Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

Syntheses of well-defined poly(siloxane)-b-poly(styrene) and poly(norbornene)-b-poly(styrene) block copolymers using functional alkoxyamines

Functional alkoxyamines, 1-[4-(4-lithiobutoxy)phenyl]-1-(2,2,6,6-tetramethylpiperidinyl-N-oxyl)ethane (2) and 1-[4-(2-vinyloxyethoxy)phenyl]-1-(2,2,6,6-tetramethylpiperidinyl-N-oxyl)ethane (3) were prepared, and well-defined poly(hexamethylcyclotrisiloxane)-b-poly(styrene)[poly(D₃)-b-poly(St)] and poly(norbornene)-b-poly(St) [poly(NBE)-b-poly(St)] were prepared using the alkoxyamines. The first step was preparation of poly(D₃) and poly(NBE) macroinitiators, which were obtained by the ring-opening anionic polymerization of D₃ using 2 as an initiator and the ring-opening metathesis polymerization of NBE using 3 as a chain transfer. The radical polymerization of St by the poly(D₃) and poly(NBE) macroinitiators proceeded in the ‘living’ fashion to give well-defined poly(D₃)-b-poly(St) and poly(NBE)-b-poly(St) block copolymers.     

Synthesis of densely grafted copolymers by nitroxide-mediated radical polymerization of styrene using poly(phenylacetylene)s as a macroinitiator

Poly(phenylacetylene)s carrying alkoxyamine moieties in the side chain were prepared by Rh-catalyzed homopolymerization of 1-(4-ethynylphenyl)-1-(2,2,6,6-tetramethyl-1-piperidinyloxyl)ethane (1) and random copolymerization of 1 and 4-methoxy-1-ethynylbenzene (2a) or 4-decyloxy-1-ethynylbenzene (2b). ¹H NMR spectra showed that the poly(phenylacetylene)s adopted a cis-transoid structure. Using the poly(phenylacetylene)s as the macroinitiator the nitroxide-mediated radical polymerization of styrene (St) was carried out at 120 °C to yield densely grafted copolymers as a light yellow powder. The side chain lengths of the graft copolymers were determined by both ¹H NMR and conversion of St, which agreed with each other. The SEC profiles of the graft copolymers were unimodal at low conversions but were not unimodal at high conversion: a shoulder was observed in the high molecular=weight region and a small peak was observed in the low molecular=weight region. ¹H NMR measurements of the graft copolymers indicated that the copolymers adopted a trans-transoid structure, revealing that isomerization from cis-transoid to trans-transoid forms took place during the polymerization of St at 120 °C.     

Aqueous dispersions of polyurethane polyacrylic acid multiblock copolymers through living radical polymerization

Polyurethane macroiniferter (PUMI) including tetraphenylethane was synthesized and used to prepare polyurethane–polyacrylic acid multiblock copolymers. Film‐forming aqueous dispersions without any added external emulsifiers were prepared from polyurethane–polyacrylic acid multiblock copolymers. The effect of varying PUMI content, polymerization time, and percent ionization on the properties of multiblock copolymeric dispersions were studied in detail. Interfacial tension of the dispersions and critical surface tension measurements of the films formed thereof have shown that the polymers exhibit a hydrophilic character in the dispersed phase and a hydrophobic character in the solid phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1109–1115, 2003     

Synthesis of amphiphilic triblock copolymer of polystyrene and poly(4-vinylbenzyl glucoside) via TEMPO-mediated living radical polymerization

4-Vinylbenzyl glucoside peracetate 1 was polymerized with α,α′-bis(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)-1,4-diethylbenzene 2 in chlorobenzene using (1S)-(+)-10-camphorsulfonic acid anhydrous (CSA) as an accelerator ([1]=0.4 M,[1]/[2]/[CSA]=75/1/1.3) at 125 °C for 5 h. The polymerization afforded poly(4-vinylbenzyl glucoside peracetate) having TEMPO moieties on both sides of the chain ends, 3, with a molecular weight (M_w,SLS) of 8500, a polydispersity index (M_w/M_n) of 1.09, and an average degree of polymerization of the 1 unit (x) of 17. Styrene (St) was polymerized with 3 in chlorobenzene at 125 °C (St/chlorobenzene=1/2, w/w). The polymerization successfully afforded polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 4, when the polymerization time was below about 2 h. Polymer 4 with the M_w,SLS of 12,500, 17,900, and 29,400, the compositions (y-x-y) of 20-17-20, 45-17-45, and 100-17-100, and the M_w/M_n of 1.12, 1.14 and 1.17 were modified by deacetylation using sodium methoxide in dry-THF into polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 5. The solubility of polymer 5 was examined using a good solvent for polystyrene such as toluene and for the saccharide such as H₂O.     

