Ring-opening Polymerization Research Articles

A new radical initiation for the ring-opening polymerization of tetrahydrofuran with a radical substitution mechanism

A new radical-Lewis acid system has been discovered to achieve the ring-opening polymerization of tetrahydrofuran. Different types of reaction mechanisms were discovered for the initiation and polymerization processes. The proposed initiation mechanism was studied by MALDI-TOF and ESI-MS as a radical substitution mechanism and polymerization was a coordination-insertion mechanism. And polytetrahydrofuran with high molecular weight (Mn = 14.6 × 104 g mol−1) and narrow molecular weight distribution (PDI = 1.44) could be obtained.

Synthesis and characterization of graft copolymer hydrogel by “grafting from” atom transfer radical polymerization using brominated macro monomeric initiator and investigation of hydrogel properties

In this study, poly(ɛ-caprolactone-g-2-hydroxy ethyl methacrylate) [P(CL-g-HEMA)] graft copolymer hydrogels were successfully synthesized through multi-step reactions. For this purpose, firstly, hydroxyl-terminated poly(ɛ-caprolactone) (PCL-OH) was obtained by ring-opening polymerization (ROP) method of ɛ-caprolactone using 3-chlor-1,2-propanediol initiator, which is suitable for ring-opening polymerization method. Then, from the reaction of synthesized PCL-OH and 3-bromopropionyl chloride, a new brominated poly(ɛ-caprolactone) (PCL-Br) was synthesized for use as a functionalized atom transfer radical polymerization (ATRP) initiator. Poly(ɛ-caprolactone-g-2-hydroxy ethyl methacrylate) [P(CL-g-HEMA)] graft copolymer hydrogels were synthesized by “grafting from” atom transfer radical polymerization (ATRP) of 2-hydroxy ethyl methacrylate (HEMA) presence the new synthesized functionalized ATRP initiator (PCL-Br) and hydrogel properties were investigated. The synthesized functionalized initiators and graft copolymer hydrogel were characterized by spectroscopic methods such as 1H-NMR, FT-IR, TGA, DSC and SEM. The observation of two different decomposition temperatures, respectively, from the TGA analysis results may support the formation of the biblock graft copolymer. A glass transition temperature (Tg) of the graft copolymer hydrogel was found by DSC, and this value is between the Tg values of the homopolymers forming the graft copolymer hydrogel. Water swelling values of graft copolymer hydrogels were measured and calculated every 24 h in pure water with pH = 7 at from + 4 to 65 °C. Considering the weight of dry graft copolymer hydrogels, it was seen that water was absorbed at most at + 4 °C. As the temperature increased, the water absorption or swelling of the hydrogel decreased.

Potassium phenoxides bearing bulky yet flexible substituents as highly active catalysts for ring opening polymerization of biobased macrolactone of ethylene brassylate

Well-controlled and efficient ring opening polymerization of biobased ethylene brassylate is of great challenge due to its stainless ring structure that often results in inferior reactivities as well as the presence of two ester groups in the monomer that often lead to extensive intra-/inter- molecular transesterification side reactions. This report discloses a family of potassium phenoxide complexes that bear bulky yet flexible substituents. The bulky nature of the ligand could suppress undesired transesterification reactions, allowing the polymerization proceed in a well controlled manner, as revealed from the detailed kinetic studies that linear relationships between −ln(1-x) (x denotes the polymer yield) and the polymerization time and between molecular weights of the obtained polymers and polymer yields. The flexible substituents on the ligand allowed more monomer accessing to the active species, which eventually gave rise to TOFs in a range of 3604–3780 h−1, that were much higher than analogues in previous reports. Moreover, systematic evaluation of the polymerization behaviors demonstrated that the catalytic efficiency of the complexes was closely related to the steric nature of the metal center, increased the steric congestion would give rise to much lower monomer conversions. A plausible mechanism was proposed based on the polymerization results, and such a mechanism was further confirmed by NMR monitoring studies.

