Polyether derivatives, uses, and methods for producing the same

Abstract

The present invention relates to certain polyether copolymers and polyether derivatives thereof and methods of making and using them. For example, starting materials can include species such as citronellol, geraniol, dihydromyrcene, adipic acid, propanediol, ethylene glycol, glycerol, 1,9-nonanediol, and 1,6-hexanediol.

Description

[Technical Field]

[0001] field The present invention relates to a polyether copolymer and its polyether derivatives, as well as methods for producing and using the 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 significant utility in applications to cosmetics and personal care products, playing important roles in display devices, 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 can be manufactured using simple methods, are easily derivatized for functional modification, and can be produced from safe and sustainable raw materials.

[0003] Monoterpenoid alcohols, such as citronellol, prenol, and isoprenol, are natural products and are commercially available in large quantities. However, these molecules possess combinations of functional groups—isobutylene groups and alcohols—that are not fully utilized 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 wide range 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 possible reason for this is that ether polymerization is an equilibrium reaction, and readily available isobutylene alcohols are 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 routes uses prenol and isoprenol as intermediates, thus greatly increasing their availability. [Overview of the project] [Problems that the invention aims to solve]

[0005] However, as mentioned above, the equilibrium of the polymerization reaction may be making large-scale production of the desired ethers difficult. There is a need for strategies and methods that enable the efficient production of these compounds. [Means for solving the problem]

[0006] overview In remarkable advances in polymer science, PCT / US2015 / 047397 (corresponding U.S. Patent US2017 / 0283553) and PCT / US2015 / 016371 (corresponding U.S. Patent US2017 / 0057940) (the contents of which are incorporated herein by reference) teach methods for utilizing such functionalities in the manufacture of novel polyether compositions. These polyethers represent advances in liquid polymer technology and bring many desirable benefits to areas of commercial application. Furthermore, U.S. Provisional Applications 62 / 539,129 and 62 / 617,924 (currently published as PCT / US2018 / 44657, 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 aforementioned patent applications do not disclose polyether polymers containing more than one repeating monomer unit (i.e., these applications only disclose homopolymers and their derivatives).

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

[0008] Generally, the present invention relates to a copolymer (i.e., a heteropolymer) formed from a combination of monomer units, wherein each monomer unit is substituted with at least one gem-dimethyl group and at least one C 3-14 Alkoxy units and C 1-14 Alkoxy, C 5-16 Alkyl and carbonyl-C 2-13 The present invention provides a copolymer comprising at least one other monomer unit selected from the group consisting of carbonyloxy.

[0009] In one embodiment of the present invention, the copolymer comprises at least one unit X and at least one unit Y, where unit X is given by formula [ka] It has units Y1, Y2, Y3 and Y4 [ka] It has an expression selected from; Here, R, R 1 , R 2 , R 3 and R 4 It is defined as follows:

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

[0011] The copolymer of the present invention is of formula A, A1, A2, A3 and / or A4 [ka] It is manufactured from one or more starting materials having [specific properties].

[0012] For example, in one embodiment, the copolymer of the present invention is of formula Y [ka] [X and Y are as defined above, A and B are each independently terminal bases selected from Z, Z1, Z2, Z3, Z4, and Z5, and n and m are each independently integers from 1 to 20.] This copolymer has a general structure. Therefore, formula Y is a linear polymer having 1 to 20 groups X and 1 to 20 groups Y, where the groups X and Y are connected in some linear arrangement, and the linear polymer ends with group A at one end and group B at the other end.

[0013] In a further embodiment, the present invention provides a method for producing the compound and a method for using the compound. [Brief explanation of the drawing]

[0014] [Figure 1] The proton-NMR spectrum obtained in Example 1 after purification of the product from the copolymerization of citronellol and 1,6-hexanediol is shown.

[0015] [Figure 2] The proton-NMR spectrum obtained in Example 2 from the crude product obtained from the copolymerization of citronellol and triethylene glycol is shown.

[0016] [Figure 3]The proton-NMR spectrum obtained in Example 2 of the crude product obtained from the copolymerization of citronellol and glycerol is shown.

[0017] [Figure 4] The proton-NMR spectrum obtained in Example 2 of the crude product obtained from the copolymerization of citronellol and linalool is shown.

[0018] [Figure 5] The proton-NMR spectrum obtained in Example 2 of the crude product obtained from the copolymerization of citronellol and ethylene glycol is shown.

[0019] [Figure 6] The proton-NMR spectrum obtained in Example 2 of the crude product obtained from the copolymerization of citronellol and 1,3-propanediol is shown. [Modes for carrying out the invention]

[0020] Detailed description While not intended to be constrained by theory, the isobutylene group can form alcohols and ethers via an acid-catalyzed mechanism. This chemistry has been used in other examples to produce ether bonds in organic synthesis.

[0021] The equilibrium of this reaction may make the large-scale production of these ethers difficult. However, the inventors have discovered that by using monomer recycling, appropriate catalyst selection, and highly concentrated reaction conditions, a sufficient degree of polymerization can be achieved for use in a variety of application areas. Furthermore, these low-molecular-weight polymers were further derivatized to much larger molecular weights and novel functionalities were achieved.

[0022] For the 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 also intended to include the isoprenol isomer.

[0023] Although methods for producing these ethers are described in PCT / US2015 / 047397 (US2017 / 0283553), the applicant has discovered that these polyethers can be produced under neat, solvent-free conditions with a higher degree of polymerization, in a shorter time, and using a resin-bonded acid catalyst such as Amberlyst®. In one embodiment, these polymerizations can be carried out below room temperature, preferably slightly above, 30–110°C or more preferably 40–90°C (e.g., about 50°C). Furthermore, in yet another embodiment, these polymerizations can be carried out in batch reactors, semi-batch reactors or even more preferably in continuous packed-bed reactors of the type described in U.S. Patent Provisional Application 62 / 384,939 (filed as related US2018 / 0064108) and PCT / US2017 / 50808 (filed as WO2018 / 049252) (the contents of which are incorporated herein by reference).

[0024] While not constrained by theory, polyether formation can occur under acidic equilibrium conditions. Therefore, it is undesirable to expose these substances to acidic conditions during subsequent derivatization in anticipation of possible depolymerization.

[0025] However, the applicant has discovered that transesterification under basic conditions can achieve the production of a wide range of novel and useful compositions. Furthermore, alkali Williamson etherification can also be achieved with organic halides. The functionalities that can be produced by these methods can modify the hydrophilicity, hydrophobicity, and / or viscosity of these polyethers. Furthermore, novel functions such as UV protection, antioxidant, anti-aging, skin whitening, antimicrobial, and / or other biological activities can also be introduced.

[0026] The inherent advantages of the compounds disclosed herein stem 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 entirely from natural ingredients. These are significant advantages in many of the commercial applications in which these compounds may be used. The compounds disclosed herein are suitable as emollients or surfactants (e.g., octyldodecanol) in many products such as cosmetic and pharmaceutical compositions, as substitutes or replacements for polymers and silicones, as adjuvants in crop care products, and as lubricants or solvents in enhanced recovery methods, hydraulic fracturing, and oilfield applications. The compounds disclosed herein may have improved physical properties such as appearance, aerobicity, viscosity, refractive index, and / or surface tension. The properties of these compounds as short polymers in moderate quantities (e.g., less than 20,000 Daltons, less than 15,000 Daltons, 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 polymerization of the compounds of the present invention stems from the properties of polymers having adjacent oxygen atoms and tertiary carbon atoms. As a result, under conditions that promote the cleavage of OC bonds, the resulting tertiary carbocations are unusually stable. This leads to the easy abstraction of adjacent hydrogen atoms, which regenerates the alcohol and alkene functional groups of the starting materials. Such depolymerization can be promoted by mildly acidic conditions (e.g., Lewis acids or Brønsted acids), thermal conditions, or enzymatic conditions (such as those by enzymes found in naturally occurring bacteria).

