Chemical modification of polypropylene by nitroxide-mediated radical graft polymerization of styrene

Nitroxide-mediated free radical polymerization (LREP) was employed for the first time to prepare graft copolymer by having arylated polypropylene (Cl-PP) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PP carrying 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, maleic anhydride was grafted onto polypropylene by peroxide-catalyzed swell grafting method (PP-MAH). Next, PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the obtained PP-OH was treated with α-phenyl chloroacetyl chloride and converted to a chloroacetyl group containing polypropylene (PP-Cl). Finally, 1-hydroxyl-2,2,6,6-tetramethylpiperidine (TEMPO-OH) was synthesized by reducing TEMPO with sodium ascorbate and this functional nitroxyl compound was coupled with α-phenyl chloroacetylated polypropylene. The resulting macroinitiator (PP-TEMPO) for free radical polymerization was then heated in the presence of styrene for the formation of the graft copolymer. The prepared graft copolymer was characterized by Fourier transform infrared spectroscopy and ¹H NMR techniques. Glass transition temperature of grafted copolymer was investigated using thermogravimetric analysis and differential scanning calorimetric techniques. This approach using nitroxide-mediated macroinitiators is an effective method for the preparation of new materials.     

Graft copolymerization of methylmethacrylate with N‐substituted maleimide‐styrene copolymer by ATRP

Atom transfer radical polymerization (ATRP) was employed to prepare graft copolymers having poly(MBr)‐alt‐poly(St) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches to obtain heat resistant graft copolymers. The macroinitiator was prepared by copolymerization of bromine functionalized maleimide (MBr) with styrene (St). The polymerization of MMA was initiated by poly(MBr)‐alt‐poly(St) carrying bromine groups as macroinitiator in the presence of copper bromide (CuBr) and bipyridine (bpy) at 110°C. Both macroinitiator and graft copolymers were characterized by ¹H NMR, GPC, DSC, and TGA. The ATRP graft copolymerization was supported by an increase in the molecular weight (MW) of the graft copolymers as compared to that of the macroinitiator and also by their monomodal MW distribution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Ring-opening copolymerization of 2,4-bisphenyl-1,3,2,4-dioxadiphosphetane-2,4-dioxide with oxetane via zwitterion intermediates

Summary Copolymerization of 2,4-bisphenyl-1,3,2,4-dioxadiphosphetane-2,4-dioxide (DPO) with oxetane, a cyclic ether, was found to take place at 90 and 120°C without initiator. Copolymers obtained have a structure of phosphonate-ether units (1), which was determined by ³¹P, ¹H and ¹³C NMR, IR and elemental analysis. Oxetane was incorporated into 1 in a slight excess in all runs(m value in 1=1.5–2.1). A small amount(<15%) of a by-product (2) was always formed. Other cyclic ethers such as ethylene oxide and propylene oxide did not afford copolymers but gave 11 addition products, 10 and 11, quantitatively. The copolymerization is reasonably explained by a mechanism in which DPO behaves as an electrophilic monomer and oxetane as a nuicleophilic one. A pyrophosphonate species is considered to be a key intermediate to lead to copolymer 1 and the whole reaction course is discussed in detail.     

Synthesis and Thermal Characterization of Some Novel ABA Block Copolymers

The synthesis of some novel ABA block copolymers is reported. The block A is a PPO while the block B is a random copoly(aryl ether sulfone), synthesized with three different molecular weights. The block copolymers were obtained by a two step procedure consisting on the functionalization of the random copoly(aryl ether sulfone) followed by a condensation with PPO. Spectroscopic techniques (¹H NMR and ¹³C NMR) were used to characterize the polymers obtained from each step. The NMR data proved the complete conversion of amino groups after the first reaction step and gave some useful insights on the completion of the second step. Copolymer formation is supported by a comparison of the thermal behavior of the block copolymers with respect to the physical blends of the two homopolymers. DSC and DMA analyses showed double glass transitions for the physical blends which could be related to the immiscibility of the two homopolymers, while, in contrast, the block copolymer showed single glass transition. Blends of ABA triblock copolymer/PPO and of ABA triblock/copoly(arylen ether sulfone)s were also prepared. These blends, tested by DSC, showed a good level of compatibility of the ABA copolymer with its singular constituents.