Multi-role heterogeneous Zn–Co double metal cyanide catalysts valid for ring-opening polymerizations and hydrofunctionalizations

Double metal cyanides (DMCs) or Prussian blue analogs are well-known solid complexes, especially because of their gas and energy storage ability and catalytic activity for epoxide polymerization. The crystal structure, as well as the electron-donating complexing agent, has a crucial effect on the catalytic activity and selectivity of these materials. In this study, we developed a feasible process for fabricating Zn–Co DMC catalysts, which have a range of crystal structures, using organosilicon complexing agents. In addition, the transformation of the complexing agent during catalyst preparation was investigated using density functional theory calculations to understand the nature of the active sites. The resultant catalysts exhibited excellent activities, good selectivities, as well as a broad substrate scope, for the homopolymerization of epoxide and lactone (turnover frequency up to 564 min−1), copolymerization of epoxide with CO2 (up to 99 % yield), and hydrofunctionalization reactions of terminal alkynes (up to 95 % yield), which are among the most important applications of DMC catalysis.

One-pot in situ bulk polymerization of triblock copolymer PCL-b-PA6-b-PCL based on PA6 by using tetraphenyl tin

The preparation of polyesteramides (PEAs) with regular block structure has long been a challenge, owing to the occurrence of the ester-amide exchange during the polymerization at high tempereture. In this work, we report a simple and green method to prepare polyamide 6 (PA6) based triblock PEA whose structure is poly(ε-caprolactone)-block-PA6-block-poly(ε-caprolactone) (PCL-b-PA6-b-PCL) using tetraphenyl tin as catalyst without solvent. The first segment PA6 was synthesized via cationic ring-opening polymerization (ROP) of ε-caprolactam (CPL), later, ROP of ε-caprolactone (CL) was involved to extend polycaprolactone (PCL) segments by using tetraphenyl tin as catalyst. By varying the proportion of CPL and CL, series PA6-based PEAs was prepared and characterized by gel permeation chromatography, 1H, DOSY, and 13C NMR. The results showed that PEA containing more proportion of CL presented a higher molecular weight with narrow polydisperse index. In particular, the lower water absorption and lower oligomers content infers that the PEA could have a prospective application in processing precision electronic devices.

Design of cross-linkable polypept(o)ide-based AB3 miktoarm star polymers through advances in PeptoMiktoStar synthesis

Advances in polymer chemistry can provide convenient access to more complex polymeric architectures, such as miktoarm star polymers. In comparison to their linear counterparts, the physical properties of miktoarm star polymers can substantially differ. Their complex synthesis, characterization, and purification, however, makes it a challenging task to prepare well-defined structures with multiple arms of adjustable chemical nature. In this work, well-defined cross-linkable polypept(o)ide-based AB3 miktoarm star polymers were achieved, taking advantage of a novel asymmetric tetrafunctional initiator system with different orthogonal protecting groups. The first controlled living ring-opening polymerization (ROP) of sarcosine N-carboxyanhydride yields a three-armed polysarcosine (pSar) macroinitiator with low molecular weight dispersity (Đ ∼ 1.1), while a reactive polypeptide arm can be synthesized upon cleavage of the remaining protective group. The established reactive S-alkylsulfonyl protecting group bearing polypeptides poly(S-ethylsulfonyl-l-cysteine) (pCys(SO2Et)) and poly(S-ethylsulfonyl-l-homocysteine) (pHcy(SO2Et) were implemented into the asymmetric star architecture. The presence of the well-defined cross-linkable AB3 PeptoMiktoStars was verified through the characterization via 1H NMR, 1H DOSY, and SEC, revealing structures with dispersity indices of 1.1–1.2 and precise control over the degree of polymerization of each individual polymer chain. In aqueous solution, both types of PeptoMiktoStars form polymeric micelles. The size and morphology can be tuned by secondary structure directed self-assembly: the pHcy(SO2Et)20(pSar100)3 polymers form spherical micelles whilst the pCys(SO2Et)20(pSar100)3 assembled into worm-like micelles. Therefore, this synthetic methodology provides not only access to well-defined reactive miktoarm star polymers, but also allows for the engineering of polymeric micelles based on PeptoMiktoStars.

Magnesium-Catalyzed Dye-Embedded Polylactide Nanoparticles for the Effective Killing of Highly Metastatic B16F10 Melanoma Cells.