[0028] This depolymerizability leads to biodegradation. This property also enables the formation of compositions containing this compound, where the depolymerization of the polymer can be controlled to allow for the slow release of the polymer constituent monomers (such as citronellol) or shortened polymer constituents (such as the release of citronellol dimers by the depolymerization of large polymers). The present invention encompasses solid and / or liquid compositions containing copolymer 1 (and subsequent compounds), where the product provides controlled depolymerization of the polymer and the release and diffusion of the monomers and / or shortened oligomers thereby produced (e.g., by vaporization at the composition surface). Such products may contain components that accelerate such depolymerization (such as Lewis acids or Bronsted acids or enzymes) or such compositions may be combined with devices containing heating elements to promote thermal depolymerization. The monomers and / or shortened oligomers produced in this way (e.g., citronellol or dimers or trimers of citronellol) are themselves beneficial for various reasons, such as, 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 alternatives to silicone, mineral oil and / or paraffin 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 monomer units, where the monomer units include at least one C substituted with at least one gem-dimethyl group 3-14 alkoxy unit and at least one other monomer unit selected from the group consisting of C 1-14 alkoxy, C 5-16 alkyl, polyethoxy and carbonyl-C 2-13 carbonyloxy.

[0031] In an embodiment of the first aspect of the present invention, the present invention further provides a copolymer (copolymer 1), wherein the copolymer comprises at least one unit X and at least one unit Y, where unit X is a function of formula [ka] It has, where unit Y is Y1, Y2, Y3 and Y4 [ka] [In the formula, R, R 1 , R 2 , R 3 and R 4 C1-C are each independently substituted depending on the case. 12 Alkyl, C 2- C 12 Alkenyl or polyethoxy (e.g., C1-C) 12 Alkyl or C 2- C 12 Alkenyl or polyethoxy, each further C1-C depending on the case. 12 Substituted with alkyl, aryl, or hydroxy. Having an expression selected from or a salt thereof; However, if the copolymer contains only groups X and Y1, the substituent R of group X is the substituent R of group Y1. 1 It's not the same.

