Unsaturated Poly Research Articles

Versatile Underwater Pressure Sensitive Adhesive: UV Curing Synthesis and Substrate-Independent Adhesion.

The demand for underwater pressure sensitive adhesives (PSAs) is rapidly increasing in fields such as underwater engineering and biomedicine. However, the achievement of underwater adhesion of PSAs remains a challenge because of the hydration layer that hinders the interaction between the adhesive and the substrate. Herein, a new type of underwater PSA was synthesized by the copolymerization of hydrophobic unsaturated poly(1,2-butylene oxide) (UPBO) and hydrophilic itaconic acid monomers using solvent-free ultraviolet curing. The PSA has demonstrated substrate-independent underwater adhesion strengths ranging from 108 to 141 kPa on both hydrophilic (glass, wood, steel) and hydrophobic (PET, PMMA, PTFE) substrates. The underwater adhesion performance of PSA remains stable during 30 adhesion-detachment cycles and incubation in water for 20 days. Notably, PSA shows cytocompatibility, antimicrobial, and degradable properties and can be used for rapid hemostasis of skin wounds. Experimental characterizations confirm that the process of underwater adhesion is achieved by hydrophobic alkyl side chains of the PBO chain segments, which repel water at the adhesive-substrate interface. This study should provide both practical and facile design strategies for multifunctional underwater PSAs that can be used in a variety of applications.

Biodegradability of unsaturated poly(ester-thioether)s synthesized by thiol-yne reactions

We prepared the dialkynyl monomers 1,4-butanediol dipropiolate, meso-erythritol dipropiolate, and isomannide dipropiolate (IMDP) via the reactions of 1,4-butanediol, meso-erythritol, and isomannide, respectively, with propiolic acid. The thiol-Michael polyaddition of three dialkynyl monomers with several dithiols, namely, 1,4-butanedithiol, ethylene bis(thioglycolate), 3,6-dioxa-1,8-octanedithiol, D,L-dithiothreitol, and D-2,5-di-O-(2-mercaptoacetate)-1,4:3,6-dianhydromannitol (MAIM), proceeded in chloroform, tetrahydrofuran, or N,N-dimethylformamide (25 °C) using triethylamine as the catalyst to give unsaturated poly(ester-thioether)s with the expected structures (Mn, 2.4 × 103 to 22.6 × 103; molecular dispersity index [Mw/Mn], 1.26–2.00). All of the poly(ester-thioester)s had single glass-transition temperature (Tg) values between −27 and 49 °C. While the rigid main chains improved the glass transition temperature, all of the poly(ester-thioester)s showed apparent enzymatic hydrolysis by lipase but low biodegradability in biodegradation tests using activated sludge. The poly(IMDP-alt-MAIM) with the highest biobased degree (55%) showed the highest biodegradability (10%) and the highest Tg (49 °C), suggesting that dianhydrosugars are suitable as biomass for improving biodegradability as well as thermal properties.

Modification of biodegradable poly(butylene carbonate) by biobased cis-2-butene-1,4-diol

Biodegradable unsaturated polyester materials have received extensive attention owing to their sustainability and functionality. This work successfully prepared a series of unsaturated poly(butylene-co-cis-2-butene carbonate) (PBcBC) polycarbonates. The effect ofcis-2-butene-1,4-diol (cB) on the structure and properties of the copolycarbonates was systematically studied from the point of view of microstructure, thermal, crystallization, and mechanical properties.No side reactions were observed during the polymerization, and the insertion of cB could regulate the thermal properties in the whole range of the copolycarbonates. Additionally, the PBcBCs exhibited superior water barrier ability and suitable mechanical properties than those commercial polyester materials such as PBAT. Our work shows that the PBcBCs as unsaturated polycarbonates have competitive advantages in commercial applications, and the cB comonomer is a suitable building block for directly synthesizing linear unsaturated copolymers. The fully biobased PBcBCs can better meet the requirements of green and sustainable development.

