Polyether polymers derived from 3,4-epoxy-1-butene and hydroxyl initiator

Abstract

Disclosed are novel polyether compounds obtained by the reaction or polymerization of 3,4-epoxy-1-butene in the presence of an onium iodide compound such as an ammonium or phosphonium iodide, an organotin compound such as a trihydrocarbyltin iodide, and a nucleophilic initiator compound. The polyether compounds comprise n units of residue (1) and m units of residue (2), wherein the total value of n+m is 2 to 70, m/(n+m) is greater than 0.75 and up to 0.98, and residues (1) and (2) have the structures: ##STR1##

Description

Claims

1. Process for the preparation of a polyether polymer with terminal primary hydroxyl groups which comprises contacting 3,4-epoxy-1-butene with an hydroxyl organic initiator compound in the presence of a catalyst system comprising an onium iodide and an organotin iodide compound, wherein (i) the polyether polymer is comprised of n units of residue (1) and m units of residue (2), wherein the total value of n+m is 2 to 70 and m/(n+m) is greater than 0.75 and up to 0.98, (ii) the polyether compound comprises at least 1 weight percent of the residue of the hydroxyl organic initiator compound, and (iii) residues (1) and (2) have the structures: ##STR2## and at least 95 percent of the terminal hydroxyl groups are primary hydroxyl groups.

2. Process according to claim 1 wherein the process is carried out at a temperature of about 40.degree. to 150.degree. C.; the organic initiator compound is selected from the group consisting of mono-hydroxy alcohol and poly-hydroxy initiator compounds; the onium iodide compound is a tetra(hydrocarbyl)ammonium iodide or a tetra(hydrocarbyl)phosphonium iodides having a total carbon atom content of about 16 to 72 carbon atoms and formula: ##STR3## wherein each R.sup.1 substituent independently is selected from alkyl of up to about 20 carbon atoms and each R.sup.2 substituent is independently selected from R.sup.1, benzyl, phenyl or phenyl substituted with up to 3 substituents selected from lower alkyl, lower alkoxy or halogen; or two R.sup.1 substituents collectively may represent alkylene of 4 to 6 carbon atoms including alkylene of 4 to 6 carbon atoms substituted with lower alkyl; and

the organotin iodide compound has the formula:

(R.sup.3).sub.(4-n) --Sn--I

wherein

each R.sup.3 independently is selected from alkyl or substituted alkyl moieties having up to about 20 carbon atoms, cycloalkyl or substituted cycloalkyl having about 5 to 20 carbon atoms, carbocyclic aryl or substituted carbocyclic aryl having about 6 to 20 carbon atoms, or heteroaryl or substituted heteroaryl moieties having about 4 up to 20 carbon atoms; and

n is 1, 2, or 3.

3. Process for the preparation of a polyether polymer with terminal primary hydroxyl groups which comprises contacting 3,4-epoxy-1-butene with an hydroxyl organic initiator compound in the presence of a catalyst system comprising tris(2-methyl-2-phenylpropyl)tin iodide and tri-n-octyl(n-octadecyl)phosphonium iodide, wherein the polyether polymer is comprised of n units of residue (1) and m units of residue (2), wherein (i) the total value of n+m is 2 to 70 and m/(n+m) is in the range of about 0.90 and 0.98, (ii) the polyether compound comprises at least 1 weight percent of the residue of the hydroxyl organic initiator compound, and (iii) residues (1) and (2) have the structures: ##STR4## and at least 95 percent of the terminal hydroxyl groups are primary hydroxyl groups.

4. Process according to claim 3 carried out at a temperature of about 40.degree. to 150.degree. C. wherein the mole ratio of the tri-n-octyl(n-octadecyl)phosphonium iodide to tris(2-methyl-2-phenylpropyl)tin iodide is about 20:1 to 0.05:1 and the organic initiator compound is selected from mono-hydroxy alcohol and poly-hydroxy initiator compounds.

5. Process for the preparation of a polyether polymer with terminal primary hydroxyl groups which comprises contacting at 80.degree. to 110.degree. C. 3,4-epoxy-1-butene with an hydroxyl organic initiator compound in the presence of a catalyst system comprising tris(2-methyl-2-phenylpropyl)tin iodide and tri-n-octyl(n-octadecyl)phosphonium iodide, the polyether polymer is comprised of n units of residue (1) and m units of residue (2), wherein (i) the total value of n+m is 7 to 50 and m/(n+m) is in the range of about 0.90 and 0.95, (ii) the polyether compound comprises about 5 to 20 weight percent of residues of the formula --O--R.sup.5 --wherein R.sup.5 is alkylene of 2 to 6 carbon atoms, (iii) residues (1) and (2) constitute at least 90 weight percent of the polymer, (iv) at least 95 percent of the terminal hydroxyl groups are primary hydroxy groups, (v) the polymer has a polydispersity value of 1 to 1.7, (vi) the mole ratio of the tri-n-octyl(n-octadecyl)phosphonium iodide to tris(2-methyl-2-phenylpropyl)tin iodide is about 5:1 to 0.02:1, and (vii) residues (1) and (2) have the structures: ##STR5##