Bio-based terephthalate polyesters

A process of making bio-based dimethyl terephthalate of Formula II:

• the process comprising:
• (a) providing a biomass comprising limonene;
• (b) converting limonene to bio-based para-cymene at a yield of at least 95%;
• (c) converting the bio-based para-cymene to bio-based terephthalic acid of Formula I:
• at a total yield of at least 85%
• by an oxidation in a two-step oxidation comprising:
• (i) a first step using a mineral acid, and
• (ii) a second step using a transition metal oxidant,
• performed substantially in the absence of chromium oxide;
• and
• (d) converting the bio-based terephthalic acid with methanol selected from the group consisting of bio-based methanol, petroleum based methanol, and combinations thereof to provide the bio-based dimethyl terephthalate of Formula II,
• wherein the bio-based terephthalic acid has a mean bio-based content of at least 5%;
• and
• 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.

A process of making a bio-based terephthalic acid composition, the process comprising:

• (a) providing a biomass comprising limonene;
• (b) converting the limonene to para-cymene at a yield of at least 95%;
• and
• (c) converting the para-cymene to terephthalic acid at a total yield of at least 85% by oxidation in 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;
• wherein the bio-based terephthalic acid has a mean bio-based content of at least 95%;
• and 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.