In the current research, dye-embedded polylactic acid (PLA) conjugate materials were synthesized using one-pot ring-opening polymerization (ROP), i.e., (dtHPLA) (2-[(2,4,6-trimethylphenyl) imino]-1(2H)-acenaphthylenone-reduced-PLA) and (dmHPLA) (monoiminoacenaphtheneone-reduced-PLA), and then, nanoparticles (NPs) were engineered in the size range of 150 ± 30 nm. P(dtHPLA) NPs were employed in the treatment of melanoma, an aggressive type of skin cancer, which mandates the development of novel techniques to enhance healing outcomes and eliminate adverse effects related to existing treatments. In addition to exhibiting strong intracellular absorption in the spheroid model, the P(dtHPLA) NPs exhibited a strong cytotoxic effect on B16F10 cells, which resulted in oxidative stress from the generation of reactive oxygen species (ROS) and cell death. Additionally, a live/dead experiment using P(dtHPLA) NPs revealed a notable reduction in cell viability.

Poly(ε-caprolactone)-grafted-chitosan copolymers: Synthesis and use as tunable and biodegradable coating for water soluble fertilizers

The urgent need for efficient agriculture to increase crop and food has fueled the development of coated fertilizers with a slow-release kinetics, water economy and full degradability to avoid negative environmental impact. In this context, we herein report the synthesis of poly(ε-caprolactone) (PCL) grafted from chitosan (CS) as a new class of biodegradable coating materials. The CS-g-PCL were prepared following a one-pot, two-step strategy, in which the primary amines of CS first react with ε-caprolactone (CL) to form CL-oligomers linked to CS via amide bonds terminated with hydroxyls, which together with the native hydroxyls of CS initiate the ring-opening polymerization of CL after addition of Sn(C ≡ CPh)4 as catalyst. Owing to the great stability of the used catalyst, the high molar mass of PCL grafted onto CS was successfully obtained under trivial open-air conditions. Different copolymers (CS-g-PCL) were prepared by varying the CS content. The structural characterization of CS-g-PCL was carried out using FTIR, 1H NMR, X-ray diffraction, contact angle and size exclusion chromatography (SEC) while the thermal and mechanical characterization of the prepared CS-g-PCL were compared to the neat PCL. Next, using a laboratory rotary drum, CS-g-PCL was implemented to uniformly coat granular diammonium phosphate fertilizer (DAP). Consequently, the kinetic releases of nitrogen and phosphorus were significantly delayed compared to that observed from uncoated DAP (conventional fertilizers). Finally, the degradation of CS-g-PCL was examined under aerobic conditions and showed a significant increase in their biodegradability with respect to neat PCL.

Simultaneous Spin Coating and Ring-Opening Metathesis Polymerization for the Rapid Synthesis of Polymer Films.

We report a highly controlled technique for the synthesis of polymer films atop a substrate by combining spin coating with ring-opening metathesis polymerization (ROMP), herein termed spin coating ROMP (scROMP). The scROMP approach combines polymer synthesis and deposition into one process, fabricating films of up to 36 cm2 in under 3 min with orders-of-magnitude reduction in solvent usage. This method can convert numerous norbornene-type molecules into homopolymers and random copolymers as uniform films on both porous and nonporous substrates. Film thickness can be varied from a few hundred nanometers to a few tens of micrometers based on spin speed and monomer concentration. The resulting polymers possess high MW (>100 kDa) and low polydispersity (PDI) (<1.2) values that are similar to ROMP polymers made in solution. We also devise a model to investigate the balance between convective monomer spin-off and polymer growth from the surface, which allows the determination of critical kinetic parameters for scROMP. Finally, translation of scROMP to porous supports enables the synthesis of thin film composite membranes that demonstrate the ability to dehydrate ethanol by pervaporation.

Non-isothermal kinetics of the organocatalytic ring-opening polymerization of ε-caprolactone with metal-free α‑hydroxy acids: Eco-friendly and facile synthesis process

