Polar Monomers Research Articles

Photochromic polymer nanoparticles as highly efficient anticounterfeiting nanoinks for development of photo-switchable encoded tags

• Synthesis of colloidal nanoparticles with different polarity and particle size, • Preparation of spiropyran-containing photochromic colloidal nanoparticles, • Effect of polarity on the fluorescence emision and photochromism of colloidal nanoparticles, • Development of the photochromic colloidal nanoparticles as anticounterfeiting nanoinks, • Application of the smart nanoinks for encrypting security documents. Dual photochromic and photoluminescent latex nanoparticles were synthesized to develop innovative anticounterfeiting nanoinks with applications in encryption technology. The colloidal nanoparticles bearing hydroxyl groups were resulted from semi-continuous miniemulsion copolymerization of 2-hydroxyethyl methacrylate and methyl methacrylate. Investigation of the particle size determination and microscopic analysis results demonstrated spherical morphologies for the latex nanoparticles with a mean size of about 80 nm and narrow size distribution. Modification of the polymer nanoparticles with hydroxyl functional groups led to the formation of a high level of hydrogen bonding between the hydroxyl groups and spiropyran chromophore, which is an advantage in the preparation of security anticounterfeiting nanoinks. In addition, optical analysis of the photochromic latex samples showed various UV-vis spectra, fluorescence emission, kinetics of isomerization, and photo-fatigue resistance depending on different amounts of the polar monomers. Further investigations on optical properties exhibited that reducing the size of the colloidal samples can affect their photoluminescence characteristics. This is an efficient way to provide remarkable photoreversible anticounterfeiting inks for different applications, such as printed photo-marking, rewritable handwriting patterns, security encoded tags, and labeling.

Syndiospecific Copolymerization of Styrene with para-Methoxystyrene Catalyzed by Functionalized Fluorenyl-Ligated Rare-Earth Metal Complexes.

The development of efficient catalysts for the copolymerization of nonpolar monomers with polar monomers remains a great challenging task in polymer synthesis. A one-pot reaction of anhydrous LnCl3 with pyridyl-methylene-functionalized octamethylfluorenyl lithium OctFlu-CH2PyLi in a 1:1 molar ratio, followed by alkylation with 2 equiv of LiCH2SiMe3 in THF afforded the fluorenyl-ligated rare-earth metal bis(alkyl) complexes (OctFlu-CH2Py)Ln(CH2SiMe3)2(THF) [Ln = Sc (1), Y (2)]. Both complexes were isolated as neutral species and were characterized by NMR spectrum and elemental analysis. Complex 2 was subjected to single-crystal X-ray diffraction, which showed that the whole modified fluorenyl ligand was coordinated to Y3+ in the η5/κ1 mode to form a constrained geometry configuration. In the presence of excess AliBu3, and on activation with 1 equiv of [Ph3C][B(C6F5)4] in toluene, complexes 1 and 2 became active for both styrene (St) and para-methoxystyrene (pMOS) polymerization, giving polymers with high syndiotacticity (rrrr > 99%) without solvent extraction. Moreover, the ternary catalyst system composed of complex 2/AliBu3/[Ph3C][B(C6F5)4] was highly effective for the syndiospecific copolymerization of styrene with pMOS, producing random copolymers with high molecular weights and narrow molecular weight distributions. The contents of pMOS in the copolymers could be easily tuned in a wide range (11-93 mol %) by simply changing the pMOS-to-St feed ratios.

