CN111393573A - Functionalized monodisperse microsphere material and preparation method thereof - Google Patents
Functionalized monodisperse microsphere material and preparation method thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 230000008961 swelling Effects 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 26
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- 239000003999 initiator Substances 0.000 claims description 36
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- 238000010438 heat treatment Methods 0.000 claims description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
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- 239000000178 monomer Substances 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
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- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 4
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- NQHAZTDQFIYTQD-UHFFFAOYSA-N SOS Chemical compound SOS NQHAZTDQFIYTQD-UHFFFAOYSA-N 0.000 description 2
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F212/00—Copolymers 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Chemical Kinetics & Catalysis (AREA)
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- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a functionalized monodisperse microsphere material and a preparation method thereof, and the functionalized monodisperse microsphere material is prepared by the following two steps: s01: preparing crosslinked microspheres by adopting a solution anion initiated polymerization method; s02: free radical polymerization is carried out by a swelling method to form monodisperse microspheres with uniform particle size. The invention can realize the controllable polymerization of the seeds by adopting an anionic polymerization method, has high clean degree of the seeds, and avoids the adhesion of microspheres which are not cleaned and are repeatedly washed and caused by using a large amount of surfactant, thereby causing poor dispersion degree after the second step of swelling.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a functionalized monodisperse microsphere material and a preparation method thereof.
Background
With the development of technology and economy, the application range of chemical catalysis, photoelectric materials and magnetic materials is gradually expanded, the metal-based composite material is not only used in an anisotropic conductive film of the photoelectric material, but also replaces the original pure metal initiator I more, the cost is reduced, or the controllability of the nanometer size of a metal site is realized by utilizing the porosity and the high specific surface property of a carrier, so that a small-size effect is generated, the activity of the metal initiator I is greatly promoted, or the cost of conductive particles is reduced by utilizing the carrier. In the process of synthesizing the nano microspheres, the commonly used methods mainly include suspension polymerization, emulsion polymerization, precipitation polymerization or seed swelling polymerization, wherein the particles obtained by the suspension polymerization are relatively small, while the emulsion polymerization can obtain large-particle nano particles, but the uniformity is not good enough, and the nano particles are difficult to use in occasions requiring particle uniformity, for example, in the preparation of Anisotropic Conductive Film (ACF), the seed swelling method can be used to realize relatively good monodisperse nano microsphere polymerization. However, the seed swelling method uses a large amount of auxiliary agents such as surfactant, and the like, so that a long washing process is generated in the later period, and the wastewater is serious; the green mass production is difficult to realize; the solution polymerization method, especially the anion solution polymerization method is a new generation of green polymerization method, has the characteristics of high activity, strong molecular chain predesigned performance, recyclable solvent and the like, and is a synthesis method for synthesizing green pure high-performance microspheres with industrial application prospect.
Disclosure of Invention
The invention aims to provide a high-efficiency functionalized core-shell type monodisperse particle and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a functionalized monodisperse microsphere material is prepared by the following two steps:
s01: preparing crosslinked microspheres by adopting a solution anion initiated polymerization method;
s02: free radical polymerization is carried out by a swelling method to form monodisperse microspheres with uniform particle size.
Preferably, in the step S01, the molecular weight of the crosslinked microspheres is 50-100 ten thousand, preferably 60-70 ten thousand, and the crosslinked microspheres are prepared by a solution anion initiation polymerization method, wherein the crosslinked microspheres are prepared from a polymerization monomer, a solvent I, an initiator I, a crosslinking agent and a polymerization inhibitor, the polymerization monomer is one or two or three of styrene, isoprene and butadiene, the mass concentration of the polymerization monomer is 5-30%, preferably 10-15%, the mass concentration of the crosslinking agent is 5-30%, preferably 10-15% of the polymerization monomer, and the concentration of the initiator I is 0.5-1.6M/L.
Preferably, the solvent I is one or more of n-hexane, cyclopentane and cyclohexane, preferably n-hexane or cyclopentane, and the water content is 10-20 ppm; the initiator I is butyl lithium or lithium cycloheximide; the crosslinking agent is DVB (divinylbenzene); the polymerization inhibitor is water, alcohol or acid in an electrophilic reagent.
