Comonomer Content Research Articles

Impact of molecular architecture and draw ratio on enhancement of targeted mechanical properties of machine direction oriented polyethylene films produced after blown film extrusion

Conventional multi-material multi-layer flexible packaging offers excellent properties. However, it has recycling challenges, necessitating a shift to mono-material multi-layer flexible packaging for example all-polyethylene (PE) packaging which can be tailored through various synthesis and processing methods for different layers. In this work, we study how the key molecular properties (number-average molecular weight ( Mn), weight-average molecular weight ( M w), molecular weight distribution (MWD), comonomer content (short chain branching)) and machine direction orientation (MDO) process draw ratio (MDX) influence the final morphology and mechanical properties of MDO-PE films which are intended as the outer layer of mono-material all-polyethylene multi-layer flexible packaging. Five PE grades and various blends were extruded and blown into films. Selected blown films were machine direction oriented to obtain the final MDO-PE films. Furthermore, one selected PE blown film was processed at different MDO process draw ratios while keeping other process parameters constant. From the molecular properties point of view, the higher molecular weight fractions provide a higher possibility for uniform stretching whereas lower molecular weight fractions provide a higher natural draw ratio and therefore higher modulus and stiffness enhancement. Further, the results show that increasing MDO process draw ratio leads to more fibrillation and increased crystallinity. Consequently, the tensile modulus and stiffness at the higher draw ratios increase as well and are comparable to conventionally used polymers in outer layers of multilayer flexible packaging. Thus, this work demonstrates that MDO-PE films with enhanced modulus can provide sufficient stiffness for the design of outer layer of mono-material multi-layer all-PE packaging which presents higher potential for mechanical recyclability.

Study on the structure and property of metallocene ethylene/1-heptene and ethylene/1-octene copolymers

Polyolefin elastomers are typically copolymers of ethylene with 1-butene, 1-hexene, or 1-octene. Other types of comonomers have not been widely applied industrially. The cost of 1-heptene obtained from Fischer-Tropsch synthesis is only half that of 1-octene, making it a viable economical substitute. This work utilized 1-heptene from Fischer-Tropsch synthesis and 1-octene from ethylene oligomerization as research subjects. Eight metallocene POEs based on 1-heptene and 1-octene were synthesized using Me2Si(C5Me4)(N t Bu)]TiCl2 (Ti-CGC) catalyst. The copolymers’ molecular structures and physical properties were characterized using HT-GPC, Temperature Rising Elution Fractionation (TREF),13C-NMR, DSC, Melt Index (MI), and Tensile tests. Compared to 1-heptene, 1-octene more effectively reduces the melting point and crystallinity, while 1-heptene’s stronger comonomer insertion capability facilitates the production of copolymers with higher comonomer content. Similar ternary sequence distributions and molecular dynamics indicate that ethylene/1-heptene and ethylene/1-octene copolymers possess comparable chain microstructures. Both ethylene/1-heptene copolymers and ethylene/1-octene copolymers exhibit excellent toughness and mechanical properties. Although the activity and insertion capacity of ethylene and 1-heptene decrease at low comonomer concentrations, they significantly improve at higher comonomer concentrations. Thus, Fischer-Tropsch synthesis of metallocene ethylene/1-heptene copolymers can effectively reduce raw material costs and be a cost-effective alternative to ethylene/1-octene copolymers.

Preparative temperature rising elution fractionation of polyolefin elastomer and its chain microstructure

AbstractPolyolefin elastomer (POE) has very weak crystalline ability, consequently, applying the conventional preparative temperature‐rising elution fractionation (P‐TREF) to separate is challenging. Here, a unique, home‐built P‐TREF apparatus with an extensive range of temperatures from −80°C to 150°C is applied to first fractionate POE depending on its crystallizability. The main fractions are eluted at 0°C, 8°C, 15°C, 20°C, 25°C, 30°C, and 35°C. The corresponding weight percentages of fractions are 8.31, 13.38, 15.59, 12.05, 13.39, 17.30, and 10.53 wt%, respectively. The chain structures of fractions are further analyzed by high‐temperature gel permeation chromatography (HT‐GPC), 13C‐nuclear magnetic resonance spectroscopy (13C‐NMR), differential scanning calorimetry (DSC), and successive self‐nucleation and annealing (SSA). The crystallinity of the fraction grows continually as the elution temperature rises. The 1‐octene comonomer concentrations within the fractions decreases from 13.8 to 7.9 mol% when the elution temperature rises from −10°C to 40°C. These findings enable for the detailed recognition of the chain microstructure of POE resin and the extension of the TREF approach to POE resins. This lays the groundwork for fundamental studies and practical uses in industry.

