vicinal diol ether derivatives of polyether polymers

Abstract

The present invention relates to vicinal diol ether derivatives of specific polyether polymers, compositions containing said derivatives, and methods for preparing said derivatives by reaction with substituted or unsubstituted epoxides and their use.

Description

[0001] Cross - Reference to Related Applications

[0002] This application is an international PCT application that claims the priority and benefit of U.S. Provisional Application No. 62 / 961,035, filed on January 14, 2020; U.S. Provisional Application No. 63 / 043,251, filed on June 24, 2020; U.S. Provisional Application No. 63 / 092,407, filed on October 15, 2020; and U.S. Provisional Application No. 63 / 125,842, filed on December 15, 2020. The entire contents of these applications are incorporated herein by reference.

[0003] Field

[0004] The present invention relates to vicinal diol ether derivatives of specific polyether polymers, and methods for preparing such derivatives by reaction with substituted or unsubstituted epoxides, compositions comprising such derivatives, and methods of using the same. Polyether polymer precursors of the derivatives include, for example, polycitronellol, polyprenol, polyisocitronellol, and polyisoprenol. Epoxides include epoxides of straight - chain and branched - chain alkanes and cycloalkanes, including epoxidized terpenes. Background Art

[0005] Liquid polymers have important uses in cosmetic and personal care applications and play important roles in visual displays, rheology, tribology, and drug delivery. For example, they can be used as lubricants, softeners, or as protective barriers for skin healing and UV protection. Ideally, these substances can be produced in a convenient manner, are amenable to derivatization to improve functionality, and even more preferably are prepared from safe and sustainable raw materials.

[0006] Citronellol, prenol, and isoprenol are all naturally occurring molecules and are also commercially available on a large scale. However, these molecules have an under - utilized combination of functional groups that allow polymerization and functionalization: isobutenyl groups and alcohols.

[0007] This type of chemical reaction has been mostly overlooked in polymer chemistry. One reason for this may be due to the fact that polymerization reactions are equilibrium reactions and sufficient isobutenol is not always available. However, in recent years, the production of citronellol has grown rapidly, and one of the largest production routes also uses prenol and isoprenol as intermediates, thus significantly increasing the availability.

[0008] WO 2019 / 028053 discloses novel polymers derived from naturally occurring and commercially available monomeric citronellol, pentenol, and isoprenol. These monomers are effectively polymerized in a controlled manner to give a number of well-characterized polyether alcohols. Additionally, since these polymers have primary alcohol functional groups upon formation, WO 2019 / 028053 also discloses functionalizing the alcohols to derive various ethers, esters, and other derivatives.

[0009] Overview

[0010] In the remarkable progress of polymer science, the applicant's prior disclosures US2017 / 0283553, US2017 / 0057940, and WO2019 / 028053 have generally taught how to prepare polyether polymers and their derivatives, the contents of which are incorporated herein by reference. These polyethers represent an advancement in liquid polymer technology and confer many suitable benefits in the field of commercial applications. It has been found that polyether polymers and their simple ether and ester derivatives can be used as lubricants, softeners, wetting agents, and surfactants.

[0011] Based on the applicant's previous research, the present application is expected to provide new compounds, compositions, and methods for preparing these polymer derivatives with different physical and chemical properties. These structurally unique vicinal diol segments can improve the performance of polyether polymers to provide various novel applications.

[0012] The polymer derivatives disclosed herein can be used in cosmetic or specialty chemical formulations and can, in some cases, be used as natural-derived alternatives to silicone polymers. These polymers can be formulated for various specialized chemical applications, including personal care compositions, thereby altering and improving the functional or application performance of the products. However, the precise functionalization of these polymers depends on their size and composition per se, and thus also on their monomer distribution, polydispersity index, and any further functionalization.

[0013] Preferably, commercially available renewable terpene oxides (epoxides) can be used in the present invention, such as limonene oxide, pinene oxide, styrene oxide, caryophyllene oxide, eugenol oxide, safrole oxide, myrcene oxide, carene oxide, menthene oxide. Alternatively, epoxides such as ethylene oxide, propylene oxide, styrene oxide, and cyclohexene oxide can be used.

[0014] In a first aspect, the present application provides a compound according to Formula I:

[0015]

[0016] wherein R 1 is an optionally substituted C 1 -C 12 alkyl;

[0017] R 2 , R 3 , R 4 and R 5 are each independently hydrogen, optionally substituted C 1 -C 12 Alkyl, optionally substituted C 2 -C 12 Alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted aryl (eg phenyl), or

[0018] R 2 With R 3 Together, R 4 With R 5 Together, or R 3 With R 5 Together they form an optionally substituted C 3 -C 12 Cycloalkyl or optionally substituted C 3 -C 12 Cycloalkenyl; and

[0019] n is an integer of 0-20 (eg, 0-5).

[0020] It should be understood that represents an optional double bond (ie, it is a single bond or a double bond), so the terminal group Any one of the three optional bonds shown may be present (ie, a double bond) or all optional bonds may be absent (ie, all are single bonds).

[0021] In other aspects, the present invention further provides compositions, as well as methods of making the compounds and methods of using the compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The product of Example 2 was shown in CDCl 3 In solvent 1 H-NMR spectrum.

[0023] Details

[0024] Without wishing to be bound by theory, isobutylene groups can form ethers with alcohols via an acid catalyzed mechanism. This chemical mechanism has been used in other contexts to form ether bonds in organic synthesis.

[0025] The equilibrium nature of this reaction can potentially pose challenges for the large-scale production of these ethers. However, the inventors have discovered that by utilizing monomer recycling, appropriate catalyst selection, and highly concentrated reaction conditions, these molecules can reach a sufficient degree of polymerization for use in many different applications. Additionally, these low molecular weight polymers can be further derivatized to achieve significantly higher molecular weights and obtain new functionalities.

[0026] In a first aspect, the present application provides a compound (Compound 1) according to Formula I below:

[0027]

[0028] wherein R 1 is an optionally substituted C 1 -C 12 alkyl;

[0029] R 2 、R 3 、R 4 and R 5 are each independently hydrogen, an optionally substituted C 1 -C 12 alkyl, an optionally substituted C 2 -C 12 alkenyl, an optionally substituted C 2 -C 12 alkynyl, an optionally substituted aryl (e.g., phenyl), or

[0030] R 2 together with R 3 、R 4 together with R 5 、or R 3 together with R 5 form an optionally substituted C 3 -C 12 cycloalkyl or an optionally substituted C 3 -C 12 cycloalkenyl; and

[0031] n is an integer from 0 - 20 (e.g., 0 - 5).

[0032] In other embodiments of the first aspect, the present application provides any one of the following embodiments:

[0033] 1.1 Compound 1, wherein R 1 is an optionally substituted straight-chain C 1 -C 12 alkyl or an optionally substituted branched C 1 -C 12 alkyl.

[0034] 1.2 Compound 1, wherein R 1is an unsubstituted straight-chain C 1 -C 12 alkyl or an unsubstituted branched C 3 -C 12 alkyl.

[0035] 1.3 Compound 1, wherein R 1 is an unsubstituted straight-chain C 1 -C 12 alkyl.

[0036] 1.4 Compound 1, wherein R 1 is an unsubstituted branched C 3 -C 12 alkyl.

[0037] 1.5 Compound 1, wherein R 1 is CH 2 .

[0038] 1.6 Compound 1, wherein R 1 is an unsubstituted branched or straight-chain C 6 alkyl.

[0039] 1.7 Compound 1, wherein R 1 is CH 2 CH 2 CH(CH 3 )CH 2 CH 2 .

[0040] 1.8 Compound 1 or any one of those described in 1.1 - 1.7, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently hydrogen.

[0041] 1.9 Compound 1 or any one of those described in 1.1 - 1.7, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently an unsubstituted C 1-12 alkyl (such as lower alkyl, such as C 1-6 alkyl).

[0042] 1.10 Compound 1 or any one of those described in 1.1 - 1.7, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, or n-decyl.

[0043] 1.11 Any one of those described in Compound 1 or 1.1 - 1.7, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently substituted C 1-12 alkyl (for example, C 1-6 alkyl substituted by 1 - 9 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, halogen, and substituted or unsubstituted aryl).

[0044] 1.12 Compound 1.11, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently C 1-6 alkyl substituted by 1 - 9 groups each independently selected from the following (for example C 1-2 alkyl): C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, halogen, and substituted or unsubstituted aryl).

[0045] 1.13 Compound 1.12, wherein the aryl is optionally substituted by 1 - 4 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, and halogen.

[0046] 1.14 Compound 1.12, wherein the aryl is phenyl.

[0047] 1.15 Compound 1.12, wherein the aryl is 3,4 - methylenedioxyphenyl.

[0048] 1.16 Compound 1.12, wherein the aryl is 3 - hydroxy - 5 - methoxyphenyl.

[0049] 1.17 Any one of those described in Compound 1 or 1.1 - 1.7, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently unsubstituted C 2-12 alkenyl (for example C3-9 alkenyl).

[0050] 1.18 Any one of those described in Compound 1 or 1.1 - 1.7, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently a substituted C 2-12 alkenyl (e.g., C 3-9 alkenyl substituted by 1 - 9 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, halogen, and substituted or unsubstituted aryl).

[0051] 1.19 Compound 1.18, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently a C 3-9 alkenyl substituted by 1 - 4 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, halogen, and substituted or unsubstituted aryl.