Preferably, the monodisperse microspheres in step S02 are prepared from the following components in parts by weight by a seed swelling method: 100 parts of crosslinking microspheres, 10-20 parts of stabilizing agent, 10-20 parts of dispersing agent, solvent II, 300 parts of swelling agent 200-; the stabilizer is PVP; the dispersant is a surfactant; swelling agent non-polar alkane or arene systems; the solvent II is a water body or a non-water system.
Preferably, the dispersant is one or more of PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol) and SDS (sodium dodecyl sulfate); the solvent II is water, ethanol or methanol; the swelling agent is one or more of benzene, toluene, xylene, dichloromethane, chlorododecane, bromododecane, octadecane and hexadecane.
Preferably, the initiator II is a peroxy initiator or azo initiator, including cyclohexanone peroxide, BPO (dibenzoyl peroxide), tert-butyl hydroperoxide, AIBN (azobisisobutyronitrile), azobisisoheptonitrile.
A preparation method of a functionalized monodisperse microsphere material comprises the following steps:
anionic polymerization of S01: replacing nitrogen in a high-pressure reactor for three times, adding a dried solvent I, adding a certain amount of polymerization monomer according to the designed molecular weight, adding an initiator I, heating for polymerization for a certain time, adding a certain amount of cross-linking agent for cross-linking, and after cross-linking is finished, stopping with a polymerization inhibitor and precipitating powder to obtain cross-linked microsphere seeds for later use (as shown in a reaction formula I);
s02 seed swelling method: adding a certain amount of stabilizing agent into the obtained crosslinked microsphere seeds, dissolving or dispersing in a solvent II, adding a certain amount of swelling agent and polymerization monomer at a certain temperature for swelling, adding an initiator II for free radical initiation, and carrying out ultrasonic dispersion under a certain condition to synthesize the monodisperse microsphere.
Preferably, the anionic polymerization in step S01 is carried out at a temperature of 40-90 deg.C, preferably 60-80 deg.C, for a time of X-X.
Preferably, the swelling temperature in step S02 is 30-40 deg.C, and the swelling time is 10-15 h.
Preferably, the reaction temperature of the seed swelling polymerization in step S02 is 70-80 ℃ and the time is 3-5 h.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, the controllable polymerization of seeds can be realized by adopting an anionic polymerization method, the cleanness degree of the seeds is very high, and the adhesion of microspheres which are not cleaned and are repeatedly washed and caused by using a large amount of surfactant is avoided, so that the dispersity is poor after the second step of swelling;
2) the monodisperse functionalized microspheres which are environment-friendly and have better uniformity are synthesized by the synergy of the anionic solution polymerization method and the later-stage seed swelling method.
Drawings
FIG. 1 is an optical mirror of the crosslinked microspheroidal seed of example 1;
FIG. 2 is a TEM transmission electron micrograph of the crosslinked microsphere seeds (dispersed in ethanol) of example 1;
FIG. 3 is an SEM electron micrograph of crosslinked microsphere seeds (dispersed in ethanol) of example 1;
FIG. 4 is SEM electron micrograph of 5.4um monodisperse microspheres (dispersed in ethanol) after swelling in example 1;
FIG. 5 is SEM electron size statistical chart of 5.4um monodisperse microspheres (dispersed in ethanol) after swelling in example 1;
FIG. 6 is an SEM image of crosslinked microsphere seed agglomeration for DVB greater than 8g in example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the 5um monodisperse microsphere comprises the following steps:
s01, replacing nitrogen for three times in a high-pressure reactor, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, adding 50g of anhydrous styrene without polymerization inhibitor, adding 45g of butadiene, adding 0.2M L of tetrahydrofuran serving as a structure regulator, adding 0.2M L of 1M/L butyl lithium initiator serving as an initiator, heating to 60 ℃ for polymerization for 2 hours, adding 5g of DVB (digital video broadcasting) for crosslinking, terminating with ethanol and precipitating powder after crosslinking is finished, and obtaining the 3.8-micron crosslinked microspheres.
