Ethene copolymer with propene

De Footer and co-workers [25] described a comprehensive C-NMR method for the analysis of composition in the most common commercial polyethylene copolymers. The method covers ethene copolymers with propene, also butene-1, hexene-1, octene-1, and 4-methyl pentene-1 in the composition range of 1-10 mol%. The chemical shift assignments and values of the resonances of the copolymers are presented... 

Water-soluble l,3-bis(di(hydroxyalkyl)phosphino)propane derivatives were thoroughly studied as components of Pd-catalysts for CO/ethene (or other a-olefins) copolymerization and for the terpolymerization of CO and ethene with various a-olefins in aqueous solution (Scheme 7.17) [59], The ligands with long hydroxyalkyl chains consistently gave catalysts with higher activity than sulfonated DPPP and this was even more expressed in copolymerization of CO with a-olefins other than ethene (e.g. propene or 1-hexene). Addition of anionic surfactants, such as dodecyl sulfate (potassium salt) resulted in about doubling the productivity of the CO/ethene copolymerization in a water/methanol (30/2) solvent (1.7 kg vs. 0.9 kg copolymer (g Pd)" h" under conditions of [59]) probably due to the concentration of the cationic Pd-catalyst at the interphase region or around the micelles which solubilize the reactants and products. Unfortunately under such conditions stable emulsions are formed which prevent the re-use... 

Butene is used in the plastics industry to make both homopolymers and copolymers. Polybutylene (1-polybutene), polymerized from 1-butene, is a plastic with high tensile strength and other mechanical properties that makes it a tough, strong plastic. High-density polyethylenes and linear low-density polyethylenes are produced through co-polymerization by incorporating butene as a comonomer with ethene. Similarly, butene is used with propene to produce different types of polypropylenes. 

At low temperatures the polymerization time to form one polymer chain is long enough to consume one monomer and add another. It thus becomes possible to synthesize block copolymers if the polymerization, especially catalyzed by hafnocenes, starts with propene and continues after the propene is nearly consumed with ethene. 

Very interesting transformations of the polyketones into other polymeric materials have been reported. An optically active isotactic poly[l-oxo-2-mefhylpro-pane-l,3-diyl] was reacted with methylenation reagents to give poly[l-methylene-2-methylpropane-l,3-diyl] ]143] apparently without racemization. A similar material was reduced to the corresponding poly[l-hydroxo-2-methylpropane-l,3-diyl] with 40% 1-diastereoselectivity using tetrabutylammonium borohydride [144]. Furthermore, ethene copolymers or efhene-propene terpolymers were transformed into... 

Synonyms EPM EPR EPR rubber Ethene, polymer with 1-propene Ethylene/propylene copolymer (INCI)... 

Because metallocene/MAO catalysts were found to be highly active polymerization catalysts not only for ethene and propene but also for longer chained 1-olefins, they are suitable for different copolymerizations. Copolymers with new microstructures... 

The ranges of the reactivity ratios obtained at the lowest [N]/[E] feed ratio are ri = 2.34-4.99 and r2 = 0.0-0.062. The r2 values are in general smaller than those obtained for propene copolymerization. The highest r x 2 values found for the copolymers prepared with catalyst 1-4 confirmed its tendency to give more random copolymers. The values of ri, r2, and ri x r2 for the E-N copolymers obtained with catalysts IV-1 and 1-5 are comparable with those of alternating ethene-propene copolymers with metallocene catalysts. The results of the second-order Markov model also showed that all rn values, as r, are similar to those found for ethene and propene copolymerization with metallocene catalysts with low reactivity ratios. Differences in ri2 and in r22 are illuminating, since they clearly show the preference of the insertion of ethene or norbomene into E-N-Mt (Mt = Metal) and N-N-Mt, respectively. Parameter ri2 increases in the order IV-1 < 1-5 I-l < 1-2, opposite to the tendency to alternate the two comonomers [88]. 

Complex 2 conducted random copolymerization of norbomene with ethene or propene in high activity combined with a suitable cocatalyst, and copolymers with narrow molecular weight distribution were obtained with dMAO [35-37]. There are many catalysts that can conduct copolymerization of ethene and norbomene [38] but very few for copolymerization of norbomene or its derivatives with 1-alkene [39-43]. We conducted copolymerization of norbomene with propene or 1-octene with 2-5 activated by dMMAO (Table 4) [44]. 

For the polymerization of vinylic monomers with a Si-O-Si linkage, only few reports can be found. Trimethylsilyloxydimethylvinylsilane is reported not to afford a copolymer with a metallocene and ethene due to the deactivation of the aaive spedes. A rdated report concerns a direct copolymetization of propene and ethene with the monovinyl-functional silsesquioxane 16 as Si-O-Si-containing comonomer by Tsuchida et For this purpose, a silsesquiox-ane with a polymerizable unsaturated chain end and different MAO-artivated metallocenes (Figure 13) was used. 

