Biorenewable hydrocarbon compositions and their uses

Patent metadata

Field	Value
Publication number	US-11572473-B2
Application number	US-202017247691-A
Country	US
Kind code	B2
Filing date	Dec 21, 2020
Priority date	Dec 19, 2019
Publication date	Feb 7, 2023
Grant date	Feb 7, 2023

Abstract

Disclosed are compositions comprising dimeric decarboxylated rosins (DDCRs), methods for making them, and applications thereof. DDCR of purity from 50-100 wt. % is obtained by decarboxylating a dimeric rosin acid or by dimerizing a decarboxylated rosin, in the presence of a catalyst, followed by one or more purification steps separation on differences in boiling point. The isolated DDCR fractions display unexpectedly high T g /M n ratios, softening points and viscosities, and low polydispersities. The DDCR product comprises 50 to 100 wt. % of polycyclic hydrocarbon compounds having one or more aliphatic, unsaturated or aromatic groups, and 34-80 carbon atoms, with a molecular weight M n of 250-900 Da, and an oxygen to carbon ratio of <5%. The DDCR product has at least 50%, and up to 100% as dimeric species, with the remainder being trimeric and larger polymeric species.

First claim

The invention claimed is:

1. A dimeric decarboxylated rosin (DDCR) composition comprising:
50 to 100 wt. % of polycyclic hydrocarbon compounds having one or more aliphatic, unsaturated or aromatic groups, and 34-80 carbon atoms;
wherein the composition has:
a molecular weight M n of 250-900 Da, measured using gel permeation chromatography and polystyrene calibration standards; and
an oxygen to carbon ratio of <5%;

wherein the composition is formed by decarboxylating a dimeric rosin acid or by dimerizing a decarboxylated rosin.

2. The DDCR composition of claim 1 , characterized as having one or more of:
an acid value of less than 80 mg KOH/g, measured using ASTM D 465;
a flash point of greater than 150° C. per ASTM D 92;
a ring and ball softening point from 30-160° C. per ASTM E28-18;
a Gardner color (neat) from 0-18 per ASTM D6166;
a Brookfield viscosity of 15-1000 mPa·s at 177° C. ASTM D2196;
a glass transition temperature (Tg) of −20-110° C. per ASTM E1356; and
a density of 1.00 to 1.04;
a polydispersity index of 1.0 to 1.2;
a T g /M n ratio of >0.6; and
a cloud point in polyolefins of <70° C.

3. The DDCR composition of claim 1 , characterized as having:
an acid value of less than 80 mg KOH/g, measured using ASTM D 465;
a flash point of greater than 150° C. per ASTM D 92;
a ring and ball softening point from 30-160° C., per ASTM E28-18;
a Gardner color (neat) from 0-18 per ASTM D6166;
a Brookfield viscosity of 15-1000 mPa·s at 177° C. per ASTM D2196;
a glass transition temperature (Tg) of −20-110° C. per ASTM E1356;
a density of 1.00 to 1.04;
a polydispersity index of 1.0 to 1.2;
a T g /M n ratio of >0.6; and
a cloud point in polyolefins of <70° C.

4. The DDCR composition of claim 1 , characterized as having an acid value of <15 mg KOH/g per ASM D 465.

5. The DDCR composition of claim 1 , characterized as having >50 wt. % dimeric species, and remainder trimeric and larger polymeric species.

6. The DDCR composition of claim 5 , characterized as having up to 100 wt. % dimeric species.

7. The DDCR composition of claim 1 , wherein decarboxylating a dimeric rosin acid comprises:
providing a feedstock comprising a dimeric rosin acid;
heating the feedstock comprising the dimeric rosin acid with a catalyst in a decarboxylating reaction at a temperature of 200-400° C., forming a crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimer rosin acids, dimeric decarboxylated rosin and residual polymeric species; and
subjecting the mixture containing the crude dimeric decarboxylated rosin (DDCR) to separation based on differences in boiling points of the monomeric decarboxylated rosin, the dimer rosin acids, the dimeric decarboxylated rosin and the residual polymeric species to form the DDCR composition, wherein the DDCR composition contains at least 50 wt. % dimeric species.

8. The DDCR composition of claim 7 , wherein providing a feedstock comprising a dimeric rosin acid comprises:
providing a feedstock comprising a rosin acid;
heating the feedstock comprising the rosin acid with a catalyst in a dimerization reaction at a temperature of −80 to 200° C., forming the dimeric rosin acid (DRA) in a mixture containing rosin acid and dimer rosin acids.

