or so.After sky stirring 10-15 minutes,
It is to slowly warm up to 68-70 DEG C.Start to keep the temperature timing, after heat preservation 4-5 hours, steam heating is to slowly warm up to 70-75 DEG C, heat preservation
6-7 hours, during which it is not related to stirring.But the invention patent specific surface area is small, pore volume is small, so its adsorption capacity is lower.
Chinese patent application CN102190751A discloses a kind of preparation method of intermediate-polarity macroporous adsorption resin.The party
Method is to take 1-50 parts of styrene by weight, the divinylbenzene that 2-10 parts of hydroxy-ethyl acrylate and weight percentage are 80%
50-100 parts are monomer；The carbon alcohol of the toluene and total weight of monomer 33%-135% that take total weight of monomer 50%-200% causes for mixing
Hole agent, takes the benzoyl peroxide of total weight of monomer 0.1%-2% and 0.1% -2% azodiisobutyronitrile is initiator, mixing
Obtain oily phase；0.2-1 parts of polyvinyl alcohol, 0.5-1 parts of gelatin are taken by weight, and 5-10 parts of sodium chloride are dissolved in 100 parts of deionized waters
In, water phase is made；Acetone extraction, ethanol rinse, until washing lotion is limpid will be used after oily mutually investment water phase temperature reaction filtering；It obtains greatly
Hole resin cation.It is extracted which solve conventional resins and problem that the obtained extract purity of separation method is lower, but its
Porosity, bad mechanical strength limit its development and application in the industry.
Currently, there are no a kind of macroporous absorbent resins, specific surface area and porosity is larger, has preferable mechanical strength, is resistance to
High temperature, and preparation process is simple, it is easy to industrialized production.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of macroporous absorbent resin, is made of following raw material: water, gelatin,
Styrene, divinylbenzene, white oil, initiator, pore-foaming agent, solvent naphtha, 1,2- dichloroethanes, zinc chloride, chloromethyl ether.
Further, the initiator is azodiisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, peroxidating ring
Hexanone；The pore-foaming agent is toluene.
Further, by weight, the resin by 200-300 parts of water, 5-10 parts of gelatin, 10-20 parts of styrene,
20-50 parts of divinylbenzenes, 10-30 parts of white oils, 2-5 parts of initiators, 2-5 parts of pore-foaming agents, 50-100 parts of solvent naphthas, 5-10 part 1,
2- dichloroethanes, 5-10 part zinc chloride, 150-200 parts of chloromethyl ether compositions.
The present invention also provides a kind of preparation methods of macroporous absorbent resin, comprising the following steps:
(1) Archon polymerize: water being heated, gelatin is added, stirring adds styrene, divinylbenzene, white oil, pore-foaming agent
And initiator, heating sizing are kept the temperature after sizing, are then heated up for the second time again, are kept the temperature for second, washing obtains Archon；
(2) Archon drying and screening: Archon is dry, until weight-loss ratio, less than 8.0%, sieving obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in solvent naphtha, stir, heat up, solvent naphtha is taken out in heat preservation, repeats above-mentioned
Operation 5-6 times, washs to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, until weight-loss ratio is not more than 3%, sieving obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is heated up, and is kept the temperature, and zinc chloride is added in two portions in cooling,
Then second of heating is carried out again, and second of heat preservation, second of cooling is separated by solid-liquid separation, washs solid phase, obtain chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, chlorination is added in stirring heating, heat preservation
Zinc, second of heating, second of heat preservation, third time heat up, keep the temperature for the third time, cool down to obtain finished ball, to finished ball and 1,2- bis-
Chloroethanes is separated by solid-liquid separation, and is washed finished ball, is filtered dry to obtain macroporous absorbent resin.
Further, in the step (1), 50-60 DEG C is heated water to；It is warming up to 70-85 DEG C；It is warming up to for the second time
85-92℃。
Further, in the step (1), gelatin is added, stirs 1-2h.
