Radical polyaddition of difunctional vinyloxirane with thiols for synthesis of linear and networked polysulfides

Radical ring‐opening polyaddition of bifunctional vinyloxirane with multifunctional thiols was investigated. The polyaddition proceeded smoothly via the ring‐opening reaction of the oxirane moiety to afford the corresponding networked polymers bearing vinyl ether and sulfide moieties in the main chain. The thermal properties of the networked polymers and volume changes upon the polyaddition were investigated. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 783–788     

逐步增长聚合的研究进展

逐步增长聚合应用面广,且聚合物分子量是逐步增加的,近来利用逐步增长聚合可以合成新型高分子材料日益引人注目。按照逐步增长聚合的不同类型,对近年来逐步增长聚合研究的新进展,特别是对合成聚酯等的缩聚反应,以及利用二异氰酸酯和Click反应的逐步加成聚合等进行了综述。为了进一步获得性能优良、分子量可控、结构理想且制备方法简便的高分子材料,加强逐步增长聚合理论研究、开发新型结构的单体,并充分开发相应的聚合新技术,是今后逐步增长聚合研究的重点。     

Polyaddition reaction of biscarbodiimides. II. Synthesis of polyguanidines by polyaddition reaction of biscarbodiimides with diamines

A series of polyguanidines was prepared by the polyaddition reaction of biscarbodiimides with diamines. The polyaddition reaction was carried out in solution. The polymers thus obtained had intrinsic viscosities up to 0.84 and molecular weights up to 15000. The structure of the polymers was identified by comparison of their infrared spectra with those of model compounds, elementary analysis, and a study of the reaction conditions. Thermogravimetric study indicated that the polyguanidines decomposed over 170°C under nitrogen. The polyguanidines were highly resistant to hydrolytic degradation by strong acid or alkali. The polyguanidines had basic groups and formed stable hydrochloric salts when they were treated with hydrochloric acid.     

Synthesis of polyamideamines from 5-oxazolones

Polyamideamines with a sequence of two amide and one amine linkage in a main chain were synthesized from the polyaddition of 2-isopropylidene-4-alkyl-3-oxazolin-5-ones and primary diamines. The polyaddition reaction proceeded through 1,4-conjugate addition of an amine group to 3-oxazolin-5-one and subsequent ring opening of the intermediate addition product with another amine. Although aliphatic diamines gave oily polymers, xylylenediamines afforded amorphous solid polymers. The reduced viscosities and polymer melt temperature of the polymers were 0.05–0.12 and 90–130°C., respectively.     

Synthesis and properties of poly(thioether amide)s from 2,6-bis(acrylamido)pyridine and dithiols

Poly(thioether amide)s containing pyridine moieties in their backbone were obtained by the polyaddition of 2,6-bis(acrylamido)pyridine (2,6-BAAP), derived from 2,6-diaminopyridine and acryloyl chloride, with an aromatic or aliphatic dithiol. The influence of various reaction conditions on the polyaddition was investigated in comparison with the polyaddition of 1,3-bis (acrylamido)benzene (1,3-BAAB). 2,6-BAAP gave the polymer even in the absence of any initiator at lower temperatures while 1,3-BAAB did not, which was attributable principally to intramolecular base catalysis of the pyridine moieties. Basic additives effectively promoted the reaction rate and increased the chain length. Those facts and NMR of the resulting polymers indicated Michael-type polyaddition. The polymers from 2,6-BAAP were amorphous and gave transparent and tough films having a high refractive index exceeding 1.7. GPC and DSC characterizations were also made. © 1993 John Wiley & Sons, Inc.     

Synthesis of head‐to‐tail polyurethanes from nonsymmetric diisocyanate and ethylene glycol with organotin catalysts

An ordered head‐to‐tail (HT) polyurethane was successfully prepared by the polyaddition reaction of p‐isocyanatobenzyl isocyanate with ethylene glycol with dibutyltin dilaurate as a catalyst. Furthermore, the HT regularity of polyurethane was improved to 83% with 1,1,3,3‐tetraphenyl‐1,3‐dichlorodistannoxane. The polymerization was conducted in N,N‐dimethylformamide at 30 °C with both monomers mixed at once. The microstructure of the polymer was investigated by ¹H and ¹³C NMR spectroscopy, and the polymer obtained by the polyaddition reaction had the expected HT linkages. The constitutional regularity of the polymers influenced the thermal properties and crystallinity. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 416–429, 2001     

A novel polyaddition of bifunctional acetylenes containing electron-withdrawing groups. III. Synthesis of polymers having β-alkoxyenoate moieties by the reaction of internal diynes with diols

Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc.     

