Yttrium and rare earth compounds catalyzed lactone polymerization

Claim 2

A process for the ring opening polymerization of lactones comprising contacting under polymerizing conditions a lactone or lactide selected from the group consisting of: ##STR6## wherein n is 4 or 5, h, i, k and m are independently one or two; each R is independently selected from H or hydrocarbyl containing up to 12 carbon atoms or substituted hydrocarbyl containing up to 12 carbon atoms; with a catalyst of the structure MZ 3 where M represents trivalent yttrium or a rare earth metal and each Z is independently selected from --OCR 1 3 , --NR 1 2 , --CR 1 3 and highly coordinating ligands, wherein each R 1 is selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, provided that Z is selected so that at least one of the groups bonded to M is not a highly coordinating ligand, and further provided that when Z is CR 1 3 , one or two of R 1 may be covalent bonds to carbon.

Claim 3

The process of claim 1 wherein the R of the lactone is H or methyl.

Claim 4

The process of claim 2 wherein the R of the lactone is methyl.

Claim 5

The process of claim 1 wherein the catalyst contains a mixture of trivalent yttrium and/or one or more trivalent rare earth metals.

Claim 6

The process of claim 2 wherein R of the lactone is H.

Claim 7

The process of claim 1 wherein Z contains less than 50 carbon atoms.

Claim 8

The process of claim 1 wherein z is biologically active.

Claim 9

The process of claim 1 wherein z is selected from the group consisting of 2-ethoxyethoxy, isopropoxy, 2-phenylthioethoxy, 2-N,N-dimethylaminoethoxy, 1-methoxycarbonylethoxy, trimethylsilylmethyl, N,N-nos(trimethylsilyl)amino, 4-hydroxymethylbenzyloxy and the alkoxide of Vitamin D 3 .

Claim 10

The process of claim 1 wherein the lactone is selected from one or more of ε-caprolactone, δ-valerolactone, lactide (3,6-dimethyl-1,4-dioxan-2,5-dione), glycolid (1,4-dioxan-2,5-dione), 1,5-dioxepan-2-one and 1,4-dioxan-2-one.

Claim 11

The process of claim 1 wherein the catalyst is soluble in the reaction medium.

Claim 12

The process of claim 1 conducted in the presence of a solvent.

Claim 13

Process of preparing the block polymer by the sequential introduction of two or more lactone monomers into the polymerization process described by claim 1.

Claim 14

Process of preparing a random copolymer by simultaneous introduction of two or more lactone monomers into the polymerization process described by claim 1.

Claim 15

The process of claim 1 wherein M is chosen from one or more of yttrium, lanthanum, samarium, dysprosium and erbium.

Claim 16

The process of claim 14 wherein M is chosen from yttrium or lanthanum.

Claim 17

The process of claim 1 wherein Mi is a mixture of two or more of yttrium and the rare earth metals.

Claim 18

The process of claim 11 wherein M is selected from one or more yttrium, lanthanum, samarium, dysprosium and erbium.

Claim 19

The process of claim 17 wherein the lactone is selected from one or more of ε-caprolactone, δ-valerolactone, lactide (3,6-dimethyl-1,4-dioxan-2,5-dione) and glycolid (1,4-dioxan-2,5-dione).

Claim 20

The process of claim 18 wherein the polymerization temperature is -80° to 200° C.

Claim 21

The process of claim 19 wherein the polymerization temperature is 0° to 110° C.

Claim 22

The process of claim 1 wherein the catalyst is one or more of lanthanum triisopropoxide, yttrium triisiopropoxide, erbium triisopropoxide, yttrium tris(2-N,N-dimethylaminoethoxide), yttrium tris(2-ethoxyethoxide), yttrium bis(2,2,6,6-tetramethylheptan-3,5-dionate) isopropoxide, Y(CH 2 SiMe 3 ) 3 .(THF) 2 , samarium triisopropoxide yttrium (O-vitamin D 3 ) 3 , samarium tris(2-N,N-dimethylaminoethoxide), dysprosium tris(2 N,N-dimethylaminoethoxide), yttrium tris(2-phenylthioethoxide), yttrium tris(1,1,1,3,3,3-hexamethyldisilylamide), yttrium tris(4-hydroxymethylbenzyloxide), and yttrium tris(1-methoxycarbonylethoxide).