[0052] 1.20 Compound 1.19, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently a C 1-6 alkenyl substituted by 1 - 4 groups each independently selected from C 1-6 alkyl, C 2-6 alkoxy, and C 3-9 alkenyl, e.g., C 2-3 alkenyl - substituted C 2-4 alkenyl.

[0053] 1.21 Any one of those described in Compound 1 or 1.1 - 1.7, wherein R 2 , R 3 , R 4 and R 5 one or more of which are each independently unsubstituted aryl (e.g., phenyl).

[0054] 1.22 Any one of those described in Compound 1 or 1.1 - 1.7, wherein R 2 , R 3 , R4 and R 5 one or more of each independently is a substituted aryl (e.g., phenyl substituted by 1 - 4 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxyl, carboxyl, and halogen).

[0055] Any one of those described in Compound 1 of 1.23 or 1.1 - 1.7, wherein R 2 and R 4 each independently is hydrogen, or unsubstituted C 1-6 alkyl (e.g., C 1-6 alkyl), and R 3 and R 5 together form an optionally substituted C 3 -C 12 cycloalkyl or an optionally substituted C 3 -C 12 cycloalkenyl (e.g., optionally substituted by 1 - 9 groups independently selected from the following: C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1-6 alkoxy, hydroxyl, carboxyl, or methylene (=CH 2 ))).

[0056] Compound 1.24 of 1.23, wherein R 2 and R 4 each independently is hydrogen or methyl.

[0057] Compound 1.25 of 1.23 or 1.24, wherein R 3 and R 5 together form a C 6 -C 12 cycloalkyl, which is optionally substituted by 1 - 6 groups independently selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and methylene (=CH 2 ).

[0058] Compound 1.26 of 1.25, wherein R 3 and R 5 together form a C 6 -C 12 cycloalkyl, which is optionally substituted by 1 - 6 groups independently selected from methyl, ethyl, isopropyl, vinyl, allyl, and methylene (=CH2 substituted by 1 - 3 groups of

[0059] 1.27 Any one of Compounds 1.23 - 1.26, wherein the C 3 -C 12 cycloalkyl (such as C 6 -C 10 cycloalkyl) or C 3 -C 12 cycloalkenyl is bicyclic cycloalkyl or bicyclic cycloalkenyl.

[0060] 1.28 Compound 1.27, wherein the C 3 -C 12 cycloalkyl is bicyclic C 6-9 cycloalkyl (such as bicyclic [4.1.0]heptane or [3.1.1]heptane).

[0061] 1.29 Compound 1.27, wherein the C 3 -C 12 cycloalkyl is bicyclic C 8-12 cycloalkyl (such as bicyclic [7.2.0]undecane).

[0062] 1.30 Compound 1 or 1.1 and any one of the following, wherein n is 0 - 8.

[0063] 1.31 Compound 1 or 1.1 and any one of the following, wherein n is 0 - 6.

[0064] 1.32 Compound 1 or 1.1 and any one of the following, wherein n is 0 - 4.

[0065] 1.33 Compound 1 or 1.1 and any one of the following, wherein n is 0, 1, 2, 3 or 4.

[0066] 1.34 Compound 1 or 1.1 and any one of the following, wherein n is 0, 1 or 2.

[0067] 1.35 Compound 1 or 1.1 and any one of the following, wherein R 1 is CH 2 CH 2 CH(CH 3 )CH 2 CH 2 , and n is 0 - 3 (such as 0, 1 or 2).

[0068] 1.36 Compound 1 or 1.1 and any one of the following, wherein the end group is

[0069] 1.37 Compound 1 or 1.1 and any one of the following, wherein the end group is

[0070] 1.38 Compound 1 or 1.1 and any one of the following, wherein the end group is

[0071] 1.39 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0072]

[0073] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0074] 1.40 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0075]

[0076] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0077] 1.41 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0078]

[0079] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0080] 1.42 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0081]

[0082] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0083] 1.43 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0084]

[0085] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0086] 1.44 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0087]

[0088] wherein n is 0 - 20 (for example, 0, 1 or 2).

[0089] 1.45 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0090]

[0091] where n is from 0 to 20 (such as 0, 1 or 2).

[0092] 1.46 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0093]

[0094] where n is from 0 to 20 (such as 0, 1 or 2).

[0095] 1.47 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0096]

[0097] where n is from 0 to 20 (such as 0, 1 or 2).

[0098] 1.48 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0099]

[0100] where n is from 0 to 20 (such as 0, 1 or 2).

[0101] 1.49 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0102]

[0103] where n is from 0 to 20 (such as 0, 1 or 2).

[0104] 1.50 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0105]

[0106] where n is from 0 to 20 (such as 0, 1 or 2).

[0107] 1.51 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0108]

[0109] where n is from 0 to 20 (such as 0, 1 or 2).

[0110] 1.52 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0111]

[0112] where n is from 0 to 20 (such as 0, 1 or 2).

[0113] 1.53 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0114]

[0115] where n is from 0 to 20 (such as 0, 1 or 2).

[0116] 1.54 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0117]

[0118] where n is from 0 to 20 (such as 0, 1 or 2).

[0119] 1.55 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0120]

[0121] where n is from 0 to 20 (such as 0, 1 or 2).

[0122] 1.56 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0123]

[0124] where n is from 0 to 20 (such as 0, 1 or 2).

[0125] 1.57 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0126]

[0127] where n is from 0 to 20 (such as 0, 1 or 2).

[0128] 1.58 Compound 1 or 1.1 and any one of the following, wherein the compound of formula I is:

[0129]

[0130] where n is from 0 to 20 (such as 0, 1 or 2).

[0131] 1.59 Compound 1 or 1.1 and any one of the following, wherein the compound is enantiomerically enriched, for example having a diastereomeric excess greater than 70% (such as enantiomeric excess (e.e.)).

[0132] 1.60 Compound 1.59, wherein the compound has a diastereomeric excess of greater than 80%, or greater than 85%, or greater than 90%, or greater than 95%, or greater than 97% or greater than 99% (e.g., enantiomeric excess (e.e.)).

[0133] 1.61 Compound 1.59 or 1.60, wherein each chiral carbon of group R 1 has the (R)-configuration.

[0134] 1.62 Compound 1.59 or 1.60, wherein each chiral carbon of group R 1 has the (S)-configuration.

[0135] It should be understood that the compound of formula I comprises a polymeric backbone, which can be formed via a controlled homopolymerization reaction between monomer units to obtain the compound of formula I(a):

[0136]

[0137] wherein n is 0 - 20 (e.g., 0, 1 or 2).

[0138] In some embodiments, the compound of formula I(a) is a compound of the following formula:

[0139]

[0140] wherein n is 0 - 20 (e.g., 0, 1 or 2).

[0141] In a subsequent reaction (or more than one reaction), the OH group of the compound of formula I(a) can react with the epoxide of formula A to form the compound of formula I:

[0142]

[0143] The resulting polymeric derivative of formula I will have to substantially retain the polymeric structural features from the corresponding compound of formula I(a) - e.g., the n value and nature of the various monomer units of the polymeric backbone and their structural relationship to each other.

[0144] The polymerization reaction for forming the precursor compound of formula I(a) will necessarily yield a mixture of products with different integer n values and thus also different in terms of the overall molecular weight of the polymer. This mixture of polymers may be difficult to fully purify, and in addition, it may be desirable to retain the mixture of polymers to utilize the unique physical and chemical properties of any mixture formed. Thus, partial purification, such as distillation or chromatography, may be preferably carried out so as to obtain, in aggregated form, a mixture of relevant polymers having the desired physical or chemical properties in a specific combination (e.g., boiling point, melting point, viscosity, surface tension, solubility, density, reactivity).

[0145] Thus, in a second aspect, the present application provides a composition (Composition 2) comprising one or more compounds according to Formula I. In other embodiments of the second aspect, the present application provides:

[0146] 2.1 A composition comprising one or more compounds according to any one of 1.1 - 1.62.

[0147] 2.2 A composition comprising one or more compounds according to any one of 1.1 - 1.62, wherein the compounds differ only in their n value.

[0148] 2.3 A composition consisting of one or more compounds according to any one of 1.1 - 1.62, wherein the compounds differ only in their n value.

[0149] 2.4 Composition 2 or any one of the compositions 2.1 - 2.3, wherein the composition comprises a single compound according to Compound 1 or any one of 1.1 - 1.62, and the amount of the compound present is greater than 40%, such as greater than 50%, greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, or 40 - 70%, or 40 - 60%, or 40 - 50%, and the percentages are determined as the percentage of the number of molecules in the composition or as the weight percentage of the total weight of the composition.

[0150] 2.5 Composition 2 or any one of the compositions 2.1 - 2.4, wherein the composition comprises one or more compounds (e.g., 1 - 10 specific compounds), and each compound is independently a compound according to Compound 1 or 1.1 - 1.62, and the amount of each compound present is at least 1% and at most 90%, such as 5 - 50%, or 5 - 40%, or 5 - 30%, or 5 - 25%, or 5 - 20%, or 5 - 15%, or 5 - 10%, or 40 - 50%, or 30 - 40%, or 20 - 30%, or 10 - 20%, or 1 - 10%, or 1 - 5%, or 1 - 2%, and the percentages are determined as the percentage of the number of molecules in the composition or as the weight percentage of the total weight of the composition.

[0151] 2.6 Composition 2, or any one of the compositions 2.1 - 2.5, wherein the number - average molecular weight (M n ) of the compounds in the composition, optionally excluding the group –(OCR 2 R 3 CR 4 R 5 )-OH, is 150 - 2000 daltons (e.g., 300 - 800 daltons).

