Polyether derivative, usage and producing method thereof

Abstract

To provide a pollyether copolymer in which as a starting material, citronellol, geraniol, linalool, citoronellic acid, limonene, dihydromyrcene, myrcenol, adipic acid, propanediol, ethylene glycol, glycerol, 1,9-nonanediol and 1,6-hexane diol are used.SOLUTION: Provided is a copolymer formed from a combination of monomer units, in which the monomer unit has at least one C3-14 alkoxy unit substituted with at least one gem-dimethyl group and at least one other monomer unit selected from the group consisting of C1-14 alkoxy, C5-16 alkyl, polyethoxy and carbonyl-C2-13 carbonyloxy.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] Field The present invention relates to certain polyether copolymers and polyether derivatives thereof and methods of making and using same. For example, the starting materials may include species such as citronellol, geraniol, linalool, citronellic acid, limonene, dihydromyrcene, myrcenol, adipic acid, propanediol, ethylene glycol, glycerol, 1,9-nonanediol, and 1,6-hexanediol. [Background technology]

[0002] background Liquid polymers have important utility in cosmetic and personal care applications, with important roles in indicators, rheology, tribology and drug delivery. For example, they can be used as lubricants, emollients or protective barriers for skin healing and UV protection. Ideally, these materials are produced in a simple manner, are easy to derivatize for functional modifications and can be produced from safe and sustainable raw materials.

[0003] Monoterpenoid alcohols, such as citronellol, prenol, and isoprenol, are natural products and commercially available in large quantities. However, these molecules have a combination of functional groups, isobutylene and alcohol, that is underutilized for polymerization and functionalization. Primary alcohols readily undergo nucleophilic addition to highly substituted alkenes to produce ethers. Furthermore, primary alcohols readily undergo nucleophilic addition reactions with carboxylic acids and carboxylic acid derivatives to produce esters. As a result, a variety of copolymerization possibilities exist between monoterpenoid alcohols, diols, and dicarboxylic acid derivatives.

[0004] This type of chemistry has been largely ignored in polymer chemistry. One reason for this may be that etherification polymerization is an equilibrium reaction, and readily abundant isobutylene alcohol is not always available. However, in recent years, the production of citronellol, geraniol, linalool, myrcenol, limonene, and nerol has increased rapidly, and one of the largest production pathways also uses prenol and isoprenol as intermediates, thus greatly increasing their availability. Summary of the Invention [Problem to be solved by the invention]

[0005] However, as noted above, the equilibrium nature of the polymerization reaction can make large-scale production of the desired ethers difficult. There is a need for strategies and methods that allow for the efficient production of these compounds. [Means for solving the problem]

[0006] overview In a surprising advance in polymer science, PCT / US2015 / 047397 (corresponding US2017 / 0283553) and PCT / US2015 / 016371 (corresponding US2017 / 0057940), the contents of each of which are incorporated herein by reference, teach how to utilize such functionality to produce novel polyether compositions. These polyethers represent an advancement in liquid polymer technology and provide many desirable benefits for commercial applications. Furthermore, U.S. Provisional Application Nos. 62 / 539,129 and 62 / 617,924 (now PCT / US2018 / 44657, published as WO2019 / 028053), the contents of which are incorporated herein by reference, teach how to further derivatize such polyether polymers to enhance their functionality and utility. However, the above patent applications do not disclose polyether polymers containing more than one type of repeating monomer unit (ie, these applications only disclose homopolymers and their derivatives).

[0007] The present invention builds upon the applicant's own aforementioned patent applications and discloses novel copolymer compounds derived from one or more hydroxyalkenes, dienes, diols and dicarboxylic acids (or dicarboxylic acid derivatives) and derivatization strategies therefor and methods for their preparation. In still further aspects, the present invention also teaches methods for the controlled release of monomers contained in these polyether polymers, for use in, for example, fragrances and pest control.

[0008] In general, the present invention relates to copolymers (i.e., heteropolymers) formed from a combination of monomeric units, where the monomeric units include at least one C substituted with at least one gem-dimethyl group. 3-14 Alkoxy units and C 1-14 Alkoxy, C 5-16 Alkyl and Carbonyl-C 2-13 The copolymer further comprises at least one other monomer unit selected from the group consisting of carbonyloxy.

[0009] In one embodiment of the invention, the copolymer comprises at least one unit X and at least one unit Y, where unit X is of the formula [ka] and the units Y are Y1, Y2, Y3 and Y4 [ka] having a formula selected from: Here, R, R 1 , R 2 , R 3 and R 4 is defined below.

[0010] In one embodiment, the copolymer comprises Z, Z1, Z2, Z3, Z4 and Z5. [ka] and terminates with at least one terminal unit Z selected from:

[0011] The copolymers of the present invention are represented by the formula A, A1, A2, A3 and / or A4 [ka] The compound is prepared from one or more starting materials having the formula:

[0012] For example, in one embodiment, the copolymer of the present invention has the formula Y [ka] (X and Y are as defined above, A and B are each independently an end group selected from Z, Z1, Z2, Z3, Z4 and Z5, and n and m are each independently an integer from 1 to 20.) Thus, formula Y is a linear polymer having 1-20 groups X and 1-20 groups Y, where the groups X and Y are connected in some linear arrangement, where the linear polymer is terminated with group A at one end and group B at the other end.

[0013] In further aspects, the invention provides methods of making the compounds and methods of using the compounds. [Brief description of the drawings]

[0014] [Figure 1] FIG. 2 shows the proton-NMR spectrum obtained according to Example 1 after purification of the product from the copolymerization of citronellol and 1,6-hexanediol.

[0015] [Diagram 2] FIG. 2 shows the proton-NMR spectrum of the crude product obtained from the copolymerization of citronellol and triethylene glycol, obtained according to Example 2.

[0016] [Diagram 3]FIG. 2 shows the proton-NMR spectrum of the crude product obtained from the copolymerization of citronellol and glycerol, obtained according to Example 2.

[0017] [Figure 4] FIG. 2 shows the proton-NMR spectrum of the crude product obtained from the copolymerization of citronellol and linalool obtained according to Example 2.

[0018] [Diagram 5] FIG. 2 shows the proton-NMR spectrum of the crude product obtained from the copolymerization of citronellol and ethylene glycol, obtained according to Example 2.

[0019] [Figure 6] FIG. 2 shows the proton-NMR spectrum of the crude product obtained from the copolymerization of citronellol and 1,3-propanediol obtained according to Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Detailed Description Without intending to be bound by theory, it is believed that isobutylene groups can form ethers with alcohols via an acid-catalyzed mechanism, a chemistry that has been used in other instances to produce ether bonds in organic synthesis.

[0021] The equilibrium nature of this reaction can make the preparation of these ethers difficult on a large scale. However, we have discovered that using monomer recycling, appropriate catalyst selection, and highly intensive reaction conditions, it is possible to achieve sufficient degrees of polymerization for these molecules to be used in a variety of applications. Furthermore, these low molecular weight polymers have been further derivatized to much higher molecular weights and to achieve novel functionality.

[0022] For purposes of this invention, the term "citronellol" is intended to include both isomers at the olefin position. Similarly, when the term "prenol" is used, it is intended to include the isoprenol isomer as well.

[0023] Methods for producing these ethers are described in PCT / US2015 / 047397 (US2017 / 0283553), however, applicants have discovered that these polyethers can be produced at even higher degrees of polymerization, in shorter times, and under neat, solvent-free conditions using a resin-bound acid catalyst such as Amberlyst®. In certain embodiments, these polymerizations can be carried out at or below room temperature, preferably at slightly elevated temperatures, such as 30-110°C, or more preferably 40-90°C (e.g., about 50°C). Additionally, in still other embodiments, these polymerizations can be carried out in batch reactors, semi-batch reactors, or even more preferably continuous packed bed type reactors of the type described in U.S. Provisional Patent Application No. 62 / 384,939 (filed as related US2018 / 0064108) and PCT / US2017 / 50808 (filed as WO2018 / 049252), the contents of each of which are incorporated herein by reference.

[0024] Without being bound by theory, polyether formation may occur at equilibrium under acidic conditions, therefore it is not advisable to expose these materials to acidic conditions during subsequent derivatization in case depolymerization occurs.

[0025] However, applicants have discovered that transesterification under basic conditions can be accomplished to produce a wide range of new and useful compositions. Additionally, alkaline Williamson-type etherification can also be accomplished with organic halides. The functionalities that can be produced by these methods can modify the hydrophilicity, hydrophobicity, and / or viscosity of these polyethers. Additionally, new functionalities such as UV protection, antioxidant, anti-aging, skin whitening, antimicrobial, and / or other bioactivity can be introduced as well.

[0026] The unique benefits of the compounds disclosed herein come from one or more of the following properties: the compounds are short chain polymers; the compounds are produced using reversible polymerization reactions; the polymers are biodegradable and biocompatible; and the polymers can be synthesized from all-natural components. These are important benefits in many of the commercial applications in which these compounds can be used. The compounds disclosed herein are suitable as emollients or surfactants (e.g., octyldodecanol), replacements or substitutes for polymers and silicones in many products such as cosmetic and pharmaceutical compositions, and adjuvants in crop care products, as well as lubricants or solvents in enhanced recovery, hydraulic fracturing, and oil field applications. The compounds disclosed herein can have improved physical characteristics such as appearance, aerobicity, viscosity, refractive index, and / or surface tension. The nature of these compounds as short polymers of moderate molecular weight (e.g., less than 20,000 daltons or less than 15,000 daltons or less than 10,000 daltons or 100-10,000 daltons or 100-5,000 daltons or 100-3,000 daltons or 100-1,500 daltons).