[0032] In a further embodiment of the first aspect, the present invention provides any of the following: 1.1 Copolymer 1, wherein at least one unit Y is Y1. 1.2 Copolymer 1, in which at least one unit Y is Y2. 1.3 Copolymer 1 in which at least one unit Y is Y3. 1.4 Copolymer 1 in which at least one unit Y is Y4. 1.5 R, R 1 , R 2 , R 3 and R 4 Linear C1-C where one or more of the following are substituted depending on the case12 Alkyl or optionally substituted branched C1-C 12 Alkyl copolymer 1 or 1.1-1.4. 1.6 R, R 1 , R 2 , R 3 and R 4 One or more of the following are 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 are 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 One or more of the following are non-substitutional branch 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 one of 1.1-1.4, in which at least one of the following is CH2. 1.10 R, R 1 , R 2 , R 3 and R 4 Copolymer 1 or any of 1.1-1.4, wherein one or more of the following are unsubstituted branched or linear C6 alkyl groups. 1.11 R, R 1 , R 2 , R 3 and R 4Copolymer 1 or any of 1.1 to 1.4, wherein one or more of the following groups are 3-methylpentyl (i.e., CH2CH2CH(CH3)CH2CH2). 1.12 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 following are linear hexyl (i.e., CH2CH2CH2CH2CH2CH2) or linear nonanyl (i.e., CH2CH2CH2CH2CH2CH2CH2CH2CH2). 1.13 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 following are linear butyl (i.e., CH2CH2CH2CH2) and / or linear propyl (i.e., CH2CH2CH2). 1.14 R, R 1 , R 2 , R 3 and R 4 Copolymer 1 or one of 1.1-1.4, wherein at least one of the following groups is ethyl (i.e., CH2CH2). 1.15 R, R 1 , R 2 , R 3 and R 4 One or more of the following is C 2-12 Alkenyls (for example, C having 1 to 4 double bonds) 2-12 Copolymer 1 or 1.1-1.4, which is an alkenyl. 1.16 R, R 1 , R 2 , R 3 and R 4 One or more of the following is C 2-6 Alkenyls (for example, C having 1-2 double bonds) 2-6 A copolymer 1.15 in which the alkenyl is linear or branched. 1.17 R, R 1 , R 2 , R 3 and R 4Copolymer 1.15 or 1.16, wherein any one or more of them is a C6 alkenyl having one double bond, such as linear hexylene or methyl-substituted pentylene. 1.18 R, R 1 , R 2 , R 3 and R 4 Copolymer 1.17, wherein any one or more of them 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 Copolymer 1 or any one of 1.1 to 1.4, wherein any one or more of them is linear nonanyl (i.e., CH2CH2CH2CH2CH2CH2CH2CH2CH2). 1.20 R, R 1 , R 2 , R 3 and R 4 Copolymer 1 or any one of 1.1 to 1.4, wherein any one or more of them is hydroxy-substituted C 1-12 alkyl (e.g., 2-hydroxypropyl, i.e., CH2CH(OH)CH2). 1.21 R, R 1 , R 2 , R 3 and R 4 Copolymer 1 or any one of 1.1 to 1.4, wherein any one or more of them is an unsubstituted linear C1-C 12 alkyl or an unsubstituted branched C3-C 12 alkyl containing at least one oxygen atom instead of a saturated carbon atom. 1.22 R, R 1 , R 2 , R 3 and R 4 Copolymer 1.21, wherein any one or more of them is polyethoxy, e.g., (OCH2CH2) n where n is 1 to 5, e.g., n is 2, 3 or 4. 1.23 The copolymer is a. Y1, wherein R1 If Y1 is 3-methylpentyl (i.e., CH2CH2CH(CH3)CH2CH2), for example, [ka] That which is; b. Y1, where R 1 For example, Y1 is a linear hexyl molecule. [ka] That which is; c. Y1, where R 1 If Y1 is 3-methyl-2-pentylene (i.e., CH2CH2C(CH3)=CHCH2), for example, [ka] That which is; d. Y1, where R 1 If Y1 is 3-methyl-3-vinylpropyl (i.e., CH2CH2C(CH3)CH=CH2), for example, [ka] is or Y1 [ka] That which is; e. Y2, where R 2 Those in which the compound is ethyl; f. Y2, where R 2 Those in which the derivative is a linear propyl group; g. Y2, where R 2 Those in which is isopropyl (i.e., CH3CHCH2); h. Y2, where R 2 Those in which the chain is linear hexyl; i. Y2, where R 2 Those in which the compound is a linear nonanyl chain; j. Y2, where R 2The formula is (OCH2CH2) n Polyethoxy such that n is 3; k. Y2, where R 2 Those in which is 2-hydroxypropyl; l. Y3, where R 3 Those in which the compound is ethyl; m. Y3, where R 3 Those in which the derivative is a linear propyl group; n. Y3, where R 3 Those in which the chain is linear hexyl; o. Y3, and here, R 3 Those in which the heptyl chain is linear; p. Y4, where R 4 If Y4 is ethyl (i.e., CH2CH2), for example, [ka] That which is; q. Y4, where R 4 is ethyl (i.e., CH2CH2), for example, Y4 is [ka] That which is; Or a copolymer containing one or more Y units selected from these combinations, for example, copolymer 1 or 1.1-1.22. 1.24 copolymer [ka] Copolymer 1 or 1.1-1.23 containing one or more units X. 1.25 copolymer [ka] A unit X greater than or equal to 1, a. Y2, where R 2 Those in which the compound is ethyl; b. Y2, where R 2Those in which the derivative is a linear propyl group; c. Y2, where R 2 Those in which are linear nonanyl chains; and d. Y2, where R 2 Those in which the chain is linear hexyl; or a combination of these Copolymer 1 or 1.1-1.24, which includes one or more units Y selected from the above. 1.26 Copolymer 1 or any of 1.1-1.25, wherein the copolymer is a linear polymer containing 1-20 units X and 1-20 units Y in any order. 1.27 All units X from 1 to 20 are the same (i.e., the base R of units X from 1 to 20 is the same), copolymer 1.26. 1.28 Copolymer 1.27 in which each group R is an unsubstituted branched or linear C6 alkyl group. 1.29 Copolymer 1.28, in which each group R is CH2CH2CH(CH3)CH2CH2. 1.30 units X [ka] This is copolymer 1.29. 1.31 All units Y from 1 to 20 are the same (for example, all R units from 1 to 20Y are the same) 1 Formula Y1 has a group or all 1 to 20Y groups are the same R 2 Formula Y2 has a group or all 1 to 20Y groups are the same R 3 Formula Y3 has a group or all 1 to 20Y groups are the same R 4 A copolymer of formula Y4 (containing a group), or one of copolymers 1.26 to 1.30. 1.32 Copolymer 1.31, in which X and Y units are organized in block form, for example, where the polymer comprises a series of monomer units (X)n(Y)m, where n and m are integers from 1 to 20. 1.33 All units Y from 1 to 20 are of two different formulas, for example, all units Y are a combination of units Y2 and Y3, and all units Y2 are of the same R2 It has substituents, and all Y3 units are the same R 3 A copolymer having substituents, any of 1.26 to 1.30. 1.34 Copolymer 1.33, in which X and Y units are organized in block form. 1.35 Copolymer 1.34 comprising a series of monomer units (X)n(Y3-Y2)m, where n and m are 1 to 25, respectively, such that the Y unit blocks consist of alternating units Y3 and Y2. 1.36 R 2 and R 3 Copolymer 1.35, in which all are linear hexyl molecules. 1.37 Copolymers Z, Z1, Z2, Z3, Z4 and Z5 [ka] Copolymer 1 or any of 1.1-1.36 ending 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 However, if applicable, the corresponding units X, Y1, Y2, Y3 and / or Y4 of the copolymer are the same as the corresponding groups of copolymer 1.37. 1.39 The copolymer is terminated by one or more terminal units Z2, Z3 and / or Z5, where R 5 H, OH, C 1-20 Alkyl (for example, lower alkyl (for example, 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), and optionally unsaturated acyl (e.g., C(O)-C 1-20Alkyl), optionally unsaturated acyloxy (e.g., OC(O)-C) 1-20 Copolymer 1.37, which is alkyl, optionally substituted arylacyl (e.g., C(O)-aryl), or optionally substituted arylacyloxy (e.g., OC(O)-aryl). 1.40 R 5 Copolymer 1.39, where H or OH. 1.41 R 5 is alkyl (for example, lower alkyl (for example, C 1-6 ) or C 1-12 ) or O-alkyl, for example, R 5 but [ka] And here, R is as defined above (i.e., C1-C which is substituted in some cases). 12 Alkyl, for example, C1-C if desired. 12 Copolymer 1.39 (which is further substituted with alkyl or aryl atoms, and is a further embodiment thereof). 1.42 R 5 Copolymer 1.39, 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. 1.43 R 5 is aryl C 1-2 Alkyl (e.g., benzyl or phenethyl) or O-aryl C 1-2 Copolymer 1.39, which is alkyl (e.g., benzyloxy or phenethyloxy). 1.44 R 5 Copolymer 1.39, where is aryl (e.g., phenyl) or O-aryl (e.g., phenoxy). 1.45 R5 Unsaturated acyl (e.g., C(O)-C) is available upon request. 1-20 Alkyl or C(O)-C 1-6 Alkyl) or optionally unsaturated acyloxy (e.g., OC(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, R if desired 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, OC(O)-C 1-5 Alkyl, OC(O)-C 1-4 Alkyl, OC(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 It is alkyl, and the C 1-6 Copolymer 1.39 in which the alkyl group is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, or n-hexyl. 1.48 R 5 Unsaturated C(O)-C as desired 7-20 Alkyl or OC(O)-C 7-20 Alkyl, R if desired 5 Unsaturated C(O)-C as desired 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, OC(O)-C 10-20 Alkyl, OC(O)-C 12-20 Alkyl, OC(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, R if desired 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), OC(O)-C 10-20 Alkyl, OC(O)-C 12-20 Alkyl, OC(O)-C 14-20 Alkyl, OC(O)-C 16-18 Alkyl or OC(O)-C 17 A copolymer of alkyl (e.g., oleyloxy) with a molecular weight of 1.39. 1.50 R 5 Saturated C(O)-C 7-20 Alkyl or OC(O)-C 7-20 Alkyl, R if desired 5 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, OC(O)-C 10-20 Alkyl, OC(O)-C 12-20 Alkyl, OC(O)-C 14-20 Alkyl, OC(O)-C 16-18 Alkyl or OC(O)-C 17 Alkyl copolymer 1.39. 1.51 R 5 Copolymer 1.39, wherein the substituents are fatty acyl chains or fatty acyloxy chains. 1.52 R 5Copolymer 1.39, where is an arylacyl (e.g., C(O)-aryl) or an arylacyloxy (e.g., OC(O)-aryl), e.g., benzoyl or benzyloxy. 1.53 R 5 The substituent further includes a cationic or anionic moiety (e.g., R 5 Copolymer 1.39, wherein the alkyl or aryl is an alkyl, aryl, alkyl ester, or aryl ester, and the alkyl or aryl is substituted with a cationic (e.g., quaternary ammonium) or anionic (e.g., carboxylic acid or sulfonic acid) moiety. 1.54 R 5 The polyether portion is, for example, R 5 Copolymer 1.39, in which substituents include polyethylene glycol chains. 1.55 R 5 Copolymer 1.39, comprising the anti-aging portion, UV-absorbing portion, antioxidant portion, hydrophobic (lipophilic) portion, or hydrophilic portion as described herein. 1.56 Copolymer is formula Y [ka] [In the formula, A and B are each independently selected terminal groups from Z, Z1, Z2, 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.] A copolymer having either 1 or 1.1-1.55. 1.57 The cross-linked dimer has the structure WOC(O)-R 6 R 5 When the terminal group Z5 or (b) terminal group, which is H, is bonded to a non-O atom of monomer units X, Y1, Y2, Y3, or Y4, R 5It has a terminal group Z5 or a (c) terminal group Z2 or Z3 which is OH, where R 5 H is R 6 C is joined or, in some cases, replaced. 1-22 Alkyl, and in some cases substituted C 2-22 If the fragment W is an alkenyl or optionally substituted aryl, and the fragment W has a second terminal hydroxyl group (i.e., structure HO-W-OH), then the crosslinked polymer has the structure HO-WOC(O)-R 6 -C(O)-[O-WO-C(O)-R 6 A crosslinked polymer (e.g., dimer) of either copolymer 1 or 1.1-1.56, where p is an integer from 0 to 100 (e.g., 0 to 10 or 0 to 5 or 0 to 3), is understood to have a repeating pattern of crosslinked units and copolymer units. 1.58 The cross-linked polymer is the dimer WOC(O)-R 6 -C(O)-OW or the polymer HO-WOC(O)-R 6 -C(O)-[O-WO-C(O)-R 6 Copolymer 1 or 1.1~1.56 containing one terminal hydroxyl group (i.e., W-OH) or two terminal hydroxyl groups (i.e., HO-W-OH) is used to form -C(O)-pOW-OH, and the copolymer is then combined with copolymer XC(O)-R 6 A cross-linked polymer (e.g., dimer) 1.57 formed by the reaction of a reactive agent of the form -C(O)-X (wherein X is a leaving group (e.g., chloro, fluoro, bromo, iodo, alkylsulfonyl, arylsulfonyl, imidazolyl) or X is OH). 1.59 A crosslinked polymer (e.g., dimer) 1.57 formed by the reaction of any copolymer 1 or 1.1-1.56 containing one terminal hydroxyl group (i.e., W-OH) or two terminal hydroxyl groups (i.e., HO-W-OH) to form a dimer WOC(O)-OW or a polymer HO-WOC(O)-[O-WO-C(O)]pOW-OH with a reactive agent of the formula XC(O)-X (wherein X is a leaving group (e.g., chloro, fluoro, bromo, iod, alkylsulfonyl, arylsulfonyl, imidazolyl)). 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 A cross-linked polymer (e.g., dimer) having -C(O)]pOW-OH, with a ratio of 1.57 or 1.58. 1.61 R 6 is non-substituted C 1-22 Alkyl, for example, linear unsubstituted C 1-22 Alkyl or branched unsubstituted C 1-22 Alkyl, cross-linked polymer (e.g., dimer) 1.60. 1.62 R 6 is non-substituted C 1-16 Alkyl, for example, linear unsubstituted C 1-16 Alkyl or branched unsubstituted C 1-16 Alkyl, cross-linked polymer (e.g., dimer) 1.60. 1.63 R 6 is non-substituted C 1-10 Alkyl, for example, linear unsubstituted C 1-10 Alkyl or branched unsubstituted C 1-10 Alkyl, cross-linked polymer (e.g., dimer) 1.60. 1.64 R 6 is non-substituted C 1-6 Alkyl, for example, linear unsubstituted C 1-6 Alkyl or branched unsubstituted C 1-6 Alkyl, cross-linked polymer (e.g., dimer) 1.60. 1.65 R 6A cross-linked polymer (e.g., dimer) 1.60 selected from methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2- or -CH2CH(CH3)-), and butylene (e.g., -CH2CH2CH2CH2- or -CH2CH(CH3)CH2- or -CH(CH3)CH2CH2-). 1.66 R 6 is non-substituted C 2-22 Alkenyls, for example, linear unsubstituted C 2-22 Alkenyl or branched unsubstituted C 2-22 A bridged polymer (e.g., a dimer) 1.60, which is an alkenyl, and optionally one of the alkenyls is monounsaturated. 1.67 R 6 is non-substituted C 2-16 Alkenyls, for example, linear unsubstituted C 2-16 Alkenyl or branched unsubstituted C 2-16 A bridged polymer (e.g., a dimer) 1.60, which is an alkenyl, and optionally one of the alkenyls is monounsaturated. 1.68 R 6 is non-substituted C 2-10 Alkenyls, for example, linear unsubstituted C 2-10 Alkenyl or branched unsubstituted C 2-10 A bridged polymer (e.g., a dimer) 1.60, which is an alkenyl, and optionally one of the alkenyls is monounsaturated. 1.69 R 6 is non-substituted C 2-6 Alkenyls, for example, linear unsubstituted C 2-6 Alkenyl or branched unsubstituted C 2-6 A bridged polymer (e.g., a dimer) 1.60, which is an alkenyl, and optionally one of the alkenyls is monounsaturated. 1.70 R 6 A cross-linked polymer (e.g., dimer) 1.60, selected from ethylene (-CH=CH-), propylene (-CH=CHCH2- or -CH2C(=CH2)-), and butylene (e.g., -CH=CHCH2CH2- or -CH2CH=CHCH2- or -CH2CH(=CH2)CH2-). 1.71 R 6A crosslinked polymer (e.g., dimer) 1.60, where is an aryl, e.g., substituted or unsubstituted phenyl. 1.72 R 6 The bond is a cross-linked polymer (e.g., dimer) 1.60. 1.73 A cross-linked polymer (e.g., a dimer) having the structure WOC(O)-OW or HO-WOC(O)-[O-WO-C(O)]pOW-OH 1.57 or 1.59.

