10-undecenoyl Chloride Research Articles

Mixing of hindered amine-grafted polyolefin elastomers with LDPE to enhance its long-term weathering and photo-stability

Polyolefins are a commodity plastic family known as low cost and recyclable material, that has displayed high potencies for wide variety of applications, resulting from their desired chemical, mechanical, and physical properties. However, further modifications are needed to improve their properties to extend their service lifetime, weathering resistance, and photostability for use in outdoor applications, which are due to their low thermal and photo-stabilities. In this research, hindered amine light stabilizers were used to enhance the photo-stability of low-density polyethylene (LDPE). For this purpose, unsaturated 4-amino-2,2,6,6-tetramethylpiperidine (UATMPP) was prepared by amidation reaction of amine groups in amino-2,2,6,6-tetramethylpiperidine with acryloylol chloride of 10-undecenoyl chloride in presence of triethylamine and 4-dimethylaminopyridine. Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) exhibited successful preparation of UATMPP. UATMPP was grafted on polyolefin elastomer (POE) through melt free radical grafting method. FTIR and NMR confirmed the successful preparation of UATMPP-grafted POE. Finally, UATMPP-containing POE was mixed by LDPE through melt compounding. The results from the calculation of carbonyl index from FTIR and tensile testing after UV irradiation exhibited desired antiaging and UV-resistant properties of LDPE/POE blends, which were influenced by grafting degree of UATMPP as well as POE content (wt%).

High-efficient lignin-based polymerizable macromolecular photoinitiator with UV-blocking property for visible light polymerization

Developing high-efficient visible light macromolecular photoinitiator (macro PI) with excellent initiation performance, low migration, high biosafety and multi-function is beneficial to broaden the application of photopolymer. Lignin contains chromophores which could generate free radicals under light irradiation. In this study, a lignin-based polymerizable macro PI (DAL-11ene-amine) was designed and synthesized through covalent grafting 10-undecenoyl chloride (11ene) and hydrogen donor 4-(dimethylaminobenzoic acid) ethyl ester (EDAB) into dealkaline lignin (DAL) skeleton. The structure of DAL-11ene-amine was characterized by UV–vis, FTIR, 1H NMR, GPC, and 31P NMR spectra. Under the irradiation of a 405 nm LED, DAL-11ene-amine can directly produce active species and initiate the polymerization of acrylate monomers or thiol-ene click reaction. The photoinitiation efficiency of DAL-11ene-amine is higher than that of DAL-11ene or the two-component combination of DAL-11ene and EDAB. Using DAL-11ene-amine as PI, the prepared polymer films exhibit excellent UV-blocking property. With only 0.5 wt% addition of DAL-11ene-amine, nearly 100% of UVB + UVC and the most of UVA can be blocked by the films. Moreover, DAL-11ene-amine exhibits higher migration stability and biosafety because it can be covalently linked into polymer cross-linking networks. The results indicate that DAL-11ene-amine has great application potentials in preparing environmentally friendly UV-blocking films and biosafety coatings.

One-Step Covalent Surface Modification to Achieve Oil-Water Separation Performance of a Non-Fluorinated Durable Superhydrophobic Fabric.

In this work, a durable superhydrophobic fabric was fabricated by a facile covalent surface modification strategy, in which the anchoring of 10-undecenoyl chloride (UC) onto the fabric through the esterification reaction and covalent grafting of n-dodecyl-thiol (DT) via thiol-ene click chemistry were integrated into one step. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurement results demonstrated that UC and DT were covalently grafted onto the fabric surface. The formed gully-like rough structure by the grafted UC and DT on the fabric surface together with the inherent microfiber structure, combined with the grafted low-surface-energy materials of UC and DT, gave the resultant modified DT–UC@fabric superhydrophobic performance. The superhydrophobic DT–UC@fabric was used for separation of oil–water mixtures; it exhibited high separation efficiency of more than 98%. In addition, it presented excellent durability against mechanical damage; even after 100 cyclic tape-peeling and abrasion tests, the DT–UC@fabric could preserve superhydrophobic performance, which was ascribed to the formed covalent interactions between the fabric surface and the grafted UC and DT. Therefore, this work provided a facile, efficient strategy for fabricating superhydrophobic composites with excellent durability, which exhibited a promising prospect in the application of self-cleaning and oil–water separation.

