Propylene-co-1-butene

Figure 6.1.22. Pyrogram of poly(propylene-co-1-butene) 14 % wt. butene. Pyrolysis done on 0.4 mg material at 60Cf C in He, with the separation on a Carbowax type column.

Poly (propylene-co-1-butene). See Propylene/butene copolymer Poly (propylene-co-ethylene). See Propylene/ethylene copolymer Poly (propylene-co-1-hexene). See Propylene/hexene copolymer Polypropylene/dibromostyrene copolymer CAS 137370-67-3... 

Textiles Polypropylene and propylene-co-1-butene France 1,516,084 1968 Eastman Kodak... 

Al-paper laminates Polypropylene, poly(propylene-co-1-butene), poly(propylene-co-pentene) and polybutene United States 3,433,777 1969 Eastman Kodak ... 

Furthermore, treatment of the aminopalladation product with bromine affords aziridines[176]. The aziridine 160 was obtained stereoselectively from methylamine and 1-decene in 43% yield. The aminopalladation of PdCl2 complexes of ethylene, propylene, and 1-butene with diethylamine affords the unstable ir-alkylpalladium complex 161, which is converted into the stable chelated acylpalladium complex 162 by treatment with CO[177],... 

We have studied the alkane and alkene yields from the radiolysis of copolymers of ethylene with small amounts of propylene, butene and hexene. These are examples of linear low density polyethenes (LLDPE) and models for LDPE. Alkanes from Ct to C6 are readily observed after irradiation of all the polymers in vacuum. The distribution of alkanes shows a maximum corresponding to elimination of the short-chain branch. This is illustrated in Figure 8 for the irradiation of poly (ethylene-co-1-butene) containing 0.5 branches per 1,000 carbon atoms at 20 C. 

Tacticity measurements can be correlated with reaction mechanisms and physical properties. For example, the incorporation of an electron donor into the polymerization catalyst formulation has been found to increase isotacticity in a propylene-1-butene copolymer [123], and the distribution of propylene and 1-butene contents as a function of molecular weight varied, depending on donor type. External donors, such as dimethox-ysilane, decrease the butene content more than internal electron donors (in this case, di-n-butyl phthalate). Mechanisms of new polymerization reactions, such as the group-transfer copolymerization of methyl methacrylate and lauryl methacrylate, can be elucidated by comparing NMR-derived structural details [124]. The presence of unanticipated peaks in the spectrum of poly(ethylene-co-norbomene) suggest the occurrence of epimerization... 

Blends of isotactic propylene-co-ethylene (EP, 3-4.6 mol% ethylene) and propylene-co-l-butene (BP, 7.6 mol% 1-butene) random copolymers were studied by Bartczak et al. [66,67]. The authors investigated the effect of type, content, and distribution of comonomer units on the miscibility of the components, the crystallization behavior, morphology, and thermal and mechanical properties. 

UNIPOL [Union Carbide Polymerization] A process for polymerizing ethylene to polyethylene, and propylene to polypropylene. It is a low-pressure, gas-phase, fluidized-bed process, in contrast to the Ziegler-Natta process, which is conducted in the liquid phase. The catalyst powder is continuously added to the bed and the granular product is continuously withdrawn. A co-monomer such as 1-butene is normally used. The polyethylene process was developed by F. J. Karol and his colleagues at Union Carbide Corporation the polypropylene process was developed jointly with the Shell Chemical Company. The development of the ethylene process started in the mid 1960s, the propylene process was first commercialized in 1983. It is currently used under license by 75 producers in 26 countries, in a total of 96 reactors with a combined capacity of over 12 million tonnes/y. It is now available through Univation, the joint licensing subsidiary of Union Carbide and Exxon Chemical. A supported metallocene catalyst is used today. 

Preferred olefins in the polymerisation are one or more of ethylene, propylene, 1-butene, 2-butene, 1-hexene, 1-octene, 1-pentene, 1-tetradecene, norbornene and cyclopentene, with ethylene, propylene and cyclopentene. Other monomers that may be used with these catalysts (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO) and vinyl ketones of the general formula H2C=CHC(0)R. Carbon monoxide forms alternating copolymers with the various olefins and cycloolefins. 

