Synthesis of well defined amino telechelic cis-1,4-oligoisoprenes from carbonyl telechelic oligomers; first studies of their potentialities as polyurethane or polyurea materials precursors

Carbonyl telechelic cis-1,4-oligoisoprene (CTPI) obtained from high molecular weight polyisoprene through an oxidative chain cleavage reaction have been chemically modified. Thus, new well defined amino telechelic cis-1,4-oligoisoprenes have been obtained in a mass range of 1600-2300 g/mol according to two different pathways. The first approach involved a standard mesylate displacement by sodium azide followed by smooth reduction using triphenylphosphine. The second pathway implied a reductive amination sequence. Primary or secondary amine functions have thus been selectively obtained at both oligomer chain-ends depending on reaction conditions. Peculiar NMR experiments conducted on these functional oligomers confirmed a precise control of functionality during the chemical modification. Moreover, their abilities to react with toluene diisocyanate or bis(succinimidyl)carbonate have been investigated.     

Remarkable improvement of thermal stability of main‐chain benzoxazine oligomer by incorporating o‐norbornene as terminal functionality

A new main‐chain benzoxazine oligomer with o‐norbornene functionality as end groups has been designed and synthesized. As compared to traditional main‐chain type benzoxazine polymers, this benzoxazine oligomer with o‐norbornene terminal functionality can undergo further crosslinking polymerization after general ring‐opening polymerization of oxazine rings. Another main‐chain benzoxazine oligomer has also been designed based on the reaction of bisphenol‐A, 4,4′‐diaminodiphenylmethane, paraformaldehyde, and phenol for comparison. The structure of the synthesized oligomers is confirmed by ¹H nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FTIR). The molecular weight has been determined by using gel permeation chromatography (GPC). The benzoxazine oligomer containing o‐norbornene functionality can polymerize with multiple polymerization mechanisms rather than the single mechanism common to traditional 1,3‐benzoxazine resins. The polymerization mechanisms are monitored by in situ FTIR and differential scanning calorimetry (DSC). Moreover, the thermoset derived from the benzoxazine oligomer containing o‐norbornene functionality exhibits high thermal stability with the transition temperature of 360 °C and a high T_d5 of 404 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45408.     

Synthesis and characterization of natural rubber-based telechelic oligomers via olefin metathesis

Metathesis degradation and functionalization of natural rubber (NR) were conducted with 1-hexene, 1-octene, 1-decene, 1-dodecene, trans-stilbene, and 4,4′-dibromo-trans-stilbene as chain transfer agents (CTAs) in presence of Grubbs 2nd generation catalyst to generate NR-based telechelic oligomers that had been a long-lasting challenge due to the structure and compositions of NR with various impurities. Orthogonal experiments were applied and the effects of the CTA type, CTA concentration, catalyst concentration, reaction time, and reaction temperature on the formation of telechelic oligomers were studied, indicating that the catalyst concentration was the major factor influencing the number average molecular weights (M_n) and polymer dispersity index (PDI) of telechelic oligomers. The structures of the oligomers were characterized using ¹H NMR, ¹³C NMR, and MALDI-TOF-MS, which confirmed the formation of the designed terminal groups. The results showed that well-defined telechelic oligomers with a M_n of a few thousand and a PDI around 1.6 were obtained, with potential applications in binder, lubricant and many other fields.     

Preparation of polysiloxane oligomers bearing benzoxazine side groups and tunable properties of their thermosets

A new pathway for the preparation of polysiloxane oligomers bearing benzoxazine side groups were reported via the hydrolysis and co‐polycondensation of benzoxazinyl siloxane (SBZ) with dimethyldiethoxysilane (DEDMS). The structures of SBZ and oligomers were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. The average molecular weights of the obtained oligomers were estimated from size exclusion chromatography and ¹H‐NMR to be in the range of 2000–4000. The oligomers gave transparent films by casting in THF solution. The films were further thermally treated to produce crosslinked films via the ring opening polymerization of benzoxazine side group. The effects of siloxane content on polymerization behavior, glass transition temperature, and mechanical properties of the polybenzoxazine thermosets were investigated. Tensile test of the films revealed that the elongation at break increased with increasing siloxane content. The elongation at break of poly(I‐50) was up to 12.1%. Dynamic mechanical analysis of the thermosets showed that the T_gs were in the range of 119–165°C. Thermogravimetic analysis also revealed a better thermal stability as evidenced by the 5% weight loss temperatures in the range of 363–390°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40960.     