     

Separation and characterization of poly(styrene‐co‐acrylonitrile)‐graft‐poly(propylene oxide) polymer stabilizer formed in dispersion polymerization of styrene and acrylonitrile in polyether

Poly(styrene‐co‐acrylonitrile)‐graft‐poly(propylene oxide) (PSAN‐graft‐PPO), the stabilizer formed in situ in the dispersion polymerization of styrene, acrylonitrile and macromonomer PPO maleate in PPO polyol, was separated from ungrafted copolymer PSAN by liquid chromatography. After the determination of the separation conditions by thin‐layer chromatography, the effective separation of the graft polymer from copolymer PSAN was achieved by liquid column chromatography. The graft efficiency and the composition of the graft polymer was determined by UV and ¹H NMR, and the formation characteristics of the graft polymer are discussed. © 2001 Society of Chemical Industry     

Optically active vinyl polymers containing fluorescent groups. 6

Summary Copolymers of carbazole-containing monomers such as 4- and 3-(9-carbazolylmethyl)styrene (1 and 2), 2(9-carbazolyl)ethyl methacrylate (3) and 2-(9-carbazolylacetyloxy)ethyl methacrylate (4) with optically active menthyl acrylate (5) and methacrylate (6) were prepared by free radical polymerization.In all cases optically active copolymers were obtained and for copolymer samples of 1 and 2 with 5 and 6, CD spectra indicate an appreciable, even if small, dissymmetric perturbation of heteroaromatic moiety.NMR and fluorescence emission spectra of the above copolymers are consistent with a monomer-type behaviour which can be associated with a high dishomogeneity of the conformational environment in which the aromatic chromophores are located.Profiles of the UV band in the 230–240nm region are analysed in terms of the different structural features of the copolymers. ¹H-NMR spectra recorded on partially deuterated po1y(1) eliminate any contribution by the carbazolyl protons to the upfield signal (6.5–5.5ppm) of the complex aromatic protons resonance.Dedicated to Prof. C.I. Simionescu on the occasion of the 60th anniversary of his birthday     

Synthesis and self-assembly behavior of POSS tethered amphiphilic polymer based on poly(caprolactone) (PCL) grafted with poly(acrylic acid) (PAA) via ROP,ATRP, and CuAAC reaction

This investigation reports the preparation and self-assembly behavior of polyhedral oligomeric silsesquioxane (POSS) containing poly(caprolactone)-graft-poly(acrylic acid) (POSS-PCL-graft-PAA) polymer. This article focuses on the self-assembly behavior of POSS tethered amphiphilic graft copolymer. In this investigation, POSS tethered alkyne functionalized polycaprolactone (PCL) was prepared by strategic ring opening polymerization (ROP) of ε-caprolactone and α-propargyl-ε-caprolactone using hydroxyl-terminated POSS as an initiator. Azide-terminated poly(tert-butyl acrylate) (P ^t BA) was grafted onto functional PCL via Cu-catalyzed azide-alkyne “click” (CuAAC) reaction. Finally, hydrolysis of the tert-butyl ester group into acid furnished the POSS tethered PCL-graft-PAA polymer. This amphiphilic graft copolymer was characterized by GPC, NMR, and FT-IR analyses and the morphology of the graft copolymer analyzed by HRTEM and FESEM analyses. On changing the graft copolymer concentration (low to high) in water, the morphology of the final graft copolymer changed from micelles to worm-like and core-shell. The structural motif of POSS plays an important role in this morphological transformation. The pH sensitivity was studied using DLS analysis as well as via release profile of rhodamine B as a model compound.     