New azo-chromophore-containing multiblock poly(butadiene)s synthesized by the combination of ring-opening metathesis polymerization and click chemistry

A combination of ring-opening metathesis polymerization (ROMP) and click chemistry approach was utilized for the first time in preparation of multiblock copolymers. The dibromo-functionalized telechelic poly(butadiene) (PBD) was synthesized firstly by ROMP of 1,5-cyclooctadiene in the presence of a symmetrical difunctional chain transfer agent and transformed into diazido-telechelic PBD, which was then reacted with a dialkynyl-containing azobenzene chromophore via click reaction, producing novel multiblock PBDs collected by azobenzene groups and newly formed triazole moieties. The monomer and polymer were characterized by IR, UV-vis, LC/MS, and NMR techniques. The produced multiblock copolymers have molecular weights within 13.3 and 57.8 kDa, and their polydispersity indices ranging from 1.98 to 2.38 by gel permeation chromatography measurement. The multiblock PBDs containing azo chromophores and triazole moieties with or without hydrogen-bonding interreaction with 4,4′-dihydroxybiphenyl molecule exhibited different photoisomerization efficiency from trans to cis as observation in UV-vis spectroscopy. The morphologies of multiblock PBDs were also investigated by atom force microscopy.     

A novel approach for synthesis of poly(norbornene)‐co‐poly(styrene) block copolymers via metathesis polymerization and free‐radical polymerization

It is successfully realized that block copolymers are synthesized via metathesis polymerization followed by free‐radical polymerization. This method is performed using styrene (St) and norbornene, one block is synthesized using the Grubbs second generation catalyst in the presence of chain transfer agents, and the subsequent polymerization of St is initiated by azo compounds to complete the additional blocks in the copolymers. The use of free‐radical polymerization instead of controlled radical polymerization or ionic polymerization can be potentially superior for industrialization. As a result, the molecular weights of the block copolymers ranging from 10.4 to 54.3 kDa and polydispersity indices ranging from 1.30 to 1.91 are obtained. In principle, this new method can be potentially useful to prepare a broad range of block copolymers with cyclic olefin groups in the main chains, which may be used in some particular applications.     

Synthesis and applications of triblock and multiblock copolymers using telechelic oligopropylene

Isotactic polypropylene (iPP)-polystyrene (PS) and iPP-poly(methyl methacrylate) (PMMA) multiblock copolymers were synthesized by atom transfer radical coupling (ATRC) of PS-iPP-PS and PMMA-iPP-PMMA triblock copolymers obtained by atom transfer radical polymerization (ATRP) of styrene (St) and methyl methacrylate (MMA), respectively, using α,ω-dibromoisobutyrateoligopropylene (iPP-Br) as a bifunctional macroinitiator. The iPP-Br was prepared by hydroxylation and subsequent esterification of telechelic oligopropylene having terminal vinylidene double bonds at both ends obtained by controlled thermal degradation of iPP. ATRP of St and (meth) acrylic monomers using iPP-Br formed the corresponding triblock copolymers. It was confirmed that the PMMA-iPP-PMMA triblock copolymer was effective as the compatibilizer for the iPP/PMMA blend. An iPP-PS multiblock copolymer (M_n: 25?000 g/mol and M_w/M_n: 4.1) was prepared by ATRC of PS-iPP-PS triblock copolymer (M_n: 8900 g/mol and M_w/M_n: 1.3). ATRC with St of PMMA-iPP-PMMA triblock copolymer (M_n: 13?000 g/mol and M_w/M_n: 1.4) provided an iPP-PMMA multiblock copolymer containing St chains (M_n: 39?000 g/mol and M_w/M_n: 2.8).     

Regioregular poly(3-alkylthiophene) conducting block copolymers

Regioregular poly(3-alkylthiophenes) (PATs) represent an important class of polymers that are environmentally stable and display high electrical conductivity. Despite their excellent electrical properties, PATs do not exhibit very good mechanical and processing properties. This issue is addressed here by integrating poly(3-alkylthiophene) in copolymer structures with various polymer blocks that display better mechanical properties, leading to a variety of polymeric materials with desired properties. We describe a new method for the synthesis of poly(3-alkylthiophene) block copolymers using vinyl terminated regioregular poly(3-alkylthiophene) as precursors via atom transfer radical polymerization (ATRP).     