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

[0034] In one embodiment, any bonds present in monomer units Y1 and Y4, Z, Z1 and Z4, and starting material species A, A1 and A4 are further extended to form intramolecular rings between appropriately bonded atoms. For example, monomer units Y1 and Y4 include at least the following structure. [ka]

[0035] In a second embodiment, the present invention provides a composition (composition 1) comprising copolymer 1 or any of 1.1 or later, a salt of any of them, or a mixture of any of them, 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 copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.2 A perfume composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.3 A soap composition comprising copolymer 1 or any of the copolymers described in 1.1 or later, a salt thereof, or a mixture thereof. 1.4 An insecticide composition comprising copolymer 1 or any of the copolymers described in 1.1 or later, a salt thereof, or a mixture thereof. 1.5 An insecticide composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.6 A detergent composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.7 A household cleaning composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.8 A deodorizing spray composition comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof. 1.9 A room spray composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.10 A pomander composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.11 A candle composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.12 Composition 1.11, wherein the composition further comprises a paraffin wax and / or beeswax base. 1.13 Composition 1.12 comprising copolymer 1 or any of 1.1 onwards, or a salt thereof, or a mixture thereof, having a suitable core dispersed in a paraffin wax and / or beeswax base and embedded therein. 1.14 Cosmetic compositions comprising copolymer 1 or any of the copolymers from 1.1 onwards, or a salt thereof, or a mixture thereof, such as lipstick, lip balm, lip gloss, eyeshadow, liquid highlighter (for example, for blush), skin ointment, skin lotion, or skin perfume. 1.15 A cosmetic composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.16 A pre- and / or aftershave lotion composition comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof. 1.17 A talcum powder composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.18 Hair care product compositions comprising copolymer 1 or any of those from 1.1 onwards, a salt thereof, or a mixture thereof, such as hair styling products (e.g., hair spray, hair gel or hair drying cream, mousse) or hair cleansing products (e.g., shampoo or conditioner). 1.19 A body deodorant composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.20 An antiperspirant composition comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof. 1.21 A shampoo composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.22 A pet litter composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.23 Topical skin care compositions comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof, wherein the skin care application is optionally a skin moisturizer; a skin penetration enhancer; a skin protectant; a skin analgesic; a skin healing agent; an ultraviolet light absorber or scatterer; a scavenger; an anti-acne agent; an anti-androgen agent; a depilatory agent; a keratolytic agent / exfoliating agent / scrub agent such as salicylic acid; a panthenol moisturizer such as D-panthenol; a soluble or colloidal-soluble moisturizer such as hyaluronic acid and starch graft sodium polyacrylate; and a sunscreen. 1.24 A composition 1.23 whose skin care application is a skin protectant. 1.25 Composition 1.23 in which the skin care application is a skin analgesic or skin moisturizer (for example, in a moisturizing lotion). 1.26 A composition 1.23 whose skin care application is a sunscreen. 1.27 A paint or coating composition comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof. 1.28 A lubricant composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.29 A plastic composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.30 An antifoaming composition comprising copolymer 1 or any of 1.1 or later, a salt thereof, or a mixture thereof. 1.31 A hydraulic composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.32 An antimicrobial composition comprising copolymer 1 or any of the copolymers from 1.1 onwards, a salt thereof, or a mixture thereof. 1.33 A crop care product comprising copolymer 1 or any of 1.1 or later, wherein the compound is, for example, an adjuvant in the crop care product. 1.34 Products for petroleum volume recovery, hydraulic fracturing and / or other oilfield applications comprising copolymer 1 or any of 1.1 or later, wherein the compound is, for example, a lubricant or solvent in the product. 1.35 A composition comprising or consisting of copolymer 1 or any of 1.1 onwards, 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 copolymer 1 or any of the copolymers described in 1.1 or later in a solvent or solvent mixture, for example, an ester, alkane, aromatic, alcohol, or ether solvent. 1.37 Composition 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 A product comprising any of the preceding compositions, wherein the composition is stored or contained in a container comprising a heating element, the operation of which results in heating of the composition, thermal decomposition of the compound, and release of volatile matter.