Hybrid polymers bearing oligo-l-lysine(carboxybenzyl)s: synthesis and investigations of secondary structure.

Hybrid polymers of peptides resembling (partially) folded protein structures are promising materials in biomedicine, especially in view of folding-interactions between different segments. In this study polymers bearing repetitive peptidic folding elements, composed of N-terminus functionalized bis-ω-ene-functional oligo-l-lysine(carboxybenzyl(Z))s (Lysn) with repeating units (n) of 3, 6, 12, 24 and 30 were successfully synthesized to study their secondary structure introduced by conformational interactions between their chains. The pre-polymers of ADMET, narrowly dispersed Lysns, were obtained by ring opening polymerization (ROP) of N-carboxyanhydride (NCA) initiated with 11-amino-undecene, following N-terminus functionalization with 10-undecenoyl chloride. The resulting Lysns were subsequently polymerized via ADMET polymerization by using Grubbs’ first generation (G1) catalyst in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) generating the ADMET polymers (A-[Lysn]m) (m = 2–12) with molecular weights ranging from 3 to 28 kDa, displaying polydispersity (Đ) values in the range of 1.5–3.2. After chemical analyses of Lysns and A-[Lysn]ms by 1H-NMR, GPC and MALDI-ToF MS, secondary structural investigations were probed by CD spectroscopy and IR spectroscopy in 2,2,2-trifluoroethanol (TFE). In order to study A-[Lysn]ms with defined molecular weights and low polydispersity values (Đ = 1.03–1.48), the ADMET polymers A-[Lysn=3]m=3 and A-[Lysn=24]m=4 were fractionated by preparative GPC, and subsequently analysed by 1H-NMR, analytical GPC, MALDI-ToF MS and CD spectroscopy. We can demonstrate the influence of chain length of the generated polymers on the formation of secondary structures by comparing Lysns with varying n values to the ADMET-polymers with the help of spectroscopic techniques such as CD and FTIR-spectroscopy in a helicogenic solvent.

Synthesis of a Fully Biobased Polyfunctional Vinyl Oligomer and Their UV Cured Films Prepared via Thiol-ene Coupling

In this paper, a fully bio-based vinyl oligomer with high functionalities was successfully prepared by three steps: epoxidation of rapeseed oil, solvent-free and catalyst-free ring opening by 10-undecylenic acid, and esterification with 10-undecenoyl chloride. Then, the renewable polymers were prepared by photo-polymerization of these modified vegetable oils and typical thiol monomers (pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate) and 1,2-ethanedithiol). The synthesis of the vinyl oligomer was monitored by nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The average number of the carbon-carbon double bonds of the resulting vinyl oligomer is high to be 7.2. The kinetic of thiol-ene photo-polymerization of vegetable oil based vinyl oligomer was studied by FTIR-ATR analyses. In addition, the thermo-physical properties and thermal stability of UV-curable films were characterized. The resulting polymers exhibit excellent water resistance and thermals stability, which is promising to find application in coatings and adhesives.

One-Step Synthesis of Quadrilateral-Shaped Silver Nanoplates with Lamellar Structures Tuned by Amylopectin Derivatives.

Polymers or small molecules with functional groups were always employed to synthesize two-dimensional (2D) silver nanostructures, but the polysaccharides and derivatives have rarely been used for their preparation, let alone of uniform quadrilateral shapes. Herein, amylopectin derivatives containing concentrated carboxyl groups were first used for the synthesis of uniform 2D quadrilateral silver nanoplates (QAgNPs) with lamellar structure. As a native hyperbranched polysaccharide, amylopectin was esterified with 10-undecenoyl chloride and then modified via thiol–ene click chemistry to introduce high amount and high density of carboxyl groups. Then, QAgNPs were synthesized via UV photoreduction in the presence of the resultant amylopectin 11-((3-carboxyl)ethylthio)undecanoate (APUE3-MPA) in water–tetrahydrofuran binary system. QAgNPs showed novel uniform quadrilateral shapes with lamellar structure, as verified by their wide-angle X-ray scattering patterns. The average interlayer distance was around 1.3 nm, whereas the average edge lengths of QAgNPs varied between 0.29 ± 0.07 and 1.09 ± 0.25 μm. The concentration of APUE3-MPA and the amount of water in the reaction system strongly affected the shapes of QAgNPs. Thus, the reaction system and the arrangement of numerous carboxyl groups were the key factors for the formation of lamellar-structured QAgNPs.