Claim 23

The process of claim 1 wherein the catalyst is chosen from Ba 2 Y(OCH 2 CH 2 OCH 2 CH 3 ) 7 and Ba 2 Y(OCH 2 CH 2 N(CH 3 ) 2 ) 7 .

Claim 24

Process of claim 1 wherein the polymerization is conducted as a batch process.

Claim 25

Process of claim 1 wherein the polymerization is conducted as a continuous process.

Claim 26

Process of claim 24 carried out in a continuous tubular reactor.

Claim 27

Process of claim 24 carried out in one or more continuous stirred tank reactors.

Claim 28

Process of claim 1 carried out as a semi-batch process.

Claim 29

Living polymers of the structure ##STR7## wherein n is 4 or 5; h, i, k and m are independently one or two; p is three or more; q and r are independently zero or an integer; e is 0 or 1; d is 0, 1 or 2; E is a monvalent highly coordinating ligand; F is a highly coordinating divalent ligand; Z is as defined above; providing that q+r are three or more; d+2e is 2 or less; d+2e+f is 0, 1 or 2 and f is 0, 1 or 2; a and b are independently zero or an integer, providing that a+b is one or more; each R is independently chosen from H or hydrocarbyl containing up to 12 carbon atoms or substituted hydrocarbyl containing up to 12 carbon atoms; M is chosen from yttrium and the rare earth metals; Q is --OCR 1 3 , wherein each R 1 is independently chosen from hydrogen, hydrocarbyl and substituted hydrocarbyl; and u, v, and w are independently zero or integers, provided that at least two of u, v and w are not zero.

Claim 30

Living polymers of the structure ##STR7## wherein n is 4 or 5; h, i, k and m are independently one or two; p is three or more; q and r are independently zero or an integer; e is 0 or 1; d is 0, 1 or 2; E is a monvalent highly coordinating ligand; F is a highly coordinating divalent ligand; Z is as defined above; providing that q+r are three or more; d+2e is 2 or less; d+2e+f is 0, 1 or 2 and f is 0, 1 or 2; a and b are independently zero or an integer, providing that a+b is one or more; each R is independently chosen from H or hydrocarbyl containing up to 12 carbon atoms or substituted hydrocarbyl containing up to 12 carbon atoms; M is chosen from yttrium and the rare earth metals; Q is --OCR 1 3 , wherein each R 1 is independently chosen from hydrogen, hydrocarbyl and substituted hydrocarbyl; and u, v, and w are independently zero or integers, provided that at least two of u, v and w are not zero.

Claim 31

The living polymers of claim 28 wherein R is hydrogen or methyl.

Claim 32

The living polymers of claim 29 wherein R is methyl.

Claim 33

The living polymers of claim 29 wherein R is hydrogen.

Claim 34

The living polymers of claim 28 wherein M is chosen from yttrium, lanthanum, samarium, dysprosium and erbium.

Claim 35

The living polymers of claim 32 wherein R is methyl or H.

Claim 36

The living polymers of claim 33 wherein R is methyl.

Claim 37

The living polymers of claim 33 wherein R is H.

Claim 38

The living polymers of claim 28 wherein at least one of R 1 is substituted hydrocarbyl.

Claim 39

The living polymers of claim 33 wherein at least one of R 1 is substituted hydrocarbyl.

Claim 40

The living polymers of claim 37 wherein at least one of R 1 is substituted hydrocarbyl.

Claim 41

Solution of the polymer of claim 28.

Claim 42

Film prepared from the solution of claim 28.

Claim 43

Coated substrate prepared from the solution of claim 28.

Claim 44

Process of quenching the living polymer of claim 28 with an active hydrogen source.