CN106397663B - A kind of method for preparing super big hole microballoon - Google Patents

A kind of method for preparing super big hole microballoon Download PDF

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CN106397663B
CN106397663B CN201610817953.6A CN201610817953A CN106397663B CN 106397663 B CN106397663 B CN 106397663B CN 201610817953 A CN201610817953 A CN 201610817953A CN 106397663 B CN106397663 B CN 106397663B
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big hole
super big
microballoon
monomer
water
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CN106397663A (en
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王银萍
任大勇
陈志勇
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University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

The present invention relates to a kind of methods for preparing super big hole microballoon.This method is polymerize using frozen suspension, using lauryl alcohol as solvent, using its crystal as pore-foaming agent, and form oil phase with function monomer, crosslinking agent and redox initiator, it is dispersed in water in the presence of a stabilizer, after when standing reaction 48 is small at 4 DEG C, washed, centrifugation, drying obtain the super big hole microballoon with micrometer grade hole gauge structure.The preparation method of the present invention is simple and reliable, and for thus obtained microsphere grain size at 10 microns ~ 100 microns, aperture is controllable between hundreds of nanometers ~ tens microns.

Description

A kind of method for preparing super big hole microballoon
Technical field
The present invention relates to a kind of methods for preparing super big hole microballoon, belong to technical field of polymer materials.
Background technology
Super big hole microballoon is a kind of polymer microballoon with the three-dimensional netted pore structure of micron order.Because it is with high pass The characteristics of amount, low mass transfer resistance and be widely used in isolating and purifying, numerous necks such as the immobilization of catalyst carrier, enzyme and cell Domain.
At present, preparing the pore method of super big hole microballoon mainly includes solid particle pore method, surfactant reverse micelle Swelling method and ice crystal pore method.（1）Solid particle pore method refers to add in the preparation process of polymer microballoon inorganic solid Body particle after polymerization, then removes solid particle, so as to form porous structure in polymer microballoon.Therefore polymer is micro- The pore size of ball can be adjusted by changing the size of inorganic solid particles.However, since solid particle is not easy to be wrapped by, This causes the pore-size distribution of thus obtained microsphere to be difficult to control, reappearance it is poor (Y Shi, Y Sun, Chromatographia, 2003, 57, 29-35；CN1695795).（2）Surfactant reverse micelle swelling method is by substantial amounts of oil-soluble cationic surfactant Agent is added in oil phase, so as to form substantial amounts of Reversed micelles in oil phase, when oil phase is arrived by the effect stable dispersion of stabilizer After water phase, water absorption and swelling that Reversed micelles that surfactant is formed can be spontaneous forms two-arch tunnel structure in oil phase, In polymerization process, water phase is gradually separated with polymer, and water mutually occupies certain space, and after the completion of polymerization, water is divided by It goes to form pore structure.The difference of water and polymer phase separation degree will form various sizes of through hole, the polymer of gained Microballoon aperture is maximum up to 500 nm, but its preparation process is relatively complicated, and after reaction, surfactant is not easy to remove Totally, application of the microballoon in terms of biology may be had adverse effect on（WQ Zhou, TY Gu, ZG Su, GH Ma, European Polymer Journal, 2007, 43, 4493-4502；CN1903890）.In addition, CN104558350A is public Opened it is a kind of using homemade amphiphilic two block macromonomers as surfactant, styrene is monomer, divinylbenzene For crosslinking agent, the method that super large pore polymer microsphere is prepared by suspension polymerisation, thus obtained microsphere grain size is 15 ~ 300 μm, aperture For 200 ~ 3000 nm.But the method needs prefabricated specific surfactant monomer, preparation process is complicated, and time-consuming, rear to locate Reason is complicated.（3）Ice crystal pore method is using ice crystal as pore-foaming agent, triggers water solubility by the way of freezing polymerization in subzero After monomer and crosslinking agent polymerization, then through heating, wash, drying obtains super big hole Hydrophilic polymeric microspheres（XY Zhan, DP Lu, DQ Lin, SJ Yao, Journal of Applied Polymer Science, 2013, 130, 3082-3089）. CN102382219A provides a kind of method that super big hole microballoon is prepared with ice crystal pore, and using acrylamide as monomer, gained is micro- 800 ~ 1300 μm of ball average grain diameter, 1~80 μm of aperture.CN102775712A discloses another and prepares super large with ice crystal pore The method of hole microballoon, this method uses inverse suspension polymerization, using acrylamide as monomer, using n-hexane as continuous phase, -30 ~ - Super big hole microballoon is obtained by free radical polymerization under the conditions of 10 DEG C, the microballoon aperture of gained is at 3 ~ 90 μm.However, due to using Ice crystal as pore-foaming agent, monomer used and crosslinking agent must be it is hydrophilic, thus available monomer and type of crosslinking agent compared with It is few, and thus obtained microsphere mechanical strength is low, the quick separating analysis being unfavorable under pressurized conditions.
The content of the invention
For above-mentioned limitation, the present invention proposes higher using lauryl alcohol fusing point（16.6 ℃）, and can dissolve most of Non-polar monomer and the characteristics of be insoluble in water, using lauryl alcohol crystal as pore-foaming agent, be aggregated in using frozen suspension under static conditions The method for preparing super big hole microballoon.
The technical scheme is that:
