CN106632769B - A kind of preparation method of micron size hybrid polymer microsphere - Google Patents

A kind of preparation method of micron size hybrid polymer microsphere Download PDF

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CN106632769B
CN106632769B CN201610880890.9A CN201610880890A CN106632769B CN 106632769 B CN106632769 B CN 106632769B CN 201610880890 A CN201610880890 A CN 201610880890A CN 106632769 B CN106632769 B CN 106632769B
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particle
added
preparation
polymer microsphere
hybrid polymer
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CN106632769A (en
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张靖仝
刘伯军
兰苗宇
任秀艳
陈佳宇
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Changchun University of Technology
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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
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • 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
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients

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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)
  • Polymerisation Methods In General (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of preparation method of micron size hybrid polymer microsphere, belongs to technical field of emulsion polymerization.Preparation method of the present invention uses lotion coalescence technology, using intermittent emulsion polymerization as main method, by the way that the SiO that surface carries negative electrical charge is added in the particle nucleation stage2Particle promotes latex particle to carry out coalescence on its surface, and anion surfactant is then added and terminates particle coalescence.The Size Distribution that final latex particle is sharpened by the growth of particle later and particle fusion effect, through the organic/inorganic polymer microsphere of the method preparation, its final size can reach micron order size, and be uniformly dispersed.Compared with prior art, the method for the present invention can prepare mono dispersed micrograde organic/inorganic polymer hybridisation microsphere, and size adjustable, simple for process, polymerization cycle is short, production efficiency is high.

