CN104744650A - Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base - Google Patents
Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base Download PDFInfo
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- CN104744650A CN104744650A CN201510161340.7A CN201510161340A CN104744650A CN 104744650 A CN104744650 A CN 104744650A CN 201510161340 A CN201510161340 A CN 201510161340A CN 104744650 A CN104744650 A CN 104744650A
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Abstract
The invention provides a preparation method of a POSS (polyhedral oligomeric silsesquioxane) based hybrid copolymer and belongs to the fields of high polymer materials and bioengineering. The preparation method specifically comprises the following steps: modifying methacrylate to mono-functional vinyl (the other seven lateral groups are isobutyl) POSS to obtain a monomer containing POSS; performing RAFT (reverse addition-fragmentation transfer) polymerization under the initiation of AIBN (azodiisobutyronitrile) to obtain a homopolymer containing POSS; and further polymerizing the product, which is obtained in the previous step and is used as a macromolecular chain transfer agent, with a monomer DMAEMA (dimethylaminoethyl methacrylate) to prepare an amphiphilic organic/inorganic hybrid copolymer. The hybrid material prepared by the method provided by the invention can be self-assembled in water to form a micelle, has temperature and pH responsiveness, and can be widely applied in the fields of biological nano materials, fiber flame-retardant materials, biosensors and the like.
Description
Technical field
The invention belongs to polymeric material field and bioengineering field, be specifically related to a kind of preparation method and application thereof of the nano material containing POSS base hybrid.
Background technology
Polyhedral polysilsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is a kind of oligosiloxane of nano-scale structures, and its general structure is (RSiO
1.5)
n, wherein n=6,8,10,12 etc., R is organo-functional group.It has the cubes cage structure of high degree of symmetry, and size is at about 1-3nm.Because nanometer size effect specific to it, do heat-resisting, low density, high antioxygenic property etc., the research and development about POSS more and more obtain the concern of people.
The preparation method of POSS based polyalcohol is a lot, usually has copolymerization, grafting, blended etc.Due to the blended characteristic that the phase separation structure of macroscopic view usually can be caused to pass its nano-hybrid material: and graft reaction is usually because grafting efficiency problem makes POSS hydridization efficiency lower.At present, prepare POSS based polyalcohol by living polymerisation process and both there is accurate structure, more POSS can be introduced in relative broad range again, and reaction conditions is gentle, in the POSS based polyalcohol of synthesizing new, have huge application prospect.
(the Hussain H such as He, Tan BH, Seah GL, Liu Y, He CB, Davis TP.Micelle Formation and Gelation of (PEG P (MA-POSS)) AmphiphilicBlock Copolymers via Associative Hydrophobic Effects.Langmuir.2010; 26 (14): 11763-73.) adopting RFAT method to synthesize containing POSS is the hybrid copolymers of structural unit.They for chain-transfer agent, synthesize P (MA-POSS) homopolymer with RAFT polymerization process with DDAT (S-1-dodecyl-S '-(α, α '-dimethyl-α 〃-acetic acid) trithiocarbonate); (the Yang C such as Dai, Deng Y, Zeng B, Yuan C, Chen M, Luo W, et al.Hybridamphiphilic block copolymers containing polyhedral oligomericsilsesquioxane:Synthesis, characterization, and self-assembly insolutions.Journal of Polymer Science Part A:Polymer Chemistry.2012; 50 (20): 4300-10.) report and synthesized PMAPOSS-b-P (AA-co-St) multipolymer by RAFT polymerization; Yuanming Deng (Deng Y, Bernard J, Alcouffe P, Galy J, Dai L, Gerard JF.Nano-structured hybrid polymernetworks from situ self-assembly of RAFT-synthesized POSS-basedblock copolymers.Journal of Polymer Science Part A Polymer Chemistry2011; 49:4343 – 52.) etc. synthesized first-stage polymerization thing PMACyPOSS-b-PMMA.