[0152] 2.7 Composition 2.6, wherein the number average molecular weight (M n ) of the compounds in the composition, optionally excluding the group –(OCR 2 R 3 CR 4 R 5 )-OH, is from 300 to 1900 daltons, such as from 300 to 1600 daltons, or from 300 to 1300 daltons, or from 300 to 1100 daltons, or from 300 to 1000 daltons, or from 300 to 800 daltons, or from 300 to 700 daltons, or from 300 to 500 daltons, or from 400 to 1000 daltons, or from 400 to 700 daltons, or from 600 to 1100 daltons, or from 600 to 1000 daltons, or from 600 to 800 daltons, or about 500 daltons, or about 414 daltons.

[0153] 2.8 Composition 2, or any one of the compositions 2.1 - 2.7, wherein the weight average molecular weight (M w ) of the compounds in the composition, optionally excluding the group –(OCR 2 R 3 CR 4 R 5 )-OH, is from 150 to 2000 daltons.

[0154] 2.9 Composition 2.8, wherein the weight average molecular weight (M w ) of the compounds in the composition, optionally excluding the group –(OCR 2 R 3 CR 4 R 5 )-OH, is from 300 to 1900 daltons, such as from 300 to 1600 daltons, or from 300 to 1300 daltons, or from 300 to 1100 daltons, or from 300 to 1000 daltons, or from 300 to 800 daltons, or from 300 to 700 daltons, or from 300 to 500 daltons, or from 400 to 1000 daltons, or from 400 to 700 daltons, or from 600 to 1100 daltons, or from 600 to 1000 daltons, or from 600 to 800 daltons, or about 438 daltons.

[0155] 2.10 Composition 2, or any one of the compositions 2.1 - 2.9, wherein the polydispersity index M w / M n (optionally disregarding the group –(OCR 2 R 3 CR 4 R 5) - The mass of -OH is in the range of 1 - 5.

[0156] 2.11 Composition 2.10, wherein the polydispersity index (M w / M n ) is in the range of 1 - 4, or 1 - 3, or 1 - 2.5, or 1 - 2, or 1 - 1.5, or about 1 - 1.25, or about 1, or 1.5 - 3.5, or 1.5 - 2.5, or about 1.5, or 2 - 4, or 2 - 3, or 2 - 2.5, or about 2, or 1 - 1.25, or 1 - 1.20, or 1 - 1.15, or 1 - 1.10, or about 1.06.

[0157] 2.12 Composition 2, or any one of the compositions 2.1 - 2.11, wherein the compound in the composition has an average n value of 0 - 8, which is measured as the weight average or number average.

[0158] 2.13 Composition 2.12, wherein the compound in the composition has an average n value of 0 - 6, which is measured as the weight average or number average.

[0159] 2.14 Composition 2.12, wherein the compound in the composition has an average n value of 0 - 5, which is measured as the weight average or number average.

[0160] 2.15 Composition 2.12, wherein the compound in the composition has an average n value of about 0, about 1, about 2, about 3, or about 4, which is measured as the weight average or number average.

[0161] 2.16 Composition 2.12, wherein the compound in the composition has an average n value of about 0, about 1, or about 2, which is measured as the weight average or number average.

[0162] 2.17 Composition 1.62, wherein the compound in the composition has an average n value of about 0.5, such as about 0.52, which is measured as the weight average.

[0163] 2.18 Composition 1 or 1.1 and any one below, wherein the compounds in the composition are all:

[0164]

[0165] wherein R 2 and n is 0 - 8 (for example 0 - 4).

[0166] 2.19 Composition 2.18, wherein at least 95% by weight of the compounds have an n value of 0, 1, 2, 3, or 4, such as at least 97% or at least 98% or at least 99% of the compounds.

[0167] 2.20 Composition 2.19 wherein at least 90% by weight of the compounds have a value of n of 0, 1 or 2, such as 90-98% or 95-98% of the compounds.

[0168] 2.21 Composition 2.20 wherein at least 70% by weight of the compounds have a value of n of 0 or 1, such as at least 80% or 80-90% or 80-85% of the compounds.

[0169] 2.22 Composition 2.21 wherein at least 30% by weight of the compounds have a value of n of 0, such as at least 40% or 40-60% or 45-55% of the compounds.

[0170] It will be understood that the compositions described above starting with composition 2 comprise a mixture of different polymers according to formula I having different integer n values ​​(and optionally any other ingredients). Therefore, the compositions described above starting with composition 2 can be understood as a mixture of multiple compounds of formula I having different integer n values, for example at least two different compounds of formula I having different integer n values ​​(for example a mixture comprising a compound of formula I wherein n is 0 and a compound of formula I wherein n is 1). Typically, in such a composition, substantially all of the polymers according to formula I in the composition will have the same group R 1 , R 2 , R 3 , R 4 and R 5 That is, the various polymers according to formula I in the composition differ only in the value of the integer n. The term "substantially all polymers according to formula I" as used in the previous sentence (and similarly elsewhere in this document) is understood to mean that small amounts of synthetic impurities may be present, wherein R 1 , R 2 , R 3 , R 4 and / or R 5 Unlike the bulk of the composition (e.g. due to small amounts of impurities in the starting materials, small amounts of by-products in the synthesis, or small amounts of unreacted intermediates, which may be present even in the case of purification). In a specific embodiment, the composition described above starting with composition 2 may comprise a mixture of compounds of formula I having one or more values ​​of n selected from 0, 1, 2, 3, 4, 5, 6 and 7.

[0171] It should be understood that the numbers mentioned regarding the average molecular weight and polydispersity index of the compounds of formula (I) can be described based on the polymer backbone of the molecule, i.e., the part corresponding to formula I(a), minus one hydroxyl hydrogen. For example, the detection and calculation of the molecular weight and polydispersity index can be carried out for the alcohol polymer (formula I(a)) before its reaction with the epoxide compound, and the obtained values can be extrapolated to the subsequently derived derivatives of formula I.

[0172] In a third aspect, the present application provides a method for preparing the compounds of formula I (Method 3), which method comprises the steps of: reacting a compound of formula I(a) with a compound of formula A in the presence of an acid or base catalyst, and then separating and completely or partially purifying the compound of formula I (for example, by distillation or chromatography).

[0173] In a further embodiment of the third aspect, the present invention provides any one of the following embodiments:

[0174] 3.1 Method 3, wherein the product of this method is a compound of formula I, or any one of those described in 1.1 - 1.62.

[0175] 3.2 Method 3, wherein the product of this method is Composition 2, or any one of those described in 2.1 - 2.22.

[0176] 3.3 Method 3, 3.1 or 3.2, wherein the catalyst is an acid catalyst (such as an acidic ion exchange resin).

[0177] 3.4 Method 3.3, wherein the acid catalyst is a resin functionalized with a carboxylic acid or sulfonic acid moiety, such as an Amberlyst type resin (a macroporous or porous resin or silica covalently linked to a sulfonic acid or carboxylic acid group).

[0178] 3.5 Method 3.3, wherein the acid catalyst is a pure acid or a soluble acid.

[0179] 3.6 Method 3.5, wherein the acid is a Lewis acid, such as selected from iron(III) chloride, calcium chloride, titanium(III) chloride, boron trifluoride, zinc trifluoromethanesulfonate, magnesium perchlorate, sodium perchlorate, and lithium perchlorate.

[0180] 3.7 Method 3.5, wherein the acid is a Brønsted acid, such as selected from sulfuric acid, hydrochloric acid, hydrobromic acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, toluenesulfonic acid, phosphoric acid, trifluoroacetic acid, trichloroacetic acid, perchloric acid, and formic acid.

[0181] 3.8 Method 3.3, wherein the catalyst is a base catalyst (such as a hydroxide, carbonate, bicarbonate, alkoxide, or hydride).

[0182] 3.9 Method 3.8, wherein the base is a lithium, sodium, potassium, calcium or magnesium salt selected from hydroxides, carbonates, bicarbonates, methoxides, ethoxides, propoxides or hydrides.

[0183] 3.10 According to any one of Methods 3.3 - 3.9, wherein the catalyst is dissolved or suspended in a solvent, such as an organic solvent, an aqueous solvent or a miscible mixture thereof, optionally mixed with a phase transfer agent.

[0184] 3.11 Method 3.10, wherein the method comprises the steps of combining a compound of formula I(a) and a compound of formula A in a solvent or solvent mixture, and then adding a catalyst to the resulting solution or suspension.

[0185] 3.12 Method 3.10, wherein the method comprises the steps of combining a compound of formula I(a) and a compound of formula A in a solvent or solvent mixture, and then passing the mixture through a fixed bed containing the catalyst (such as a catalyst bound to a resin).

[0186] 3.13 According to any one of Methods 3.3 - 3.9, wherein the catalyst is dissolved or suspended in a pure mixture of a compound of formula I(a) and a compound of formula A.

[0187] 3.14 Any one of Method 3 or Methods 3.1 - 3.13, wherein the temperature of the reaction is 30 - 120 °C, such as 40 - 60 °C.

[0188] 3.15 Any one of Method 3 or Methods 3.1 - 3.14, wherein the reaction is carried out in a batch reactor.

[0189] 3.16 Any one of Method 3 or Methods 3.1 - 3.14, wherein the reaction is carried out in a continuous packed bed reactor.

[0190] 3.17 Any one of Method 3 or Methods 3.1 - 3.16, wherein the product is separated by distillation, such as vacuum distillation.

[0191] The terms "compounds of the present application" and "compositions of the present application" include compounds of formula I and compounds 1 and 1.1 - 1.62, and compositions 2 and 2.1 - 2.22, respectively, and any one and all other embodiments thereof.