[0036] In another embodiment, the present invention provides copolymer 1 or any of copolymers 1.1 to 1.73 for use in composition 1 or any of 1.1 to 1.38.

[0037] In a third embodiment, the present invention provides a method for producing copolymer 1 or any of 1.1 or later, wherein the method comprises (1) a reactor containing formula A [ka] Compounds of formula A1, A2, A3 or A4 [ka] [In the formula, R, R 1 , R 2 , R 3 and / or R4 Each of these C1-C is substituted depending on the case. 12 Alkyl, C 2- C 12 Alkenyl or polyethoxy (e.g., C1-C) 12 Alkyl or C 2- C 12 Alkenyl or polyethoxy, each further C1-C as applicable. 12 Substituted with alkyl, aryl, or hydroxy. 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, A2, A3 and / or A4 to form copolymer 1 or any copolymer of 1.1 to 1.56 (where R 5 If R exists, 5 It produces H; (3) Isolate and / or purify (e.g., by distillation) copolymer 1, for example, a group of related copolymers 1 having the same or substantially the same monomer composition. Includes the process.

[0038] In a further embodiment of a third aspect, the present invention provides the following: 1.1 Method 1, in which polymerization occurs on an ion exchange resin at a high temperature (e.g., 30-120°C). 1.2 Polymerization occurs on an ion exchange resin at 40-90°C, method 1.1. 1.3 Polymerization occurs on the ion exchange resin at approximately 50°C, method 1.2. 1.4 The solid exchange resin is a resin functionalized with a resin-bonded acid catalyst, for example, a carboxylic acid or sulfonic acid moiety, according to either Method 1 or 1.1 to 1.4. 1.5 Polymerization occurs in a batch reactor using one of the methods described above. 1.6 Polymerization occurs in a continuous packed-bed reactor using one of the methods described above. 1.7 Any of the above methods, wherein the monomer of formula A is polymerized by an acid catalyst, and subsequently any of the non-polymerized monomers are distilled and recycled. 1.8 Any of the preceding methods, wherein the resin-bonded acid catalyst is selected from silicon-propanesulfonic acid, montmorillonite, or Amberlyst® (e.g., a large network or porous resin or silica covalently bonded to sulfonic acid groups or carboxylic acid groups). 1.9 The method of 1.7, wherein the catalyst is Amberlyst®. 1.10 Copolymer 1 is purified by fractional distillation using one of the methods described above. 1.11 Furthermore, copolymer 1 (wherein the copolymer has at least one terminal hydroxyl group (e.g., group R 5 , here, R 5 The group R in the copolymer 5 The reaction comprises a step of reacting a compound (which is H or OH due to its linkage) with a reactant suitable for converting the terminal hydroxyl group to an alkyl ester or aryl ester moiety (e.g., for producing copolymers 1.41-1.55 or embodiments thereof), for example, the alkyl ester being a methyl ester and using ketene as a suitable reactant, any of the above methods. 1.12 Method 1.11, where esterification is an alkali transesterification reaction using a functionalized ester. 1.13 Furthermore, copolymer 1 (wherein the copolymer has at least one terminal hydroxyl group (e.g., group R 5 , here, R 5 The group R in the copolymer 5 Method 1 or any of 1.1 to 1.10, comprising the step of a reaction with a reactant suitable for converting the terminal hydroxyl group to an alkyl ether or aryl ether moiety (e.g., for producing compounds 1.41 to 1.55 or embodiments thereof). 1.14 Method 1.13 is a Williamson-type etherification reaction using an alkyl halide and a base suitable for etherification. 1.15 Furthermore, copolymer 1 (wherein the copolymer has at least one terminal hydroxyl group (e.g., group R 5 , here, R 5 The group R in the copolymer 5Method 1 or any of methods 1.1 to 1.14, comprising a reaction step with a reactant suitable for converting the copolymer into a crosslinked dimer of any of compounds 1.57 to 1.73 (containing H or OH due to their linkage). 1.16 The crosslinked dimer has the formula WOC(O)-OW, and the suitable reactant is phosgene, method 1.15. 1.17 The cross-linked dimer has the formula WOC(O)-R 6 It has -C(O)-OW and a suitable reactant is of the formula HO-C(O)-R 6 It is a diacid of -C(O)-OH, method 1.15. 1.18 The cross-linked dimer has the formula WOC(O)-R 6 It has -C(O)-OW and a suitable reactant is of the formula XO-C(O)-R 6 Reactive diacyl species of -C(O)-OX (wherein 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 present invention provides copolymers produced by Method 1 or any of Methods 1.1 to 1.18.

[0040] Examples of monomer species suitable for use in the manufacture of copolymer 1 or any of the methods 1.1 to 1.18, or suitable for use in method 1 or any of methods 1.1 to 1.18, include, but are not limited to, acyclic monoterpenoid alcohols (e.g., citronellol, geraniol, nerol, linalool, linalool, coriandolol, 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 (e.g., diethylene glycol, triethylene glycol and tetraethylene glycol); and dicarboxylic acids (e.g., azelaic acid, adipic acid and succinic acid). Further reacting species that may participate in the formation of copolymer 1 or later, or are suitable for use in methods 1 or 1.1 to 1.18, include dienes (e.g., 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 2,6-octadiene, and limonene) and alkenic acids (e.g., citronellic acid).

[0041] In certain embodiments, copolymer 1 may be produced by Method 1 or any of 1.1 to 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 produced by Method 1 or any of 1.1 to 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 one embodiment, the UV-absorbing portion 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 one embodiment, the anti-aging and / or antioxidant portion includes, but is not limited to, hyaluronic acid, ascorbic acid, azelaic acid, carnosine, glycolic acid, nicotinic acid, phenolic acid, phenolic ether, benzophenone, sulfite, sulfone, sulfonic acid, and phosphoric acid.

[0044] In one embodiment, the hydrophobic portion includes acetate, propionate, linear or branched fatty acids, linear or branched alkyl chains, organosilicon, fluoroalkane, and graphene derivatives. The hydrophilic portion includes sulfonic acid, ethoxylate, polyglycerol, polypropylene glycol, carbohydrates, carboxylic acids, and other polyols.

[0045] For example, copolymers 1 and later, such as those produced by Method 1 (and subsequent methods), are bonded (e.g., esterified or etherified) to other biologically active molecules such as antimicrobial compounds, pharmaceutical compounds, skin healing compounds, and sensient molecules such as coolants, 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 a wide range of applications. They may be used in cosmetic products, paints or coatings, personal care products, household goods, such as cleaning products, electronic equipment, lubricants, plastics, defoamers, petroleum filler and gas recovery (including hydraulic fracturing and other oilfield applications), pharmaceutical applications, crop care products, and hydraulic compositions. The compounds disclosed herein are suitable as substitutes or replacements for surfactants, polymers, silicones, and solvents in these various applications. These substances, particularly low molecular weight molecules, can also be advantageously used as insect repellents. For example, copolymer 1 (and subsequent compounds) produced by Method 1 and subsequent methods may be used in combination with or incorporated with insecticides, insect repellents, and bioactive ingredients.

[0047] In a fourth aspect, the present invention provides a method for using copolymers 1 and later, produced, for example by Method 1 (and later methods), in compositions (for example, Composition 1 (and later), for example, fragrance compositions, perfumes, soaps, insect repellents and insecticides, detergents, household cleaning agents, deodorizing sprays, room sprays, pomanders, candles, cosmetics, lotions, pre- and / or aftershave lotions, talcum powder, hair care products, body deodorants, antiperspirants, shampoos, skin care applications, pharmaceuticals, antimicrobials, pet litter, crop care products, or oilfield, hydraulic fracturing or petroleum volume recovery methods).

