Oligoesters and compositions thereof

• US 10,435,586 B2
• Filed: 12/30/2016
• Issued: 10/08/2019
• Est. Priority Date: 12/31/2015
• Status: Active Grant

• Current Assignee: Kraton Chemical LLC (DL Holdings Co., Ltd.)
• Original Assignee: Kraton Chemical LLC (DL Holdings Co., Ltd.)
• Inventors: Schaapman, Mark C, Lange, Jos H. M., Eduard, Pieter, Zeeman, Ronnie
• Primary Examiner(s): Choi, Ling Siu
• Assistant Examiner(s): Mesh, Gennadiy
• Application Number:
  US15/396,258
• Publication Number:
  US 20170190935A1
• Time in Patent Office: 1,012 Days
• CPC Class Codes: C08G 63/12 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 63/48 by unsaturated higher fatty oils or their acids; by resin acids
• CPC Class Codes: C08K 5/053 Polyhydroxylic alcohols
• CPC Class Codes: C08K 5/09 Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08L 9/06 Copolymers with styrene
• CPC Class Codes: C08L 93/04 Rosin
• CPC Class Codes: C09F 1/04 Chemical modification, e.g. esterification resin soaps C11D
• CPC Class Codes: C09J 193/04 Rosin

Abstract

An oligoester composition is disclosed, which is a reaction product of a reactant mixture comprising one or more rosins selected from the group consisting of tall oil rosin and gum rosin; at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms; and one or more polyhydric alcohols comprising 2-36 carbon atoms, wherein each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms. A method for preparing an oligoester composition is also provided. Also disclosed is an oligoester composition which is an esterification reaction product of one or more rosins, one or more monocarboxylic acids, one or more polyhydric alcohols, and optionally one or more polycarboxylic acids. The composition has a weight average molecular weight of from 500 g/mol to 8,000 g/mol and a T_g of between −80° C. and 100° C.

Claims

1. An oligoester composition which is a reaction product of a reactant mixture comprising:

one or more rosins selected from the group consisting of tall oil rosin and gum rosin;

at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms, wherein the monocarboxylic acid is selected from the group consisting of aromatic monofunctional carboxylic acids, heteroaromatic monofunctional carboxylic acids, aliphatic monofunctional carboxylic acids, and cycloaliphatic monofunctional carboxylic acids; and

5 to 30% by weight of one or more polyhydric alcohols comprising 2-36 carbon atoms, wherein each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms, and the polyhydric alcohol has an average hydroxyl functionality of 2-10;

wherein the composition has a weight average molecular weight of from 500 g/mol to 8,000 g/mol and a T_g of between −

80°

C. and 100°

C.; and

wherein the composition has a hydroxyl number of less than 30 mg KOH/gram.

2. The oligoester composition of claim 1, wherein the reactant mixture further comprises:

less than Q % by weight one or more polycarboxylic acids, where Q is defined by the formula

3. The oligoester composition of claim 1, wherein the reaction is an esterification reaction, a transesterification reaction, an interesterification reaction, or combinations thereof.

4. The oligoester composition of claim 2 wherein the reactant mixture comprises from greater than 0% to 4% by weight one or more dicarboxylic acids.

5. The oligoester composition of claim 2, wherein the reactant mixture comprises from greater than 0% to 4% by weight one or more dicarboxylic acids and from 9% to 18% by weight of one or more polyhydric alcohols.

6. The oligoester composition of claim 2, wherein the one or more polycarboxylic acids are selected from the group consisting of adipic acid, 3-methyladipic acid, succinic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, rosin dimer, isophthalic acid, terephthalic acid, phthalic acid, tall oil fatty acid dimer, hydrogenated tall oil fatty acid dimer, 2-(2-carboxyphenyl)benzoic acid, 2,5-furandicarboxylic acid, camphoric acid, cis-norbornene-endo-2,3-dicarboxylic acid, trimellitic acid, and combinations thereof.