[0027] The reversibility of the polymerization of the compounds of the present invention stems from the nature of the polymers having adjacent oxygen atoms and tertiary carbon atoms. As a result, under conditions that promote cleavage of the O-C bond, the resulting tertiary carbocation is unusually stable. This leads to the facile abstraction of adjacent hydrogen atoms to regenerate the alcohol and alkene functional groups of the starting material. Such depolymerization can be promoted by mildly acidic conditions (e.g., Lewis or Bronsted acids) or thermal or enzymatic conditions (such as by enzymes found in naturally occurring bacteria).

[0028] This depolymerization leads to biodegradation. This property also allows the formation of compositions containing the compounds, where the depolymerization of the polymer can be controlled to allow for the slow release of monomeric polymeric components (e.g., citronellol) or shortened polymeric components (e.g., release of citronellol dimers by depolymerization of larger polymers). The invention encompasses solid and / or liquid compositions containing copolymer 1 (and subsequent compounds), where the product provides for the gently controlled depolymerization of the polymer and the release and diffusion of the resulting monomers and / or shortened oligomers from the composition (e.g., by vaporization at the surface of the composition). Such products may include components that accelerate such depolymerization (e.g., Lewis or Bronsted acids or enzymes) or such compositions may be combined with devices that include heating elements to accelerate thermal depolymerization. The monomers and / or shortened oligomers (e.g., citronellol or citronellol dimers or trimers) produced in this manner are themselves useful for a variety of reasons, for example, as fragrances, insect repellents, antioxidants, antimicrobial agents or active pharmaceutical ingredients (e.g., when the composition is a pharmaceutical composition).

[0029] The compounds disclosed herein are suitable as replacements for silicones, mineral oils and / or paraffins in cosmetic compositions such as concealers, primers and / or moisturizers.

[0030] In a first aspect, the present invention provides a copolymer (i.e., a heteropolymer) formed from a combination of monomeric units, wherein the monomeric unit comprises at least one C substituted with at least one gem-dimethyl group. 3-14 Alkoxy units and C 1-14 Alkoxy, C 5-16 Alkyl, polyethoxy and carbonyl-C 2-13 A copolymer is provided that includes at least one other monomer unit selected from the group consisting of carbonyloxy.

[0031] In an embodiment of the first aspect, the present invention further provides a copolymer (Copolymer 1), wherein the copolymer comprises at least one unit X and at least one unit Y, wherein unit X is of the formula [ka] where the units Y are Y1, Y2, Y3 and Y4 [ka] [In the formula, R, R 1 , R 2 , R 3 and R 4 each independently represents an optionally substituted C-C 12 Alkyl, C 2- C 12 Alkenyl or polyethoxy (e.g., C1-C 12 Alkyl or C 2- C 12 alkenyl or polyethoxy, each optionally further represented by C1-C 12 substituted with alkyl, aryl or hydroxy). or a salt thereof; However, if the copolymer contains only the group X and the group Y1, the substituent R of the group X is not the same as the substituent R of the group Y1. 1 is not the same as.