Metal-free and green α‑hydroxy acids (AHA) such as l-malic (MA), DL-mandelic acid (MDL), and citric acid (CA) were successfully and effectively utilized as an effective initiator for the solvent-free ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). The performance of AHAs in the polymerization of ε-CL was completely and powerfully investigated via the non-isothermal differential scanning calorimetry (DSC). The proceed of ROP of ε-CL with AHAs could be real-time monitored by the obtained polymerization exotherms at different heating rates. The polymerization exotherms obtained from the ROP of ε-CL with CA occurred at a lower temperature range than MA, and MDA, respectively. From the kinetics study, the average activation energy (Ea) values for the ROP of ε-CL with CA (38.0 ± 1.8 kJ mol−1) were lower than MA (45.2 ± 3.6 kJ mol−1) and MDA (48.8 ± 6.2 kJ mol−1). Using the first-order model fitting, the values of pre-exponential factor (lnA0) for the ROP of ε-CL with CA, MA, and MDA were 7.0 ± 0.3, 8.5 ± 0.2, and 8.9 ± 0.3, respectively. The effectiveness of AHAs in the synthesis of PCL was clarified by conducting a larger-scale (4.0000 g) polymerization using conventional heating and microwave (MW) irradiation methods. From conventional heating, the green AHAs produced PCL with the number average molecular weight (Mn) and dispersity (Đ) values in the range of 5.18 × 103 - 1.43 × 104 g mol−1 and 1.14–2.02, respectively. The irradiation by MW could enhance the synthesis of PCL by reducing the synthesis time. By using the MW power of 450 W and irradiation time of 30 min, the PLC was obtained from the ROP of ε-CL with MA and MDA initiators, and the Mn of the obtained PCL from MW heating was 4.28 × 103 - 8.45 × 103 g mol−1. The mechanism for the ROP of ε-CL with all AHAs was proposed through the activated monomer mechanism.

Abstract 481: Proteomimetic polymers limit tumor growth in multiple models via potent antigen-specific T cell activation

Abstract Background: Patient-specific cancer vaccines derived from tumor antigen have been explored as a promising therapeutic strategy, however, challenges delivering vaccine components in a coordinated fashion to elicit antitumor responses remain. To overcome these, we utilize a novel nanoplatform called the Protein-Like Polymer (PLP), which allows for sustained and targeted delivery of tumor antigens in conjunction with adjuvants. Methods: PLPs containing peptide antigens were synthesized via ring-opening metathesis polymerization (ROMP) and characterized. A library of compounds with different sidechain linkage chemistries, degrees of polymerization (DP), and inclusion/exclusion of Oligo-ethylene glycol (OEG) were made to determine design rules for immune activation. Cell uptake and functional assays using payload-specific T Cells were conducted. Immunization in three independent tumor models was done to show generalizability. Ability of PLPs to co-deliver adjuvants was tested by electrostatically coupling small molecule STING agonist, 2’3’ cGAMP. Results: Conjugating peptide antigens to the polymer via a cleavable disulfide linkage, which reduces intracellularly in APCs, resulted in increased endosomal localization, higher levels of induced T cell proliferation, cytokine production, and expression of activation markers in CTLs and APCs. Incorporating a diluent amount of OEG side chains reduced enzymatic degradation while increasing immunogenicity and uptake. Additionally, increasing the DP, and therefore the density of antigen side chains, further improved vaccine efficacy and resistance to proteolysis. Antigen-PLP conjugates enhanced dendritic cell activation and T-cell response only when paired with cells from their cognate system, with no activity in immune cells not expressing receptors for the payload demonstrating antigen-specificity. Mice bearing established B16F10, MC38, or TC-1 tumors treated with PLPs containing gp100, adpgk, or E7 respectively all showed increased survival times, reduced tumor burden with corresponding changes in immune cell profiles, and immunological memory upon rechallenge. Impressively, mice treated with STING-PLP complexes had significantly smaller tumors vs control at day 14 (0.038g vs 0.76g; p &amp;lt;0.0001) and allowed for subcutaneous administration of 2’3’ cGAMP, which traditionally requires intratumoral injection. Studies on the effects of vaccinating with pools of neoantigens multiplexed onto one PLP are ongoing. Conclusion: This work validates the ability of PLPs to overcome major limitations in cancer vaccine development. The modularity of the platform allows for complex nano-architectures including systems capable of delivering challenging compounds, ie small molecule STING agonists, subcutaneously through electrostatic coupling, highlighting its potential to revolutionize cancer vaccinology. Citation Format: Max Wang, Miran Choi, Bin Zhang, Nathan Gianneschi. Proteomimetic polymers limit tumor growth in multiple models via potent antigen-specific T cell activation [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 481.