Polyesters of phosphoric acid: Synthesis and kinetics of hydrolysis

Three major methods have been elaborated in our laboratory for preparation of polymers with poly(alkylene phosphates) backbones: ring-opening polymerization, poly-condensation and transesterification, and polyaddition. The second method is based on the reaction of the commercially available compounds, namely dialkyl (or diaryl)-H-phosphonates and glycols. Reaction of the aliphatic H-phosphonates with aliphatic glycols is a reversible process, whereas polycondensation of diphenyl H-phosphonates with aliphatic and cycloaliphatic diols is practically irreversible. This latter method has recently been developed and is described in this paper. Poly H-phosphonates with M̄_n up to 40–10³ were prepared. Polymers are easily oxidized and quantitatively converted into the relatively stable poly(alkylene phosphates). Some physical properties of these polymers and kinetics of their hydrolysis is discussed.     

Polyaddition of p-benzenedithiol to p-diethynylbenzene in solid state under UV irradiation

A novel polyaddition of p-benzenedithiol (BDT) to p-diethynylbenzene (DEB) was studied in solid state under UV or γ-ray irradiation at 25–99°C. Thin layer crystals of the 1:1 mixture of BDT and DEB mounted on a glass plate were prepared by a sublimation of an equimolar amount of the mixture of BDT and DEB at 45–80°C under a reduced pressure of nitrogen. The thin layer crystal of the 1:1 mixture of BDT and DEB and that of polymers exhibited almost similar and high crystalline diffraction patterns on x-ray diagraph. Consequently, the polyaddition in the solid state was a topotactic reaction controlled by the crystal lattice of the 1:1 mixture of BDT and DEB. The arrangement of both compounds in the thin layer crystal of the 1:1 mixture of BDT and DEB is seemingly quite ordered induced by a molecular interaction between BDT and DEB, and this is supported on the basis of the broad absorption at 340–450 nm by the diffuse reflectance spectrum taken with the thin layer crystal of the 1:1 mixture of BDT and DEB. The melting point of the 1:1 mixture of BDT and DEB was 90–94°C. However, the polyaddition at 87°C proceeded in a molten state perhaps due to heat evolved in the polyaddition. In the solid state polyaddition M _n of polymers obtained was 3–4 × 10³, whereas in the molten state polyaddition the crystallinity of polymers remarkably decreased, and M _n increased several times.     

New aspects on intrinsically conducting organic systems and their synthesis

Organic polymer films with intrinsic conductivity can be produced in a continuous process directly from the monomers by anodic oxidation. This paper describes the synthesis, the scope available for variation in the process, and the main properties of the new polymers. Electrochemical oxidation, e.g. of pyrrole to polypyrrole, is a new polymerization principle that differs essentially from those adopted for classical plastics, i.e. radical or ionic polymerization and polyaddition or polycondensation techniques. It is not only the principle underlying the synthesis that differs, and the properties of the new polymers are unusual.     

Novel fluorinated polymers by radical polyaddition: Inspiration and progress

The story of the outset and the growth of radical polyaddition of bisperfluoroisopropenyl derivatives [CF₂?C(CF₃)? R? C(CF₃)? CF₂] with several organic compounds possessing carbon–hydrogen bonds is described. The reaction afforded novel fluorinated polymers bearing such organic segments in polymer main chains as 1,4‐dioxane, diethyl ether, dimethoxyethane, 18‐crown‐6, triethylamine, glutaraldehyde, and alkanes which have never been supposed as direct starting compounds for preparation of polymers. The facile method for preparation of fluorinated hybrid polymers bearing alkylsilyl groups was developed with diethoxydimethylsilane and silsesquioxanes. Taking advantage of the high reactivity of the perfluoroisopropenyl group as a radical acceptor, self‐polyaddition and cyclopolymerization were investigated. Triethysilyl perfluoroisopropenyl ether [CF₂? C(CF₃)? O? Si(C₂H₅)₃] was proved to be the most probable candidate for self‐polyaddition. Cyclopolymerization of perfluoroisopropenyl vinylacetate [CF₂?C(CF₃) OCO? CH₂CH? CH₂] was investigated to afford polymers possessing five‐membered‐ring units in main chains. The interconversion of the unstable fluorinated carbon radical and the stable hydrocarbon radical had an important role in the reaction. The radical addition reaction presented herein may be developed for preparation of a wide variety of novel fluorinated polymers and organic compounds possessing functional groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4101–4125, 2004     

Chiral liquid-crystalline polymers. XI. Thermotropic behavior and chiroptical properties in solution of a new series of optically active poly (ester β-sulfide)s

