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A series of azo-containing triblock copolymer complexes with a majority poly(n-butyl acrylate) (PnBA) middle block and minority outer blocks composed of quaternized poly(dimethylaminoethyl methacrylate) (PDM) complexed with methyl orange (MO) were prepared from a single parent PDM-PnBA-PDM block copolymer (BCP) by varying the degree of PDM quaternization and supramolecular ionic complexation. The...
There is much need in advancing rational design of synthetic cationic polymers as gene carriers. Inspired by the molecular blueprint of the famed branched polyethylenimine (bPEI), here we describe a new series of acid-labile branched poly(ortho ester amino alcohol)s (bPOEAAs) that embodies multiple design principles about polymer degradability, chain branching, and type of cationic amino groups. The...
A novel hyperbranched polyether epoxy (HBPEE) bearing a stiff fluorene unit and flexible aliphatic chains has been synthesized using a one-pot approach and used as a toughener for bis-benzoxazine resin (MDA-BOZ). Effects of loadings and molecular weight of HBPEE on curing behavior, rheology properties, static mechanical, dynamic mechanical and thermal properties of the hybrid systems have been studied...
Diblock copolymer poly[(N-3,4-dihydroxyphenethyl acrylamide)-b-(borneolacrylate)] (PDA-b-PBA) containing mussel-inspired adhesive dopamine and natural herb-based antibacterial borneol was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization and further used to fabricate efficient and durable antibacterial coating. The synthesized monomers, polymers, and prepared PDA-b-PBA...
One acetylenic monomer (APCB) containing carborane with extremely thermal and thermo-oxidative stability was synthesized and used as the thermal copolymerization component with acetylene-terminated imide monomer (m-EFDA) to improve the thermal and thermo-oxidative stability of the polyimide materials. The curing behavior of the blends of imide monomer and APCB was investigated by FT-IR and DSC. Rheometer...
High thermally and thermo-oxidatively stable poly(phenylene-carborane) (PPB) was synthesized via Ni(0)-catalyzed polymerization of bis(aryl chloride) monomer containing carborane. This polymer was soluble in THF and NMP at room temperature, thus allowing molecular weight and spectroscopic analysis. Number-average molecular weight determined by 1H-NMR spectroscopy was 5.4 × 103 g/mol. The crystalline...
Herein, acid-degradable poly(ortho ester urethanes) (POEUs) were synthesized via polycondensation between an acid-labile ortho ester diamine and active esters of poly(ε-caprolactone) (PCL) diols with different molecular weights. The POEUs nanoparticles were easily fabricated using an oil-in-water emulsion technique, whose ortho ester bonds in main-chains could be degraded at different rate in acidic...
PEGylated poly(ortho ester amides) copolymer micelles (POEAd-g-MPEG micelles) with ultra-pH-sensitivity, which exhibited a dynamic change in size under mildly acidic conditions, were constructed by facile method, therefore achieving: (i) remaining stealthy and long-circulating in the blood; (ii) small NPs once in the tumor extracellular space for enhancing penetration; (iii) bigger NPs after penetration...
A new type of linear copolymers, poly(ortho ester amino alcohols) (POEAAs), has been synthesized by ring-opening polymerization between diglycidyl ethers and amine monomer with ortho ether bonds. POEAAs have uniform distribution of tertiary amine main-chains along with abundant hydroxyl groups and acid-cleavable tertiary amine side-chains. POEAA1 and 2 containing different diglycidyl ether moieties...
H-bonding organocatalysis using (thio)urea/amine achieved massive success. H-bonding binding with Brønsted acid catalysis, especially in polymerizations, was scarcely explored. Here we disclosed 1,3-bis-(3,5-bis(trifluoromethyl)phenyl)thiourea (TU) as hydrogen bond donor (HBD), combined with trifluoroacetic acid (TFA) as a Brønsted acid (BA), promoted efficient controlled/living ring-opening polymerization...
We report a novel, scalable and inexpensive approach to fully disperse carbon nanotubes in silicone rubber by the addition of graphene. In comparison to graphene, the dispersion of multi-walled carbon nanotubes (MWNTs) in silicone rubber matrix is extremely difficult although both of them possess similar physical structure. The different dispersion behavior of graphene and MWNTs could be contributed...
A series of flame-retardant epoxy resins (EP) with different content of poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) (PFR) were prepared. The PFR was synthesized via the polycondensation between 10-(2,5-dihydroxyl phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-BQ) and pentaerythritol diphosphonate dichloride (SPDPC). The structure of PFR was confirmed by...
Poly(methylmethacrylate) (PMMA) and polystyrene(PS)/PMMA particles with Janus-like morphology were prepared via the internal phase separation followed by extraction of hexadecane (HD) template. The internal phase separation was triggered by evaporation of dichloromethane (DCM) from the polymer/HD/DCM-in-water emulsion droplets, which led to the formation of HD/PMMA or HD/PMMA/PS microparticles. After...
Cationic polymers have been studied as promising nonviral gene delivery vectors. In contrast to the conventional polycations with long sequences of covalently bonded repeating units, this work reports a supramolecular gene carrier where many cationic cyclic units are threaded over a polymer chain to form a chain-interlock structured gene carrier. A series of novel supramolecular cationic polyrotaxanes...
This report covers the results of a study on identifying the thermal conduction mechanism of nano-sized SiC/diglycidyl ether of bisphenol-A glycidol ether epoxy resin/2-ethyl-4-methylimidazole (nano-SiC/DGEBA/EMI-2,4) composites. The analysis using FTIR provided an in-depth understanding about how the pretreatment of micro/nano-sized SiC (micro/nano-SiC) particles affects the surface structure of...
The geometry, energy, internal rotation, vibrational spectra, dipole moments and molecular polarizabilities of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of the poly(vinylidene fluoride) (PVDF) homopolymer. The chain length and the trifluoroethylene (TrFE) concentration...
A novel benzodithioate compound with a pyrene structure in the R group, pyrenylmethyl benzodithioate (PMB) was synthesized. Using PMB as the chain transfer agent (CTA), the RAFT polymerizations of styrene with AIBN as an initiator were carried out in different reaction conditions. The results indicated that PMB was an effective CTA for the RAFT polymerizations of styrene with the “living”/controlled...
Inclusion complexes (ICs) formed with cyclodextrins (CDs) and polymers have been an interesting topic over the past decade. Recently, more focus has been shifted to the ICs with biodegradable polymers or copolymers because of their potential applications as novel biomaterials. This work reports the IC formation between CDs and biodegradable poly(ε-caprolactone)-poly(tetrahydrofuran)-poly(ε-caprolactone)...
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