Rational design of aldimine imidazolidin-2-imine/guanidine nickel catalysts for norbornene (Co)polymerizations with enhanced catalytic performance

The development of late transition metal catalysts bearing novel ligand platforms is a convenient pathway to obtain prospective systems with enhanced catalytic performance, however, it remains a challenge in the field of olefin (co)polymerizations. In this contribution, a new family of [N,N]-type of bidentate aldimine imidazolidin-2-imine/guanidine ligands and their nickel complexes Ni1–Ni7 bearing a distinct six-membered chelate ring were successfully synthesized, and characterized. All of the nickel catalysts were active for norbornene polymerization with high activity of up to 7.44 × 105 g mol–1 h−1. These catalysts also copolymerized norbornene and 1-alkenes (1-dodecene and 1-octadecene) while keeping high activities to produce various norbornene-based high-molecular-weight (Mn = 5.75–36.0 kg mol−1) cyclic olefin copolymers (COCs) with adjustable 1-alkene incorporations (1.44–13.30 mol%) and a wide range of Tg values (102.2–271.4 °C). Moreover, with the decoration of bulky N-aryl substituents, these nickel catalysts exhibited strong tolerance towards polar monomer to promote the direct copolymerization of norbornene and methyl 10-undecenoate with high activity (up to 9.88 × 104 g mol–1 h−1), and furnished polar functionalized COCs with a high molecular weight (Mn up to 72.4 kg mol−1) and reasonable polar monomer incorporations (0.19–0.45 mol%). These nickel complexes are rare examples and also promising candidates as catalysts for the efficient synthesis of various COCs.

Progress in the catalyst for ethylene/α‐olefin copolymerization at high temperature

AbstractEthylene/α‐olefin copolymers are one of the most widely‐used polyolefin materials. With the continuous improvement of polyolefin catalysts, high‐performance polyolefin materials were synthesized by adjusting the chain microstructure, changing the comonomer type and comonomer insertion amount, among which the ethylene/α‐olefin random copolymer elastomer (POE) and olefin block copolymer elastomer (OBC) are the most famous and well accepted by the market. The excellent properties of POE and OBC first depend on their polymer chain microstructure. The chain microstructure of polyolefins is fundamentally determined by the catalysts, polymerization conditions, comonomer feed policies, and reaction engineering. High‐performance ethylene/α‐olefin copolymer elastomers are currently prepared by high‐temperature solution polymerization process, which needs to be carried out at a temperature above the melting point of the polymer and is beneficial to speed up the polymerization reaction rate and control the polyolefin chain microstructure. However, the high‐temperature solution polymerization process launched more stringent requirements for the olefin coordination polymerization catalyst. Systematic reports on catalysts for high‐temperature solution copolymerization of ethylene and α‐olefins are lacking. In this review, we screened some catalysts suitable for the controllable copolymerization and high‐temperature solution copolymerization of ethylene/α‐olefin based on the catalyst's heat resistance, copolymerization activity, comonomer insertion ability, molecular weight, and distribution of the copolymer, including traditional Z–N catalysts, metallocene catalysts, and post‐metallocene catalysts. And the future development of catalysts for high‐temperature solution copolymerization of olefins, catalysts for precise control of polyolefin chain microstructures, and catalysts for olefin copolymerization with polar monomers at high temperature are envisaged.

Photodegradable polar-functionalized polyethylenes.

The degradation of plastics has attracted much attention from the global community. Polyethylenes (PEs), as the most abundant synthetic plastics, are most frequently studied. PE is non-degradable and non-polar because of the sole presence of the pure hydrocarbon components. Concurrent incorporation of both in-chain cleavable and functional groups into the PE chain is an effective pathway to overcome the non-degradable and non-polar issue; however, the method for achieving this pathway remains elusive. Here, we report a strictly non-alternating (>99%) terpolymerization of ethylene with CO and fundamental polar monomers via a coordination-insertion mechanism using late transition metal catalysts, which effectively prevents the formation of undesired chelates originating from both co-monomers under a low CO concentration. High-molecular-weight linear PEs with both in-chain isolated keto (>99%) and main-chain functional groups are prepared. The incorporation of key low-content isolated keto groups makes PEs photodegradable while retaining their desirable bulk material properties, and the introduction of polar functional groups considerably improves their surface properties.