S02, dispersing 5g of the obtained PS particles in 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L0.05.05 g of toluene at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, ultrasonically dispersing and heating to synthesize monodisperse nano microsphere B of about 5.4um, centrifugally washing and drying.
Example 2
The preparation method of the 10um monodisperse microsphere comprises the following steps:
s01, replacing nitrogen for three times in a high-pressure reactor, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, adding 50g of anhydrous styrene without polymerization inhibitor, adding 45g of butadiene, adding 0.2M L of tetrahydrofuran serving as a structure regulator, adding 0.2M L of 1M/L butyl lithium initiator serving as an initiator, heating to 60 ℃ for polymerization for 2 hours, adding 2g of DVB (digital video broadcasting) for crosslinking, terminating with ethanol and precipitating powder after crosslinking is finished, and obtaining the 5.1um crosslinked microspheres.
S02, dispersing 5g of the obtained PS nano-particles in 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L0.05.05 g of chlorododecane at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize monodisperse nano-microsphere B microspheres of about 10.2um, centrifuging, washing and drying.
Example 3
The preparation method of the 10um nitrogen-dimethyl functionalized monodisperse microsphere material comprises the following steps:
s01, replacing nitrogen for three times in a high-pressure reactor, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, 45g of butadiene and 10g of nitrogen-dimethyl styrene, adding 0.05M L of structure regulator tetrahydrofuran, adding 0.22M L of initiator 1M/L butyl lithium initiator, reacting at 60 ℃, continuously adding 150g of anhydrous styrene without polymerization inhibitor for half an hour, heating to 60 ℃, polymerizing for 1 hour, cooling to 40 ℃, adding 2g of DVB (digital video broadcasting) for crosslinking, heating to 60 ℃, continuously reacting for half an hour, cooling, stopping with ethanol, precipitating powder, and obtaining 4.8um crosslinked microspheres containing nitrogen functionalization;
s02, dispersing 5g of the obtained PS nano-particles into 5% SDS aqueous solution of 0.2L, adding PVP0.5g, adding 3g of styrene, 10m L0.3.3 g of octadecane and 0.15g of AIBN at 40 ℃ for ultrasonic swelling for 12 hours, heating to 70 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize monodisperse nano-microsphere B microspheres of about 9.2um, centrifuging, washing and drying to obtain the functionalized microspheres.
Example 4
The preparation method of the 8um mercaptoether functionalized microsphere material comprises the following steps: (Octadecane swelling)
S01, in a high-pressure reactor, replacing nitrogen for three times, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, adding 5g of mercapto-functionalized monomer, adding 40g of butadiene, adding 1M/L of butyl lithium initiator 0.2M L, heating to 60 ℃ for reaction for 1 hour, continuously adding 150g of anhydrous styrene without polymerization inhibitor, continuously reacting for 1 hour, cooling to 40 ℃, rapidly adding 2g of DVB (digital video broadcasting) for crosslinking, stopping with ethanol after crosslinking is finished, and precipitating powder to obtain mercaptomethyl-functionalized 5.4um crosslinked microspheres;
s02, dispersing 5g of the obtained PS nano-particles in 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L of octadecane at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize monodisperse nano-microsphere B microspheres of about 8.2um, centrifuging, washing and drying.
Example 5
The preparation method of the 6um mercapto ether functionalized microsphere material comprises the following steps: (Chlorododecane swelling)
S01, in a high-pressure reactor, replacing nitrogen for three times, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, adding 5g of mercapto-functionalized monomer, adding 40g of butadiene, adding 1M/L of initiator, namely 0.2M L of butyl lithium, heating to 60 ℃, reacting for 1 hour, continuously adding 150g of anhydrous styrene without polymerization inhibitor, continuously reacting for 1 hour, cooling to 40 ℃, rapidly adding DVB2g for crosslinking, stopping with ethanol and precipitating powder after crosslinking is finished, and obtaining mercaptomethyl-functionalized 3.9um crosslinked microspheres;
s02, dispersing 5g of the obtained PS nano-particles in 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L0.05.05 g of chlorododecane at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize monodisperse nano-microsphere B microspheres of about 6.3um, centrifuging, washing and drying.
