Patent Application
20220194912
The present disclosure relates to elastomers comprising the reaction product of at least one epoxidized molecule and at least one crosslinker and methods of preparing such compositions. Further, these elastomers can be converted to elastomer gels. The present disclosure also relates to personal care formulations containing such elastomers or elastomer gels.
The personal care industry thrives on being able to deliver multiple performance products based on mixtures of several components, with each having performance characteristics important to or desirable in the final formulation. Silicone gels are commonly added in a variety of personal care formulations to enhance their aesthetics with respect to sensory, texture, rheology, and optical performance. See for example, U.S. Pat. Nos. 4,987,169; 5,654,362; 5,760,116; 6,423,322; and 5,811,487.
However, traditional silicone gels have limited versatility in terms of compatibility with many natural oils, ester oils, and other biobased ingredients which have growing interest in personal care formulation. Moreover, silicone polymers are difficult to degrade, biologically or otherwise. Particular silicone compounds used in various personal care products, cyclic siloxanes D4 (octamethylcyclotetrasiloxane) and D5 (decamethylcyclopentasiloxane), are air and water pollutants and show negative health effects on test animals. In light of the growing environmental awareness, increasing societal concern and new environmental rules and regulations, biodegradable natural polymers gel made from biorenewable raw material with no health and environmental concerns is highly desirable.
Vegetable oils or natural oils, such as soybean oil and linseed oil, are one of the most promising raw materials for the synthesis of renewable compounds. These natural materials are inexpensive, highly abundant, come from reliable and sustainable sources, and have high potential for modification. Vegetable oils are triglycerides which contains different kinds of unsaturated fatty acids and saturated fatty acids with varying carbon chain lengths. Soybean oil, as an example, has three unsaturated fatty acids with average unsaturation degree of 4.6. Epoxidized vegetable oil (EVO) are functionalized triglyceride with oxirane ring moieties. Epoxidized soybean oil (ESO) has been used as a composite (Thielemans W., et al., Journal of Applied Polymer Science, 2002, 83:323-331 and Lu J., et al., Polymer, 2005, 46:71-80), a lubricant, a plasticizer, a thermal stabilizer (Lathi P. S., Applied Catalysis B. Environmental, 2007, 69:207-212, Demertzis P. G. et al., European Polymer Journal, 1991, 27(3):231-235 and Liu P. et al., Polymer Degradation and Stability, 2007, 92:503-508), and flooring materials (U.S. Pat. No. 7,196,124).
Despite its broad usage mentioned above, epoxidized vegetable oil and their derivatives, including polymers, have rarely been used in personal care application. Given these known properties of epoxidized vegetable oil, particularity epoxidized soybean oil, these oils are excellent candidates as a renewable resource monomer units to develop a biodegradable natural polymer gel for personal care formulations.
In an aspect, the disclosure relates to elastomer comprising the reaction product of at least one epoxidized molecule and at least one crosslinker.
In an aspect, the at least one epoxidized molecule is a compound of formula (I)
wherein
R1 is C6-C100,000 alkyl group, C6-C100,000 heteroalkyl group, C6-C100,000 alkene group, C6-C100,000 heteroalkene group, C6-C100,000 alkyne group, C6-C100,000 heteroalkyne group, C6-C100,000 cyclic group, or C6-C100,000 heterocyclic group;
R2 is hydrogen, C1-C100,000 alkyl group, C1-C100,000 heteroalkyl group, C2-C100,000 alkene group, C2-C100,000 heteroalkene group, C2-C100,000 alkyne group, C2-C100,000 heteroalkyne group, C3-C100,000 cyclic group, or C3-C100,000 heterocyclic group; and
m is an integer from 2 to 1,000.
In another aspect, the disclosure relates to an elastomer prepared by reacting at least one epoxidized molecule and at least one crosslinker in the presence of a first solvent thereby forming a crosslinking polymer structure.
In yet another aspect, the disclosure relates to a method of preparing an elastomer comprising reacting at least one epoxidized molecule and at least one crosslinker in the presence of a first solvent thereby forming a crosslinking polymer structure.
In another aspect, the disclosure relates to a personal care formulation comprising a gel prepared from an elastomer composition that is the reaction product of at least one epoxidized molecule and at least one crosslinker.
In still yet another aspect, the disclosure relates to use of a gel described herein for personal care formulations.
Unless otherwise indicated, any atom with unsatisfied valences is assumed to have hydrogen atoms sufficient to satisfy the valences.
The singular forms “a,” “an,” and “the” include plural referents unless the context dictates otherwise.
Furthermore, “and/or”, where used herein, is to be taken as specific disclosure of each of the two specified features or components with or without the other. Thus, the term “and/or” as used in a phrase such as “A and/or B” herein is intended to include “A and B,” “A or B,” “A” (alone), and “B” (alone). Likewise, the term “and/or” as used in a phrase such as “A, B, and/or C” is intended to encompass each of the following aspects: A, B, and C; A, B, or C; A or C; A or B; B or C; A and C; A and B; B and C; A (alone); B (alone); and C (alone).
It is understood that wherever aspects are described herein with the language “comprising,” otherwise analogous aspects described in terms of “consisting of” and/or “consisting essentially of” are also provided.
The term “about” is used herein to mean approximately, roughly, around, or in the regions of. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. In general, the term “about” can modify a numerical value above and below the stated value by a variance of, e.g., 10 percent, up or down (higher or lower).
As used herein, the following definitions shall apply unless otherwise indicated. For purposes of the present disclosure, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, and the Handbook of Chemistry and Physics, 75th Ed. 1994. Additionally, general principles of organic chemistry are described in “Organic Chemistry,” Thomas Sorrell, University Science Books, Sausalito: 1999, and “March's Advanced Organic Chemistry,” 6thEd., Smith, M. B. and March, J., eds. John Wiley & Sons, New York: 2007, the entire contents of which are hereby incorporated by reference.
The term “alkyl”, as used herein by itself or as part of a group, refers to a straight- or branched-chain aliphatic hydrocarbon containing one to two hundred carbon atoms, i.e., a C2-C200 alkyl, or the number of carbon atoms designated, e.g., a C1 alkyl such as methyl, a C2 alkyl such as ethyl, etc. In one embodiment, the alkyl is a C2-C200 alkyl group. In another embodiment, the alkyl is a C6-C60 alkyl group. In another embodiment, the alkyl is a C5-C22 alkyl group. Examples of alkyl group include butyl, octyl, decyl, lauryl, cetyl (palmityl), and stearyl.
The term “alkene”, as used herein by itself or as part of a group, refers to an alkyl group containing one, two, three, or more carbon-to-carbon double bonds. In one embodiment, the alkene group is a C2-C200 alkene group. In another embodiment, the alkene group is a C6-C60 alkene group. In another embodiment, the alkene group is a C6-C60 alkene group. In another embodiment, the alkene group is a C5-C22 alkene group. Examples of alkene include linoleyl, oleyl, dilinoleyl, and trilinoleyl.
The term “alkyne”, as used herein by itself or as part of a group, refers to an alkyl group containing one, two, three, or more carbon-to-carbon triple bonds. In another embodiment, the alkyne is a C2-C200 alkyne group.
The term “cyclic”, as used herein by itself or as part of a group, refers to a stable cyclic compound containing three or more carbon atoms. In an embodiment, the cyclic is a C3-C200 cyclic group. In an embodiment, the cyclic is a C6-C60 cyclic group. In an embodiment, the cyclic is a C5-C22 cyclic group. Examples of cyclic compound include benzene, cyclopentane, and cyclohexane.
The term “heteroalkyl”, as used herein by itself or as part of a group, refers to a stable straight or branched chain alkyl radical containing 2 to 200 carbon atoms and at least one heteroatoms, which can be the same or different, selected from O, N, or S, wherein the sulfur atom(s) can optionally be oxidized. The heteroatoms can be placed at any interior position of the heteroalkyl group or at a position at which the heteroalkyl group is attached to the remainder of the molecule. In an embodiment, the heteroalkyl is a C2-C60 heteroalkyl group. Examples include, but are not limited to, hydroxy ethylene, hydroxy stearyl, glyceryl stearyl, succinyl, adipoyl, and sebacoyl.