Further, in the step (1), 2-3h is kept the temperature after sizing, second of heat preservation 6-9h, with 60 DEG C of water washings.
Further, it in the step (1), washs water washing 5 times for 60 DEG C.
Further, in the step (2), drying temperature is not higher than 80 DEG C, and it is 0.5mm-1.0mm that sieving, which obtains partial size,
Archon.
Further, in the step (3), it is warming up to 35-60 DEG C, keeps the temperature 0.5-2h, solvent naphtha is No. 120 solvent naphthas.
Further, in the step (4), drying temperature is not higher than 80 DEG C, and it is 0.5mm-1.0mm that sieving, which obtains partial size,
Archon.
Further, in the step (5), qualified wax ball is added in chloromethyl ether, is warming up to 30-40 DEG C, heat preservation
2-5h is cooled to 30 DEG C hereinafter, zinc chloride is added in two portions, is then warming up to 35-45 DEG C for the second time again, protects for second
Warm 60-100h is cooled to 30 DEG C hereinafter, separation of solid and liquid, ethanol washing solid phase 5 times, obtains chlorine ball for the second time.
Further, in the step (6), drying temperature is 80-90 DEG C.
Further, in the step (7), it is warming up to 35-50 DEG C, keeps the temperature 2-5h；It is warming up to 85-100 DEG C for the second time,
Second of heat preservation 0.2-2h；Third time is warming up to 105-150 DEG C, and third time keeps the temperature 8-20h.
Further, in the step (7), 40 DEG C or less are cooled to.
Further, in the step (7), washing process is first to use ethanol washing 5 times, be washed with water and wash 5 times.
Further, the step (5) is identical as the amount of zinc chloride that step (7) is added.
Archon reaction principle is as follows:
The lifter have the advantages that macroporous absorbent resin creativeness produced by the invention customizes standby raw material really and its matches
Than, and by the cooling process that reasonably heats up, so that obtained product specific surface area and porosity is larger, has preferable machinery
Intensity, high temperature resistant, and preparation process is simple, it is easy to industrialized production.
Specific embodiment
The invention will now be further described with reference to specific embodiments, and the advantages and features of the present invention will be with describing
And it is apparent, but these examples are merely exemplary, it is not intended to limit the scope of the present invention in any way.This field skill
Art personnel should be understood that without departing from the spirit and scope of the invention can details to technical solution of the present invention and
Form is modified or is replaced, but these modifications and replacement are fallen within the protection scope of the present invention.
Embodiment 1
Raw material composition: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzenes, 10 parts of white oils, 5 parts of azos two
Isobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent naphthas, 5 parts of 1,2- dichloroethanes, 10 parts of zinc chloride, 150 parts of chloromethyl ethers.
Preparation method:
(1) Archon polymerize: heating water to 50 DEG C, gelatin is added, stir 1h, add styrene, divinylbenzene, white
Oil, toluene and azodiisobutyronitrile, are warming up to 70 DEG C of sizings, 2h are kept the temperature after sizing, are then warming up to 85 DEG C, for the second time again
Secondary heat preservation 6h obtains Archon with water washing 5 times of 60 DEG C after heat preservation；
(2) Archon drying and screening: Archon is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is less than 8.0%, then
Archon after drying is sieved, the Archon that partial size is 0.5mm-1.0mm is obtained, obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in No. 120 solvent naphthas, stirring is warming up to 35 DEG C, keeps the temperature 0.5h, takes out
Solvent naphtha repeats aforesaid operations 6 times, wax ball is washed with water to obtain；
(4) drying of wax ball and screening: wax ball is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is not more than 3%, it will
Wax ball after drying is sieved, and obtains the wax ball that partial size is 0.5mm-1.0mm, obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is warming up to 30 DEG C, keeps the temperature 2h, be cooled to 30 DEG C hereinafter,
5 parts of zinc chloride are added in two portions, is then warming up to 35 DEG C again, keeps the temperature 60h, is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation, ethyl alcohol is washed
It washs solid phase 5 times, obtains chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and drying temperature is 80 DEG C, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine
Ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, and stirring is warming up to 35 DEG C, keeps the temperature 2h,
5 parts of zinc chloride are added, are warming up to 85 DEG C for the second time, second of heat preservation 0.2h is warming up to 105 DEG C, third time is kept the temperature for the third time
8h is cooled to 40 DEG C and obtains finished ball, and to finished ball and 1,2- dichloroethanes is separated by solid-liquid separation, and finished ball is carried out using ethyl alcohol
Washing, after washing five times, then deionized water is washed five times, and macroporous absorbent resin is filtered dry to obtain.
