The effect of short-chain branching (SCB) on the persistence length l p of polyethylene (PE) was studied using small-angle neutron scattering (SANS). In thermodynamically good solvents, l p can be measured directly from the scattering vector q tr at the crossover from good solvent mass-fractal scaling to the rodlike persistent scaling, using the unified equation described in the text. The method was used to study l p of both linear and branched PE in deuterated p-xylene, which is a good solvent for PE at 125 °C. The results indicate an increase in l p of the backbone chain with increasing SCB content, independently measured using Fourier transform infrared spectroscopy (FTIR). These results corroborate the behavior previously reported in Monte Carlo simulations of short-chain branched polymers. A functional relationship for l p in terms of the number of SCBs is proposed.

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Small-angle neutron scattering (SANS) is employed to investigate the structure and longchain branch (LCB) content of metallocene-catalyzed polyethylene (PE). A novel scaling approach is applied to SANS data to determine the mole fraction branch content (φ br ) of LCBs in PE. The approach also provides the average number of branch sites per chain (n br ) and the average number of branch sites per minimum path (n br,p ). These results yield the average branch length (z br ) and number of inner segments n i , giving further insight into the chain architecture. The approach elucidates the relationship between the structure and rheological properties of branched polymers. This SANS method is the sole analytic measure of branch-onbranch structure and average branch length for topologically complex macromolecules.

ABSTRACT:The bulk properties of two types of amphiphilic networks, poly(2-hydroxyethyl methacrylate)-l-polyisobutylene (PHEMA-l-PIB, H-network) and poly( N,N-dimethylacrylamide)-l-polyisobutylene (PDMAAm-l-PIB, A-network), have been investigated. Tensile strengths decreased considerably by swelling, and the decrease was more severe by swelling in water than in n-heptane. Elongations increased by swelling in water; however, the change was not consistent upon swelling in n-heptane. The hardness of dry networks decreased with increasing PIB content, while for wet networks it was similar to dry networks containing 85 wt % PIB. Small-angle X-ray scattering showed that average interdomain spacings decreased with increasing PIB content. According to dynamic mechanical thermal analysis (DMTA) the glass transition temperatures (T g ) of the respective hydrophobic and hydrophilic components shift toward each other with increasing PIB content. A ''liquid-liquid transition'' ( T ll ) above the T g of the hydrophilic component was apparent by DMTA, but could not be found by differential scanning calorimetry (DSC).