[0032] In a further embodiment of the first aspect, the present invention provides any of the following: 1.1 A copolymer 1, in which at least one unit Y is Y1. 1.2 Copolymer 1, where at least one unit Y is Y2. 1.3 Copolymer 1, where at least one unit Y is Y3. 1.4 Copolymer 1, where at least one unit Y is Y4. 1.5 R, R 1 , R 2 , R 3 and R 4 One or more of the following may be optionally substituted:12 Alkyl or optionally substituted branched C-C 12 The copolymer 1 or any of 1.1 to 1.4 is alkyl. 1.6 R, R 1 , R 2 , R 3 and R 4 One or more of the following is unsubstituted linear C1-C 12 Alkyl (e.g., CH2, CH2CH2, or CH2(CH2)7CH2) or unsubstituted branched C3-C 12 Copolymer 1 or any of 1.1-1.4, which is alkyl (e.g., CH2CH2CH(CH3)CH2CH2). 1.7 R, R 1 , R 2 , R 3 and R 4 One or more of the following is unsubstituted linear C1-C 12 Copolymer 1 or any of 1.1-1.4, which is alkyl (e.g., CH2, CH2CH2, or CH2(CH2)7CH2). 1.8 R, R 1 , R 2 , R 3 and R 4 At least one of the following is an unsubstituted branched C3-C 12 Copolymer 1 or any of 1.1-1.4, which is alkyl (e.g., CH2CH2CH(CH3)CH2CH2). 1.9 R, R 1 , R 2 , R 3 and R 4 Copolymer 1 or any of 1.1 to 1.4, wherein one or more of the above is CH2. 1.10 R, R 1 , R 2 , R 3 and R 4 Any of copolymers 1 or 1.1 to 1.4, wherein one or more of is an unsubstituted branched or linear C6 alkyl. 1.11 R, R 1 , R 2 , R 3 and R 4any one of copolymers 1 or 1.1 to 1.4, wherein any one or more of is 3-methylpentyl (i.e., CH2CH2CH(CH3)CH2CH2). 1.12 R, R 1 , R 2 , R 3 and R 4 any of Copolymers 1 or 1.1-1.4, wherein any one or more of is linear hexyl (i.e., CH2CH2CH2CH2CH2CH2CH2) or linear nonanyl (i.e., CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2). 1.13 R, R 1 , R 2 , R 3 and R 4 Any of Copolymers 1 or 1.1-1.4, wherein any one or more of is linear butyl (i.e., CH2CH2CH2CH2) and / or linear propyl (i.e., CH2CH2CH2). 1.14 R, R 1 , R 2 , R 3 and R 4 Any one of copolymers 1 or 1.1 to 1.4, wherein one or more of is ethyl (i.e., CH2CH2). 1.15 R, R 1 , R 2 , R 3 and R 4 At least one of the following is C 2-12 Alkenyl (e.g., C having 1 to 4 double bonds) 2-12 alkenyl), either copolymer 1 or 1.1 to 1.4. 1.16 R, R 1 , R 2 , R 3 and R 4 At least one of the following is C 2-6 Alkenyl (e.g., C having 1-2 double bonds) 2-6 alkenyl), where alkenyl is linear or branched. 1.17 R, R 1 , R 2 , R 3 and R 4Copolymers 1.15 or 1.16, wherein any one or more of is a C6 alkenyl having one double bond, e.g., linear hexylene or methyl-substituted pentylene. 1.18 R, R 1 , R 2 , R 3 and R 4 is 3-methyl-2-pentylene (i.e., CH2CH2C(CH3)=CHCH2) or 3-methyl-3-vinylpropyl (i.e., CH2CH2C(CH3)CH=CH2). 1.19 R, R 1 , R 2 , R 3 and R 4 any one of copolymers 1 or 1.1 to 1.4, wherein one or more of is linear nonanyl (i.e., CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2). 1.20 R, R 1 , R 2 , R 3 and R 4 Any one or more of the following is hydroxy-substituted C 1-12 Copolymer 1 or any of 1.1-1.4, wherein the aryl group is alkyl (e.g., 2-hydroxypropyl, i.e., CH2CH(OH)CH2). 1.21 R, R 1 , R 2 , R 3 and R 4 Unsubstituted linear C1-C, one or more of which contains at least one oxygen atom in place of a saturated carbon atom 12 Alkyl or unsubstituted branched C3-C 12 The copolymer 1 or any of 1.1 to 1.4 is alkyl. 1.22 R, R 1 , R 2 , R 3 and R 4 Any one or more of the above may be polyethoxy, for example, (OCH2CH2) n where n is 1 to 5, for example, n is 2, 3 or 4. Copolymer 1.21. 1.23 Copolymer a. Y1, where R1 is 3-methylpentyl (i.e., CH2CH2CH(CH3)CH2CH2), for example, [ka] What is; b. Y1, where R 1 is linear hexyl, for example, Y1 is [ka] What is; c. Y1, where R 1 is 3-methyl-2-pentylene (i.e., CH2CH2C(CH3)=CHCH2), for example, [ka] What is; d. Y1, where R 1 is 3-methyl-3-vinylpropyl (i.e., CH2CH2C(CH3)CH=CH2), for example, [ka] or Y1 is [ka] What is; e. Y2, where R 2 is ethyl; f. Y2, where R 2 is linear propyl; g. Y2, where R 2 is isopropyl (i.e., CH3CHCH2); h. Y2, where R 2 is linear hexyl; i. Y2, where R 2 is linear nonanyl; j. Y2, where R 2Formula (OCH2CH2) n where n is 3; k. Y2, where R 2 is 2-hydroxypropyl; l. Y3, where R 3 is ethyl; m. Y3, where R 3 is linear propyl; n. Y3, where R 3 is linear hexyl; o. Y3, where R 3 is linear heptyl; p. Y4, where R 4 is ethyl (i.e., CH2CH2), for example, Y4 is [ka] What is; q. Y4, where R 4 is ethyl (i.e., CH2CH2), e.g., Y4 is [ka] What is; or a combination thereof, for example, any of Copolymers 1 or 1.1-1.22. 1.24 Copolymer [ka] Any of copolymers 1 or 1.1 to 1.23, comprising one or more units X where 1.25 Copolymer [ka] Let X be one or more units, a. Y2, where R 2 is ethyl; b. Y2, where R 2is linear propyl; c. Y2, where R 2 is linear nonanyl; and d. Y2, where R 2 is linear hexyl; or a combination of these In combination with one or more units Y selected from the following copolymers: 1.26 Any of copolymers 1 or 1.1-1.25, wherein the copolymer is a linear polymer containing 1 to 20 units X and 1 to 20 units Y, in any order. 1.27 Copolymer 1.26, in which all of 1 to 20 units X are the same (i.e., 1 to 20 units X have the same groups R). 1.28 Copolymer 1.27, wherein the groups R are each unsubstituted branched or linear C6 alkyl. 1.29 Copolymer 1.28, in which each R group is CH2CH2CH(CH3)CH2CH2. 1.30 Units X [ka] , copolymer 1.29. 1.31 All of 1 to 20 Y units are the same (e.g., all of 1 to 20 Y groups are the same R 1 or all of the 1 to 20 Y groups are the same R 2 or all of the 1 to 20 Y groups are the same R 3 or all of the 1 to 20 Y groups are the same R 4 (having the formula Y4 having a group), any of copolymers 1.26 to 1.30. 1.32 Copolymer 1.31, in which the X and Y units are arranged in a block fashion, e.g., where the polymer comprises a series of monomer units (X)n(Y)m, where n and m are each integers from 1 to 20. 1.33 All of the 1 to 20 Y units are of two different formulas, for example, all of the Y units are a combination of Y2 and Y3 units, and optionally all of the Y2 units are of the same R2 All of the Y3 units have the same R 3 Any of copolymers 1.26 to 1.30 having a substituent. 1.34 Copolymer 1.33 in which the X and Y units are arranged in a block format. 1.35 Copolymer 1.34, the polymer comprising a series of monomeric units (X)n(Y3-Y2)m, where n and m are each 1 to 25 such that a block of Y units consists of alternating units Y3 and Y2. 1.36 R 2 and R 3 Copolymer 1.35, in which both are linear hexyls. 1.37 Copolymers of Z, Z1, Z2, Z3, Z4 and Z5 [ka] Copolymer 1 or any of 1.1 to 1.36 terminated with at least one terminal unit Z selected from: 1.38 Substituents R, R of terminal units Z, Z1, Z2, Z3 and / or Z4 1 , R 2 , R 3 and / or R 4 is the same as the group of the corresponding units X, Y1, Y2, Y3 and / or Y4 of the copolymer, where applicable. 1.39 The copolymer terminates with one or more terminal units Z2, Z3 and / or Z5, where R 5 H, OH, C 1-20 Alkyl (e.g., lower alkyl (e.g., C 1-6 Alkyl) or C 1-12 alkyl), aryl (e.g., phenyl), aryl C1-2 alkyl (e.g., benzyl), OC 1-20 Alkyl (e.g., lower alkyl (e.g., OC 1-6 alkyl) or OC 1-12 alkyl), O-aryl (e.g., phenoxy), O-aryl C1-2 alkyl (e.g., benzyloxy), optionally unsaturated acyl (e.g., C(O)-C 1-20alkyl), optionally unsaturated acyloxy (e.g., O-C(O)-C 1-20 Copolymer 1.37 which is alkyl, optionally substituted arylacyl (eg, C(O)-aryl) or optionally substituted arylacyloxy (eg, OC(O)-aryl). 1.40 R 5 is H or OH. Copolymer 1.39. 1.41 R 5 is alkyl (e.g., lower alkyl (e.g., C 1-6 ) or C 1-12 ) or O-alkyl, e.g., R 5 but [ka] where R is as defined above (i.e., optionally substituted C-C 12 Alkyl, for example optionally C-C 12 Further substituted with alkyl or aryl and further embodiments thereof), copolymer 1.39. 1.42 R 5 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, or n-decyl; or methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-octyloxy, or n-decyloxy. Copolymer 1.39. 1.43 R 5 Aryl C 1-2 Alkyl (e.g., benzyl or phenethyl) or O-arylC 1-2 Copolymer 1.39, which is alkyl (eg, benzyloxy or phenethyloxy). 1.44 R 5 is aryl (e.g., phenyl) or O-aryl (e.g., phenoxy). 1.45 R5 is optionally unsaturated acyl (e.g., C(O)-C 1-20 Alkyl or C(O)-C 1-6 alkyl) or optionally unsaturated acyloxy (e.g., O-C(O)-C 1-20 Alkyl or OC(O)-C 1-6 alkyl), copolymer 1.39. 1.46 R 5 is C(O)-C 1-6 Alkyl or OC(O)-C 1-6 Alkyl, optionally R 5 is C(O)-C 1-5 Alkyl, C(O)-C 1-4 Alkyl, C(O)-C 1-3 Alkyl, C(O)-C 1-2 Alkyl, O-C(O)-C 1-5 Alkyl, O-C(O)-C 1-4 Alkyl, O-C(O)-C 1-3 Alkyl or OC(O)-C 1-2 Alkyl, copolymer 1.39. 1.47 R 5 is C(O)-C 1-6 Alkyl or OC(O)-C 1-6 is an alkyl group, 1-6 Copolymer 1.39, in which alkyl is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl. 1.48 R 5 optionally unsaturated C(O)-C 7-20 Alkyl or OC(O)-C 7-20 Alkyl, optionally R 5 optionally unsaturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl or C(O)-C 16-18 Alkyl, C(O)-C 17 Alkyl, O-C(O)-C 10-20 Alkyl, O-C(O)-C 12-20 Alkyl, O-C(O)-C 14-20 Alkyl or OC(O)-C16-18 Alkyl or OC(O)-C 17 Alkyl, copolymer 1.39. 1.49 R 5 Monounsaturated C(O)-C 7-20 Alkyl or OC(O)-C 7-20 Alkyl, optionally R 5 Monounsaturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl, C(O)-C 16-18 Alkyl, C(O)-C 17 Alkyl (e.g., oleyl), O-C(O)-C 10-20 Alkyl, O-C(O)-C 12-20 Alkyl, O-C(O)-C 14-20 Alkyl, O-C(O)-C 16-18 Alkyl or OC(O)-C 17 Copolymer 1.39, which is alkyl (eg, oleyloxy). 1.50 R 5 is saturated C(O)-C 7-20 Alkyl or OC(O)-C 7-20 Alkyl, optionally R 5 is saturated C(O)-C 10-20 Alkyl, C(O)-C 12-20 Alkyl, C(O)-C 14-20 Alkyl, C(O)-C 16-18 Alkyl, C(O)-C 17 Alkyl, O-C(O)-C 10-20 Alkyl, O-C(O)-C 12-20 Alkyl, O-C(O)-C 14-20 Alkyl, O-C(O)-C 16-18 Alkyl or OC(O)-C 17 Alkyl, copolymer 1.39. 1.51 R 5 Copolymer 1.39, in which the substituents are fatty acyl or fatty acyloxy chains. 1.52 R 5is aryl acyl (eg, C(O)-aryl) or aryl acyloxy (eg, OC(O)-aryl), such as benzoyl or benzyloxy. 1.53 R 5 The substituents may further comprise cationic or anionic moieties (e.g., R 5 is an alkyl, aryl, alkyl ester, or aryl ester, the alkyl or aryl being substituted with a cationic (e.g., quaternary ammonium) or anionic (e.g., carboxylic acid or sulfonic acid) moiety, copolymer 1.39. 1.54 R 5 is a polyether moiety, e.g., R 5 Copolymer 1.39, in which the substituents contain polyethylene glycol chains. 1.55 R 5 Copolymer 1.39, comprising an anti-aging moiety, a UV absorbing moiety, an antioxidant moiety, a hydrophobic (lipophilic) moiety or a hydrophilic moiety as described herein. 1.56 A copolymer of formula Y [ka] (In the formula, A and B are each independently an end group selected from Z, Z1, Z2, Z3, Z4 and Z5, and n and m are each independently an integer from 1 to 20, where n units X and m units Y are arranged in a linear sequence in any order.) Either copolymer 1 or 1.1 to 1.55 having the formula: 1.57 The bridged dimer has the structure WOC(O)-R 6 or WOC(O)-OW, where the substituent W is a radical fragment of any of the copolymers 1 or 1.1-1.56 that contains at least one terminal hydroxy group, e.g., the copolymer has at least (a) an end group bonded to an O atom of the monomer unit X, Y1, Y2, Y3 or Y4, such that R 5 or (b) an end group Z5 where Z is H; or (b) an end group where R is bonded to a non-O atom of a monomer unit X, Y1, Y2, Y3 or Y4. 5or (c) an end group Z2 or Z3, where R 5 is H;R 6 is bonded or optionally substituted C 1-22 Alkyl, optionally substituted C 2-22 alkenyl or optionally substituted aryl; and if fragment W has a second terminal hydroxy group (i.e., the structure HO-W-OH), then the bridged multimer has the structure HO-WOC(O)-R 6 -C(O)-[O-WO-C(O)-R 6 Crosslinked multimers (e.g., dimers) of any of copolymers 1 or 1.1-1.56, wherein the crosslinked multimers (e.g., dimers) may have a repeating pattern of crosslinking units and copolymer units such that p is an integer from 0 to 100 (e.g., 0 to 10 or 0 to 5 or 0 to 3), or HO-WOC(O)-[O-WO-C(O)]pOW-OH ..., where p is an integer from 0 to 100 (e.g., 0 to 10 or 0 to 5 or 0 to 3). 1.58 Cross-linked oligomers are dimers WOC(O)-R 6 -C(O)-OW or multimeric HO-WOC(O)-R 6 -C(O)-[O-WO-C(O)-R 6 a copolymer containing one terminal hydroxy group (i.e., W-OH) or two terminal hydroxy groups (i.e., HO-W-OH) of formula XC(O)-R to form a copolymer having the formula XC(O)-R-OH; 6 Bridged multimers (e.g., dimers) 1.57 formed by reaction of a reactive agent -C(O)-X, where X is a leaving group (e.g., chloro, fluoro, bromo, iodo, alkylsulfonyl, arylsulfonyl, imidazolyl) or X is OH. 1.59. Crosslinked multimers (e.g., dimers) 1.57, formed by reaction of any of copolymers 1 or 1.1-1.56 containing one terminal hydroxy group (i.e., W-OH) or two terminal hydroxy groups (i.e., HO-W-OH) with a reactive agent of formula XC(O)-X, where X is a leaving group (e.g., chloro, fluoro, bromo, iodo, alkylsulfonyl, arylsulfonyl, imidazolyl), to form dimers WOC(O)-OW or multimers HO-WOC(O)-[O-WO-C(O)]pOW-OH. 1.60 The polymer has the structure WOC(O)-R 6 -C(O)-OW or HO-WOC(O)-R 6 -C(O)-[O-WO-C(O)-R 6 -C(O)]pOW-OH, bridged multimers (e.g., dimers) 1.57 or 1.58. 1.61 R 6 is unsubstituted C 1-22 Alkyl, e.g., linear unsubstituted C 1-22 Alkyl or branched unsubstituted C 1-22 Alkyl, bridged multimers (eg, dimers) 1.60. 1.62 R 6 is unsubstituted C 1-16 Alkyl, e.g., linear unsubstituted C 1-16 Alkyl or branched unsubstituted C 1-16 Alkyl, bridged multimers (eg, dimers) 1.60. 1.63 R 6 is unsubstituted C 1-10 Alkyl, e.g., linear unsubstituted C 1-10 Alkyl or branched unsubstituted C 1-10 Alkyl, bridged multimers (eg, dimers) 1.60. 1.64 R 6 is unsubstituted C 1-6 Alkyl, e.g., linear unsubstituted C 1-6 Alkyl or branched unsubstituted C 1-6 Alkyl, bridged multimers (eg, dimers) 1.60. 1.65 R 6is selected from methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2CH(CH3)-), butylene (e.g., -CH2CH2CH2CH2- or -CH2CH(CH3)CH2- or -CH(CH3)CH2CH2-). 1.66 R 6 is unsubstituted C 2-22 Alkenyl, e.g., linear unsubstituted C 2-22 Alkenyl or branched unsubstituted C 2-22 Bridged multimers (eg, dimers) 1.60 of alkenyl, optionally in which any of the alkenyls is monounsaturated. 1.67 R 6 is unsubstituted C 2-16 Alkenyl, e.g., linear unsubstituted C 2-16 Alkenyl or branched unsubstituted C 2-16 Bridged multimers (eg, dimers) 1.60 of alkenyl, optionally in which any of the alkenyls is monounsaturated. 1.68 R 6 is unsubstituted C 2-10 Alkenyl, e.g., linear unsubstituted C 2-10 Alkenyl or branched unsubstituted C 2-10 Bridged multimers (eg, dimers) 1.60 of alkenyl, optionally in which any of the alkenyls is monounsaturated. 1.69 R 6 is unsubstituted C 2-6 Alkenyl, e.g., linear unsubstituted C 2-6 Alkenyl or branched unsubstituted C 2-6 Bridged multimers (eg, dimers) 1.60 of alkenyl, optionally in which any of the alkenyls is monounsaturated. 1.70 R 6 is selected from ethylene (-CH=CH-), propylene (-CH=CHCH2- or -CH2C(=CH2)-), butylene (e.g., -CH=CHCH2CH2- or -CH2CH=CHCH2- or -CH2CH(=CH2)CH2-). 1.71 R 6is aryl, for example, substituted or unsubstituted phenyl. 1.72 R 6 is the bond, cross-linked multimers (e.g., dimers) 1.60. 1.73 Cross-linked multimers (e.g., dimers) 1.57 or 1.59, where the multimers have the structure WOC(O)-OW or HO-WOC(O)-[O-WO-C(O)]pOW-OH.