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group‐containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group‐terminated polymethylphenylsilane in 15–32% yield. The isolated polymethylphenylsilane (M_n = 3350 g mol^?1, M_w/M_n = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (M_n = 4730 g mol^?1, M_w/M_n = 1.2) in 38% yield. The ratio of monomer units (? MeSiPh? to? BuSiBu? ) of the copolymer was determined to be 75:25 using ¹H NMR analysis, which was in good agreement with the calculated ratio (74:26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)‐block‐poly(dibutylsilane), was also confirmed by comparing its ¹H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group‐terminated polydibutylsilane, and polydibutylsilane‐block‐polymethylphenylsilane was also obtained using this macroinitiator. Copyright © 2011 Society of Chemical Industry     

Addition of dichlorocarbene to cis-1,4-poly(2-trimethylsilylmethyl-1,3-butadiene)

Summary Copolymers made up of 1,4-(2,3-dichloromethylene-2-trimethylsilylmethyl-1,3-butadiene) (I) and 1,5-(3-chloro-2-methylene-pent-3-ene) (II) units have been prepared by potassium fluoride elimination of trimethylchlorosilane from cis-1,4-poly(2.3-dichloromethylene-2-trimethylsilylmethyl-1,3-butadiene) (III). III was prepared by the addition of dichlorocarbene to 1,4-poly-(2-trimethylsilylmethyl-1,3-butadiene) (cis/trans = 9/1) (IV). Polymer III was characterized by ¹h, ¹³C and ²⁹Si NMR as well as by elemental analysis. The copolymer was characterized by ¹H, ¹³C and ²⁹Si NMR spectroscopy. The ratio of I and II units in the copolymer were determined by ¹H NMR and elemental analysis.     

Study of macroinitiator efficiency and microstructure–thermal properties in the atom transfer radical polymerization of methyl methacrylate

The atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with poly vinylacetate macroinitiator (PVAc-CCl₃) and CuCl/PMDETA as catalyst was successfully carried out in bulk and solution. The apparent propagation rate constant () and concentration of active species ([P°]) were higher in the bulk. In solution they increased with polarity of solvent. Two different molecular weights of macroinitiators were used in ATRP of MMA. The linear relation of Ln[M]₀/[M] versus time was only confirmed for the low molecular weight macroinitiator. The ratio of was calculated in the bulk reaction with the low molecular weight macroinitiator, this ratio was 1.77 × 10¹⁴ M⁻¹ s⁻¹ for larger macroinitiator in solution. The MWD of block copolymers were sharper with lower molecular weight macroinitiator in the solution, but it appeared broader in the bulk polymerization. Our results indicated that smaller molecular weight macroinitiator was more efficient and formed a block copolymer with lower PDI. Thermal analysis and microstructure of the block copolymers are investigated by ¹H NMR, FT-IR, TGA and DSC. The chain tacticity of the MMA units is found not to be sensitive to the kinetic of the reactions with two different molecular weights of macroinitiator. DSC measurement shows two different transitions at 39 and 108 °C assigned to PVAc and PMMA blocks. The TGA profile shows a three-step degradation. The initial small weight loss that occurs around 220 °C and two large weight loss around 238 and 310 °C are attributed to dechlorination step and decomposition of the PMMA and PVAc blocks.     

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.     

New amphiphilic fluorescent CBABC-type pentablock copolymers containing pyrene group by two-step atom transfer radical polymerization (ATRP) and its self-assembled aggregation