Direct Synthesis of Ultrahigh Molecular Weight Functionalized Isotactic Polypropylene

Open AccessCCS ChemistryRESEARCH ARTICLES10 Jan 2023DirectSynthesis of Ultrahigh Molecular Weight Functionalized Isotactic Polypropylene Guanglin Zhou, Hongliang Mu, Xin Ma, Xiaohui Kang and Zhongbao Jian Guanglin Zhou Google Scholar More articles by this author , Hongliang Mu Google Scholar More articles by this author , Xin Ma Google Scholar More articles by this author , Xiaohui Kang Google Scholar More articles by this author and Zhongbao Jian Google Scholar More articles by this author https://doi.org/10.31635/ccschem.023.202202621 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Ultrahigh molecular weight functionalized isotactic polypropylene (f-UHMW-iPP) through the direct copolymerization of propylene with polar monomers is highly desired but has not been accessed thus far, as it involves challenging regio- and stereo-chemistry along with usually reduced molecular weight. Herein, in contrast to the unsuccessful catalyst strategy, a polar monomer assisted strategy is used to access the above material. The introduction of O- or S-functionalized long-chain polar olefins into the hafnium-catalyzed copolymerization of propylene (and also bulkier α-olefins) significantly increases the copolymer molecular weight with a maximum observed increase of +488%. f-UHMW-iPP and isotactic poly(α-olefin)s (Mw> 2,000 kDa, [mmmm]: 99%) are thus prepared at ambient conditions. The incorporation of 1 mol% of polar monomer improves the surface property and significantly increases the long-sought toughness (860%) of brittle iPP, without reducing the tensile strength (42 MPa) due to the key achievement on ultrahigh molecular weight. A discussion of the mechanism involved in the beneficial effects of incorporating the polar monomer is presented by an in-depth density functional theory (DFT) calculation. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2023 Chinese Chemical Society Downloaded 0 times PDF downloadLoading ...

Polar Group-Promoted Copolymerization of Ethylene with Polar Olefins

Copolymerization of ethylene (E) and polar vinyl monomers is a great challenge but remains attractive, especially for early transition metal catalysts featuring strong oxophilicity. Herein, we present the copolymerization of E with 6-phenoxy-1-hexene (POH) by scandium precatalysts with different steric hindrances: (FluCH2CH2NHC)Sc(CH2SiMe3)2 (1), (FluCH2C5H4N)Sc(CH2SiMe3)2 (2), (FluCH2Ph)Sc(CH2SiMe3)2(THF) (3), and (C5Me4Ph)Sc(CH2C6H4NMe2-o)2 (4). In comparable conditions, precatalyst 1, activated by [Ph3C][B(C6F5)4] and AliBu3, shows high activity (1.4 × 105 g molSc–1 h–1) but gives a low POH incorporation ratio of 0.7 mol %. Under identical conditions, the activity of 2 drops to 0.1 × 105 g molSc–1 h–1. In contrast, the half-sandwich scandium precatalyst 3 displays a much higher activity (8.1 × 105 g molSc–1 h–1) and affords a copolymer with 7.0 mol % POH. The highest activity (18.0 × 105 g molSc–1 h–1) and incorporation ratio (8.6 mol %) are achieved by 4. After optimization of the reaction conditions, up to 16 mol % of POH could be incorporated into the copolymer produced with 4. The resultant copolymers are readily transformed into brominated products and, subsequently, ethylene-based ionomers featuring excellent mechanical properties. Density functional theory (DFT) simulations are employed to illustrate the mechanisms of polar group incorporation and the control of activity from kinetic, thermodynamic, and geometric viewpoints.