Embodiment 2
Raw material composition: 300 parts of water, 5 parts of gelatin, 20 parts of styrene, 20 parts of divinylbenzenes, 10 parts of white oils, 2 parts of initiators,
5 parts of pore-foaming agents, 50 parts of solvent naphthas, 10 parts of 1,2- dichloroethanes, 5 parts of zinc chloride, 200 parts of chloromethyl ethers.
Preparation method:
(1) Archon polymerize: heating water to 60 DEG C, gelatin is added, stir 2h, add styrene, divinylbenzene, white
Oil, toluene and azobisisovaleronitrile, are warming up to 85 DEG C of sizings, 3h are kept the temperature after sizing, are then warming up to 92 DEG C, for the second time again
Secondary heat preservation 9h obtains Archon with water washing 6 times of 60 DEG C after heat preservation；
(2) Archon drying and screening: Archon is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is less than 8.0%, then
Archon after drying is sieved, the Archon that partial size is 0.5mm-1.0mm is obtained, obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in No. 120 solvent naphthas, stirring is warming up to 60 DEG C, keeps the temperature 2h, takes out molten
Agent oil, repeats aforesaid operations 6 times, washs to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is not more than 3%, it will
Wax ball after drying is sieved, and obtains the wax ball that partial size is 0.5mm-1.0mm, obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is warming up to 40 DEG C, keeps the temperature 5h, be cooled to 30 DEG C hereinafter,
2.5 parts of zinc chloride are added in two portions, is then warming up to 45 DEG C again, keeps the temperature 100h, is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation, ethyl alcohol
Washing solid phase 5 times, obtains chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and drying temperature is 80 DEG C, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine
Ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, and stirring is warming up to 50 DEG C, keeps the temperature 5h,
2.5 parts of zinc chloride are added, are warming up to 100 DEG C for the second time, second of heat preservation 2h is warming up to 150 DEG C, third time is kept the temperature for the third time
20h is cooled to 40 DEG C and obtains finished ball, and to finished ball and 1,2- dichloroethanes is separated by solid-liquid separation, and finished ball is carried out using ethyl alcohol
Washing, after washing five times, then deionized water is washed five times, and macroporous absorbent resin is filtered dry to obtain.
Embodiment 3
Raw material composition: 250 parts of water, 8 parts of gelatin, 15 parts of styrene, 35 parts of divinylbenzenes, 20 parts of white oils, 4 parts of peroxidating
Benzoyl, 3 parts of pore-foaming agents, 80 parts of solvent naphthas, 7 parts of 1,2- dichloroethanes, 8 parts of zinc chloride, 170 parts of chloromethyl ethers.