A series of novel amphiphilic fluorescent CBABC-type pentablock copolymers (Py-PMMA-PEG4600-PMMA-Py) were prepared from BAB-type amphiphilic triblock copolymer (PMMA-PEG4600-PMMA) as macroinitiator with various contents of 1-(methacryloyloxyethylamino-carboxylmethyl) pyrene (PyMOI) by atom transfer radical polymerization (ATRP) in toluene using CuBr/2,2-bipyridine as catalyst system. Triblock copolymer (PMMA-PEG4600-PMMA) was prepared by ATRP and obtained from Br-PEG4600-Br as macroinitiator with methyl methacrylate in tetrahydrofuran using the same catalyst. The molecular weights of pentablock copolymers which were reinitiated by PMMA-PEG4600-PMMA macroinitiator were calculated from ¹H NMR spectra up to 42,400 gmol⁻¹. The polydispersity of pentablock copolymers obtained from GPC analysis was narrow between 1.10 and 1.38. The crystallinity of triblock copolymer (PMMA-PEG4600-PMMA) was decreased slightly with incorporating PMMA segment. Introducing the bulky pyrene substituent into pentablock copolymer, the melting temperature was not observed and all pentablock copolymers showed amorphous patterns in wide-angle X-ray scattering (WAXS) due to decrease in the degree of crystallinity of polymer chain because of disturbing regular packing. The temperatures at 10% weight loss (Td₁₀), examined by TG analysis, showed values ranging from 265 to 323 °C in nitrogen and 264 to 313 °C in air. Fluorescence spectra of Py-PMMA-PEG4600-PMMA-Py exhibited stronger excimer emission at ca. 480 nm due to the aggregations of pyrene group formed via interaction of the hydrophobic chains. The more content of PyMOI segment in pentablock copolymers can obtain the higher emission intensity ca. 480 nm. When there were higher PyMOI contents (84.9 wt% PyMOI) in pentablock copolymers, they formed larger aggregates (210 nm) in SEM micrographs. On the other hand, while increasing the concentration of the polymer solution in THF, the morphology was changed from spherical (0.1 mg/mL) to chainlike (1.0 mg/mL) aggregates.     

Substituent Effects on 13C Chemical Shifts of Aromatic Carbons in β-O-4 and β-5 type Lignin Model Compounds

Abstract

Substituent effects on the chemical shifts of aromatic carbons in lignin model compounds have been elucidated from ¹³C NMR spectra of guaiacyl and syringyl type monomerio and β-O-4 model compounds and guaiacyl type β-5 model compounds. Evaluation of the observed values of substituent chemical shift (SCS) for the aromatic carbons leads to elucidation of a generalized SCS additivity rule, for estimation of the chemical shifts of aromatic carbons in ring A of β-O-4 and β-5 type substructures in model compounds and in ring B of β-O-4 substructures in lignin preparations, with errors of less than 1 ppm. The rule is applicable to substructures of both guaiacyl and syringyl types, using an appropriate parent compound as reference instead of benzene. Signals in the aromatic region of the ¹³C NMR spectra of β-O-4 and β-5 type model compounds are reassigned on the basis of the observed SCS's as well as APT spectra of the compounds.     

Synthesis of polymers with benzo-13-crown-4 and benzo-9-crown-3 units via cyclopolymerization

Summary Polymers containing crown ether units were synthesized by cyclopolymerization of divinyl and diepoxide monomers. These are 1,2-bis-(2-ethenyloxyethoxy)-benzene (1) and 1,2-bis-(2,3-epoxypropyl)-benzene (3) producing polymers with 13 and 9-membered rings 4 and 5, respectively. Both the monomers and polymers were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy. Finally, the polymers were contacted with an aqueous solution of lithium chloride.     

Synthesis of photodegradable polymers by SH-En polyaddition

Summary The polyaddition reaction of the Michael donor 1.2-bis(2-mercaptoethoxy)ethane (Bis-SH) 2 as dithiol to various Michael acceptors such as divinyl sulfone (DVS) 1, N,N-bismaleimido-4,4-diphenylmethane 3, 4,4-(N-maleimido)diphenyliodoniumchloride 4 and diallyl succinate 5 in the presence of tributylamine is described. Polymers were characterized by NMR-spectroscopy, elemental analysis, DSC and TG-analysis. In particular we synthesized a photosensitive polymer with 4,4-(N-maleimido)diphenyliodonium chloride as comonomer, which eliminated analytical amounts of HCl during irradiation.     