Stimuli-responsive nanoparticles from ionic cellulose derivatives.

Stimuli-responsive nanoparticles (NPs) based on sustainable polymeric feedstock still need more exploration in comparison with NPs based on synthetic polymers. In this report, stimuli-responsive NPs from novel ionic cellulose derivatives were prepared via a facile nanoprecipitation. Cellulose 10-undecenoyl ester (CUE) with a degree of substitution (DS) of 3 was synthesized by esterification of cellulose with 10-undecenoyl chloride. Then, CUE was modified by photo-induced thiol-ene reactions, in order to obtain organo-soluble ionic cellulose derivatives with DSs of ∼3, namely cellulose 11-((3-carboxyl)ethylthio)undecanoate (CUE-MPA), cellulose 11-((2-aminoethyl)thio)undecanoate (CUE-CA), cellulose 11-(2-(2-(diethylamino)ethyl)thio)undecanoate (CUE-DEAET) and cellulose 11-(2-(2-(dimethylamino)ethyl)thio)undecanoate (CUE-DMAET). CUE-MPA could be transformed into NPs with average diameters in the range of 80-330 nm, but these NPs did not show particular stimuli-responsive properties. Moreover, the dropping technique resulted in smaller NPs than a dialysis technique. Stable NPs with average diameters in the range of 90-180 nm showing pH-responsive and switchable sizes were obtained from CUE-DEAET and CUE-DMAET possessing tertiary amines using nanoprecipitation. Thus, altering the terminal functional groups will be a new approach to prepare stimuli-responsive cellulose-derived polymeric NPs.

Preparation of tourmaline-containing functional copolymer p(TUC/BA/MMA) and its performances

ABSTRACTIn order to develop the tourmaline-containing functional polymer, the double-bond-containing undecenoyl group was introduced onto the surface of tourmaline to synthesize a polymerizable organic tourmaline undecylenate (TUC) by the surface modification of tourmaline with 10-undecenoyl chloride. The TUC was then copolymerized with butyl acrylate (BA) and methyl methacrylate (MMA) to obtain the tourmaline-containing functional copolymer p(TUC/BA/MMA), which showed an excellent storage stability. The structures of TUC and its copolymers were characterized by means of IR, XRD, SEM, and EDX. The results indicated that the tourmaline-containing functional copolymer displayed excellent mechanical, far-infrared radiating, and negative ion releasing performances.

Sustainable Polyesters Derived from Glucose and Castor Oil: Building Block Structure Impacts Properties.

Using the glucose derivatives isosorbide and glucarodilactone along with a castor oil derivative, 10-undecenoyl chloride, two monomers were synthesized: glucarodilactone undecenoate (GDLU) and isosorbide undecenoate (IU). These monomers were polymerized via acyclic diene metathesis (ADMET) polymerization to yield two homopolymers, P(GDLU) and P(IU), and two copolymers, P1(GDLU-co-IU) and P2(GDLU-co-IU), of similar number-averaged molecular weight and relative composition (51 and 61 kDa, Đ = 1.8 and 1.4, 46:54 and 52:48 mol percent). Comparison of the physical properties and degradation behavior of these polymers revealed divergent characteristics arising from differences in the nature of the carbohydrate building blocks. P(IU) is more thermally stable and has a lower glass transition temperature (Td = 369 °C, Tg = -10 °C) than P(GDLU) (Td = 206 °C, Tg = 32 °C) and P1,2(GDLU-co-IU) (Td = 210 and 203 °C, Tg = 1 and 7 °C). While all of the polymers were stable in acidic and neutral aqueous conditions, the two analogs containing GDLU hydrolytically degraded in the presence of base. Tensile testing of the systems revealed that both homopolymers are brittle materials while the P(GDLU-co-IU) is more tough. Notably, P1,2(GDLU-co-IU) was found to be a rubbery material with a low Young's modulus (0.020 and 0.002 GPa, respectively), displaying an average elongation at break of 480 and 640%, and shape memory properties.

