The present invention describes a prepolymer of an aliphatic polyoxaester having a polymerizable end group that may be used to produce hydrogels, surgical devices such as sutures, sutures with attached needles, molded devices, and the like.

Copolymers of absorbable polyoxaesters

The synthesis and properties of a number of very strong iminophosphorane bases up to an extremely high level of steric hindrance are described. They cover a range of ca. 4 pK units in basicity and a range of more than 11 orders of magnitude in their rates of methylation with methyl iodide. Most of the systems are readily prepared in up to molar quantities, conveniently recovered from their salts and are of high chemical and thermal stability. Crystal structures were determined in order to parametrize a force field, which is utilized in molecular modeling studies offering a rationalization of the observed differences in steric hindrance and basicity. Depending on the degree of steric protection of the basic center, these novel bases are proposed as unprecedented, versatile auxiliary bases in E2 eliminations and in reactions involving deprotonation in the presence of more or less strong electrophiles.

Novel, Very Strong, Uncharged Auxiliary Bases; Design and Synthesis of Monomeric and Polymer‐Bound Triaminoiminophosphorane Bases of Broadly Varied Steric Demand

The present invention describes a polyoxaester copolymers containing amines and/or amido groups and blends thereof with other polymers that may be used to produce surgical devices such as sutures, sutures with attached needles, molded devices, and the like. The polyoxaesters copolymer of the present invention is formed from a first divalent repeating unit of formula IA: [--C(O)--R.sub.30 --C(O)--] IA a second divalent repeating unit of the formula IB: [O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)-- ]I and a third repeating unit of the formula: [--O--R.sub.12 --].sub.U, XVI and optionally a fourth repeating unit with a formula selected from the group consisting of: [--O--R.sub.4 --].sub.A, II [--O--R.sub.5 --C(O)--].sub.B, III ([--O--R.sub.5 --C(O)].sub.P --O--).sub.L G XI and combinations thereof wherein R 12 contains an internal amine or internal amide group.

Absorbable polyoxaesters containing amines and/ or amido groups

The present invention describes a crosslinked aliphatic polyoxaesters containing amines and/or amido groups and blends thereof with other polymers that may be used to produce surgical devices such as sutures, sutures with attached needles, molded devices, and the like. The crosslinked aliphatic polyoxaesters of the present invention is formed from an aliphatic polyoxaester having a first divalent repeating unit of formula I: O--C(O)--C(R.sub.1)(R.sub.2)--O--(R.sub.3)--O--C(R.sub.1)(R.sub.2)--C(O)-- !I and a second repeating unit of the formula: --O--R.sub.12 --!.sub.U, XVI and optionally a third repeating unit with a formula selected from the group consisting of: --O--R.sub.4 --!.sub.A, II --O--R.sub.5 --C(O)--!.sub.B, III ( --O--R.sub.5 --C(O)!.sub.P --O--).sub.L G XI and combinations thereof wherein R 12 contains an internal amine or internal amide group wherein the aliphatic polyoxaester has been crosslinked.

Hydrogels of absorbable polyoxaesters containing amines and/or amido groups

The present invention describes aliphatic polyoxaesters containing amines and/or amido groups and blends thereof with other polymers that may be used to produce surgical devices such as sutures, sutures with attached needles, molded devices, and the like. The aliphatic polyoxaesters of the present invention have a first divalent repeating unit of formula I: [O-C(O)-C(R1)(R2)-O-(R3)-O-C(R1)(R2)-C(O)-] I and a second repeating unit of the formula: [-O-R12-]u, XVI and optionally a third repeating unit with a formula selected from the group consisting of: [-O-R4-]A, II [-O-R5-C(O)-]B III ([-O-R5-C(O)]p-O-)LG XI and combinations thereof wherein R12 contains an internal amine or internal amide group.

Blends of absorbable polyoxaesters containing amines and/or amido groups

The known reaction of dichlorotriazines of the formula II ##STR1## in which Q is an ether or amino radical, with diamines of the formula III Pip--NH--R--NH--Pip (III) in which Pip is a radical of the formula ##STR2## in which R 1 is hydrogen, C 1 -C 12 -alkyl, C 3 -C 8 -alkenyl, C 7 -C 11 -phenylalkyl, C 2 -C 8 -alkanoyl or C 3 -C 5 -alkenoyl and R is a divalent organic radical leads to undesirable, sparingly soluble by-products. The formation of these by-products can be suppressed if the reaction is carried out in a water-immiscible organic solvent with the addition of an aqueous base--preferably NaOH or KOH--under pressure at 140°-220° C.

Process for the preparation of polyaminotriazines

Steuerung der nickel‐katalysierten Mischoligomerisierung von Butadien mit Schiffschen Basen durch Cokatalysatoren

If the transesterification of esters of the formula ##STR1## with alcohols of the formula III A--(OH)m is catalyzed by successive treatment with catalytic amounts (a) of a tin compound of a metal of the fourth main group or the fourth sub-group of the periodic system and (b) of an acid earth, compounds of the formula I ##STR2## are obtained in virtually quantitative yield. The products thus obtained contain no troublesome by-products and do not have to be additionally purified. R is methyl or ethyl, A is a radical derived from an m-hydric aliphatic alcohol, n is 0 to 2, and m is 1 to 4.

Process for the preparation of sterically hindered hydroxphenylcarboxylic acid esters

New unsaturated 1,2-diazacyclododecanes, more particularly 1,2-diazacyclododecatrienes-1,5,9 and 1,2-diazacyclododecanes-1 and a novel process for the preparation thereof are disclosed which process comprises reacting a 1,3-diolefin with an azine in the presence of certain nickel catalysts. Said process unexpectedly yields 12-membered ring compounds only, and more especially oligomerization products of 2 mols of a 1,3-diolefin and 1 mol of an azine, while deactivation of the nickel catalyst by the -N=N-bond is avoided.

Eduard Dr. Troxler

Papers

Process for the preparation of polyaminotriazines

Steuerung der nickel‐katalysierten Mischoligomerisierung von Butadien mit Schiffschen Basen durch Cokatalysatoren

Process for the preparation of sterically hindered hydroxphenylcarboxylic acid esters

Novel 1,2-diaza-1,5,9-cyclo dodecatrienes and 1,2-diaza-1-cyclododecenes

Zur katalytischen Mischoligomerisation von Butadien und Allenen