The effect of dynamic vulcanization on the morphology and biodegradability of super toughened poly(lactic acid)/unsaturated poly(ether-ester) blends

Preparing a super-tough polylactic acid (PLA) material while maintaining its biodegradability is a significant challenge. This study synthesized a biodegradable unsaturated poly(butylene succinate-co-fumarate)-poly(ethylene glycol) multiblock copolymer (PBSFG) and dynamically vulcanized it with PLA to obtain super-tough blends. The PBSFG self-vulcanized and formed a crosslinked “hard-soft” core-shell rubber phase in the blending process, where the PBSF segment acted as the core and PEG as the shell. As a result, the elongation at break and notched Izod impact strength of PLA increased significantly from 3 % to 66 % and from 3.2 to 58.0 kJ/m2, respectively. Furthermore, adding a small amount of dicumyl peroxide (DCP) promoted dynamic vulcanization and improved the compatibility between PLA and PBSFG. With the addition of 0.03 % DCP, the elongation at break and notched Izod impact strength of PLA/PBSFG were further increased to 218 % and 88.9 kJ/m2, respectively. Meanwhile, the crystallization rate of PLA was enhanced by the addition of PBSFG and DCP. The PLA/PBSFG blends also degraded in a proteinase K Tris-HCl buffered buffer solution. Finally, fully biodegradable and super-tough PLA blends were achieved.

Supertough and Biodegradable Poly(Lactic Acid) Blends with “Hard–Soft” Core–Shell Unsaturated Poly(ether-ester) through Self-Vulcanization

Supertough and Biodegradable Poly(Lactic Acid) Blends with “Hard–Soft” Core–Shell Unsaturated Poly(ether-ester) through Self-Vulcanization

Towards ductile and high barrier poly(L-lactic acid) ultra-thin packaging film by regulating chain structures for efficient preservation of cherry tomatoes

The irreconcilable paradox between barrier performance and ductility is a “stumbling block” restricting the development of poly(L-lactic acid) (PLLA) films in the packaging industry. In this work, we reported the fabrication of an ultra-thin PLLA-based film with barrier properties and ductility by adjusting the polarity and conformational behavior of the polymer chains. Firstly, a novel unsaturated poly(L-lactic acid-co-butyrate itaconate) P(LA-BI) copolymer containing CC double bonds was synthesized using melt polycondensation. The results reveal that the addition of 60 % of P(LA-BI) enables PLLA film to achieve an elongation at a break of 83.6 % due to P(LA-BI) containing partially branched structures, which resulted in the polymer chains being arranged more in a high-energy gg conformer. Meanwhile, because of the large number of CO polar groups in P(LA-BI), PLLA/P(LA-BI)60 film show CO2 and O2 permeability coefficients (CDP and OP) of 1.8 and 0.45 × 10−8 g·m·m−2·h−1·Pa−1 respectively, which means that it has excellent gas barrier properties. Moreover, PLLA/P(LA-BI)60 film shows a 33.3 % increase in CO2/O2 ratio and an excellent ultraviolet (UV) barrier performance compared to neat PLLA. Preservation results suggested that the CO2 and O2 levels within the package could be regulated by varying the amount of P(LA-BI) added. Among them, PLLA/P(LA-BI)40 film generated a more desirable CO2 and O2 atmosphere for cherry tomatoes preservation, which was reflected by the delaying of senescence, discoloration, and decay, inhibition of oxidative cell damage through reduced malondialdehyde production, and maintenance of nutritional and flavor substances in cherry tomatoes. This PLLA-based film offers the advantages of operational simplicity, environmental friendliness, and inexpensive cost, making it great promising for food preservation and other applications requiring barrier properties and ductility.

Preparation A Cross-Linked Copolymer By Using Unsaturated Poly(2-Butene Maleate) Polyester and Methyl Methacrylate

In this study, synthesis of unsaturated Poly(2-Butene Maleate) polyester by condensation polymerization and preparation of cross-linked graft copolymer with methyl methacrylate are presented. For this purpose, unsaturated polyesters were synthesized in four different time periods (12h, 24h, 36h, 48h) in the presence of hydroquinone using 1,4-Butanediol-2-ene and maleic anhydride. Then, the obtained unsaturated polyester was purified on the alumina column and used to obtain cross-linked copolymer with methyl methacrylate. Here in, methyl methacrylate acts as both co-monomer and cross-linking agent.
 In the preparation of Poly(2-Butene Maleate), the optimization study of the molecular weight and yield ratios with the time parameter was carried out. In the results obtained, it was observed that the maximum molecular weight was reached after almost 36 hours (Mn=3400). It was observed that time did not have much effect on the yield. Structural characterizations of the obtained products were supported by FT-IR and NMR analyzes. In thermal analysis, it was observed that the thermal stability of Cross-linked graft copolymer is higher than unsaturated polyester but lower than pure Poly(methyl methacrylate).