The POSS base block polymer using RAFT polymerization process to synthesize in document is owing to being subject to the steric influence of cage structure, and living polymerization efficiency is lower, and the polymerization degree upper limit is all no more than 26.In order to obtain the higher POSS based polyalcohol of the polymerization degree, needing the self structure improving POSS monomer, living polymerization efficiency is improved.
Summary of the invention
One object of the present invention is the preparation method providing a kind of oligomeric silsesquioxanes novel monomeric.
Another object of the present invention is to provide a kind of preparation method of Polyhedral oligomeric silsesquioxanes homopolymer.
Another object of the present invention there is provided more than one, and to state Polyhedral oligomeric silsesquioxanes homopolymer be the first block, polymethyl acrylic acid N, N-dimethylamino ethyl ester is the multipolymer of the second block, and the mol ratio of POSS monomer and chain-transfer agent is 10-100, preferred 30-50; The mol ratio of chain-transfer agent and initiator is 1-10, preferably 3; The mol ratio of PDMAEMA and Polyhedral oligomeric silsesquioxanes homopolymer is 10-1000, preferred 30-900, and the mass ratio that described first block accounts for Polyhedral oligomeric silsesquioxanes homopolymer is 20%-70%; Described POSS monomer structure formula I is as follows:
Wherein, R=-iBu, isobutyl-, or R=-Ph, phenyl, or R=-Cy, the one in cyclopentyl etc.
The preparation method of a kind of POSS base hybrid multipolymer of the present invention comprises the following steps: (1) vinyl (other seven side bases are identical inertia group) oligomeric silsesquioxane is dissolved in solvent orange 2 A; add the B solution of Thiovanic acid and Diisopropyl azodicarboxylate (AIBN); in 80 DEG C, 6h is stirred under nitrogen protection; filtration is washed with water, vacuum-drying 24h at 40 DEG C after reaction terminates.Above-mentioned product is dissolved in dry solvent C, adds HEMA and DMAP, be placed in flask and stir, in constant pressure funnel, add the C solution of DCC, instill in flask in 1h under ice-water bath condition and react, and at room temperature continue reaction 24h.Reaction terminates rear solvent C and water washs, and gets upper strata oil solution, uses MgSO
4be spin-dried for after drying, product obtains the monomer containing POSS after carrying out column chromatography for separation.
(2) the POSS monomer of step (1) gained is added in long-neck polymerization bottle, add the B solution (CDB) of the withered ester of dithiobenzoic acid and the B solution (AIBN) of Diisopropyl azodicarboxylate simultaneously, through 3 freeze-thaw cycle, vacuumize tube sealing under state.In 65 DEG C of oil baths, react 48h, reaction terminates rear liquid nitrogen cancellation reaction.Precipitate 3 times in the precipitation agent D of ice, and the sample of suction filtration gained is put into 30 DEG C of dry 24h of vacuum drying oven.Obtain the homopolymer containing POSS.
Using the homopolymer of the POSS of step (2) gained as chain-transfer agent, be dissolved in solvent orange 2 A, add DMAEMA monomer, and the B solution of Diisopropyl azodicarboxylate (AIBN).Through three freeze-thaw cycle operations, vacuumize tube sealing, in 65 DEG C of oil baths, react 10h, reaction terminates rear liquid nitrogen cancellation.Put into dialysis tubing after dissolving with solvent orange 2 A, dialyse in A and water mixed solution, remove excess monomer completely, lyophilize, obtain organic/inorganic hybridization material.
The present invention by the POSS monomer of synthesizing new, and has synthesized by reversible addition and fragmentation chain transfer polymerization process that molecular weight is controlled obtains oligomeric silsesquioxanes homopolymer.The method breaches the restriction of the polymerization degree caused due to POSS steric factor in polymerization process in the past, obtains the POSS segmented copolymer that the polymerization degree is higher.
Adopt reversible addition and fragmentation chain transfer polymerization means, with above-mentioned POSS segmented copolymer for Macromolecular chain transfer agent, select suitable ratio to add monomer and initiator, preparation POSS base hybrid multipolymer.
Accompanying drawing explanation
Fig. 1 is POSS monomer
1hNMR nmr spectrum.