Olefin Cross-Metathesis as a Source of Polysaccharide Derivatives: Cellulose ω-Carboxyalkanoates

Cross-metathesis has been shown for the first time to be a useful method for the synthesis of polysaccharide derivatives, focusing herein on preparation of cellulose ω-carboxyalkanoates. Commercially available cellulose esters were first acylated with 10-undecenoyl chloride, providing esters with olefin-terminated side chains. Subsequent cross-metathesis of these terminal olefin moieties with acrylic acid was performed in solvents including acrylic acid, THF, and CH2Cl2. Complete conversion to discrete, soluble cross-metathesis products was achieved by using the Hoveyda-Grubbs second generation ruthenium catalyst and an excess of acrylic acid. Oligomerization during storage, caused by a free radical mechanism, was observed and successfully suppressed by the addition of a free radical scavenger (BHT). Furthermore, the cross-metathesis products exhibited glass transition temperatures (Tg) that were at least 50 °C higher than ambient temperature, supporting the potential for application of these polymers as amorphous solid dispersion matrices for enhancing drug aqueous solubility.

Enhancement of the impact strength of cationically cured cycloaliphatic diepoxide by adding hyperbranched poly(glycidol) partially modified with 10-undecenoyl chains

A hyperbranched poly(glycidol) has been synthesized and modified by acylation with 10-undecenoyl chloride to obtain hyperbranched polymers (HBPs) with different degree of modification. These HBPs have been used as reactive modifiers in a proportion of 3%, 5%, and 10% with respect to a biscicloaliphatic diepoxide cured using ytterbium triflate as thermal cationic initiator. The materials obtained have been characterized and their mechanical properties evaluated. Phase separated materials have been obtained, with a 2-fold increase in impact resistance without sacrificing thermomechanical properties, thermal stability or processability. This good combination of properties can be explained by the achievement of a regular microphase separation with a good interfacial interaction between the microparticles and the epoxy matrix. The compatibility between the HBP and the matrix can be tuned by changing the degree of modification, which leads to a variable amount of available hydroxyl groups of the HBP that can react with the epoxy groups. This chemical bonding occurs through the activated monomer mechanism (AM) which is typical of the cationic homopolymerization of epoxides.

Efficient impact resistance improvement of epoxy/anhydride thermosets by adding hyperbranched polyesters partially modified with undecenoyl chains

Boltorn H30 hyperbranched polyester has been modified by acylation with 10-undecenoyl chloride to obtain HBPs with different degree of modification. These HBPs have been used as reactive modifiers, in a proportion of 5 and 10%, of DGEBA/MHHPA/BDMA formulations. The materials obtained have been characterized and their mechanical properties evaluated. Depending on the degree of modification of the HBP, homogeneous or phase separated materials were obtained, which influence the properties. When the degree of modification of the HBP was a 76%, a 4-fold increase in impact resistance was achieved without sacrificing thermomechanical characteristics, thermal stability or processability. This has been attributed to the regular microphase separation achieved and to the good interfacial interaction of the microparticles with the epoxy matrix by formation of covalent bonds between the remaining hydroxyl groups at the shell of the HBP and the anhydride as the curing agent.