Effects of molecular structure and temperature field on the crystallization behavior of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether)

Despite the wide industrial application of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether) (PFA) in semiconductor processing, its crystallization behavior has little been studied. In this work, three PFA resins with similar molecular weight but different comonomer content and distribution were synthetized. Then the non-isothermal crystallization kinetics and crystalline structures were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction systematically. It is found that the incorporation of comonomers destroys the chain regularity and reduces the crystallizability of PFA thermodynamically, while the comonomer insertion improves the chain flexibility to accelerate the crystal growth dynamically. When the comonomer content of PFA is low, both the nucleation and growth rates are quite fast, which is favorable for the formation of spherulite. As the comonomer content increases or distribute uniformly in the chain, the nucleation rate declines notably and the side groups distort the crystal cell to increase the spacing of [100] plane. Moreover, two-dimensional growth mode is dominant to form bundle-like structure when crystallizing at slow cooling, where nucleation is suppressed by growth. But three-dimensional symmetrical spherulite can be activated and perfected at high cooling rate due to the initiation of substantial nucleation sites. This unique crystallization behavior is opposite to that of conventional polymers, providing a guidance for the polymerization and processing of PFA.

Terpolymerization of Ethylene with Hexene and Styrene Derivatives by Half-Sandwich Scandium Catalyst.

The terpolymerization of ethylene with hexene and styrene derivatives was achieved with a rare earth metal catalyst (C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2 to prepare functional polyethylene. The catalyst system exhibited high activity in the terpolymerization of ethylene with hexene and amine-substituted styrene, affording terpolymers a moderate molecular weight and a unimodal molecular weight distribution. In addition, the comonomer content of the terpolymers can be controlled by changing the feeding ratio of monomers. The aliphatic region of the 13C NMR spectra reveals that the structural units of the comonomers are separately incorporated into the polyethylene backbone. Terpolymers containing styrene derivatives exhibit enhanced tensile strength and significantly improve hydrophilic properties.

Order-Order Transition in Statistical Copolymer Thin Film Induced by LCST-Type Behavior.

In this paper, we describe the formation of an ordered structure in a copolymer thin film through hydration, which subsequently transitions to a different ordered structure upon dehydration. A statistical copolymer of poly(N-octadecyl acrylamide-stat-hydroxymethyl acrylamide) with a comonomer content ratio of 1:1, denoted as p(ODA50/HEAm50), was synthesized via free radical copolymerization. We prepared a thin film of this copolymer on a solid substrate and annealed it at 60 °C under humid conditions. This treatment formed a side-chain segregated lamellar (SCSegL) structure, in which the ODA and HEAm units are oriented perpendicularly to the polymer backbone and opposite each other. Increasing the annealing temperature to 90 °C led to a transition to a side-chain mixed lamellar (SCMixL) structure, where the ODA and HEAm units are also oriented perpendicularly to the polymer backbone but in both directions. The quartz crystal microbalance (QCM) data indicate that p(ODA50/HEAm50) exhibits LCST-like behavior with a transition temperature of approximately 50 °C. We conclude that the formation of the SCSegL structure at 60 °C is due to pronounced segregation between the water-adsorbed HEAm groups and the hydrophobic ODA. Conversely, dehydration at 90 °C reduces the segregation forces, forming the SCMixL structure, which exhibits lower strain. These results demonstrate that the p(ODA50/HEAm50) film undergoes an order-to-order transition driven by the hydration-dehydration process. Additionally, we found that changes in the lamellar structure significantly alter the swelling properties of the film.

Improving Environmental Stress Cracking Resistance of High-Density Polyethylene Grades by Comonomer Addition and Nanocomposite Approach.

