synopsisPolyamideurethans of structures I and I1 were prepared by reacting N,N'-di-(6-hy-droxycaproy1)alkylenediamines and N-hydroxyalkyl-6hydroxycaproamide with hexa-met>hylene diisocyanate and 4,4'-diphenylmethane diisocyanate : I1where R1 is either a dimethylene or hexamethylene radical, and Rz is a hexamethylene or 4,4'-diphenylmethane radical. Polymers I and I1 were of a high degree of polymerization and crystallinity, had high enough melting points for practical use, and gave colorless tough flms both by dry and melt castings. The polymers from hexamethylene diisocyanate were much more crystalline and thermally more stable above the melting points than those from 4,4'-diphenylmethane diisocyanate. Polymerization conditions and characteristic properties of the resulting polymers were studied. a ECA = N-(2-Hydroxyethyl)-6-hydroxycaproamide; CED = N,N'-di-(6-hydroxy-caproy1)ethylenediamine; CHD = N,N'-di-(6-hydroxycaproyl)hexamethylenediamine; CLn = ccaprolactone; AcCN = acetonitrile. b By the method of Rose et al.l0

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.

Radical copolymerizations of β‐propiolactone (denoted 2) with acrylonitrile (denoted 1) and with styrene (also denoted 1) and the structures of the resulting copolymers were studied. The bulk copolymerization with acrylonitrile by α,α′‐azobisisobutyronitrile at 50°C gave polyesteracrylonitriles of high enough molecular weight to form tough and transparent films, with the monomer reactivity ratios, r1 = 0.84, r2 = 0.00, and the structure of the copolymers was magnified image Radical copolymerization with the same initiator in N,N‐dimethylformamide gave polyesteracrylonitriles of the same structure as that of the bulk polymer, blended with β‐propiolactone homopolymer which was due to the competing anionic homopolymerization of β‐propiolactone. The reactivity ratios on the bulk copolymerization with styrene were r1 = 6.2 and r2 = 0.0 with benzoyl peroxide at 80°C, and r1 ≅ 32, r2 = 0 with α,α′‐azobisisobutyronitrile at 50°C. Polyesterstyrenes of intrinsic viscosity up to 0.83 were obtained.

Anionic copolymerizations of acrylonitrile (monomer 1) with β‐propiolactone (monomer 2) and the structures of the resulting copolymers were studied. The copolymerization with sodium cyanide in N,N‐dimethylformamide gave copolymers of the structure I containing acid anhydride linkage in the molecular chains, with the monomer reactivity ratios, r1 = 1.20, r2 = 0.00. The copolymerization with potassium hydroxide gave either copolymers of the structure II (r1 = 0.00, r2 = 3.64 at 30°C; r1 = 0.00, r2 = 5.00 at 40°C) in N,N‐dimethylformamide or only β‐propiolactone homopolymer in toluene.

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