The term “heteroalkene”, as used herein by itself or as part of a group, refers to a stable straight or branched chain alkene radical containing 2 to 200 carbon atoms and at least one heteroatoms, which can be the same or different, selected from O, N, or S, wherein the sulfur atom(s) can optionally be oxidized. The heteroatoms can be placed at any interior position of the heteroalkyl group or at a position at which the heteroalkyl group is attached to the remainder of the molecule. Examples of heteroalkene compound include oleoyl, ricinolyl, and linoleoyl
The term “heteroalkyne”, as used herein by itself or as part of a group, refers to a stable straight or branched chain alkyne radical containing 2 to 200 carbon atoms and at least one heteroatoms, which can be the same or different, selected from O, N, or S, wherein the sulfur atom(s) can optionally be oxidized. The heteroatoms can be placed at any interior position of the heteroalkyl group or at a position at which the heteroalkyl group is attached to the remainder of the molecule.
The term “heterocyclic”, as used herein by itself or as part of a group, refers to a stable cyclic compound containing two or more carbon atoms and at least one heteroatom, which can be the same or different, selected from O, N, or S. In an embodiment, the heterocyclic is a C2-C200 heterocyclic group. In an embodiment, the heterocyclic is C6-C60 heterocyclic group. Examples include, but are not limited to, furan, oxolane, and thiophene.
Various aspect of the disclosure are described in greater detail below.
In an aspect, the present disclosure is directed to elastomer comprising the reaction product of at least one epoxidized molecule and at least one crosslinker.
a. Components
i. Epoxidized Molecule
In an aspect, the at least one epoxidized molecule is a compound of formula (I)
wherein
R1 is C6-C100,000 alkyl group, C6-C100,000 heteroalkyl group, C6-C100,000 alkene group, C6-C100,000 heteroalkene group, C6-C100,000 alkyne group, C6-C100,000 heteroalkyne group, C6-C100,000 cyclic group, or C6-C100,000 heterocyclic group;
R2 is hydrogen, C1-C100,000 alkyl group, C1-C100,000 heteroalkyl group, C2-C100,000 alkene group, C2-C100,000 heteroalkene group, C2-C100,000 alkyne group, C2-C100,000 heteroalkyne group, C3-C100,000 cyclic group, or C3-C100,000 heterocyclic group; and
m is an integer from 2 to 1,000.
In an aspect, the at least one epoxidized molecule may be an epoxidized vegetable oil. In a further aspect, the epoxidized vegetable oil may be selected from the group consisting of epoxidized soybean oil, epoxidized safflower oil, epoxidized linseed oil, epoxidized corn oil, epoxidized sunflower oil, epoxidized olive oil, epoxidized canola oil, epoxidized sesame oil, epoxidized cottonseed oil, epoxidized palm oil, epoxidized rapeseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized peanut oil, epoxidized cuphea oil, epoxidized milkweed oil, epoxidized salicornia oil, epoxidized high oleic safflower oil, epoxidized high oleic soybean oil, epoxidized high oleic peanut oil, epoxidized high oleic sunflower oil, epoxidized high erucic rapeseed oil (crambe oil), and combinations thereof. In a further aspect, the epoxidized vegetable oil may be epoxidized soybean oil, epoxidized linseed oil, and combinations thereof. In yet a further aspect, the epoxidized vegetable oil may be epoxidized soybean oil.
In an aspect, the epoxidized vegetable oil may be prepared by treating a vegetable oil with a peroxyacid to fully epoxidized the double bonds in the vegetable oil. Epoxidation of vegetable oils may be carried out as described by Qureshi et al. Polymer Science and Technology, Vol. 17, Plenum Press, p. 250, the entire contents of which is hereby incorporated by reference. Additional methods for epoxidation of vegetable oils are generally known in the art. In some aspects, the epoxidation reaction is carried to completion. In a non-limiting aspect, the epoxidation may be carried out by reacting milkweed oil with formic acid and hydrogen peroxide at about 75° C.
In some aspects, the degree of epoxidation may be greater than 3 oxirane rings per triglyceride molecule. In other aspects, the degree of epoxidation may be from 3 to 5 oxirane rings per triglyceride molecule. In a further aspect, the degree of epoxidation may be 4 oxirane rings per triglyceride molecule.
ii. Crosslinker
In an aspect, the at least one crosslinker is selected from the group consisting of:
(i) a carboxylic acid comprising the structure of formula (II)
wherein
R3 is C2-C200 alkyl group, C2-C200 heteroalkyl group, C2-C200 alkene group, C2-C200 heteroalkene group, C2-C200 alkyne group, C2-C200 heteroalkyne group, C3-C200 cyclic group, or C2-C200 heterocyclic group; and
n is an integer from 2 to 10;
(ii) an anhydride comprising the structure of formula (III)
(iii) an amine comprising the structure of formula (IV)
(iv) an alcohol comprising the structure of formula (V)
(v) a hydroxyl carboxylic acid comprising the structure of formula (VI)
(vi) a amine carboxylic acid comprising the structure of formula (VII)
In an aspect, the carboxylic acid comprises the structure of formula (II), wherein R2 is C2-C60 alkyl group, C2-C60 heteroalkyl group, C2-C60 alkene group, or C2-C60 heteroalkene group; and n is an integer from 2 to 10. In a further aspect, R2 may be succinyl, adipoyl, sebacoyl, dilinoleyl, or trilinoleyl.
In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is an integer of 2 to 6. In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is 2, 3, 4, 5, or 6.
In an aspect, the carboxylic acid may be selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimesic acid, carballylic acid, C54 trimer acid, mellitic acid, reaction product of ricinoleic acid and sebacic acid, reaction product of C36 dimer acid, and C36 dimer diol, and combinations thereof. In a further aspect, the carboxylic acid may be selected from the group consisting of citric acid, C54 trimer acid, and combinations thereof.
In an aspect, the carboxylic acid is a dicarboxylic acid. In an aspect, the dicarboxylic acid may be selected from the group consisting of malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, C21 dimer acid, C36 dimer acid, hydrogenated C36 dimer acid, aspartic acid, glutamic acid, tartaric acid, malic acid, and combinations thereof. In a further aspect, the dicarboxylic acid may be selected from the group consisting of malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, C21 dimer acid, C36 dimer acid, hydrogenated C36 dimer acid, and combinations thereof. In one aspect, the dicarboxylic acid is C36 dimer acid.
In an aspect, the anhydride comprises the structure of formula (III), wherein R4 is C2-C10 alkyl group or C2-C10 alkene group. In a further aspect, R4 is C2-C8 alkyl group.
In an aspect, the anhydride may be selected from the group consisting of malonic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, azelaic anhydride, sebacic anhydride, undecanedioic anhydride, dodecanedioic anhydride, tridecanedioic anhydride, hexadecanedioic anhydride, C21 dimer acid anhydride, C36 dimer acid anhydride, hydrogenated C36 dimer acid anhydride, aspartic anhydride, glutamic anhydride, tartaric anhydride, malic anhydride, and combinations thereof. In a further aspect, the anhydride may be selected from the group consisting of succinic anhydride, adipic anhydride, sebacic anhydride, C36 dimer acid anhydride, hydrogenated C36 dimer acid anhydride, and combinations thereof.
In an aspect, the amine comprises the structure of formula (IV), wherein p is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the amine comprises the structure of formula (IV), wherein p is an integer of 2 to 6. In an aspect, the amine comprises the structure of formula (IV), wherein p is 2, 3, 4, 5, or 6.
