Linear amine functionalized poly(trimethylene ether) compositions

A process for making a poly(trimethylene ether) diamine of the formula

• comprising:
• a) contacting poly(trimethylene ether) glycol of the formula
• with thionyl halide and optionally with dimethylformamide, optionally in the presence of a solvent, at a temperature of less than about 25° C. to form a reaction mixture;
• b) raising the temperature of the reaction mixture to a temperature of 50 to 150° C. and holding the reaction mixture at at the raised temperature for about 2 to 24 hours;
• c) forming a poly(trimethylene ether) halide of the formula
• wherein X is Cl or Br;
• d) combining the poly(trimethylene ether) with 1-10 molar equivalents of alkali metal azide in the presence of a solvent at a temperature of 25 to 200° C. to form a poly(trimethylene ether) azide of the formula
• e) contacting the poly(trimethylene ether) azide with a reducing agent, or under hydrogen gas with catalytic amount of catalyst, in a solvent or solvent mixture, at a pressure of about 15 to 500 psi and at a temperature of 25 to 200° C., to form a poly(trimethylene ether) amine of the structure
• wherein n is 4 to 170.

A process for making a poly(trimethylene ether) diamine of the formula

• comprising:
• a) converting the chain-end hydroxyl groups of poly(trimethylene ether) glycol of the formula
• to leaving groups to form a compound of formula
• where Z is selected from the group consisting of:
• mesylate (—OMs), tosylate (—OTs), nosylate (—ONs), brosylate (—OBs), triflate (—OTf), nonaflate, tresylate, iodide (—I)
• b) combining the compound from step (a) with 1-10 molar equivalents of alkali metal azide in the presence of a solvent at a temperature of 25 to 200° C. to form a poly(trimethylene ether) azide of the formula
• and
• c) contacting the poly(trimethylene ether) azide with a reducing agent, or under hydrogen gas with a catalytic amount of catalyst, in a solvent or solvent mixture, at a pressure of about 15 to 500 psi and at a temperature of 25 to 200° C., to form a poly(trimethylene ether) amine of the structure
• wherein n is 4 to 170.

A process for making a poly(trimethylene ether) diamine of the formula

• comprising:
• a) contacting poly(trimethylene ether) glycol of the formula
• with thionyl halide and optionally with catalytic amount of dimethylformamide (DMF), optionally in the presence of a solvent, at a temperature of less than about 25° C. to form a reaction mixture;
• b) raising the temperature of the reaction mixture to a temperature of 50 to 150° C., and holding the reaction mixture at the raised temperature for about 2 to 24 hours to form a poly(trimethylene ether) halide;
• wherein X is Cl or Br;
• c) contacting the poly(trimethylene ether) halide with anhydrous ammonia, or with a mixture of aqueous ammonia and a suitable solvent, under a pressure of 15 to 500 psi and at a temperature of 25 to 150° C. to form a poly(trimethylene ether) diamine of the formula
• wherein n is 4 to 170.