[0048] Therefore, the present invention provides a method using copolymer 1 or any of 1.1 to 1.73 (Method 2), and a method for producing composition 1 or any of compositions 1.1 to 1.38.

[0049] In a further embodiment of the fourth aspect, Method 2 may provide any of the following: 2.1 The method of Method 2, wherein copolymer 1 or any of 1.1 to 1.73 is used in the fragrance composition. 2.2 Method 2, wherein either copolymer 1 or 1.1-1.73 is used in the perfume. 2.3 Method 2, wherein copolymer 1 or either of 1.1-1.73 is used in the soap. 2.4 Method 2, wherein copolymer 1 or either 1.1-1.73 is used as an insect repellent. 2.5 Method 2, wherein copolymer 1 or either 1.1-1.73 is used as an insecticide. 2.6 Method 2, wherein copolymer 1 or 1.1-1.73 is used in the detergent. 2.7 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in household cleaning agents. 2.8 Method 2, wherein either copolymer 1 or 1.1-1.73 is used in the deodorizing 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, wherein copolymer 1 or any of 1.1-1.73 is used in the pomander. 2.11 Method 2, wherein copolymer 1 or either of 1.1-1.73 is used in the candle. 2.12 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in cosmetics. 2.13 Method 2, wherein either copolymer 1 or 1.1-1.73 is used in the lotion. 2.14 Method 2, wherein copolymer 1 or either of 1.1-1.73 is used in the pre- and / or aftershave lotion. 2.15 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in talcum powder. 2.16 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in a hair care product. 2.17 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in a body deodorant. 2.18 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in the antiperspirant. 2.19 Method 2, in which either copolymer 1 or 1.1-1.73 is used in the shampoo. 2.20 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in the pet litter. 2.21 A method of Method 2, wherein copolymer 1 or any of 1.1 to 1.73 is used for topical application in skin care, wherein the skin care application may be selected from skin moisturizers; skin penetration enhancers; skin protectants; skin analgesics; skin healing agents; UV light absorbers or scatterers; UV light capturers; anti-acne agents; anti-androgen agents; depilatory agents; keratolytic agents / exfoliating agents / scrubs such as salicylic acid; panthenol moisturizers such as D-panthenol; soluble or colloidal-soluble moisturizers such as hyaluronic acid and starch graft sodium polyacrylate; and sunscreens. 2.22 The skin care application is a skin protectant, according to the method of 2.21. 2.23 The skin care application is a skin analgesic agent, according to the method of 2.21. 2.24 If the skin care application is a sunscreen, follow the method of 2.21. 2.25 Method 2, wherein copolymer 1 or either 1.1-1.73 is used in the paint or coating. 2.26 Method 2, wherein copolymer 1 or any of 1.1-1.73 is used as a lubricant. 2.27 Method 2, wherein copolymer 1 or any of 1.1 to 1.73 is used for plasticity. 2.28 The method of Method 2, wherein copolymer 1 or any of 1.1 to 1.73 is used in pharmaceuticals. 2.29 A method of Method 2, wherein copolymer 1 or any of 1.1 to 1.73 is used in a crop care product, and the compound is an adjuvant in the crop care product. 2.30 A method of Method 2 in which copolymer 1 or any of 1.1 to 1.73 is used in products for petroleum volume recovery, hydraulic fracturing and / or other oilfield applications, for example, in which the compound is a lubricant or solvent in the application.

[0050] A further benefit of these substances described herein is that they are expected to be fully biodegradable and biocompatible.

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

[0052] In one embodiment, thermal depolymerization is used to release monomers into the air in a controlled release. In one embodiment, the present invention is intended for use, for example, in thermal dispensers for candles or odor control and / or mosquito control, low-pH industrial detergents having depolymerized monomer components released over time to promote a beneficial odor, and laundry detergents using enzymes that digest the polymer over time to maintain a fresh scent for an extended period.

[0053] In other embodiments, the fragrance composition comprises, for example, a compound of copolymer 1 (or later) produced by Method 1 or later, and the fragrance compositions of this application are selected from perfumes, soaps, insect repellents and insecticides, detergents, household cleaning agents, deodorizing sprays, room sprays, pomanders, candles, cosmetics, lotions, pre- and / or aftershave lotions, talcum powder, hair care products, body deodorants, antiperspirants, shampoos, colognes, shower gels, hairsprays and pet litter.

[0054] In other embodiments, for example, the copolymer 1 (and subsequent compounds) produced by Method 1 (and subsequent methods) can be used in antifungal compositions. In certain embodiments, the antifungal composition comprises, for example, a polyether of copolymer 1 (and subsequent compounds) produced by subsequent to Method 1 and at least one of the above fragrance components selected from the group consisting of aliphatic or aromatic aldehydes, aliphatic or aromatic alcohols, acetals and esters, which exhibit a synergistic effect, thereby enabling the content of the active ingredient to be reduced to a lower amount than when used alone.

[0055] In other embodiments, for example, the compounds of copolymer 1 (and subsequent compounds) produced by Method 1 (and subsequent methods) 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-androgen agents; depilatory agents; keratolytic / desquamating / scrubbing agents such as salicylic acid; panthenol moisturizers such as D-panthenol; soluble or colloidal-soluble moisturizers such as hyaluronic acid and sodium starch polyacrylate; and sunscreens.

[0056] In other embodiments, the polyether of copolymer 1 (and subsequent compounds) produced by subsequent to Method 1 can be used in a delivery system, for example, any fragrance delivery system where long-term constant release of the above aromatic compounds is desired. For example, the fragrance delivery systems described herein can be used in, for example, functional fragrances, products used in other articles that are exposed to sunlight during use or subsequently exposed to sunlight.

[0057] In further embodiments, the invention provides a Delivery System 4.0 that includes, for example, liquid and solid deodorant sprays, along with the delivery system of the invention. Still further examples include delivery systems for delivering window and household cleaners, general-purpose cleaners, and furniture polish. Surfaces are cleaned with such cleaners. In further examples, delivery systems that include detergents and fabric softeners for clothing also include the delivery system of the invention, and clothing is washed or treated with such detergents or fabric softeners.

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

[0059] In certain embodiments, Delivery System 4.0 can include any of the following delivery systems: 4.1 A drug delivery system that includes Copolymer 1 or any of 1.1 - 1.73 or any salts thereof or mixtures thereof. 4.2 A fragrance delivery system that includes Copolymer 1 or any of 1.1 - 1.73 or any salts thereof or mixtures thereof. 4.3 A detergent delivery system that includes Copolymer 1 or any of 1.1 - 1.73 or any salts thereof or mixtures thereof. 4.4 A household cleaner delivery system that includes Copolymer 1 or any of 1.1 - 1.73 or any salts thereof or mixtures thereof.

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

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

[0062] The singular expressions used here include plurals unless it is clearly contrary to the context. Therefore, for example, the description of "reactant" includes not only one reactant but also combinations or mixtures of two or more different reactants, and the description of "substituent" includes one substituent and two or more substituents, etc.

[0063] The terms “for example,” “etc.,” or “including” used herein are intended to provide examples that clarify the general subject. These examples are provided solely to aid in understanding this disclosure and are not intended to limit it in any way. Furthermore, the terms “may,” “optionally,” “optionally,” or “may be optional” used herein are intended to mean that something may or may not happen, including the cases in which the preceding circumstances may and may not happen. For example, the term “to exist as desired” means that the thing may or may not exist, and therefore this statement includes both the case in which the thing exists and the case in which it does not exist.