In an aspect, the amine may be selected from the group consisting of 1,2-diaminoethane, propane-1,3-diamine, butane-1,4-diamine, pentane-7,5-diamine, hexane-1,6-diamine, 1,7-heptanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, C54 trimer triamine, and combinations thereof. In a further aspect, the amine may be selected from the group consisting of hexane-1,6-diamine, C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, the amine may be selected from the group consisting of include ethylenediamine, 1,3-diaminopropane (1,3-propanediamine), putrescine (1,4-butanediamine), cadaverine (1,5-pentanediamine), hexamethylenediamine (1,6-hexanediamine), trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, diphenylethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, triethylenetetramine, xylylenediamine, phenylenediamine, spermidine, spermine, polyethylenimine, C36 dimer diamine, hydrogenated C36 dimer diamine, poly(ethylene glycol) bis(amine), lysine, and combinations thereof. In some aspects, the amine may be selected from the group consisting of spermidine, spermine, polyethylenimine, and combinations thereof. In other aspects, the amine may be selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, wherein the amine may be a diamine. In an aspect, the diamine may be selected from the group consisting of ethylenediamine, 1,3-diaminopropane (1,3-propanediamine), putrescine (1,4-butanediamine), cadaverine (1,5-pentanediamine), hexamethylenediamine (1,6-hexanediamine), trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, diphenylethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, xylylenediamine, phenylenediamine, polyethylenimine, C36 dimer diamine, hydrogenated C36 dimer diamine, poly(ethylene glycol) bis(amine), lysine, and combinations thereof. In a further aspect, the diamine may be selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, the alcohol comprises the structure of formula (V), wherein R6 is C2-C200 alkyl group, C2-C200 heteroalkyl group, C2-C200 alkene group, or C2-C200 heteroalkene group; and q is an integer from 2 to 10. In a further aspect, the alcohol comprises the structure of formula (V), wherein R6 is C2-C60 alkyl group, C2-C60 heteroalkyl group, C2-C60 alkene group, or C2-C60 heteroalkene group; and q is an integer from 2 to 10.
In an aspect, the alcohol comprises the structure of formula (V), wherein q is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the alcohol comprises the structure of formula (V), wherein q is an integer of 2 to 6. In an aspect, the alcohol comprises the structure of formula (V), wherein q is 2, 3, 4, 5, or 6.
In an aspect, the alcohol may be selected from the group consisting of glycerol, diglycerol, polyglycerol, sorbitan, castor oil, hydrogenated castor oil, sugar alcohol, monosaccharide, disaccharides, oligosaccharide, polysaccharides, tannin, gallic acid, gluconic acid, lactobionic acid, gluconolactone, and combinations thereof. In a further aspect, the alcohol may be selected from the group consisting of glycerol, diglycerol, polyglycerol, castor oil, hydrogenated castor oil, sorbitol, gallic acid, and combinations thereof.
In an aspect, the alcohol may be a diol. In some aspects, the diol may be selected from the group consisting of ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 1,1,5-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, C36 dimer diol, hydrogenated C36 dimer diol, and combinations thereof. In a further aspect, the diol may be selected from the group consisting of 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, C36 dimer diol, hydrogenated C36 dimer diol, and combinations thereof. In one aspect, the alcohol is C36 dimer diol.
In an aspect, the hydroxyl carboxylic acid may be selected from the group consisting of glycolic acid, lactic acid, salicylic acid, tropic acid, ricinoleic acid, isoricinoleic acid, lesquerolic acid, densipolic acid, auricolic acid, dimorphecolic acid, hydroxy palmitoleic acid, hydroxy palmitic acid, hydroxy oleic acid, 2-hydroxy stearic acid, 12-hydroxy stearic acid, and combinations thereof. In a further aspect, the hydroxyl carboxylic acid may be selected from the group consisting of ricinoleic acid, 12-hydroxy stearic acid, and combinations thereof.
In an aspect, the amine carboxylic acid may be selected from the group consisting of glycine, β-alanine, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, aminocaprylic acid, 12-aminolauric Acid, 14-aminotetradecanoic acid, 18-aminostearic acid, lysine, alanine, aspartic acid, glutamic acid, serine, threonine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine and combination thereof. In a further aspect, the amine carboxylic acid may be selected from the group consisting of β-alanine, 6-aminocaproic acid, 8-aminocaprylic acid, lysine, and combinations thereof.
In an aspect, the amine carboxylic acid may be selected from the group consisting of 3-aminopropanoic acid, 2-aminobutanoic acid, glycine, alanine, isoleucine, leucine, methionine, phenylalanine, valine, tryptophan, asparagine, glutamine, lysine, glutamic acid, and combinations thereof. In a further aspect, the amine carboxylic acid may be selected from the group consisting of 2-aminobutanoic acid, lysine, glutamic acid, and combinations thereof.
iii. Ratio
In an aspect, the molar ratio of the epoxy functional group from the epoxidized molecule to the carboxylic acid functional group (—COOH), the carboxylic anhydride functional group (—COOCO—), the hydroxyl functional group (—OH), or the amine functional group (—NH2) of the crosslinker ranges from 2:1 to 1:2. In some aspect, the molar ratio of the epoxy functional group from the epoxidized molecule to the carboxylic acid functional group (—COOH), the carboxylic anhydride functional group (—COOCO—), the hydroxyl functional group (—OH), or the amine functional group (—NH2) is about 2:1, about 1.5:1, about 1:1, about 1:1.5, or about 1:2.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to carboxylic acid functional group (—COOH) in the carboxylic acid comprising the structure of formula (II) is about 1:2 to about 2:1 In some aspects, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to carboxylic acid functional group (—COOH) in the carboxylic acid comprising the structure of formula (II) is about 1:2, about 1:1.9, about 1:1.8, about 1:1.7, about 1:1.6, about 1:1.5, about 1:1.4, about 1:1.3, about 1:1.2, about 1:1.1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, or about 2:1. In a further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to carboxylic acid functional group (—COOH) in the carboxylic acid comprising the structure of formula (II) is about 1:1.5 to about 1.5:1.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the anhydride functional group (—COOCO—) in the anhydride comprising the structure of formula (III) is about 1:1 to about 4:1. In some aspects, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the anhydride functional group (—COOCO—) in the anhydride comprising the structure of formula (III) is about 1:1, about 1.1:1, about 1.15:1, about 1.2:1, about 1.25:1, about 1.3:1, about 1.35:1, about 1.4:1, about 1.45:1, about 1.5:1, about 1.55:1, about 1.6:1, about 1.65:1, about 1.7:1, about 1.75:1, about 1.8:1, about 1.85:1, about 1.9:1, about 1.95:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 3.1:1, about 3.2:1, about 3.3:1, about 3.4:1, about 3.5:1, about 3.6:1, about 3.7:1, about 3.8:1, about 3.9:1, or about 4:1. In a further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the anhydride functional group (—COOCO—) in the anhydride comprising the structure of formula (III) is about 1.33:1 to about 3:1.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the amine functional group (—NH2) in the amine comprising the structure of formula (IV) is about 1:2 to about 2:1. In some aspects, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the amine functional group (—NH2) in the amine comprising the structure of formula (IV) is about 1:2, about 1.1.9, about 1:1.8, about 1:1.7, about 1.1.6, about 1:1.5, about 1:1.4, about 1.1.3, about 1:1.2, about 1:1.1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, or about 2:1. Ina further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the amine functional group (—NH2) in the amine comprising the structure of formula (IV) is about 1:1.5 to 1.5:1.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the hydroxyl functional group (—OH) in the alcohol comprising the structure of formula (V) is about 1:2 to about 2:1. In some aspects, the epoxy functional group in the at least one epoxidized molecule to the hydroxyl functional group (—OH) in the alcohol comprising the structure of formula (V) is about 1:2, about 1:1.9, about 1:1.8, about 1:1.7, about 1:1.6, about 1:1.5, about 1:1.4, about 1:1.3, about 1:1.2, about 1:1.1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, or about 2:1. In a further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the hydroxyl functional group (—OH) in the alcohol comprising the structure of formula (V) is about 1:1.5 to 1.5:1.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the hydroxyl carboxylic acid comprising the structure of formula (VI) is about 1:1 to about 4:1. In some aspects, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the hydroxyl carboxylic acid comprising the structure of formula (VI) is about 1:1, about 1.1:1, about 1.15:1, about 1.2:1, about 1.25:1, about 1.3:1, about 1.35:1, about 1.4:1, about 1.45:1, about 1.5:1, about 1.55:1, about 1.6:1, about 1.65:1, about 1.7:1, about 1.75:1, about 1.8:1, about 1.85:1, about 1.9:1, about 1.95:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 3.1:1, about 3.2:1, about 3.3:1, about 3.4:1, about 3.5:1, about 3.6:1, about 3.7:1, about 3.8:1, about 3.9:1, or about 4:1. Ina further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the hydroxyl carboxylic acid comprising the structure of formula (VI) is about 1.33:1 to about 3:1.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the amine carboxylic acid comprising the structure of formula (VII) is about 1:1 to about 4:1. In some aspects, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the amine carboxylic acid comprising the structure of formula (VII) is about 1:1, about 1.1:1, about 1.15:1, about 1.2:1, about 1.25:1, about 1.3:1, about 1.35:1, about 1.4:1, about 1.45:1, about 1.5:1, about 1.55:1, about 1.6:1, about 1.65:1, about 1.7:1, about 1.75:1, about 1.8:1, about 1.85:1, about 1.9:1, about 1.95:1, about 2:1, about 2.1:1, about 2.2:1, about 2.3:1, about 2.4:1, about 2.5:1, about 2.6:1, about 2.7:1, about 2.8:1, about 2.9:1, about 3:1, about 3.1:1, about 3.2:1, about 3.3:1, about 3.4:1, about 3.5:1, about 3.6:1, about 3.7:1, about 3.8:1, about 3.9:1, or about 4:1. In a further aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the amine carboxylic acid comprising the structure of formula (VII) is about 1.33:1 to about 3:1.