Multifunctional elastomer cardiac patches for preventing left ventricle remodeling after myocardial infarction in vivo

Myocardial infarction (MI) is still a major cause of mortality and morbidity worldwide. Elastomer cardiac patches have shown great potential in preventing left ventricle (LV) remodeling post-MI by providing mechanical support to the infarcted myocardium. Improved therapeutic outcomes are expected by mediating pathological processes in the necrosis phase, inflammation phase, and fibrosis phase, through orchestrated biological and mechanical treatments. In this study, a mechanically robust multifunctional cardiac patch integrating reactive oxygen species (ROS)-scavenging, anti-inflammatory, and pro-angiogenic capabilities was developed to realize the integrative strategy. An elastomeric polyurethane (PFTU) containing ROS-sensitive poly (thioketal) (PTK) and unsaturated poly (propylene fumarate) (PPF) segments was synthesized, which was further clicked with pro-angiogenic Arg-Glu-Asp-Val (REDV) peptides to obtain PFTU-g-REDV (PR), and was formulated into a macroporous patch containing rosuvastatin (PRR). The mechanical support and multifunctional effects of the patch were confirmed in a rat MI model in vivo compared to the patches with only mechanical support, leading to reduced cell apoptosis, suppressed local inflammatory response, alleviated fibrosis, and induced angiogenesis. The cardiac functions and LV morphology were also well maintained. These results demonstrate the advantages of the integrated and orchestrated treatment strategy in MI therapy.

Hydrogenation of poly(myrcene) and poly(farnesene) using diimide reduction at ambient pressure

AbstractAmbient pressure chemical hydrogenation using p‐toluene sulfonyl hydrazide (TSH) via thermal diimide formation (N2H2) permitted reduction of double bonds of poly(myrcene) (poly[Myr]) and poly(farnesene) (poly[Far]). Both pendent and backbone double bonds in poly(Myr) (Mn = 56 kg/mol) and poly(Far) (Mn = 62 kg/mol) synthesized by conventional free radical polymerization were hydrogenated to almost completion. Furthermore, TSH semi‐batch addition efficiently hydrogenated double bonds, while avoiding undesired autohydrogenation of diimides that occurred in batch mode. Thermal stability improved for hydrogenated poly(Myr) and poly(Far), where temperature at 10% weight loss (T10%) increased from 188 to 404°C for poly(Myr) and from 310 to 379°C for poly(Far). Tgs of poly(Myr) and poly(Far) also increased by about 10–25°C, indicating increased stiffness after hydrogenation. Finally, viscosities of poly(Myr) and poly(Far) were also increased after hydrogenation, and a greater increase was observed for poly(Myr) (by two orders of magnitude from 102 to 104 Pa s) due to its Mn being much higher than its entanglement molecular weight. Poly(Far) viscosity only increased by 1.5 times after hydrogenation (~104 Pa s), comparable to the poly(Myr) after hydrogenation, suggesting unsaturated poly(Far) was more entangled than unsaturated poly(Myr) because of its longer side chains.

Self-Diagnostic Polymers-Inline Detection of Thermal Degradation of Unsaturated Poly(ester imide)s.

Monitoring polymer degradation is an important quest, particularly relevant for industry. Although many indirect methodologies for assessing polymer degradation exist, only few are applicable for an inline-monitoring via optic detection-systems. An inline-monitoring system is introduced for the thermal degradation of crosslinked poly(ester imide)s (PEIs) by embedding trifluoroacetyl functionalized stilbene molecules, serving as chemosensors to track the release of generated alcoholic byproducts. Nucleophilic addition of an alcohol to the sensors trifluoroacetyl functionality triggers hemiacetal formation which is accompanied by significant changes in optical properties, in turn allowing monitoring of sensor activation by direct spectroscopy. Fluorescence spectroscopy offers an easy detection tool for the inline thermal monitoring of PEI-degradation.