Fig. 9. Experimental (a and b) and simulated (c and d) partial pressure oscillations for the CO/02/propylene reaction (a and c), and the CO/O2/1-butene reaction (b and d), both over Pt. The simulated curves are obtained by an elementary-step model. (From Ref. 207.)...

Two examples of propylene copolymers pyrolysis are given below. The first example is for poly(propyiene-co-l-butene) 14 % wt. butene, CAS 29160-13-2. The pyrogram is shown in Figure 6.1.22. The pyrolysis was done at 600° C in He with separation on a Carbowax column and MS detection, similarly to other polymers previously discussed in this book (see also Table 4.2.2). 

CO, CH4, CO2, acetone, ketene. ethene. propene. 1-butene, benzene, toluene, xylene, cydopentene, methyl ethyl ketone, diethyl ketone, methyl-n-propyl ketone, di-n-propyl ketone, methyl vinyl ketone, methyl Isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone, trace amounts of methyl-n-bulyl ketone, cyclopentanone, cydohexanone. acrolein, ethanal. butanal. chain fragments, some monomer CO. CH4, COj, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl n-propyl ketone, 1,4-cyclohexadiene. toluene, l-methy. l.3-cydohexadlene, 2-hexanone, cydopentene, 1-methyl cydopentene. mesityl oxide, xylenes, benzene, ethene, cyclopentanone, 1.3-cyclopentad iene, diethyl ketone, short chain fragments, traces of monomer CO, CH4, COi, ketene, 1-butene, propene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl-n-propyl ketone, diethyl ketone, methyl propenyl ketone, 3-hexanone. toluene, 2-hexanone. 1,3-cydopentadiene, cyclopentanone, 2-melhylcydopenlanone, mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde ethene, short chain fragments, traces of monomer CO, COj, H2O, CH4. acetone, ketene, ethene, propylene, 1-butene, methyl vinyl ketone, benzene, acrylic add, toluene, xylene, short chain fragments such as dimer to octamer with unsaturated and anhydride functionalities... 

Ethylene has been co-polymerized with virtually any conceivable a-olefin, from propylene to vinyl-terminated PE and PP macromonomers. Ethylene/propylene (E/P) copolymerization to produce saturated rubbers and ethylene/propylene/diene (EPD) terpolymerization to produce unsaturated, vulcanizable rubbers will be discussed in Section 4.09.4.1.3. 1-Butene, 1-hexene, and 1-octene are the most commonly used co-monomers for the production of LLDPE. Ethylene/octene co-polymers, developed by Dow and marketed under the Engage tradename, have been shown to have improved thermal properties compared to ethylene/butene and ethylene/hexene co-polymers.503 In ethylene/a-olefin (E/O) co-polymeriza-tions, the critical parameters are co-monomer reactivity and co-monomer distribution . The former is most conveniently described by the relative reactivity parameter, R, defined as the ratio between polymer composition and reactor medium composition. 

Figure 20 Glass transition temperature (Tg) for ethylene/a-olefin co-polymers in the range 0 mol%< ethylene <100 mol%.454 504,507 515. O propylene 1-butene <> 1-hexene 1-octene.

Introduction of CO + (760 Torr) in a molar ratio 2 1 in the glass equipment was followed by a stepwise increase of temperature from 25 up to 200°C. Analysis of the gas phase gave the results represented on Figure la. At 176°C the conversion of CO to hydrocarbons is close to 1 % with mainly propylene (32%), methane (26,1 %) ethylene (9,2 %), 1-butene (7,3 %), cis-2-butene (3,6 %), trans-2-butene (5,5 %), isobutene (1 %) and C, hydrocarbons (7 %). All the paraffins except methane are present in much smaller amount than olefins. Figure (lb) represents typical results obtained in Fischer-Tropsch synthesis in a dynamic reactor using a catalyst derived from Fe CO) jj/A Oj (3e). 

In addition to propylene, other nonconjugated olefins have been copolymerized with CO using enantiopure palladium catalysts. Allylbenzene, 1-butene, 1-heptene, 4-methyl-l-pentene, and cis-2-butene [84,85] as well as hydroxy- and carboxylic acid-functionalized monomers [87] have been polymerized to give optically active polymers. Waymouth, Takaya and Nozaki have recently reported the enantioselective cyclocopolymerization of 1,5-hexadiene and CO [88,89]. 

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