[0033] It is understood that in substituents having optional bonds (e.g., groups Y1, Y4, Z, Z1 and Z4), all such structures depicted herein embody both groups with and without each optional bond, including all chemically permissible combinations thereof. For example, the groups Z, Z1 and Z4 each include at least the following structures: [ka] [ka] [ka] Analogous structures are also encompassed by monomer units Y1 and Y4 and starting material species A, A1 and A4.

[0034] In some embodiments, any bond present in monomer units Y1 and Y4, Z, Z1 and Z4, and starting species A, A1 and A4 may be further extended to form an intramolecular ring between the atoms bonded as appropriate. For example, monomer units Y1 and Y4 may include at least the following structure: [ka]

[0035] In a second aspect, the present invention provides a composition (Composition 1) comprising Copolymer 1 or any of 1.1 onwards, or any salt thereof, or any mixture thereof, together with at least one suitable solvent, carrier or additive. In a further embodiment of the second aspect, the present invention provides the following composition: 1.1 A fragrance composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.2 Perfume compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.3 Soap compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or mixtures of any of them. 1.4 An insect repellent composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.5 An insecticide composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.6 A detergent composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.7 Household cleaning compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.8 A deodorant spray composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.9 Room spray compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.10 A pomander composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.11 A candle composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or a mixture of any of them. 1.12. Composition 1.11, wherein the composition further comprises a paraffin wax and / or beeswax base. 1.13 Composition 1.12 consisting of copolymer 1 or any of 1.1 et seq. or a salt thereof or any mixture thereof dispersed in a paraffin wax and / or beeswax base and having a suitable core embedded therein. 1.14 Cosmetic compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof, such as, for example, lipsticks, lip balms, lip glosses, eye shadows, liquid highlighters (e.g. for blush), skin ointments, skin lotions or skin balms. 1.15 A cosmetic composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.16 A pre- and / or aftershave composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.17 A talcum powder composition comprising any of the copolymers 1 or 1.1 et seq. or their salts or any mixtures thereof. 1.18 Hair care product compositions, such as hair styling products (e.g. hairsprays, hair gels or hair drying creams, mousses) or hair washing products (e.g. shampoos or conditioners), comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.19 A body deodorant composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.20 An antiperspirant composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.21 A shampoo composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.22 A pet litter composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.23 A topical skin care composition comprising any of Copolymer 1 or 1.1 et seq. or a salt thereof or any mixture thereof, optionally wherein the skin care application is a skin moisturizer; a skin penetration enhancer; a skin protectant; a skin soothing agent; a skin healing agent; an ultraviolet light absorber or scattering agent; a scavenger; an anti-acne agent; an anti-androgenic agent; a depilatory agent; a keratolytic / exfoliant / scrubbing agent such as salicylic acid; a panthenol moisturizer such as D-panthenol; a soluble or colloidal-soluble moisturizer such as hyaluronic acid and starch-grafted sodium polyacrylate; and a sunscreen. 1.24 Composition 1.23, wherein the skin care application is a skin protectant. 1.25 Composition 1.23, wherein the skin care application is a skin soothing agent or a skin moisturizer (e.g., in a moisturizing lotion). 1.26 Composition 1.23, wherein the skin care application is a sunscreen. 1.27 Paint or coating compositions containing any of the copolymers 1 or 1.1 et seq. or their salts or any mixtures thereof. 1.28 A lubricant composition comprising any of the copolymers 1 or 1.1 et seq. or a salt thereof or any mixture thereof. 1.29 A plastic composition comprising any of the copolymers 1 or 1.1 et seq. or their salts or any mixtures thereof. 1.30 An antifoam composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.31 Hydraulic compositions comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.32 An antimicrobial composition comprising any of the copolymers 1 or 1.1 et seq. or salts thereof or any mixtures thereof. 1.33 Crop care products comprising any of the copolymers 1 or 1.1 et seq., for example, where the compound is an adjuvant in a crop care product. 1.34 Products for enhanced oil recovery, hydraulic fracturing and / or other oil field applications comprising any of Copolymers 1 or 1.1 et seq., where the compound is, for example, a lubricant or solvent in the product. 1.35 A composition comprising or consisting of any of the copolymers 1 or 1.1 et seq. dissolved or suspended in a solvent or solvent mixture, such as an ester, alkane, aromatic, alcohol or ether solvent. 1.36 A solution or suspension of a copolymer 1 or any of 1.1 et seq. in a solvent or solvent mixture, for example an ester, alkane, aromatic, alcohol or ether solvent. 1.37 Compositions 1.35 or 1.36, wherein the solvent is selected from C1-4 esters (e.g., methyl acetate, ethyl acetate, isopropyl acetate), C4-18 esters, C3-10 alkanes (e.g., hexane, heptane, octane), C10-18 alkanes (linear or branched), C2-10 alcohols (e.g., ethanol, propanol, isopropanol), C2-10 ethers (e.g., diethyl ether, diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane) and C6-12 aromatics (e.g., toluene, xylene). 1.38 An article of manufacture comprising any of the preceding compositions, wherein the composition is stored or contained in a container containing a heating element, and activation of the heating element results in heating of the composition, thermal decomposition of the compounds and release of volatiles.

[0036] In other embodiments, the invention provides Copolymer 1, or any of 1.1-1.73, for use in Composition 1, or any of 1.1-1.38.