Synthesis of a New Organic Linker Molecule for Protein Immobilization

Recent biological and medicinal experimental techniques for diagnosis and drug discovery utilize microarrays of proteins immobilized on solid substrates. Such protein “chips” can have proteins on surface attached covalently or non-covalently between proteins and linker molecules frequently by chemisorption of the film components to the substrate from solution. For the well defined systems, organic monolayer films have formed versatile model study. The arrays of proteins attached to a solid surface have a great potential for detecting interactions of protein-ligand, proteinprotein, and antibody-antigen. Among several self-assembling systems, organosulfur compounds including dialkyl sulfides, dialkyl disulfides, and thiols have been investigated intensively on gold. It has been recognized that self-assembled monolayers (SAM) using organosufur compounds on gold are advantageous over other SAM systems because of higher structural order by densely packing long chains. In addition, versatile functionalization of terminal group at the monolayer surface suggests ideal model systems for immobilization and interfacial interaction. Several functional groups including anhydride, succinimidyl ester, maleimide, and phosphinothioester have been applied for the chemoselective binding of proteins. Here, we report a new potential substrate for the covalent and specific immobilization of nucleophilic molecules. The new organic linker, disulfide 1, has 4, 5-difluoro-2-nitroaniline amide moiety on the head and a long carbon chain with a triazole group. We envisioned that the compound would be prepared via 1,3-dipolar cycloaddition of azide 2 and alkyne 3, and hoped that a Meisenheimer complex of 4,5-difluoro-2-nitroaniline amide moiety would serve for a covalent attachment of amine or thiol moieties, and eventually proteins on the surface (Scheme 1). Prior to the synthesis of the molecule, we wanted to evaluate the reactivity of the substrate 1 toward nucleophilic aromatic substitution. Therefore, we first prepared a amide 4 from 4,5-difluoro-2-nitroaniline and 10-undecenoyl chloride and have tried the substitution reaction with various amines and a thiol as a model study (Table 1). The reaction was carried out in THF/water at room temperature. Primary and secondary amines reacted with the nitroaniline in minutes to afford good yields. Cyclic amines provided better than noncyclic secondary amines, and thiol provided the best yield in the shortest reaction time as expected. On the basis of the result, we anticipate the functional groups in proteins, amine or thiol, would show the similar reaction pattern toward the

Polysulfones tethered with benzimidazole

Benzimidazole units have been grafted onto a polysulfone (PSU) backbone via long alkyl thio–ether chains using a two-step procedure. In the first step, lithiated PSU was reacted with 10-undecenoyl chloride to graft PSU with undecenoyl side chains. The second step involved a free-radical thiol–ene coupling reaction between the C C bonds of the pendant undecenoyl chains and 2-(2-benzimidazolyl)ethanethiol. In this reaction, all the C C bonds were converted into thio–ether linkages without any detectable structural degradation, as confirmed by 1H NMR spectroscopy and size-exclusion chromatography. The procedure constitutes a convenient and general pathway to attach functional or mesogenic groups to PSU via long flexible spacers. Thermogravimetry showed that the benzimidazole-functionalized polymers were stable up to 250 °C under nitrogen atmosphere, and that the first degradation step was attributed to the cleavage of the thio–ether bond. While the grafting of the undecenoyl side chains was found to significantly decrease the glass transition temperature ( T g), the subsequent tethering of the benzimidazole only slightly increased the T g of the grafted PSU backbone. The concentration of benzimidazole was probably too low for the formation of a percolating benzimidazole domain. This explains the quite modest proton conductivity measured under completely dry conditions, e.g. 34 nS/cm at 180 °C for a polymer functionalized with 1.7 benzimidazole units per repeating unit of PSU.

Core crosslinkable polymeric micelles from PEG–lipid amphiphiles as drug carriers

Core crosslinkable micelles were prepared based on PEG–lipid amphiphiles. The branched hydrophobic domain was prepared by acylation of 2,2-bis(hydroxymethyl)propionic acid (DMPA) with 10-undecenoyl chloride and pyridine as catalyst. Monohydroxyl poly(ethylene glycol) (m-PEG) was conjugated onto the hydrophobic domain to form the branched polymeric amphiphiles. Following micelle formation of the amphiphiles, the vinylic groups at the peripheral ends of the 10-undecenoyl acid chains were polymerized with AIBN to crosslink the hydrophobic domains in aqueous solution. The solution properties of the crosslinked micelles were evaluated in various solvents and temperatures; relative to the uncrosslinked micelle controls, the core crosslinked micelles demonstrated improved thermodynamic stability in solution to high temperatures and non-selective solvents. Furthermore, the core crosslinked micelles show much higher drug loading capacity (nearly 80 wt%) than the uncrosslinked micelles (ca. 10 wt%).