Biomimetic, Stiff, and Adhesive Periosteum with Osteogenic-Angiogenic Coupling Effect for Bone Regeneration.

Current periosteal grafts have limitations related to low mechanical strength, tissue adhesiveness, and poor osteogenesis and angiogenesis potential. Here, a periosteum mimicking bone aid (PMBA) with similar structure and function to natural periosteum is developed by electrospinning photocrosslinkable methacrylated gelatin (GelMA), l-arginine-based unsaturated poly(ester amide) (Arg-UPEA), and methacrylated hydroxyapatite nanoparticles (nHAMA). Such combination of materials enhances the material mechanical strength, favors the tissue adhesion, and guarantees the sustained activation of nitric oxide-cyclic guanosine monophosphate (NO-cGMP) signaling pathway, with well-coordinated osteogenic-angiogenic coupling effect for accelerated bone regeneration. This work presents a proof-of-concept demonstration of thoroughly considering the progression of implant biomaterials: that is, the initial material components (i.e., GelMA, Arg-UPEA, and nHAMA) equip the scaffold with suitable structure and function, while its degradation products (i.e., Ca2+ and l-arginine) are involved in long-term mediation of physiological activities. It is envisioned that the strategy will inspire the design of high-performance bioscaffolds toward bone and periosteum tissue engineering.

Synthesis of Bio-Based Poly(Butylene Adipate-co-Butylene Itaconate) Copolyesters with Pentaerythritol: A Thermal, Mechanical, Rheological, and Molecular Dynamics Simulation Study.

Bio-based unsaturated poly(butylene adipate-co-butylene itaconate) (PBABI) aliphatic copolyesters were synthesized with pentaerythritol (PE) as a modifier, observing the melting point, crystallization, and glass transition temperatures were decreased from 59.5 to 19.5 °C and 28.2 to −9.1 °C as an increase of itaconate concentration, and Tg ranged from −54.6 to −48.1 °C. PBABI copolyesters tend to the amorphous state by the existence of the BI unit above 40 mol%. The yield strength, elongation, and Young’s modulus at different BA/BI ratios were valued in a range of 13.2–13.8 MPa, 575.2–838.5%, and 65.1–83.8 MPa, respectively. Shear-thinning behavior was obtained in all BA/BI ratios of PBABI copolyesters around an angular frequency range of 20–30 rad s−1. Furthermore, the thermal and mechanical properties of PBABI copolyesters can be well regulated via controlling the itaconic acid contents and adding the modifier. PBABI copolyesters can be coated on a 3D air mesh polyester fabric to reinforce the mechanical property for replacing traditional plaster applications.

Advancing the Synthesis of Isocyanate-Free Poly(oxazolidones)s: Scope and Limitations

Poly(oxazolidone) is an emerging class of polyurethanes (PUs) that is easily accessible by an isocyanate-free pathway via the step-growth copolymerization of CO₂-based monomers (bis(α-alkylidene cyclic carbonate)s) with primary diamines at room temperature. Here, we explore the scope and limitation of this process by investigating the influence of the diamine and the reaction conditions on the structure and macromolecular parameters of the polymer. Less hindered diamines (aliphatic and benzylic) provide selectively poly(hydroxyoxazolidone)s, whereas the bulkier ones (cycloaliphatic) furnish polymer chains bearing two types of linkages, oxo-urethane and hydroxyoxazolidone ones. The increase of the reaction temperature or the addition of DBU as a catalyst enables to accelerate the polymerizations. The quantitative polymer dehydration is also achieved by refluxing in acetic acid, providing a new class of unsaturated poly(oxazolidone)s composed of α-alkylidene oxazolidone linkages (for hindered polymers) or a mixture of α- and β-alkylidene oxazolidone linkages (for the less hindered ones). These unsaturated poly(oxazolidone)s present a high glass transition temperature (90 °C ≤ Tg ≤ 130 °C) and a remarkable thermal stability (Td > 360 °C), rendering these polymers attractive for applications requiring high temperatures. This work is therefore opening an avenue to novel functional isocyanate-free PUs, with the pendant hydroxyl or olefin groups that are expected to be easily derivatized.