Preparation method:
(1) Archon polymerize: heating water to 55 DEG C, gelatin is added, stir 2h, add styrene, divinylbenzene, white
Oil, toluene and benzoyl peroxide, are warming up to 80 DEG C of sizings, 3h are kept the temperature after sizing, are then warming up to 90 DEG C, for the second time again
Secondary heat preservation 7h obtains Archon with water washing 6 times of 60 DEG C after heat preservation；
(2) Archon drying and screening: Archon is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is less than 8.0%, then
Archon after drying is sieved, the Archon that partial size is 0.5mm-1.0mm is obtained, obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in No. 120 solvent naphthas, stirring is warming up to 60 DEG C, keeps the temperature 2h, takes out molten
Agent oil, repeats aforesaid operations 6 times, washs to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is not more than 3%, it will
Wax ball after drying is sieved, and obtains the wax ball that partial size is 0.5mm-1.0mm, obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is warming up to 35 DEG C, keeps the temperature 4h, be cooled to 30 DEG C hereinafter,
4 parts of zinc chloride are added in two portions, is then warming up to 40 DEG C again, keeps the temperature 80h, is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation, ethyl alcohol is washed
It washs solid phase 5 times, obtains chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and drying temperature is 80 DEG C, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine
Ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, and stirring is warming up to 50 DEG C, keeps the temperature 5h,
Adding 4 parts to enter zinc chloride, is warming up to 90 DEG C for the second time, second of heat preservation 2h is warming up to 120 DEG C for the third time, and third time keeps the temperature 10h,
It is cooled to 40 DEG C and obtains finished ball, to finished ball and 1,2- dichloroethanes is separated by solid-liquid separation, and finished ball is washed using ethyl alcohol
It washs, after washing five times, then deionized water is washed five times, and macroporous absorbent resin is filtered dry to obtain.
Compared with Example 1, only raw material composition is different for comparative example 1, does not contain white oil.
Compared with Example 1, only parts by weight of raw materials composition is different for comparative example 2.
Raw material composition: 200 parts of water, 10 parts of gelatin, 70 parts of styrene, 80 parts of divinylbenzenes, 10 parts of white oils, 1 part of azo two
Isobutyronitrile, 2 parts of toluene, 20 parts of No. 120 solvent naphthas, 5 parts of 1,2- dichloroethanes, 10 parts of zinc chloride, 150 parts of chloromethyl ethers.
Compared with Example 1, (7) one step of step (1) heats up comparative example 3, without insulating process.
Raw material composition: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzenes, 10 parts of white oils, 5 parts of azos two
Isobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent naphthas, 5 parts of 1,2- dichloroethanes, 10 parts of zinc chloride, 150 parts of chloromethyl ethers.
Preparation method:
(1) Archon polymerize: heating water to 50 DEG C, gelatin is added, stir 1h, add styrene, divinylbenzene, white
Oil, toluene and azodiisobutyronitrile, are warming up to 85 DEG C of sizings, then with water washing 5 times of 60 DEG C, obtain Archon；
(2) Archon drying and screening: Archon is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is less than 8.0%, then
Archon after drying is sieved, the Archon that partial size is 0.5mm-1.0mm is obtained, obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in No. 120 solvent naphthas, stirring is warming up to 35 DEG C, keeps the temperature 0.5h, takes out
Solvent naphtha repeats aforesaid operations 6 times, washs to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, and drying temperature is no more than 80 DEG C, until weight-loss ratio is not more than 3%, it will
Wax ball after drying is sieved, and obtains the wax ball that partial size is 0.5mm-1.0mm, obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is warming up to 35 DEG C, keeps the temperature 4h, be cooled to 30 DEG C hereinafter,
4 parts of zinc chloride are added in two portions, is then warming up to 40 DEG C again, keeps the temperature 80h, is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation, ethyl alcohol is washed
It washs solid phase 5 times, obtains chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and drying temperature is 80 DEG C, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine
Ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, and 4 parts of zinc chloride, stirring heating is added
It to 105 DEG C, is cooled to 40 DEG C and obtains finished ball, to finished ball and 1,2- dichloroethanes is separated by solid-liquid separation, and finished ball uses ethyl alcohol
It is washed, after washing five times, then deionized water is washed five times, and macroporous absorbent resin is filtered dry to obtain.
Compared with Example 1, step (2) (4) (6) drying temperature is different for comparative example 4.
