TWI393742B - Polyfarnesenes and compositions comprising thereof - Google Patents

Description

Polyfarnesene and composition containing polyfarnesene

The present invention provides polyfarnesenes and compositions containing polyfarnesene. In particular, these compositions include a farnesene-derived farnesene homopolymer, a farnesene molecule and at least one vinyl monomer-derived farnesene interpolymer. The present invention also provides a method of preparing a polyfarnesene, and a method of using the polyfarnesene of the present invention, such as in a molded article and an adhesive formulation.

Terpenes or isoprenoid compounds are a wide variety of molecular molecules of various molecular weights and can be widely produced from a variety of plants such as amaranth plants and insects such as Swallowtail. Some isoprenoid compounds can also be converted from organic matter such as sugars by microorganisms prepared by microorganisms such as bioengineering techniques. Because terpenes or isoprenoid compounds are available from a variety of renewable resources, these compounds are ideal monomers for the preparation of economical and reusable polymers.

Terpene polymers derived from terpene or isoprenoid compounds are very useful polymeric materials. For example, polyisoprene, polypime hydride and polymeric terpenes (polymerized 1,8 decadiene) can be used to produce paper coatings, adhesives, rubber compounds, and other industrial products. Most existing terpene polymer is generally derived from C ₅ to C ₁₀ terpenoids, such as isoprene, limonene, myrcene, 3-carene, pinene, and ocimene. These terpene monomers may be polymerized or copolymerized with other monomers to form the corresponding terpene homopolymer or copolymer. However, polymers or copolymers of terpene or isoprene having at least 15 carbon atoms are rare or absent. Due to their long chain length, isoprene compounds such as farnesene (farnesene), farnesol (farnesol), nerolidol, valencene, ruthenium, geranyl And elemene can produce polymers or copolymers with unique physical, chemical and biological properties.

There is a need for polymers that are more environmentally friendly and/or more recyclable, such as polymers that can be obtained from natural raw materials to obtain isoprene compounds. In addition, there is a need for a new polymer with unique physical, chemical and biological properties.

An adhesive is a substance (such as an adherend or substrate) that bonds materials together by surface attachment. Pressure sensitive adhesives (PSAs) typically require pressure to create a bond to the adherend so that the material can bond to the adherend. The pressure sensitive adhesive can be a permanent or removable adhesive. Removable pressure sensitive adhesives have been widely used in adhesive-replaceable stickers such as Post-it ^® notes. Pressure sensitive adhesives are generally based on polymers, tackifiers and petroleum materials. Some common pressure sensitive adhesives are based on, for example, natural rubber, synthetic rubbers (such as styrene butadiene rubber and styrene-isoprene-styrene copolymers), polypropylene, polymethacrylates, and poly-α-olefins. polymer.

Hot melt adhesives are typically solid at ambient temperatures and can be heated to melt to bond the adherend or substrate to the material after cooling and curing. Sometimes in use, if the substrate is not heat resistant, the bonded substrate can be removed by remelting the hot melt adhesive. Hot melt adhesives are commonly used in paper products, packaging materials, plywood strips, kitchen countertops, vehicles, tapes, labels, and various disposable items such as disposable diapers, medical mattresses, feminine napkins, and surgical drapes. Generally, these hot melt adhesives are based on a polymer, tackifier and wax. Some common pressure sensitive adhesives are based on, for example, natural rubber, synthetic rubbers (such as styrene butadiene rubber and styrene-isoprene-styrene copolymers), polypropylene, polymethacrylates, and poly-α- a polymer such as an olefin. The desirable property of hot melt adhesives is that no liquid carrier is required, thereby eliminating the costly and solvent potential risks associated with solvent removal.

Polymers derived from terpene or isoprenoid compounds are useful polymeric materials. For example, polyisoprene, polypimehydride, and polymeric terpenes (polymerized 1,8-decadiene) can be used to produce paper coatings, rubber compounds, and other industrial products. However, an adhesive composition consisting of a terpene compound or an isoprene-derived polymer is rare, and a polymer produced from an isoprene compound having at least 15 carbon atoms is more rare.

Although we have a variety of hot melt adhesives and pressure sensitive adhesives available, there is still a need for new adhesive compositions with unique adhesive properties to meet new requirements. Moreover, there is a need for polymers that are more environmentally friendly or more recyclable, such as polymers that can be obtained from natural raw materials to obtain isoprene compounds.