The synthesis and characterization are described of a series of optically active semiflexible poly(ester β-sulfide)s 6*Sn with repeating units constituted by two p-oxybenzoyl diads spaced in an alternating fashion by a sulfide-containing polymethylene segment of variable length (n = 2-10) and a chiral (R)-3-methylhexanediyl segment of high enantiomeric purity. The polymers were prepared with good yields and relatively high molecular weights and narrow degrees of dispersity by a Michael-type polyaddition reaction of bis-thiols to the same chiral mesogenic bisacrylate monomer. Data are reported on the characterization of their chiroptical properties in dilute solution and thermal-optical properties in the bulk, with attention being devoted to the distinct odd-even alternations of the cholesteric-isotropic melt transition parameters. A comparison of the mesomorphic behavior and relevant thermodynamic quantities is presented between the present series of polymers and the achiral analogues of series 6Sn as well as the chiral, positional isomers of series mS6* . The dependence of the overall properties and their trends on very subtle structural changes is stressed, thus highlighting the critical interconnection between mesogenic cores and spacer segments in semiflexible liquid-crystalline polyesters.     

Synthesis and polymerization reactions of cyclic imino ethers. VI. Polymers with biphenyl structure

A monomer of the AB‐type and a bifunctional comonomer of the AA‐type containing two 2‐oxazoline rings and a biphenyl structural unit were prepared from the corresponding carboxylic acids via their esterification and subsequent amidation with an aminoalcohol. The cyclization of an amide to 2‐oxazoline structure was achieved by treatment with thionyl chloride followed by liberation of the free base with sodium hydrocarbonate in an aqueous solution. The prepared monomers were used for the polyaddition polymerization of the AB‐type monomer having a 2‐oxazoline and phenol group bound on adjacent rings of the biphenyl structure in solution. The monomer of the AA‐type was used for AA+BB‐type polyaddition reactions with aliphatic dicarboxylic acids. Both types of polymerizations have been performed in melt and in solution. The structures of the polymers were determined, and the thermal properties of the polymers were evaluated. Liquid‐crystalline (LC) structures of the prepared polymers were observed by DSC measurements and optical microscopy. The polyaddition reactions of the monomers containing a 2‐oxazoline ring and a biphenyl unit represent a new efficient way for the preparation of a biphenyl unit containing poly(ether amide)s and poly(ester amide)s. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Click chemistry step growth polymerization of novel alpha-azide-omega-alkyne monomers

A novel step growth polymerization A-B strategy based on the click chemistry polyaddition of tailor-made alpha-azide-omega-alkyne low molar mass monomers was developed, leading to polytriazole (co)polymers with tunable structures and properties.     

Modular Alcohol Click Chemistry Enables Facile Synthesis of Recyclable Polymers with Tunable Structure

The facile synthesis of chemically recyclable polymers derived from sustainable feedstocks presents enormous challenges. Here, we develop a novel, modular, and efficient click reaction for connecting primary, secondary, or tertiary alcohols with activated alkenes via a bridge molecule of carbonyl sulfide (COS). The click reaction is successfully applied to synthesize a series of recyclable polymers by the step polyaddition of diols, diacrylates, and COS. Diols and diacrylates are common chemicals and can be produced from biorenewable sources, and COS is released as the industrial waste. In addition to sustainable monomers, the approach is atom-economical, wide in scope, metal-free, and performed under mild conditions, affording unprecedented polymers with nearly quantitative yields. The produced polymers also possess predesigned and widely tunable structure owing to the versatility of our method and the broad variety of monomers. The in-chain thiocarbonate and ester polar groups can play as breakpoints, allowing these polymers to be easily recycled. Overall, the polymers have broad prospects for green materials given their facile synthesis, readily available feedstocks, desirable performance, and chemical recyclability.     

Polyaddition reaction of pseudoxazolones with dimercaptans

Polymers having thioether, thiolester, and amide linkages in each repeating unit of a polymer main chain were prepared by the polyaddition reaction of pseudoxazolones (2-isopropylidene-4-alkyl-3-oxazolin-5-ones) and dimercaptans. The polymers had inherent viscosities in a range of 0.08–0.22 and gave transparent films by solution casting.     

Thermotropic poly(azomethine-urethane)s with non linear optical properties: Synthesis and characterization

Two series of the thermotropic main chain poly(azomethine-urethane)s were synthesized by the polyaddition of azadiol, 1,8-octandiol with methylene bis(phenyl isocyanate) (MDI) and tolylene 2,4-diisocyanate (TDI) respectively. The mesomorphic properties and phase transition temperature of the polymers were characterized by differential scanning calorimetry and hot stage polarizing microscopy. These polymers showed nematic messophase. The non linear optical (NLO) activity of the polymers was also investigated.     

