Ordered polymers

The ordered polymer chains are consistently oriented perpendicularly to the radius of the spherulite. 

In acidic solutions, equiUbtium is achieved more slowly. Polymerization of smaller species appears to occur sequentially a given polymer species first increases in size and then disappears, presumably because of its inclusion in higher order polymers. Depolymerization of siUcate species appears to be rapid, because crystalline Na2Si02 and Na2H2Si04 8H2O yield equivalent distributions of siUcate species in water upon dissolution. 

Polymerization. Spills of chemicals that are monomers or low-order polymers can be polymerized by adding a catalyst. Compounds that may be treated by polymerization include aromatics, aHphatics, and other oxygenated monomers such as vinyl chloride and acrylonitrile [107-13-1]. 

Some immunoglobulins such as immune IgG exist only in the basic tetrameric structure, while others such as IgA and IgM can exist as higher order polymers of two, three (IgA), or five (IgM) tetrameric units (Figure 50-10). 

A perfectly ordered polymer composite by four-centre-type photopolymerization of a molecular complex 166... 

A PERFECTLY ORDERED POLYMER COMPOSITE BY FOUR-CENTRE-TYPE PHOTOPOLYMERIZATION OF A MOLECULAR COMPLEX... 

This is the first example of a topochemical reaction of a molecular complex of a perfectly ordered polymer composite. Complex 2,5-DSP-l OEt is also obtained by simple grinding of homocrystals 2,5-DSP and l OEt, as is observed for the pair of diolefinic compounds described on p. 166. 

The preparation of helically well-ordered polymers with stable screw-sense, which is able to be transmitted to newly formed polymer main-chains effectively, is highly desired for the development of new methodology for the synthesis of optically active helical polymers. An aromatizing polymerization of 1,2-diisocyanobenzenes is promoted by methylpalladium(II) complexes, producing poly(quinoxaline-2,3-diyl)s.146-148 The polymerization proceeds with successive insertion of the two isocyano groups of the diisocyanobenzene to the carbon palladium bond of... 

Stereochemistry Coordination Polymerization. Stereoisomerism is possible in the polymerization of alkenes and 1,3-dienes. Polymerization of a monosubstituted ethylene, such as propylene, yields polymers in which every other carbon in the polymer chain is a chiral center. The substituent on each chiral center can have either of two configurations. Two ordered polymer structures are possible — isotactic (XII and syndiotactic (XIII) — where the substituent R groups on... 

Mesomorphic forms characterized by conformationally ordered polymer chains packed in lattices with different kinds of lateral disorder have been described for various isotactic and syndiotactic polymers. For instance, for iPP,706 sPP,201 sPS,202 syndiotactic poly(p-methylstyrene) (sPPMS),203 and syndiotactic poly(m -methylstyrene),204 mesomorphic forms have been found. In all of these cases the X-ray fiber diffraction patterns show diffraction confined in well-defined layer lines, indicating order in the conformation of the chains, but broad reflections and diffuse haloes on the equator and on the other layer lines, indicating the presence of disorder in the arrangement of the chain axes as well as the absence of long-range lateral correlations between the chains. 

Scheme 17 Electropolymerization route to sequence-ordered polymers.

It should also be noted that ternary and higher order polymer-polymer interactions persist in the theta condition. In fact, the three-parameter theoretical treatment of flexible chains in the theta state shows that in real polymers with finite units, the theta point corresponds to the cancellation of effective binary interactions which include both two body and fundamentally repulsive three body terms [26]. This causes a shift of the theta point and an increase of the chain mean size, with respect to Eq. (2). However, the power-law dependence, Eq. (3), is still valid. The RG calculations in the theta (tricritical) state [26] show that size effect deviations from this law are only manifested in linear chains through logarithmic corrections, in agreement with the previous arguments sketched by de Gennes [16]. The presence of these corrections in the macroscopic properties of experimental samples of linear chains is very difficult to detect. 

Amorphous polymers with irregular bulky groups are seldom crystallizable, and unless special techniques are used even ordered polymers are seldom 100% crystalline. The combination of amorphous and crystalline structures varies with the structure of the polymer and the precise conditions that have been imposed on the material. For instance, rapid cooling often decreases the amount of crystallinity because there is not sufficient time to allow the long chains to organize themselves into more ordered structures. The reason linear ordered polymers fail to be almost totally crystalline is largely kinetic, resulting from an inability of... 

Clarity is typical for light passing through a homogeneous material, such as a crystalline-ordered polymer or completely amorphous polymer. Interference occurs when the light beam... 

When all of the double bonds in the polymer molecule have the same configuration, the result is two different ordered polymer structures—transtactic and cistactic. Figure 8-5 shows the structures of the completely cis and completely trans polymers of isoprene. The stereochemistry of these polymers is indicated in their names. For example, the trans polymer (IX) is named as trans-1,4-polyisoprene or poly( -l-methylbut-l-ene-l,4-diyl). The first name is the IUPAC-recommended trivial name the second name is the IUPAC structure-based (Sec. l-2c) [IUPAC, 1966, 1981, 1996],... 

The occurrence of stereoisomerism in polymers plays a major role in their practical utilization. There are very significant differences in the properties of unordered and ordered polymers as well as in the properties of ordered polymers of different types (cis versus trans, isotactic versus syndiotactic). The ordered polymers are dramactically different from the corresponding unordered structures in morphological and physical properties. 

Linear polymers prepared by step reaction polymerization, such as nylon 66, and linear, ordered polymers prepared by the chain polymerization of symmetrical vinylidene monomers, such as polyvinylidene chloride (PVDC), can usually be crystallized because of symmetry and secondary-bonding. Isotactic polymers, such as isotactic polypropylene (PP), usually crystallize as helices. 

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