[0064] The terms "having a formula" or "having a structure" used herein are not intended as limitations and are used in the same way that the term "contains" is generally used.

[0065] In some of the formulas of this application, one or more chiral centers are attached to the side of the chiral carbon. Ta This is indicated by the risk. In other formulas, chiral isomers are included in these formulas even if the chiral center is not specified.

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

[0067] A "tautomer" is a compound whose structure differs significantly in atomic arrangement but which readily and rapidly exists in equilibrium. It is understood that the compounds of the present invention can be described as various tautomers. If a compound has tautomer forms, it is intended that all tautomer forms fall within the scope of the present invention, and the naming of the compounds does not exclude any tautomer forms. Furthermore, even if only one tautomer can be described, the present invention includes all tautomers of that compound.

[0068] The term "salt" as used herein includes acid addition salts, including hydrochlorides, hydrobroms, phosphates, sulfates, bisulfates, alkylsulfons, arylsulfons, acetates, benzoates, citrates, maleates, fumarates, succinates, lactates, and tartrates; alkali metal cations, such as Na. + , K + Li + , alkaline earth metal salts, such as Mg 2+ or Ca 2+ Alternatively, it may contain an organic amine salt or an organic phosphonium salt.

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

[0070] The term "alkenyl" used here typically refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group containing 2 to about 12 carbon atoms and 1 to 10 carbon-carbon double bonds, such as ethylene, n-propylene, isopropylene, n-butylene, isobutylene, t-butylene, and octylene.

[0071] The term "alkynyl" used here typically refers to a monovalent or divalent, branched or unbranched, unsaturated hydrocarbon group containing 2 to approximately 12 carbon atoms and 1 to 8 carbon-carbon triple bonds, such as ethyne, propyne, butyn, pentyn, hexyn, heptyn, and octine.

[0072] The term "aryl" as used herein refers to an aromatic hydrocarbon moiety that includes at least one aromatic ring of 5-6 carbon atoms, for example, an aromatic hydrocarbon having two fusion rings and 10 carbon atoms (i.e., naphthalene).

[0073] In terms of "substituted alkyl," "substituted alkenyl," and "substituted alkynyl," "substituted" means that at least one hydrogen atom bonded to a carbon atom in the alkyl, alkenyl, alkynyl, or other part is substituted with one or more nonhydrogen substituents, such as functional groups.

[0074] For example, C a ~C b When referring to the alkyl moiety of a carbon atom, the terms “branched” and “linear” (or “unbranched”) apply to the carbon atom that defines the alkyl moiety. For example, for a C4 alkyl moiety, its branched embodiment includes isobutyl, and its unbranched embodiment is n-butyl. However, isobutyl is also clarified as the linear C3 alkyl moiety (propyl) itself, substituted with a C1 alkyl (methyl).

[0075] Examples of functional groups include halo, hydroxyl, sulfhydryl, and C1-C. 24 Alkoxy, C2-C 24 Alkenyloxy, C2-C 24Alkynyloxy, 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-C 20 Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X, where X is a halo), C2-C 24 Alkylcarbonato (-O-(CO)-O-alkyl), C6-C 20 Arylcarbonato (-O-(CO)-O-aryl), Carboxylate (-COOH), Carboxylalato (-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), carboamide(-NH-(CO)-NH2), cyano(-C≡N), isocyano(-N + ≡C - ), cyanato(-OC≡N), isocyanato(-ON) + ≡C - ), isothiocyanates (-SC≡N), azides (-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 acids, 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 Ariel, C6-C20 Alkaline, C6-C 20 Aralkyl (e.g., aralkyl), 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), sulfonate (-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)(OH)2) - )2) phosphina(-P(O)(O - )), phospho(-PO2), phosphino(-PH2), mono- and di-(C1-C 24 Alkyl)-substituted phosphino, mono- and di-(C5-C 20 Aryl)-substituted phosphinos; and hydrocarbyl moieties, e.g., C1-C 24 Alkyl (C1-C 18 Contains alkyl, and further C1-C 12 (containing alkyl and further containing C1-C6 alkyl), C2-C 24 Alkenyl (C2-C 18 Including alkenyls, further C2-C 12 (containing alkenyls and further containing C2-C6 alkenyls), C2-C 24 Alkinyl (C2-C 18 Including alkynyl, further C2-C 12 (containing alkynyls and further containing C2-C6 alkynyls), C5-C 30 Aryl (C5-C 20 Contains aryl and further C5-C 12aryl-containing) and C6-C 30 aralkyl (C6-C 20 aralkyl-containing and further C6-C 12 including, but not limited to, aralkyl-containing). Further, the functional group may be further substituted with one or more additional functional groups or one or more hydrocarbyl moieties as specifically listed above, provided that such substitution is acceptable with its particular group. For example, an alkyl or alkenyl group may be branched. For example, the "substituent" is an alkyl group, such as a methyl group.

[0076] As used herein, the term "perfume composition" means a mixture of perfume ingredients, including, for example, optional substances if desired, dissolved in a suitable solvent or mixed with a powdered substrate, for imparting a desired odor to a product, and including polyether compounds of Method 1 and later and Method 2 and later.

[0077] The copolymers of Method 1 and later, the polyether compounds of Method 1 and later and Method 2 and later can be used with, for example, perfumes, soaps, insect repellents and pesticides, 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.

[0078] The perfumes and ingredients and perfume ingredient mixtures that can be used in combination with the compounds of the present invention in the manufacture of perfume compositions include natural products including extracts, animal products and essential oils, absolutes, resinoids, resins and concretes, and synthetic perfume substances including, but not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furanketals, nitriles, acids and both saturated and unsaturated compounds and aliphatic carbocyclic and heterocyclic compounds including animal products.

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

[0080] In this specification, the structural formulas of compounds sometimes represent specific isomers for simplicity, but the present invention includes all isomers, such as geometric isomers, optical isomers based on chiral carbons, stereoisomers, tautomers, etc. Furthermore, while crystalline polymorphisms may exist for compounds combined by formula, all crystalline forms, mixtures of crystalline forms, or their anhydrous or hydrates are included within the scope of the present invention.

[0081] All percentages used here are based on volume unless otherwise specified.

[0082] All ratios used here are in molar concentration unless otherwise specified. [Examples]

[0083] Example 1. Synthesis of citronellol / 1,6-hexanediol copolymer Thoroughly mix 500 g of citronellol and 94.5 g of 1,6-hexanediol (0.25 equivalents) at 50°C. Pump the mixture at a flow rate of 2 mL / min into a 6 ft, 1 / 4 inch tube filled with Amberlyst ion exchange resin. Allow the reaction to proceed at 50°C. Collect the crude product at the end of the tube and use nuclear magnetic resonance spectroscopy (NMR) and gas chromatography (GC) to monitor the reaction. After the reaction is considered complete, dilute the crude product with hexane and wash with saturated sodium carbonate solution until the pH of the aqueous phase is approximately 8. Then collect the organic phase, concentrate it, and prepare it for distillation to remove any monomers. Remove unreacted monomers by distillation at a vessel temperature of 83–165°C and a pressure of 0.7–2.85 mBar. The total yield of the reactants is a viscous, colorless, transparent, odorless fluid with a yield of 56.4%.

[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 product by 1H-NMR allows for characterization of the degree of alcohol incorporation and / or olefin etherification. The characteristic ether methylene peak shifts to the 3.0–3.5 ppm range in CDCl3 solvent, compared to the corresponding alcoholic methylene peak at 3.5–4.0 ppm. The characteristic methyl peak associated with the dimethyl ether motif of the citronellol monomer and polymer products appears in the 1.0–1.5 ppm range.