The aim of this paper is to determine the effect of polymer density, correlated to the comonomer content, and nanosilica addition on the mechanical and Environmental Stress Cracking Resistance (ESCR) characteristics of high-density polyethylene (HDPE). In this regard, five HDPE samples with similar Melt Flow Index (MFI) and molar mass but various densities were acquired from a petrochemical plant. Two polymerization reactors work in series and differ only in the amount of 1-buene comonomer fed to the second reactor. To ascertain the microstructure of the studied samples, GPC and SSA (successive self-nucleation and annealing) analyses were accomplished. All samples resulted having similar characteristics but slightly various SCB/1000 C=7.26-9.74 (SCB=Short Chain Branching). Consequently, meanwhile studied HDPEs reveal similar notched impact and stress at yield values, the tensile modulus, stress-at-break, and elongation-at-break tend to demonstrate different results with the SCB content. More significantly, ESCR characteristic varied considerably with SCB/1000 C extent, so that higher amount of SCB acknowledged advanced ESCR. Notably, blending HDPE sample containing higher amount of SCB/1000 C, with 3 wt.% of chemically modified nanosilica enhanced ESCR characteristic by 40 %. DFT (Density Functional Theory) calculations unveiled the role of the comonomer, quantitatively by binding energies and qualitatively by Non Covalent Interaction (NCI) plots.

Poly(butylene terephthalate) Copolyesters with Dilinoleic Derivatives: Solution Properties and Influence of Short‐Chain Branching

AbstractThe solution behavior of poly(butylene terephthalate) (PBT) copolyesters with dilinoleic monomer units (dilinoleic diol (LD) / dilinoleic diacid (LA)) is studied to understand the processing behavior from melt. NMR investigations show that the short‐chain branches are characterized by a distribution of different alkyl chain lengths, where n‐butyl (C4) and longer chains have the largest content (>55 mol%). High‐temperature size exclusion chromatography with threefold detection (multi‐angle light‐scattering, refractive index, and viscosity detector) in 1,2,4‐trichlorobenzene is performed to determine molar masses, hydrodynamic radii, viscosity radii, and Kuhn–Mark–Houwink–Sakurada (KMHS) exponents α in dependence of the molar amount of short‐chain branched comonomers. Low concentrations of dilinoleic comonomers in PBT copolyesters improve the solubility of the copolyesters significantly. Higher amounts cause contraction of the polymer coils as illustrated by smaller hydrodynamic radii as well as lower KMHS exponents. The α values decrease with increasing amount of short‐chain branched comonomer except for very low concentrations. The solution behavior of LA and LD copolyesters with a higher aliphatic content shows different trends of the influence of short‐chain branches on the melt behavior, which reflects the influence of intramolecular versus intermolecular entanglements in solution and in melt.

Thermo and pH-responsive nanocarriers based on mesocellular silica foam and poly(N-vinylcaprolactam-co-methacrylic acid): Synthesis, characterization, and in vitro cytotoxicity assay

Smart hybrid nanocarriers were prepared by grafting poly(N-vinylcaprolactam-co-methacrylic acid) (poly(NVCL-co-MAA)) onto mesocellular silica foams (MCF silica) to evaluate them as controlled delivery systems of doxorubicin (DOX). The development of these nanocarriers began with the synthesis of MCF silica with interconnected porous structures and an average pore diameter of 27 nm. Then, free radical polymerization was used to graft the smart copolymer, and some parameters such as comonomer concentration and reaction time were studied. The DOX was loaded by immersion in an aqueous drug solution, while the in vitro release was investigated at different pHs (7.4, 5.8) and temperatures (25, 37 °C). In addition, the cytotoxicity of nanocarriers was investigated in vitro using the direct contact method with human breast cancer cells (SKBR3). In general, hybrid nanocarriers with copolymer graft percentages ranging from 30 to 60 % were obtained. On the other hand, at higher grafting of poly(NVCL-co-MAA) onto MCF silica, higher drug loading (up to 6.41 × 10−2 mg DOX/mg HN) was observed. Furthermore, in vitro DOX release results suggested that the nanocarriers released up to 52 % at 37 °C and a pH of 5.8. Finally, the in vitro cytotoxicity assay revealed that the DOX-loaded hybrid nanocarriers were cytotoxic to SKBR3 cells, indicating a controlled administration of DOX from the nanocarriers compared to free DOX. These results suggest that nanocarriers could have great potential for use as controlled delivery systems of anticancer drugs.