Raw material composition: 200 parts of water, 10 parts of gelatin, 10 parts of styrene, 50 parts of divinylbenzenes, 10 parts of white oils, 5 parts of azos two
Isobutyronitrile, 2 parts of toluene, 100 parts of No. 120 solvent naphthas, 5 parts of 1,2- dichloroethanes, 10 parts of zinc chloride, 150 parts of chloromethyl ethers.
Preparation method:
(1) Archon polymerize: heating water to 50 DEG C, gelatin is added, stir 1h, add styrene, divinylbenzene, white
Oil, toluene and azodiisobutyronitrile, are warming up to 70 DEG C of sizings, 2h are kept the temperature after sizing, are then warming up to 85 DEG C, for the second time again
Secondary heat preservation 6h obtains Archon with water washing 5 times of 60 DEG C after heat preservation；
(2) Archon drying and screening: Archon is dry, it 85 DEG C of drying temperature, until weight-loss ratio is less than 8.0%, then will dry
Archon afterwards is sieved, and obtains the Archon that partial size is 0.5mm-1.0mm, obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in No. 120 solvent naphthas, stirring is warming up to 35 DEG C, keeps the temperature 0.5h, takes out
Solvent naphtha repeats aforesaid operations 6 times, washs to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, 90 DEG C of drying temperature, until weight-loss ratio is not more than 3%, after drying
Wax ball be sieved, obtain partial size be 0.5mm-1.0mm wax ball, obtain qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is warming up to 30 DEG C, keeps the temperature 2h, be cooled to 30 DEG C hereinafter,
5 parts of zinc chloride are added in two portions, is then warming up to 35 DEG C again, keeps the temperature 60h, is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation, ethyl alcohol is washed
It washs solid phase 5 times, obtains chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and drying temperature is 70 DEG C, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine
Ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes is mixed with qualified chlorine ball, and stirring is warming up to 35 DEG C, keeps the temperature 2h,
5 parts of zinc chloride are added, are warming up to 85 DEG C for the second time, second of heat preservation 0.2h is warming up to 105 DEG C, third time is kept the temperature for the third time
8h is cooled to 40 DEG C and obtains finished ball, and to finished ball and 1,2- dichloroethanes is separated by solid-liquid separation, and finished ball is carried out using ethyl alcohol
Washing, after washing five times, then deionized water is washed five times, and macroporous absorbent resin is filtered dry to obtain.
The measurement of 1 specific surface area and porosity of experimental example
The measurement of specific surface area and porosity is carried out to product using BTE.
Sample is weighed, by heating and vacuumizing degassing, is then weighed.Vacuum cools down 30min under room temperature, then
It is placed on BET and is analyzed, experimental result is as follows:
The measurement of rate of small round spheres after 2 mechanical strengths of experimental example-mill
The measuring method of rate of small round spheres is referring to GB/T 11992-2008 after mill, the method recorded in 8.2.Experimental result is such as
Under:
Experimental example 3
Using thermogravimetric analyzer, the glass transition temperature of product is measured.
Sample is weighed, sample is put into instrument, measures the glass transition temperature of sample.
Experimental result is as follows:
Through comparing, the product specific surface area and porosity that the present invention obtains is larger, has preferable mechanical strength, high temperature resistant,
And preparation process is simple, easy to industrialized production.
The technical means disclosed in the embodiments of the present invention is not limited only to above-mentioned disclosed technological means, further includes by above
Technical solution composed by any combination of technical features.The foregoing is a specific embodiment of the present invention, it is noted that right
For those skilled in the art, without departing from the principle of the present invention, if the improvement can also be made
And modification, these also will be regarded as protection scope of the present invention.
Claims (10)
1. a kind of macroporous absorbent resin, which is characterized in that be prepared from the following raw materials: water, gelatin, styrene, divinylbenzene, white
Oil, initiator, pore-foaming agent, solvent naphtha, 1,2- dichloroethanes, zinc chloride, chloromethyl ether.