The various aspects disclosed herein can satisfy the above needs. In one aspect, the invention discloses a polyfarnesene composition consisting of one or more polymer molecules having the structure of formula (X'): Wherein n is an integer from 1 to about 100,000; m is an integer from 0 to about 100,000; and X has one or more structures encompassed by the following formulas (I') - (VIII'): Y has the structure of formula (IX'): Wherein R ¹ has the structure of formula (XI): Wherein R ² has the structure of formula (XII): Wherein R ³ has the structure of formula (XIII): Wherein R ⁴ has the structure of formula (XIV): Wherein R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each independently hydrogen, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkane An oxycarbonyl group, an amine carbhydryl group, an alkylamine carbhydryl group, a dialkylamine carbhydryl group, a decyloxy group, a nitrile group or a halogen; wherein the condition is that when m is 0, the content of the compound of the formula (I') Up to about 80% by weight of the total weight of the polyfarnesene and a molecular percentage when m is 1 or greater than 1 and X to Y is from about 1:4 to about 100:1.

In certain embodiments, the compound of formula (II') comprises from about 5 wt.% to 99 wt.%, based on the total weight of the polyfarnesene. In certain embodiments, the compound of formula (III') comprises about 70 wt.% of the total weight of the polyfarnesene. In certain embodiments, at least a portion of one or more compounds having formula (I')-(III'), (V')-(VII'), (XI)-(XIV), and stereoisomers The bond is hydrogenated.

In certain embodiments, m of formula (X') is 0 and X has one or more structures of formula (I') - (IV'). In certain embodiments, m in the formula (X') is 0 and X has one or more structures of the formula (V') - (VIII'). In certain embodiments, the compounds of formula (V') and (VI') comprise from about 1 wt.% to about 99 wt.%, based on the total weight of the polyfarnesene. In certain embodiments, the compound of formula (VII') comprises from about 1 wt.% to 99 wt.%, based on the total weight of the polyfarnesene.

In certain embodiments, m is from about 1 to 100,000 in formula (X'), and R ⁵ , R ⁶ , R ⁷ and R ⁸ are both H. In certain embodiments, m is from about 1 to 100,000 in formula (X'), and R ⁵ is aryl, and R ⁶ , R ⁷ and R ⁸ are both H. In certain embodiments, the aryl group is a phenyl group.

In certain embodiments, m is from about 1 to 100,000 in formula (X') and the polyfarnesene is any farnesene copolymer. In certain embodiments, m is from about 1 to 100,000 in formula (X') and the polyfarnesene is a block farnesene copolymer. In certain embodiments, the block farnesene copolymer consists of one block containing X and two blocks containing Y, wherein the block containing X is located between two blocks containing Y.

In certain embodiments, the polyfarnesene disclosed in the present invention has a _Mw molecular weight greater than about 60,000 Daltons. In certain embodiments, the polyfarnesene disclosed in the present invention has a _Tg of less than about -60 °C. In some implementations, the sum of the values of m and n in formula (X') is greater than 300.

In another aspect, the present invention provides a polyfarnesene obtained by polymerizing β-farnesene in the presence of a catalyst, wherein the cis-1,4 microstructure of the polyfarnesene accounts for the total weight of the polyfarnesene. The ratio is up to 80 wt.%.

In another aspect, the present invention provides a polyfarnesene obtained by polymerizing α-farnesene in the presence of a catalyst, wherein the ratio of the cis-1,4 microstructure of the polyfarnesene to the total weight of the polyfarnesene is The maximum is 1 wt.% to 99 wt.%.

In another aspect, the present invention provides an unsaturated polyfarnesene obtained by polymerizing β-farnesene in the presence of a catalyst; at least a part of double bonds in the unsaturated polyfarnesene in the presence of a hydrogenation reagent are hydrogenated .

In certain embodiments, the farnesene used in the polymerization step disclosed in the present invention is copolymerized with a vinyl monomer to form a farnesene copolymer. In certain embodiments, the vinyl monomer is a phenyl group. In certain embodiments, the farnesene is prepared by a microorganism. In a further embodiment, the farnesene is prepared by a monosaccharide.

In certain embodiments, the hydrogenation reagent used in the hydrogenation reaction step is hydrogen in a hydrogenation catalyst. In certain embodiments, the hydrogenation catalyst is a 10% palladium on carbon catalyst.

In another aspect, the invention provides a method of making polyfarnesene comprising copolymerizing farnesene and at least one vinyl monomer in the presence of a catalyst, said farnesene and vinyl The molar percentage of monomer is from about 1:4 to about 100:1.

In another aspect, the invention provides a method of making a polyfarnesene comprising: causing a microorganism to utilize a monosaccharide to form a farnesene; and, in the presence of the catalyst, co-farnesene and at least one vinyl monomer polymerization. In certain embodiments, the molar percentage of farnesene to vinyl monomer is from about 1:4 to 100:1.

In a specific implementation, at least one vinyl monomer does not contain a terpene. In other real In the application, at least one ethylene monomer is ethylene, an α-olefin, a substituted or unsubstituted vinyl halide, a vinyl ether, an acrylonitrile, an acrylate, a methacrylate, an acrylamide or a methacryl Amine or a combination thereof. In a further implementation, the at least one vinyl monomer is a phenyl group.

In certain embodiments, the catalyst used in the polymerization or copolymerization step is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent or The combination. In other implementations, the catalyst is an organolithium reagent. In a further implementation, the catalyst may further comprise 1,2-bis(dimethylamino)ethane. In a further implementation, the organolithium reagent is n-butyllithium or sec-butyllithium.

In another aspect, the invention discloses a method of preparing a polyfarnesene as referred to herein.

In another aspect, the invention discloses a polymeric composition of polyfarnesene and at least one additive as referred to herein. In a specific implementation, the additive is a filler, a graft initiator, a tackifier, a slip agent, an anti-blocking agent, a plasticizer, an antioxidant, a foaming agent, a foaming agent activator, a UV stabilizer, and an acid. Scavengers, colorants or pigments, coagents, lubricants, antifogging agents, flow aids, processing aids, extrusion aids, coupling agents, crosslinking agents, stability control agents, nucleating agents, surface active agents Agent, flame retardant, antistatic agent or a combination thereof. In a specific implementation, the additive is a filler or a crosslinking agent.

In a specific implementation, the polymer composition provided by the present invention may further comprise a second polymer. In other implementations, the ratio of polyfarnesene to second polymer ranges from 1:99 to 99:1. In a further implementation, the second polymer is a polyolefin, a polyurethane, Polyester, polyamide, styrene polymer, phenolic resin, polyacrylate, polymethacrylate or combinations thereof.

In another aspect, the invention discloses an article comprised of the polyfarnesene or polymer composition of the invention. In certain implementations, the article is a molded article, film, sheet, or foam. In other implementations, the article is a molded article selected from the group consisting of toys, clamps, soft handles, cushion strips, flooring, automotive mats, wheels, casters, furniture and electrical pads, labels, seals, gaskets, and dynamics. Gaskets, car doors, buffer belts, grille components, rocker plates, hoses, linings, office supplies, seals, liners, diaphragms, tubes, covers, stoppers, punches, carrying systems, kitchen appliances, shoes, shoe covers And soles.

In another aspect, the adhesive composition of the present invention comprises a polyfarnesene and a tackifier, and wherein the polyfarnesene has the formula (X') disclosed herein, wherein n is from 1 to about An integer of 100,000; m is an integer from 0 to about 100,000; X is derived from farnesene, and Y is derived from an ethylene monomer. When the condition is m is greater than or equal to 1, the molar percentage of X to Y is 1:4 to 100. Between:1. In certain embodiments, X in formula (X') has one or more of the structures of formula (I')-(VIII') or stereoisomers thereof disclosed herein. In still other embodiments, Y in formula (X') has the structure of formula (IX') or a stereoisomer thereof disclosed herein. In a further implementation, the tackifier is present in an amount from about 5 wt.% to 70 wt.%, based on the total weight of the ingredients of the composition.

In a specific implementation, the adhesive composition disclosed herein comprises an additive selected from the group consisting of plasticizers, oils, waxes, antioxidants, UV stabilizers, colorants and pigments, fillers, glidants, coupling agents, Crosslinkers, surfactants, solvents, and combinations thereof.

In certain implementations, the adhesive compositions disclosed herein may also comprise a second polymer. In other implementations, the second polymer is natural rubber, synthetic rubber, polyacrylate, polymethacrylate, polyalphaolefin, ethylene homopolymer, ethylene copolymer, styrene block copolymer or The combination.

In another aspect, the invention discloses an adhesive composition comprising a polyfarnesene and a tackifier, wherein the polyfarnesene is prepared according to the process disclosed herein. In a specific implementation, the farnesene is alpha-farnesene, beta-farnesene or a combination thereof. In other embodiments, the cis-1,4-microstructure content of the polyfarnesene is up to about 80 wt.% of the total weight of the polyfarnesene. In a further embodiment, a vinyl monomer is present and the polyfarnesene is a farnesene copolymer. In certain embodiments, the composition is a hot melt adhesive composition or a pressure sensitive adhesive composition.

In another aspect, the invention discloses an article in which all or a portion of the substrate coating is an adhesive composition disclosed herein. In a specific implementation, the articles are paper products, packaging materials, plywood strips, kitchen countertops, vehicles, labels, disposable diapers, medical mattresses, feminine sanitary napkins, surgical drapes, tapes, boxes, cartons, trays, medical Equipment or bandages. In other implementations, the article is a tape, box, carton, tray, medical device, or bandage.

In another aspect, the invention discloses a method of attaching an adhesive to another adhesive using the adhesive composition disclosed herein. In some implementations, the first adhesive is the same as the second one. In other implementations, the first adhesive is different from the second one. In a further implementation, the first and second adhesives each comprise metal, wood, paper, plastic, rubber, glass, stone, granite, marble, masonry, porcelain, ceramic, ceramic tile, porcelain, cement, clay , sand, chalk, fabric, cloth, non-woven fabric, leather, or a combination thereof. In a further implementation, the first The form of the second adhesive and the second adhesive are each a sheet, a strip, a tape, a label, a sign, a net, a disc, a sheet, a film or any model.

In another aspect, the invention discloses an adhesive composition comprising a rubber and a tackifier, wherein the tackifier comprises the polyfarnesene disclosed herein. In certain embodiments, the polyfarnesene is present in an amount from about 5 wt.% to 70 wt.%, based on the total weight of the adhesive composition. In other embodiments, the polyfarnesene has a ring and ball softening point greater than or equal to 80 ° C as determined by ASTM 28-67. In a further implementation, the rubber has a Tg of less than 20 °C.

General definition

"Polymer" refers to a polymeric compound formed by the polymerization of the same or different types of monomers. "Polymer" is a generic term that includes "homopolymer," "copolymer," "trimer," and "interpolymer."

"Interpolymer" refers to a polymer formed by the polymerization of at least two different types of monomers. "Interpolymer" is a generic term for a "copolymer" (generally a polymer from which two different monomers are polymerized) and a "trimer" (generally a polymer from which three different monomers are polymerized). . "Interpolymers" also include polymers formed by the polymerization of four or more types of monomers.

"Organic" refers to any organically substituted group regardless of the type of function, one of which has a free valence, such as CH ₃ CH ₂ -, ClCH ₂ -, CH ₃ C(=O)-, 4 - Pyridylmethyl group.

"Hydrocarbon group" means any one formed by removing one hydrogen atom from a hydrocarbon molecule. Monovalent groups (such as ethyl), cycloalkyl (such as cyclohexane) and aryl (such as phenyl).

"Heterocyclyl" refers to any monovalent group formed by the removal of one hydrogen atom from an atom in the ring of a heterocyclic ring.

"Alkyl" or "alkyl group" means derived from a saturated, unbranched or branched aliphatic hydrocarbon obtained by removal of one hydrogen atom having the general formula C _n H _{2n + 1} monovalent radical, n is here for An integer or an integer between 1 and 20 or an integer between 1 and 8. For example, an alkyl group can include, but is not limited to, the following groups: (C ₁ -C ₈ )alkyl groups, such as methyl, ethyl, propyl, isopropyl, 2-methyl-1-propyl ester, 2 -methyl-dipropyl, 2-methyl-1-butyl, 3-methyl-1-butyl ester, 2-methyl-3-butyl ester, 2,2-dimethyl-1- Propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2- Pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3 dimethyl-1-butyl, diethyl-1-butyl, butyl ester, Isobutyl, tert-butyl, pentylene, isopentyl, neopentyl, hexane, heptyl, octyl. Longer alkyl groups include decyl and decyl groups. One alkyl group may be substituted or unsubstituted with one or more suitable substituents. Further, the alkyl group may be a branched group or a linear group. In certain embodiments, the alkyl group contains at least 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

"Cycloalkyl" or "cycloalkyl group" refers to a monovalent group formed by the removal of one hydrogen atom from a non-aromatic, monocyclic or polycyclic ring group containing a hydrocarbon atom in a cycloalkane molecule. group. For example, a cycloalkyl group can include, but is not limited to, the following groups: (C ₃ -C ₇ )cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, saturated cyclodecene And bicyclodecenyl and (C ₃ -C ₇ )cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl, unsaturated cyclodecenyl and bicyclononenyl. One cycloalkyl group may be substituted or unsubstituted with one or more suitable substituents. Further, the cycloalkyl group may be monocyclic or polycyclic. In certain embodiments, the cycloalkyl group contains at least 5, 6, 7, 8, 9, or 10 carbon atoms.