Synthesis and characterization of amphiphilic conetworks based on multiblock copolymers

Model amphiphilic conetworks based on cross-linked block copolymers of the hydrophilic ionizable 2-(dimethylamino)ethyl methacrylate (DMAEMA, 25 nominal units per block) and the hydrophobic n-butyl methacrylate (BuMA, 5 nominal units per block) bearing three, five, seven and nine blocks were synthesized using group transfer polymerization. 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane and ethylene glycol dimethacrylate were used as the bifunctional initiator and the cross-linker, respectively. Network synthesis was performed by sequential monomer/cross-linker additions to the reaction flask, which was pre-loaded with tetrabutylammonium bibenzoate (polymerization catalyst), tetrahydrofuran (THF, solvent), and initiator. All linear conetwork precursors were characterized using gel permeation chromatography and proton nuclear magnetic resonance spectroscopy and found to have molecular weights (MWs) and compositions reasonably close to the theoretically expected values. All polymer conetworks were characterized in terms of their degree of swelling (DS) in THF, in neutral water, and in aqueous media as a function of the solution pH. It was found that the DSs were highest in acidic pH due to the repulsive forces and the osmotic pressure developed by the ionization of the DMAEMA units. Intermediate values of the DSs were observed in THF, whereas the lowest DSs were measured in neutral water. In THF, the DSs increased with the MWs of the (final) linear (co)polymer precursors, while in acidic water the DSs increased with the DMAEMA content in the (co)networks.     

Atom transfer radical polymerization of methyl methacrylate initiated with a macroinitiator of poly(vinyl acetate)

Well‐defined poly(vinyl acetate‐b‐methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p‐xylene with CuBr as a catalyst, 2,2′‐bipyridine as a ligand, and trichloromethyl‐end‐grouped poly(vinyl acetate) (PVAc–CCl₃) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H‐NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl₃] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006     

Synthesis and characterization of dendritic-linear-dendritic triblock copolymers based on poly(amidoamine) and polystyrene

Dendritic-linear-dendritic triblock copolymers composed of linear polystyrene (PSt) and poly(amidoamine) dendrons have been successfully synthesized. Two bromines-terminated PSt with M_n = 13,000 was prepared by atom transfer radical polymerization (ATRP) using α,α′-dibromo-p-xylene as initiator. Then the terminal bromines at both ends of PSt chains were replaced by one imine group of piperazine (PZ), and further Michael addition reaction of terminal PZ with excess 1,3,5-triacryloylhexahydro-1,3,5-triazine (TT) produced the first generation (G₁) of the triblock copolymer. Continuous growth of dendrons from G1.5 to G4 at the both ends of PSt chains was carried out by the iterative Michael addition reactions with excess PZ and following TT. The ABA triblock copolymers composed of the G₁-G₄ dendrons and the linear PSt were obtained. Structures of the triblock polymers were characterized by GPC and ¹H NMR spectra. Thermal phase transitions of the polymers were studied by DSC measurements, and all of the copolymers displayed a glass transition temperature.     

Dithioester functionalization of poly(cyclohexene oxide) and its application to obtain block copolymers

A new method of introducing dithioester groups into the polymer chain of poly(cyclohexene oxide) is reported. It includes the use of diaryliodonium salt and an aromatic dithioacid as a redox couple to initiate the cationic polymerization of cyclohexene oxide. It was found that the dithioacid by itself cannot start the polymerization of cationic polymerizable monomers; however, in combination with a diaryliodonium salt, an exothermic reaction was produced, yielding a thiocarbonylthio‐functionalized polyether. Thermal profiles of the redox polymerizations were determined by means of optical pyrometry. A preliminary study showed that when the poly(cyclohexene oxide) functionalized with dithioester groups was introduced into the radical polymerization of styrene, the polystyryl growing radicals reacted with the dithioester‐functionalized polyether to form a block polymer. The amount of polyether actually incorporated into the block copolymer was calculated to be 70% of the initial amount of poly(cyclohexene oxide)/dithiobenzoic acid charged into the reactor. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