2. resin according to claim 1, which is characterized in that the initiator is azodiisobutyronitrile, azo diisoamyl
One of nitrile, benzoyl peroxide, cyclohexanone peroxide are a variety of；The pore-foaming agent is toluene.
3. resin according to claim 1, which is characterized in that be composed of the following raw materials by weight: 200-300 parts of water, 5-
10 parts of gelatin, 10-20 parts of styrene, 20-50 parts of divinylbenzenes, 10-30 parts of white oils, 2-5 parts of initiators, 2-5 parts of pore-foaming agents,
50-100 parts of solvent naphthas, 5-10 parts of 1,2- dichloroethanes, 5-10 parts of zinc chloride, 150-200 parts of chloromethyl ethers.
4. the preparation method of any resin of claim 1-3, which comprises the following steps:
(1) Archon polymerize: water being heated, gelatin is added, stirring adds styrene, divinylbenzene, white oil, pore-foaming agent and draws
Agent is sent out, heating sizing is kept the temperature after sizing, is then heated up, is kept the temperature for the second time again for second, washing obtains Archon；
(2) Archon drying and screening: Archon is dry, until weight-loss ratio, less than 8.0%, sieving obtains qualified Archon；
(3) it mentions wax: qualified Archon is added in solvent naphtha, stir, heat up, solvent naphtha is taken out in heat preservation, repeats aforesaid operations 5-
6 times, wash to obtain wax ball；
(4) drying of wax ball and screening: wax ball is dry, until weight-loss ratio is not more than 3%, sieving obtains qualified wax ball；
(5) chlorination: qualified wax ball is added in chloromethyl ether, is heated up, and is kept the temperature, and zinc chloride is added in two portions, then again in cooling
Heat up for the second time, second of heat preservation, second of cooling is separated by solid-liquid separation, washs solid phase, obtain chlorine ball；
(6) chlorine ball is dried: chlorine ball is dry, and weight-loss ratio 1.5%-9.5% obtains qualified chlorine ball；
(7) post-crosslinking reaction: 1,2- dichloroethanes being mixed with qualified chlorine ball, stirring heating, and zinc chloride is added in heat preservation, the
Secondary temperature elevation, second of heat preservation, third time heat up, and third time is kept the temperature, and cool down to obtain finished ball, to finished ball and 1,2- dichloroethanes
It is separated by solid-liquid separation, washs finished ball, be filtered dry to obtain macroporous absorbent resin.
5. the preparation method according to claim 4, which is characterized in that in the step (1), heat water to 50-60 DEG C；
It is warming up to 70-85 DEG C；It is warming up to 85-92 DEG C for the second time.
6. the preparation method according to claim 4, which is characterized in that in the step (2), sieving obtains partial size and is
The Archon of 0.5mm-1.0mm；In the step (4), sieving obtains the Archon that partial size is 0.5mm-1.0mm.
7. the preparation method according to claim 4, which is characterized in that in the step (3), be warming up to 35-60 DEG C, heat preservation
0.5-2h, solvent naphtha are No. 120 solvent naphthas.
8. the preparation method according to claim 4, which is characterized in that in the step (5), qualified wax ball is added to
In chloromethyl ether, it is warming up to 30-40 DEG C, keeps the temperature 2-5h, be cooled to 30 DEG C hereinafter, zinc chloride is added in two portions, then carries out the again
Secondary temperature elevation is to 35-45 DEG C, and second of heat preservation 60-100h is cooled to 30 DEG C hereinafter, being separated by solid-liquid separation for the second time, and ethanol washing is solid
Phase obtains chlorine ball.
9. the preparation method according to claim 4, which is characterized in that in the step (6), drying temperature is 80-90 DEG C.