A kind of preparation method of super big hole microballoon prepares super big hole microballoon using the method for frozen suspension polymerization, and step is such as Under：
Monomer, crosslinking agent and initiator are added in solvent, mixing is gone in the water containing stabilizer, is passed through nitrogen After deoxygenation, sealing, concussion makes it be uniformly dispersed；When standing reaction 48 is small at 4 DEG C, sunk in succession with ethyl alcohol and water washing, centrifugation It forms sediment, obtain super big hole microballoon after drying；
The monomer is glycidyl methacrylate, and the crosslinking agent is trimethylol-propane trimethacrylate Or ethylene glycol dimethacrylate；
The molar ratio of the monomer and crosslinking agent is 60:40~90:10；
The mass ratio of the initiator and comonomer is 0.01 ~ 0.08:1.00；
The solvent is lauryl alcohol, and the volume ratio for accounting for oil phase is 0.6 ~ 0.9；
The initiator is the redox initiation system of benzoyl peroxide and n,N-Dimethylaniline composition, is rubbed You are than being 1:1.
It is preferred according to the present invention, when the crosslinking agent is trimethylol-propane trimethacrylate, crosslinking agent Molar ratio is 0.2.
It is preferred according to the present invention, when the crosslinking agent is ethylene glycol dimethacrylate, the molar ratio of crosslinking agent For 0.4.
Preferred according to the present invention, the solvent volume ratio is 0.7.
Preferred according to the present invention, the initiator quality ratio is 0.05.
Super big hole microballoon produced by the present invention, granularity are micron orders, are concentrated mainly between 10 ~ 100 μm, aperture is in number It is controllable between hundred nanometers ~ tens microns.
According to the present invention most preferably, a kind of preparation method of super big hole microballoon, step are as follows：
1.01 ml glycidyl methacrylate monomers and 0.61 ml trimethylol-propane trimethacrylates are handed over Connection agent is added in 3.78 ml lauryl alcohols, after mixing, adds in 86.5 mg benzoyl peroxides, is passed through 5 min of nitrogen except deoxidation After gas, 45 μ l n,N-Dimethylaniline, mixing are added in；It is transferred in 30 ml water, is uniformly dispersed in the presence of a stabilizer；So It is placed at 4 DEG C and stands 48 h of reaction；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, it is dry after Obtain super big hole microballoon.
The present invention combines the advantages of suspension polymerisation and freezing polymerization, and suspension polymerisation is placed in a freezing system and is carried out. Under the enclosed system of low temperature, using organic solvent crystal as pore-foaming agent, super big hole microballoon can be made in standing.
The preparation method of the present invention is simple and reliable, using solvent crystal pore, without stirring, stands reaction, super big hole is micro- For the grain size of ball between 10 ~ 100 μm, aperture is controllable between hundreds of nanometers ~ tens microns.
Description of the drawings
Fig. 1, Fig. 2：Super big hole microballoon（Embodiment 1）Scanning electron microscope (SEM) photograph
Fig. 3, Fig. 4：Super big hole microballoon（Embodiment 2）Scanning electron microscope (SEM) photograph
Fig. 5, Fig. 6：Super big hole microballoon（Embodiment 3）Scanning electron microscope (SEM) photograph
Fig. 7, Fig. 8：Super big hole microballoon（Embodiment 4）Scanning electron microscope (SEM) photograph.
Specific embodiment
Embodiment 1
1.35 ml glycidyl methacrylate monomers and 0.81 ml trimethylol-propane trimethacrylates are handed over Connection agent is added in 3.24 ml lauryl alcohols, and mixing adds in 23.1 mg benzoyl peroxides, is passed through 5 min of nitrogen, removes oxygen Afterwards, 12 μ l n,N-Dimethylaniline, mixing are added in；It is transferred in the water of 30 ml, is uniformly dispersed in the presence of a stabilizer；So Be placed at 4 DEG C stand reaction 48 it is small when；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, drying After obtain super big hole microballoon (Fig. 1, Fig. 2；Wherein Fig. 1 amplification factors are that 1,000, Fig. 2 amplification factor is 10,000).
Embodiment 2
0.83 ml glycidyl methacrylate monomer adds with 0.79 ml ethylene glycol dimethacrylate crosslinking agents Enter into 3.78 ml lauryl alcohols, mixing, add in 17.2 mg benzoyl peroxides, be passed through 5 min of nitrogen, after removing oxygen, add Enter 8.9 μ l n,N-Dimethylaniline, mixing；It is transferred in the water of 30 ml, is uniformly dispersed in the presence of a stabilizer；Then put When standing reaction 48 is small at 4 DEG C；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, it is dry after To super big hole microballoon (Fig. 3, Fig. 4；Wherein the amplification factor of Fig. 3 is that 1,000, Fig. 4 amplification factor is 5,000).
Embodiment 3
1.01 ml glycidyl methacrylate monomers and 0.61 ml trimethylol-propane trimethacrylates are handed over Connection agent is added in 3.78 ml lauryl alcohols, and mixing adds in 86.5 mg benzoyl peroxides, is passed through 5 min of nitrogen, removes oxygen Afterwards, 45 μ l n,N-Dimethylaniline, mixing are added in；It is transferred in the water of 30 ml, is uniformly dispersed in the presence of a stabilizer；So Be placed at 4 DEG C stand reaction 48 it is small when；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, drying After obtain super big hole microballoon (Fig. 5, Fig. 6；The amplification factor that wherein amplification factor of Fig. 5 is 800, Fig. 6 is 30,000).
Embodiment 4
0.83 ml glycidyl methacrylate monomer adds with 0.79 ml ethylene glycol dimethacrylate crosslinking agents Enter into 3.78 ml lauryl alcohols, mixing, add in 86.5 mg benzoyl peroxides, be passed through 5 min of nitrogen, after removing oxygen, add Enter 45 μ l n,N-Dimethylaniline, mixing；It is transferred in the water of 30 ml, is uniformly dispersed in the presence of a stabilizer；It is subsequently placed in When standing reaction 48 is small at 4 DEG C；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, it is dry after obtain Super big hole microballoon (Fig. 7, Fig. 8；Wherein the amplification factor of Fig. 7 is that 1,000, Fig. 8 amplification factor is 30,000).