Example 6
The preparation method of the 5um butadiene long haired core-shell microsphere material comprises the following steps:
s01, in a high pressure reactor, replacing nitrogen for three times, adding 1kg of dried solvent (containing 10-20 ppm of water) n-hexane, adding 100g of butadiene, adding 1M/L of butyl lithium initiator 0.13M L, preparing butadiene hair with the molecular weight of 85 ten thousand, adding 50g of anhydrous styrene without polymerization inhibitor and 10g of butadiene after the butadiene is polymerized, adding 5g of DVB, continuously adding 1M/L of butyl lithium initiator 0.05M L, heating to 60 ℃, polymerizing for 2 hours, finishing crosslinking, stopping with ethanol and precipitating powder to obtain 2.1um of crosslinked core-shell microspheres with long butadiene hair, (if the DVB is more than 8g, the phenomenon of seed agglomeration occurs, as shown in figure 6)
S02, dispersing 5g of the obtained PS nano-particles into a 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L0.05.05 g of toluene at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize the monodisperse core-shell microsphere B with the butadiene long hair, wherein the thickness of the core-shell microsphere B is about 4.1um, and centrifuging, washing and drying.
Example 7
The preparation method of the 4um isoprene long haired core-shell microsphere material comprises the following steps:
s01, in a high-pressure reactor, replacing nitrogen for three times, adding 1kg of dried n-hexane (containing 10-20 ppm of water) as a solvent, adding 100g of isoprene, adding 1M/L of butyl lithium initiator 0.13M L as an initiator, preparing isoprene hair with the molecular weight of 80 ten thousand, adding 50g of anhydrous styrene (except polymerization inhibitor) and 10g of butadiene after the isoprene is polymerized, adding DVB5g, continuously adding 0.05M L of 1M/L of butyl lithium initiator as an initiator, heating to 60 ℃, polymerizing for 2 hours, terminating with ethanol and precipitating powder after crosslinking is finished, and obtaining 2.1um of core-shell crosslinked microspheres with isoprene long hair;
s02, dispersing 5g of the obtained PS nano-particles into a 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 3g of styrene and 10m L0.05.05 g of toluene at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize the monodisperse core-shell microsphere B with isoprene long hair, wherein the diameter of the core-shell microsphere B is about 4.3um, and centrifuging, washing and drying.
Example 8
The preparation method of the 4um isoprene long haired core-shell microsphere material comprises the following steps: (sulfhydryl nucleus)
S01, in a high-pressure reactor, replacing nitrogen for three times, adding 1kg of dried n-hexane (containing 10-20 ppm of water) as a solvent, adding 100g of isoprene, adding 1M/L of butyl lithium initiator 0.13M L as an initiator, preparing isoprene hair with the molecular weight of 80 ten thousand, adding 50g of anhydrous styrene (except polymerization inhibitor) and 10g of butadiene after the isoprene is polymerized, adding DVB5g, continuously adding 0.05M L of 1M/L of butyl lithium initiator as an initiator, heating to 60 ℃, polymerizing for 2 hours, terminating with ethanol and precipitating powder after crosslinking is finished, and obtaining 2.1um of core-shell crosslinked microspheres with isoprene long hair;
s02, dispersing 5g of the obtained PS nano-particles into a 5% SDS aqueous solution of 0.2L, adding 0.5g of PVP, adding 2g of styrene, 2g of a sulfydryl functional reagent, 10m of toluene L0.2.2 g and 0.05g of AIBN at 40 ℃ for ultrasonic swelling for 12 hours, heating to 80 ℃ for initiating polymerization, performing ultrasonic dispersion and heating to synthesize the monodisperse sulfydryl functional core-shell microsphere B with isoprene long hair, wherein the diameter of the core-shell microsphere B is about 4.3um, and performing centrifugal washing and drying.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (10)
1. A functionalized monodisperse microsphere material is characterized by being prepared by the following two steps:
s01: preparing crosslinked microspheres by adopting a solution anion initiated polymerization method;
s02: free radical polymerization is carried out by a swelling method to form monodisperse microspheres with uniform particle size.