Synthesis and optical properties of cholesteric liquid‐crystalline oligomers displaying reversible thermochromism

A series of side‐chain liquid crystalline oligomers (P₁–P₇) have been synthesized with cyclo(methylhydrogeno)siloxane and two cholesteric liquid crystalline monomers cholesteryl 4‐(10‐undecylen‐1‐yloxy)benzoate (M₁) and cholesterol 4‐{6‐[(4‐(allyloxyl)‐benzoyl]‐hexanoxocarbonyl}‐benzoate (M₂). The chemical structures and liquid crystalline properties of the synthesized oligomers were investigated using various experimental techniques such as FTIR, ¹H‐NMR, DSC, POM, and XRD. All monomers and chiral oligomers show a cholesteric mesophase with very wide mesophase temperature ranges. They appear highly thermally stable with decomposition temperatures (T_d) at 5% weight loss greater than 300°C. The optical properties of the oligmers have been characterized by reflection spectra and optical rotation analysis. All synthesized oligomers display colors at room temperature, and show reversible thermochromism within a wide temperature range (>120°C). The λ_max values of the oligomers also nearly coincide during the first, second, and third heating cycles. The specific rotation of each oligomer is very sensitive to temperature, and the specific rotation value of P₃ smoothly changes from ?21.7° to ?0.7° when it is heated. The optical properties of the oligomers offer tremendous potential for various optical applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1321‐1327, 2013     

Synthesis and characterization of asymmetric bismaleimide oligomers with improved processability and thermal/mechanical properties

Novel asymmetric bismaleimide (BMI) oligomers with different molecular weights and dianhydrides were designed and synthesized by 3,4′‐oxydianiline (3,4′‐ODA), 2,3,3′,4′‐oxydiphthalic dianhydride (a‐ODPA), and 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA). The chemical structures of BMI oligomers were confirmed by Fourier transform infrared spectrometry (FTIR) and gel permeation chromatography (GPC). X‐ray diffraction (XRD) exhibited broad peaks, suggesting amorphous structures. Heat flow curves of oligomers measured by differential scanning calorimeter (DSC) displayed wide processing window due to low glass transition temperatures (T_g). BMI oligomers exhibited high solubility in common organic solvents. Particularly, the OD‐BMI‐1 oligomer exhibited excellent solubility of more than 50 wt% in DMAc solvent. T_g value and minimum complex viscosity of OD‐BMI‐1 oligomer were only 121 °C and 8.1 Pa · s, respectively. The cured BMI resins possess high thermal and thermal‐oxidative stability. The T_g and the temperature of 5% weight loss in nitrogen were above 256 and 449 °C, respectively, and the residual weight percentages at 800 °C were all >49%. Moreover, films made of BMI resins exhibited excellent mechanical properties flexibility, as confirmed by photograph and DMA results of films. The elongation at break of the prepared films was found to be high (almost >9.6%). POLYM. ENG. SCI., 59:2265–2272, 2019. © 2019 Society of Plastics Engineers     

Herstellung und Eigenschaften von niedermolekularen epoxydierten aromatischen Polyäthern

The synthesis of low molecular weight epoxidated aromatic polyethers from oligomers with phenolates of alkali metals as terminal groups with epichlorohydrin in anhydrous aprotonic, polar solvents is presented. The oligomers having ? ONa or ? OK terminal groups have been synthesized by condensation of alkali metal salts of bisphenols with chlorobisphenyl compounds containing bivalent electronacceptor groups between the aromatic rings. The molar ratio of chlorobisphenyl compounds to bisphenol was in the range of 0,5:1 to 0,9:1. The dependence of reactivity of the above mentioned epoxidated oligomers in the curing reaction with diaminodiphenylsulfone (DDS) on the molecular weight and type of bisphenol has been investigated. Thermal and thermomechanical properties of these resins have been determined. The degradation temperature of the uncured resin (mw 800) obtained on the base of polysulfone oligomer was 325°C (1,5 wt.-% weight loss). The resin cured by means of DDS had a glass transition temperature of 160°C, and a tensile strength of 160–190 kg/cm², measured as adhesive between aluminium plates.     

