CN102199262B - Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof - Google Patents
Polyhedral oligomeric silsesquioxane amphiphilic block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polyhedral oligomeric silsesquioxane amphiphilic block copolymer and a preparation method thereof, and relates to macromolecular copolymer. Polyhedral oligomeric silsesquioxane POSS is taken as a hydrophobic block, and polyacrylic acid is taken as a hydrophilic block. The preparation method comprises the following steps of: adding a POSS monomer, a chain transfer agent and an initiator into a solvent, performing freeze degassing in a reaction container, and introducing argon into the reaction container, sealing for reaction, stopping the reaction until liquid nitrogen is frozen to obtain the hydrophobic block of polyhedral oligomeric silsesquioxane POSS; and adding tert-Butyl acrylate, an initiator and a solvent, performing freeze thawing degassing, introducing argon, sealing for polymerization, stopping the reaction until liquid nitrogen is frozen, removing unreacted tert-Butyl acrylate by using a dissolving precipitated method, adding a solvent for dilution, precipitating by using a precipitator, drying, stirring, soaking and purifying in an excessive selective solvent, filtering, drying to obtain polyhedral oligomeric silsesquioxane POSS-poly(tert-butyl acrylate) block copolymer, adding a cosolvent and an acidolysis reagent, and performing rotary evaporation to obtain the product.
Description
Technical field
The present invention relates to a kind of high-molecular copolymer, relate in particular to a kind of reversible addition---the cracking chain shift (RAFT) polymerization with POSS as amphiphilic block copolymer of hydrophobic block and preparation method thereof.This amphiphilic block copolymer first block is polymethyl acyl-oxygen propyl group POSS, and the second block is polyacrylic acid.This invention can be used for parents' macromolecular design and the research of self-assembly morphology.
Background technology
Over nearly 10 years, polyhedral silsesquioxane (Polyhedral oligomeric silsesquioxane, POSS) causes increasing concern as a kind of organic-inorganic hybrid nanomaterials.POSS has cage structure, and its classical structural formula is (RSiO
1.5)
n(n 〉=4, R=H, alkyl, aryl or organo-functional group) is between silicon-dioxide (SiO
2) and silicone resin (R
2SiO)
nBetween, diameter 1.5nm～3nm, due to performances such as its peculiar nanometer size effect, low density, high heat-resisting, high anti-oxidations, POSS becomes one of the most useful raw material of research and development organic-inorganic nano hybrid composite material.
The preparation method of POSS based polyalcohol is a lot, and blend, copolymerization, grafting etc. are arranged usually.Nowadays, the report for preparing nano composite material by copolymerization is more, and with respect to physical blending, the effect of chemical bond is can be more effectively polymer-modified from the molecular structure.The method of copolymerization has polycondensation, anionoid polymerization, active free radical polymerization, traditional radical polymerization and ring opening metathesis polymerization etc.At present, existing many investigators have done a large amount of research work to the synthetic POSS group block copolymer of Controlled Living Radical Polymerization.Pyun etc. (1, J.Pyun, K.Matyjaszewski.Macromolecules.2000,33,217-220; 2, J.Pyun, K.Matyjaszewski, J.Wu et al.Polymer.2003,44,2739-2750) prepared the positive butyl ester of polymethyl acyl-oxygen propyl group POSS-polyacrylic acid-polymethyl acyl-oxygen propyl group POSS triblock polymer (MAPOSS-BA-MAPOSS) with atom transfer radical polymerization (ATRP), and its structure and performance are studied, be limited to 15 on the polymerization degree of its MAPOSS block.Xu etc. (3, W.T.Xu, C.H.Chung, Y.Kwon.Polymer, 2007,48,6286-6293) also reported by norbornene POSS (NBEPOSS) and two trimethyl silane ester (NBETMS) ring-opening polymerizations of norbornylene dioctyl phthalate and obtained polynorbornene POSS-polynorbornene dioctyl phthalate two trimethyl silane ester block copolymers (PNBETMS-b-PNBEPOSS), and obtained polynorbornene POSS-polynorbornene dioctyl phthalate segmented copolymer (PNBECOOH-b-PNBEPOSS) after hydrolysis PNBETMS.Hirai etc. (4, T.Hirai, M.Leolukman et al.Macromolecules.2009,42,8835-8843; 5, T.Hirai, M.Leolukman et al.Macromolecules.2008,41,4558-4560) prepare methacryloxypropyl POSS homopolymer (PMAPOSS) and polymethylmethacrylate-polymethyl acyl-oxygen propyl group POSS segmented copolymer (PMMA-b-PMAPOSS), polystyrene-poly methacryloxypropyl POSS segmented copolymer (PS-b-PMAPOSS) by anionoid polymerization, and the polymerization degree of MAPOSS segment can reach more than 30, and this is pointed out that due to due to the low-activation energy of negatively charged ion chainpropagation.In addition, they have also carried out sufficient research to its phase structure.Compare with above-mentioned segmented copolymer preparation method, reversible addition---cracking chain shifts more late being found of (RAFT) polymerization process, but but has its unique advantage, applicable monomer scope is wide, and reaction conditions is gentle, even can carry out in water solvent, therefore cause widely and paid close attention to.