[0037] In a third aspect, the present invention provides a method for making any of Copolymers 1 or 1.1 et seq., comprising: (1) introducing into a reactor a copolymer of formula A [ka] and compounds of formula A1, A2, A3 or A4 [ka] [In the formula, R, R 1 , R 2 , R 3 and / or R4 each of which is optionally substituted C-C 12 Alkyl, C 2- C 12 Alkenyl or polyethoxy (e.g., C1-C 12 Alkyl or C 2- C 12 alkenyl or polyethoxy, each optionally further comprising C-C 12 substituted with alkyl, aryl or hydroxy). at least one of the compounds; and (2) contacting the compound with a solid ion exchange resin, thereby inducing copolymerization of the compound of formula A with the compounds of formula A1, A2, A3 and / or A4 to produce copolymer 1 or any of copolymers 1.1-1.56, where R 5 If exists, then R 5 is H); and (3) isolating and / or purifying (e.g., by distillation) copolymer 1, e.g., a group of related copolymers 1 having the same or substantially the same monomer composition. The process includes:

[0038] In a further embodiment of the third aspect, the present invention provides: 1.1 Method 1, where the polymerization takes place on an ion exchange resin at high temperatures (e.g., 30-120°C). 1.2 Method 1.1, where the polymerization takes place on an ion exchange resin at 40-90°C. 1.3 Method 1.2, where the polymerization takes place on an ion exchange resin at about 50°C. 1.4 Any of methods 1 or 1.1-1.4, wherein the solid exchange resin is a resin functionalized with a resin-bound acid catalyst, such as a carboxylic acid or sulfonic acid moiety. 1.5 Any of the preceding processes wherein the polymerization occurs in a batch reactor. 1.6 Any of the preceding processes, wherein the polymerization occurs in a continuous packed bed reactor. 1.7 Any of the preceding processes wherein monomers of formula A are polymerized by acid catalysis, followed by distillation and recycling of any unpolymerized monomer. 1.8 Any of the preceding processes wherein the resin bound acid catalyst is selected from Silicycle propane sulfonic acid, montmorillonite, or Amberlyst® (e.g., macroreticular or porous resin or silica covalently bonded to sulfonic or carboxylic acid groups). 1.9 The method of 1.7, wherein the catalyst is Amberlyst®. 1.10 Any of the preceding processes, wherein copolymer 1 is purified by fractional distillation. 1.11 Copolymer 1, wherein the copolymer further comprises at least one terminal hydroxy group (e.g., group R 5 , where R 5 is the group R 5 Any of the preceding methods comprising the step of reacting a terminal hydroxy group (including a hydroxy group which is H or OH depending on the linkage) with a suitable reactant to convert the terminal hydroxy group to an alkyl ester or aryl ester moiety (e.g., to produce a copolymer 1.41-1.55 or an embodiment thereof), e.g., the alkyl ester is a methyl ester and the reaction uses ketene as the suitable reactant. 1.12. Method 1.11, wherein the esterification is an alkaline transesterification reaction using a functionalized ester. 1.13 Copolymer 1, wherein the copolymer further comprises at least one terminal hydroxy group (e.g., group R 5 , where R 5 is the group R 5 Any of Methods 1 or 1.1-1.10, comprising the step of reacting a terminal hydroxy group (including a hydroxy group which is H or OH depending on the connectivity of the hydroxy group) with a suitable reactant to convert the terminal hydroxy group to an alkyl ether or aryl ether moiety (e.g., to produce compounds 1.41-1.55 or an embodiment thereof). 1.14 Method 1.13, where the etherification is a Williamson-type etherification reaction using an appropriate alkyl halide and base. 1.15 Copolymer 1, wherein the copolymer further comprises at least one terminal hydroxy group (e.g., group R 5 , where R 5 is the group R 5Any of Methods 1 or 1.1-1.14, comprising the step of reacting a copolymer of formula (I) with a suitable reactant to convert the copolymer to a crosslinked dimer of any of compounds 1.57-1.73. 1.16 Method 1.15, wherein the bridged dimer has the formula WOC(O)-OW and the suitable reactant is phosgene. 1.17 If the bridged dimer has the formula WOC(O)-R 6 -C(O)-OW, and suitable reactants have the formula HO-C(O)-R 6 -C(O)-OH diacid, Method 1.15. 1.18 The bridged dimer has the formula WOC(O)-R 6 -C(O)-OW, and suitable reactants have the formula XO-C(O)-R 6 Reactive diacyl species of -C(O)-OX, where X is a leaving group (e.g., chloro, fluoro, bromo, iodo, alkylsulfonyl (e.g., methanesulfonyl or ethanesulfonyl), arylsulfonyl (e.g., benzenesulfonyl or toluenesulfonyl), imidazolyl), Method 1.15.

[0039] In other embodiments, the invention provides a copolymer made by Method 1 or any of Methods 1.1-1.18.

[0040] Examples of monomer species suitable for use in making any of Copolymers 1 or 1.1 et seq. or for use in any of Methods 1 or 1.1-1.18 include, but are not limited to, acyclic monoterpenoid alcohols (e.g., citronellol, geraniol, nerol, linalool, linalool, coriandrol, myrcenol, and dihydromyrcenol; cyclic monoterpenoid alcohols (e.g., isopulegol and menthol), acyclic monoterpenes (e.g., dihydromyrcene); alkanediols (e.g., 1,9-nonanediol, 1,6-hexanediol, 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, glycerol, and ethylene glycol); polyethylene glycols, such as diethylene glycol, triethylene glycol, and tetraethylene glycol); and dicarboxylic acids (e.g., azelaic acid, adipic acid, and succinic acid). Further reactive species which may participate in the formation of copolymer 1 or 1.1 et seq. or suitable for use in Methods 1 or 1.1-1.18 include dienes (e.g. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 2,6-octadiene and limonene) and alkenoic acids (e.g. citronellic acid).

[0041] In certain embodiments, copolymer 1 may be prepared by any of methods 1 or 1.1-1.18 using a combination of (1) citronellol monomer and (2) one or more monomers selected from 1,6-hexanediol, linalool, geraniol, nerol, limonene (e.g., d-limonene), glycerol, dihydromyrcene, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,9-nonanediol, and ethylene glycol. In further embodiments, copolymer 1 may be prepared by any of methods 1 or 1.1-1.18 using a combination of (1) citronellol monomer and (2) one or more monomers selected from 1,6-hexanediol, 1,3-propanediol, 1,2-propanediol, 1,9-nonanediol, and ethylene glycol.

[0042] In some embodiments, the UV absorbing moiety includes, but is not limited to, conjugated aromatic esters, conjugated aromatic ethers, and conjugated olefins. Specific examples include, but are not limited to, cinnamic acid, cinnamic acid derivatives, salicylic acid, salicylic acid derivatives, dimethylaminobenzoic acid, para-aminobenzoic acid, benzoic acid, 3,3-diphenylcyanoacrylate, diethylaminohydroxybenzoylbenzoate, and methoxycinnamic acid.

[0043] In certain embodiments, the anti-aging and / or antioxidant moieties include, but are not limited to, hyaluronic acid, ascorbic acid, azelaic acid, carnosine, glycolic acid, nicotinic acid, phenolic acids, phenolic ethers, benzophenones, sulfites, sulfones, sulfonic acids, and phosphoric acids.

[0044] In some embodiments, the hydrophobic moieties include acetates, propionates, linear or branched fatty acids, linear or branched alkyl chains, organosilicones, fluoroalkanes, and graphene derivatives.The hydrophilic moieties include sulfonic acids, ethoxylates, polyglycerols, polypropylene glycols, carbohydrates, and carboxylic acids and other polyols.

[0045] For example, copolymers 1 and subsequent, as produced by method 1 (and subsequent methods), may be conjugated (e.g., esterified or etherified) to other biologically active molecules, such as antimicrobial compounds, medicinal compounds, skin healing compounds, and sensitive molecules such as cooling agents, anti-inflammatory agents, and / or warming agents.

[0046] For example, copolymer 1 (and subsequent compounds) produced by method 1 (and subsequent methods) are used in many applications. They can be used in cosmetic products, paints or coatings, personal care products, household products, such as cleaning products, electronics, lubricants, plastics, defoamers, oil enhanced oil and gas recovery (including hydraulic fracturing and other oil field applications), pharmaceutical applications, crop care products and hydraulic compositions. The compounds disclosed herein are suitable as replacements or substitutes for surfactants, polymers, silicones and solvents in these various applications. These materials, especially low molecular weight molecules, can also be advantageously used as insect repellents. For example, copolymer 1 (and subsequent compounds) produced by method 1 or subsequent methods can be combined with or included in insecticides, insect repellents and bioactive ingredients.

[0047] In a fourth aspect, the present invention provides a method of using Copolymer 1 or later, e.g., produced by Method 1 (and later methods), in a composition (e.g., Composition 1 (and later), e.g., a fragrance composition, perfume, soap, insect repellent and insecticide, detergent, household cleaner, deodorant spray, room spray, pomander, candle, makeup, toner, pre- and / or after shave lotion, talcum powder, hair care product, body deodorant, antiperspirant, shampoo, skin care application, pharmaceutical, antimicrobial, pet litter, crop care product or oil field, hydraulic fracturing or enhanced oil recovery process).

[0048] Thus, the present invention provides a method (Method 2) using Copolymer 1 or any of Copolymers 1.1 to 1.73, a method for producing Composition 1 or any of Compositions 1.1 to 1.38.