Fig. 2 is homopolymer containing POSS
1hNMR nmr spectrum.
Embodiment
For a more detailed description to the present invention by embodiment below.
Embodiment 1
The synthesis of novel POSS monomer: vinyl (other seven side bases are isobutyl-) oligomeric silsesquioxane is dissolved in 50mL tetrahydrofuran (THF) (THF); add 0.35mL Thiovanic acid and AIBN (0.42mL; 70mg); in 80 DEG C, 6h is stirred under nitrogen protection; reaction terminates rear 1L water washing and filters, vacuum-drying 24h at 40 DEG C.Above-mentioned product is dissolved in dry CH
2cl
2in, add HEMA (1mmol, 0.12mL) and DMAP (0.5mmol, 65mg), be placed in 50mL flask and stir, in constant pressure funnel, add the CH of DCC (0.5mmol, 0.1g)
2cl
2solution, instills in flask and reacts under ice-water bath condition in 1h, and at room temperature continues reaction 24h.Reaction terminates rear methylene dichloride and water washs, and gets upper strata oil solution, uses MgSO
4be spin-dried for after drying, product carries out column chromatography for separation.Obtain the novel monomeric (productive rate 75%) containing POSS.
The synthesis of the homopolymer containing POSS: in long-neck polymerization bottle, add MAHPOSS (1g, 0.92mmol), toluene solution (the CDB of the withered ester of 417.1 μ L dithiobenzoic acid, 20mg/mL, toluene solution (the AIBN of 0.0185mmol) He 164.2 μ L Diisopropyl azodicarboxylates, 10mg/mL, 0.01mmol), add 0.5mL toluene again to dissolve, through 3 freeze-thaw cycle, vacuumize tube sealing under state, in 65 DEG C of oil baths, react 48h, reaction terminates rear liquid nitrogen cancellation reaction.Precipitate 3 times in the methanol solution of ice, and the sample of suction filtration gained is put into 30 DEG C of dry 24h of vacuum drying oven.Obtain the homopolymer that P contains POSS.
POSS base hybrid multipolymer synthesizes:, the homopolymer of POSS above-mentioned for 0.2g (0.0056mmol) is added in dry long-neck polymerization bottle, add 0.4gDMAEMA (2.52mmol) simultaneously, the THF solution (10mg/mL, 0.0013mmol) of 22 μ L AIBN and 1mL THF solution, as solvent, put into stirrer, through three freeze-thaw cycle operations, vacuumize tube sealing, in 65 DEG C of oil baths, react 10h, reaction terminates rear liquid nitrogen cancellation.Put into dialysis tubing after dissolving with 10mL THF, dialyse in the mixing solutions of THF and water, remove excess monomer completely, lyophilize, obtain POSS base hybrid multipolymer.Mn＝67900g/mol,Mw/Mn＝1.22。
Embodiment 2
Similar with example 1, its mol ratio being different from POSS homopolymer in step 3 and PDMAEMA is 1:250, and all the other are with embodiment one.Obtain POSS base hybrid multipolymer.Mn＝42300g/mol,Mw/Mn＝1.20。
Embodiment 3
Similar with example 1, its mol ratio being different from POSS homopolymer in step 3 and PDMAEMA is 1:900, and all the other are with embodiment one.Obtain POSS base hybrid multipolymer.Mn＝105000g/mol,Mw/Mn＝1.25。
Claims (6)
1. a preparation method for POSS base hybrid copolymers, comprises the following steps:
A. vinyl oligomeric silsesquioxane is dissolved in solvent orange 2 A, adds the B solution of Thiovanic acid and Diisopropyl azodicarboxylate, stirs 6h under nitrogen protection in 80 DEG C, washes filtration with water, vacuum-drying 24h at 40 DEG C after reaction terminates; Above-mentioned product is dissolved in dry solvent C, adds HEMA and DMAP, be placed in flask and stir, in constant pressure funnel, add the C solution of DCC, instill in flask in 1h under ice-water bath condition and react, and at room temperature continue reaction 24h; Reaction terminates rear solvent C and water washs, and gets upper strata oil solution, uses MgSO
4be spin-dried for after drying, product obtains the monomer containing POSS after carrying out column chromatography for separation;