Synthesis and endosomolytic properties of poly(amidoamine) block copolymers

The poly(amidoamine)s (PAAs) ISA 1 and ISA 23 display pH-dependent conformational change and pH-dependent membrane perturbation. These properties confer potential for use as endosomolytic polymers for intracytoplasmic delivery of toxins and genes. Both polymers are relatively non-toxic, and moreover ISA 23 has the beneficial property in vivo, of being non hepatotropic when administered intravenously. Although ISA 23 and ISA 1 demonstrate ability to transfect cells, ISA 1 is also able to promote intracellular delivery of non-permeant toxins. The aim of this study was to synthesise random and block copolymers of ISA 1 and ISA 23 and investigate whether these second generation hybrids would allow optimisation of PAA biological characteristics. Random and block copolymers of ISA 1 and ISA 23 were synthesised by hydrogen transfer polyaddition to generate a library of PAAs with an ISA 23:ISA 1 molar ratios of 2:1 to 4:1. The resultant polymers have a pI slightly below 7.4 and a M(w) of 19,900-49,000 g/mol and a M(n) of 13,100-24,100 g/mol. Whereas none of the random or block copolymers were haemolytic at pH 7.4 all demonstrated pH-dependent membrane activity. At pH 5.5 they caused 50-60% haemoglobin (Hb) release over 1 h. This was slightly less than that seen for ISA 23 (80% Hb release). None of the copolymers were cytotoxic against B16F10 cells during a 72 h incubation (IC(50) > 2 mg/ml; MTT assay). The ability of the random and block copolymer PAAs to deliver the toxin gelonin was also examined, but only ISA 1 and the block copolymer B2 (ISA 23:ISA 1 at a 2:1 molar ratio) were able to promote intracellular delivery, as measured by cytotoxic activity. It would be interesting to study the body distribution of B2 and determine whether this toxin-delivering PAA is able to escape liver capture.     

Investigation of nitrogen‐rich energetic polymers based on alkylbridged bis‐(1‐methyl‐tetrazolylhydrazines)

Nitrogen‐rich energetic polymers were synthesized by the polyaddition reaction of 1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1a ), 1‐methyl‐1,2‐bis(5‐monomethylhydrazinyl‐1H‐tetrazolyl)ethane ( 1b ), and 1,4‐bis(5‐mono‐methylhydrazinyl‐1H‐tetrazolyl)butane ( 1c ) with hexamethylene diisocyanate. The experiments showed that neither a polymerization from solution or bulk was possible. Therefore, a new method for the polymerization of tetrazolyl hydrazines had to be developed. The formed polymers were characterized by vibrational spectroscopy (IR) and elemental analysis. The energetic properties were investigated by bomb calorimetric measurements along with calculations using the EXPLO5 software. The thermal stability was investigated by DSC measurements. The properties render the polymers into promising compounds regarding an application as energetic binder. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 122–127, 2010     

Synthesis of new linear polymers containing phosphorus atom in the main chain by the radical polyaddition: Addition polymers of phenylphosphine with 1,4-divinylbenzene or 1,4-diisopropenylbenzene and their properties

A polyaddition of phenylphosphine (PH) to 1,4-divinylbenzene (DVB) or 1,4-diisopropenylbenzene (DIPB) was carried out by radical initiations or UV irradiation at 60–80°C in toluene under a nitrogen atmosphere. The soluble polymer with higher molecular weight () was obtained in a high yield with AIBN initiator for 95 h in the presence of 5% excess of PH to DVB (monomer feed ratio [DVB]₀/[PH]₀ = 1/1.05). On the other hand, a polyaddition of PH to DIPB proceeded much slower than the case of DVB, but the high polymer was obtained in a high yield by choosing polyaddition conditions such as polyaddition temperature and initiator concentration. From ¹H-NMR, IR analyses, and phosphorus content of the polymers, it was characterized that both polymers have the alternating structure consisting of PH and DVB or DIPB units in 1 : 1 ratio. The glass transition and decomposition temperatures of both polymers under a nitrogen atmosphere were almost similar: 15–30°C and 380–385°C, respectively; but, the polymers were oxidized by heating under an atmosphere of air. The polymers had a self-extinguishing property and the polymer blend of the flammable polymers such as polystyrene and polyethylene with the phosphorus-containing polymers exhibited an excellent flame resistance. © 1994 John Wiley & Sons, Inc.