Synthesis and characterization of poly[2-(10-undecenoyloxy)ethyl methacrylate

By Schotten-Baumann's esterification of poly(2-hydroxyethyl methacrylate) with 10-undecenoyl chloride a new multimonomer - poly[2-(10-undecenoyloxy)ethyl methacrylate] was prepared. Based on the results of elemental analysis, FTIR, 1H-NMR and 13C-NMR spectra, the structure of the multimonomer was proposed. The thermal properties of the multimonomer were studied by DSC and TG. The rate of disappearance of double bonds in the multimonomer during UV irradiation was examined in the solid state to obtain a crosslinked product.

Synthesis of Various Functional Propylene Copolymers Usingrac-Et[1-Ind]2ZrCl2/MAO as the Catalyst System

Propylene copolymers with different polar groups were synthesised using rac-Et[1-Ind] 2 ZrCl 2 /MAO as the catalyst system. 10-Undecen-1-ol, 10-undecenoyl chloride, 10-undecenoic acid, 2-(9-decen-1-yl)-1,3-oxazolien, 2-(9-decen-1-yl)-4,4-dimethyl-1,3-oxazoline, and 2-[4-(10-undecene-1-oxy)phenyl]-1,3-oxazoline were used as comonomers. The addition of water to the 10-undecenoyl chloride copolymer solution led to an acid-functionalised copolymer. In the case of 2-(9-decen-1-yl)-1,3-oxazoline and its homopolymers, polymerization temperature was varied. Up to 0.61 mol-% comonomer were incorporated into the poly(propylene)s. The catalyst activities for 10-undecen-1-ol, 10-undecenoyl chloride and 10-undecenoic acid were much higher than for the oxazoline comonomers.

Unsaturated modified poly(vinyl alcohol). Crosslinking through double bonds

Poly(vinyl alcohol) (PVA) was esterified with 10-undecenoyl chloride to give polymers with different degrees of modification which were studied in order to find how the concentration of reactive sites can influence the crosslinking process. The polymers obtained were characterized by spectroscopic techniques, elemental analysis and thermal methods. Weight average molecular weights and viscosities were determined. Thermal crosslinking of the double bonds on the side chain took place in all cases, but was overlapped by the degradation process. Thus, dicumyl peroxide had to be used to obtain the cured material and avoid degradation. Activation energies for radical initiated crosslinking were determined by means of dynamic DSC studies. Isoconversional kinetic analysis was applied to DSC data and the dependences of activation energies on conversion degrees were obtained and compared with those obtained from polymers with the same pendant chain but a more flexible polyether main chain.

Polyanion inhibitors of human immunodeficiency virus and other viruses. 1. Polymerized anionic surfactants.

A series of polyanionic compounds was synthesized and evaluated for their activity against human immunodeficiency virus (HIV-1, HIV-2) and various other RNA and DNA viruses. Several compounds, i.e., 2p, 3p, 8p, 13p, 14p, 15p, 17p, 18p, and 19p, proved active against HIV-1 within the concentration range of 0.1-3 micrograms/mL while not being toxic to the host cells (CEM, MT-4) at concentrations up to 100 micrograms/mL or higher. As a rule, these polyanionic compounds proved also active, albeit at somewhat higher concentrations than those required for HIV-1 inhibition, against a number of other enveloped viruses, including HIV-2, human cytomegalovirus, influenza A virus, respiratory syncytial virus, and arenaviruses (Junin and Tacaribe). Among the most potent HIV-1 inhibitors ranked compounds 18p and 19p, the sodium salts of N-methylamides obtained by polymerization of monomers prepared starting from 10-undecenoyl chloride and omega-aminoalkanoic acids.