Multiple comonomer concentrations prediction from FTIR spectra with quantum chemistry-based interpretation

Multiple comonomer concentrations prediction from FTIR spectra with quantum chemistry-based interpretation

Nickel‐ and Palladium‐Catalyzed Copolymerizations of Norbornene with Polar α‐Olefins

AbstractRecent progress regarding the copolymerization of norbornene with various polar α‐olefins catalyzed by nickel and palladium catalysts is reviewed here with special attention paid to the diverse catalyst frameworks, polar monomer scopes as well as polymer microstructures. Both the influences of steric effect and electron property of ligand substituents and the type of polar monomers on the catalytic behaviors (activity, stability, polarity tolerance, etc.) and the polymer microstructures (molecular weight and distribution, comonomer contents, etc.) have been summarized. The introduction of noncyclic‐olefins, such as polar vinyl monomers, polar higher α‐olefins, and polar styrenes, into rigid cyclic‐based polynorbornene chain resulted in significant modifications on the polarity, compatibility, thermostability, processibility, transparency, and many other properties of the material, which has also been discussed in the review. The contents of this review have been classified according to the type of polar monomers involved in the norbornene copolymerization, and each section included nickel and palladium catalysts bearing different ligand structures, which will be meaningful for the development of new types of catalysts and new families of norbornene‐based cyclic olefin copolymer materials in the future.

Polyester networks based on Tulipalin A and ε‐caprolactone and activation of the Thioether groups by incorporation of trialkylsulfonium salts

AbstractLinear and star‐shaped poly(ε‐caprolactone‐co‐α‐methylene‐γ‐butyrolactone) P(CL‐co‐MBL) copolyesters with a pendant functional double bond of α‐methylene‐γ‐butyrolactone (MBL) comonomer were used as polymeric precursor for organo‐gels formation. Crosslinking was carried out by light‐initiated thia‐Michael reaction using 1,5‐pentanedithiol (PDT) and pentaerythritol tetrakis(3‐mercaptopropionate) (PETK). Double bond conversion and the content of free thiol groups in the obtained networks was followed and rationally estimated using confocal Raman spectroscopy. The gel content and the crosslinking density varied based on MBL comonomer and crosslinker content and were highest for slight thiol to double bond excess (SH/vinyl; 2/1 molar ratio) while decreasing with further thiol excess. These parameters were more pronounced by the replacement of linear PDT with the star‐shaped PETK crosslinker. The thermal and rheological properties investigation of the obtained materials was performed employing DSC, TGA and using frequency and temperature sweeps rheological measurements. Shear moduli in the range 0.14 up to 0.93 MPa were obtained due to different content of MBL in pre‐polymer and crosslinker in network formation. The strength was caused by the crystalline phase of the PCL segments up to a temperature of 50°C. Formed thioether bond within the network were not reversible up to 150°C as it was found based on temperature sweep rheology. Following, the activation and conversion of thioether bonds within the obtained materials into trialkylsulfonium salts was attained through the alkylation using butyl brosylate. The dynamic nature of the transalkylation at elevated temperature 150°C allowed network rearrangement, which was proved by stress relaxation experiment and investigation of the self‐healing capabilities.

Cold crystallization of polytrimethylene terephthalate and copolymers

The melt of crystalline polymers normally crystalize on cooling and the polymer melts with low critical cooling rate would easily solidify as glass during cooling to their glass transition temperature (Tg). The glassy process exhibits variety within each kind of polymer melts in the slope of the viscosity-temperature visibility, and the rate of the excess conformational entropy in the polymer melt over the crystalline phase changes in the Tg approaching. Polytrimethylene terephthalate (PTT) and a series of polytrimethylene terephthalate copolyesters (PTTG) with different molar ratios of 1,3-propylene glycol (1,3-PDO) to 1,4-cyclohexanedimethanol (1,4-CHDM) were synthesized to modify the chain flexibility and the critical cooling rate. The glassy samples were obtained via quenching the melts of PTT and copolymers below the Tg to characterize the cold crystallization behaviors. The evolutions of the crystalline structure of the amorphous samples were in situ investigated via DSC and simultaneous WAXS/SAXS approaches during heating. The polymer chain dynamics and the critical cooling rates of the PTT and copolymers were estimated by rheological testing and DSC characterization. The results indicate that the chain conformation adjustment of PTT and copolymers is relate to the comonomers in the copolymers, and the cold crystallization behaviors can be divided into three temperature ranges during heating. The first involves rapid transition from a pre-ordered phase to a crystalline phase, the second is the adjustment of defects in an imperfect crystalline phase, and the third may refer crystal reorganization before melting. The crystallization ability of the samples could be due to the ability of chain conformation adjustment with comonomer content till the crystallization is no longer obvious during heating. The cold crystallization behaviors of the samples were discussed based on the polymer chain dynamics and it is convinced that would be helpful to understand the crystallization and processing of polymers.