Effect of segment structure of monotrimethoxysilylethyl-terminated asymmetric polysiloxanes on the thermal management performance of AlN-filled silicone pastes

Three kinds of α-triethylsiloxyl-ω-trimethoxysilyethyl-terminated oligomers (TES-PDMS-TMOS, TES-PTFPMS-TMOS, and TES-PDES-TMOS) were synthesized through an anion catalyzed non-equilibrium ring-opening polymerization reaction of cyclotrisiloxanes and subsequent hydrosilylation reaction with vinyltrimethoxysilane. As the in situ surface modification agent for mixed-size AlN inorganic fillers (1, 20 and 50 μm blended in a mass ratio of 3:5:9), these oligomers have been mixed with Vi-PDMS in a mass ratio of 1:2. Relative to that of silicone pastes using Vi-PDMS as the polymer matrix, the thermal conductivity of silicone pastes made from AlN particles treated with these oligomers is enhanced, while their thermal resistances decreased. With the change of the repeating unit structure in the oligomers, the silicone pastes prepared from these oligomer-treated AlN fillers differ significantly in filler content, thermal conductivity, and thermal resistance. When TES-PTFPMS-TMOS is used and filled with 800 parts (70.3 vol%) of hybrid AlN powders, a silicone paste with a thermal conductivity of 4.56 W/(m. K) could be achieved, which was 37.8% higher than that silicone paste using pure Vi-PDMS as the matrix. When TES-PDES-TMOS is used and filled with 900 parts (72.7 vol%) of hybrid AlN powders, the thermal conductivity of the silicone paste reaches 4.13 W/(m. K). Despite its thermal conductivity being only 3.5% higher relative to the silicone paste using only Vi-PDMS as the polymer matrix, its thermal resistance decreased by 20.3%. When TES-PDMS-TMOS is used and filled with 1200 parts (78.0 vol%) of hybrid AlN powders, the thermal conductivity of the silicone paste could reach up to 4.59 W/(m. K), together with a thermal resistance 29.6% lower than that of silicone paste where 1000 parts (74.7 vol%) of hybrid AlN particles filled in the Vi-PDMS. The heat dissipation of the 30 W high-brightness LED chip also illustrated the excellent thermal conductivities of these silicone pastes. The effect of another terminal group on the monotrimethoxysilylethyl-terminated asymmetric polysiloxanes on the thermal resistance of thermal interface materials was also discussed in detail.

Boosting the Reactivity of Bis-Lactones to Enable Step-Growth Polymerization at Room Temperature.

The development of new sustainable polymeric materials endowed with improved performances but minimal environmental impact is a major concern, with polyesters as primary targets. Lactones are key monomers thanks to ring-opening polymerization, but their use in step-growth polymerization has remained scarce and challenging. Herein, we report a powerful bis(γ-lactone) (γSL) that was efficiently prepared on a gram scale from malonic acid by Pd-catalyzed cycloisomerization. The γ-exomethylene moieties and the spiro structure greatly enhance its reactivity toward ring-opening and enable step-growth polymerization under mild conditions. Using diols, dithiols, or diamines as comonomers, a variety of regioregular (AB)n copolymers with diverse linkages and functional groups (from oxo-ester to β-thioether lactone and β-hydroxy-lactame) have been readily prepared. Reaction modeling and monitoring revealed the occurrence of an original trans-lactonization process following the first ring-opening of γSL. This peculiar reactivity opens the way to regioregular (ABAC)n terpolymers, as illustrated by the successive step-growth polymerization of γSL with a diol and a diamine.

Extended Hydrogen-Bonded Molybdenum Arrays Derived from Carboxylic Acids and Dianilines: ROP Capability of the Complexes and Parent Acids and Dianilines