7. The oligoester composition of claim 1, wherein the reaction mixture comprises from 40% to 80% by weight one or more monocarboxylic acids.

8. The oligoester composition claim 7, wherein the one or more monocarboxylic acids comprise a fatty acid, a tall oil fatty acid, or combinations thereof.

9. The oligoester composition of claim 1, wherein the one or more polyhydric alcohols are selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, neopentylglycol, trimethylene glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,4-cyclohexanediol, polyglycerol, polyglycerol-3, polyglycerol-4, cyclohexane-1,4-dimethanol, tricyclo[5.2.1.0^(2.6)]decane-4,8-dimethanol, hydrogenated bisphenol A (4,4′

-Isopropylidenedicyclohexanol), mannitol, sorbitol, xylitol, maltitol, lactitol, and combinations thereof.

10. The oligoester composition of claim 2, wherein the reaction mixture comprises:

from 5% to 75% by weight of the one or more rosins;

from 25% to 85% by weight of the one or more monocarboxylic acids;

from 9 to 18% by weight of the one or more polyhydric alcohols; and

from greater than 0% to less than 4% by weight of the one or more polycarboxylic acids.

11. The oligoester composition of claim 1, wherein the composition exhibits a mass loss of less than 10% at 160°

C. over a time period of 4 hours.

12. A plasticizer comprising the oligoester composition of claim 1.

13. A tire tread composition comprising a rubber polymer, a filler, and the oligoester composition of claim 1.

14. A polymeric composition comprising

(a) a polymer, and

(b) the oligoester composition of claim 1.

15. The polymeric composition of claim 14, wherein the polymer is selected from the group consisting of a polyacrylate, a polyolefin, a polyamide, a polyvinyl ether, a polyurethane, a polyester, a polyvinyl ester, copolymers thereof, and blends thereof.

16. The polymeric composition of claim 14, wherein the polymer is selected from the group consisting of acrylonitrile-butadiene-styrene, an acrylic polymer, an acrylic copolymer, bromobutyl rubber, butyl terpolymer, cellulose acetate, cellulose butyrate, cellulose propionate, cellulose nitrate, chlorinated polyvinylchloride, polyvinylchloride, chlorosulphonated polyethylene, cyanoacrylates, styrenic block copolymer consisting of polystyrene blocks and rubber blocks wherein the rubber blocks consist of polybutadiene, polyisoprene or hydrogenated versions thereof, caprolactone-styrene diblock copolymers, urethane acrylic copolymer, urethanes, polyolefins, ethylene-propylene-diene copolymer, epoxy resins, ethylene-vinyl acetate copolymer, ionomers, nitrile rubber, polyacrylonitrile, polyamides, polyamine, polyaniline, polybutadiene, polybutylene, poly(butyl methacrylate), polycarbonate, polyester, polyetherimide, polyethylacrylate, polyethylene, poly(ethylene)oxide, polyisobutylene, polyisoprene, polyimide, polylactide, polymethylmethacrylate, polypropylene, poly(N-vinylcarbazole), poly(N-vinyl pyrrolidone), polyphenylene ether, polystyrene, polysulfone, polysulfide, polyvinylacetate, polyvinylalcohol, polyvinylbutyral, polyvinylchloride, polyvinylidinefluoride, polyvinylidinechloride, polyurethanes, protein, natural rubber, silicone, styrene-butadiene rubber, styrene-butadiene-styrene, starch, copolymers thereof, and blends thereof.

17. A method for preparing an oligoester composition comprising:

esterifying a mixture comprising

one or more rosins selected from the group consisting of tall oil rosin and gum rosin, at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms,

wherein the monocarboxylic acid is selected from the group consisting of aromatic monofunctional carboxylic acids, heteroaromatic monofunctional carboxylic acids, aliphatic monofunctional carboxylic acids, and cycloaliphatic monofunctional carboxylic acids,

optionally from greater than 0% to 4% by weight of one or more polycarboxylic acids,

wherein the polycarboxylic acid comprises 2-54 carbon atoms and is selected from the group consisting of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids, and with 5 to 30% of one or more polyhydric alcohols, to form the oligoester composition,

wherein the polyhydric alcohol comprises 2-36 carbon atoms, each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms, and the polyhydric alcohol has an average hydroxyl functionality of 2-10;

wherein the oligoester composition has a weight average molecular weight of from 500 g/mol to 8,000 g/mol and a T_g of between −

80°

C. and 100°

C.; and

wherein the oligoester composition has a hydroxyl number of less than 30 mg KOH/gram.