[0086] Figure 1 shows the purified product. 1 The 1H NMR spectrum is shown. The spectrum is consistent with a copolymer system predominantly capped by OH groups (both olefin protons and the corresponding isoprenylmethyl protons), indicated by a high degree of reduction in the present isoprenyl moiety, and the dominant presence of 3.5–3.7 ppm of hydroxymethylene protons. Furthermore, it shows significant endogenous oligomerization related to the ether bond, indicated by 3.2–3.4 ppm of ethermethylene protons and the corresponding methyl group adjacent to the ether.

[0087] Although not constrained by theory, the NMR spectrum matches the copolymer structure shown below. [ka]

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

[0089] Example 2: Synthesis of other citronellol copolymers Copolymers derived from the following monomer combinations are obtained using synthesis and analytical methods similar to those described in Example 1: (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. The rough analysis of these products before removal of unreacted monomer species is as follows: 1 The 1H NMR spectra are shown in Figures 2-6.

[0090] Figure 2: Copolymerization of citronellol and triethylene glycol yields a crude mixture containing all the characteristic peaks of the desired copolymer product. The presence of methyl groups adjacent to the newly formed ether bonds and 3–3.5 ppm of ether-methylene protons indicates that the desired polymerization has occurred.

[0091] Figure 3: Copolymerization of citronellol and glycerol yields a crude mixture containing all the characteristic peaks of the desired copolymer product. The presence of methyl groups adjacent to the newly formed ether bonds and 3–3.5 ppm of ether-methylene protons indicates that the desired polymerization has occurred.

[0092] Figure 4: Copolymerization of citronellol and linalool yields a crude mixture containing all the characteristic peaks of the desired copolymer product. The presence of methyl groups adjacent to the newly formed ether bonds and 3–3.5 ppm of ether-methylene protons indicates that the desired polymerization has occurred.

[0093] Figure 5: Copolymerization of citronellol and ethylene glycol yields a crude mixture containing all the characteristic peaks of the desired copolymer product. The presence of methyl groups adjacent to the newly formed ether bonds and 3–3.5 ppm of ether-methylene protons indicates that the desired polymerization has occurred.

[0094] Figure 6: Copolymerization of citronellol and triethylene glycol yields a crude mixture containing all the characteristic peaks of the desired copolymer product. The presence of methyl groups adjacent to the newly formed ether bonds and 3–3.5 ppm of ether-methylene protons indicates that the desired polymerization has occurred.

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

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

[0097] Skin products are manufactured using the following method: (A) In a 150 mL glass beaker, combine the copolymer of Example 1 with the triglyceride blend, triglycerides, cetyl alcohol, stearyl alcohol, and magnesium stearate. (B) Heat the beaker on a hot plate to 70-75°C (±5°C) while continuously 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 from step (C) to the mixture from step (B) and stir until homogenized. (E) Cool the stirred mixture to approximately 30-40°C, then add the vitamins and flavorings, and mix gently. (F) Pour the mixture into a 15 ml spherical glass container and store 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 applied smoothly to the skin, providing a glossy and lustrous effect without causing excessive skin dryness.

[0098] This product is safe and has been found to be effective as a coloring agent for lipstick and blush.

Claims

1. The copolymer comprises at least one monomer unit X and at least one monomer unit Y, where unit X is given by formula 【Chemistry 1】 It has a unit Y of Y2 【Chemistry 2】 [In the formula, R ２ C is replaced in some cases. １ -C １２ Alkyl, C ２ -C １２ It is Alkenil. It is a copolymer having the structure; However, the units X and Y are not the same. At least one terminal unit Z 【Transformation 3】 [In the formula, R is CH₂CH₂CH(CH₃)CH₂CH₂.] A copolymer that ends with [this].

2. R ２ The copolymer according to claim 1, wherein is 3-methylpentyl, linear hexyl, linear nonanyl, linear propyl, or ethyl.

3. R ２ C ２－１２ The copolymer according to claim 1, wherein the copolymer is an alkenyl.

4. R ２ is 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 ) and the copolymer according to claim 3.

5. The monomer unit Y a. Y2, where R ２ Those in which the compound is ethyl; b. Y2, where R ２ Those in which the propyl group is linear; c. Y2, where R ２ isopropyl (i.e., CH ３ CHCH ２ ) things that are; d. Y2, where R ２ Those in which the chain is linear hexyl; e. Y2, where R ２ Those in which the compound is a linear nonanyl chain; f. Y2, where R ２ Those in which is 2-hydroxypropyl; Or a copolymer according to claim 1, selected from a combination thereof.

6. The monomer unit Y a. Y2, where R ２ Those in which the compound is ethyl; b. Y2, where R ２ Those in which the propyl group is linear; c. Y2, where R ２ Those in which are linear nonanyl chains; and d. Y2, where R ２ Those in which the chain is linear hexyl; or a combination of these A copolymer according to claim 1, selected from the following.

7. The copolymer according to any one of claims 1 to 6, wherein the copolymer is a linear polymer comprising 1 to 20 units X and 1 to 20 units Y in any order.

8. The copolymer according to claim 7, wherein all 1 to 20 units Y are the same.

9. The copolymer according to claim 7 or 8, wherein the X units and Y units are organized in a block format.

10. The copolymer according to claim 8, wherein the polymer comprises a series of monomer units (X)n(Y)m, where n and m are each integers from 1 to 20.

11. Copolymer Z2 and Z5 【Chemistry 4】 [In the formula, R ２ This is the same as the corresponding base Y2, 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. A copolymer according to any one of claims 1 to 10, which ends in at least one terminal unit selected from.

12. Copolymer formula Y 【Transformation 5】 [In the formula, A is the terminal group Z, and B is Z, Z2 and Z5] 【Transformation 6】 [In the formula, R is CH₂CH₂CH(CH₃)CH₂CH₂, and R₂ is the same as the corresponding group Y₂, R5 is selected from H, OH, C1-20 alkyl, aryl, aryl C1-2 alkyl, OC1-20 alkyl or OC1-12 alkyl, O-aryl, O-aryl C1-2 alkyl, C(O)-C1-20 alkyl, OC(O)-C1-20 alkyl, C(O)-aryl or O-C(O)-aryl. A terminal group selected from, where n and m are each independent integers from 1 to 20, where n units X and m units Y are arranged in a linear sequence in any order; where R is CH ２ CH ２ CH(CH ３ )CH ２ CH ２ That is the case. A copolymer according to any one of claims 1 to 10, having the following characteristics.

13. 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 compositions, antimicrobial agents, crop care products, or petroleum volume recovery compositions comprising the copolymer described in any of claims 1 to 12.

14. The composition according to claim 13, which is a fragrance, perfume, soap, insect repellent, insecticide, candle, cosmetic, or lubricant composition.

15. The composition according to claim 13, which is stored or contained in a container containing a heating element, wherein activation of the heating element results in heating of the composition, thermal decomposition of the compound, and release of volatile substances.

16. A method for producing a copolymer or a salt thereof according to any one of claims 1 to 12, wherein (1) a reactor contains formula A 【Transformation 7】 Compounds and formula A2 【Transformation 8】 [In the formula, R ２ C is replaced in some cases. １ -C １２ Alkyl, C ２ -C １２ It is Alkenil. Add at least one of the compounds; (2) The compound is exposed to a solid ion exchange resin, thereby inducing copolymerization of the compound of formula A and the compound of formula A2 to obtain the copolymer according to any one of claims 1 to 12 (where R ５ If R exists, ５ It produces H; (3) Isolate and / or purify the copolymer. A method that includes a process.

17. The method according to claim 16, wherein the solid exchange resin is a resin functionalized with a resin-bonded acid catalyst, such as a carboxylic acid or sulfonic acid moiety.

18. The method according to claim 16, wherein monomers of formulas A and A2 are polymerized by an acid catalyst, and then some non-polymerized monomers are distilled and recycled.

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