[0049] In further embodiments of the fourth aspect, method 2 may provide any of the following: 2.1 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in the fragrance composition. 2.2 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a perfume. 2.3 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in the soap. 2.4 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in an insect repellent. 2.5 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in an insecticide. 2.6 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a detergent. 2.7 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a household cleaning product. 2.8 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a deodorant spray. 2.9 Method 2, in which either copolymer 1 or 1.1-1.73 is used in a room spray. 2.10 Method 2, in which either copolymer 1 or 1.1-1.73 is used in the pomander. 2.11 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a candle. 2.12 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a cosmetic. 2.13 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a lotion. 2.14 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a pre- and / or aftershave lotion. 2.15 A method according to method 2, in which either copolymer 1 or 1.1-1.73 is used in talcum powder. 2.16 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a hair care product. 2.17 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a body deodorant. 2.18 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in an antiperspirant. 2.19 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used in a shampoo. 2.20 Method 2, in which either copolymer 1 or 1.1-1.73 is used in pet litter. 2.21 The method of Method 2, wherein any of Copolymer 1 or 1.1-1.73 is used in a topical application in skin care, wherein the skin care application may be selected from skin moisturizers; skin penetration enhancers; skin protectants; skin soothing agents; skin healing agents; ultraviolet light absorbers or scattering agents; ultraviolet light scatterers; anti-acne agents; anti-androgenic agents; depilatories; keratolytic / exfoliating / scrubbing agents such as salicylic acid; panthenol moisturizers such as D-panthenol; soluble or colloidal-soluble moisturizers such as hyaluronic acid and starch-grafted sodium polyacrylate; and sunscreens. 2.22 The method of method 2.21, wherein the skin care application is a skin protectant. 2.23 The method of Method 2.21, wherein the skin care application is a skin soothing agent. 2.24 The method of method 2.21, wherein the skin care application is a sunscreen. 2.25 Method 2, in which either copolymer 1 or 1.1-1.73 is used in a paint or coating. 2.26 The method of method 2, wherein either copolymer 1 or 1.1-1.73 is used as the lubricant. 2.27 Method 2, in which either copolymer 1 or 1.1-1.73 is used in plasticizer. 2.28 The method of method 2, wherein the copolymer 1 or any of 1.1-1.73 is used in medicine. 2.29 The method of method 2, wherein the copolymer 1 or any of 1.1-1.73 is used in a crop care product, wherein the compound is an adjuvant in the crop care product. 2.30 The method of method 2, wherein any of copolymers 1 or 1.1-1.73 are used in products for enhanced oil recovery, hydraulic fracturing, and / or other oil field applications, e.g., the compound is a lubricant or solvent in the application.

[0050] An added benefit of these materials described herein is that they are expected to be fully biodegradable and biocompatible.

[0051] During evaluation of these polyethers, it was surprisingly observed that depolymerization back to monomer for citronellol-based polymers occurs spontaneously at about 180° C. This thermal depolymerization property, or similar enzyme and / or acid catalyzed depolymerization properties, can be advantageously used to deliver citronellol monomer in a controlled manner over time.

[0052] In some embodiments, thermal depolymerization is used to release the monomer into the air in a controlled release. In some embodiments, the present invention contemplates the use of compounds of Copolymer 1 (or later), e.g., produced by Method 1 (or later), in, e.g., candles or thermal dispensers for odor control and / or mosquito control, low pH industrial cleaners with depolymerized monomer components released over time to promote beneficial odors, and laundry detergents that use enzymes to digest the polymer over time to smell fresh for extended periods of time.

[0053] In other embodiments, a fragrance composition comprises a compound of Copolymer 1 (or later), e.g., produced by Method 1 (or later), and the fragrance composition of the present application is selected from perfumes, soaps, insect repellents and insecticides, detergents, household cleaners, deodorant sprays, room sprays, pomanders, candles, cosmetics, lotions, pre- and / or after-shave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hair sprays, and pet litter.

[0054] In other embodiments, for example, copolymer 1 (and subsequent compounds) produced by method 1 (and subsequent methods) can be used in antifungal compositions. In some embodiments, the antifungal composition includes, for example, a polyether of copolymer 1 (and subsequent compounds) produced by method 1 or later and at least one compound of the type that exhibits a synergistic effect in the presence of the fragrance ingredient selected from the group consisting of aliphatic or aromatic aldehydes, aliphatic or aromatic alcohols, acetals, and esters, thereby allowing the content of the active ingredient to be reduced to a lower amount than when each is used alone.

[0055] In other embodiments, for example, the compound of copolymer 1 (or later) produced by method 1 (or later) can be used for topical application in skin care applications.For example, skin care applications can be selected from skin moisturizers; skin penetration enhancers; skin protectants; skin soothing agents; skin healing agents; ultraviolet light absorbers or scatterers; scavengers; anti-acne agents; anti-androgens; depilatories; keratolytic / exfoliating / scrubbing agents such as salicylic acid; panthenol moisturizers such as D-panthenol; soluble or colloidal-soluble moisturizers such as hyaluronic acid and starch-grafted sodium polyacrylate; and sunscreens.

[0056] In other embodiments, the polyethers of copolymer 1 (and subsequent compounds) prepared by method 1 or later can be used in delivery systems, such as any perfume delivery system where a long-term constant release of the fragrance compound is desired. For example, the perfume delivery systems described herein can be used in products that are used, for example, functional perfumes, other articles that are exposed to sunlight during use or that are subsequently exposed to sunlight.

[0057] In further embodiments, the present invention provides delivery system 4.0, which includes, for example, liquid and solid deodorant sprays together with the delivery system of the present invention. Still further examples include delivery systems that deliver window and household cleaners, general purpose cleaners and furniture polishes. Surfaces are cleaned with such cleaners. In further examples, delivery systems that include detergents and fabric softeners also include the delivery system of the present invention, and fabrics are washed or treated with such detergents or fabric softeners.

[0058] In still other embodiments, polyethers of Copolymer 1 (and subsequent compounds), for example, produced by method 1 or subsequent methods, can be used in drug delivery systems.

[0059] In certain embodiments, delivery system 4.0 may include any of the following delivery systems: 4.1 A drug delivery system comprising copolymer 1 or any of 1.1-1.73 or any salt thereof or mixtures thereof. 4.2 A fragrance delivery system comprising copolymer 1 or any of 1.1-1.73 or any salt thereof or mixtures thereof. 4.3 A detergent delivery system comprising copolymer 1 or any of 1.1-1.73 or any salt thereof or mixtures thereof. 4.4 A household cleaning delivery system comprising copolymer 1 or any of 1.1-1.73 or any salt thereof or mixtures thereof.

[0060] The details of one or more embodiments of the present invention are set forth below. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly used by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification controls.

[0061] It is to be understood that, unless otherwise specified, the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. In this specification and the appended claims, several terms are set forth that shall have the following definitions.

[0062] As used herein, the singular includes the plural unless the context clearly dictates otherwise. Thus, for example, reference to a "reactant" includes not only one reactant but also a combination or mixture of two or more different reactants, reference to a "substituent" includes one substituent as well as two or more substituents, etc.

[0063] As used herein, the terms "for example," "such as," or "including" are intended to introduce examples that make the general subject matter clearer. These examples are provided only as an aid in understanding the disclosure and are not intended to be limiting in any manner. Additionally, as used herein, the terms "may," "any," "optionally," or "may optionally" are intended to mean that the preceding described situation may or may not occur, including cases where it occurs and cases where it does not occur. For example, the term "optionally present" means that the thing may or may not be present, and thus the description includes cases where the thing is present and cases where the thing is not present.

[0064] As used herein, "having the formula" or "having the structure" is not intended to be limiting and is used in the same manner that the term "comprising" is generally used.

[0065] In some of the formulas in this application, one or more chiral centers are indicated by an asterisk next to the chiral carbon. In other formulas, even if a chiral center is not specified, chiral isomers are encompassed by these formulas.

[0066] Some of the compounds of the present invention can exist in tautomeric forms which are also intended to be within the scope of the present invention.

[0067] "Tautomer" refers to a compound whose structure differs significantly in atomic arrangement, but which exists in easy and rapid equilibrium. It is understood that the compounds of the present invention may be described as various tautomers. If a compound has tautomeric forms, it is understood that all tautomeric forms are intended to fall within the scope of the present invention, and the naming of the compound does not exclude any tautomeric form. Furthermore, even if one tautomer may be described, the present invention includes all tautomers of the compound.

[0068] As used herein, the term "salt" refers to acid addition salts, including hydrochlorides, hydrobromides, phosphates, sulfates, bisulfates, alkylsulfonates, arylsulfonates, acetates, benzoates, citrates, maleates, fumarates, succinates, lactates, and tartrates; salts of alkali metal cations, such as Na + , K + , Li + , alkaline earth metal salts, e.g. Mg 2+ or Ca 2+ Or it may comprise an organic amine salt or an organic phosphonium salt.

[0069] The term "alkyl" as used herein refers to a monovalent or divalent, branched or unbranched saturated hydrocarbon group having 1 to 22 carbon atoms, typically, but not necessarily, having 1 to about 12 carbon atoms, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, and the like. The term alkyl can also include cycloalkyl groups. Thus, for example, the term C6 alkyl includes cyclohexyl groups. For example, in certain embodiments, R, R 1 , R 2 , R 3 or R 4 For example, [ka] C containing a cyclohexane ring selected from 6-12 It may be an alkyl group.

[0070] The term "alkenyl," as used herein, refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group, typically, but not necessarily, containing from 2 to about 12 carbon atoms and from 1 to 10 carbon-carbon double bonds, e.g., ethylene, n-propylene, isopropylene, n-butylene, isobutylene, t-butylene, octylene, and the like.