Un-OH can also be copolymetized with propene on a MAO-pretreated glass surface by Et(Ind)2ZrCl2. Parts of the resulting copolymer are chemically bonded to the surface, as shown by extraction experiments, scanning electron microscopy (SEM) microscopy as well as Fourier transformation infrared spectroscopy (FUR) analysis. Similar results were reported for the copolymerization of ethene with Un-OH by the same catalyst system on the organically modified silicate montmorillonite (OMMT) resulting in PE-Un-OH/OMMT nanocomposites which consist of well-exfoliated OMMT dispersions and controlled degrees of PE functionalization. ... 

Poly(methyl methacrylate -block-t-butylaziridine) ABA type copolymer with MW 12000 butylaziridine (B) and MW 16000 Ambient to 600 CO, CH4, CO2, ethene, propene, isobutene, aziridine, methanol, methyl methacrylate, cc-methylstyrene, 2-phenyl-2-butene, 1 -t-butylamino-2-isopropenylamino-ethane, 2-r-butylaminoethyl-ethyl-isopropenylamine, 2-aminoethyl-2-r-butylaminoethyl-isopropenylamine, oligomers - principally butylaziridine based 287... 

Poly(ethylene-co-propylene-tf)- 5-methylene-2-norbomene) Ethylene-ethylidenebicycloheptene-propene copolymer ethylene— ethylidenenorbomene-propylene polymer 25038-36-2 Bicyclo(2.2. 1 )hept-2-ene, 5-ethylidene-, polymer with ethene and 1-propene R (C9H12 -t-iHa C2H4>4... 

The C-NMR spectroscopic characterisation of propene homopolymers and copolymers with low amounts of [l- C]-ethene obtained with the above catalysts allowed Busico and co-workers [18, 21] to prove that this type of (predominantly) syndiotactic chain propagation proceeds via 1,2 (primary) propene insertion (as already known for the isotactic propagation), under the steric control of the monomeric unit added last. 

The water-soluble palladium complex prepared from [Pd(MeCN)4](Bp4)2 and tetrasulfonated DPPP (34, n=3, m=0) catalyzed the copolymerization of CO and ethene in neutral aqueous solutions with much lower activity [21 g copolymer (g Pd) h ] [53] than the organosoluble analogue in methanol. Addition of strong Brpnsted acids with weakly coordinating anions substantially accelerated the reaction, and with a catalyst obtained from the same ligand and from [Pd(OTs)2(MeCN)2] but in the presence of p-toluenesulfonic acid (TsOH) 4 kg copolymer was produced per g Pd in one hour [54-56] (Scheme 7.16). Other tetrasulfonated diphosphines (34, n=2, 4 or 5, m=0) were also tried in place of the DPPP derivative, but only the sulfonated DPPB (n=4) gave a catalyst with considerably higher activity [56], Albeit with lower productivity, these Pd-complexes also catalyze the CO/ethene/propene terpolymerization. 

Polymerization of propene by the Ziegler process gives a very useful plastic material. It can be made into durable fibers or molded into a variety of shapes. Copolymers (polymers with more than one kind of monomer unit in the polymer chains) of ethene and propene made by the Ziegler process have highly desirable rubberlike properties and are potentially the cheapest useful elastomers... 

Although both linear polyethene and isotactic polypropene are crystalline polymers, ethene-propene copolymers prepared with the aid of Ziegler catalysts are excellent elastomers. Apparently, a more or less random introduction of methyl groups along a polyethene chain reduces the crystallinity sufficiently drastically to lead to an amorphous polymer. The ethene-propene copolymer is an inexpensive elastomer, but having no double bonds, is not capable of vulcanization. Polymerization of ethene and propene in the presence of a small amount of dicyclopentadiene or 1,4-hexadiene gives an unsaturated heteropolymer, which can be vulcanized with sulfur in the usual way. 

Of great industrial interest are the copolymers of ethene and propene with a molar ratio of 1/0.5, up to 1/2. These EP-polymers show elastic properties and, together with 2-5 wt% of dienes as third monomers, they are used as elastomers (EPDM). Since they have no double bonds in the backbone of the polymer, they are less sensitive to oxidation reactions. As dienes, ethylidenenorbomene, 1,4-hexadiene, and dicyclopentadiene are used. In most technical processes for the production of EP and EPDM rubber in the past, soluble or highly disposed vanadium components are used [69]. Similar elastomers can be obtained with metallocene/MAO catalysts by a much higher activity which are less colored [70-72]. The regiospecificity of the metallocene catalysts toward propene leads exclusively to the formation of head-to-tail enchainments. The ethylidenenor-bornene polymerizes via vinyl polymerization of the cyclic double bond and the tendency to branching is low. The molecular weight distribution of about 2 is narrow [73]. 

The excellent performance of metallocenes in copolymerizations also offer improvements in impact copolymers. In the wide variety of properties of impact copolymers, the stiffness of the material is determined by the matrix material, while the impact resistance largely depends on the elastomeric phase. While conventional catalysts show some inhomogeneities in the ethene/propene rubber phase due to crystalline ethene rich sequences, the more homogenous comonomer distribution obtained with metallocene catalysts results in a totally amorphous phase [153]. 

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