From reactions involving sodium molybdate and dianilines [2,2′-(NH2)C6H4]2(CH2)n (n = 0, 1, 2) and amino-functionalized carboxylic acids 1,2-(NH2)(CO2H)C6H4 or 2-H2NC6H3-1,4-(CO2H)2, in the presence of Et3N and Me3SiCl, products adopting H-bonded networks have been characterized. In particular, the reaction of 2,2′-diaminobiphenyl, [2,2′-NH2(C6H4)]2, and 2-aminoterephthalic acid, H2NC6H3-1,4-(CO2H)2, led to the isolation of [(MoCl3[2,2′-N(C6H4)]2}{HNC6H3-1-(CO2),4-(CO2H)]·2[2,2′-NH2(C6H4)]2·3.5MeCN (1·3.5MeCN), which contains intra-molecular N–H∙∙∙Cl H-bonds and slipped π∙∙∙π interactions. Similar use of 2,2′-methylenedianiline, [2,2′-(NH2)C6H4]2CH2, in combination with 2-aminoterephthalic acid led to the isolation of [MoCl2(O2CC6H3NHCO2SiMe3)(NC6H4CH2C6H4NH2)]·3MeCN (2·3MeCN). Complex 2 contains extensive H-bonds between pairs of centrosymmetrically-related molecules. In the case of 2,2′ethylenedianiline, [2,2′-(NH2)C6H4]2CH2CH2, and anthranilic acid, 1,2-(NH2)(CO2H)C6H4, reaction with Na2MoO4 in the presence of Et3N and Me3SiCl in refluxing 1,2-dimethoxyethane afforded the complex [MoCl3{1,2-(NH)(CO2)C6H4}{NC6H4CH2CH2C6H4NH3}]·MeCN (3·MeCN). In 3, there are intra-molecular bifurcated H-bonds between NH3 H atoms and chlorides, whilst pairs of molecules H-bond further via the NH3 groups to the non-coordinated carboxylate oxygen, resulting in H-bonded chains. Complexes 1 to 3 have been screened for the ring opening polymerization (ROP) of both ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) using solvent-free conditions under N2 and air. The products were of moderate to high molecular weight, with wide Ð values, and comprised several types of polymer families, including OH-terminated, OBn-terminated (for PCL only), and cyclic polymers. The results of metal-free ROP using the dianilines [2,2′-(NH2)C6H4]2(CH2)n (n = 0, 1, 2) and the amino-functionalized carboxylic acids 1,2-(NH2)(CO2H)C6H4 or 2-H2NC6H3-1,4-(CO2H)2 under similar conditions (no BnOH) are also reported. The dianilines were found to be capable of the ROP of δ-VL (but not ε-CL), whilst anthranilic acid outperformed 2-aminoterephthalic acid for both ε-Cl and δ-VL.

Synergetic binary organocatalyzed ring opening polymerization for the precision synthesis of polysiloxanes

Organocatalytic ring-opening polymerization (ROP) is a versatile method for synthesizing well-defined polymers with controlled molecular weights, dispersities, and nonlinear macromolecular architectures. Despite spectacular advances in organocatalytic ROP, precision synthesis of polysiloxanes remains challenging due to the mismatch in polarity between highly polar initiators and nonpolar monomers and polymers and the difficulty in suppressing the formation of scrambling products via transetherification reactions during ROP of cyclic siloxanes. Here, we describe a binary organocatalytic ROP (BOROP) of hexamethylcyclotrisiloxane (D3) employing organic bases as catalysts and (thio)ureas as cocatalysts. The BOROP of D3 using triazabicyclodecene (TBD) and (thio)ureas generates polydimethylsiloxanes (PDMSs) with narrow dispersity (Mw/Mn < 1.1). Despite the similar basicities of TBD and 1,8-bis(tetramethylguanidino)naphthalene (TMGN), which is known as a proton sponge, a unitary organocatalytic system using TMGN was inactive for the ROP of D3. When the TMGN was paired with acidic urea, the BOROP of D3 yielded PDMSs with narrow dispersity (Mw/Mn < 1.1). Data suggest that the synergetic effect of TMGN and urea is results in an unprecedented activation–deactivation equilibrium between dormant and propagating species. The benefits of the present BOROP system are demonstrated by the formation of PDMS elastomers with more uniform network structures that are highly stretchy and have excellent mechanical properties.

An applicability study on various methods for determining the monomer conversion rate of polyamide 6

AbstractAnionic ring opening polymerization of ε‐caprolactam (CL) results in the formation of high molecular weight polyamide 6 (PA6) within a few minutes. The monomer conversion rate is an important characterization parameter for polymerization process as well as the end products. This paper used PA6 films with different polymerization degrees as research object for the first time, and systematically compared the performance of four methods for measuring CL conversion rate. The analytical methods were solvent extraction (methanol, ethanol, or water), vacuum removal, thermogravimetric analysis (TGA), and absorbance ratio respectively. For all PA6 products, solvent extraction based on methanol/water and vacuum removal were effective methods for determine their conversion rates. And TGA was only applicable for samples with high degree of polymerization. The CL conversion rate obtained by solvent extraction based on ethanol and absorbance ratio was slightly higher than the real value, especially the latter. Moreover, a new method was discovered and validated during the research process, namely atmospheric devolatilization. The methodology and results in this study can be employed for guiding the production and application of polymers, especially the reactive processing of PA6.