Polycondensation of N-Chlorobenzoquinonimines

Summary Self-condensations of 4-chloroimino-2, 5-cyclohexadiene-1-one 1 (benzoquinone N-chloroimine), 2-tert-butyl-4-chloroimino-2, 5-cyclohexadiene-1-one 2, and 3-tert-butyl-4-chloroimino-2, 5-cyclohexadiene-1-one 3 in N-methylpyrrolidinone containing inorganic bases have been investigated. Monomer 1 gave polymers having inherent viscosities of 0.27–0.33 dLg^–1. Monomers 2 and 3 only gave oligomers. ¹H NMR spectra suggest that polymerization of 1 mainly occurs at C-2 and C-6 positions. A Michael-type addition mechanism, based on the high -effect nucleophilicity of =NCl, is proposed.     

Preparation and flocculation behavior of cellulose‐g‐PMOTAC copolymer

As a contribution to the wider use of biodegradable materials, this article reports the synthesis and testing of cationic polyelectrolyte cellulose derivatives for use as flocculation chemicals. Cellulose macroinitiator is synthesized in DMAc/LiCl solvent system by direct acylation of cellulose with 2‐bromoisobutyryl bromide. Cellulose‐graft‐poly(N,N‐dimethyl aminoethyl methacrylate) (cellulose‐g‐PDMAEMA) copolymers are prepared by copper‐mediated radical polymerization in homogeneous medium. Formation of the macroinitiator and graft copolymers is confirmed by ATR‐FTIR and ¹H NMR. Quaternization of the graft chains to poly(methacryloxyethyl trimethylammonium chloride) (PMOTAC) produces cellulose‐g‐PMOTAC, which performs similarly to a commercial product in flocculation of pulp and kaolin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40448.     

Graft copolymers from commercial chlorinated polypropylene via Cu(0)‐mediated atom transfer radical polymerization

Commercially available chlorinated polypropylene has been used as a macroinitiator for the Cu(0)‐mediated atom transfer radical polymerization of methyl methacrylate and tert‐butyl acrylate to obtain well‐defined graft copolymers. The relatively narrow molecular weight distribution in the graft copolymers and linear kinetic plots indicated the controlled nature of the copolymerization reactions. Both Fourier transform infrared and ¹H NMR studies confirmed that the graft reactions had taken place successfully. After graft copolymer formation, tert‐butyl groups of poly(tert‐butyl acrylate) side chains were completely converted into poly(acrylic acid) chains to afford corresponding amphiphilic graft copolymers. © 2016 Society of Chemical Industry     

Microstructure of copolymers of vinylidene cyanide,methacrylonitrile and acrylonitrile with methyl α acetoxyacrylate,a captodative monomer

Summary Copolymers of vinylidene cyanide (1a) methacrylonitrile (1b) and acrylonitrile (1c) with a captodative monomer, methyl acetoxyacrylate were synthesized by radical copolymerization and their microstructures were studied by ¹³C NMR spectroscopy.The copolymer of 1a with methyl -acetoxyacrylate (2) has mostly an alternating structure but the copolymers of 1b and 1c with 2 are rather statistical. The measurement of their reactivity ratios for these two reactions is in agreement with the proposed structures.     

壳聚糖/聚己内酯接枝共聚物的均相合成与表征

以离子液体1-丁基-3-甲基咪唑醋酸盐（［BMIM］Ac）为反应介质,研究了壳聚糖与ε-己内酯的均相接枝共聚反应,考察了反应温度、时间、催化剂用量等对接枝率的影响,并利用红外光谱、核磁共振氢谱、热重分析、X射线衍射等对接枝共聚物进行了表征。结果表明,均相条件下壳聚糖与ε-己内酯的接枝共聚反应时间短、效率高,在反应温度为105℃,反应时间为8 h,催化剂Sn(OCt)₂的用量为ε-己内酯质量的0.1%,ε相似文献