[0071] The term "alkynyl" as used herein refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group typically, but not necessarily, containing from 2 to about 12 carbon atoms and from 1 to 8 carbon-carbon triple bonds, e.g., ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, and the like.

[0072] The term "aryl" as used herein refers to an aromatic hydrocarbon moiety containing at least one aromatic ring of 5 to 6 carbon atoms, including, for example, aromatic hydrocarbons having 2 fused rings and 10 carbon atoms (i.e., naphthalene).

[0073] "Substituted," as in "substituted alkyl," "substituted alkenyl," "substituted alkynyl," and the like, means that at least one hydrogen atom bonded to a carbon atom in an alkyl, alkenyl, alkynyl, or other moiety, is replaced with one or more non-hydrogen substituents, e.g., a functional group.

[0074] For example, C a ~C b The terms "branched" and "straight-chain" (or "unbranched"), when used in reference to an alkyl moiety of a carbon atom, apply to the carbon atom that defines the alkyl moiety. For example, for a C4 alkyl moiety, a branched embodiment thereof includes isobutyl, and an unbranched embodiment thereof is n-butyl. However, isobutyl is also defined as a straight-chain C3 alkyl moiety (propyl) substituted with a C1 alkyl (methyl) per se.

[0075] Examples of functional groups are halo, hydroxyl, sulfhydryl, C1-C 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24 Alkynyloxy, C5-C 20 Aryloxy, acyl (C2-C 24 Alkylcarbonyl (-CO-alkyl) and C6-C 20 Arylcarbonyl (-CO-aryl), acyloxy (-O-acyl), C2-C 24 Alkoxycarbonyl (-(CO)-O-alkyl), C6-C20 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X where X is halo), C2-C 24 Alkylcarbonate (-O-(CO)-O-alkyl), C6-C 20 Arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (-COO - ), carbamoyl (-(CO)-NH2), monosubstituted C1-C 24 Alkylcarbamoyl(-(CO)-NH(C1-C 24 alkyl)), disubstituted alkylcarbamoyl (-(CO)-N(C1-C 24 alkyl)2), monosubstituted arylcarbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH2), carboxamido (-NH-(CO)-NH2), cyano (-C≡N), isocyano (-N + ≡C - ), cyanate (-OC≡N), isocyanate (-ON + ≡C - ), isothiocyanato (-SC≡N), azido (-N=N + =N - ), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono- and di-(C1-C 24 Alkyl) substituted amino, mono- and di-(C5-C 20 Aryl) substituted amino, C2-C 24 Alkylamide (-NH-(CO)-alkyl), C5-C 20 Arylamide (-NH-(CO)-aryl), imino (-CR=NH, where R=hydrogen, C1-C 24 Alkyl, C5-C 20 Aryl, C6-C 20 Alkaryl, C6-C 20aralkyl, etc.), alkylimino (-CR=N(alkyl), where R=hydrogen, alkyl, aryl, alkaryl, etc.), arylimino (-CR=N(aryl), where R=hydrogen, alkyl, aryl, alkaryl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonato (-SO2-O - ), C1-C 24 Alkylsulfanyl (-S-alkyl; also known as "alkylthio"), arylsulfanyl (-S-aryl; also known as "arylthio"), C1-C 24 Alkylsulfinyl (-(SO)-alkyl), C5-C 20 Arylsulfinyl (-(SO)-aryl), C1-C 24 Alkylsulfonyl (-SO2-alkyl), C5-C 20 Arylsulfonyl (-SO2-aryl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O - )2), phosphinato (-P(O)(O - )), phospho (-PO2), phosphino (-PH2), mono- and di-(C1-C 24 Alkyl) substituted phosphino, mono- and di-(C5-C 20 aryl) substituted phosphino; and hydrocarbyl moieties, such as C1-C 24 Alkyl (C1-C 18 Contains alkyl, and also C1-C 12 alkyl and further including C1-C6 alkyl), C2-C 24 Alkenyl (C2-C 18 Alkenyl, including C2-C 12 alkenyl and further including C2-C6 alkenyl), C2-C 24 Alkynyl(C2-C 18 Alkynyl, including C2-C 12 alkynyl and further including C2-C6 alkynyl), C5-C 30 Aryl (C5-C 20 Aryl and further C5-C 12 (including aryl) and C6-C 30 Aralkyl(C6-C20 Aralkyl and C6-C 12 Examples of "substituents" include, but are not limited to, alkyl, aryl, arylalkyl ...

[0076] The term "perfume composition" as used herein means a mixture of perfume ingredients, including polyether compounds according to method 1 or later and method 2 or later, dissolved in a suitable solvent or mixed with a powdered base, optionally including auxiliary substances, to impart a desired odor to a product.

[0077] The polyether compounds of Copolymer 1 et seq., Method 1 et seq. and Method 2 et seq. may be used with, for example, perfumes, soaps, insect repellents and insecticides, detergents, household cleaners, deodorant sprays, room sprays, pomanders, candles, cosmetics, lotions, pre- and / or after-shave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hair sprays, and pet litters.

[0078] Perfume ingredients and perfume ingredient mixtures which may be used in combination with the compounds of the present invention to prepare perfume compositions include, but are not limited to, extracts, animal products and natural products including essential oils, absolutes, resinoids, resins and concretes, as well as synthetic perfume materials including, but not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furan ketals, nitriles, acids and hydrocarbons including both saturated and unsaturated compounds and aliphatic carbocyclic and heterocyclic compounds, and animal products.

[0079] As used herein, "citronellol polymer" and "prenol polymer" are intended to include all derivatives and cyclic forms of citronellol and prenol and polymers.

[0080] In this specification, the structural formula of a compound may in some cases show a specific isomer for convenience, but the present invention includes all isomers, such as geometric isomers, optical isomers based on asymmetric carbons, stereoisomers, tautomers, etc. Furthermore, for compounds represented by the formula, crystal polymorphism may exist, and any crystal form, crystal form mixture, or anhydride or hydrate thereof is included within the scope of the present invention.

[0081] All percentages used herein are by volume unless otherwise specified.

[0082] All percentages used herein are in molar terms unless otherwise specified. EXAMPLES

[0083] Example 1. Synthesis of citronellol / 1,6-hexanediol copolymer 500 g of citronellol and 94.5 g of 1,6-hexanediol (0.25 equivalents) are mixed thoroughly at 50°C. The mixture is pumped at a flow rate of 2 mL / min into a 6 ft, 1 / 4 inch tube filled with Amberlyst ion exchange resin. The reaction is allowed to proceed at 50°C. The crude product is collected at the end of the tube and nuclear magnetic resonance spectroscopy (NMR) and gas chromatography (GC) are used to monitor the reaction. After the reaction is deemed complete, the crude product is diluted with hexane and washed with saturated sodium carbonate solution until the pH of the aqueous phase is about 8. The organic phase is then collected, concentrated, and prepared for distillation to remove any monomer. Unreacted monomer is distilled off at vessel temperatures of 83-165°C and pressures of 0.7-2.85 mBar. The overall yield of the reaction is 56.4% viscous, clear, colorless, odorless fluid.

[0084] The resulting product has the following physical properties: Density (g / ml): 0.915 Refractive index (@20C): 1.465 Surface tension (cP@21C):598

[0085] 1 Analysis of the products by H-NMR allows characterization of the degree of alcohol incorporation and / or olefin etherification. The characteristic ether methylene peaks shift to the 3.0-3.5 ppm range in CDCl3 solvent compared to the corresponding alcoholic methylene peaks at 3.5-4.0 ppm. The characteristic methyl peaks associated with the dimethyl ether motif in the citronellol monomer and polymer products appear in the 1.0-1.5 ppm range.

[0086] Figure 1 shows the purified product. 1 The H NMR spectrum is shown. The spectrum is consistent with a copolymer system capped predominantly with OH groups (both olefinic protons and the corresponding isoprenyl methyl protons) as indicated by the high depletion of isoprenyl moieties present, and the predominant presence of hydroxy-methylene protons at 3.5-3.7 ppm. Additionally, it shows that there is significant intrinsic oligomerization of the ether linkages as indicated by the ether-methylene protons at 3.2-3.4 ppm and the corresponding methyl groups adjacent to the ethers.

[0087] Without being bound by theory, the NMR spectrum is consistent with the copolymer structure as follows: [ka]

[0088] The product obtained in this example is a glossy, shiny film former that can be used as a solvent and emollient. The physical and chemical properties of the polymer are similar to the emollient octyldodecanol, suggesting that it can be used as a replacement for octyldodecanol.

[0089] Example 2: Synthesis of other citronellol copolymers Using synthetic and analytical methods similar to those described in Example 1, copolymers are obtained from the following combinations of monomers: (1) citronellol and linalool; (2) citronellol and geraniol; (3) citronellol and nerol; (4) citronellol and d-limonene; (5) citronellol and glycerol; (6) citronellol and dihydromyrcene; (7) citronellol and triethylene glycol; (8) citronellol and 1,3-propanediol; (9) citronellol and 1,2-propanediol; (10) citronellol and ethylene glycol. A rough breakdown of these products prior to removal of unreacted monomer species is shown below. 1 The H NMR spectra are shown in Figures 2 to 6.

[0090] Figure 2: Copolymerization of citronellol and triethylene glycol results in a crude mixture with all of the characteristic peaks of the desired copolymer product. It shows the presence of methyl groups adjacent to the newly formed ether linkages and ether-methylene protons at 3-3.5 ppm, indicating that the desired polymerization has occurred.