Synthesis and ultraviolet‐curing behaviors of vinyl ether functionalized polyurethane oligomers

The vinyl ether functionalized oligomer is one of the most basic components of vinyl ether functionalized materials for cationic UV‐curable coatings. In this study, three types of vinyl ether functionalized polyurethane oligomers (i.e., polyether, polyester, and polydimethylsiloxane) were synthesized with diisocyanate, diol, and hydroxyethyl vinyl ether. These oligomers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The effect of the raw material ratio on the oligomer, UV‐curing behaviors, and thermal properties of these oligomers were investigated. The UV‐curing behavior was analyzed by real‐time Fourier transform infrared spectroscopy. The vinyl ether terminated polyester urethane oligomer exhibited better UV curing, with a higher final conversion and maximum UV‐curing rates. In addition, the light intensity was enhanced for oligomers with better UV‐curing properties. Research on these vinyl ether functionalized oligomers is essential to the development and applications of cationic vinyl ethers systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40501.     

Discussion of aqueous urethane acrylate oligomers with sulfoisophthalate on the antistatic hydrophilic finishing of different fabrics

In this study, PEG(SE) containing sulfonic acid group was produced by transesterification of dimethyl 5‐sulfoisophthalate sodium salt (SIP) with PEG. The reactive urethane acrylate oligomers were synthesized by using SE as soft segment, isophorone diisocyanate (IPDI) as hard segment, and hydroxyethyl methacrylate (HEMA) as blocking agent. Their solution properties and thermal properties were investigated. Dipping process was carried out on polyethylene terephthalate (PET) fabric, polyamide (nylon) fabric, and cotton fabric for hydrophilic finishing and the effects of processing condition on the fixation behavior and hydrophilic property of treated fabric have been discussed. The conclusions are as follows: the particle size of oligomer solutions are about 45–90 μm, surface tension of solutions are below 43 dyn/cm, and they have smaller contact angle than water. The particle size, particle variance, and streaming current reading decreased, but the surface tension and contact angle enhanced upon increasing PEG molecular weight. The melting point of oligomer is 38°C–52°C and the glass transition point is −18°C to −25°C. In comparison with the fabric finishing, the add‐on of PET fabric is the highest, followed by nylon, then cotton. The durability of treated cotton fabric is the highest, followed by PET, then nylon. The hydrophilicity is most stable for nylon fabric with PEG molecular weight of 2,000, and cotton and PET fabric with molecular weight of 1,000. POLYM. COMPOS., 29:45–57, 2008. © 2007 Society of Plastics Engineers     

Electro‐active oligomers containing pendent carbazolyl or indolyl groups as host materials for OLEDs

Oligoethers containing electroactive carbazolyl, indolyl or 2‐phenylindolyl fragments were synthesized and characterized by NMR spectroscopy, elemental analysis and gel permeation chromatography. The oligomers represent amorphous materials of high thermal stability with glass transition temperatures of 107–161°C. The electron photoemission spectra of layers of the synthesized oligomers showed ionization potentials of 5.9–5.95 eV. Some of the derivatives were tested as host materials in phosphorescent OLEDs with iridium(III) [bis(4,6‐difluorophenyl)‐pyridinato‐N,C2′]picolinate as the guest. The device based on oligomer containing carbazolyl fragments exhibited the best overall performance with a turn‐on voltage of 3.5 V, maximum power efficiency of 4.1 lm/W and maximum brightness of 937 cd/m². © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of polystyrene oligomers by nitroxide‐mediated radical polymerization using diethylketone triperoxide as a multifunctional radical initiator

Styrene oligomers (M_n, 2500–3000 g/mol) with low polydispersity index and containing peroxidic groups within their structure were synthesized using a novel trifunctional cyclic radical initiator, diethylketone triperoxide (DEKTP), through nitroxide‐mediated radical polymerization (NMRP), using OH‐TEMPO. During the synthesis of the polystyrene (PS) oligomers, camphorsulfonic acid (CSA) was used to inhibit the thermal autoinitiation of styrene at the evaluated temperatures (T = 120–130°C). The polymerization rate, which can be related to the slope of the plot of monomer conversion with reaction time, was monitored as a function of OH‐TEMPO, DEKTP, and CSA concentrations. The experimental results showed that all the synthesized polymers presented narrow molecular weight distributions, and the monomer conversion and the molecular weight of the polymers increased as a function of reaction time. Under the experimental conditions, T = 130°C, [DEKTP] = 10 mM, and [DEKTP]/[OH‐TEMPO] = 6.5, PS oligomers containing unreacted O? O sites in their inner structure were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Determination of glass transition temperature from dielectric analysis for a series of epoxide oligomers

