Bio-based terephthalate polyesters

Patent metadata

Field	Value
Publication number	US-9328045-B2
Application number	US-201414151418-A
Country	US
Kind code	B2
Filing date	Jan 9, 2014
Priority date	Dec 31, 2008
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

Bio-based terephthalic acid (bio-TPA), bio-based dimethyl terephthalate (bio-DMT), and bio-based polyesters, which are produced from a biomass containing a terpene or terpenoid, such as limonene are described, as well as the process of making these products. The bio-based polyesters include poly(alkylene terephthalate)s such as bio-based poly(ethylene terephthalate) (bio-PET), bio-based poly(trimethylene terephthalate) (bio-PTT), bio-based poly(butylene terephthalate) (bio-PBT), and bio-based poly(cyclohexylene dimethyl terephthalate) (bio-PCT).

First claim

What is claimed is:

1. A process of making a compound comprising bio-based 1,4-cyclohexane dimethanol of Formula VII:

the process comprising:
(a) providing a biomass comprising a terpene, terpenoid or a mixture thereof;
(b) converting the terpene, terpenoid, or mixture thereof to para-cymene at a yield of at least 95%;
(c) converting the para-cymene to terephthalic acid at a total yield of at least 85% by a two-step oxidation comprising:
(i) a first step using a mineral acid, and
(ii) a second step using a transition metal oxidant, the oxidation being performed in the absence of chromium oxide; and

(d) converting the terephthalic acid to the bio-based 1,4-cyclohexane dimethanol, wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%;
wherein the biomass is a biological material which excludes organic material that has been transformed by geological processes into a member selected from the group consisting of petroleum, petrochemicals, and combinations thereof.

2. The process of claim 1 further comprising converting the bio-based 1,4-cyclohexane dimethanol of Formula VII to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII:

wherein n is an integer between about 50 and about 130.

3. The process of claim 2 wherein the step of converting the bio-based 1,4-cyclohexane dimethanol of Formula VII to bio-based poly(cyclohexylene dimethylene terephthalate) of Formula VIII is performed by reacting bio-based terephthalic acid with the bio-based 1,4-cyclohexane dimethanol, wherein the bio-based terephthalic acid has a mean bio-based content of at least 5%, as determined by ASTM D6866; and wherein the bio-based 1,4-cyclohexane dimethanol is isotopically rich in Carbon-14, by at least 5%, as compared to a petroleum source, as determined by ASTM D6866.

4. The process according to claim 1 wherein the transition metal oxidant is a permanganate compound.

5. The process of claim 1 wherein the terpene is limonene which is converted to para-cymene in the presence of a catalyst selected from the group consisting of transition metal catalysts, Group IA catalysts, amine catalysts, and combinations thereof.

6. The process of claim 1 wherein the first step (i) comprises obtaining an oxidized product that is directly extracted using an organic layer.

7. The process of claim 1 wherein the first step (i) comprises heating the p-cymene with water and mineral acid to obtain an oxidized product, which is then cooled down, extracted with organic solvent, concentrated, dissolved in water, and further oxidized with the transition metal oxidant to obtain the bio-based terephthalic acid.

8. The process of claim 7 wherein the concentrated oxidized product is dissolved in water with sodium hydroxide.

9. The process of claim 1 wherein the biomass is obtained from lemons.

10. A process of making a compound comprising bio-based 1,4-cyclohexane dimethanol of Formula VII:

the process comprising:
(a) providing a biomass comprising a terpene, terpenoid or a mixture thereof;
(b) converting the terpene, terpenoid, or mixture thereof to para-cymene at a yield of at least 95%;
(c) converting the para-cymene to terephthalic acid at a total yield of at least 85% by a two-step oxidation comprising:
(i) a first step, using a mineral acid, comprising heating a reaction mixture comprising p-cymene, mineral acid, and water, which reaction mixture is then cooled down and extracted with organic solvent; and
(ii) a second step using a transition metal oxidant, and oxidized with the oxidant to obtain bio-based terephthalic acid;
wherein the oxidation is performed substantially in the absence of chromium oxide;

(d) converting the terephthalic acid to the bio-based 1,4-cyclohexane dimethanol, wherein the bio-based 1,4-cyclohexane dimethanol has a mean bio-based content of at least 5%;
wherein the biomass is a biological material which excludes organic material that has been transformed by geological processes into a member selected from the group consisting of petroleum, petrochemicals, and combinations thereof.

Assignees

• Sabic Innovative Plastics Ip
• Saudi Basic Ind Corp

Inventors

• Berti Corrado
• Binassi Enrico
• Colonna Martino
• Fiorini Maurizio
• Kannan Ganesh
• Karanam Sreepadaraj
• Mazzacurati Marzia
• Odeh Ihab

Classifications

• C07C29/19 Primary

  in six-membered aromatic rings · CPC title

• C07C31/276

  with a six-membered ring · CPC title

• C07C5/10

  of aromatic six-membered rings · CPC title

• C08G63/199

  Acids or hydroxy compounds containing cycloaliphatic rings · CPC title

• C07C2101/14

  Chemistry & Metallurgy · mapped topic