Recent Advances in Controlled Production of Long-Chain Branched Polyolefins.

Polyolefins, composed of carbon and hydrogen atoms, dominate global polymer production. This stems from the wide range of physical and mechanical properties that various polyolefins can cover. Their versatile properties are largely tuned by chain microstructure, including molar mass distribution, comonomer content, and long-chain branching (LCB). Specifically, LCB imparts unique characteristics, notably enhances processability crucial for downstream applications. Tailoring LCB structural features has encouraged academic and industrial efforts, chronicle in this review from a chemistry standpoint. While encompassing post-reaction modification based traditional methods like peroxide grafting, ionizing beam irradiation, and coupling reactions, the main focus is given to catalyst-centric strategies and innovative polymerization schemes. The advent of single-site catalysts-metallocenes and late transition metals catalysts-amplifies interest in tailored chemical methods, but the progress in LCB formation flourishes via tandem catalytic systems and bimetallic catalysts under controlled reaction conditions. Specifically, the breakthrough in coordinative chain transfer polymerization unveils a novel avenue for controlled LCB synthesis by sequential chain propagation, transfer, liberation, and enchainment. This short review highlights recent approaches for the production of LCB polyolefins that can provide a roadmap crucial for researchers in academia and industry, steering their efforts toward further advancements in the production of tailored polyolefin.

Biofunctional Polyacrylamide Hydrogels using Tetrazole‐Methylsulfone Comonomer for Thiol Conjugation

AbstractBiofunctionalized polyacrylamide (PAAm) hydrogels are important 2D substrates for studying cell physics and mechanobiology. In this work, an arylmethylsulfone (MS) comonomer is developed that can be incorporated into PAAm gels under aqueous radical polymerization conditions. The resulting hydrogels show similar properties to unmodified PAAm gels, indicating that the comonomer is incorporated without affecting PAAm physical properties. The MS‐containing PAAm hydrogels allow efficient conjugation of thiol derivatized biomolecules and require very low comonomer content (2 mM, 0.18 mol% relative to AAm) and thiol incubation amounts (≥ 0.15 µg per gel) to achieve functional densities that elicit cell responses. Compared to carboxyl‐functionalized PAAm hydrogels, a 10‐fold lower comonomer concentration and a 10‐fold lower ligand feed concentration are sufficient to achieve comparable cell adhesion responses. The new comonomer opens up possibilities for efficient and straightforward biofunctionalization of PAAm hydrogels used in cell biophysical studies.

Advanced analysis of ethylene vinyl acetate copolymer materials for photovoltaic modules

Ethylene vinyl acetate (EVA) copolymers are commonly used as encapsulation material and as adhesive layer for backsheet laminates of photovoltaic (PV) modules. While Fourier-Transform Infrared spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC) are well established to analyse EVA encapsulants in PV modules, X-ray Photoelectron Spectroscopy (XPS) is seldomly used. Hence, the objective of this paper was to evaluate the potential and limitations of XPS for advanced analysis and testing of EVA encapsulants. Consequently, EVA grades of different vinyl acetate (VA) comonomer content were characterized and evaluated systematically by XPS, FTIR and DSC. Independent on the analytic technique linear relationships between the obtained values and VA contents were confirmed. Slightly higher VA contents on the surface deduced by XPS were attributed to a surface layer rich of amorphous phase material. In addition, XPS analysis of peroxide modified encapsulants with a VA comonomer content of 30.2 wt% revealed a higher carbon content on the surface after crosslinking. Hence, it is proposed that peroxide crosslinking is associated with deacetylation and the subsequent release of low molar mass decomposition products. Overall, the exceptional surface sensitivity of XPS was clearly confirmed for analysis and testing of EVA grades, highlighting the potential of the method for further degradation and interaction studies of components of PV modules.

Study of Heterogeneity of Ethylene/1-Octene Copolymers Synthesized with Zirconium and Titanium Complexes Bearing Diamine-bis(phenolate) Ligands.