Description

A kind of preparation method of micron size hybrid polymer microsphere
Technical field
The invention belongs to technical field of emulsion polymerization, and in particular to a kind of micron size hybrid high score The preparation method of sub- microballoon.
Background technology
Currently, big grain size monodisperse polymer micro-sphere is widely used in chromatograph packing material, ink, coating and adhesive Equal fields.And in actual application process, the heat resistance of big grain size microballoon itself limits polymer microballoon certain special The practical application in field, for enhance polymer microballoon heat resistance, one of method the simplest be exactly utilize inorganic particulate into Row is modified.Facts proved that a small amount of inorganic particulate is added in polymer microballoon can significantly improve the hot of polymer itself Can, and polymer microballoon can also be made to have some other special natures, a small amount of Fe is such as coated in polymer microballoon3O4 Particle can make polymer microballoon have magnetism；A small amount of rare metal is coated in polymer microballoon, and polymer can be made micro- Ball has the effect of sustained release catalyst.Just because of the particularity of polymer particle micro-spheres inorganic particulate, countries in the world scientific research Sight is focused on inorganic/organic hybrid polymer microsphere preparation field by personnel.
Inorganic/organic hybrid polymer microsphere is prepared at present usually using inoganic particle modified method, by silane coupled The particular monomers such as agent handle inorganic particulate, its particle surface is made to have specific functional groups, recycle the chemistry between functional group anti- Inorganic particulate and organic polymer particle should be combined together, realize the effect of particle cladding.And it prepares with this method Inorganic/organic hybrid polymer microsphere its particle diameter distribution be difficult to control, majority shows multi-modal, and the size of particle compared with It is small, it is typically between tens to hundreds of nanometers, it is difficult to break through micron-scale.
Invention content
Purpose of the present invention is to propose a kind of method preparing micron size hybrid polymer microsphere, with Overcome the shortcomings that current technology production technology is complicated, the production cycle is long, product cut size is unevenly distributed.
Preparation method of the present invention uses lotion coalescence technology, using intermittent emulsion polymerization as main method, by particle The SiO that surface carries negative electrical charge is added in nucleation stage2Particle promotes latex particle to carry out coalescence on its surface, be then added it is cloudy from Sub- surfactant terminates particle coalescence.The ruler of final latex particle is sharpened by the growth of particle later and particle fusion effect Very little distribution, through the organic/inorganic polymer microsphere of the method preparation, its final size can reach micron order size, and disperse equal It is even.Compared with prior art advantage of this approach is that：It is micro- that mono dispersed micrograde organic/inorganic polymer hybridisation can be prepared Ball, and size adjustable, simple for process, polymerization cycle is short, production efficiency is high.
A kind of preparation method of micron size hybrid polymer microsphere proposed by the invention, including Following steps：
(1) in parts by mass, 10~50 parts of monomers, 0.2~1.5 part of electrolyte are added in reaction kettle, are passed through N2It sets After changing the air 2~3 times in reaction kettle, 50~90 parts of deionized waters are added, start to start stirring, mixing speed is set as 150 ~450rpm, and it is warming up to 65~75 DEG C；
(2) under stiring, 0.1~5 part of cationic initiators initiation is added into above-mentioned system to polymerize, after 5~10min 0.1~5 part of surface is added, and there is the inorganic particulate dispersion liquid of negative electrical charge to cause primary particle coalescence, and 0.1 is added after 2~10min ~8 parts of cationic emulsifiers promote the secondary coalescence of particle, and 0.1~8 part of anionic emulsifier, which is added, after 2~10min terminates Coalescence is reacted；80~90 DEG C are warming up to after 65~75 DEG C of maintenance reaction 5~8 hours, 1~3 hour postcooling of heat preservation is normal to room temperature Material is extruded to get to micron size hybrid polymer microsphere of the present invention.
Monomer as described above is selected from one or more of methyl methacrylate, styrene, butyl acrylate.
Electrolyte as described above is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus.
Cationic initiators as described above are selected from two isobutyl imidazoline hydrochloride of azo, 2,2 '-azo diisobutyls One or more of amidine hydrochloride, azo diimidazole quinoline base propane.
There is the inorganic particulate dispersion liquid of negative electrical charge to be selected from surface carboxylation SiO on surface as described above2Aqueous dispersions, table Face carboxylated Fe3O4One or more of aqueous dispersions.
Cationic emulsifier as described above is selected from dodecyl trimethyl ammonium chloride, tetradecyltrimethylammonium chlorination Ammonium, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide, myristyl three One or more of methyl bromide ammonium, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide.
Anionic emulsifier as described above is selected from lauryl sodium sulfate, dodecyl sulphate potassium, detergent alkylate One kind or or several in sodium sulfonate, Potassium dodecylbenzenesulfonate, disproportionated rosin acid soap, fatty acid soaps, potassium oleate, enuatrol.
Description of the drawings
Fig. 1：Polystyrene/SiO prepared by the embodiment of the present invention 12Micron size hybrid macromolecule is micro- The TEM pictures of ball；
As seen from Figure 1, monodisperse is presented in microballoon, and grain size is 1.22 microns；
Fig. 2：Polystyrene/SiO prepared by the embodiment of the present invention 22Micron size hybrid macromolecule is micro- The TEM pictures of ball；
As seen from Figure 2, monodisperse is presented in microballoon, and grain size is 1.72 microns；
Fig. 3：Polystyrene/SiO prepared by the embodiment of the present invention 32Micron size hybrid macromolecule is micro- The TEM pictures of ball；
As seen from Figure 3, monodisperse is presented in microballoon, and grain size is 2.25 microns；
Embodiment 1
Monomer styrene 20g, electrolyte potassium carbonate 0.32g are added in reaction kettle, N is passed through2In replacement reaction kettle After air 3 times, deionized water 70g is added, starts to start stirring, mixing speed is set as 200rpm, and is warming up to 65 DEG C；Work as temperature After degree is stablized, 2,2 '-azo diisobutyl amidine hydrochloride 0.48g of cationic initiators part is added and (is dissolved in 10g deionized waters In) cause polymerization.The surfaces 0.32g are added after 6min has the SiO of negative electrical charge2Particle dispersion causes primary particle coalescence, adds Enter surface carboxylation SiO20.16g cationic emulsifier tetradecyl trimethyl ammonium chlorides are added after particle water dispersion liquid 2min Promote the secondary coalescence of particle, 0.8g anionic emulsifier lauryl sodium sulfate termination agglomeration reaction is added after reacting 2min. 85 DEG C are warming up to after 65 DEG C of maintenance reaction 6 hours, 2 hours postcoolings of heat preservation to room temperature normal pressure discharge.To obtain institute of the present invention The grain size stated is 1.22 microns, monodisperse polystyrene/SiO2Organic inorganic hybridization microballoon.
Embodiment 2
Monomer styrene 30g, electrolyte potassium carbonate 0.32g are added in reactor, N is passed through2In replacement reaction kettle After air 2 times, deionized water 60g is added, starts to start stirring, mixing speed is set as 200rpm, and is warming up to 65 DEG C；Work as temperature After degree is stablized, 2,2 '-azo diisobutyl amidine hydrochloride 0.48g of cationic initiators part is added and (is dissolved in 10g deionized waters In) cause polymerization.The surfaces 0.32g are added after 8min has the SiO of negative electrical charge2Particle dispersion causes primary particle coalescence, adds Enter surface carboxylation SiO20.16g cationic emulsifier tetradecyl trimethyl ammonium chlorides are added after particle water dispersion liquid 2min Promote the secondary coalescence of particle, 0.8g anionic emulsifier lauryl sodium sulfate termination agglomeration reaction is added after reacting 4min. 85 DEG C are warming up to after 65 DEG C of maintenance reaction 7 hours, 2 hours postcoolings of heat preservation to room temperature normal pressure discharge.To obtain institute of the present invention The grain size stated is 1.72 microns, monodisperse polystyrene/SiO2Organic inorganic hybridization microballoon.
Embodiment 3
Monomer styrene 30g, electrolyte potassium carbonate 0.32g are added in reactor, N is passed through2In replacement reaction kettle After air 2 times, deionized water 60g is added, starts to start stirring, mixing speed is set as 200rpm, and is warming up to 65 DEG C；Work as temperature After degree is stablized, 2,2 '-azo diisobutyl amidine hydrochloride 0.6g of cationic initiators part is added and (is dissolved in 10g deionized waters In) cause polymerization.The surfaces 0.48g are added after 8min has the SiO of negative electrical charge2Particle dispersion causes primary particle coalescence, adds Enter surface carboxylation SiO20.16g cationic emulsifier tetradecyl trimethyl ammonium chlorides are added after particle dispersion 4min to promote Into the secondary coalescence of particle, 0.8g anionic emulsifier lauryl sodium sulfate termination agglomeration reaction is added after reacting 6min.Dimension It is warming up to 85 DEG C after holding 65 DEG C of reactions 7 hours, 2 hours postcoolings of heat preservation to room temperature normal pressure discharge.It is of the present invention to obtain Grain size be 2.25 microns, monodisperse polystyrene/SiO2Organic inorganic hybridization microballoon.

