# US 9,040,635 B1 · Renewable polymer and method of making

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- Number: US 9,040,635 B1
- Document ID: US9040635B1
- Status: Granted
- Kind: B1
- Application number: 14/158,612
- Filed: 2014-01-17
- Granted: 2015-05-26
- Earliest claimed: 2013-01-17
- Assignees: TDA Research, Inc.
- Applicants: TDA Research, Inc.
- Inventors: Silvia DeVito Luebben; James William Raebiger; Aaron Jeremy Skaggs
- Web page: https://patentgrep.com/patent/US9040635B1

## CPC

- C08G 65/48: Polymers modified by chemical after-treatment
- C08G 65/34: from hydroxy compounds or their metallic derivatives {(C08G65/26 takes precedence)}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

A polymer, optionally made from renewable sources, comprising a specific chemical structure that is a result of the polymerization of α-hydroxycarbonyl compounds (alpha-hydroxycarbonyl compounds), particularly α-hydroxyaldehydes (alpha-hydroxyaldehydes) and α-hydroxyketones (alpha-hydroxyketones), or glycolaldehyde. A method of polymerization, the method comprising the step of reacting trimethylsilyl trifluoromethanesulfonate with the cyclic dimer of one or more α-hydroxycarbonyl compounds. A method of making said polymer, the method comprising dehydrating a cyclic dimer of one or more α-hydroxycarbonyl compounds. An end-capped polymer made from one or more α-hydroxycarbonyl compounds and terminal end-cap groups.

## Claims

### Claim 1

A polymer comprising the chemical formula:
wherein: “n” is an integer number from 4 to 10,000,000, and “m” is an integer number from zero to 10,000,000; and
R1, R2, R3, R4, R5, R6, R7, R8, R10, R12, R13, and R14, are independently from each other selected from the group consisting of hydrogen (—H), deuterium (-D), a halogen atom (—F, —Cl, —Br, —I), a hydroxyl group (—OH), an amino group (—NH2), an alkylamino group (—NHR9), a (bisalkylamino) group [—N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an acyl group, an alkyl carbonate group, a thiol group (—SH), alkylthio (—SR9), a nitro group (—NO2), a cyano group (—C≡N), a isocyanate group (—N═C═O), a azide group (—N3), a cyanate group (—O═C═N), a nitroso group (—NO), a phosphine group [—P(R9)2], a phosphate group [—OP(O)(OR9)2], a phosphonate group [—P(O)(OR9)2], a sulfate group (—O—SO3R9), a sulfonate group (—SO3R9), a thiocyanate group (—S═C═N), a iso thiocyanate group (—N═C═S), a —COR9 group, a —COOR9 group, a —CON(R9)2 group, a —CSR9 group, a —CS—OR9 group, a —N(R9)2 group, a —CO—O—CO—R9, a —CO—NR9—CO—R9, a —N═C(R9)2, and a —CR9═NR9; and
wherein, each R9 is independently from each other selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkenyl and an alkynyl group; and
R9 may be optionally substituted with one or more of the group consisting of halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, and thiocyanate group.

### Claim 2 (depends on 1)

The polymer of claim 1, wherein one or more of R1, R2, R3, R4, R5, R6, R7, R8, R10, R12, R13, and R14 is an oligomer, a pre-polymer or a polymer, the oligomer, the pre-polymer or the polymer is selected from the group consisting of end-capped polyethers, uncapped polyethers, poly(fluoroethers), polyglycols, polyacetals, polyolefins, polystyrene, polyfluoroolefins, polyoxides, polychlorolefins, polychlorofluoroolefins, polysiloxanes, polyesters, polybromoesters, natural and synthetic rubbers, polyols, polyalcohols, polyacids, polycarbonates, polyanhydrides, polysulfides, polyamides, polyamines, polyimides, vinyl polymers, polymers derived from the polymerization of unsaturated monomers, polyacrylates, polymethacrylates, polyacrylonitriles, polybutadiene, alkyds, polyurethanes, epoxies, cellulose and its derivatives, starch, starch derivatives, and polypeptides, or copolymers thereof.