[0192] In some embodiments of the present application, the compounds and compositions of the present application have a number average molar weight (M w ) of the polyether backbone of 150 - 3000 g / mol, preferably 200 - 500 g / mol, which is detected, for example, by constant solvent chromatography, wherein THF is used as the mobile phase in HPLC.

[0193] In some embodiments, the compositions of the present application have a polydispersity index (M w / M n ) in the range of 1-5, preferably in the range of 1-2. In some embodiments, the compounds of the present application are polyether alcohols derived from homopolymerization products of the following substances: citronellol, geraniol, linalool, citronellic acid, limonene, dihydro myrcene, myrcenol, adipic acid, propylene glycol, ethylene glycol, glycerol, 1,9-nonanediol or 1,6-hexanediol. Preferably, the compounds are based on the polymerization of citronellol and its derivatization reaction.

[0194] In some embodiments, the compositions of the present application contain compounds having a number average molecular weight of 100-1000 g / mol, preferably 100-500 g / mol, for the polyether alcohol and its derivatives. The number average molecular weight can be detected by constant solvent chromatography, for example, using an Agilent Oligopore GPC column and THF as the mobile phase in HPLC.

[0195] The compounds and compositions of the present application, particularly those having a polydispersity index of 1-2, have one or more of the following advantageous features: the compounds are short-chain polymers; the compounds are prepared by reversible polymerization reactions; the polymers are biodegradable and biocompatible; and the polymers can be prepared using all-natural ingredients. These features bring important benefits in many commercial applications where these compounds can be used. The compositions disclosed herein having a polydispersity index of 1-5, preferably 1-2, are suitable as substitutes or replacements for surfactants, polymers, and silicones in various commercial products, such as in cosmetic and pharmaceutical compositions, and are suitable as adjuvants in crop protection formulations, as well as lubricants or solvents in enhanced oil recovery, fracturing, and oilfield applications. The compounds and compositions disclosed herein provide improved physical properties, such as appearance, odor, viscosity, refractive index, and / or surface tension.

[0196] In some embodiments, the compositions of the present application contain compounds having a weight average molecular weight (M w ) equal to or greater than 100, 200, 300, 400, 500, 600, 700, 800, 900, and 1000 daltons. In another embodiment, the weight average molecular weight can be selected from the group consisting of: 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346, 347, 348, 349, 350, 351, 352, 353, 354, 355, 356, 357, 358, 359, and 360 daltons.

[0197] In some embodiments of the present invention, the polydispersity index (PDI) of the compounds and compositions is less than or equal to about 1.25, 1.24, 1.23, 1.22, 1.21, 1.20, 1.19, 1.18, 1.17, 1.16, 1.15, 1.14, 1.13, 1.12, 1.11, or 1.10. In some embodiments, the PDI can be equal to or greater than 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, or 1.09.

[0198] In some embodiments of the present application, the compounds and compositions disclosed herein can be used for the following purposes: for retaining fragrance, fixing fragrance, or serving as a fragrance carrier; as a malodor counteractant; in paints and coatings; as an adjuvant for crop control; as a cosmetic ingredient (e.g., as a substitute for silicone or white oil); in nail polishes; in writing or printing inks; as a resin or resin substitute; as an insect repellent (e.g., a mosquito repellent); and in sunscreen formulations. The polymeric compounds having the above properties can have an average molecular weight (M w ) of one of: 390, 391, 392, 393, 394, 395, 396, 397, 398, 399, 400, 401, 402, 403, 404, 405, 406, 407, 408, 409, 410, 411, 412, 413, 414, 415, 416, 417, 418, 419, and 420 daltons. In other embodiments, the polymeric compounds having the above properties can have the following polydispersity index (PDI): equal to or greater than 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, and 1.09.

[0199] The method for preparing the polyether of formula I(a) can be found in US2017 / 0283553 and WO2019 / 028053, the contents of which are incorporated herein by reference in their entirety. These polymers can generally be prepared in a short time with a high degree of polymerization under pure solvent-free conditions using an acid catalyst bound to a resin, such as Amberlyst-type resins are well-known in the art and are understood to be macroporous or porous resins covalently bonded to sulfonic or carboxylic acid groups, preferably bonded to sulfonic acid groups. Such polymerization reactions can be carried out at room temperature or lower temperatures, preferably at a slightly elevated temperature of 30-110 °C, or even more preferably 40-90 °C (e.g., about 50 °C). Such polymerization reactions can be carried out in batch reactors, semi-batch reactors, or even more preferably in continuous packed-bed type reactors, see U.S. Provisional Application No. 62 / 384,939 and PCT / US2017 / 50808 and US 2019-0210948, the contents of which are incorporated herein by reference.

[0200] The reversibility of the polymerization reaction of the claimed compounds stems from the nature of these polymers, which have adjacent oxygen atoms and tertiary carbon atoms. Thus, under conditions that promote the cleavage of the O-C bond, the resulting tertiary carbocation is unusually stable. This results in an easy uptake of adjacent hydrogen atoms, thereby regenerating the starting alcohol and olefin functional groups. The depolymerization reaction can be promoted by weak acidic conditions (e.g., with Lewis acids or Bronsted acids) or by thermal conditions or by enzymatic conditions (e.g., enzymes found in naturally occurring bacteria).

[0201] This depolymerization property leads to biodegradation. This property also allows the formation of compositions containing the compounds, where the depolymerization of the polymer can be controlled, thereby allowing for the slow release of the monomeric components of the polymer (e.g., citronellol) or shorter polymer components (e.g., citronellol dimer released by greater polymer depolymerization). The disclosure of the present application encompasses solid and / or liquid formulations (e.g., products) containing any of the aforementioned compounds or compositions, where the formulations provide slow, controlled depolymerization of the polymer and diffusion of the resulting monomers and / or shorter oligomers such that they can be released from the composition (e.g., by evaporation at the surface of the composition). The formulations can consist of components that promote such depolymerization (e.g., Lewis acids or Bronsted acids or enzymes), or the formulations can be combined with a device containing an electric heating element to promote thermal depolymerization. For various reasons, the monomers and / or shorter oligomers obtained in this way (e.g., citronellol, or the dimer or trimer of citronellol) are beneficial in themselves, for example as fragrances, insect repellents, antioxidants, antimicrobials, or as active pharmaceutical ingredients (e.g., where the composition is a pharmaceutical composition).

[0202] The compounds and compositions disclosed herein are particularly suitable for replacing silicones, mineral oils, and / or paraffins in cosmetic compositions such as concealers, primers, and / or moisturizers.

[0203] In a fourth aspect, the present application provides a product composition (Product 1), wherein the product composition comprises Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, and comprises at least one suitable solvent, carrier or other excipient. In other embodiments of the fourth aspect, the present application provides the following product compositions:

[0204] 1.1 Product 1, wherein the product composition is a fragrance product composition.

[0205] 1.2 Product 1, wherein the product composition is a perfume product composition.

[0206] 1.3 Product 1, wherein the product composition is a soap product composition.

[0207] 1.4 Product 1, wherein the product composition is a repellent product composition, such as a mosquito repellent product composition.

[0208] 1.5 Product 1, wherein the product composition is an insecticide product composition.

[0209] 1.6 Product 1, wherein the product composition is a detergent product composition.

[0210] 1.7 Product 1, wherein the product composition is a household cleaner product composition.

[0211] 1.8 Product 1, wherein the product composition is an air freshener product composition.

[0212] 1.9 Product 1, wherein the product composition is an indoor spray product composition.

[0213] 1.10 Product 1, wherein the product composition is an incense pill product composition.

[0214] 1.11 Product 1, wherein the product composition is a candle product composition.

[0215] 1.12 Product composition 1.11, wherein the product composition further comprises a paraffin and / or beeswax matrix.

[0216] 1.13 Product composition 1.12, wherein the product composition consists of Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22 dispersed in a paraffin and / or beeswax matrix, and a suitable candle wick is embedded therein.

[0217] 1.14 Product 1, wherein the product composition is a cosmetic product composition.

[0218] 1.15 Product 1, wherein the product composition is a floral water product composition.

[0219] 1.16 Product 1, wherein the product composition is a pre-shave lotion and after-shave lotion product composition.

[0220] 1.17 Product 1, wherein the product composition is a talcum powder product composition.

[0221] 1.18 Product 1, wherein the product composition is a hair care product composition.

[0222] 1.19 Product 1, wherein the product composition is a body deodorant product composition.

[0223] 1.20 Product 1, wherein the product composition is an antiperspirant product composition.

[0224] 1.21 Product 1, wherein the product composition is a shampoo product composition.

[0225] 1.22 Product 1, wherein the product composition is a pet litter product composition.

[0226] 1.23 Product 1, wherein the product composition is a topically applied skin care product composition, optionally wherein the skin care product is selected from: skin conditioners; skin penetration enhancers; skin protectants; skin emollients; shaving creams and gels; skin creams and lotions (such as moisturizing creams and lotions); skin healing agents; ultraviolet light absorbers or scatterers; chelating agents; anti-acne agents; anti-androgens; depilatory agents; stratum corneum separating / peeling / exfoliating agents, such as salicylic acid; panthenol moisturizers, such as D-panthenol; soluble or colloidally soluble moisturizers, such as hyaluronic acid and starch-grafted sodium polyacrylate; and sunscreens.

[0227] 1.24 Product composition 1.23, wherein the skin care product is a skin protectant.

[0228] 1.25 Product composition 1.23, wherein the skin care product is a skin emollient.

