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The microstructure of polyolefins determines their macroscopic properties. Consequently, it is essential to predict how polymerization conditions will affect polyolefin microstructure. The most important microstructural distributions of ethylene/alfa-olefin copolymers made with coordination catalysts are their molecular weight (MWD), chemical composition (CCD), and comonomer sequence length (CSLD). Several mathematical models have been developed to predict these microstructural distributions; reliable techniques to estimate parameters for these models, however, are still poorly developed, especially for catalysts that have multiple site types, such as heterogeneous Ziegler-Natta complexes. Most commercial polyolefins are made with heterogeneous Ziegler-Natta catalysts, which make polyolefins with broad MWD, CCD, and CSLD. This behavior is attributed to the presence of several active site types, leading to a final product that can be seen as a blend of polymers made on the different catalyst site types. The main objective of this project is to develop a methodology to estimate the most important parameters needed to describe the microstructure of ethylene/alfa-olefin copolymers made with these multiple site-type catalysts. To accomplish this objective, we developed the Integrated Deconvolution Estimation Model (IDEM). IDEM estimates ethylene/alf-olefin reactivity ratios for each site type in two-steps. In the first step, the copolymer MWD, measured by high-temperature gel permeation chromatography, is deconvoluted into several Flory’s most probable distributions to determine the number of site types and the weight fractions of copolymer made on each of them. In the second estimation step, the model uses the MWD deconvolution information to fit the copolymer triad distributions measured by 13C NMR and estimate the reactivity ratios per site type. This is the first time that MWD and triad distribution information is integrated to estimate the reactivity ratio per site type of multiple site-type catalysts used to make ethylene/alfa-olefin copolymers. IDEM was applied to two sets of ethylene-co-1-butene copolymers made with a commercial Ziegler-Natta catalyst, covering a wide range of 1-butene fractions. In the first set of samples (EBH), hydrogen was used as a chain transfer agent, whereas it was absent in the second set (EB). Comparison of the reactivity ratio estimates for the sets of samples permitted the quantification of the hydrogen effect on the reactivity ratios of the different site types present in the Ziegler-Natta catalyst used in this thesis. Since 13C NMR it is an essential analytical step in IDEM, triad distributions for the EB and EBH copolymers were measured in two different laboratories (Department of Chemistry at the University of Waterloo, and Dow Chemical Research Center at Freeport, Texas). IDEM was applied to both set of triad measurements to find out the effect of interlaboratory 13C NMR analysis on reactivity ratio estimation.

The microstructure of polyolefins determines their macroscopic properties. Consequently, it is essential to predict how polymerization conditions will affect polyolefin microstructure. The most important microstructural distributions of ethylene/alfa-olefin copolymers made with coordination catalysts are their molecular weight (MWD), chemical composition (CCD), and comonomer sequence length (CSLD). Several mathematical models have been developed to predict these microstructural distributions; reliable techniques to estimate parameters for these models, however, are still poorly developed, especially for catalysts that have multiple site types, such as heterogeneous Ziegler-Natta complexes. Most commercial polyolefins are made with heterogeneous Ziegler-Natta catalysts, which make polyolefins with broad MWD, CCD, and CSLD. This behavior is attributed to the presence of several active site types, leading to a final product that can be seen as a blend of polymers made on the different catalyst site types. The main objective of this project is to develop a methodology to estimate the most important parameters needed to describe the microstructure of ethylene/alfa-olefin copolymers made with these multiple site-type catalysts. To accomplish this objective, we developed the Integrated Deconvolution Estimation Model (IDEM). IDEM estimates ethylene/alf-olefin reactivity ratios for each site type in two-steps. In the first step, the copolymer MWD, measured by high-temperature gel permeation chromatography, is deconvoluted into several Flory’s most probable distributions to determine the number of site types and the weight fractions of copolymer made on each of them. In the second estimation step, the model uses the MWD deconvolution information to fit the copolymer triad distributions measured by 13C NMR and estimate the reactivity ratios per site type. This is the first time that MWD and triad distribution information is integrated to estimate the reactivity ratio per site type of multiple site-type catalysts used to make ethylene/alfa-olefin copolymers. IDEM was applied to two sets of ethylene-co-1-butene copolymers made with a commercial Ziegler-Natta catalyst, covering a wide range of 1-butene fractions. In the first set of samples (EBH), hydrogen was used as a chain transfer agent, whereas it was absent in the second set (EB). Comparison of the reactivity ratio estimates for the sets of samples permitted the quantification of the hydrogen effect on the reactivity ratios of the different site types present in the Ziegler-Natta catalyst used in this thesis. Since 13C NMR it is an essential analytical step in IDEM, triad distributions for the EB and EBH copolymers were measured in two different laboratories (Department of Chemistry at the University of Waterloo, and Dow Chemical Research Center at Freeport, Texas). IDEM was applied to both set of triad measurements to find out the effect of interlaboratory 13C NMR analysis on reactivity ratio estimation.

Darbo objektas – grynų eglynų pomiškis Lietuvos miškuose. Darbo tikslas – ištirti savaiminio žėlimo priklausomybę eglynuose nuo jų erdvinės struktūros. Darbo metodai : miškų inventorizacijos ir laikinų apskaitos aikštelių duomenų analizės, matematinės statistikos metodai. Darbo rezultatai. Remiantis miškų inventorizacijos bei laikinų apskaitos aikštelių duomenimis, išanalizuotas pomiškio kiekis eglynuose priklausomai nuo jų augavietės, amžiaus, skalsumo bei medyne susidariusių aikščių dydžio. Nustatyta, kad tik 20 % vyresnių nei 40 metų eglynų turi pomiškio. Didžiausias kiekis pomiškio rastas Ld ir Nb augavietėse (1,9 tūkst. vnt./ha). 4 – 12 amžiaus klasių eglynuose didėjant amžiui pastebimas nežymus pomiškio kiekio didėjimas. Ištyrus pomiškio kiekio priklausomybę nuo skalsumo nustatyta, kad skalsumui mažėjant, pomiškio kiekis didėja. Pomiškio kiekis priklausomai nuo aikštės dydžio svyruoja nuo 12 iki 17 tūkst. vnt./ha aikštės plotui didėjant nuo 2 iki 10 arų. / Work subject – Undergrowth of spruce stands in Lithuanian forests. Work objective – To estimate forest grows in itself of spatial structure in spruce stand. Work methods: Data analyses of forest inventory and temporary of free space in forest, mathematical statistics methods. Work results. Was made analyses of spruce undergrowth quantity in different forest site type, age, growing stock and free space size in forest. It was established that 20 % of older then 40 years spruce forests has undergrowth. The biggest amount of growth was found in Ld and Nb forest site types. When age is growing in 4 – 12 age class of spruce the undergrowth quantity is growing too. It is ascertain that undergrowth quantity is rise up when growing stock is felling down. Undergrowth quantity variations of 12 to 17 thous.units/ha when free space size in forest variation of 2 to 10 are.