10. the preparation method according to claim 4, which is characterized in that in the step (7), be warming up to 35-50 DEG C, protect
Warm 2-5h；It is warming up to 85-100 DEG C for the second time, second of heat preservation 0.2-2h；Third time is warming up to 105-150 DEG C, and third time is kept the temperature
8-20h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160753.1A CN109833854B (en) | 2019-03-04 | 2019-03-04 | Macroporous adsorption resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910160753.1A CN109833854B (en) | 2019-03-04 | 2019-03-04 | Macroporous adsorption resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109833854A true CN109833854A (en) | 2019-06-04 |
| CN109833854B CN109833854B (en) | 2019-12-20 |
Family
ID=66885356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910160753.1A Active CN109833854B (en) | 2019-03-04 | 2019-03-04 | Macroporous adsorption resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833854B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389377A (en) * | 2020-03-25 | 2020-07-10 | 旬阳领盛新材料科技有限公司 | Method for producing post-crosslinked adsorption resin by one-pot method |
| CN112742356A (en) * | 2020-12-15 | 2021-05-04 | 蚌埠市天星树脂有限责任公司 | Adsorption resin for treating waste water and gas and preparation method thereof |
| CN114479128A (en) * | 2021-12-08 | 2022-05-13 | 湖北石河医药科技有限公司 | Method for preparing macroporous adsorption resin |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1858088A (en) * | 2006-04-25 | 2006-11-08 | 南京大学 | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method |
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
| CN101016357A (en) * | 2007-02-09 | 2007-08-15 | 南开大学 | Preparation of screening type adsorption resin and application thereof in separating panaxoside monomer Rb1 |
| CN101088601A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101088602A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101088599A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101543764A (en) * | 2009-04-30 | 2009-09-30 | 南京大学 | Hydrophobic carbonyl modified superhigh crosslinked adsorption resin as well as synthetic method and application thereof |
| CN102585074A (en) * | 2012-02-24 | 2012-07-18 | 蚌埠市天星树脂有限责任公司 | Preparation method of high-performance macroporous adsorption resin |
| CN102924253A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for extracting acetoin from fermentation liquor |
| CN103980403A (en) * | 2014-05-16 | 2014-08-13 | 李涛 | Styrene system ion exchange resin as well as preparation method and application thereof |
| CN105289538A (en) * | 2015-11-04 | 2016-02-03 | 珠海健帆生物科技股份有限公司 | DNA immunity adsorbent and preparation method thereof |
| CN105418946A (en) * | 2015-12-23 | 2016-03-23 | 珠海健帆生物科技股份有限公司 | Preparation method of secondarily-crosslinked adsorption resin |
| WO2017088032A1 (en) * | 2015-11-27 | 2017-06-01 | Trajan Scientific Australia Pty Ltd | Novel porous polymer monoliths adapted for sample preparation |
| CN107216415A (en) * | 2017-06-14 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of preparation method for adsorbing the resin of anion in the steady salt of heat in amine liquid |
-
2019
- 2019-03-04 CN CN201910160753.1A patent/CN109833854B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1858088A (en) * | 2006-04-25 | 2006-11-08 | 南京大学 | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method |
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
| CN101088599A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101088601A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101088602A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN101016357A (en) * | 2007-02-09 | 2007-08-15 | 南开大学 | Preparation of screening type adsorption resin and application thereof in separating panaxoside monomer Rb1 |
| CN101543764A (en) * | 2009-04-30 | 2009-09-30 | 南京大学 | Hydrophobic carbonyl modified superhigh crosslinked adsorption resin as well as synthetic method and application thereof |
| CN102585074A (en) * | 2012-02-24 | 2012-07-18 | 蚌埠市天星树脂有限责任公司 | Preparation method of high-performance macroporous adsorption resin |
| CN102924253A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for extracting acetoin from fermentation liquor |