Claims (2)

  1. A kind of 1. method for preparing super big hole microballoon, which is characterized in that it is micro- that super big hole is prepared using the method for frozen suspension polymerization Ball, step are as follows：
    Monomer, crosslinking agent and initiator are added in solvent, mixing is gone in the water containing stabilizer, is passed through nitrogen deoxygenation Afterwards, seal, concussion makes it be uniformly dispersed；When standing reaction 48 is small at 4 DEG C, ethyl alcohol and water washing, centrifugation are used in succession, is done Super big hole microballoon is obtained after dry；
    The monomer is glycidyl methacrylate, and the crosslinking agent is trimethylol-propane trimethacrylate or second Diol dimethacrylate；
    The molar ratio of the monomer and crosslinking agent is 60:40~90:10；
    The mass ratio of the initiator and monomer is 0.01~0.08:1.00；
    The solvent is lauryl alcohol, and the volume ratio for accounting for oil phase is 0.6~0.9；
    The redox initiation system that the initiator forms for benzoyl peroxide with n,N-Dimethylaniline, molar ratio For 1:1；
    The method prepare super big hole microballoon, granularity is micron order, is concentrated between 10-100 μm, aperture hundreds of nanometers- It is controllable between tens microns.
  2. 2. the method for super big hole microballoon is prepared as described in claim 1, which is characterized in that step is as follows：
    0.83ml glycidyl methacrylate monomer is added to 0.79ml ethylene glycol dimethacrylate crosslinking agents In 3.78ml lauryl alcohols, mixing adds in 86.5mg benzoyl peroxides, is passed through nitrogen 5min, after removing oxygen, adds in 45 μ l N,N-Dimethylaniline, mixing；It is transferred in the water of 30ml, is uniformly dispersed in the presence of a stabilizer；It is subsequently placed at 4 DEG C and stands React 48 it is small when；Stop reaction, washed with a certain amount of second alcohol and water, centrifugation, it is dry after obtain super big hole microballoon.
CN201610817953.6A 2016-09-13 2016-09-13 A kind of method for preparing super big hole microballoon Expired - Fee Related CN106397663B (en)

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CN102382219A (en) * 2011-08-17 2012-03-21 浙江工业大学 Oversized porous crystal adhesive microspheres and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382219A (en) * 2011-08-17 2012-03-21 浙江工业大学 Oversized porous crystal adhesive microspheres and preparation method thereof

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冷冻聚合法制备多孔P(NIPAm-co-AAm)水凝胶及其性能研究;杨桔等;《功能材料》;20110220;第42卷(第02期);第343-350页 *

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