[0091] Figure 3: Copolymerization of citronellol and glycerol results in a crude mixture with all of the characteristic peaks of the desired copolymer product. Shown is the presence of a methyl group adjacent to the newly formed ether bond and ether-methylene protons at 3-3.5 ppm, indicating that the desired polymerization has occurred.

[0092] Figure 4: Copolymerization of citronellol and linalool results in a crude mixture with all of the characteristic peaks of the desired copolymer product. Shown is the presence of a methyl group adjacent to the newly formed ether bond and ether-methylene protons at 3-3.5 ppm, indicating that the desired polymerization has occurred.

[0093] Figure 5: Copolymerization of citronellol and ethylene glycol results in a crude mixture with all of the characteristic peaks of the desired copolymer product. Shown is the presence of a methyl group adjacent to the newly formed ether bond and ether-methylene protons at 3-3.5 ppm, indicating that the desired polymerization has occurred.

[0094] Figure 6: Copolymerization of citronellol and triethylene glycol results in a crude mixture with all of the characteristic peaks of the desired copolymer product. It shows the presence of methyl groups adjacent to the newly formed ether linkages and ether-methylene protons at 3-3.5 ppm, indicating that the desired polymerization has occurred.

[0095] The reaction conditions can be modified to adjust the molar ratios of monomers and / or to incorporate more than two different monomers to obtain a large number of different copolymer products.

[0096] Example 3: Cosmetic Skin Products The citronellol / 1,6-hexanediol copolymer obtained in Example 1 is used to obtain cosmetic skin products as shown in the table below. [Table 1]

[0097] The skin products are prepared using the following method. (A) In a 150 mL glass beaker, the copolymer of Example 1 is combined with the triglyceride blend, triglyceride, cetyl alcohol, stearyl alcohol and magnesium stearate. (B) Heat the beaker on a hot plate to 70-75 °C (± 5 °C) with continuous stirring. (C) Titanium dioxide and iron oxide are ground together using a mortar and pestle in the ratio required to obtain the desired color to obtain a powder. (D) Add the dye powder of step (C) to the mixture of step (B) and mix until uniform. (E) The stirred mixture is cooled to about 30-40° C., and then vitamins and flavorings are added followed by gentle mixing. (F) The mixture is poured into a 15 ml glass sphere and stored in a refrigerator at approximately 4° C. to cool. The resulting product is a uniform, deep pink semi-solid with a pH of 5.0-5.5. It can be smoothly applied to the skin with a glossy and lustrous effect and does not over-dry the skin.

[0098] The product proves to be safe and effective as a lipstick and blush colorant.

Claims

1. A copolymer comprising at least one unit X and at least one unit Y, wherein unit X is given by formula: 【Chemistry 1】 It has units Y1, Y3 and Y4: 【Chemistry 2】 [In the formula, R １ , R ３ , and R ４ Each of these is independently substituted depending on the case. １ -C １２ Alkyl and C ２ -C １２ It is Alkenil. It has an expression selected from; However, units X and Y1 are not identical; and At least one terminal unit Z: 【Transformation 3】 [In the formula, R is CH ２ CH ２ CH(CH ３ )CH ２ CH ２ .] A copolymer that ends with [this].

2. The copolymer according to claim 1, wherein at least one unit Y is Y1.

3. The copolymer according to claim 1, wherein at least one unit Y is Y3.

4. The copolymer according to claim 1, wherein at least one unit Y is Y4.

5. R １ , R ３ , and R ４ The copolymer according to any one of claims 1 to 4, wherein one or more of the molecules are 3-methylpentyl, linear hexyl, linear nonanyl, linear propyl, or ethyl.

6. R １ , R ３ , and R ４ One or more of the following are C ２ -C １２ The copolymer according to any one of claims 1 to 5, wherein the copolymer is an alkenyl.

7. R １ , R ３ , and R ４ One or more of these are 3-methyl-2-pentylene (i.e., CH ２ CH ２ C(CH ３ ) = CHCH ２ ) or 3-methyl-3-vinylpropyl (i.e., CH ２ CH ２ C(CH ３ )CH=CH ２ The copolymer according to claim 6, wherein the copolymer is as follows:

8. Copolymer: a. Y1, where R １ is a linear hexyl, or Y1 is 【Chemistry 9】 That which is; b. Y1, where R １ 3-methyl-2-pentylene (i.e., CH ２ CH ２ C(CH ３ ) = CHCH ２ ) or Y1 is 【Chemistry 10】 That which is; c. Y1, where R １ 3-methyl-3-vinylpropyl (i.e., CH ２ CH ２ C(CH ３ )CH=CH ２ ) or Y1 is 【Chemistry 11】 is or Y1 【Chemistry 12】 That which is; The copolymer according to claim 1, comprising one or more Y units selected from combinations thereof.

9. Copolymer: a. Y3, where R ３ Those in which the compound is ethyl; b. Y3, where R ３ Those in which the derivative is a linear propyl; c. Y3, where R ３ Those in which the chain is linear hexyl; d. Y3, where R ３ Those in which the heptyl chain is linear; or a combination of those The copolymer according to claim 1, comprising one or more Y units selected from.

10. Copolymer: a. Y4, where R ４ is ethyl (i.e., CH ２ CH ２ ) or Y4 is 【Chemistry 13】 That which is; b. Y4, where R ４ is ethyl (i.e., CH ２ CH ２ ), or Y4 is 【Chemistry 14】 That which is; The copolymer according to claim 1, comprising one or more Y units selected from those combinations.

11. The copolymer according to any one of claims 1 to 10, wherein the copolymer is a linear polymer comprising 1 to 20 units X and 1 to 20 units Y in any order.

12. The copolymer according to any one of claims 1 to 11, wherein all 1 to 20 units Y are the same.

13. The copolymer according to claim 12, wherein the X units and Y units are organized in a block format.

14. The copolymer according to claim 13, wherein the polymer comprises a series of monomer units (X)n(Y)m, where n and m are each integers from 1 to 20.

15. Copolymers Z1, Z3, Z4 and Z5: 【Chemistry 10】 [In the formula, R is CH ２ CH ２ CH(CH ３ )CH ２ CH ２ And R １ is the same as the corresponding base Y1 as defined in any one of claims 1 to 14, and R ３ The corresponding group Y3 is the same as the group Y3, and R ４ and R ５ H, OH, C １－２０ Alkyl, aryl, aryl C １ - ２ Alkyl, OC １－２０ Alkyl, or OC １－１２ Alkyl, O-aryl, O-aryl C １ - ２ Alkyl, C(O)-C １－２０ Alkyl, OC(O)-C １－２０ Selected from alkyl, C(O)-aryl, or O-C(O)-aryl. The copolymer according to any one of claims 1 to 14, wherein the copolymer is terminated with at least one terminal unit Z selected from the following.

16. Substituents R, R of terminal units Z, Z1, Z3, and / or Z4 １ , R ３ and / or R ４ The copolymer according to claim 15, wherein, where applicable, it is identical to the corresponding units X, Y1, Y3 and / or Y4 of the copolymer.

17. Copolymer formula Y: 【Chemistry 20】 [In the formula, A and B are each independently selected terminal groups from Z, Z1, Z3, Z4, and Z5, and n and m are each independently integers from 1 to 20, where n units X and m units Y are arranged in a linear sequence in any order; R is CH] ２ CH ２ CH(CH ３ )CH ２ CH ２ And R １ is the same as the corresponding base Y1 as defined in any one of claims 1 to 16, and R ３ The corresponding group Y3 is the same as the group Y3, and R ４ This is the same as the corresponding base Y4. A copolymer according to any one of claims 1 to 16, having the following characteristics.

18. Fragrances, perfumes, soaps, insect repellents, insecticides, detergents, household cleaning agents, deodorizing sprays, room sprays, pomanders, candles, cosmetics, lotions, pre- and / or aftershave lotions, talcum powders, hair care products, body deodorants, antiperspirants, shampoos, pet litter, topical skin care products, paints or coatings, lubricants, plasticizers, defoamers, hydraulic agents, antimicrobial agents, crop care products, or petroleum volume recovery compositions comprising a copolymer according to any one of claims 1 to 17, or a solution or suspension containing a copolymer according to any one of claims 1 to 17 dissolved in a solvent or solvent mixture.

19. The composition according to claim 18, which is a fragrance, perfume, soap, insect repellent, insecticide, candle, cosmetic, or lubricant composition.

20. The composition according to claim 18, which is stored or contained in a container containing a heating element, wherein the operation of the heating element results in heating of the composition, thermal decomposition of the compound, and release of volatile matter.

21. A method for producing a copolymer according to any one of claims 1 to 17, comprising: (1) a reactor containing formula A 【Chemistry 25】 [In the formula, R is CH] ２ CH ２ CH(CH ３ )CH ２ CH ２ That is the case. Compounds of formula A1, A3 or A4 【Chemistry 26】 [In the formula, R １ , R ３ and / or R ４ each is optionally substituted C １ -C １２ alkyl or C ２－ C １２ alkenyl.] Prepare at least one of the compounds; (2) The compound is brought into contact with a solid ion exchange resin, thereby inducing copolymerization of the compound of formula A with the compounds of formulas A1, A3 and / or A4, to obtain the copolymer according to any one of claims 1 to 17 (where R ５ If R exists, ５ It produces H; (3) Isolate and / or purify the copolymer. A method that includes a process.

22. The method according to claim 21, wherein the solid exchange resin is a resin functionalized with a resin-bonded acid catalyst, a carboxylic acid, or a sulfonic acid moiety.

23. The method according to claim 22, wherein a monomer of formula A is polymerized by an acid catalyst, and subsequently any non-polymerized monomer is distilled and recycled.

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