SynopsisAlternating polyamide esters of structures A and B were obtained by melt polymerization of dimethyl adipate and terephthalate or by solution polymerization of adipoyl and terephthaloyl chlorides, with N,N'-di(6-hydroxycaproy1)diamines and an N-6-hydroxycaproyl aminoalcohol:where R1 is selected from dimethylene, hexamethylene, and p-phenylene radicals, and Rz is selected from tetramethylene or p-phenyl radical. Polyamide esters of structure A' were also prepared:Average values of melting points of the resulting polyamide esters were dependent on the starting diacid derivatives, amide diols, and methods of polymerizations as follows:where CPZ, CHD, CED, and CPPD are N,N'-di(6-hydroxycaproy1)-, each in this order: piperazine, hexamethylenediamine, ethylenediamine, and p-phenylenediamine. ECA is N-(2-hydroxyethyl)6-hydroxycaproamide. For a given polyamide ester obtained from the same starting materials and by the same method of polymerization, the melting points increased with inherent viscosities. Polyamide esters of high molecular weight were obtained from CHD with both adipic and terepbthalic derivatives both by melt and solution polymerizations. the other amide diols gave lower molecular weights. Solution polymerization gave colorless or light-colored polymers, while melt polymerization gave deeper-colored polymers.

Several ionene bromides were used as reagents for the displacement of decyl methanesulfonate into 1-bromodecane. They were very reactive when adsorbed by silica gel. The enhanced activities of the ionenes were hardly dependent on their structures and molecular weights but decreased gradually with increasing the amount of ionene adsorbed by silica gel. Ionene chlorides exhibited a similar enhancement of reactivity when adsorbed by silica gel. However, unlike the ionenes, a large increase in activity due to adsorption was not observed with pendant-type polycations such as poly(4-vinylpyridinium bromide) and poly[(4-vinylbenzyl)tributylammonium chloride]. The silica gel-supported ionenes also exhibited excellent catalytic activities for solid–liquid–solid triphase substitution reactions, particularly for the reactions between 1-bromodecane and such inorganic salts as consisted of relatively hard-basic nucleophilic anions.

Table 1. Quaternary salts prepared from poly (p-chloromethylstyrene) and various tertiary amines.

No abstract

SynopsisThree series of block copolymers, namely, polystyrenecaproamide (I), polystyrenehexamethyleneadipamide (II), and poly(styreneethy1ene terephthalate) (III), were prepared, and the properties of the copolymers in relation to the block sequence lengths and the compositions were studied. Styrene was polymerized in the presence of aluminum chloride and thionyl chloride to give w,w'dichloropolystyrenes of various degrees of polymerization from 12.0 to 51.0, which were either ammonolyzed to w,w'-diaminopolystyrene or hydrolyzed to w,w'-dihydroxypolystyrene. w,w'-Diaminopolystyre was treated with adipic acid to give the corresponding salts, namely, w,w'-diammoniumpolystyrene adipate, which was melt-polymerized either with c-amino-n-caproic acid to give polystyrenecaproamide (I) or with hexamethylenediammonium adipate to give polystyrenehexamethyleneadipamide (11). w,w'-Dihydroxypolystyrene was melt-polymerized with dimethyl terephthalate and ethylene glycol to give,poly(styreneethylene terephthalate) (111). All the block copolymers were of high enough molecular weight to be cast or spun into films or filaments. Upon polymerization, the increase of the block sequence of PSt units increased the amide content but decreased the ester content of the resulting copolymers. Also, an increase in n decreased the inherent viscosities of the copolymers at a constant monomer feed f c counted by the polymer equivalent of PSt but increased the inherent viscosities at a constant monomer feed rc counted by the monomer equivalent of PSt. The melting points of the copolymers decreased with increasing n values. Also, an increase in n decreased the densities of I and 111 but increased the density of I1 at a constant amide or ester composition F, counted by polymer units but increased the densities of I, 11, and 111 at a constant amide or ester composition R , counted by the monomer unit.