In an aspect, the elastomer may be crumbled to form a crosslinked polyester elastomer powder.
In an aspect, a composition may be prepared by shearing the elastomer, or elastomer with a solvent, as described herein, to form a sheared gel. In another aspect, a composition may be prepared by combining the elastomer, as described herein, with a solvent thereby forming a mixture and shearing the mixture. In an aspect, the composition is a gel or a paste. In a further aspect, the composition is a gel.
In some aspects, the solvent will be as discussed below.
In some aspects, the viscosity of the gel may be from about 10 cp to about 1,000,000 cp as measured by rheometer at a shear rate of 0.1 s−1. In another aspect, the viscosity of the gel may be from about 30,000 cp to about 500,000 cp. In some aspects, the viscosity of the gel may be about 10 cp, about 1,000 cp, about 5,000 cp, about 10,000 cp, about 15,000 cp, about 20,000 cp, about 25,000 cp, about 30,000 cp, about 35,000 cp, about 40,000 cp, about 45,000 cp, about 50,000 cp, about 55,000 cp, about 60,000 cp, about 65,000 cp, about 70,000 cp, about 75,000 cp, about 80,000 cp, about 85,000 cp, about 90,000 cp, about 95,000 cp, about 100,000 cp, about 150,000 cp, about 200,000 cp, about 250,000 cp, about 300,000 cp, about 350,000 cp, about 400,000 cp, about 450,000 cp, about 500,000 cp, about 550,000 cp, about 600,000 cp, about 650,000 cp, about 700,000 cp, about 750,000 cp, about 800,000 cp, about 850,000 cp, about 900,000 cp, about 950,000 cp, or about 1,000,000 cp.
In some aspects, the gel is comprised of particles of size from about 1 μm to about 500 μm as measured by laser diffraction particle size analyzer. In another aspect, the gel is comprised of particles of size from about 25 μm to about 400 μm. In some aspects, the gel is comprised of particles of size of about 1 μm, about 5 μm, about 10 μm, about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 75 μm, about 100 μm, about 125 μm, about 150 μm, about 175 μm, about 200 μm, about 225 μm, about 250 μm, about 275 μm, about 300 μm, about 325 μm, about 350 μm, about 375 μm, or about 400 μm.
In an aspect, the elastomer may be prepared using the methods described herein.
The disclosure also relates to a method of preparing an elastomer comprising reacting at least oe epoxidized molecule (e.g., epoxidized soybean oil) and at least one crosslinker (C36 dimer acid and/or C36 dimer diol) in the presence of a first solvent thereby forming a crosslinking polymer structure.
In some aspects, the method of preparing the gel, as described herein, is produced in an environmentally friendly process. In additional aspects, the method of preparing the gel, as described herein, utilizes no toxic raw materials. In further aspects, the method of preparing the gel, as described herein, generates no toxic side products.
a. Components
i. Epoxidized Molecule
In an aspect, the at least one epoxidized molecule is a compound of formula (I) described above. In an aspect, the at least one epoxidized molecule may be an epoxidized vegetable oil described above, e.g., epoxidized soybean oil.
ii. Crosslinker
In an aspect, the at least one crosslinker is selected from the group consisting of:
(i) a carboxylic acid comprising the structure of formula (II) described above;
(ii) an anhydride comprising the structure of formula (III) described above;
(iii) an amine comprising the structure of formula (IV) described above;
(iv) an alcohol comprising the structure of formula (V) described above;
(v) a hydroxyl carboxylic acid comprising the structure of formula (VI) described above;
(vi) an amine carboxylic acid comprising the structure of formula (VII) described above.
In an aspect, the carboxylic acid comprises the structure of formula (II), wherein R2 is C2-C60 alkyl group, C2-C60 heteroalkyl group, C2-C60 alkene group, or C2-C60 heteroalkene group; and n is an integer from 2 to 10. In a further aspect, R2 may be succinyl, adipoyl, sebacoyl, dilinoleyl, or trilinoleyl.
In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is an integer of 2 to 6. In an aspect, the carboxylic acid comprises the structure of formula (II), wherein n is 2, 3, 4, 5, or 6.
In an aspect, the carboxylic acid may be selected from the group consisting of citric acid, isocitric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimesic acid, carballylic acid, C54 trimer acid, mellitic acid, reaction product of ricinoleic acid and sebacic acid, reaction product of C36 dimer acid and C36 dimer diol, and combinations thereof. In a further aspect, the carboxylic acid may be selected from the group consisting of citric acid, C54 trimer acid, and combinations thereof.
In an aspect, the carboxylic acid is a dicarboxylic acid. In an aspect, the dicarboxylic acid may be selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, C21 dimer acid, C36 dimer acid, hydrogenated C36 dimer acid, aspartic acid, glutamic acid, tartaric acid, malic acid, and combinations thereof. In a further aspect, the dicarboxylic acid may be selected from the group consisting of malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, C21 dimer acid, C36 dimer acid, hydrogenated C36 dimer acid, and combinations thereof. In another aspect, the dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, C21 dimer acid, C36 dimer acid, hydrogenated C36 dimer acid, and combinations thereof. In one aspect, the carboxylic acid is C36 dimer acid.
In an aspect, C36 dimer acid is the dicarboxylic acids prepared by dimerizing unsaturated fatty acids from plant oil.
In an aspect, C54 trimer acid is the polycarboxylic acid prepared by trimerizing unsaturated fatty acids from plant oil.
In some aspects, the unsaturated fatty acids are palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, or linolenic acid.
In some aspects, the plant oils are soybean oil, safflower oil, linseed oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, peanut oil, or milkweed oil.
In an aspect, the anhydride comprises the structure of formula (III), wherein R4 is C2-C10 alkyl group or C2-C10 alkene group. In a further aspect, R4 is C2-C8 alkyl group.
