Lichtstreuungs-und Viskositatsmessungen von PE-HD-Fraktionen in n-Dekan wurden durchgefuhrt. Aus der Molmassenabhangigkeit des Tragbeitsradius wird auf eine Kontraktion der PE-HD-Molekule geschlossen. Die expzrimentelle Streufunktion hochmolekularer Fraktionen entspricht der von kugelformigen Partikeln. Die lg [q]-lg Mm-Kurve ist nicht linear. Mit zunehmender Molmasse und abnehmender Temperatur verlauft sie flacher. Rayvenue npoyeccoe paaeememnu yennwx a m e q n . X l i l . Rtwepeiiue csemopacce~nu~ u eaaxocmu e pacmeopax $paiEyuii D E ebzcomzo daedenu npu paa~curcnbcx medmepamypax IIposegeHu n s~e p e~v r s cseTopaccerrHaa H B~K O C T H pacTBopoB @paKqHl II3 BucoKoro n a m e m a B H-neKaHe. llcxonrr ~3 3aBHCHMOCTH papiyca mepqnn OT MoneKympHoB Macm AeaaeTcR aaKnmeHHe o Haammi KompaKqtlu c@epmecmx racmq. K p m a s ~~B H C H M O C T H lg[q] OT lgMw O K~B M B~~T C H HenmieiHol, T. e. I I~O X O J~~T MeHee KPYTO c y6entrrerraeM MoneKynapziol Macczd m npx noHkImeHm TeMnepaTypH.Investigations on the branching of chain molecules. X I I I . Light scattering and viscosity measurements with PE-HD fractions at different temperatures Light scattering and viscosity measurements with PE-HD fractions in n-decane were carried out. Based on the dependence of the radius of gyration on the molecular weight the PE-HD molecules are suggested to contract. The experimental scatte$ng function of the high molecular weight fraction corresponds to that of spherical particles.The lg [ql-lg Nw relationship shows no linearity but increases less with rising molecular weight and decreasing temperature.MOJIeHyJr n3. aKCIlepHMeHTaJIbHaf3 @YHKqHFI AHClIepCHO~TH BHCOKOMOJIeKyJlHpHHX @paKqHa COOTBeTCTByeT TaKOft
Eine Analyse von Literaturdaten zeigt, da13 die Molekulkontraktion, die als MeBgroSe zur Bestimmung von Langkettenverzweigungen dient, u. a. auch vom thermodynamischen Losungszustand abhangig ist. Bus der Untersuchung dcs Losungszustandes von verzweigtem und linearem Polyethylen ergibt sich, daR bci Annaherung an die Ausfalltemperatur Molekulaggregate gebildet werden. Nayvenue npoyeccoe o p a 3 s e m s~e n u~ yennaax MoJtemjA. X I I . Cocmosnue qenmzx &onemjn s paernsope u ux xonmpaxyus h I E IIOKa3bIBaeT aHaJIH3 JlHTepaTypHMX AaHHbIX, KOHTpaHqHR IJeIIHbIX MOJIeKyJI, CJlyHtauaH BeJIHqHHOt npH OIIpeAeJIeHHR AJ'IHHOqelIO~HbIX pa3BeTBJIeHH#, 3PBHCHT TaKHte OT TepMOAHHaMAqeCHOI' O COCTORHHX MOJIeKyJI B paCTBOpe. npH H3Y9eHEiH COCTORHHH MOJIeKyJI Pa3BeTBJIeHHOI' O H JIHHetHOrO nOJIH3THJleHa B PaCTBOpe yCTaHOBJIeH0 06paao-Bame arperaToB MoJreKyn no Mepe ~~H~J I H H~~H H R K TeMnepaType BMcawcAeHm.Znvestigations on the branching of chain molecules. X II. State of dissolution and molecular contraction By literature data the molecular contraction, being a measure of long chain branching, was proved to depend on tlic thermodynamic state of dissolution. By investigations on the state of dissolution of branched and linear polyethylene, molecule aggregates were found to be formed on approximating the precipitation temperature.
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