[0229] 1.26 Product composition 1.23, wherein the skin care product is a sunscreen.

[0230] 1.27 Product 1, wherein the product composition is a paint or coating product composition.

[0231] 1.28 Product 1, wherein the product composition is a lubricant product composition.

[0232] 1.29 Product 1, wherein the product composition is a plastic product composition.

[0233] 1.30 Product 1, wherein the product composition is an antifoaming agent product composition.

[0234] 1.31 Product 1, wherein the product composition is a hydraulic fluid product composition.

[0235] 1.32 Product 1, wherein the product composition is an antimicrobial product composition.

[0236] 1.33 Product 1, wherein the product composition is a crop protection product composition, for example, wherein the compound is an adjuvant in a crop protection formulation.

[0237] 1.34 Product 1, wherein the product composition is a product composition for enhanced oil recovery, fracturing, and / or other oilfield applications, for example, wherein the compound is a lubricant or a solvent in the formulation.

[0238] 1.35 A product comprising any of the above compositions, wherein the composition is stored or contained in a container comprising an electric heating element, and actuation of the heating element causes heating of the composition, thermal decomposition of the compound, and release of volatile substances.

[0239] 1.36 A fragrance or perfume product comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, wherein the compound is used as a fragrance retention agent, a fragrance fixative, or a fragrance carrier.

[0240] 1.37 A cosmetic product comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, wherein the compound is used as a substitute for silicone and / or as a substitute for white oil.

[0241] 1.38 A nail polish product comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof.

[0242] 1.39 A writing ink or printing ink product comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof.

[0243] 1.40 An adhesive product composition comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof.

[0244] 1.41 An oral care product composition comprising compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof; optionally, wherein the oral care product composition is selected from toothpaste, dental gel, or mouthwash.

[0245] 1.42 A food product composition comprising compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof; optionally, wherein the food product composition is selected from chewing gum or carbonated beverages.

[0246] 1.43 A pharmaceutical product comprising compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof; optionally, wherein the pharmaceutical product composition is selected from capsules, tablets (e.g., chewable tablets), syrups (e.g., cough syrups), lozenges (e.g., cough tablets), and liquids (e.g., solutions or suspensions for oral administration).

[0247] 1.44 Any of the above product compositions, wherein the product composition is an aerosol product.

[0248] 1.45 The product composition 1.44, wherein the product is an aerosol deodorant, aerosol antiperspirant, aerosol body spray, aerosol air freshener, aerosol fragrance or perfume product, aerosol insecticide, aerosol lubricant, aerosol hair care product (e.g., hairspray), aerosol sunscreen, aerosol throat analgesic, or aerosol insect repellent.

[0249] 1.46 The product 1.44 or 1.45, wherein the product composition further comprises an aerosol propellant, such as propane, n - butane, isobutane, dimethyl ether, diethyl ether, methyl ethyl ether, chlorofluorocarbons, fluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons (e.g., 1,1 - difluoroethane, or 1,1,1 - trifluoroethane, or 1,1,1,2 - tetrafluoroethane, or 1,1,1,3,3 - pentafluoropropane, or 1,1,1,3,3 - pentafluorobutane, or 1,1,1,2,3,3,3 - heptafluoropropane, or 1,3,3,3 - tetrafluoropropene, or 2,3,3,3 - tetrafluoropropene), nitrous oxide, carbon dioxide, nitrogen, air, or any combination thereof.

[0250] 1.47 Any one of the product compositions 1.44 - 1.46, wherein the product is an aerosol body spray, which optionally contains a propellant selected from the following: propane, n-butane, isobutane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,3,3-heptafluoropropane, and combinations thereof, such as in particular a combination of propane, n-butane, isobutane, and 1,1-difluoroethane.

[0251] In another embodiment, the present application provides compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, which is used in product composition 1 or a product according to any one of 1.1 - 1.47.

[0252] In other embodiments of the above aspects, the present application provides a composition, which contains compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, or product 1 or a product according to any one of 1.1 - 1.47, wherein the composition or product further contains one or more additives selected from the following: cooling sensate, warming sensate, and / or stinging sensate; flavoring agent or fragrance; vitamin, mineral, health food, stimulant, emollient, coloring agent, amino acid antioxidant, preservative, pH improver, viscosity regulator, and any combination thereof.

[0253] In a specific embodiment, these compositions contain cooling, warming, and / or stinging sensates. The composition can improve or reduce the effect of the sensate, for example by dilution, or can weaken or change the performance or perception of the sensate, due to the antagonistic or synergistic effect between the components of the composition. The sensate is used to impart a cooling, warming, and / or stinging sensation to the skin or the mucous membranes of the oral cavity or pharynx. Thus, the sensate can be used as a flavoring agent or fragrance in a wide range of compositions and products. For example, these compositions can give an immediate warming, cooling, and / or stinging sensation when applied to the body. In some embodiments, it helps to provide a softening effect. In some embodiments, the compound of the present application (such as compound 1 or any one of 1.1 - 1.62) or the composition of the present application (such as composition 2 or any one of 2.1 - 2.22) can also be used in the composition as one or more viscosity regulators, carriers, dispensers, diluents, or retainers for the sensate. This can help obtain a sensate composition that can impart a controlled, long-lasting, and / or delayed cooling, warming, or stinging sensation.

[0254] In some embodiments of the above aspects, the sensory agent interacts with the TRPV protein, thereby causing or reducing the desired cooling or warming effect. In some embodiments of the above aspects, the sensory agent is a natural compound; in other embodiments, the sensory agent is a synthetic compound.

[0255] Suitable cooling sensory agents include: menthol, levomenthol, peppermint oil, n-N-substituted-p-menthane-3-carboxamide, acyclic tertiary and secondary amides, 3-1-menthoxypropane-1,2-diol, and mixtures thereof.

[0256] Suitable warming sensory agents include: vanillyl butyl ether, vanillyl propyl ether, vanillyl isopropyl ether, vanillyl isobutyl ether, vanillyl n-amino ether, vanillyl isopentyl ether, vanillyl n-hexyl ether, vanillyl methyl ether, vanillyl ethyl ether, gingerol, shogaol, acetaminophen, zingerone, capsaicin, dihydrocapsaicin, nordihydrocapsaicin, homocapsaicin, homodihydrocapsaicin, ethanol, isopropanol, isoamyl alcohol, benzyl alcohol, eugenol, cinnamon oil, cinnamaldehyde and its phosphate derivatives, pine needle oil, wintergreen oil, rosemary oil, eucalyptus oil, incense oil, and mixtures thereof. In some embodiments, the cooling sensory agent is combined with metal ions (such as tin, calcium, zinc, copper, etc.) or non-metal counterions (such as fluoride ions, etc.), thereby improving the initial activity, strength, or impact and persistence of the coolant.

[0257] Suitable stinging sensory agents include Jambu oleoresin extract, which is particularly used in food products.

[0258] In some embodiments, the sensory agent is used to cause a mutagenic effect, particularly in topical compositions. Sensory agents suitable for this purpose include menthol, pine needle oil, orange oil, lemon oil, wintergreen oil, bergamot oil, rosemary oil, lavender oil, glycosaminoglycan, and mixtures thereof.

[0259] In some embodiments, the sensory agent is a chemosensory compound, which is a compound that elicits trigeminal sensation.

[0260] The product compositions of the present application containing the sensory agent include: cosmetics (such as lipsticks, aftershaves, foundations, etc.), personal care products (such as skin creams, astringents, cleansing lotions, deodorants, shampoos, conditioners, soaps, hairsprays, hair conditioners, hair growth stimulants, shaving foams, shaving creams, bath bombs, insect repellent sprays, etc.) and pharmaceutical products (such as analgesic preparations, lozenges, etc.).

[0261] Other suitable additives include: edible flavors (such as berry flavorings, such as pomegranate, acai, raspberry, blueberry, strawberry, boysenberry, and / or cranberry; natural or synthetic flavorings or spices, such as peppermint, spearmint, wintergreen, chocolate, licorice, citrus; fruit flavorings, such as apple, peach, pear, cherry, plum, orange, lime, grape, mango, passion fruit, pineapple, and grapefruit, γ-octalactone, vanillin, ethyl vanillin, butter, rum, coconut, almond, pecan, walnut, hazelnut, French vanilla, cane sugar, maple syrup, blackcurrant, caramel, banana, malt, espresso, white chocolate; spicy flavorings, such as cinnamon, clove, coriander, basil, oregano powder, garlic, mustard, nutmeg, rosemary, thyme, tarragon, dill, sage leaf, anise, fennel, methyl salicylate, linalool, jasmine, coffee, olive oil, sesame oil, sunflower oil, bergamot oil, geranium oil, peanut oil, lemon oil, ginger oil, balsamic vinegar, rice wine vinegar, red wine vinegar; plant flavorings, such as tomato, carrot, spinach, broccoli, pumpkin, onion, beet, turnip, parsnip, asparagus, pepper, fennel, zucchini, potato; and any combination thereof); supplementary vitamins (such as vitamin A, vitamin D, vitamin E, vitamin K, thiamine, riboflavin, niacin, folic acid, pyridoxine, choline, inositol, vitamin B12, PABA, vitamin C, and mixtures thereof); preservatives (such as methyl paraben, propyl paraben, sodium propionate, citric acid, ascorbic acid, alkali metal salts of sorbic acid, such as potassium sorbate, alkali metal salts of benzoic acid, such as sodium benzoate, etc.); health foods (such as compounds derived from natural food sources and / or genetically modified food sources); and amino acids (such as valine, leucine, isoleucine, lysine, threonine, tryptophan, methionine, phenylalanine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, histidine, proline, serine, tyrosine, and mixtures thereof). Another particularly useful additive is arrowroot powder, which can be used as a substitute for talc, for example, in cosmetic compositions.