In an aspect, the anhydride may be selected from the group consisting of malonic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, azelaic anhydride, sebacic anhydride, undecanedioic anhydride, dodecanedioic anhydride, tridecanedioic anhydride, hexadecanedioic anhydride, C21 dimer acid anhydride, C36 dimer acid anhydride, hydrogenated C36 dimer acid anhydride, aspartic anhydride, glutamic anhydride, tartaric anhydride, malic anhydride, and combinations thereof. In a further aspect, the anhydride may be selected from the group consisting of succinic anhydride, adipic anhydride, sebacic anhydride, C36 dimer acid anhydride, hydrogenated C36 dimer acid anhydride, and combinations thereof.
In an aspect, the C36 dimer diamine is the diamine produced from a C36 dimer acid.
In an aspect, the amine comprises the structure of formula (IV), wherein p is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the amine comprises the structure of formula (IV), wherein p is an integer between 2 and 6. In an aspect, the amine comprises the structure of formula (IV), wherein p is 2, 3, 4, 5, or 6.
In an aspect, the amine may be selected from the group consisting of 1,2-diaminoethane, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexane-1,6-diamine, 1,7-heptanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, C54 trimer triamine, and combinations thereof. In a further aspect, the amine may be selected from the group consisting of hexane-1,6-diamine. C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, the amine may be selected from the group consisting of include ethylenediamine, 1,3-diaminopropane (1,3-propanediamine), putrescine (1,4-butanediamine), cadaverine (1,5-pentanediamine), hexamethylenediamine (1,6-hexanediamine), trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, diphenylethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, triethylenetetramine, xylylenediamine, phenylenediamine, spermidine, spermine, polyethylenimine, C36 dimer diamine, hydrogenated C36 dimer diamine, poly(ethylene glycol) bis(amine), lysine, and combinations thereof. In some aspects, the amine may be selected from the group consisting of spermidine, spermine, polyethylenimine, and combinations thereof. In other aspects, the amine may be selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, wherein the amine may be a diamine. In an aspect, the diamine may be selected from the group consisting of ethylenediamine, 1,3-diaminopropane (1,3-propanediamine), putrescine (1,4-butanediamine), cadaverine (1,5-pentanediamine), hexamethylenediamine (1,6-hexanediamine), trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, diphenylethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, xylylenediamine, phenylenediamine, polyethylenimine, C36 dimer diamine, hydrogenated C36 dimer diamine, poly(ethylene glycol) bis(amine), lysine, and combinations thereof. In a further aspect, the diamine may be selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, C36 dimer diamine, hydrogenated C36 dimer diamine, and combinations thereof.
In an aspect, the alcohol comprises the structure of formula (V), wherein R6 is C2-C200 alkyl group, C2-C200 heteroalkyl group, C2-C200 alkene group, or C2-C200 heteroalkene group; and q is an integer from 2 to 10. In a further aspect, the alcohol comprises the structure of formula (V), wherein R6 is C2-C60 alkyl group, C2-C60 heteroalkyl group, C2-C60 alkene group, or C2-C60 heteroalkene group; and q is an integer from 2 to 10.
In an aspect, the alcohol comprises the structure of formula (V), wherein q is 2, 3, 4, 5, 6, 7, 8, 9, or 10. In an aspect, the alcohol comprises the structure of formula (V), wherein q is an integer from 2 to 6. In an aspect, the alcohol comprises the structure of formula (V), wherein q is 2, 3, 4, 5, or 6.
In an aspect, the alcohol may be selected from the group consisting of glycerol, diglycerol, polyglycerol, sorbitan, castor oil, hydrogenated castor oil, sugar alcohol, monosaccharide, disaccharides, oligosaccharide, polysaccharides, tannin, gallic acid, gluconic acid, lactobionic acid, gluconolactone, and combinations thereof. In a further aspect, the alcohol may be selected from the group consisting of glycerol, diglycerol, polyglycerol, castor oil, hydrogenated castor oil, sorbitol, gallic acid, and combinations thereof. In another aspect, the alcohol may be selected from the group consisting of glycerol, diglycerol, polyglycerol, castor oil, hydrogenated castor oil, sorbitol, and combinations thereof.
In an aspect, the alcohol may be a diol. In some aspects, the diol may be selected from the group consisting of ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 1,1,5-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, C36 dimer diol, hydrogenated C36 dimer diol, and combinations thereof. In a further aspect, the diol may be selected from the group consisting of 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, C36 dimer diol, hydrogenated C36 dimer diol, and combinations thereof. In another aspect, the diol may be selected from the group consisting of 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, C36 dimer diol, and combinations thereof. In one aspect, the alcohol is C36 dimer diol. In an aspect, C36 dimer diol is a diol produced from C36 dimer acid.
In an aspect, the hydroxyl carboxylic acid may be selected from the group consisting of glycolic acid, lactic acid, salicylic acid, tropic acid, ricinoleic acid, isoricinoleic acid, lesquerolic acid, densipolic acid, auricolic acid, dimorphecolic acid, hydroxy palmitoleic acid, hydroxy palmitic acid, hydroxy oleic acid, 2-hydroxy stearic acid, 12-hydroxy stearic acid, and combinations thereof. In a further aspect, the hydroxyl carboxylic acid may be selected from the group consisting of ricinoleic acid, 12-hydroxy stearic acid, and combinations thereof.
In an aspect, the amine carboxylic acid may be selected from the group consisting of glycine, β-alanine, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, aminocaprylic acid, 12-aminolauric Acid, 14-aminotetradecanoic acid, 18-aminostearic acid, lysine, alanine, aspartic acid, glutamic acid, serine, threonine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine and combination thereof. In a further aspect, the amine carboxylic acid may be selected from the group consisting of β-alanine, 6-aminocaproic acid, 8-aminocaprylic acid, lysine, and combinations thereof.
In an aspect, the amine carboxylic acid may be selected from the group consisting of 3-aminopropanoic acid, 2-aminobutanoic acid, glycine, alanine, isoleucine, leucine, methionine, phenylalanine, valine, tryptophan, asparagine, glutamine, lysine, glutamic acid, and combinations thereof. In a further aspect, the amine carboxylic acid may be selected from the group consisting of 2-aminobutanoic acid, lysine, glutamic acid, and combinations thereof.
iii. Ratio
In an aspect, the molar ratio of the epoxy functional group from the epoxidized molecule to the carboxylic acid functional group (—COOH), the carboxylic anhydride functional group (—COOCO—), the hydroxyl functional group (—OH), or the amine functional group (—NH2) of the crosslinker is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to carboxylic acid functional group (—COOH) in the carboxylic acid comprises the structure of formula (II) is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the anhydride functional group (—COOCO—) in the anhydride comprises the structure of formula (III) is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the amine functional group (—NH2) in the amine comprises the structure of formula (IV) is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the hydroxyl functional group (—OH) in the alcohol comprises the structure of formula (V) is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the hydroxyl carboxylic acid comprises the structure of formula (VI) is described above.
In an aspect, the molar ratio of the epoxy functional group in the at least one epoxidized molecule to the carboxylic acid functional group (—COOH) in the amine carboxylic acid comprises the structure of formula (VII) is described above.
b. Catalyst
In an aspect, the reaction may further occur in the presence of at least one catalyst. In some aspects, the at least one catalyst may be selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, benzene sulfonic acid, sulfuric acid, amidosulfonic acid, sulfamic acid, sodium bisulfate, phosphoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, bismuth neodecanoate, bismuth(III) citrate, bismuth(III) chloride, bismuth(III) acetate, bismuth(III) phosphate, tin chloride, tin-pyrone, dibutyltin dilaurate, di-nbutyl-oxo-stannane, butyl stannoic acid, zinc chloride, zinc bromide, zinc carboxylic salt, zinc oxide, zinc hydroxy nitrate salt, zinc hydroxy acetate, triethylamine, tripropylamine, cocamidopropyl dimethylamine, stearamidopropyl dimethylamine, isostearamidopropyl dimethylamine, and combinations thereof. In a further aspect, the at least one catalyst is p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, bismuth neodecanoate, or combinations thereof.
c. Solvent
In some aspects, the solvent may be biobased or naturally derived. In an aspect, the first solvent may be a triglyceride solvent, a mono-ester solvent, a di-ester solvent, a citrate ester solvent, an ether solvent, a carbonate solvent, a hydrocarbon solvent, a silicone solvent, and combinations thereof.
In an aspect, the solvent may be a triglyceride. In an aspect, the triglyceride solvent may be a compound of formula (VIII)
wherein
R9, R10, and R11 are independently C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, and C2-C35 heteroalkene group.
In an aspect, the compound of formula (VIII), wherein R9, R10, and R11 are independently C5-C17 alkyl group or C5-C17 alkene group.
In an aspect, the triglyceride solvent may be selected from the group consisting of caprylic/capric triglyceride, triheptanoin, corn oil, soybean oil, olive oil, rape seed oil, cotton seed oil, coconut oil, almond oil, argon oil, rosehip oil, black seed oil, grape seed oil, avocado oil, apricot kernel oil, geranium oil, lavender oil, rosehip oil, macadamia oil, eucalyptus oil, sardine oil, herring oil, safflower oil, linseed oil, sunflower oil, olive oil, canola oil, sesame oil, cottonseed oil, palm oil, rapeseed oil, tung oil, fish oil, peanut oil, cuphea oil, milkweed oil, salicornia oil, whale oil, castor oil, and combinations thereof. In a further aspect, the triglyceride solvent may be selected from the group consisting of caprylic/capric triglyceride, triheptanoin, and combinations thereof.
In an aspect, the solvent may be a mono-ester. In an aspect, the mono-ester solvent may be a compound of formula (IX)
wherein
R12 is C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, or C2-C35 heteroalkene group; and
R13 is H, C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, or C2-C35 heteroalkene group.
In an aspect, the compound of formula (IX), wherein R12 is C5-C17 alkyl group or C5-C17 alkene group and R13 is C2-C18 alkyl group.
In an aspect, the mono-ester solvent may be selected from the group consisting of coco-caprylate/caprate, coco-caprylate, coco-caprate, jojoba oil, jojoba esters, isopropyl jojobate, ethyl macadamiate, isoamyl laurate, heptyl undecylenate, methylheptyl isostearate, isostearyl isostearate, glyceryl ricinoleate, isostearyl palmitate, myristyl myristate, octyldodecyl myristate, octyldodecyl hydroxystearate, butyl myristate, ethylhexyl cocoate, ethylhexyl palmitate, ethylhexyl stearate, butyl stearate, decyl oleate, isocetyl behenate, isocetyl myristate, isocetyl palmitate, isocetyl stearate, isodecyl oleate, isopropyl isostearate, isopropyl myristate, isopropyl palmitate, oleyl oleate, propylene glycol laurate, octydodecyl erucate, C12-C13 alkyl lactate, C12-C15 alkyl lactate, isostearyl lactate, glycereth-5 lactate, lauryl lactate, myristyl lactate, oleyl lactate, laureth-2 benzoate, C12-C15 alkyl benzoate, C12-C15 pareth-3 benzoate, dipropylene glycol benzoate, isodecyl salicylate, C12-C15 alkyl salicylate, tridecyl salicylate, ethylhexyl isononanoate, cetyl ethylhexanoate, isononyl isononanoate, isodecyl ethylhexanoate, isodecyl isononanoate, tridecyl ethylhexanoate, isotridecyl isononanoate, isostearyl isononanoate, cetearyl isononanoate, laureth-2 ethylhexanoate, cetearyl ethylhexanoate, isodecyl neopentanoate, isostearyl neopentanoate, nyristyl neopentanoate, isostearyl behenate, octyldodecyl neopentanoate, tridecyl neopentanoate, and combinations thereof.
In an aspect, the mono-ester solvent may be selected from the group consisting of coco-caprylate/caprate, coco-caprylate, jojoba oil, isoamyl laurate, methylheptyl isostearate, C12-C13 alkyl lactate, C12-C15 alkyl lactate, ethylhexyl isononanoate, cetyl ethylhexanoate, isononyl isononanoate, isodecyl ethylhexanoate, isodecyl isononanoate, tridecyl ethylhexanoate, isotridecyl isononanoate, isostearyl isononanoate, cetearyl isononanoate, and combinations thereof. In a further aspect, the mono-ester solvent may be selected from the group consisting of coco-caprylate/caprate, coco-caprylate, isoamyl laurate, isononyl isononanoate, heptyl undecylenate, jojoba oil, jojoba esters, and combinations thereof. In one aspect, the mono-ester solvent is coco-caprylate/caprate.
In an aspect, the solvent may be a di-ester solvent. In an aspect, the di-ester solvent may be a compound of formula (X), formula (XI), or formula (XII)
wherein
R14 is C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, or C2-C35 heteroalkene group; and\
R15 and R16 are independently H, C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, or C2-C35 heteroalkene group.
In an aspect, the compound of formula (X), formula (XI), or formula (XII), wherein R14 is C2-C10 alkyl group or C2-C10 alkene group and R15 and R16 are independently C1-C12 alkyl group or C2-C12 alkene group.
In an aspect, the di-ester solvent may be selected from the group consisting of diethyl succinate, dibutyl succinate, diethyhexyl succinate, diisopropyl sebacate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, diisostearyl dimer, diisostearyl malate, isostearyl stearoyl stearate, isocetyl stearoyl stearate, octyldodecyl stearoyl stearate, diethylhexyl malate, diethylhexyl maleate, dipropylene glycol dibenzoate, dicapryl adipate, dicaprylyl maleate, diisopropyl dimer, diisopropyl adipate, diisobutyl adipate, diisopropyl sebacate, diisostearyl dimer, diethyhexyl succinate, diethylene glycol diethylhexanoate, neopentyl glycol dicaprate, propylene glycol dicaprylate/dicaprate, neopentyl glycol diisostearate, neopentyl glycol diethylhexanoate, neopentyl glycol diheptanoate, and combinations thereof. In a further aspect, the di-ester solvent may be selected from the group consisting of dicapryl adipate, dicaprylyl maleate, diisopropyl adipate, diisobutyl adipate, diethyl succinate, dibutyl succinate, diethyhexyl succinate, diisopropyl sebacate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, neopentyl glycol diethylhexanoate, neopentyl glycol diheptanoate, and combinations thereof.
In an aspect, the solvent may be a citrate ester. In an aspect, the citrate ester may be a compound of formula (XIII)
wherein
R17, R18, R19, and R20 are independently H, C1-C35 alkyl group, C1-C35 heteroalkyl group, C2-C35 alkene group, or C2-C35 heteroalkene group.
In an aspect, the compound of formula (XIII), wherein R17, R18, and R19 are independently C1-C10 alkyl group or C2-C10 alkene group and R20 is an acetyl group.
In an aspect, the citrate ester solvent may be a compound selected from the group consisting of tricaprylyl citrate, triisostearyl citrate, triisocetyl citrate, trioctyldodecyl citrate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, trioctyldodecyl citrate, triisocetyl citrate, and combinations thereof.
In an aspect, the solvent may be an ether solvent. In an aspect, the ether solvent may be a compound of formula (XIV)
wherein
R21 and R22 are independently H, C2-C20 alkyl group, C2-C20 heteroalkyl group, C2-C20 alkene group, or C2-C20 heteroalkene group.
In an aspect, the compound of formula (XIV), wherein R2′ and R22 are independently C2-C20 alkyl group.
In an aspect, the ether solvent may be selected from the group consisting of dicaprylyl ether, didecyl ether, panthenyl ethyl ether, dicetyl ether, dimyristyl ether, distearyl ether, distearyl ether, dilauryl ether, and combinations thereof. In a further aspect, the ether solvent may be selected from the group consisting of dicaprylyl ether, didecyl ether, and combinations thereof.
In an aspect, the solvent may be a carbonate solvent. In an aspect, the carbonate solvent may be a compound of formula (XV)
wherein
R23 and R24 are independently H, C2-C20 alkyl group, C2-C20 heteroalkyl group, C2-C20 alkene group, or C2-C20 heteroalkene group.