| CN103980403A (en) * | 2014-05-16 | 2014-08-13 | 李涛 | Styrene system ion exchange resin as well as preparation method and application thereof |
| CN105289538A (en) * | 2015-11-04 | 2016-02-03 | 珠海健帆生物科技股份有限公司 | DNA immunity adsorbent and preparation method thereof |
| WO2017088032A1 (en) * | 2015-11-27 | 2017-06-01 | Trajan Scientific Australia Pty Ltd | Novel porous polymer monoliths adapted for sample preparation |
| CN105418946A (en) * | 2015-12-23 | 2016-03-23 | 珠海健帆生物科技股份有限公司 | Preparation method of secondarily-crosslinked adsorption resin |
| CN107216415A (en) * | 2017-06-14 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of preparation method for adsorbing the resin of anion in the steady salt of heat in amine liquid |
Non-Patent Citations (3)
| Title |
|---|
| 李培元 等: "《发电厂水处理及水质控制》", 30 September 2012, 中国电力出版社 * |
| 汪多仁编著: "《合成树脂与工程塑料生产技术》", 31 August 2001, 中国轻工业出版社 * |
| 靳学远 等: "《天然产物降血糖功能性成分研究》", 30 June 2009, 上海交通大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389377A (en) * | 2020-03-25 | 2020-07-10 | 旬阳领盛新材料科技有限公司 | Method for producing post-crosslinked adsorption resin by one-pot method |
| CN112742356A (en) * | 2020-12-15 | 2021-05-04 | 蚌埠市天星树脂有限责任公司 | Adsorption resin for treating waste water and gas and preparation method thereof |
| CN114479128A (en) * | 2021-12-08 | 2022-05-13 | 湖北石河医药科技有限公司 | Method for preparing macroporous adsorption resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109833854B (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101912770B (en) | Polymeric adsorbent and preparation method thereof | |
| CN109833854A (en) | A kind of macroporous absorbent resin and preparation method thereof | |
| CN105504128B (en) | A kind of absorption resin and its preparation method and application for Phenol-Containing Wastewater Treatment | |
| CN108355626B (en) | Modified styrene series adsorption resin, preparation method thereof and application thereof in refining lignocellulose hydrolysate | |
| WO2016011900A1 (en) | Chelating resin adsorbing material and preparation method therefor | |
| CN1858088A (en) | Pyridyl modified composite function super high crosslinked adsorptive resin and its preparing method | |
| CN111530432B (en) | Preparation method of adsorbing material for blood perfusion | |
| CN107892733B (en) | Heavy metal wastewater ion adsorption resin and preparation method thereof | |
| CN104262521B (en) | The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier | |
| CN101987291A (en) | Macropore adsorption resin as well as preparation method and application thereof | |
| MXPA03001677A (en) | Functionalized polymeric media for separation of analytes. | |
| CN110117379B (en) | Adsorbing material for removing LDL (low density lipoprotein) in blood perfusion and preparation method thereof | |
| CN104292383A (en) | Gallium-adsorbing chelating resin and preparation method thereof | |
| CN111040065A (en) | Preparation method of solvent-free gel type styrene cation exchange resin | |
| CN104004131B (en) | High specific surface area amphoteric adsorption resin containing pyrrolidone bases and preparation method thereof | |
| CN109320650B (en) | Preparation method of macroporous weakly-alkaline acrylic anion exchange resin | |
| Li et al. | Synthesis and adsorption aspect of crosslinked PVA-based blood compatible adsorbents for LDL apheresis | |
| KR100332859B1 (en) | High density, large surface area adsorbent | |
| WO2016018870A1 (en) | Method and composition for water treatment and methods for preparing the composition | |
| CN103464222A (en) | Preparation method of special anion exchange resin for adsorbing heparin sodium | |
| JPS6361618B2 (en) | ||
| CN114573864B (en) | Porous adsorption resin and preparation method and application thereof | |
| CN108948255A (en) | A kind of styrene resin and preparation method thereof | |
| KR101921824B1 (en) | Matrix resin of chelate resin for adsorbing boron ions, chelate resin for adsorbing boron ions prepared from the same, and method for preparing the chelate resin | |
| CN106467594B (en) | A kind of preparation of polyacrylonitrile-polyvinyl tetrazole chelating resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |