Cyclic polydicyclopentadiene and methods of preparing the same

Abstract

Disclosed herein are cyclic polymers comprising dicyclopentadiene (DCPD) and dicyclopentadiene derivatives without cross-linking that can act as chemical additives to enhance the application and texture of cosmetic compositions.

Description

CYCLIC POLYDICYCLOPENTADIENE AND METHODS OF PREPARING THE SAME STATEMENT OF US GOVERNMENT SUPPORT

[0001] This invention was made with government support under Grant No.2154377, awarded by the National Science Foundation. The government has certain rights in the invention. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the priority benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No.63 / 701,281, filed September 30, 2024, the entire disclosure of which is incorporated herein by reference. FIELD

[0003] The disclosure relates generally to cyclic polymers of dicyclopentadiene and compositions thereof. BACKGROUND

[0004] Polydicyclopentadiene (PDCPD) is a polymer formed through ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) and exhibits high impact resistance, good chemical corrosion resistance, and high heat deflection temperature due to the highly cross-linked nature of PDCPD. PDCPD is frequently used in the automotive industry to make body panels, bumpers, and other components for trucks, buses, tractors, and construction equipment.

[0005] PDCPD is also commonly used in cosmetic compositions to make the application of the composition easier and enhance the texture of the applied cosmetic composition. Chemical additives are used in cosmetic compositions to reduce the rough texture of cosmetic materials and enhance their application. The primary function of the cosmetic agent is to limit the formation of turbulent eddies in the cosmetic material by absorbing the energy produced during application and lowering friction under shear stress.SUMMARY

[0006] Provided herein are cyclic polymers having a structure according to Formula (I):wherein: each ofandis independently a single bond or a double bond; n can range from 1 to 10,000; each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0- 2alkylene–O(O)CRA, C0-2alkylene–CO(O)C(RA)3, or C0-2alkylene–N(RA)2; each RA, when present, is independently H, C1-3alkyl, or C1-3haloalkyl; and the cyclic polymer has less than 1% crosslinking defects.

[0007] Also provided herein are methods of preparing cyclic polymers disclosed herein comprising: admixing a plurality of monomers each independently having a structure of Formula (IV):wherein: each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene–O(O)CRA, C0-2alkylene–CO(O)C(RA)3, or C0-2alkylene–N(RA)2; and each RA, when present, is independently H, C1-3alkyl, or C1-3haloalkyl; and a catalyst; under conditions sufficient to polymerize the plurality of monomers to form the cyclic polymer of Formula (II). BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 shows (top)1H NMR spectrum for cyclic poly(dicyclopentadiene) prepared in accordance with the disclosure at 1000:1 monomer-to-catalyst ratio; (middle)1H NMRspectrum for cyclic poly(dicyclopentadiene) prepared in accordance with the disclosure at 100:1 monomer-to-catalyst ratio; (bottom)1H NMR spectrum for dicyclopentadiene as reference.

[0009] Figure 2 shows an FTIR Spectrum of cyclic poly(dicyclopentadiene) prepared in accordance with the disclosure.

[0010] Figure 3 shows a1H NMR spectrum of cyclic poly(dicyclopentadiene) according to the disclosure.

[0011] Figure 4 shows a chromatograph of polymerization mixtures with 1000-fold and 100-fold monomer to catalyst ratios.

[0012] Figure 5 shows an FTIR spectrum of hydrogenated cyclic-poly(dicyclopentadiene) (c-hDCPD) prepared in accordance with the disclosure. DETAILED DESCRIPTION

[0013] Provided herein are cyclic polymers comprising dicyclopentadiene (DCPD) and dicyclopentadiene derivatives without cross-linking that can act as chemical additives to enhance the application and texture of cosmetic compositions. Linear polymers, including linear poly(DCPD), have been used in cosmetic compositions due to their high ductility. Linear polymers can be unsuitable as cosmetic agents because linear polymers are less resistant to shear degradation as molecular weight increases, yet the effectiveness of the linear polymer increases as the molecular weight of the polymer increases. As a result, the ability of the linear polymer as a cosmetic agent is limited, in part, due to shear degradation. Additionally, linear polymers are typically dense than their cyclic analogues which can cause linear polymers to contain voids that preclude crystallization The cyclic polymers disclosed herein can be particularly advantageous as chemical additives for cosmetic compositions in view of the limitations of linear polymers in cosmetic compositions.

[0014] Cyclic polymers differ in their structure and properties relative to their equivalent molecular weight linear counterparts due to the absence of chain-ends. These differences are observed in solution and in bulk. These differences include smaller hydrodynamic volume and radius of gyration (Rg), higher glass transition temperature (Tg), lower intrinsic viscosity, higher critical solution temperature, increased rate of crystallization, and higher refractive index. Cyclic polymers can provide cosmetic agents with improved resistance to shear degradation relative to linear analogues because when cyclic polymers undergo shear degradation, linear polymers with larger relative hydrodynamic volumes than the cyclic polymer are formed. Thus, upon shearing of a cyclic polymer, the hydrodynamic volume initially increases, increasing the effectiveness of the polymer as a cosmetic agent.

[0015] The presence of a small amount of linear polymer in a cyclic polymer composition can dramatically alter the measured polymer properties. These linear polymer impurities can occur during the synthesis of the cyclic polymer. Known methods such as ring closing of linear polymers and ring-expansion metathesis are known to provide linear impurities. Additionally, if the polymerization catalysts used to form cyclic polymers are air-sensitive, such catalysts can react with oxygen and water to change the geometry and / or oxidation state of the catalyst, which can lead to formation of linear polymer impurities. Further, aromatic side products can form during the formation of cyclic polymers. Typically, compositions are heated to eliminate these aromatic side products, but can generate linear impurities and cross-linking between polymer chains.

[0016] Also contemplated are blends of the cyclic polymers of the disclosure with linear poly(dicyclopentadiene). Blending cyclic poly(dicyclopentadiene) into linear poly(dicyclopentadiene) will modify the properties of poly(dicyclopentadiene) materials. Cyclic polymers have inherently lower densities than linear polymers at the same molecular weight thus blends will differentiate the density of the polymer material. Also, the cyclic structure will alter the chain entanglement concentrations thus allowing the fine tuning of expansion strain and extension, and ultimately cross-linking between chains.

[0017] The cyclic polymers of the disclosure can be used in a variety of cosmetic materials, such as compositions and formulations for the skin. It is believed that due to the lower entanglement concentrations of cyclic polymers, lack of cross-linking between polymer chains, and lack of chain ends, the cyclic polymers of the disclosure should be denser than their linear analogues and exhibit improved properties.

[0018] Modifications and other embodiments will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented herein and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims.

[0019] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” can include the aspect of “consisting of.” Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0020] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

[0021] As used herein, the term “alkyl” refers to straight chained and branched saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty two carbon atoms, or one to twenty carbon atoms, or one to ten carbon atoms. The term Cn means the alkyl group has “n” carbon atoms. For example, C4 alkyl refers to an alkyl group that has 4 carbon atoms. C1-20alkyl and C1-C20alkyl refer to an alkyl group having a number of carbon atoms encompassing the entire range (i.e., 1 to 20 carbon atoms), as well as all subgroups (e.g., 1-20, 2-15, 1-10, 5-12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,18, 19, and 20 carbon atoms). Nonlimiting examples of alkyl groups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl (1,1-dimethylethyl), 3,3- dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. A specific substitution on an alkyl can be indicated by inclusion in the term, e.g., “haloalkyl” indicates an alkyl group substituted with one or more (e.g., one to 10) halogens.

[0022] As used herein, “alkylene” refers to a bivalent saturated aliphatic radical. The term Cn means the alkylene group has "n" carbon atoms. For example, C0-2alkylene refers to an alkylene group having a number of carbon atoms encompassing the entire range, including absent, as well as all subgroups, as previously described for "alkyl" groups.

[0023] As used herein, the term “hydroxy” or “hydroxyl” refers to an “–OH” group. Accordingly, a “hydroxyalkyl” refers to an alkyl group substituted with one or more –OH groups.

[0024] As used herein, the term “alkoxy” refers to a “—O-alkyl” group.

[0025] As used herein, the term "halogen" is defined as fluoro, chloro, bromo, and iodo. Accordingly, a “haloalkyl” refers to an alkyl group substituted with one or more halogen atoms. In some cases, the haloalkyl group is a perhaloalkyl, i.e., all hydrogen atoms of the alkyl group have been substituted with a halogen. Some non-limiting examples of haloalkyl groups include CF3, CHF2, CH2F, CCl3, CI3, and CH2CF3.

[0026] All ranges set forth herein include all possible subsets of ranges and any combinations of such subset ranges. By default, ranges are inclusive of the statedendpoints, unless stated otherwise. Where a range of values is provided, it is understood that each intervening value between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also contemplated to be part of the disclosure. Monomers

[0027] The cyclic polymers of the disclosure can be prepared from a plurality of cyclic alkenes. In some cases, the plurality of alkenes comprises the same alkene. In some cases, the plurality of alkenes comprises a mixture of alkenes.

[0028] Suitable monomers for preparing cyclic polymers for cosmetic compositions can generally include monomers of dicyclopentadiene. Suitable monomers for preparing cyclic polymers for cosmetic compositions can generally include monomers that will provide a “branch” off the polymer backbone. Such branching in polymers can lower the ability of the polymer chains to entangle and cross-link. Suitable branches can include cyclopentyl rings substituted with alkyl groups, alkoxy groups, ester groups, amino groups, and carboxylate groups. Examples of suitable monomers include, but are not limited to, dicyclopentadiene, and substituted derivatives thereof. Further examples of suitable monomers include, compounds having a structure of Formula (IV):

[0029] In compounds of Formula (IV), each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene–O(O)CRA, C0-2alkylene–CO(O)RA, or C0-2alkylene– N(RA)2. In some cases, at least one R is H, C1-6alkyl, or C1-6haloalkyl. In some cases, each R is H, C1-6alkyl, or C1-6haloalkyl.

[0030] In compounds of Formula (IV), each RA, when present, is independently H, C1-6alkyl, or C1-6haloalkyl.

[0031] In some cases, the plurality of monomers comprises dicyclopentadiene. In some cases, the plurality of monomers comprises endo-dicyclopentadiene. PolymerizationThe polymerization or copolymerization of cyclic polymers can be carried out using the tethered alkylidene catalysts and methods disclosed in Publication No. US-2023-0303600- A1, the entirety of which is incorporated by reference herein. For example, the polymerization catalyst can be a tethered alkylidene having a structure of: selected from the group of:, and. In some cases, the polymerization catalyst is a tethered alkylidene having a structure of

[0032] The polymerization of cyclic alkenes to cyclic polymers occurs upon combining a metal complex (catalyst) with a plurality of cyclic alkene monomers in a fluid state, which can be in solution. Examples of solvents that may be used in the polymerization or copolymerization reaction include organic, protic, or aqueous solvents that are inert under the polymerization conditions, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Suitable halogenated hydrocarbon solvents include methylene chloride, chloroform, chlorobenzene, 1,2- dichloroethane, dichlorobenzene, and mixtures thereof. In some cases, the polymerization or copolymerization reaction solvent does not include aqueous solvents or protic solvents (e.g., the polymerization reaction occurs in the presence of a non-aqueous and / or aprotic solvent). In embodiments, the polymerization reaction solvent comprises aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, or combinations thereof. The concentration of the monomers is not particularly limited. In cases wherein the cyclic alkenes are liquid, the monomers can be provided neat. In cases wherein the monomer is provided in the presence of a solvent, the monomers can be provided at concentrations in a range of 0.01 M to 5 M, for example in a range of 0.01 M to 4.5 M, 0.01 M to 4 M, 0.01 M to 3 M, 0.05 M to 3 M, 0.1 M to 3 M, 0.1 M to 3.5 M, 0.5 M to 3.5 M, 0.5 M to 4 M, or 0.5 M to 5 M.

[0033] The polymerization or copolymerization can be carried out at, for example, ambient temperatures at dry conditions under an inert atmosphere. The polymerization can be carried out at a temperature in the range of about 30°C to about 100°C or greater, for example, in a range of about 35°C to about 85°C or about 40°C to about 60°C. Polymerization or copolymerization times will vary, depending on the particular monomer(s), metal complex (catalyst), and desired molecular weight of the cyclic polymer product. The progress of the reaction can be monitored by standard techniques, e.g., nuclear magnetic resonance (NMR) spectroscopy.

[0034] Polymerization and copolymerization proceed by successive addition / insertion of a monomer to the growing macrocycle on the metal complex, and the intermediate macrocyclic complex undergoes intramolecular chain transfer to yield the cyclic polymer. Polymerization and copolymerization may be terminated at any time by addition of a solvent effective to precipitate the polymer, for example, methanol. The precipitated polymer may then be isolated by filtration or other conventional means.

[0035] The molecular weight of the cyclic polymers can be small, equivalent to oligomers of three to ten repeating units, or the molecular weights can be of any size up to tens and hundreds of thousands or millions in molecular weight, for example, in a range of about 200 Da to about 5,000,000 Da, about 500 Da to about 4,000,000 Da, about 1,000 Da to about 3,000,000 Da, about 5,000 Da to about 2,000,000 Da or about 10,000 to about 1,000,000 Da. The cyclic polyalkenes can be used as prepared or converted into cyclic polyalkanes upon reduction of the double bonds of the cyclic polyalkene polymer. The cyclic polyalkene can be converted to substituted cyclic polyalkanes by addition reaction at the alkene groups of the cyclic polyalkenes, for example the addition of halogens, alcohols, amines, or any other olefin addition reactions.

[0036] The present process has enabled preparation of cyclic poly(dicyclopentadiene). Cyclic polymers prepared from cyclic alkene monomers can display one or more geometries across the resulting double bonds of the resulting polyalkene backbone. In some cases, the cyclic polymer is syndiotactic. In some cases, the alkene groups of the cyclic polymer are at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% syndiotactic. In some cases, the cyclic polymer is isotactic. In some cases, the alkene groups of the cyclic polymer are at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% isotactic. In some cases, the cyclic polymer is atactic. In some cases, the alkene groups of the cyclic polymer are at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% atactic.

[0037] Following polymer synthesis and recovery, an olefinic polymer may be hydrogenated using conventional means, e.g., via standard H2 / Pd / C procedures or via tosyl-hydrazine decomposition. Generally, either procedure will result in a saturated polymer having hydrogenated more than 99% of the olefinic functionalities in the polymer backbone, as may be determined by1H and13C NMR spectroscopy. As used herein, a cyclic polymer is fully hydrogenated if more than 99% of the olefinic functionalities are hydrogenated. The stereoregularity of the polymers can be maintained during hydrogenation, providing for stereoregular saturated cyclic polymers. In embodiments, a deficiency of hydrogen can be included in the hydrogenation mixture and an olefinic polymer can be converted to a macrocyclic poly (alkene-co-alkane).

[0038] As with any polymer, each individual cyclic polymer chain of the cyclic poly(dicyclopentadiene) can comprise a different amount of polymerized monomer units. As disclosed herein, the number of polymerized monomer units refers to the average amount of polymerized monomer units in a mixture of discrete cyclic poly(dicyclopentadiene) polymers. In embodiments, the cyclic poly(dicyclopentadiene) can have at least 50 polymerized monomer units. In embodiments, the cyclic poly(dicyclopentadiene) can have 50 to 50,000 polymerized monomer units, e.g., 100 to 50,000, 200 to 25,000, 100 to 25,000, or 50 to 25,000. In embodiments, the cyclic poly(dicyclopentadiene) can have at least 80 polymerized monomer units. In embodiments, the cyclic poly(dicyclopentadiene) can have at least 100 polymerized monomer units. For example, the cyclic poly(dicyclopentadiene) can have at least 100, at least 200, at least 300, at least 500, at least 1000, at least 1500, at least 2000, at least 5000, at least 10,000, or at least 20,000, polymerized monomer units. Cyclic Poly(dicyclopentadiene) of the Disclosure

[0039] Provided herein are cyclic polymers having a structure according to Formula (I): wherein:eachandis independently a single bond or a double bond; n can range from 1 to 10,000;each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene– O(O)CRA, C0-2alkylene–CO(O)C(RA)3, or C0-2alkylene–N(RA)2; each RA, when present, is independently H, C1-3alkyl, or C1-3haloalkyl; and the cyclic polymer has less than 1% crosslinking defects.

[0040] In cyclic polymers of Formula (I), eachandcan independently be a single bond or a double bond. In some cases, at least one ofandare a double bond. In some cases, each ofandare a double bond and the cyclic polymer can have a structure of Formula

[0041] In some cases, at least one ofandare a single bond. In some cases, each of andis a single bond and having a structure of Formula (III):

[0042] In cyclic polymers of Formula (I), (II), and (III), n can range from 1 to 10,000. In some cases, n is the range 100 to 10,000. In some cases, n is the range 1,000 to 10,000.

[0043] In cyclic polymers of Formula (I), (II), and (III), each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene–O(O)CRA, C0-2alkylene–CO(O)C(RA)3,C0-2alkylene–N(RA)2.. In some cases, each R is independently H, C1-6alkyl, or C1-6haloalkyl. In some cases, R is H or C1-6alkyl. In some cases, R is H.

[0044] In cyclic polymers of Formula (I), (II), and (III), each RA, when present, is independently H, C1-2alkyl, or C1-2haloalkyl.

[0045] In various cases, the cyclic polymers of Formula (I), (II), and (III), have a structure

[0046] In some cases, the cyclic polymer has a structure ofIn some cases, the cyclic polymer has a structure of

[0047] In some cases, the cyclic polymer has a structure of, or. In some cases, the cyclic polymer has a structure of or

[0048] In some cases, the cyclic polymer has a structure of , orIn some cases, the cyclic polymer has a structure of

[0049] In compounds of Formula (I), and (II), the cyclic polymer can have at least 80% cis double bonds. For example, the cyclic poly(dicyclopentadiene) can have 80% to 99.9% cis double bonds, or 85% to 99.9% cis double bonds, or 90% to 99.9% cis double bonds, or 95% to 99.9% cis double bonds, such as, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 99.9% cis double bonds. In embodiments, the cyclic poly(dicyclopentadiene) can comprise a minor amount of trans double bonds, such as less than 1%. The number of trans double bonds in a cyclic poly(dicyclopentadiene) can be assessed according to any method known in the art.

[0050] The cyclic poly(dicyclopentadiene) disclosed herein has low crosslinking defects – i.e., less than 1% crosslinking defects – that is, less than 1% of the polymer molecules in a particular sample comprise a crosslinking defect. In embodiments, the cyclic poly(dicyclopentadiene) can have less than 0.5% crosslinking defects. For example, the cyclic poly(dicyclopentadiene) can have less than 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% crosslinking defects. In embodiments, cyclic poly(dicyclopentadiene) can have less than 0.5% crosslinking defects. In embodiments, the cyclic poly(dicyclopentadiene) can have less than 0.1% crosslinking defects. As used herein, the term “crosslinking defects” is defined as a covalent bond(s) that joins two or more distinct cyclic polymers together or more than one covalent bond that joins a discrete cyclic polymer to itself. The crosslinking defects in a cyclic poly(dicyclopentadiene) can be assessed according to known methods in art. For example, NMR spectroscopy can be used to assess crosslinking defects in a cyclic polymer. In many cases, comparison of integration values for aliphatic and olefinic1H and13C resonances can be used to determine if crosslinking is present. Further, it is believed that the presence of only 1% crosslinking defect in cyclic poly(dicyclopentadiene), can make the polymer insoluble in most if not all organic or aqueous solvent. Cyclic poly(dicyclopentadiene) Blends

[0051] Also contemplated herein are cyclic poly(dicyclopentadiene) blends with linear poly(dicyclopentadiene) for improved cyclic poly(dicyclopentadiene) blends. Blending cyclic poly(dicyclopentadiene) into linear poly(dicyclopentadiene) will modify the properties of poly(dicyclopentadiene) materials. Cyclic polymers have inherently lower densities than linear polymers at the same molecular weight thus blends will differentiate the density of the polymer material. Also, the cyclic structure will alter the chain entanglement concentrations thus allowing the fine tuning of expansion strain and extension, and ultimately cross-linking between chains. It will also allow for the use of poly(dicyclopentadiene) in a wide variety of applications, such as cosmetic compositions, as well as structural components, based on fine tuning the poly(dicyclopentadiene) blend.Physiologically Acceptable Compositions

[0052] The cyclic polymers of the disclosure can be incorporated into cosmetic compositions such as those disclosed in WO2012131083 and US20120308621, the entirety of which are incorporated by reference herein. Also provided herein are cosmetic compositions that comprise cyclic poly(dicyclopentadiene). It is believed that the cyclic poly(dicyclopentadiene) will enhance the texture and ease of application, while being hypoallergenic and non-irritating, as well as by presenting a transparent or translucent appearance, depending on the additional components included in the composition.

[0053] Cosmetic compositions, for instance foundations, are commonly used to give the skin, especially the face, a color and an aesthetic effect. These makeup products generally contain oils, pigments, fillers and optionally additives such as cosmetic or dermatological active agents. As such, the cosmetic compositions of the disclosure may comprise another series of compounds selected from the ones normally used in the manufacturing of composite products. These compounds may be preferably selected, in a non-limiting manner, from a group consisting of odoriferous (perfumes, fragrances or aromas), stabilizing, pH-regulating and antioxidant substances, biocides and conservatives, medicinal, soothing, anti-cellulite, anti-wrinkle and anti-dandruff substances, hair straighteners, detangling, reaffirming, anti-corrosive, chelating, anti-foam, solvent, thickening, gelling, emollient, emulsifying, anti-binding, surfactant (anionic, cationic, amphoteric or non-ionic), emulsifying, exfoliating, moisturizing, humectant, makeup-removing, pigment-removing, pearlizing, solvent, deodorizing, antiperspirant, tanning, coloring, opacifying, whitening and bleaching substances, as well as any combination thereof.

[0054] The aforementioned compounds may consist, for example, of vitamins, emollient esters, lanolins, UV filters or protectors (antioxidant, organic or inorganic), vegetable oils, medicinal, pharmaceutical or cosmetic mineral oils (paraffinic, naphthenic or aromatic), essential oils, biological products, galenic products, plant extracts (flower or fruit extracts, dry extracts, glycolic, hydroglycolic, oily, colourless and water-soluble extracts), amino acids, alcohols, glycerines and vegetable glycerines, olive oil derivatives, vegetable petrolatums, silicones, fatty acids, oligo-elements, proteins, peptides, liposomes, active organic oils, natural active ingredients from vegetable, sea or synthetic origin, Aloe Vera and lipids, as well as any combination thereof.

[0055] Provided herein is a composition comprising a physiologically acceptable medium and at least one cyclic polymer of the disclosure. In various cases, the cyclic polymer has a structure of:,, , or. In various cases, n is in the range 100 to 10,000.

[0056] In various cases, the cyclic polymer has a structure of: and n is in the range 1,000 to 10,000. In various cases, thecyclic polymer has a structure of:,, orand n is in the range 1,000 to 10,000. In various cases, the cyclic polymer has a structure of:and n is in the range 1,000 to 10,000. EXAMPLES

[0057] The following examples are provided for illustration and are not intended to limit the scope of the invention. Materials & Methods

[0058] DCPD (96%) and 1-(2-allylphenyl)ethan-1-ol were purchased from Sigma Aldrich. Schrock’s Catalyst was purchased from STREM Chemicals. Solvents were purchased from any chemical supplier. Synthesis of Polymerization Catalyst (3)

[0059] The double tethered metallacyclobutane polymerization catalyst (3) was prepared according to the scheme below.

[0060] Generally, in a nitrogen filled glovebox, an aluminum reaction block was put into roughly a -60°C cold well. A 20 mL vial was then charged with Schrock’s Catalyst (1) (17.0 mg, 0.0309 mmol) and dissolved in 0.5 mL of toluene. In another vial, (R)-1-(2- allylphenyl)ethan-1-ol (2) (10.04 mg, 0.0619 mmol) was dissolved in 0.207 mL of toluene. The solution containing 1 was then added to the solution containing 2 at room temperature. After 10 min, the reaction mixture changed from orange to reddish-brown and the mixture was stirred for an additional 10 min to provide the double tethered metallacyclobutane polymerization catalyst (3). Example 1 – Preparation of Cyclic Poly(dicyclopentadiene)

[0061] Cyclic poly(dicyclopentadiene) was prepared according to the scheme below.

[0062] Generally, in a nitrogen-filled glovebox, a stock solution (42 mg / mL) of catalyst 3 was prepared in toluene (1.0 mL). A 20 mL vial was then charged with dicyclopentadiene (100 equiv) in 1.0 mL of toluene. An aliquot of the stock catalyst solution (1.49x10-5mol, 1 equiv) was added to the vigorously stirred dicyclopentadiene solution and the reaction was allowed to stir for 24 h at ambient temperature (about 20-25°C). After this period, the reaction vessel was brought outside the glovebox, and the reaction mixture was added to stirring methanol. Cyclic poly(dicyclopentadiene) precipitated and was isolated by filtrationand dried overnight under vacuum (~100% yield). An additional experiment was run with a monomer-to-catalyst ratio of 1000: 1 in order to determine the effect of the monomer-to- catalyst ratio on the cyclic poly(dicyclopentadiene). The products were analyzed by1H NMR and13C NMR spectroscopy and these1H NMR spectra are shown in Figure 1 (top, middle), the1H NMR spectrum of dicyclopentadiene is also shown for comparison (bottom). The FTIR spectrum for the cyclic poly(dicyclopentadiene) is shown in Figure 2, where the peak at ~1700 cm-1indicated presence of double bonds.

[0063] The1H NMR spectrum of the cyclic poly(dicyclopentadiene) was assigned as shown in Figure 3. The cyclic poly(dicyclopentadiene) prepared according to the disclosure was consistent with a cis geometry around the alkene bonds of the polymer backbone.

[0064] Chromatographic analyses were also performed and are shown in Figure 4. The cyclic poly(dicyclopentadiene) prepared with a monomer to catalyst ratio of 1000:1 exhibited a Mn of 114 kDa and a PDI of 3.7 as well as a shorter elution time, while the cyclic poly(dicyclopentadiene) prepared with a monomer to catalyst ratio of 100:1 was found to have a Mn of 7 kDa and a PDI of 12.9. Example 2 – Additional Preparation of Cyclic Poly(dicyclopentadiene)

[0065] Additional samples of cyclic poly(dicyclopentadiene) were prepared using different ratios of monomer and catalyst.

[0066] In a nitrogen filled glovebox, a 20 mL vial was then charged with dicyclopentadiene (50 mg, 0.378 mmol) and 2.43 mL of toluene for a [1:100] catalyst to monomer reaction at [0.15M]. The aluminum reaction block was taken out of the cold well and put onto a stir plate, then 87.7 uL of the catalyst 3 stock solution (25 mg / mL) was charged into the reaction block. The resulting mixture was stirred for 2 h as the reaction block warmed to room temperature. After 2 h, the vial was brought outside the glovebox, and the reaction mixture was added to rapidly stirring methanol. The resulting precipitate was isolated by filtration and dried in vacuo for 16 h to provide cyclic poly(dicyclopentadiene) (49.2 mg, 98%).

[0067] The appropriate amount of a stock solution (25 mg / mL) of 3 dissolved in toluene is added to an appropriate amount of dicyclopentadiene dissolved in toluene for an overall concentration of [0.15M] and stirred for 2 h while in a cooled reaction block, slowly coming to room temperature.

[0068] Table 1. Yield (%), Mn(kDa) and MW / Mnvalues observed for cyclic poly(dicyclopentadiene) prepared at varied [monomer] / [catalyst] ratios.aDetermined by size exclusive chromatography equipped with multi-angle light scattering;bNot Reported.

[0069] For all [monomer] / [catalyst] ratios, the1H and13C NMR spectra observed for cyclic poly(dicyclopentadiene) were consistent with previous reports (not shown). DMA measurements (not shown) indicated the T95temperature was 408 °C.

[0070] Accordingly, cyclic poly(dicyclopentadiene) can be prepared with a variety of [monomer] / [catalyst] ratios. Example 3 –Preparation of Cyclic Hydrogenated Poly(dicyclopentadiene)

[0071] In a nitrogen filled glovebox, c-polyDCPD (99.1 mg, 1.5 mmol), Ni(acac)2 (0.77 mg, 0.0029 mmol), AliBu3 (11.9 µL, 0.012 mmol), and H2O (0.755 mg, 0.755 µL) were added to a 20 mL scintillation vial with 10 mL of cyclohexane. The vial was then added to a Parr bomb reactor and charged with H2 gas to 400 psi, then heated to 80°C and stirred for 2 d. After, the reactor was cooled and vented off, then the solution was added to rapidly stirring solution of methanol. A precipitate formed, which was isolated by filtration and dried in vacuo for 16 h to provide hydrogenated cyclic poly(dicyclopentadiene) (80 mg, 80%).

[0072] As shown in Figure 5, the FTIR spectrum of the hydrogenated cyclic poly(dicyclopentadiene) was consistent with previous reports. In particular, the peak at ~1700 cm-1was absent in the FTIR spectrum of the hydrogenated cyclic poly(dicyclopentadiene), which indicated that few to no double bonds were present in the hydrogenated cyclic poly(dicyclopentadiene). Thermogravimetric analyses (not shown) of the hydrogenated cyclic poly(dicyclopentadiene) were performed which indicated T95and Tgtemperatures of 446 ºC and 62.2 ºC, respectively.

[0073] Accordingly, prepared cyclic poly(dicyclopentadiene) can be hydrogenated to provide hydrogenated cyclic poly(dicyclopentadiene).

Claims

What is claimed is:

1. A cyclic polymer having a structure according to Formula (I):wherein: each of andis independently a single bond or a double bond;n can range from 1 to 10,000; each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene– O(O)CRA, C0-2alkylene–CO(O)C(RA)3, or C0-2alkylene–N(RA)2; each RA, when present, is independently H, C1-3alkyl, or C1-3haloalkyl; and the cyclic polymer has less than 1% crosslinking defects.

2. The cyclic polymer of claim 1, wherein at least one of and are adouble bond.

3. The cyclic polymer of claims 1 or 2, wherein eachis a double bond.

4. The cyclic polymer of claim 1, wherein each ofandare a double bond and having a structure of Formula (II):

5. The cyclic polymer of any one of the proceeding claims, wherein the alkene groups of the backbone of the cyclic polymer are at least 50% syndiotactic.

6. The cyclic polymer of any one of the proceeding claims, wherein the alkene groups of the backbone of the cyclic polymer are at least 50% isotactic.

7. The cyclic polymer of any one of the proceeding claims, wherein the alkene groups of the backbone of the cyclic polymer are at least 50% atactic.

8. The cyclic polymer of claim 1, wherein at least one of and are asingle bond.

9. The cyclic polymer of claims 1 or 9, wherein each of and is asingle bond and having a structure of Formula (III):

10. The cyclic polymer of any one of the proceeding claims, wherein each R is independently H, C1-6alkyl, C1-6alkoxy, or C1-6haloalkyl.

11. The cyclic polymer of any one of the proceeding claims , wherein R is H or C1-6alkyl.

12. The cyclic polymer of any one of the proceeding claims, wherein R is H.

13. The cyclic polymer of claim 1, having a structure of:

14. The cyclic polymer of claim, having a structure of:

15. The cyclic polymer of claim, having a structure of:

16. The cyclic polymer of claim, having a structure of:

17. The cyclic polymer of any one of the proceeding claims, wherein n is in the range 100 to 10,000.

18. The cyclic polymer of any one of the proceeding claims, wherein n is in the range 1000 to 10,000.

19. The cyclic polymer of any one of the proceeding claims, having less than 0.5% crosslinking defects.

20. The cyclic polymer of any one of the proceeding claims, having less than 0.2% crosslinking defects.

21. The cyclic polymer of any one of the proceeding claims, having less than 0.1% crosslinking defects.

22. A method of preparing the cyclic polymer of any one of the proceeding claims comprising: admixing a plurality of monomers each independently having a structure of Formula (IV):wherein: each R is independently H, C1-6alkyl, C1-6haloalkyl, C1-6alkoxy, C1-6haloalkoxy, C0-2alkylene–O(O)CRA, C0-2alkylene–CO(O)C(RA)3, or C0-2alkylene–N(RA)2; and each RA, when present, is independently H, C1-3alkyl, or C1-3haloalkyl; and a catalyst; under conditions sufficient to polymerize the plurality of monomers to form the cyclic polymer of Formula (II).

23. The method of claim 22, wherein the catalyst is selected from the group of:

24. The method of claim 23, wherein the catalyst is25. The method of claim 22, wherein the catalyst is provided in a catalyst solution comprising the catalyst and an aprotic solvent.

26. The method of claim 25, wherein the aprotic solvent is dichloromethane, dichlorobenzene, chloroform, pentane, hexane, benzene, toluene, pyridine, or a combination thereof.

27. The method of claims 25 or 26, wherein the catalyst has a concentration in the catalyst solution of 0.01 mg / mL to 50 mg / mL.

28. The method of claim 27, wherein the catalyst has a concentration of 1 mg / mL to 10 mg / mL.

29. The method of any one of claims 22 to 28, wherein at least one R is H, C1- 6alkyl, or C1-6haloalkyl.

30. The method of any one of claims 22 to 29, wherein the plurality of monomers comprises a mixture of alkenes.

31. The method of any one of claims 22 to 29, wherein each R is H, C1-6alkyl, or C1-6haloalkyl.

32. The method of claim 31, wherein each R is H.

33. The method of claims 31 or 32, wherein the plurality of monomers comprises the same alkene.

34. The method of claim 33, wherein the plurality of monomers comprises dicyclopentadiene.

35. The method of claim 34, wherein the plurality of monomers comprises endo- dicyclopentadiene.

36. The method of any one of claims 22 to 35, wherein the cyclic polymer comprises at least 80 polymerized monomer units.

37. The method of any one of claims 22 to 36, wherein the cyclic polymer comprises at least 100 polymerized monomer units.

38. The method of claim 22, further comprising a hydrogenation step to provide a partially saturated cyclic polymer.

39. The method of claim 38, wherein the partially saturated cyclic polymer comprises a structure of Formula (I)().

40. The method of claim 22, further comprising a hydrogenation step to provide a fully saturated cyclic polymer.

41. The method of claim 40, wherein the partially saturated cyclic polymer comprises a structure of Formula (III).

42. A composition comprising a physiologically acceptable medium and at least one cyclic polymer of any one of claims 1 to 21.

43. The composition according to claim 42, wherein the at least one cyclic polymer has a structure of:

44. The composition according to claim 43, wherein n is the range 100 to 10,000.

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