[0262] In other embodiments of the above aspects, especially the fourth aspect, the present application provides a composition comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, or Product 1 or a product according to any one of 1.1 - 1.47; optionally, wherein the composition or product further comprises one or more of the additives as described above, and wherein the composition or product is packaged in a container or device comprising a packaging material made of high - density polyethylene (HDPE), low - density polyethylene (LDPE), polypropylene (PP), polyethylene terephthalate (PET), or a combination thereof. Preferably, the composition or product is packaged in a container or device comprising a packaging material made of high - density polyethylene (HDPE). In other embodiments, the present application provides:

[0263] 4.1 A composition comprising Compound 1 or a compound according to any one of 1.1 - 1.62, or Composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, or Product 1 or a product according to any one of 1.1 - 1.47, optionally wherein the composition or product further comprises one or more of the additives as described above, and wherein the composition or product is packaged in a container or device comprising a packaging material made of high - density polyethylene (HDPE), low - density polyethylene (LDPE), polypropylene (PP), polyethylene terephthalate (PET), or a combination thereof.

[0264] 4.2 The composition or product of 4.1, wherein the packaging material comprises or consists of HDPE.

[0265] 4.3 The composition or product of 4.1 or 4.2, wherein the composition or product is a fragrance composition, perfume, soap, insect repellent and pesticide, detergent, household cleaner, air freshener, indoor spray, incense pill, candle, cosmetic, floral water, pre - shave and after - shave lotion, talcum powder, hair care product, body deodorant, antiperspirant, shampoo, skin care application, drug, antimicrobial agent, pet litter, crop protection formulation, or a formulation for oil fields, fracturing, or enhanced oil recovery.

[0266] 4.4 The composition or product of 4.3, wherein the composition or product is a cosmetic composition or cosmetic product.

[0267] 4.5 The composition or product according to 4.4, wherein the composition or product comprises a cosmetic formulation in the form of an emulsion.

[0268] 4.6 The composition or product according to 4.5, wherein the emulsion is an oil - in - water emulsion (o / w emulsion).

[0269] 4.7 The composition or product according to 4.5, wherein the emulsion is a water-in-oil emulsion (w / o emulsion).

[0270] 4.8 The composition or product according to 4.7, 4.8 or 4.9, wherein the cosmetic preparation comprises 0.1 - 10% by weight of compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, based on the weight of the cosmetic preparation.

[0271] 4.9 The composition or product according to any one of 4.4 - 4.10, wherein the composition or product comprises 0.1 - 10% by weight of compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, based on the weight of the cosmetic composition or product.

[0272] In a fifth aspect, the present application provides a method of using compound 1 or a compound according to any one of 1.1 - 1.62, or composition 2 or a composition according to any one of 2.1 - 2.22, or any mixture thereof, for example a fragrance composition, perfume, soap, insect repellent and pesticide, detergent, household cleaner, air freshener, indoor spray, incense pellet, candle, cosmetic, toilet water, aftershave and aftershave lotion, talcum powder, hair care product, body deodorant, antiperspirant, shampoo, skin care application, drug, antimicrobial agent, pet litter, crop protection formulation, or a formulation for oil fields, fracturing or enhanced oil recovery, in the preparation of a product composition (such as product composition 1 and those following it) or composition or product 4.1 - 4.9.

[0273] An additional benefit of these materials described herein is that they are expected to be fully biodegradable and biocompatible.

[0274] During the evaluation of these polyethers, it was surprisingly observed that for polymers of the citronellol type, the reaction of depolymerization back to monomers will occur spontaneously at about 180 °C. This thermal depolymerization property or similar enzymatic and / or acid-catalyzed depolymerization properties can be advantageously used to deliver citronellol monomers in a controlled manner over time.

[0275] On the one hand, pyrolytic depolymerization can be used to deliver monomers into the air in a controlled release manner. On the one hand, the present invention contemplates the use of Compound 1 and its specific embodiments and / or Composition 2 and its specific embodiments, such as those prepared by Method 3 and its specific embodiments, for example, in candles or in heat distributors for odor control and / or mosquito control; in low pH industrial cleaners, which may have a depolymerized monomer component that is released over time, thereby promoting a favorable odor; and in laundry detergents, which may use enzymes to absorb the polymer over time, thereby having a fresh odor for a longer period of time.

[0276] For other aspects regarding the use of the compounds and compositions of the present application, reference can be made to US2017 / 0283553 and WO2019 / 028053, the contents of which are hereby incorporated by reference in their entirety.

[0277] Details of one or more embodiments of the invention are given in the description below. Unless otherwise defined, 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 shall prevail.

[0278] Unless otherwise stated, it should be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to be limiting. Many terms will be mentioned in this specification and the following claims, and the said terms shall be defined as having the meanings set forth below.

[0279] As used herein, the singular forms "a / an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a reactant" includes not only a single reactant but also a composition or mixture of two or more different reactants; reference to "a substituent" includes a single substituent as well as two or more substituents, and the like.

[0280] The phrases "for example", "such as" or "including" as used herein are intended to introduce examples that further clarify a more general subject. These examples are provided only to assist in understanding the present disclosure and are not meant to be limiting in any way. In addition, the terms "may", "optional", "optionally" or "may optionally" as used herein mean that the subsequently described situation may or may not occur, such that the description includes both the situation where the event occurs and the situation where the event does not occur. For example, the phrase "optionally present" means that an object may or may not be present, and thus the description includes both the situation where the object is present and the situation where the object is not present.

[0281] The phrase "having the formula" or "having the structure" as used herein is not intended to be limiting and is used in the same manner as the commonly used term "comprising".

[0282] In some of the formulas of the present application, one or more chiral centers are identified by an asterisk placed next to the chiral carbon. In other formulas, the chiral centers are not determined, but these formulas still include chiral isomers.

[0283] Some compounds of the present invention may exist in tautomeric forms, which are also expected to be included within the scope of the present invention.

[0284] "Tautomers" means that the structures of the compounds are significantly different in the arrangement of atoms, but exist in an easy and rapid equilibrium. It should be understood that the compounds of the present invention can be described as different tautomers. It should also be understood that when a compound has a tautomeric form, all tautomeric forms are expected to be within the scope of the present invention, and the naming of the compound does not exclude any tautomeric form. In addition, even if one tautomer may be described, the present invention includes all tautomers of the compound.

[0285] The term "salt" as used herein may include acid addition salts, which include hydrochloride, hydrobromide, phosphate, sulfate, bisulfate, alkyl sulfonate, aryl sulfonate, acetate, benzoate, citrate, maleate, fumarate, succinate, lactate, and tartrate; alkali metal cations such as Na + 、K + 、Li + , alkaline earth metal salts such as Mg 2+ or Ca 2 + , or organic amine salts, or organic phosphonium salts.

[0286] The term "alkyl" as used herein refers to a monovalent or divalent, branched or straight-chain saturated hydrocarbon group having 1-22 carbon atoms, usually (but not necessarily) containing 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, octyl, etc. It should be understood that in some cases, "alkyl" represents a divalent group rather than a monovalent group. In the case where the group is a divalent group, although the term "alkyl" may also be exemplified as "methyl", "ethyl", "propyl", etc., when used as a divalent group, these terms should be understood to represent "-CH 2 -", "-CH 2 CH 2 -", and "-CH 2 CH 2 CH 2 -", respectively.

[0287] As used herein, the term "alkenyl" refers to a monovalent or divalent, branched or straight-chain unsaturated hydrocarbon group, typically (but not necessarily) containing from 2 to about 12 carbon atoms and from 1 to 10 carbon-carbon double bonds, such as ethene, n-propene, isopropene, n-butene, isobutene, tert-butene, octene, and the like.

[0288] As used herein, the term "alkynyl" refers to a monovalent or divalent, branched or straight-chain unsaturated hydrocarbon group, typically (but not necessarily) containing from 2 to about 12 carbon atoms and from 1 to 8 carbon-carbon triple bonds, such as ethyne, propyne, butyne, pentyne, hexyne, heptyne, octyne, and the like.

[0289] As used herein, the term "aryl" refers to an aromatic hydrocarbon group containing at least one aromatic ring of 5 to 6 carbon atoms, which includes, for example, an aromatic hydrocarbon having two fused rings and 10 carbon atoms (i.e., naphthalene).

[0290] With respect to "substituted" in "substituted alkyl", "substituted alkenyl", "substituted alkynyl", etc., it means that in an alkyl, alkenyl, alkynyl, or other group, at least one hydrogen atom bonded to a carbon atom is replaced by one or more non-hydrogen substituents, such as being replaced by a functional group.

[0291] When used to describe, for example, an alkyl structural moiety of C a -C b carbon atoms, the terms "branched" and "straight-chain" (or "unbranched") apply to those carbon atoms that define the alkyl structural moiety. For example, for a C 4 alkyl structural moiety, its branched embodiments should include isobutyl, while its unbranched embodiment should be n-butyl. However, isobutyl can also be regarded as a straight-chain C 1 alkyl (methyl)-substituted C 3 alkyl structural moiety (propyl).