含端基氯低聚物引发剂的合成及其引发苯乙烯聚合的研究

通过对４种端羟基低聚物进行氯乙酰化反应,制备了一系列含端基氯的低聚物,然后以这些含端基氯的低聚物为大分子引发剂,在ＣｕＣｌ／ｂｐｙ存在下引发苯乙烯的ＡＴＲＰ反应,得到ＡＢＡ嵌段共聚物。用＾１Ｈ－ＮＭＲ分析证明了聚合物的嵌段结构,以ＳＥＣ测定了聚合物的相对分子质量及其分布,发现嵌段聚合物的相对分子质量和单体转化率成正比,并和相对分子质量的理论值Ｍ↑－ｎ,ｔｈ＝（Δ［Ｍ］／［ｏｌｉｇｏｍｅｒ－Ｃｌ］）     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Synthesis of (ABCB)n type ternary amphiphilic multiblock copolymer via poly(ethylene oxide) macro-chain transfer agent

A novel (ABCB)_n type ternary amphiphilic multiblock copolymer was synthesized by stepwise insertion of monomers into the trithiocarbonate-embedded poly(ethylene oxide) (PEO) macro-chain transfer agent (PEO-CTA)_n. (PEO-CTA)_n was synthesized first by coupling of α,ω-dihydroxyl PEO with dicarboxylic trithiocarbonate, then styrene (St) and t-butyl acrylate (^tBA) were inserted into the (PEO-CTA)_n successively to yield (PEO-b-PS)_n and (PEO-b-PS-b-P^tBA-b-PS)_n, respectively. After hydrolysis of the (PEO-b-PS-b-P^tBA-b-PS)_n, the final product (PEO-b-PS-b-PAA-b-PS)_n was obtained.     

Characterization of aqueous micellar solutions of amphiphilic block copolymers of poly(acrylic acid) and polystyrene prepared via ATRP. Toward the control of the number of particles in emulsion polymerization

A series of diblock, triblock and star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by ATRP. The structure of the copolymers, the size of the blocks and the composition were varied, keeping however a short polystyrene block and a poly(acrylic acid) content larger than 60 mol% to allow solubility in alkaline water. Their micellization was studied by static and dynamic light scattering and the influence of their structural characteristics on the aggregation number, N_agg, was examined at low salt concentration and alkaline pH. It was shown that micelles were in thermodynamic equilibrium and that N_agg followed the power law N_agg∼N_A^−0.9N_S² (with N_A, the total number of acrylic acid units in the copolymer and N_S, the total number of styrene units), that is characteristic of amphiphile micelles formed from strongly segregated block copolymers. Moreover, N_agg was independent of salt concentration in the investigated range. The same copolymers were previously used as stabilizers in emulsion polymerization [Macromolecules 34 (2001) 4439]. The final latex particle concentration, N_p, was compared with N_m, the initial micelle concentration. This enabled us to conclude that among the block copolymers studied, those with high acid content behaved like low molar mass surfactants. In contrast, those with low acid content formed stable micelles that could be directly nucleated to create latex particles, allowing a good control over N_p.     

Synthesis of random and block copolymers of styrene and styrenesulfonic acid with low polydispersity using nitroxide-mediated living radical polymerization technique

Poly(styrene-ran-styrenesulfonic acid) and poly(styrene-block-styrenesulfonic acid) with low polydispersity were prepared using nitroxide-mediated living radical polymerization technique. Random or block copolymerization of styrene and neopentyl p-styrenesulfonate smoothly proceeded by AIBN/2,2,5,5-tetramethyl-4-diethylphosphono-3-azahexane-3-nitroxide initiating system. Transformation of the sulfonate ester to sulfonic acid was carried out by the reaction with trimethylsilyl iodide or by thermolysis at 150 °C. Those polymers showed amphiphilic characters.     

Block copolymers of acrylonitrile and poly(dimethylsiloxane)s

The chemical redox system of ceric ammonium nitrate(Ce⁴⁺) and poly(dimethylsiloxane)s (PDMS) with monohydroxy (MH), dihydroxy (DH), and diamine(DA) chain ends was used to polymerize acrylonitrile (AN) to produce monohydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (MH.PDMS‐b‐PAN), dihydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DH.PDMS‐b‐PAN), and α, ω‐diamine poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DA.PDMS‐b‐PAN) block copolymers. The concentration, reaction time, and the type of poly(dimethylsiloxane) affect the yield and the molecular weight of the copolymers. The ratio of AN/ceric salt/PDMS has remarkably affects the properties of formed copolymers. DH.PDMS‐b‐PAN copolymers were also prepared by electroinduced polymerization in the presence of catalytic amount of Ce⁴⁺ in a divided electrochemical cell where Ce³⁺ is readily oxidized into Ce⁴⁺ at the anode. The products were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, DSC, and their surface properties were investigated through contact‐angle measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013