Recently, the parents' macromole that contains POSS of various structures novelty is continuing to bring out and is drawing attention gradually.Zhang etc. (6, L.Zhang, D.Lu et al.Macromol.Rapid.Commun.2009,30,1015-1020) introduced underslung POSS at the junction point of polystyrene (PS) and polyoxyethylene glycol (PEG) two blocks, and observed its desirable vesica form in the aqueous solution.Kim etc. (7, B-S Kim, P.T.Mather.Macromolecules, 2002,35,8378-8384; 8, B-S Kim, P.T.Mather.Polymer, 2006,47,6202-6207; 9, B-S Kim, P.T.Mather.Macromolecules.2006,39,9253-9260) synthesized huge legendary turtle parents macromole POSS-PEG-POSS far away with POSS urea groups end-blocking, and find that by hot platform polarization optics microscope (POM) and wide-angle x-ray diffraction (WAXD) microphase-separated appears in product, and the form that POSS assembles with nano microcrystalline exists.Zhang etc. (10, W.A.Zhang, B.Fang et al.Macromolecules.2009,42,2563-2569) successfully the synthetic RAFT chain-transfer agent that contains POSS also is used for initiated polymerization tert-butyl acrylate (tBA), obtain POSS as parents' macromole of Dan Yuanao group through acidolysis again, the resulting larger-size aggregate of self-assembly is evenly dispersed in system.
In sum, have not yet to see relevant to reversible addition---cracking chain transfer polymerization method prepares with the report of POSS as the amphiphilic block copolymer of hydrophobic block.
Summary of the invention
The present invention aims to provide a kind of with polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer and the preparation method of POSS as hydrophobic block.
Polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer of the present invention is as hydrophobic block with polymethyl acyl-oxygen propyl group POSS, with the multipolymer of polyacrylic acid as hydrophilic block, the POSS monomer concentration is 0.3～1.0mol/L, preferred 0.5mol/L, the mol ratio of POSS monomer and chain-transfer agent is 2～50, preferred 25; The mol ratio of chain-transfer agent and initiator is 2～20, preferred 3; The mol ratio of tert-butyl acrylate (tBA) and polymethyl acyl-oxygen propyl group POSS is 20～5000, and is preferred 1200～3600, and the mol ratio of polymethyl acyl-oxygen propyl group POSS and initiator is 2～20, preferred 20;
Described POSS monomer is methacryloxypropyl isobutyl-POSS (MAiBuPOSS), and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-.
Described initiator also can cause the compound of POSS monomer and tert-butyl acrylate polymerization for adding the thermogenesis free radical, preferred azo, particularly preferably Diisopropyl azodicarboxylate (AIBN).
Described chain-transfer agent is two thioesters, and preferred dithiobenzoic acid cumyl ester (CDB) is (referring to document: Le, T.P.T.; Moad, G.; Rizzardo, E.; Thang, S.H.PCT Int.Pat.Appl.WO 9801478 A1 980115,1998), its structural formula is as follows:
The preparation method's of described polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer concrete steps are as follows:
1) add POSS monomer, chain-transfer agent and initiator in solvent, be placed in reaction vessel freezing degassed and be filled with sealed reaction after argon gas, the liquid nitrogen freezing stopped reaction gets hydrophobic block polymethyl acyl-oxygen propyl group POSS, and the nuclear-magnetism test is carried out in sampling;
In step 1) in, described solvent can be toluene etc.; The temperature of described reaction can be 40～80 ℃, and preferred 65 ℃, the reaction times can be 48h.