2. The functionalized monodisperse microsphere material of claim 1, wherein the molecular weight of the crosslinked microsphere of step S01 is 50-100 ten thousand, and the functionalized monodisperse microsphere material is prepared by a solution anion initiated polymerization method from a polymerization monomer, a solvent I, an initiator I, a crosslinking agent and a polymerization inhibitor, wherein the polymerization monomer is one or two or three of styrene, isoprene and butadiene, the mass concentration of the polymerization monomer is 5-30%, the mass concentration of the crosslinking agent is 5-30% of the polymerization monomer, and the concentration of the initiator I is 0.5-1.6M/L.
3. The functionalized monodisperse microsphere material of claim 2, wherein the solvent I is one or more of n-hexane, cyclopentane and cyclohexane; the initiator I is butyl lithium or lithium cycloheximide; the cross-linking agent is DVB; the polymerization inhibitor is water, alcohol or acid in an electrophilic reagent.
4. The functionalized monodisperse microsphere material of claim 1, wherein the monodisperse microsphere is prepared from the following components in parts by weight by a seed swelling method in step S02: 100 parts of crosslinking microspheres, 10-20 parts of stabilizing agent, 10-20 parts of dispersing agent, solvent II, 300 parts of swelling agent 200-; the stabilizer is PVP; the dispersant is a surfactant; swelling agent non-polar alkane or arene systems; the solvent II is a water body or a non-water system.
5. The functionalized monodisperse microsphere material of claim 4, wherein the dispersant is one or more of PVP, PVA and SDS; the solvent II is water, ethanol or methanol; the swelling agent is one or more of benzene, toluene, xylene, dichloromethane, chlorododecane, bromododecane, octadecane and hexadecane.
6. A functionalized monodisperse microsphere material according to claim 4, wherein the initiator II is a peroxy initiator or azo initiator, including cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile.
7. The preparation method of the functionalized monodisperse microsphere material based on any one of claims 1 to 6, which is characterized by comprising the following steps:
anionic polymerization of S01: in a high-pressure reactor, replacing nitrogen for three times, adding a dried solvent I, adding a certain amount of polymerization monomers according to the designed molecular weight, adding an initiator I, heating for polymerization for a certain time, adding a certain amount of cross-linking agent for cross-linking, and after cross-linking is finished, stopping by using a polymerization inhibitor and precipitating powder to obtain cross-linked microsphere seeds for later use;
s02 seed swelling method: adding a certain amount of stabilizing agent into the obtained crosslinked microsphere seeds, dissolving or dispersing in a solvent II, adding a certain amount of swelling agent and polymerization monomer at a certain temperature for swelling, adding an initiator II for free radical initiation, and carrying out ultrasonic dispersion under a certain condition to synthesize the monodisperse microsphere.
8. The method for preparing a functionalized monodisperse microsphere material according to claim 7, wherein the anionic polymerization reaction temperature in step S01 is 40-90 ℃ and the time is 1-3 h.
9. The method of claim 7, wherein the swelling temperature in step S02 is 30-40 ℃ and the swelling time is 10-15 h.
10. The method of claim 7, wherein the polymerization temperature of the seed swelling polymerization in step S02 is 70-80 ℃ for 3-5 h.
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| CN1927899A (en) * | 2006-09-01 | 2007-03-14 | 烟台硕德新材料有限公司 | Preparation method of micron-sized monodisperse copolymerized microspheres |
| CN102718910A (en) * | 2012-04-23 | 2012-10-10 | 苏州异导光电材料科技有限公司 | Preparation method of crosslinked polystyrene microsphere |
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| JP2005060479A (en) * | 2003-08-08 | 2005-03-10 | Sekisui Chem Co Ltd | Production method for highly monodisperse fine particle |
| CN1927899A (en) * | 2006-09-01 | 2007-03-14 | 烟台硕德新材料有限公司 | Preparation method of micron-sized monodisperse copolymerized microspheres |
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