18. An oligoester composition formed by the method of claim 17.

19. An oligoester composition which is an esterification reaction product of a reactant mixture comprising:

one or more rosins selected from the group consisting of tall oil rosin and gum rosin,

at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms and selected from the group consisting of aromatic monofunctional carboxylic acids, heteroaromatic monofunctional carboxylic acids, aliphatic monofunctional carboxylic acids, and cycloaliphatic monofunctional carboxylic acids,

9% by weight to 18% by weight of one or more polyhydric alcohols comprising 2-36 carbon atoms, wherein each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms, and the polyhydric alcohol has an average hydroxyl functionality of 2-10, and

optionally from greater than 0% to 4% by weight of one or more polycarboxylic acids, wherein the polycarboxylic acid comprises 2-54 carbon atoms and is selected from the group consisting of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids,

wherein the composition has a weight average molecular weight of from 500 g/mol to 8,000 g/mol and a T_g of between −

80°

C. and 100°

C.; and

wherein the oligoester composition has a hydroxyl value of 30 mg KOH/g or less.

20. An oligoester composition which is the reaction product of:

one or more rosins selected from the group consisting of tall oil rosin and gum rosin;

at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms and selected from the group consisting of aromatic monofunctional carboxylic acids, heteroaromatic monofunctional carboxylic acids, aliphatic monofunctional carboxylic acids, and cycloaliphatic monofunctional carboxylic acids;

5 to 30% by weight of one or more polyhydric alcohols comprising 2-36 carbon atoms, wherein each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms, and the polyhydric alcohol has an average hydroxyl functionality of 2-10; and

less than Q % by weight one or more polycarboxylic acids, wherein the polycarboxylic acid comprises 2-54 carbon atoms and is selected from the group consisting of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids; and

where Q is defined by the formula;

21. A pressure sensitive adhesive (PSA) comprising a polymer and an oligoester composition,

wherein the adhesive exhibits a loop tack adhesion value on stainless steel of at least 25 Newton/25 mm, a 180°

peel adhesion on stainless steel after 20 minutes of at least 20 Newton/25 mm, a shear adhesion time of at least 3000 minutes, and a SAFT failure temperature of at least 55°

C.; and

wherein the oligoester composition is a reaction product of a reactant mixture comprising;

one or more rosins selected from the group consisting of tall oil rosin and gum rosin;

at least 15% by weight of one or more monocarboxylic acids comprising 6-36 carbon atoms, wherein the monocarboxylic acid is selected from the group consisting of aromatic monofunctional carboxylic acids, heteroaromatic monofunctional carboxylic acids, aliphatic monofunctional carboxylic acids, and cycloaliphatic monofunctional carboxylic acids;

optionally from greater than 0% to 4% by weight of one or more polycarboxylic acids, wherein the polycarboxylic acid comprises 2-54 carbon atoms and is selected from the group consisting of dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids; and

5 to 30% by weight of one or more polyhydric alcohols comprising 2-36 carbon atoms, wherein each hydroxyl group of the polyhydric alcohol is separated from the other hydroxyl groups by at least 2 carbon atoms, and the polyhydric alcohol has an average hydroxyl functionality of 2-10;

wherein the composition has a weight average molecular weight of from 500 g/mol to 8,000 g/mol and a T_g of between −

80°

C. and 100°

C.; and

wherein the oligoester has a hydroxyl number of less than 30 mg KOH/gram.