B. add in long-neck polymerization bottle by the POSS monomer of step a gained, add the B solution of the withered ester of dithiobenzoic acid and the B solution of Diisopropyl azodicarboxylate, after freeze-thaw cycle is degassed, tube sealing is polymerized simultaneously, and reaction terminates rear liquid nitrogen cancellation reaction; Precipitate 3 times in the precipitation agent D of ice, and the sample of suction filtration gained is put into 30 DEG C of dry 24h of vacuum drying oven; Obtain the homopolymer containing POSS;
C. using the homopolymer of the POSS of step b gained as chain-transfer agent, be dissolved in solvent orange 2 A, add DMAEMA monomer, and the B solution of Diisopropyl azodicarboxylate; After three freeze-thaw cycle are degassed, tube sealing is polymerized, and reaction terminates rear liquid nitrogen cancellation; Put into dialysis tubing after dissolving with solvent orange 2 A, dialyse in A and water mixed solution, remove excess monomer completely, lyophilize, obtain POSS base hybrid multipolymer.
2. the preparation method of a kind of POSS base hybrid copolymers according to claim 1, is characterized in that: described solvent orange 2 A is tetrahydrofuran (THF), DMF or dimethyl sulfoxide (DMSO).
3. the preparation method of a kind of POSS base hybrid copolymers according to claim 1, is characterized in that: described solvent B is toluene, benzene or tetrahydrofuran (THF).
4. the preparation method of a kind of POSS base hybrid copolymers according to claim 1, is characterized in that: described solvent C is methylene dichloride, tetrahydrofuran (THF) or DMF.
5. the preparation method of a kind of POSS base hybrid copolymers according to claim 1, is characterized in that: described precipitation agent D is the one or both mixture in methyl alcohol, acetone and ethyl acetate.
6. the preparation method of a kind of POSS base hybrid copolymers according to claim 1, is characterized in that: in described step b, polymerization temperature is 65 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670004A (en) * | 2016-01-19 | 2016-06-15 | 武汉纺织大学 | Preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles |
| CN107057046A (en) * | 2017-03-23 | 2017-08-18 | 河南师范大学 | Nucleocapsid hybrid copolymers POSS (PDMAEMA b PDLA)8And its synthetic method and application |
| CN108531513A (en) * | 2018-03-20 | 2018-09-14 | 天津大学 | Star-like multiple target function genophore based on POSS and application |
| US20200015699A1 (en) * | 2018-07-12 | 2020-01-16 | Shin-Etsu Chemical Co., Ltd. | Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode |
| CN114716814A (en) * | 2022-05-13 | 2022-07-08 | 安徽康采恩包装材料有限公司 | High-barrier packaging material and preparation process thereof |
-
2015
- 2015-04-07 CN CN201510161340.7A patent/CN104744650A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670004A (en) * | 2016-01-19 | 2016-06-15 | 武汉纺织大学 | Preparation method of POSS (polyhedral oligomeric silsesquioxane)-based nanohybrid micelles |
| CN107057046A (en) * | 2017-03-23 | 2017-08-18 | 河南师范大学 | Nucleocapsid hybrid copolymers POSS (PDMAEMA b PDLA)8And its synthetic method and application |
| CN108531513A (en) * | 2018-03-20 | 2018-09-14 | 天津大学 | Star-like multiple target function genophore based on POSS and application |
| US20200015699A1 (en) * | 2018-07-12 | 2020-01-16 | Shin-Etsu Chemical Co., Ltd. | Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode |
| US11517236B2 (en) * | 2018-07-12 | 2022-12-06 | Shin-Etsu Chemical Co., Ltd. | Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode |
| CN114716814A (en) * | 2022-05-13 | 2022-07-08 | 安徽康采恩包装材料有限公司 | High-barrier packaging material and preparation process thereof |
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Application publication date: 20150701 |