In an aspect, the compound of formula (XV), wherein R23 and R24 are independently C2-C20 alkyl group.
In an aspect, the carbonate solvent may be selected from the group consisting of dicaprylyl carbonate, diethylhexyl carbonate, and combinations thereof.
In an aspect, the hydrocarbon solvent is selected from the group consisting of farnesene, hydrogenated farnesene, coconut alkanes, coconut/palm kernel alkanes, C9-C12 alkane, C10-C13 alkane, alkane, C12-C14 alkane, C13-C15 alkane, alkane, C14-C19 alkane, C14-C20 alkane, C14-C22 alkane, C15-C19 alkane, C11-C28 alkane, C17-C23 alkane, C9-C12 isoalkane, C9-C13 isoalkane, C9-C14 isoalkane, C9-C16 isoalkane, C10-C11 isoalkane, C10-C12 isoalkane, C10-C13 isoalkane, isoalkane, C11-C13 isoalkane, isoalkane, C12-C14 isoalkane, C12-C15 isoalkane, C12-C20 isoalkane, C13-C14 isoalkane, C13-C16 isoalkane, C14-C16 isoalkane, C15-C19 isoalkane, diethylhexylcyclohexane, undecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, docosane, squalane, hydrogenated polyisobutene, polybutene, hydrogenated polydecene, hydrogenated didecene, mineral oil, paraffin, isoparaffin, paraffium liquidum, petrolatum, dodecane, isohexadecane, isododecane, isoeicosane, and combinations thereof. In a further aspect, hydrocarbon solvent is selected from the group consisting of farnesene, hydrogenated farnesene, coconut alkanes, C9-C12 alkane, C13-C15 alkane, C14-C19 alkane, C14-C20 alkane, C14-C22 alkane, C15-C19 alkane, C13-C16 isoalkane, dodecane, undecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, squalane, isododecane, isohexadecane, and combinations thereof.
In an aspect, the solvent may be a silicone solvent. In some aspects, the silicone solvent may be selected from the group consisting of dimethicone, phenyl dimethicone, caprylyl methicone, ethyl trisiloxane, cyclotetrasiloxane, cyclopentasiloxane, cyclohexasiloxane, and combinations thereof.
In an aspect, the amount of the first solvent in the reaction may be present from about 10% to about 70% of the total weight of the epoxidized vegetable oil, the crosslinker, and the solvent. In an aspect, the amount of the first solvent in the reaction may be present from about 20% to about 70% of the total weight of the epoxidized vegetable oil, the crosslinker, and the solvent. In a further aspect, the amount of the solvent present may be from about 30% to about 50% of the total weight of the epoxidized vegetable oil, the crosslinker, and the solvent. In another aspect, the amount of the solvent present may be about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or about 70% of the total weight of the epoxidized vegetable oil, the crosslinker, and the solvent.
d. Temperature
In an aspect, the reaction can occur at a temperature from about 10° C. to about 250° C. In an aspect, the reaction may occur at a temperature from about 15° C. to about 250° C., from about 15° C. to about 225° C., from about 20° C. to about 220° C., from about 25° C. to about 200° C., from about 25° C. to about 175° C., from about 20° C. to about 175° C., or from about 20° C. to about 150° C. In a further aspect, the reaction can occur at a temperature from about 25° C. to about 200° C. In yet a further aspect, the reaction can occur at a temperature from about 20° C. to about 150° C. In another aspect, the reaction can occur at a temperature of about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., about 50° C., about 55° C., about 60° C., about 65° C., about 70° C., about 75° C., about 80° C., about 85° C., about 90° C., about 95° C., about 100° C., about 105° C., about 110° C., about 115° C., about 120° C., about 125° C., about 130° C., about 135° C., about 140° C., about 145° C., about 150° C., about 155° C., about 160° C., about 165° C., about 170° C., about 175° C., about 180° C., about 185° C., about 190° C., about 195° C., about 200° C., about 205° C., about 210° C., about 215° C., about 220° C., about 225° C., about 230° C., about 235° C., about 240° C., about 245° C., or about 250° C. In one aspect, the reaction can occur at a temperature from about 70° C. to about 140° C.
e. Time
In an aspect, the reaction time can be from about 4 hours to about 100 hours. In some aspects, the reaction time can be from about 4 hours to about 80 hours, from about 4 hours to about 50 hours, from about 4 hours to about 25 hours, from about 8 hours to about 25 hours, or from about 8 hours to about 24 hours. In another aspect, the reaction time can be about 4, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95, or about 100 hours. In yet another aspect, the reaction time can be about 8, about 10, about 12, about 14, about 16, about 18, about 20, about 22, or about 24 hours. In one aspect, the reaction time is about 12 hours to about 80 hours.
f. Swelling the Crosslinking Polymer Structure
In an additional aspect, the method can further comprise (i) combining the crosslinking polymer structure with a second solvent thereby forming a swollen crosslinking polymer structure and (ii) subjecting the swollen crosslinking polymer structure to shear force thereby forming a uniform polyester elastomer which can be processed into a gel. The second solvent can be one or more of the first solvents listed above.
In an aspect, the amount of the second solvent in the method may be from about 100 wt. % to about 900 wt. % of the crosslinking polymer. In another aspect, the amount of the second solvent in the method may be about 100 wt. %, about 150 wt. %, about 200 wt. %, about 250 wt. %, about 300 wt. %, about 350 wt. %, about 400 wt. %, about 450 wt. %, about 500 wt. %, about 550 wt. %, about 600 wt. %, about 650 wt. %, about 700 wt. %, about 750 wt. %, about 800 wt. %, about 850 wt. %, or about 900 wt. % of the crosslinking polymer. In an aspect, the amount of the second solvent can be dependent on the crosslinking polymer structure.
i. Shear Force
In some aspects, the shear force may be provided by any type of mixing and shearing equipment. In a further aspect, the mixing and shearing equipment may be batch mixer, planetary mixer, single or multiple screw extruder, dynamic or static mixer, colloid mill, homogenizer, sonolator, or a combination thereof.
g. Properties
The viscosity of the gel prepared from an elastomer described herein is described above. Additionally, the gel is comprised of particles of size described above.
In an additional aspect of the present disclosure, the products of the present disclosure, i.e., the gel prepared from a thermoset elastomer, may be formulated into a personal care formulation.
In some aspects, the personal care formulation may be a cosmetic or a medical product.
In an aspect, the personal care formulation further comprises a preservative, an antioxidant, a chelating agent, a gum or thickener, an oil, a wax, a fragrance, an essential oil, an emulsifier, a surfactant, and combinations thereof.
In some aspects, the personal care formulation may be formulated with a preservative, an antioxidant, a chelating agent, a gum or thickener, an oil, a wax, a fragrance, an essential oil, an emulsifier, a surfactant, and combinations thereof.
In some aspects, the products of the present disclosure may be added to formulations comprising make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners, mascaras, oil removers, color cosmetic removers, and powders
In some aspects, the products of the present disclosure may function as delivery systems for oil and water soluble substances such as vitamins.
In one aspect, the products of the present disclosure are compatible with a particulate additive. In one aspect, the particulate additive is an inorganic particulate, polymeric latex, and/or a pigment. In another aspect, the polymers are capable of suspending these particles for a prolonged period in personal care formulations.
Once the desired emulsion is prepared, the resulting material is usually a high viscosity cream with good feel characteristics and high absorbance of volatile solvents. The emulsion can then be blended into personal care formulations for hair care, skin care, and the like.
The personal care formulation can be a personal care application including deodorants, antiperspirants, antiperspirant/deodorants, shaving products, skin lotions, moisturizers, toners, bath products, cleansing products, hair care products such as shampoos, conditioners, mousses, styling gels, hair sprays, hair dyes, hair color products, hair bleaches, waving products, hair straighteners, manicure products (e.g., nail polish, nail polish remover, nail creams and lotions, cuticle softeners), protective creams (e.g., sunscreen, insect repellent and anti-aging products), color cosmetics (e.g., lipsticks, foundations, face powders, eye liners, eye shadows, blushes, makeup, and mascaras). The personal care application can also be a drug delivery system for topical application of a medicinal composition that can be applied to the skin.