Dielectric properties have been investigated for a bisphenol-A type epoxide oligomer, whose weight average molecular weight (M?_w) was 9454. The dielectric α-relaxation of the oligomer was found to be governed by the Havriliak–Negami equation as well as the same series of oligomers with smaller M?_ws (388≦M?_w ≦ 3903). The dielectric relaxation times (τ)s for the oligomers with different M?_ws (1396 ≦ M?_w ≦ 9454) can be expressed by the Williams–Landel–Ferry (WLF) equation as a function of the glass transition temperature (T_g) at fixed temperatures from 70 to 100°C. The finding indicates that the T_g of the epoxide oligomer is calculated from the τ through the WLF equation, providing the relation between T_g and τ. The same type of WLF equation was also successfully applied to describe the T_g, dependence of the practical dielectric relaxation time (τ_p), which was obtained from the peak of the dielectric loss vs. frequency curve. The τ_p can be calculated more easily than the τ, based on the Havriliak–Negami equation, not only in the measurement of epoxide oligomer, but also in that of the reactive epoxy resin systems during curing. The T_g of an epoxy–aromatic amine system, which was determined from the τ_p nondestructively detected in the dielectric cure monitoring, was consistent with the T_g experimentally measured by differential scanning calorimetry (DSC).     

Structure modification and crosslinking of methacrylated polylactide oligomers

The effect of molecular architecture on the properties of crosslinked polylactides was studied. D,L ‐Lactide‐based telechelic oligomers with different numbers of arms were functionalized with methacrylic anhydride. Functionalized oligomers were crosslinked with thermal initiation at 90°C, and the mechanical and thermal properties, as well as the gel content, were evaluated. The crosslinking density increased with the number of arms in the oligomers, and the compressive yield strength was built up at the same time. The best mechanical properties (compressive yield strength = 120 MPa, modulus = 2800 MPa, and strain = 5.0%) were obtained with cured polymers prepared with a 100 : 8 ratio of lactide to pentaerythritol. When dimethacrylated butanediol was used as a reactive monomer in curing, polymers with high crosslinking density and mechanical strength were obtained at 37, 60, and 90°C. The use of the reactive monomer also enabled high conversions with photoinitiated crosslinking. Finally, hydrolytic degradation and strength retention were demonstrated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3616–3624, 2002     

High-pressure synthesis and optical limiting property of cyclic diphenylacetylene oligomer

New conjugated oligomers were synthesized by reacting diphenylacetylene under high pressure of 0.13–0.76 GPa at 250 and 300°C for 1–10 h. The number-average molecular weight M _n, and the weight-average molecular weight M _w increased with pressure, but those values were independent of temperature and time (M _n, 320–490; M _w, 350–580). Elementary analysis, field desorption mass spectrometry, Fourier transform infrared, and ¹³C nuclear magnetic resonance experiments revealed that the oligomer above and including pentamer was a new compound having cyclic structure. Toluene solutions of the oligomer (400 M _n) contained within a quartz cell were irradiated with the pulse from a frequency-doubled Nd : Yag laser at 532 nm. The transmittance of the solution decreased with input fluence, and we observed an optical limiting property with saturated output fluence. As the concentration of the oligomer increased, the saturated output fluence decreased. The optical limiting property was analyzed according to the reverse saturable absorption mechanism. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:129–135, 1998     

Preparation of sodium salts of N‐sulfonic acids by sulfomethylation of nitro oligomers obtained from waste rubbers

The sulfomethylation of nitro oligomers obtained from waste rubbers (NO‐GWR) with sodium hydroxymethane sulfonate was studied in aqueous–alkali solutions from 50 to 80°C for reaction times of 3.5–5.5 h with weight ratios of 1.0:0.3–0.6. The initial NO‐GWR was produced by the oxidation/destructive nitration of waste rubbers with nitric acid in a heterogeneous medium. The influence of the reaction conditions on the yields and functional compositions of the sodium salts of two types of N‐sulfonic acids was investigated. Some of the nitro groups transformed into sulfaminate groups at 80°C or lower. One type of N‐sulfonic acid was isolated from its sodium salt by ion exchange. The oligosulfo derivatives were characterized by elemental and thermal analyses, IR and ¹H‐NMR spectroscopy, and the number‐average molecular weight. The sodium salts of the N‐sulfonic acids obtained from NO‐GWR possessed functional compositions similar to those of sodium salts from butadiene–styrene nitro oligomers prepared from butadiene–styrene latexes. Therefore, NO‐GWR obtained from available raw materials can be used as the initial derivative for the preparation of salts of N‐sulfonic acids instead of the nitro oligomers used now from elastomers. The salts can be used in galvanic coating techniques as brighteners. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1002–1013, 2005     