[0292] Examples of functional groups include, but are not limited to: halogen, hydroxy, mercapto, C 1 -C 24 alkoxy, C 2 -C 24 alkenyloxy, C 2 -C 24 alkynyloxy, C 5 -C 20 aryloxy, acyl (including C 2 -C 24 alkylcarbonyl (-CO-alkyl) and C 6 -C 20 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl), C 2 -C 24 alkoxycarbonyl (-(CO)-O-alkyl), C 6 -C 20Aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-(CO)-X where X is a halogen), C 2 -C 24 Alkyl carbonate (-O-(CO)-O-alkyl), C 6 -C 20 Aryl carbonate (-O-(CO)-O-aryl), carboxyl (-COOH), carboxylate (-COO - ), carbamoyl (-(CO)-NH 2 ), monosubstituted C 1 -C 24 Alkylcarbamoyl (-(CO)-NH(C 1 -C 24 alkyl)), disubstituted alkylcarbamoyl (-(CO)-N(C 1 -C 24 alkyl) 2 ), monosubstituted arylcarbamoyl (-(CO)-NH-aryl), thiocarbamoyl (-(CS)-NH 2 ), carbamoylamino (-NH-(CO)-NH 2 ), cyano (-C≡N), isocyano (-N + ≡C - ), cyanato (-OC≡N), isocyanato (-O-N + ≡C - ), isothiocyanato (-SC≡N), azido (-N=N + =N - ), formyl (-(CO)-H), thiocarbonyl (-(CS)-H), amino (-NH 2 ), mono- and di-(C 1 -C 24 alkyl) substituted amino, mono- and di-(C 5 -C 20 aryl) substituted amino, C 2 -C 24 Alkylacylamino (-NH-(CO)-alkyl), C 5 -C 20 Arylacylamino (-NH-(CO)-aryl), imino (-CR=NH where R = hydrogen, C 1 -C 24 alkyl, C 5 -C 20 aryl, C 6 -C 20 alkaryl, C 6 -C 20Arylalkyl, etc.), alkylimino (-CR=N(alkyl), where R = hydrogen, alkyl, aryl, alkaryl, etc.), arylimino (-CR=N(aryl), where R = hydrogen, alkyl, aryl, alkaryl, etc.), nitro (-NO 2 ), nitrosyl (-NO), sulfo (-SO 2 -OH), sulfonate (-SO 2 -O - ), C 1 -C 24 Alkylthio (-S-alkyl; also known as "alkylthio"), arylthio (-S-aryl; also known as "arylthio"), C 1 -C 24 Alkylsulfinyl (-(SO)-alkyl), C 5 -C 20 Arylsulfinyl (-(SO)-aryl), C 1 -C 24 Alkylsulfonyl (-SO 2 -alkyl), C 5 -C 20 Arylsulfonyl (-SO 2 -aryl), phosphonyl (-P(O)(OH) 2 ), phosphonate (-P(O)(O - )) 2 ), phosphonite (-P(O)(O - ))), dioxophosphino (-PO 2 ), phosphino (-PH 2 ), mono- and di-(C 1 -C 24 alkyl) substituted phosphino, mono- and di-(C 5 -C 20 aryl) substituted phosphino; and hydrocarbon moieties, such as C 1 -C 24 alkyl (including C 1 -C 18 alkyl, further including C 1 -C 12 alkyl, and further including C 1 -C 6 alkyl), C 2 -C 24 alkenyl (including C 2 -C 18 alkenyl, further including C 2 -C 12 alkenyl, and further including C 2 -C 6 alkenyl), C 2 -C 24 alkynyl (including C2 -C 18 alkynyl, further including C 2 -C 12 alkynyl, and further including C 2 -C 6 alkynyl), C 5 -C 30 aryl (including C 5 -C 20 aryl, and further including C 5 -C 12 aryl) and C 6 -C 30 aralkyl (including C 6 -C 20 aralkyl, and further including C 6 -C 12 aralkyl). Additionally, if a particular group permits, the above functional groups may be further substituted by one or more other functional groups or by one or more hydrocarbon groups, such as those structural moieties specifically listed above. For example, the alkyl or alkenyl group may be branched. For example, the "substituent" is an alkyl group, such as a methyl group.

[0293] As used herein, the term "perfume composition" refers to a mixture of perfume ingredients, such as including any one of Method 1 or 1.1 - 1.62, or any one of Composition 2 or 2.1 - 2.22, and may include, if desired, auxiliary substances dissolved in a suitable solvent or mixed with a powdered substrate, for providing the desired odor to a product, and the product is optionally packaged according to that described in Composition or Product 4 or 4.1 - 4.9.

[0294] Perfumes, ingredients, and mixtures of perfume ingredients that can be used in combination with the compounds to produce a perfume composition include, but are not limited to: natural products, including extracts, animal products, and essential oils, absolutes, resinoids, resins, and concentrates; and synthetic perfumes, which include, but are not limited to, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, phenols, ethers, lactones, furansketals, nitriles, acids, and hydrocarbons, including saturated compounds and unsaturated compounds, as well as aliphatic carbocyclic and heterocyclic compounds, and animal products.

[0295] As used herein, "citronellol polymer" and "pentenol polymer" are meant to include all derivatives and cyclic forms of citronellol and pentenol and polymers.

[0296] In this specification, for convenience, the structural formula of a compound represents a certain isomer in some cases, but the present invention includes all isomers, such as geometric isomers, optical isomers based on asymmetric carbons, stereoisomers, tautomers, etc. Additionally, the compounds represented by the said formula may exist in polymorphic forms, and it should be noted that any crystal form, crystal form mixture, or its anhydride or hydrate is included within the scope of the present invention.

[0297] When referring to a range, such as 0 - 10 or 1 - 7, this range includes all integer values within the range, as well as sub - ranges of integers. Thus, the range 0 - 10 includes 0 - 9, 0 - 8, 0 - 7, 0 - 6, 0 - 5, 0 - 4, 0 - 3, 0 - 2, 1 - 10, 1 - 9, 1 - 8, 1 - 7, 1 - 6, 1 - 5, 1 - 4, 1 - 3, 1 - 2, 1 - 9, 2 - 10, 2 - 9, 2 - 8, 2 - 7, 2 - 6, 2 - 5, 2 - 4, 2 - 3, 3 - 10, 3 - 9, 3 - 8, 3 - 7, 3 - 6, 3 - 5, 3 - 4, 4 - 10, 4 - 9, 4 - 8, 4 - 7, 4 - 6, 4 - 5, 4 - 4, 4 - 3, 5 - 10, 5 - 9, 5 - 8, 5 - 7, 5 - 6, 6 - 10, 6 - 9, 6 - 8, 6 - 7, 7 - 10, 7 - 9, 7 - 8, 8 - 10, 8 - 9, 9 - 10, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0298] Unless otherwise stated, all percentages used herein are by volume.

[0299] Unless otherwise stated, all ratios used herein are by mole. Examples

[0300] Example 1: Continuous polymerization of citronellol on cation exchange resin

[0301] An Amberlyst resin was filled in a 0.25 - inch smooth - bore stainless - steel tube that was 6 feet long and had a wall thickness of 0.01 inches. The tube was coiled and a PTFE tube was fitted at one of the two ends for continuous flow. The coil was heated to 50 °C in an oil bath, and 300 g of citronellol was pumped into the filled coil at a rate of 2 ml / min. The material coming out of the coil had reached a high degree of polymerization, as shown by 1 1H - NMR analysis. The NMR indicated that the number of protons associated with the methylene group adjacent to the ether oxygen atom (~3.3 ppm) increased significantly compared to the protons associated with the methylene group adjacent to the alcohol oxygen atom (~3.6 ppm). For these two different sets of protons, an integral ratio of approximately 1:1 was found.

[0302] Then, all the material is removed from the coil using pressurized nitrogen. The collected material is further distilled under vacuum (0.7 mbar) and elevated temperature (up to 160 °C) to remove monomers and dimers, yielding a clear, odorless liquid as identified below:

[0303]

[0304] Fractions can be collected, each having different values in terms of number average molecular weight, weight average molecular weight, polydispersity index, and n value. These fractions have different physical properties such as viscosity, refractive index, boiling point, and surface tension.

[0305] One fraction is obtained in which the citronellol polymer has an average n value of 0 - 4. Another fraction is obtained in which the citronellol polymer has an average n value of 1 - 7.

[0306] Example 2: Product of polycitronellol - limonene oxide

[0307]

[0308] A mixture of polycitronellol (141 g) and limonene oxide (34.4 g, 0.75 equivalents) was treated with Amberlyst resin (5%, 7 g) and stirred at room temperature for 2 hours. During this process, the reaction was monitored by thin layer chromatography (TLC) and 1 1H NMR. No change was observed compared to the starting materials. Then, the reaction was heated at 40 °C for another 2 hours. The product in the mixture was evident, but the reaction was incomplete. The reaction was heated at 45 °C for 4 hours. TLC and NMR showed consumption of the starting materials (see Figure 1 ). The reaction mixture was filtered through Celite to remove the resin. 70 g of the reaction mixture was collected. The mixture was distilled at elevated temperature and reduced pressure (temperature from 123.5 °C to 132.3 °C, pressure from 2.43 mbar to 2.51 mbar). The resulting product was characterized by NMR and was consistent with the desired product.