Amide-Functionalized Polyolefins and Facile Post-Transformations

Direct copolymerization of olefins with polar monomers to produce functionalized polyolefins has attracted much attention; however, highly efficient incorporation of amide functions into polyolefins is a long-standing challenge because the amide function is pronounced to retard chain growth. In this contribution, Vince Lactam’s derivatives (VLH, VLMe, and VLBoc) that contain high ring strain and an amide moiety are utilized in ethylene copolymerization mediated by palladium catalysts. Amide-functionalized polyethylenes, poly(E-VLBoc)s, are accessible with key characteristics of high amide incorporations (up to 30.1 mol %), high copolymer molecular weights, and high catalytic activities. The incorporation of the amide comonomer converts crystalline poly(E-VLBoc)s (Tm = 115–125 °C) to noncrystalline and transparent poly(E-VLBoc)s (Tg = 98–196 °C, optical transmittance (T) = 87.6%–90.4%). Both characteristics of cyclic amide functions and high amide incorporations in poly(E-VLBoc) enable facile post-transformations under mild conditions to produce hydrogen bond-containing (-C(O)NH-) poly(E-VLH), difunctionalized (-COOH and -NHR) poly(E-VLNHBoc), and water-soluble ammonium-functionalized poly(E-VLNH3+). The ammonium functionality endows polyolefin with antibacterial properties.

Copolymerization of Norbornene and Methyl Acrylate by Nickel Catalyst Bearing 2-(Diarylphosphino)-N-phenylbenzenamine Ligands

The synthesis of polar functionalized cyclic olefin copolymers (COCs) from the coordination copolymerization of norbornene (NB) and polar monomers catalyzed by late transition metal catalysts has been a recent research hotspot. However, few catalysts have achieved efficient copolymerization with commercial vinyl-type polar monomers, such as methyl acrylate (MA). In this contribution, nickel complexes bearing 2-(diarylphosphino)-N-phenylbenzenamine ligands were synthesized and applied as pre-catalysts to catalyze the (co)polymerization of norbornene. Upon the activation of methylaluminoxane (MAO), these nickel catalysts were active for norbornene polymerization with the highest activity achieved being 3.6 × 106 g mol−1 h−1 and the highest number average molecular weight (Mn) of polynorbornene (PNB) reaching 27.4 × 105 g mol−1. Moreover, these nickel catalysts also promoted the copolymerization of norbornene and MA to furnish high-molecular-weight NB/MA copolymers (Mn up to 6.20 × 104 g mol−1) with reasonable MA contents (3.07−5.90 mol%). The molecular weight of PNB and NB/MA copolymers obtained by the present nickel catalysts are remarkably higher than those of the (co)polymers from our previous reported dimethyl substituted phosphinobenzenamine nickel catalyst, suggesting significant progress in this field.

Recent Advances in Transition Metal-Based Catalysts for Ethylene Copolymerization with Polar Comonomer.

The synthesis of polar functionalized polyolefin (PFP) offers improvement in mixing properties, polymer surface, and rheological properties with the potential of upgraded polyolefins for modern and ingenious applications. The synthesis of PFP from metal-based catalyzed olefin (non-polar in nature) copolymerization with polar comonomers embodies energy-efficient, atom-efficient, and apparently an upfront methodology. Despite their outstanding success during conventional polymerization of olefin, 3rd and 4th group (early transition metal)-based catalysts, owing to their electrophilic nature, face challenges mainly due to Lewis basic sites of the polar monomers. On the contrary, late transition metal-based catalysts have also made progress, in recent years, for PFP synthesis. The recent past has also witnessed several advancements in the development of dominating palladium-based catalysts while their lower resistance towards ligand functional groups has limited the practical application of abundant and cheaper nickel-based catalysts. However, the relentless efforts of the scientific community, during the past half-decade, have indicated rigorous progress in the development of nickel-based catalysts for PFP synthesis. In this review, we have abridged the recent research trends in both early as well as late transition metal-based catalyst development. Furthermore, we have highlighted the role of transition metal-based catalysts in influencing the polymer properties.