2) add tert-butyl acrylate, initiator and solvent in hydrophobic block polymethyl acyl-oxygen propyl group POSS, freeze thawing is degassed and be filled with sealed reaction after argon gas, polymerization, the liquid nitrogen freezing stopped reaction, adopt dissolving precipitated method to remove unreacted tert-butyl acrylate, precipitate with precipitation agent after adding solvent cut, dry, be placed in excessive selective solvent and stir the immersion purification, after filtration drying, get polymethyl acyloxy isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer, the nuclear-magnetism test is carried out in sampling;
In step 2) in, described solvent can be toluene etc.; The temperature of described reaction can be 40～80 ℃, and preferred 65 ℃, the reaction times can be 4～60h; Described precipitation agent can be methyl alcohol etc.; Described selective solvent can be sherwood oil etc.
3) add cosolvent in polymethyl acyloxy isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer, be stirred to dissolving fully, add again acidolysis reagent, rotary evaporation is removed the volatile product after cosolvent, acidolysis reagent and acidolysis, gets polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer.
In step 3) in, described cosolvent can be methylene dichloride etc., and described acidolysis reagent can be trifluoroacetic acid etc., and described volatile product is the trimethyl carbinol, methylene dichloride etc.
The present invention adopts reversible addition---and cracking chain transfer polymerization method prepares polymethyl acyl-oxygen propyl group isobutyl--polyacrylic acid tert-butyl ester segmented copolymer (PMAPOSS-b-PtBA), then obtains polymethyl acyl-oxygen propyl group isobutyl--polyacrylic acid amphiphilic block copolymer (PMAPOSS-b-PAA) by trifluoroacetic acid (TFA) hydrolysis.The present invention has following outstanding advantages:
Polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer of the present invention, by regulating the planned adjustment block length of the mol ratio ratio of monomer and chain-transfer agent, on purpose with segmented copolymer optionally acidolysis realize, its reaction conditions is gentle, prepare easy, the POSS loss is few, and product purity is high.
Description of drawings
Fig. 1 is that the basic structure of polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer reaches
1The HNMR spectrogram.In Fig. 1, X-coordinate is chemical shift chemical shift (ppm).
Fig. 2 is that the basic structure of polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer reaches
1The HNMR spectrogram.In Fig. 2, X-coordinate is chemical shift chemical shift (ppm).
Embodiment
The present invention is a kind of method of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer.Specific embodiments is provided in detail by following examples.Yet should be appreciated that, these embodiment are mainly in order to illustrate, to the present invention includes but be not limited to following examples; The present invention can explain aspect wider at it, and not be subjected to the restriction of these embodiment.
Preparation MAiBuPOSS: CDB: AIBN=25: 1: 0.33 toluene solution system, monomer concentration is 0.5mol/L, is placed in the freezing degassed 65 ℃ of oil bath 48h after three times repeatedly of bottle sealing, freezing stopped reaction.Take out appropriate reaction solution vacuum-drying,
1The transformation efficiency that HNMR records the first monomer is 90.2%.Measure by mol than tert-butyl acrylate (tBA): polymethyl acyl-oxygen propyl group POSS (MCTA): initiator (AIBN)=2400: 20: 1, tBA and the AIBN of metering are joined in reaction soln, rear freezing degassed 3 times repeatedly of sealing, 65 ℃ of oil bath 12h, freezing stopped reaction, add after a small amount of dilution with toluene with methanol extraction, join after drying to stir in excessive sherwood oil and spend the night, filtration drying obtains polymethyl acyloxy isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer, be pink solid, its
1H NMR schemes as shown in Figure 1, and the transformation efficiency that records tert-butyl acrylate is 27.2%.Be stirred to dissolving fully with methylene dichloride, the trifluoroacetic acid (TFA) that adds metering, be placed under room temperature and stir rotary evaporation desolventizing and trifluoroacetic acid after 24h, vacuum-drying obtains polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer (ABCP1), be yellow solid, its
1H NMR figure as shown in Figure 2.
Similar to Example 1, its difference is step 1 preparation MAiBuPOSS: CDB: AIBN=15: 1: 0.33 toluene solution system, all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP2.
1The transformation efficiency that H NMR records the first monomer is 92.3%.
Similar to Example 1, its difference is that the POSS monomer concentration of step 1 is 0.3mol/mL, and all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP3.
1The transformation efficiency that H NMR records the first monomer is 85.6%.
Similar to Example 1, its difference is the CDB of step 1: AIBN=5: 1, and all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP4.
1The transformation efficiency that H NMR records tert-butyl acrylate is 88.2%.
Similar to Example 1, its difference is the tert-butyl acrylate (tBA) of step 2: polymethyl acyl-oxygen propyl group POSS (MCTA)=160: 1, all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP5.