"Aryl" or "aryl group" refers to an organic group formed by the removal of one hydrogen atom from a monocycloalkane or polycyclic aromatic hydrocarbon. There are many examples of aryl groups, including groups of benzene, naphthalene, benzyl or diphenylacetylene, hexaphenyldiamine, phenanthrenyl, anthracenyl, coronenyl and diphenyl. Acetylene phenyl. An aryl group may be substituted or unsubstituted with one or more suitable substituents. Further, the aryl group may be a monocyclic group or a polycyclic group. In certain embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms.

The terms "isoprene" and "isoprenoid compound" are used interchangeably herein to refer to a compound derived from isopentenyl diphosphate.

"Substituted" when used to describe a compound or a partial molecular composition of a compound, means that at least one hydrogen atom of a portion of the molecular composition of the compound or compound is replaced by a second molecular composition. The second molecular composition herein can be any ideal substitute that does not adversely affect the desired activity of the compound. Specific examples of the substituent include some typical compounds mentioned in the present invention and the compounds mentioned in the examples, and halogen, alkyl; heteroalkyl, alkenyl, alkynyl, aryl, heterocyclic aryl, hydroxy, Alkoxy, amine, nitro, thiol, thioether, imido, cyano, decyl, phosphate, phosphine, carboxyl, thiocarbonyl, sulfonyl, sulfonamide, anthracene Base, aldehyde, oxime, alkoxycarbonyl, carbonyl, alkyl halide (such as trifluoromethyl), carbocyclic cycloalkyl, monocyclic or fused or non-fused polycyclic aromatic hydrocarbons (such as cyclopropyl, butyl Or cyclohexylcyclopentyl) or heterocycloalkyl, monocyclic or fused or non-fused polycyclic aromatic hydrocarbons (such as pyrrole, acridine, pyridazine, morpholinyl or thiazinyl); carbocyclic or heterocyclic, single Ring or fused or non-fused polycyclic aryl (such as benzene, naphthalene, pyrrole, indole, furan, thiophene, imidazole, oxazole, isoxazole, azo, triazole, tetrazole, pyrazole, pyridine, quinolin Porphyrin, isoquinolinyl, acridine, pyridinium, pyridazine, pyrimidine, imidazole, benzothiophenyl or furan), amine (primary, secondary or tertiary), ortho-low alkyl O - aryl - aryl, aryl - lower _{alkyl; -CO 2 CH 3; -CONH 2} ; -OCH 2 CONH 2; -NH 2; -SO 2 NH 2; -OCHF 2; -CF 3; - OCF ₃ ; -NH(alkyl); -N(alkyl) ₂ ; -NH(aryl); -N(alkyl)(aryl); -N(aryl) ₂ ;-CHO;-CO( Alkyl); -CO(aryl); -CO ₂ (alkyl) and -CO ₂ (aryl); and these molecular compositions can also be selectively substituted by a fused ring structure or bridged such as -OCH ₂ O- . These substituents may be further substituted by substituents of these groups. All of the chemical groups disclosed herein can be substituted unless otherwise stated.

"Organic lithium reagent" refers to an organolithium compound that directly forms a chemical bond between a carbon atom and a lithium atom. Examples of the organolithium are not limited to these examples, and include lithium lithium, aromatic lithium (such as lithium benzoate), and alkyl lithium (for example, n-butyllithium, sec-butyllithium, t-butyllithium, methyllithium, Lithium isopropyl or other alkyl lithium reagent having 1-20 carbon atoms).

By "substantially free" a composition in a composition is meant to comprise a composition which comprises less than 20 wt.%, less than 10 wt.%, less than 5 wt% of the total composition. %, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.1 wt.%, less than 0.01 wt.%.