CO2‐based amphiphilic block copolymers: Facile one‐step synthesis and aqueous self‐assembly

AbstractConstruction of CO2‐based amphiphilic block copolymers (ABCs) is an efficient method for providing CO2‐based polycarbonates with self‐assembly properties in aqueous media. It is challenging to construct CO2‐based ABCs by one‐step strategies from mixed monomers because hydrophilic blocks, usually composed of polar monomers, have negative effects on the synthesis of polycarbonates. In this work, we report a one‐step method to construct CO2‐based ABCs obtained by simultaneous ring‐opening copolymerization (ROCOP) of CO2/epoxides and reversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐isopropyl acrylamide (NIPAM). A trithiocarbonate/carboxy compound was used as the bifunctional chain transfer agent, and an aluminum porphyrin complex was used as the catalyst for ROCOP, which proved to be efficient in CO2 copolymerization even in the presence of NIPAM with strong polarity. This strategy allows flexible control over the molecular weight (5–16 kg/mol) and the hydrophilic‐hydrophobic balance (HLB 9–18) of the ABCs, and ensures narrow polydispersity Đ (1.1–1.3) of the polymers. The ABCs can further self‐assemble into micelles in water with controllable diameters and reversible phase transformation behavior with temperature changes from 25 to 40 °C. This simple route to CO2‐based ABCs with multiple functions has large potential in biomedical applications.

Stereoselective Polymerization of Aromatic Vinyl Polar Monomers

AbstractPolar vinyl polymers, a class of polymers with polar groups as side chains, have significant advantages over conventional nonpolar polyolefin materials in terms of viscosity, toughness, interfacial properties (dyeability and printability), and compatibility with solvents or other polymers. Among them, aromatic polar vinyl polymers are of interest because of their good heat resistance properties. In addition, stereoselective polymerization of aromatic polar vinyl monomers has been rapidly developed because the steric structure of the polymer has a significant impact on its physical properties. In this paper, we review the research progress of stereoselective polymerization catalysts for aromatic polar vinyl monomers in recent years, discuss in detail the influence of ligand structure, electronic effect of substituents, spatial site resistance effect, central rare earth metal species and polymerization solvents on the activity and stereoselectivity of polymerization reactions, and explore the possible mechanism of polymerization reaction.

Cu(0)-RDRP of 2-hydroxyethyl methacrylate in a non-polar solvent enables rapid synthesis of high-molecular weight homopolymers and direct access to amphiphilic copolymers

2-Hydroxyethyl methacrylate (HEMA) is an important functional monomer affording (co)polymers with numerous applications in different fields. Nevertheless, we still lack a reliable polymerization method for the synthesis of well-defined, high-molecular weight (MW) HEMA homopolymers, as well as for controlled copolymerization of unprotected HEMA with lipophilic comonomers. Herein, we report that rapid and well-controlled (co)polymerization of HEMA can be achieved via metallic copper-mediated reversible-deactivation radical polymerization (Cu(0)-RDRP) in a non-polar solvent (1,4-dioxane) using a chlorine-based initiation/catalytic system. With purified HEMA monomer, this protocol affords very well-defined (Ɖ ≤ 1.26) HEMA homopolymers in an unprecedently wide range of molecular weights from 10,000 to 500,000. Conversely, the structurally analogous bromine-based initiation/catalytic system leads to an uncontrolled polymerization. The use of a non-polar solvent enables, for the first time, a direct access to low-dispersity HEMA-rich copolymers with non-polar comonomers, including highly lipophilic ones. This is demonstrated on the successful copolymerization of HEMA with an equimolar amount of 2-ethylhexyl methacrylate and of lauryl methacrylate, yielding well-defined amphiphilic copolymers at quantitative conversion. This work significantly expands the application scope of the HEMA monomer and demonstrates for the first time that Cu(0)-RDRP in a non-polar solvent is applicable also to comparatively polar monomers.