[0309] Example 3: Detection of the polydispersity index of citronellol polymer derivatives

[0310] Weigh a sample of the citronellol polymer derivative (e.g., 20 - 25 mg in a 10 mL flask) and dilute it to the flask volume with a solvent (e.g., THF, unstabilized). Shake the mixture well until homogeneous. Constant solvent chromatographic conditions are used to separate the polymer peaks for analysis. The chromatographic parameters are shown below:

[0311] Column: Agilent Oligopore GPC, 6 μm, 3.5 mm x 700 mm

[0312] Diluent: THF, without BHT inhibitor (unstabilized)

[0313] Mobile phase: THF, without BHT inhibitor (unstabilized)

[0314] Flow rate: 1.0 mL / min

[0315] Column temperature: 25 ± 2 °C

[0316] Detection: 220 nm

[0317] Injection volume: 30 μL

[0318] Run time: 25 minutes

[0319] Calculation: Since one double bond in each polymer molecule is the only functional group that can absorb light at a wavelength of 220 nm, the area % value measured from the chromatogram is equal to the mole %. Therefore, the values reported for the peaks in the HPLC data are used for calculation, and calibration is only required when calculating weight percentages.

[0320] Mass = (theoretical molecular weight) x (area %)

[0321] Mass % = (mass / total mass) x 100

[0322] Mn (number average) = area in mAU / molecular weight

[0323] Mw (weight average) = (area in mAU) x (molecular weight)

[0324] PDI (polydispersity index) = Mw / Mn.

[0325] According to the HPLC chromatogram, each peak can be characterized by its retention time, area %, and molecular weight. From these values, mass and mass % can be derived. Then, the number average molecular weight, weight average molecular weight, and polydispersity index are calculated from these values.

[0326] The polydispersity indices of various citronellol polymers and citronellol polymer derivatives are detected according to this procedure. For one polymer, the data show that a major component of the citronellol polymer derivative composition is the dimer, and its estimated amount is 50 wt%. The remaining major components are the trimer, tetramer, pentamer, and hexamer, and their total estimated amount is 50.36 wt%. For another polymer, the data show that a major component of the citronellol polymer derivative composition is the trimer, and its estimated amount is 45 - 57 wt%. The remaining major components are the tetramer, pentamer, and hexamer, and their total estimated amount is 42 - 46 wt%, and the balance is the dimer, heptamer, and octamer.

Claims

1. A compound according to formula I: wherein R 1 is an optionally substituted C 1 -C 12 alkyl; R 2 、R 3 、R 4 and R 5 each independently is hydrogen, optionally substituted C 1 -C 12 alkyl, optionally substituted C 2 -C 12 alkenyl, optionally substituted C 2 -C 12 alkynyl, optionally substituted aryl, or R 2 Together with R 3 Together, R 4 Together with R 5 Together, or R 3 Together with R 5 Together form an optionally substituted C 3 -C 12 cycloalkyl or an optionally substituted C 3 -C 12 cycloalkenyl; and n is an integer from 0 to 20.

2. The compound according to claim 1, wherein n is an integer from 0 to 5.

3. The compound according to claim 1, wherein R 1 is an optionally substituted C 1 -C 12 alkylene, wherein the C 1 -C 12 alkylene is straight-chain or branched.

4. The compound according to claim 1, wherein R 1 is an unsubstituted straight-chain C 1 -C 12 alkylene or an unsubstituted branched C 3 -C 12 alkylene.

5. The compound according to claim 1, wherein R 1 is CH 2 CH 2 CH(CH 3 )CH 2 CH 2 .

6. The compound according to any one of claims 1-5, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently hydrogen.

7. The compound according to any one of claims 1-5, wherein R 2 , R 3 , R 4 and R 5 are each independently one or more of unsubstituted C 1-12 alkyl.

8. The compound according to claim 7, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently unsubstituted C 1-6 alkyl.

9. A compound according to any one of claims 1-5, wherein R 2 , R 3 , R 4 and R 5 are each independently a substituted C 1-12 alkyl group.

10. The compound according to claim 9, wherein one or more of R 2 , R 3 , R 4 and R 5 are each independently C 1-6 alkyl substituted by 1-9 groups each independently selected from the following: C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 2-6 alkynyl, hydroxy, carboxy, halogen, and substituted or unsubstituted aryl.

11. The compound according to any one of claims 1 - 5, wherein R 2 and R 4 are each independently hydrogen or unsubstituted C 1-6 alkyl, and R 3 and R 5 together form an optionally substituted C 3 -C 12 cycloalkyl or an optionally substituted C 3 -C 12 cycloalkenyl.

12. The compound according to claim 11, wherein said C 3 -C 12 cycloalkyl or C 3 -C 12 cycloalkenyl is independently substituted with 1-9 groups each independently selected from: C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1-6 alkoxy, hydroxy, carboxy, or methylene.

13. The compound according to claim 1, wherein the aryl is phenyl.

14. The compound according to any one of claims 1 - 5, wherein n is 0, 1, 2, 3 or 4.

15. The compound according to any one of claims 1-5, wherein the end group is 16. The compound according to any one of claims 1-5, wherein R 1 is CH 2 CH 2 CH(CH 3 )CH 2 CH 2 , is and n is an integer from 0 to 20.

17. The compound according to any one of claims 1 - 5, wherein the compound of formula I is: wherein n is from 1 to 20; wherein n is from 1 to 20; where n is from 1 to 20; where n is from 1 to 20; where n is from 1 to 20; where n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; where n is from 1 to 20; where n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20; wherein n is from 1 to 20.

18. The compound according to claim 17, wherein the compound of formula I is: wherein n is 1 or 2.

19. A composition comprising a compound of formula I according to any one of claims 1 - 18.

20. The composition according to claim 19, wherein the composition comprises more than 40% of the compound of formula I wherein n is 0, said percentage being determined as a percentage of the number of molecules in the composition or as a weight percentage of the total weight of the composition.

21. The composition according to claim 20, wherein the composition comprises more than 50% of the compound of formula I wherein n is 0.

22. The composition according to claim 20, wherein the composition comprises more than 60% of the compound of formula I wherein n is 0.

23. The composition according to claim 20, wherein the composition comprises more than 70% of the compound of formula I wherein n is 0.

24. The composition according to claim 20, wherein the composition comprises more than 80% of the compound of formula I wherein n is 0.

25. The composition according to claim 20, wherein the composition comprises more than 90% of the compound of formula I wherein n is 0.

26. The composition according to claim 19, wherein the composition comprises 40 - 70% of the compound of formula I wherein n is 0, said percentage being determined as a percentage of the number of molecules in the composition or as a weight percentage of the total weight of the composition.

27. The composition according to claim 26, wherein the composition comprises 40 - 60% of the compound of formula I wherein n is 0.

28. The composition according to claim 26, wherein the composition comprises 40 - 50% of the compound of formula I wherein n is 0.

29. The composition according to claim 19, wherein the composition comprises one or more compounds of formula I, wherein each compound of formula I independently has an n value of 0 - 4, and the amount of each compound of formula I is at least 1% and at most 90%, said percentage being determined as a percentage of the number of molecules in the composition or as a weight percentage of the total weight of the composition.

30. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 50%.

31. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 40%.

32. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 30%.

33. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 25%.

34. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 20%.

35. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 15%.

36. The composition according to claim 29, wherein the amount of each compound of formula I is 5 - 10%.

37. The composition according to claim 29, wherein the amount of each compound of formula I is 40 - 50%.

38. The composition according to claim 29, wherein the amount of each compound of formula I is 30 - 40%.

39. The composition according to claim 29, wherein the amount of each compound of formula I is 20 - 30%.

40. The composition according to claim 29, wherein the amount of each compound of formula I is 10 - 20%.

41. The composition according to claim 29, wherein the amount of each compound of formula I is 1 - 10%.

42. The composition according to claim 29, wherein the amount of each compound of formula I is 1 - 5%.

43. The composition according to claim 29, wherein the amount of each compound of formula I is 1 - 2%.

44. The composition according to any one of claims 19 - 43, wherein the compound in the composition has an average n value of 0, which is determined as the weight - average or number - average value.

45. The composition according to any one of claims 19 - 43, wherein the compound in the composition has an average n value of 0.5, which is determined as the weight - average or number - average value.

46. A method for preparing the compound according to claim 16, comprising the following steps: reacting a compound of formula I(a): wherein n is 0 - 20, with a compound of formula A: wherein R 2 、R 3 、R 4 and R 5 are as defined in claim 1, in the presence of an acid or base catalyst, and then separating and completely or partially purifying the compound of formula I.

47. The method according to claim 46, wherein the compound of formula I is separated and completely or partially purified by distillation or chromatography.

48. A product composition, wherein the product composition comprises the compound according to any one of claims 1 - 18 or the composition according to any one of claims 19 - 45.

49. The product composition according to claim 48, wherein the product is selected from: fragrance products, perfume products, soap products, insect repellent products, pesticide products, detergent products, air freshener products, indoor spray products, candle products, cosmetic products, talcum powder products, hair care products, body deodorant products, antiperspirant products, pet litter products, topically applied skin care products, paint or coating products, lubricant products, plastic products, defoaming agent products, hydraulic fluid products, antibacterial products, crop protection products, products for enhanced oil recovery, fracturing and / or other oilfield applications, adhesive products, oral care products, food products, or pharmaceutical products.

50. The product composition according to claim 49, wherein the product is selected from: incense pill products, lotion products, floral water products, or writing ink or printing ink products.

51. The product composition according to claim 49, wherein the product is selected from: household cleaner products, shampoo products, or nail polish remover products.

52. The product composition according to any one of claims 48 - 51, wherein the composition further comprises one or more additives selected from: cooling sensation agents, warming sensation agents, and / or stinging sensation agents; flavoring agents or fragrances; vitamins, minerals, health foods, stimulants, emollients, colorants, amino acid antioxidants, preservatives, pH modifiers, viscosity regulators, and any combination thereof.

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