9. The DDCR composition of claim 1 , wherein dimerizing a decarboxylated rosin comprises:
providing a feedstock comprising a dimeric rosin acid;
heating the feedstock comprising the dimeric rosin acid with a catalyst in a decarboxylating reaction at a temperature of 200-400° C., forming a decarboxylated rosin;
heating the decarboxylated rosin with a catalyst in a dimerization reaction at a temperature of −80 to 200° C., forming a crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimer rosin acids, dimeric decarboxylated rosin and residual polymeric species; and
subjecting the mixture containing the crude dimeric decarboxylated rosin (DDCR) to separation based on differences in boiling points of the monomeric decarboxylated rosin, the dimer rosin acids, the dimeric decarboxylated rosin and the residual polymeric species to form the DDCR composition, wherein the DDCR composition contains at least 50 wt. % dimeric species.

10. The DDCR composition of claim 1 , wherein the composition is hydrogenated, and wherein the hydrogenated DDCR composition has a Gardner color of <5.

11. A polymer composition comprising 1-80 wt. % of the DDCR composition of claim 1 , and at least a polymer selected from styrenic block copolymers, homopolymers, copolymers, polyolefin homopolymers, plastomers, polyolefins, polyamides, polyesters, polycarbonates, polymethylmethacrylates, polyesters, polypropylene terephthalates, natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), synthetic polyisoprene rubber, epoxylated natural rubber, polybutadiene rubber, nitrile-hydrogenated butadiene rubber NHBR, hydrogenated styrene-butadiene rubber HSBR, ethylene propylene diene monomer rubber, ethylene propylene rubber, maleic acid-modified ethylene propylene rubber, butyl rubber, isobutylene-aromatic vinyl or diene monomer copolymers, brominated-NR, chlorinated-NR, brominated isobutylene p-methyl styrene copolymer, chloroprene rubber, epichlorohydrin homopolymers rubber, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubbers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubbers, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid-modified chlorinated polyethylene, methyl vinyl silicone rubber, dimethyl silicone rubber, methylphenylvinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubbers, tetrafluoroethylene-propylene rubbers, fluorinated silicone rubbers, fluorinated phosphagen rubbers, styrene elastomers, thermoplastic olefin elastomers, polyester elastomers, urethane elastomers, and polyamide elastomers.

12. An article comprising the composition of claim 11 .

13. A method for forming a dimeric decarboxylated rosin (DDCR) composition, the method comprises:
providing a feedstock comprising dimeric rosin acid (DRA);
heating the feedstock comprising the dimeric rosin acid (DRA) with a catalyst in a decarboxylating reaction at a temperature of 200-400° C., forming a crude dimeric decarboxylated rosin (DDCR) in a mixture containing monomeric decarboxylated rosin, dimer rosin acids, dimeric decarboxylated rosin and residual polymeric species; and
subjecting the mixture containing the crude dimeric decarboxylated rosin (DDCR) to separation based on differences in boiling points of the monomeric decarboxylated rosin, the dimer rosin acids, the dimeric decarboxylated rosin and the residual polymeric species to form the DDCR composition,
wherein the DDCR composition comprises 50 to 100 wt. % of polycyclic hydrocarbon compounds having one or more aliphatic, unsaturated or aromatic groups, and 34-80 carbon atoms; and
wherein the DDCR composition has an acid value of less than 80 mg KOH/g, measured using ASTM D 465; a molecular weight M n of 250-900 Da, measured using gel permeation chromatography and polystyrene calibration standards; and an oxygen to carbon ratio of <5%.

14. The method of claim 13 , wherein providing the dimeric rosin acid (DRA) feedstock comprises heating a feedstock comprising a rosin acid with a catalyst in a dimerization reaction at a temperature of −80 to 200° C., forming the dimeric rosin acid (DRA).

15. A method for forming a dimeric decarboxylated rosin (DDCR) composition, the method comprises:
providing a feedstock comprising a rosin acid;
heating the feedstock comprisin

Assignees

• Kraton Polymers Llc

Inventors

• Van Herrikhuyzen Jeroen
• Schaapman Mark
• Eduard Pieter

Classifications

• C08L23/02

  not modified by chemical after-treatment · CPC title

• B01J21/063

  Titanium; Oxides or hydroxides thereof · CPC title

• C09F1/04 Primary

  Chemical modification, e.g. esterification (resin soaps C11D) · CPC title

• C08L93/04 Primary

  Rosin · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title