A series of ethylene/1-octene copolymers synthesized with diamine-bis(phenolate) complexes activated with Al(iBu)3/[Ph3C][B(C6F5)4] were subjected to preparative temperature rising elution fractionation (TREF). The complexes used differed in the type of metallic center (Zr or Ti) or the amine donor in the pendant arm of the ligand (NMe2 or NiPr2). The obtained fractions were then characterized via FTIR, DSC and GPC methods. It was found that all the copolymers had very broad chemical composition distributions, and the most heterogeneous was the copolymer produced by the titanium complex bearing a ligand with the NiPr2 donor group. The difference in the comonomer incorporation into the macromolecules of the fractions was as high as 8.3 mol%. The melting temperature and molecular weight of the fractions changed nearly linearly with the increased elution temperature. Copolymers produced by zirconium catalysts were also fractionated by molecular weight using the solvent/non-solvent technique with subsequent analysis of the fractions. It was shown that the fractions have a similar composition, low molecular weight distribution and very broad comonomer distribution. Therefore, the comonomer content in the fractions was not a function of the molecular weight as was observed for the copolymers synthesized with the Ziegler-Natta catalysts.

Exploring microgel adsorption: synthesis, classification, and pollutant removal dynamics.

Microgels have gained significant importance for the removal of pollutants owing to their stimulus-responsive behavior, high stability, and reusable capacity. However, despite these advantages, several hurdles need to be overcome to fully maximize their potential as effective adsorbents for eradicating various contaminants from the environment, such as metallic cations, organic compounds, anions, harmful gases, and dyes. Therefore, a critical review on the adsorption of pollutants by microgels is needed. In this regard, this review presents the latest developments in the adsorptive properties of microgels. The synthetic methods, architectural structures, and stimulus-responsive behavior of microgels are explained in detail. In addition, this review explores various factors that directly influence the adsorption of pollutants by microgels, such as pH, feed composition, content of pollutants, content of comonomers, agitation time, temperature, microgel dose, nature of both adsorbates (pollutants) and adsorbents (microgels), nature of the medium, and ionic strength. Various adsorption isotherms are also explored together with the kinetic aspects of the adsorption process to provide a comprehensive understanding.

Синтез и сополимеризация бензамидметакрилата со стиролом

It has been synthesized a new monomer — benzamide methacrylate and its free radical copolymerization with styrene in mass and solution in benzene in the presence of diazoisobutyric acid AIBN) has been carried out and investigated. The ratio of comonomers was changed in the range of 90:10 – 10:90 mol. %. The total concentration of comonomers is 1.7 mol/l at temperature 70 °C. The composition of the synthesized copolymers was determined by the method of elemental analysis on nitrogen content. The monomer and copolymer have been characterized by spectroscopic methods (IR and NMR). The relative activity constant values of the monomer have been determined and Q – e parameters according to Alfrey – Price have been calculated. For estimation of the nature of the links distribution in the macromolecular chain, the microstructure parameters have been calculated. It has been revealed that in all cases r1 > r2, therefore the copolymer is enriched with benzamide methacrylate links. It has been found that the composition of the formed copolymers depends on the composition of the initial monomer mixture. It has been established that the obtained copolymer has a sufficiently high medical-biological activity, which opens up the possibility of using it as bactericides and fungicides. It has been shown that the copolymers obtained on the basis of benzamide methacrylate are non-toxic and can be used as bactericidal preparations. It has been revealed that the biocidal effect has been primarily connected with the availability of benzamide fragment links in the macro-chain.

Photophysical, thermal and imaging studies on vancomycin functional branched poly(N-isopropyl acrylamide) of differing degrees of branching containing nile red for detection of Gram-positive bacteria.

Highly branched poly(N-isopropyl acrylamide) additives chain end functionalised with vancomycin have been designed to agglutinate and report on targetted Gram-positive strains of bacteria (S. aureus). These branched systems selectively desolvate with temperature or binding interactions depending on their chain architecture. We have prepared samples with three different degrees of branching which have incorporated Nile red acrylate as a low concentration of co-monomer to report upon their solution properties. A linear analogue polymer functionalised with vancomycin along the chain instead of the termini is presented as a control which does not bind to targeted bacteria. These samples were analysed by diffusion NMR spectrometry (DOSY), calorimetry, fluorescence lifetime measurements, optical microscopy and scanning electron microscopy to gain a full understanding of their solution properties. The branched polymers are shown conclusively to have a core-shell structure, where the chain ends are expressed from the desolvated globule even above the lower critical solution temperature - as demonstrated by NMR measurements. The level of desolvation is critically dependent on the degree of branching, and as a result we have found intermediate structures provide optimal body temperature bacterial sensing as a consequence of the Nile red reporting dye.