1The transformation efficiency that H NMR records tert-butyl acrylate is 28.2%.
Similar to Example 1, its difference is step 2 polymethyl acyl-oxygen propyl group POSS (MCTA): initiator (AIBN)=10: 1, all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP6.
1The transformation efficiency that H NMR records tert-butyl acrylate is 25.3%.
Similar to Example 1, its difference is that step 2 reaction times is 24h, and all the other are with embodiment 1.Get polymethyl acyl-oxygen propyl group isobutyl-POSS-polyacrylic acid amphiphilic block copolymer ABCP7.
1The transformation efficiency that H NMR records tert-butyl acrylate is 44.1%.
Claims (12)
1. polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer, it is characterized in that with polymethyl acyl-oxygen propyl group POSS as hydrophobic block, with the multipolymer of polyacrylic acid as hydrophilic block, the POSS monomer concentration is 0.3～1.0mol/L, the mol ratio of POSS monomer and chain-transfer agent is 2～50, the mol ratio of chain-transfer agent and initiator is 2～20, the mol ratio of tert-butyl acrylate and polymethyl acyl-oxygen propyl group POSS is 20～5000, and the mol ratio of polymethyl acyl-oxygen propyl group POSS and initiator is 2～20;
Described POSS monomer is methacryloxypropyl isobutyl-POSS, and its structural formula is as follows:
Wherein, R is-iBu, isobutyl-;
Described chain-transfer agent is two thioesters.
2. a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 1, is characterized in that described initiator also can cause the compound of POSS monomer and tert-butyl acrylate polymerization for adding the thermogenesis free radical.
3. a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 2, is characterized in that described initiator is azo.
4. a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 3, is characterized in that described azo is selected from Diisopropyl azodicarboxylate.
5. a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 1, is characterized in that described pair of thioesters is selected from dithiobenzoic acid cumyl ester, and its structural formula is as follows:
6. a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 1, is characterized in that described POSS monomer concentration is 0.5mol/L, and the mol ratio of POSS monomer and chain-transfer agent is 25; The mol ratio of chain-transfer agent and initiator is 3; The mol ratio of tert-butyl acrylate and polymethyl acyl-oxygen propyl group POSS is 1200～3600, and the mol ratio of polymethyl acyl-oxygen propyl group POSS and initiator is 20.
7. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 1 is characterized in that its concrete steps are as follows:
1) add POSS monomer, chain-transfer agent and initiator in solvent, be placed in reaction vessel freezing degassed and be filled with sealed reaction after argon gas, the liquid nitrogen freezing stopped reaction gets hydrophobic block polymethyl acyl-oxygen propyl group POSS; The temperature of described reaction is 40～80 ℃;
2) add tert-butyl acrylate, initiator and solvent in hydrophobic block polymethyl acyl-oxygen propyl group POSS, freeze thawing is degassed and be filled with sealed reaction after argon gas, polymerization, the liquid nitrogen freezing stopped reaction adopts dissolving precipitated method to remove unreacted tert-butyl acrylate, precipitates with precipitation agent after adding solvent cut, dry, be placed in excessive selective solvent and stir the immersion purification, after filtration drying, get polymethyl acyloxy isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer; The temperature of described reaction is 40～80 ℃;
3) add cosolvent in polymethyl acyloxy isobutyl-POSS-polyacrylic acid tert-butyl ester segmented copolymer, be stirred to dissolving fully, add again acidolysis reagent, rotary evaporation is removed the volatile product after cosolvent, acidolysis reagent and acidolysis, gets polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer; Described acidolysis reagent is trifluoroacetic acid.
8. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 7, is characterized in that in step 1), and described solvent is toluene.
9. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 7, is characterized in that in step 1), and the temperature of described reaction is 65 ℃, and the reaction times is 48h.
10. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 7, is characterized in that in step 2) in, described solvent is toluene; The temperature of described reaction is 65 ℃, and the reaction times is 4～60h.
11. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 7 is characterized in that in step 2) in, described precipitation agent is methyl alcohol; Described selective solvent is sherwood oil.
12. the preparation method of a kind of polyhedron oligomeric silsesquioxanes base amphiphilic block copolymer as claimed in claim 7 is characterized in that in step 3) described cosolvent is methylene dichloride.
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| CN112142979A (en) * | 2020-09-20 | 2020-12-29 | 南开大学 | Pyramid type polyoxometallate-cage type silsesquioxane hybrid molecule and preparation method and application thereof |
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