Research Progress in Precision Polymerization of Polar Olefin Monomers by Lewis Pairs★

Research Progress in Precision Polymerization of Polar Olefin Monomers by Lewis Pairs^★

Rare-earth-metal-catalyzed highly 3,4-regioselective polymerization of polar 1-phenyl-1,3-butadiene derivates

The incorporation of polar functionalities into non-polar polymers represents a feasible strategy to tailor polymeric properties, and the direct metal-catalyzed coordination (co)polymerization of polar monomers is always a challenging topic.

Direct Synthesis of Partially Chain-Straightened Propylene Oligomers and P-MA Co-Oligomers Using Axially Flexible Shielded Iminopyridyl Palladium Complexes.

In this study, a series of partially chain-straightened propylene oligomers and functional propylene−methyl acrylate (P-MA) co-oligomers were synthesized with 8-alkyl-iminopyridyl Pd(II) catalysts. The molecular weight and polar monomer incorporation ratio could be tuned by using Pd(II) catalysts with various 8-alkyl-naphthyl substituents (8-alkyl: H, Me, and n-Bu). In propylene oligomerization, all the 8-alkyl-iminopyridyl Pd(II) catalysts convert propylene to partially chain-straightened (119−136/1000 C) oligomers with low molecular weights (0.3−1.5 kg/mol). Among the catalysts, Pd1 with non-substituent (H) on the ligand showed the highest activity of 5.4 × 104 g/((mol of Pd) h), generating oligomers with the lowest molecular weight (Mn: 0.3 kg/mol). Moreover, polar-functionalized propylene-MA co-oligomers with very high incorporation ratios (22.8−36.5 mol %) could be obtained in the copolymerization using these 8-alkyl-iminopyridyl Pd(II) catalysts. Additionally, Pd1 exhibited the best performance in propylene-MA copolymerization as it displayed the highest MA incorporation ratio of up to 36.5 mol%. All the three catalysts are capable of generating partially chain-straightened P-MA co-oligomers and the activities decrease gradually while the molecular weight increases with the increasing steric hindrance of the alkyl substituent (H < Me < n-Bu). Compared to Pd4 with the rigid 8-aryl substituent, the flexible 8-alkyl-iminopyridyl Pd(II) catalysts (Pd1-3) not only showed much higher activities in the propylene oligomerization, but also yielded P-MA co-oligomers with significantly higher incorporation ratios in the propylene co-oligomerization.

Compounded Interplay of Kinetic and Thermodynamic Control over Comonomer Sequences by Lewis Pair Polymerization.

The design of facile synthetic routes to well-defined block copolymers (BCPs) from direct polymerization of one-pot comonomer mixtures, rather than traditional sequential additions, is both fundamentally and technologically important. Such synthetic methodologies often leverage relative monomer reactivity toward propagating species exclusively and therefore are rather limited in monomer scope and control over copolymer structure. The recently developed compounded sequence control (CSC) by Lewis pair polymerization (LPP) utilizes synergistically both thermodynamic (Keq) and kinetic (kp) differentiation to precisely control BCP sequences and suppress tapering and misincorporation errors. Here, we present an in-depth study of CSC by LPP, focusing on the complex interplay of the fundamental Keq and kp parameters, which enable the unique ability of CSC-LPP to precisely control comonomer sequences across a variety of polar vinyl monomer classes. Individual Lewis acid equilibrium and polymerization rate parameters of a range of commercially relevant monomers were experimentally quantified, computationally validated, and rationalized. These values allowed for the judicious design of copolymerizations which probed multiple hypotheses regarding the constructive vs conflicting nature of the relationship between Keq and kp biases, which arise during CSC-LPP of comonomer mixtures. These relationships were thoroughly explored and directly correlated with resultant copolymer microstructures. Several examples of higher-order BCPs are presented, further demonstrating the potential for materials innovation offered by this methodology.

Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations.