### Claim 3 (depends on 1)

The polymer of claim 1, wherein one or more of the R1, R2, R3, R4, R5, R6, R7, R8, R10, R12, R13, and R14 is substituted by one or more species in the group consisting of a deuterium (-D), a halogen atom (—F, —Cl, —Br, —I), a hydroxyl group (—OH), an amino group (—NH2), an alkylamino group (—NHR9), a (bisalkylamino) group [—N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an acyl group, an alkyl carbonate group, a thiol group (—SH), an alkylthio (—SR9), a nitro group (—NO2), a cyano group (—C≡N), a isocyanate group (—N═C═O), a azide group (—N3), a cyanate group (—O═C═N), a nitroso group (—NO), a phosphine group [—P(R9)2], a phosphate group [—OP(O)(OR9)2], a phosphonate group [—P(O)(OR9)2], a sulfate group (—O—SO3R9), a sulfonate group (—SO3R9), a thiocyanate group (—S═C═N), a iso thiocyanate group (—N═C═S), a —COR9 group, a —COOR9 group, a —CON(R9)2 group, a —CSR9 group, a —CS—OR9 group, a —N(R9)2 group, —CO—O—CO—R9, —CO—NR9—CO—R9, —N═C(R9)2, and —CR9═NR9.

### Claim 4 (depends on 1)

The polymer of claim 1, wherein R1, R2, R3, R4, R5, R6, R10, R12, R13, and R14 are hydrogen; and R7, and R8 are selected from the group consisting of hydrogen, a linear or branched C1-C20 alkyl group, and a C1-C20 acyl group.

### Claim 5 (depends on 1)

The polymer of claim 1, wherein R1, R3, R10, and R13 are the same group and are selected from a linear or branched C1-C20 alkyl group; R2, R4, R5, R6, R12, and R14 are hydrogen; and R7, and R8 are independently selected from hydrogen, a linear or branched C1-C20 alkyl group, or a C1-C20 acyl group.

### Claim 6 (depends on 1)

The polymer of claim 1, wherein R1, R3, R10, and R13 are the same group and are selected from a C4-C20 aryl or alkylaryl group; R2, R4, R5, R6, R12, and R14 are hydrogen; and R7, and R8 are independently selected from the group consisting of hydrogen, a linear or branched C1-C20 alkyl group, and a C1-C20 acyl group.

### Claim 7 (depends on 1)

The polymer of claim 1 wherein “n” is at least 15.

### Claim 8 (depends on 1)

The polymer of claim 1 wherein “n” is at least 245.

### Claim 9

A method of polymerization, the method comprising the step of reacting trimethylsilyl trifluoromethanesulfonate with a compound that comprises the structure:
wherein, the R1, R2, and R4, are independently from each other selected from the group consisting of hydrogen (—H), deuterium (-D), an halogen atom (—F, —Cl, —Br, —I), a hydroxyl group (—OH), an amino group (—NH2), an alkylamino group (—NHR9), a (bisalkylamino) group [—N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an acyl group, an alkyl carbonate group, a thiol group (—SH), alkylthio (—SR9), a nitro group (—NO2), a cyano group (—C≡N), a isocyanate group (—N═C═O), a azide group (—N3), a cyanate group (—O═C═N), a nitroso group (—NO), a phosphine group [—P(R9)2], a phosphate group [—OP(O)(OR9)2], a phosphonate group [—P(O)(OR9)2], a sulfate group (—O—SO3R9), a sulfonate group (—SO3R9), a thiocyanate group (—S═C═N), a iso thiocyanate group (—N═C═S), —COR9 group, —COOR9 group, —CON(R9)2 group, —CSR9 group, —CS—OR9 group, —N(R9)2 group, —CO—O—CO—R9, —CO—NR9—CO—R9, —N═C(R9)2, and —CR9═NR9;
wherein each R9 is independently selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkenyl and an alkynyl group; and
each R9 may be optionally substituted with one or more of the groupo consisting of halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, and thiocyanate group.

### Claim 10 (depends on 9)

The product of the method of claim 9.

### Claim 11 (depends on 10)

The product of claim 10 that contains at least 20 monomer repeat units as determined by gel permeation chromatography.