In one aspect, the personal care formulation further comprises one or more personal care ingredients. Suitable personal care ingredients include, without limit, emollients, moisturizers, humectants, pigments (e.g., pearlescent pigments such as bismuth oxychloride and titanium dioxide coated mica), colorants, fragrances, biocides, preservatives, antioxidants, anti-fungal agents, antiperspirant agents, exfoliants, hormones, enzymes, medicinal compounds, vitamins, salts, electrolytes, alcohols, polyols, absorbing agents for ultraviolet radiation, botanical extracts, surfactants, silicone oils, organic oils, waxes, film formers, thickening agents (e.g., fumed silica or hydrated silica), particulate fillers (e.g., talc, kaolin, starch, modified starch, mica, nylon, clays, such as, for example, bentonite and organo-modified clays).
In some aspects, the one or more personal care components included in the personal care formulations are selected from the group consisting of a humectant, emollient, moisturizer, pigment, colorant, fragrance, biocide, preservative, antioxidant, anti-fungal agent, antiperspirant agent, exfoliant, hormone, enzyme, medicinal compound, vitamin, salt, electrolyte, alcohol, polyol, absorbing agent for ultraviolet radiation, botanical extract, surfactant, silicone oil, organic oil, wax, film former, and thickening agent. In some aspects, the one or more emollients is selected from the group consisting of triglyceride esters, wax esters, alkyl or alkenyl ester of fatty acids, polyhydric alcohol esters, and mixtures thereof. In some aspects, the one or more personal care components is a silicone oil, an organic oil, or mixtures thereof.
In one aspect, the personal care formulation is an antiperspirant composition that comprises a polymer composition or product described herein and one or more active antiperspirant agents. Suitable antiperspirant agents include, but are not limited to, the Category I active antiperspirant ingredients listed in the U.S. Food and Drug Administration's Oct. 10, 1993 Monograph on antiperspirant drug products for over-the-counter human use including aluminum halides, aluminum hydroxyhalides, for example, aluminum chlorohydrate, and complexes or mixtures thereof with zirconyl oxyhalides and zirconyl hydroxyhalides, (e.g., aluminum-zirconium chlorohydrate, and aluminum zirconium glycine complexes, such as aluminum zirconium tetrachlorohydrex gly).
In another aspect, the personal care formulation is a skin care composition comprising a polymer composition or product described herein, and a vehicle, such as a silicone oil or an organic oil. The skin care composition can also include emollients, such as triglyceride esters, wax esters, alkyl or alkenyl esters of fatty acids or polyhydric alcohol esters, pigments, vitamins (e.g., Vitamin A, Vitamin C and Vitamin E), sunscreen or sunblock compounds (e.g., titanium dioxide, zinc oxide, oxybenzone, octylmethoxy cinnamate, butylmethoxy dibenzoylm ethane, p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic acid).
In yet another aspect, the personal care formulation is a color cosmetic composition such as a lipstick, a makeup or mascara. The color cosmetic composition comprises a polymer composition or product described herein and a coloring agent (e.g., pigment, water-soluble dye, or liposoluble dye).
In still yet another aspect, the personal care formulation comprises a thermoset elastomer described herein and fragrant materials. The fragrant materials can be fragrant compounds, encapsulated fragrant compounds or fragrance releasing compounds that either the neat compounds or are encapsulated.
In one aspect, the disclosure relates to the use of a gel composition described herein for personal care formulation, such as a personal care application. The personal care applications can be any described above.
The following examples are included to demonstrate various aspects of the present disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples that follow represent techniques discovered by the inventors to function well in the practice of the disclosure, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific examples which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the disclosure.
In a suitable vessel equipped with agitation, heat and an ability to distill off water, 100 g of epoxidized soybean oil was added along with 90 g of hydrogenated dimer acid. Next 190 g of hemisqualane was added as solvent. After all ingredients have been charged under agitation, the temperature of the mass was raised to 140° C., and water was stripped off if needed. The temperature was held for 12-20 hours or until gelation took, place and polymer elastomer was formed. Thereafter the elastomer was broken into a powder by mechanical stirring.
In a suitable vessel equipped with agitation, heat and an ability to distill off water, 100 g of epoxidized soybean oil was added along with 16 g of succinic anhydride. Next 58 g of dicaprylyl ether was added as solvent. After all ingredients have been charged under agitation, the temperature of the mass was raised to 140° C., and water was stripped off if needed. The temperature was held for 12-20 hours or until gelation took, place and polymer elastomer was formed. Thereafter the elastomer was broken into a powder by mechanical stirring.
In a suitable vessel equipped with agitation, heat and an ability to distill off water, 110 g of epoxidized soybean oil was added along with 30 g of 1,10-diaminodecane. Next 140 g hemisqualane was added as solvent. After all ingredients have been charged under agitation, the temperature of the mass was raised to 140° C., and water was stripped off if needed. The temperature was held for 12-20 hours or until gelation took, place and polymer elastomer was formed. Thereafter the elastomer was broken into a powder by mechanical stirring.
In a suitable vessel equipped with agitation, heat and an ability to distill off water, 95 g of epoxidized soybean oil was added along with 30 g of sebacic acid and 9 g of 12-hydroxylstearic acid. Next 130 g of dicaprylyl ether was added as solvent. After all ingredients have been charged under agitation, the temperature of the mass was raised to 180° C., and water was stripped off if needed. The temperature was held for 10-15 hours or until gelation took place and polymer elastomer was formed. Thereafter the elastomer was broken into a powder by mechanical stirring.
After a very nice elastomer was produced which did not separate upon standing, 350 g of MCT oil was added into the vessel to mix with 120 g of elastomer. After the gel and solvent mixture sit in vessel for 12 hours it was homogenized with an Gaulin homogenizer to produce a creamy, translucent gel of very smooth consistency, suitable for use in personal care formulations.
Components of a natural oil/water foundation are listed in Table 1.
Combine phase A ingredients and heat to 50° C. with stirring. Wet powders with solvent mixture in phase B and homogenize. Add the homogenized mixture to the rest of phase B and heat to 50° C. Add phases B into phase A and mix for 10 minutes until content is homogeneous. Add phase C and homogenize.
Mix phase A and heat to 50° C. Wet powders with solvents and homogenize until smooth. Add to the rest of phase B and heat to 50° C. Slowly add phase A to phase B while mixing. Homogenize phase A+B. Cool down and add phase® C.
Combine the phase (A) ingredients and heat to 70 C until homogenous. Pour into mold.
Mix all ingredients and heat to 80-90° C. using cowles mixer. Ensure the oil thickener is dissolved, then pour the mixture into the jar and let it cool overnight.
Mix all the ingredients of phase A, heat to 75° C. Mix all the ingredients of phase B, heat to 70° C. Add phase B to phase A with intensive stirring. Homogenize the mixture for 1-2 minutes. Cool to 50° C. under gentle stirring. Add preservative and fragrance as desired, and mix well.
Wet xanthan gum with glycerin and butylene glycol; add the rest of the ingredients of phase A and heat to 40° C. until homogenous. Mix ingredients of phase B and heat to 70-80° C. until homogenous. Add phase C to B and mix. Slowly add phase B+C to A. Homogenize the mixture 11,000 rpm for 1 minute. Cool down and add preservative.
All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Where a term in the present application is found to be defined differently in a document incorporated herein by reference, the definition provided herein is to serve as the definition for the term.
While the present disclosure has been described in connection with specific aspects thereof, it will be understood that present disclosure is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure that come within known or customary practice within the art to which the invention pertains and can be applied to the essential features hereinbefore set forth, and follows in the scope of the claimed.
| Number | Date | Country | |
|---|---|---|---|
| 63130271 | Dec 2020 | US |