Among various catalyst design strategies used in the α-diimine nickel(II) and palladium(II) catalyst systems, the unsymmetrical strategy is an effective and widely utilized method. In this contribution, unsymmetrical nickel and palladium α-diimine catalysts (Ipty/iPr-Ni and Ipty/iPr-Pd) derived from the dibenzobarrelene backbone were constructed via the combination of pentiptycenyl and diisopropylphenyl substituents, and investigated toward ethylene (co)polymerization. Both of these catalysts were capable of polymerizing ethylene in a broad temperature range of 0-120 °C, in which Ipty/iPr-Ni could maintain activity in the level of 106 g mol-1 h-1 even at 120 °C. The branching densities of polyethylenes generated by both nickel and palladium catalysts could be modulated by the reaction temperature. Compared with symmetrical Ipty-Ni and iPr-Ni, Ipty/iPr-Ni exhibited the highest activity, the highest polymer molecular weight, and the lowest branching density. In addition, Ipty/iPr-Pd could produce copolymers of ethylene and methyl acrylate, with the polar monomer incorporating both on the main chain and the terminal of branches. Remarkably, the ratio of the in-chain and end-chain polar monomer incorporations could be modulated by varying the temperature.

PRINCIPAL TECHNOLOGICAL SCHEME OF OBTAINING COMPOSITION MATERIALS FROM MODIFICATION OF POLYISOBUTYLE WITH POLYAR MONOMERS WITH THE PARTICIPATION OF FRIDEL–CRAFTS CATALYSTS

The reactor used to destroy and modify polyisobutylene in the laboratory has been made of pyrex glass. For the first time, Friedel-Crafts catalysts were found to be the initiators of a radical chain-chain mechanism for the destruction of polyisobutylene. Based on this mechanism, it has been modified with polar monomers (acrylonitrile and vinilacetate). This creates conditions for the production of new types of copolymers. At the same time, the destruction of polyisobutylene with the participation of Fridel-Krafts catalysts has been fully proven to be the initiator of the radical-chain mechanism. Polyisobutylen polyacrylonitrile (PIB-PAN) and polyisobutylene polyvinyl acetate (PIB-PAV) copolymers obtained are suitable raw materials for the production of various types of composite products. One of the main issues of chemical technology in the article is the transition of processes from a laboratory experimental plant to an industrial production facility. The problem set have been solved, mathematical calculations of the studied processes have been carried out, the basic technological scheme of modification of polyisobutylene with polar monomers acrylonitrile and vinilacetate and production of compositions based on them have been reflected.

Vitamins as Active Agents for Highly Emissive and Stable Nanostructured Halide Perovskite Inks and 3D Composites Fabricated by Additive Manufacturing

AbstractThe use of non‐toxic and low‐cost vitamins like α‐tocopherol (α‐TCP, vitamin E) to improve the photophysical properties and stability of perovskite nanocrystals (PNCs), through post‐synthetic ligand surface passivation, is demonstrated for the first time. Especially interesting is its effect on CsPbI3 the most unstable inorganic PNC. Adding α‐TCP produces that the photoluminescence quantum yield (PLQY) of freshly prepared and aged PNCs achieves values of ≈98% and 100%, respectively. After storing 2 months under ambient air and 60% relative humidity, PLQY is maintained at 85% and 67%, respectively. α‐TCP restores the PL features of aged CsPbI3 PNCs, and mediates the radiative recombination channels by reducing surface defects. In addition, the combination of α‐TCP and PNCs facilitates the chemical formulation to prepare PNCs‐acrylic polymer composites processable by additive manufacturing. This enables the development of complex shaped parts with improved luminescent features and long‐term stability for 4 months, which is not possible for non‐modified PNCs. A PLQY ≈92% is reached in the 3D printed polymer/PNC composite, the highest value obtained for a red‐emitting composite solid until now as far as it is known. The passivation shell provided by α‐TCP makes that PNCs inks do not suffer any degradation process avoiding the contact with the environment and preserve their properties after reacting with polar monomers during composite polymerization.