The meaning of a polymer being "substantially linear" means that the polymer contains a branch, a star structure or other regular or irregular structural composition in a proportion of less than 20 wt.% of the total amount of the polymer, Less than 10 wt.%, less than 5 wt.%, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.1 wt.%, less than 0.01 wt.%.

The meaning of a polymer as "substantially branched" means that the polymer contains a linear, star-shaped structure or other regular or irregular structural composition in a proportion of less than 20 wt.% of the total amount of the polymer, Less than 10 wt.%, less than 5 wt.%, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.1 wt.%, less than 0.01 wt.%.

The meaning of a polymer being "substantially star-shaped" means that the polymer contains a branch, a linear structure or other regular or irregular structural composition in a proportion of less than 20 wt.% of the total amount of the polymer, Less than 10 wt.%, less than 5 wt.%, less than 3 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.1 wt.%, less than 0.01 wt.%.

In the following, the stated number of disclosures is an approximation regardless of the expression "about" or "approximately". Values may vary by 1, 1%, 5 percent, and sometimes 10 percent or 20 percent. Values within the range are expressly disclosed, regardless of the range of values disclosed in the lower limit R ^L , or the upper limit R ^U . In particular, the values in the following ranges are clearly disclosed: R = R ^L + k * (R ^{U -} R ^L ), where k is a variable between 1% t and 100%, with an increment of 1%, ie k is 1 %, 2%, 3%, 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98%, 99% or 100%. Moreover, any range of values defined by the two R values specified above will also be disclosed.

The compositions disclosed herein contain polyfarnesene and may also contain a tackifier. In other implementations, the compositions disclosed herein do not contain a tackifier. In a further implementation, the compositions disclosed herein contain a tackifier.

In certain embodiments, the polyfarnesene is a farnesene homopolymer, a farnesene interpolymer, or a combination thereof. In a specific implementation, the polyfarnesene is a farnesene homopolymer, and the farnesene homopolymer is derived from at least one farnesene such as alpha-farnesene, beta-farnesene, or a combination thereof. In a specific implementation, the polyfarnesene is a farnesene interpolymer, and the farnesene is interpolymerized. The composition contains at least one farnesene derived from at least one copolymerizable ethylene monomer. In a further implementation, the farnesene interpolymer is derived from styrene and at least one farnesene. In still further embodiments, the farnesene interpolymer is a random, block or alternating interpolymer. In still further implementations, the farnesene interpolymer is a 2-block, 3-block or other multi-block interpolymer.

In certain embodiments, the farnesene homopolymer is prepared by polymerization of beta-farnesene in the presence of a catalyst suitable for the polymerization of an olefin such as ethylene, styrene or isoprene. In other embodiments, the farnesene homopolymer comprises one or more constituent units having the formula (I), (II), (III), (IV) or a stereoisomer thereof or a combination thereof: Wherein R ¹ has the structure of formula (XI): Wherein R ² has the structure of formula (XII): Wherein m, n, l and k are each an integer, respectively, ranging from 1 to about 5,000, 1 to about 10,000, 1 to about 50,000, 1 to about 100,000, 1 to about 200,000, 1 to about 500,000, 2 to about 10,000, 2 to about 50,000, 2 to about 100,000, 2 to about 200,000 or 2 to about 500,000. In certain embodiments, m, n, l and k are each an integer from 1 to about 100,000, respectively. In other implementations, m, n, l and k are each an integer from 2 to 100,000, respectively.

In a specific implementation, the farnesene homopolymer comprises at least one unit component of formula (I) wherein the value of m is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (II) wherein the value of n is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (III) wherein the value of 1 is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (IV) wherein the value of k is greater than 300, 500 or 1000.

In certain embodiments, the farnesene homopolymer comprises at least one unit component of formula (I) and at least one formula (II) wherein the sum of the values of m and n is greater than 300, 500 or 1000. In certain embodiments, the farnesene homopolymer comprises at least one unit component of formula (I) and at least one formula (III) wherein the sum of the values of m and l is greater than 300, 500 or 1000. In certain embodiments, the farnesene homopolymer comprises at least one unit of formula (II) and at least one unit of formula (III) wherein the sum of the values of n and l is greater than 300, 500 or 1000. In still further implementations, the farnesene homopolymer comprises at least one unit of formula (I), at least one formula (II), and at least one unit of formula (III), wherein the sum of the values of m, n and l is greater than 300 , 500 or 1000. In still further embodiments, the farnesene homopolymer comprises at least one unit of formula (I), at least one formula (II), at least one formula (III), and at least one unit of formula (IV), wherein m, n, The sum of the values of l and k is greater than 300, 500 or 1000. In still further implementations, one or more of the constituent units of the farnesene homopolymer disclosed herein have Formula (I), (II), (III) or (IV) arranged in any order.