A novel amphiphilic polypeptoid based ultrafiltration membrane with excellent biocompatible property

Polysarcosine (PSar), a polypeptoid with a chemical structure resembling natural amino acids, stands out as a prominent non-ionic polypeptoid due to its outstanding water solubility and biocompatibility. These extraordinary properties make PSar a highly appealing material for a wide range of biomedical applications, especially in biocompatible membranes. However, due to its high-water solubility, PSar is inherently not stable enough for membranes. It is an effective way to apply PSar in membrane field by improving its stability while ensuring the hydrophilicity. Here, a novel copolymer, consisting of PSar and polysulfone (PSF) blocks (PSF-b-PSar, denoted as PSbS), is presented and synthesized by ring-opening polymerization (ROP) of N-phenyloxycarbonyl-sarcosine (Sar-NPC), which is used as a functional skin layer on PSF substrates. The results demonstrated that the PSbS performed a highly hydrated layer on the membrane surface, thus mitigating interactions between biomolecules and biological entities. Notably, the PSbS/PSF membrane showed improved antifouling, biocompatibility, hemocompatibility and stability. Moreover, the hemolysis rate of the composite membrane was reduced to 0.56%, and the activated partial thromboplastin time (APTT) was effectively prolonged. In summary, this work proposed a strategy for solidifying PSar on the membrane surface as the non-water-soluble amphiphilic polymer, which is promising in the biomedical applications, especially in biocompatible membranes.

Card-bisphenol based bio-silica reinforced poly(urethane-co-benzoxazine) foam for an electrical insulation

Agricultural waste by-products such as cashew nut shell liquid and rice husk ash were utilized for the syntheses of card-bisphenol (C) and precipitated bio-silica (S), respectively. A hydroxyl terminated card-bisphenol based benzoxazine resin (CHB) was synthesized and then converted it into soft-foam namely benzoxazine-co-urethane pre-polymer (CHB-UF) by polymerizing with hexamethylene diisocyanate (HMDI) in the absence of any catalysts or foaming agents. Subsequent thermal ring opening polymerization of CHB-UF at 200 °C provides poly(benzoxazine-co-urethane) hard-foam (PCHB-UF) with little shrinkage. Similarly, different weight ratios of precipitated bio-silica (0–15 wt%) reinforced bio-based PCHB-UF hard-foam composites (PCHB-UFS) were prepared to utilize them for high-k dielectrics and hydrophobic applications. The foam microstructure was ascertained through the field emission scanning electron microscopy (FE-SEM). The reinforcement of bio-silica into the CHB-UF foam increases the value of dielectric constant according to the increase in weight percentage concentration, which might be due to the reduction in volume of voids. The neat PCHB-UF possesses the value of dielectric constant of 7.04 with lower value of dielectric loss of 0.01. Similarly, the values of dielectric constant and dielectric loss of 15 wt% bio-silica reinforced composites (PCHB-UFS15) are 10.1 and 0.08 respectively. The PCHB-UFS15 has shown hydrophobic nature with the value of water contact angle of 135°. Data obtained from different studies suggest that the bio-foam composites obtained from sustainable sources can be considered as an efficient dielectric materials used for electronics insulation.

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Cross-Linked Polyolefins through Tandem ROMP/Hydrogenation.

Cross-linked polyolefins have important advantages over their thermoplastic analogues, particularly improved impact strength and abrasion resistance, as well as increased chemical and thermal stability; however, most strategies for their production involve postpolymerization cross-linking of polyolefin chains. Here, a tandem ring-opening metathesis polymerization (ROMP)/hydrogenation approach is presented. Cyclooctene (COE)-co-dicyclopentadiene (DCPD) networks are first synthesized using ROMP, after which the dispersed Ru metathesis catalyst is activated for hydrogenation through the addition of hydrogen gas. The reaction temperature for hydrogenation must be sufficiently high to allow mobility within the system, as dictated by thermal transitions (i.e., glass and melting transitions) of the polymeric matrix. COE-rich materials exhibit branched-polyethylene-like crystallinity (25% crystallinity) and melting points (Tm = 107 °C), as well as excellent ductility (>750% extension), while majority DCPD materials are glassy (Tg = 84 °C) and much stiffer (E = 710 MPa); all materials exhibit high tensile toughness. Importantly, hydrogenation of olefins in these cross-linked materials leads to notable improvements in oxidative stability, as saturated networks do not experience the same substantial degradation of mechanical performance as their unsaturated counterparts upon prolonged exposure to air.