### Claim 12 (depends on 11)

The product of claim 11 wherein R2 and R4 are hydrogen, R1 is selected from the group consisting of hydrogen, branched C1-C20 alkyl group, C4-C20 aryl and alkylaryl group.

### Claim 13

A method of polymerization, the method comprising the step of dehydrating a monomer that comprises the chemical structure:
the method comprising the step of using a Lewis acid catalyst to promote the dehydration of the monomer;
wherein, the R1, R2, and R4, are independently from each other selected from the group consisting of hydrogen (—H), deuterium (-D), a halogen atom (—F, —Cl, —Br, —I), a hydroxyl group (—OH), an amino group (—NH2), an alkylamino group (—NHR9), a (bisalkylamino) group [—N(R9)2], an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkenyl group, an alkoxyalkynyl group, an haloalkyl group, an haloalkenyl group, an haloalkynyl group, an haloalkoxy group, an aryl group, an alkoxyaryl group, an haloaryl group, an alkylaryl group, an acyl group, an alkyl carbonate group, a thiol group (—SH), alkylthio (—SR9), a nitro group (—NO2), a cyano group (—C≡N), a isocyanate group (—N═C═O), a azide group (—N3), a cyanate group (—O═C═N), a nitroso group (—NO), a phosphine group [—P(R9)2], a phosphate group [—OP(O)(OR9)2], a phosphonate group [—P(O)(OR9)2], a sulfate group (—O—SO3R9), a sulfonate group (—SO3R9), a thiocyanate group (—S═C═N), a iso thiocyanate group (—N═C═S), —COR9 group, —COOR9 group, —CON(R9)2 group, —CSR9 group, —CS—OR9 group, —N(R9)2 group, —CO—O—CO—R9, —CO—NR9—CO—R9, —N═C(R9)2, and —CR9═NR9;
wherein, each R9 is independently from each other selected from the group consisting of a hydrogen, an alkyl, an aryl, an alkenyl and an alkynyl group;
wherein, each R9 may be optionally substituted with one or more of the group consisting of halogen, hydroxy group, nitro group, cyano group, isocyano group, oxo group, thioxo group, azide group, cyanate group, isocyanate group, nitroso group, phosphine group, phosphate group, thiocyano group, and thiocyanate group;
wherein the Lewis acid is a salt of an element selected from the group consisting of Fe(II), Cu(II), Zn(II), Cd(II), In(III), Pb(II), Sc(III), Y(III), Ln(III)), B(III), Si(IV), P(III), P(IV), Ti(IV), V(III), Ge(IV), Zr(IV), Nb(V), Mo(V), Sn(IV), Sb(V), Hf(IV), Ta(V), W(VI), Re(V), Tl(III) Li(I), Na(I), Mg(II), AI(III), K(I), Ca(II), Cr(III), Mn(II), Co(II), Ni(II), Ga(III), Ru(III), Rh(III), Pd(II), Ag(I), Ba(II), Os(III), Ir(III), Pt(II), Au(I), Hg(II), and Bi(III); and
wherein the Lewis acid catalyst is used in an amount ranging from 0.001 to 0.2 equivalents by mole with respect to the monomer.

### Claim 14 (depends on 13)

The method of claim 13 where the Lewis acid is selected from the group consisting of salts of Sc(III), La(III), Yb(III), and Zn(II).

### Claim 15 (depends on 14)

The method of claim 14 where the Lewis acid is selected from the group consisting of Sc(OTf)3, La(OTf)3, Yb(OTf)3, Zn(OTf)2 and Sc(NTf2)3.

### Claim 16 (depends on 13)

The product of the method of claim 13.

### Claim 17 (depends on 16)

The product of claim 16 that contains at least 15 monomer repeat units as determined by gel permeation chromatography.

### Claim 18 (depends on 12)

The product of claim 12 wherein R2 and R4 are hydrogen, R1 is selected from the group consisting of hydrogen, branched C1-C20 alkyl group, C4-C20 aryl and alkylaryl group.

### Claim 19 (depends on 13)

The method of claim 13 that further comprises the step of reacting the product of the polymerization with an end-capping reagent.

### Claim 20 (depends on 1)

The polymer of claim 1, further comprising the chemical formula:
wherein, “n” is an integer from 4 to 10,000,000.