Phenol Novalac Epoxy-modified unsaturated polyester hybrid networks by Silica Nanoparticles/ and Cross linking with Silane Compounds

In this study epoxy phenol novalac resin which consists of silica nanoparticles and unsaturated poly ester resin linked to the Silane and cross linking to that structure and also parameters affecting the processes involved have been evaluated. Cross linking in phenol novalac epoxy resins effects on many properties such as thermal, electrical, mechanical and chemical attributes especially in elevated temperatures. Silane cross-linking’s in phenol novalac epoxy resin with respect to other methods like proxiding, irradiation and utilization of Azo compounds, looks to be a very simple and low cost route, which makes it very encouraging for various industries. Unsaturated poly ester resin is compatible with phenol novalac epoxy resin and also creates some cross-linking and as far as tri methoxy Silane is added to the mentioned resin, its thermal, physical and mechanical properties are optimized. In this literature impact, tension, glass transition temperature, humidity absorption, FTIR and Scanning electron microscopy (SEM) tests were done and the results revealed that as the cross-linking occurs, tension in rupture region increases. This increase is more common at elevated temperatures. The growth in content of silica nanoparticles leads to a drop in water permeability of phenol novalac epoxy resin nanocomposite which contains unsaturated poly ester resin.

Straightforward Synthetic Protocol to Bio-BasedUnsaturated Poly(ester amide)s from Itaconic Acidwith Thixotropic Behavior.

In the field of polymer chemistry, tremendous efforts have been made over the last decade to replace petrochemical monomers with building blocks from renewable resources. In this respect, itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturated polyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s from itaconic acid are scarce. Under standard polycondensation reactions, the presence of free amines leads to aza-Michael addition reactions at the α,β-unsaturated double bond of the itaconic acid and isomerization reactions to mesaconic acid. Both reactions make the resulting materials useless as UV-curing polymer resins. To avoid these undesired side reactions, we herein report the use of preformed, well-defined diols containing internal amide bonds. The resulting unsaturated poly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscosity measurements revealed a strong thixotropic behavior induced by the amide groups, which is usually not detected in structurally similar polyester resins.

First Example of Unsaturated Poly(Ester Amide)s Derived From Itaconic Acid and Their Application as Bio-Based UV-Curing Polymers

Recently, itaconic acid has drawn considerable attention as a novel radical-curing building block for polyester resins. These bio-based materials have been used in thermal, as well as ultra violet (UV) curing applications, such as printing inks or coatings. Poly(ester amide)s from itaconic acid could be very interesting, as the amide group could alter the properties of the resins as well as cured materials. However, standard polycondensation reactions with diamines are not possible with itaconic acid as the amines preferably react via an aza-Michael addition at the α,β-unsaturated double bond. Therefore, alternative and more elaborate synthetic strategies have to be developed. Herein, we present two different synthetic strategies to poly(ester amide)s from itaconic acid that circumvent the addition reaction of the amines. This is in both cases done by a pre-reaction to form stable amide building blocks that are then reacted with itaconic acid or polyesters derived thereof. The structural composition and the properties of the resin are characterized, and the UV-curing reactivity is examined. All properties are compared to corresponding polyesters from itaconic acid.

Unsaturated Poly(ester-urethanes) with Stereochemically Dependent Thermomechanical Properties

Polymer crystallinity is known to be dependent upon backbone stereochemistry, and this concept has emerged as an effective means of altering bulk material properties. Herein we describe a simple, step-growth polymerization to synthesize unsaturated poly(ester-urethane)s using the thiol-Michael addition reaction. The absolute control of alkene stereochemistry (0–100% trans content) in the polymer backbone was achieved by varying the cis/trans double bond content of the monomer feedstock. In turn, the crystallinity of the polymer was systematically varied which manifested in control over the resultant tensile properties such as Young’s modulus, ultimate tensile strength, and elongation at break. Generally, the crystallinity and tensile strength were positively correlated with increasing trans double bond content within the polymer.

