Catalyst isotactic

The position of the monomer is a schematic representation of relative isotactic polymerization activity of the monomer by the catalysts. Isotactic steric control is found only in a narrow range of cationidty of vinylether catalysts. Atactic polymer is produced toward the more ionic side and no polymer toward the less ionic range. 

Fig, 51. Super active 3rd generation catalyst Isotactic index vs. polymerization time. Polymerization in hexane at 70 °C and 7 bar... 

In the 1980s, fourth-generation high yield, high selectivity (HY/HS) catalysts (30 000kg-PP per kg-catalyst, isotactic index 95-99%) provided a real breakthrough in process simplification, eliminating the need for catalyst and atactic removal. 

Since the discovery of Ziegler-Natta catalyst, isotactic polypropylene has been widely used as a commodity material due to its low cost and excellent physical properties. As the modulus of the resin is closely related to isotacticity, an understanding in polymerization mechanism is important in the chemistry of propylene polymerization as well as in the industry. 

Tacticity (stereoregularity) % Coordination polymerization, cadmium thiolate catalyst Isotactic 90-100 meso dyads (6, 9-11)... 

Generation Composition Productivity, kg of PP/g of catalyst Isotactic index Morphology control Process requirements... 

Of course, catalyst structure is very important for highly isoselective polymerization. However, tacticity of polyolefins depends not only on catalyst structures but also on co-catalysts, reaction conditions such as temperature, monomer concentrations and Al/metal ratios. For example, in the case of a certain catalyst, isotacticity of polymers can strongly depend on the temperature for pre-mixing MAO and a catalyst precursor. The effect of reaction pressure up to 1500 MPa was also reported in hexene polymerization [49]. 

When propene is polymerized under free radical conditions the polypropylene that results IS atactic Catalysts of the Ziegler-Natta type however permit the preparation of either isotactic or syndiotactic polypropylene We see here an example of how proper choice of experimental conditions can affect the stereochemical course of a chemical reaction to the extent that entirely new materials with unique properties result... 

Figure 7.10 shows the 60-MHz spectra of poly (methyl methacrylate) prepared with different catalysts so that predominately isotactic, syndiotactic, and atactic products are formed. The three spectra in Fig. 7.10 are identified in terms of this predominant character. It is apparent that the spectra are quite different, especially in the range of 5 values between about 1 and 2 ppm. Since the atactic polymer has the least regular structure, we concentrate on the other two to make the assignment of the spectral features to the various protons. 

Tacticity of products. Most solid catalysts produce isotactic products. This is probably because of the highly orienting effect of the solid surface, as noted in item (1). The preferred isotactic configuration produced at these surfaces is largely governed by steric and electrostatic interactions between the monomer and the ligands of the transition metal. Syndiotacticity is mostly produced by soluble catalysts. Syndiotactic polymerizations are carried out at low temperatures, and even the catalyst must be prepared at low temperatures otherwise specificity is lost. With polar monomers syndiotacticity is also promoted by polar reaction media. Apparently the polar solvent molecules compete with monomer for coordination sites, and thus indicate more loosely coordinated reactive species. 

After the discovery of isotactic polymerisation of propylene using shconocene catalysts, stmcturaHy analogous hafnium catalysts produced from hafnium tetrachloride [13499-05-3] were found to produce high yields of high molecular weight polypropylene (55), but not enough to lead to commercial development. 

Syndiotactic polypropylene has an ultimate melting point of 174°C, and extrapolated heat of fusion of 105 J/g (25.1 cal/g) both lower than those of isotactic polymer. The heat of fusion of the polymer produced using a metallocene catalyst is reported as 79 J/g (19 cal/g) (41). 

In the early 1950s, Ziegler observed that certain heterogeneous catalysts based on transition metals polymerized ethylene to a linear, high density material at modest pressures and temperatures. Natta showed that these catalysts also could produce highly stereospecific poly-a-olefins, notably isotactic polypropylene, and polydienes. They shared the 1963 Nobel Prize in chemistry for their work. 

Modem catalysts produce a much higher percentage of isotactic polypropylene than ia the past, eliminating the need for a cosdy extraction step to remove an atactic fraction. Yields ate high enough (>10,000 g polymer/g catalyst) so that a catalyst removal (de-ashing) step is no longer requited. 

This conceptual link extends to surfaces that are not so obviously similar in stmcture to molecular species. For example, the early Ziegler catalysts for polymerization of propylene were a-TiCl. Today, supported Ti complexes are used instead (26,57). These catalysts are selective for stereospecific polymerization, giving high yields of isotactic polypropylene from propylene. The catalytic sites are beheved to be located at the edges of TiCl crystals. The surface stmctures have been inferred to incorporate anion vacancies that is, sites where CL ions are not present and where TL" ions are exposed (66). These cations exist in octahedral surroundings, The polymerization has been explained by a mechanism whereby the growing polymer chain and an adsorbed propylene bonded cis to it on the surface undergo an insertion reaction (67). In this respect, there is no essential difference between the explanation of the surface catalyzed polymerization and that catalyzed in solution. 

Polymerization. Supported catalysts are used extensively in olefin polymerization, primarily to manufacture polyethylene and polypropylene. Because propylene can polymerize in a stereoregular manner to produce an isotactic, or crystalline, polymer as well as an atactic, or amorphous, polymer and ethylene caimot, there are large differences in the catalysts used to manufacture polyethylene and polypropylene (see Olefin polymers). 

Polypropylene. There is an added dimension to the catalytic polymerization of propylene, since in addition to the requirement that the catalyst be sufficiently active to allow minute amounts of catalyst to yield large quantities of polymer, it must also give predominantly polypropylene with high tacticity that is, a highly ordered molecular stmcture with high crystallinity. The three stmctures for polypropylene are the isotactic, syndiotactic, and atactic forms (90) (see Olefin polya rs, polypropylene). 

The syndiotactic polymer configuration is not obtained in pure form from polymerizations carried out above 20°C and, thus has not been a serious concern to most propylene polymerization catalyst designers. Eor most commercial appHcations of polypropylene, a resin with 96+% isotacticity is desired. Carbon-13 nmr can be used to estimate the isotactic fraction in a polypropylene sample. Another common analytical method is to dissolve the sample in boiling xylene and measure the amount of isotactic polymer that precipitates on cooling. 

Erom 1955—1975, the Ziegler-Natta catalyst (91), which is titanium trichloride used in combination with diethylaluminum chloride, was the catalyst system for propylene polymerization. However, its low activity, which is less than 1000 g polymer/g catalyst in most cases, and low selectivity (ca 90% to isotactic polymer) required polypropylene manufacturers to purify the reactor product by washing out spent catalyst residues and removing unwanted atactic polymer by solvent extraction. These operations added significantly to the cost of pre-1980 polypropylene. 

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