Claims (5)

1. a kind of preparation method of micron size hybrid polymer microsphere, its step are as follows：
(1) in parts by mass, 10~50 parts of monomers, 0.2~1.5 part of electrolyte are added in reaction kettle, are passed through N2Displacement reaction After air 2~3 times in kettle, 50~90 parts of deionized waters are added, start to start stirring, mixing speed is set as 150~ 450rpm, and it is warming up to 65~75 DEG C；
(2) under stiring, 0.1~5 part of cationic initiators is added into above-mentioned system and causes polymerization, is added after 5~10min There is the inorganic particulate dispersion liquid of negative electrical charge to cause primary particle coalescence on 0.1~5 part of surface, and 0.1~8 part is added after 2~10min Cationic emulsifier promotes the secondary coalescence of particle, and it is anti-that 0.1~8 part of anionic emulsifier termination coalescence is added after 2~10min It answers；80~90 DEG C are warming up to after 65~75 DEG C of maintenance reaction 5~8 hours, 1~3 hour postcooling of heat preservation to room temperature normal pressure discharges, Obtain micron size hybrid polymer microsphere；
Monomer is selected from one or more of methyl methacrylate, styrene, butyl acrylate；Surface has the nothing of negative electrical charge Machine particle dispersion is selected from surface carboxylation SiO2Aqueous dispersions, surface carboxylation Fe3O4One or more of aqueous dispersions.
2. a kind of preparation method of micron size hybrid polymer microsphere as described in claim 1, special Sign is：Electrolyte is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus.
3. a kind of preparation method of micron size hybrid polymer microsphere as described in claim 1, special Sign is：Cationic initiators are selected from two isobutyl imidazoline hydrochloride of azo, 2,2 '-azo diisobutyl amidine hydrochlorides, idol One or more of nitrogen diimidazole quinoline base propane.
4. a kind of preparation method of micron size hybrid polymer microsphere as described in claim 1, special Sign is：Cationic emulsifier is selected from dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, cetyl three Ammonio methacrylate, octadecyltrimethylammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide, ten One or more of six alkyl trimethyl ammonium bromides, Cetyltrimethylammonium bromide.
5. a kind of preparation method of micron size hybrid polymer microsphere as described in claim 1, special Sign is：Anionic emulsifier is selected from lauryl sodium sulfate, dodecyl sulphate potassium, neopelex, 12 One or more of alkyl benzene sulphonate potassium, disproportionated rosin acid soap, fatty acid soaps, potassium oleate, enuatrol.
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