Arginine based poly (ester amide)/ hyaluronic acid hybrid hydrogels for bone tissue Engineering

Bone transplantations are still facing many serious challenges, hydrogel as a new kind of artificial bone substitutes has developed into a promising bone scaffold material. However, it is still a challenge to combine bioactive agents and hydrogel matrix to promote osteoinductivity. Herein, we developed a novel bioactive hydrogel based on arginine-based unsaturated poly (ester amide) (Arg-UPEA) and methacrylated hyaluronic acid (HA-MA) via photo-crosslinking. As the results indicated, we found that the introduction of Arg-UPEA into HA-MA hydrogels could finely modulate their compressive modulus, swelling level and porous structure. Besides, among groups of different feed ratio, groups of 10 % and 15 % of Arg-UPEA content effectively enhanced osteogenic differentiation in osteoblasts when compared with HA-MA hydrogel. Furthermore, better bone regeneration and expression of osteogenesis-related factors in vivo also verified the Arg-UPEA/HA-MA hybrid hydrogels as a promising scaffold material for bone tissue engineering.

Covalently Binding of Bovine Serum Albumin to Unsaturated Poly(Globalide-Co-ε-Caprolactone) Nanoparticles by Thiol-Ene Reactions.

When nanoparticles (NPs) are introduced to a biological fluid, different proteins (and other biomolecules) rapidly get adsorbed onto their surface, forming a protein corona capable of giving to the NPs a new "identity" and determine their biological fate. Protein-nanoparticle conjugation can be used in order to promote specific interactions between living systems and nanocarriers. Non-covalent conjugates are less stable and more susceptible to desorption in biological media, which makes the development of engineered nanoparticle surfaces by covalent attachment an interesting topic. In this work, the surface of poly(globalide-co-ε-caprolactone) (PGlCL) nanoparticles containing double bonds in the main polymer chain is covalently functionalized with bovine serum albumin (BSA) by thiol-ene chemistry, producing conjugates which are resistant to dissociation. The successful formation of the covalent conjugates is confirmed by flow cytometry (FC) and fluorescence correlation spectroscopy (FCS). Transmission electron microscopy (TEM) allows the visualization of the conjugate formation, and the presence of a protein layer surrounding the NPs can be observed. After conjugation with BSA, NPs present reduced cell uptake by HeLa and macrophage RAW264.7 cells, in comparison to uncoated NP. These results demonstrate that it is possible to produce stable conjugates by covalently binding BSA to PGlCL NP through thiol-ene reaction.

Effect of graphene oxide on features of functionalizable Poly(Butylene fumarate) and functional Poly(Butylene succinate) doped polyaniline

A novel material that obtained through combining a biodegradable polymer with a conductive polymer, has been successfully developed by graphene oxide (GO). For the first time, unsaturated poly(butylene fumarate) grafted reduced GO (PBF:RGO) was synthesized via in-situ polymerization method and simultaneous in-situ thermal reduction of GO. It was modified through post-polymerization modification to form sulfonated poly(butylene succinate) grafted reduced GO (PBSS:RGO). Then, PBSS:RGO was incorporated as a polymeric dopant in the synthesis of polyaniline (PANI) to prepare the conductive and anticorrosive compound. Functionalizable PBF and PBF:RGO along with functional PBSS and PBSS:RGO were characterized by 1HNMR. Thermal and crystallization properties of PBF and PBF:RGO were studied using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) with Avrami and Tobin models. Further investigation of crystallinity and dispersion of graphene sheets in the polymer matrix was carried out by X-ray diffraction (XRD). PBF:RGO exhibits higher thermal stability, higher crystallization rate, and lower crystallinity compared with pristine PBF. Final composites (PANI:PBSS and PANI:RGO:PBSS) were also characterized through Fourier transform infrared (FT-IR), contact angle analysis, electrochemical impedance spectroscopy (EIS) and electrical conductivity measurements. PANI:RGO:PBSS indicates a higher conductivity, higher inhibition efficiency and more hydrophilicity than PANI:PBSS.