Effect of immobilized neutral protease on the preparation and physicochemical properties of low molecular weight chitosan and chito‐oligomers

Neutral protease was immobilized on glutaraldehyde‐pretreated N‐succinyl chitosan hydrogel beads and the biocatalyst obtained was used for the preparation of low molecular weight chitosan and chito‐oligomers with molecular weight of 1.9–23.5 kDa from commercial chitosan. Factors affecting the chitinolytic hydrolysis were described. The degradation was monitored by gel permeation chromatography. The structure of degraded chitosan was characterized by Fourier transform infrared, X‐ray diffraction and liquid chromatography‐mass spectrometry. Immobilized neutral protease showed optimal depolymerization at pH 5.7 and 50°C. The degree of deacetylation of the hydrolysates did not change compared to that of the initial chitosan. The decrease of molecular weight led to transformation of crystal structure but the chemical structures of residues were not modified. The degree of polymerization of chito‐oligomers was mainly from 3 to 8. The method allows cyclic procedures of immobilized enzyme and N‐succinyl chitosan support utilization, and is suitable for a large‐scale production of the low molecular weight chitosan and chito‐oligomers free of protein admixtures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4185–4193, 2006     

Fluorinated siloxane amine oligomers

Fluorine‐containing siloxane oligomers were made from bis(aminopropyl)tetramethyldisiloxane and trimethyltris(trifluoropropyl)cyclotrisiloxane. These materials were characterized by IR spectroscopy, size exclusion chromatography, nonaqueous colorimetric end group titration, and ¹H‐NMR. The end groups of one oligomer were chemically modified for an increased NMR signal for molecular weight determination. The cyclic trimeric siloxane starting material was additionally studied via ¹³C‐, ²⁹Si‐, and ¹⁹F‐NMR. Two forms of it were used: a white solid obtained at room temperature, and a colorless liquid isolated at low temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1315–1320, 2000     

Propylene oligomers: extraction methods and characterization by FTIR,HPLC, and SEC

Propylene oligomers were isolated from polymer matrix by dissolution precipitation and Soxhlet methods and characterized by Fourier transform infrared spectrometry, ultraviolet, high‐performance liquid chromatography, and gel permeation chromatography. Both extracts showed that these hydrocarbon chemicals have a maximal absorption at 210 nm and are eluted from a C8 column with a strong mobile phase (tetrahydrofuran). However, their average molecular weights are different depending upon the quality of extraction: the fraction obtained by the dissolution‐precipitation method is homogeneous in molecular weight, whereas the one obtained by Soxhlet extraction has a higher polydispersity index (M_n /M_w ). The specific migration test of propylene oligomers in a food simulant (isooctane) shows total diffusion within 60 min. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 371–375, 1999     

Preparation and characterization of maleimide-terminated poly(arylene ether sulfone) oligomers of various molecular weights

A new variation in the bismaleimide (BMI) resin family, maleimide-terminated poly(oxy-1,4-phenylene sulfonyl-1,4-phenylene) oligomers, has been synthesized. The preparation of oligomers (n = 1–12) is described in this study. The structure of these oligomers is characterized by FT-IR and NMR spectroscopy. These oligomers are light yellow to light gray powders that can be melted or dissolved in solvents. Their terminating group bismaleimide has relatively high reactivity. Therefore, these BMI resins can be cured at 250°C to form a crosslinked product. Since the backbone chain is poly(arylene ether sulfone), the cured polymers have high T_g's, which increased from 220°C to higher than 340°C as the number of repeating units n of the corresponding oligomers decreases.     

Curing system involving SiH-containing organic oligomers

We describe here the preparation and properties of a novel curing system, which has been derived from an SiH-containing organic oligomer 1 and an allyloxy end-blocked organic oligomer 2 . The composition of these oligomers could be crosslinked via a platinum-catalyzed hydrosilylation reaction, that is, the addition reaction of the SiH bonds of 1 to the allyl functionality of 2 , above 100°C, yields a rubbery material in a short period of time. The compatibility of the SiH-containing oligomer 1 with the allyloxy end-blocked oligomer 2 was governed by the oligomer main chain employed. Hence the SiH-containing oligomer 1 was completely miscible with 2 , having the same main chain and, thus, the system yielded a homogeneously cured material. The poly(propylene oxide) curing system 1a / 2a was systematically investigated in detail to manifest its curing behavior and crosslink structure. © 1993 John Wiley & Sons, Inc.