In a specific implementation, the preparation of the farnesene homopolymer is accomplished by polymerization of alpha-farnesene in the presence of a catalyst suitable for the polymerization of olefins. In other embodiments, the farnesene homopolymer comprises one or more constituent units having the formula (V), (VI), (VII), (VIII) or a stereoisomer thereof or a combination thereof: Wherein R ³ has the structure of formula (XIII): Wherein R ⁴ has the structure of formula (XIV): Wherein m, n, l and k are each an integer, respectively, ranging from 1 to about 5,000, 1 to about 10,000, 1 to about 50,000, 1 to about 100,000, 1 to about 200,000, 1 to about 500,000, 2 to about 10,000, 2 to about 50,000, 2 to about 100,000, 2 to about 200,000 or 2 to about 500,000. In other implementations, m, n, l and k are each an integer from 2 to 100,000, respectively.

In a specific implementation, the farnesene homopolymer comprises at least one unit component of formula (V) wherein the value of m is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (VI), wherein the value of n is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (VII) wherein the value of l is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (VIII) wherein the value of k is greater than 300, 500 or 1000.

In certain embodiments, the farnesene homopolymer comprises at least one unit component of formula (V) and at least one formula (VI) wherein the sum of the values of m and n is greater than 300, 500 or 1000. In certain embodiments, the farnesene homopolymer comprises at least one unit component of formula (V) and at least one formula (VII) wherein the sum of the values of m and l is greater than 300, 500 or 1000. In other embodiments, the farnesene homopolymer comprises at least one unit component of formula (VI) and at least one formula (VII) wherein the sum of the values of n and l is greater than 300, 500 or 1000. In still further implementations, the farnesene homopolymer comprises at least one unit of formula (V), at least one formula (VI), and at least one unit of formula (VII), wherein the sum of the values of m, n and l is greater than 300 , 500 or 1000. In still further embodiments, the farnesene homopolymer comprises at least one unit of formula (V), at least one formula (VI), at least one formula (VII), and at least one formula (VIII), wherein m, n, The sum of the values of l and k is greater than 300, 500 or 1000. In still further embodiments, one or more of the constituent units of the farnesene homopolymer disclosed herein have the formula (V), (VI), (VII), or (VIII) arranged in any order.

In certain embodiments, the farnesene homopolymer is prepared by the polymerization of alpha-farnesene with beta-farnesene in the presence of a catalyst suitable for the polymerization of olefins. In other embodiments, the farnesene homopolymer comprises one or more constituent units having the formulae (I), (II), (III), (IV), (V), (VI) disclosed herein, (VII) or (VIII) or a stereoisomer thereof or a combination thereof. In still further implementations, one or more of the constituent units of the farnesene homopolymer disclosed herein have the formula (I), (II) disclosed herein, (III), (IV), (V), (VI), (VII) or (VIII), and arranged in any order.

In certain embodiments, the farnesene homopolymer comprises two or more constituent units having two different formulas, each of which is a formula (I), (II), (III) disclosed herein, (IV), (V), (VI), (VII), (VIII) or a stereoisomer thereof or a combination thereof. In other embodiments, the formula of these farnesene homopolymers can be expressed as: A _x B _y , wherein x and y are each at least 1, and wherein A and B each have formula (I), (II), ( III), (IV), (V), (VI), (VII) or (VIII), and A and B are different in formula. In a further implementation, x and y are each greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40 or greater. In some implementations, A and B are joined together in a substantially linear manner, as opposed to a substantially branched or star-shaped manner. In other implementations, A and B are randomly distributed along the farnesene homopolymer chain. In other implementations, A and B form a farnesene homopolymer having a segmental structure, such as AA--A-BB--B, in two "segments". In other embodiments, A and B may be alternately distributed along the farnesene homopolymer chain to form a farnesene homopolymer having a variable structure, such as AB, ABA, ABAB, ABABA or the like.

In certain embodiments, the farnesene homopolymer comprises three or more constituent units having three different formulas, each of which is a formula (I), (II), (III) disclosed herein, (IV), (V), (VI), (VII), (VIII) or a stereoisomer thereof or a combination thereof. In other embodiments, the formula of these farnesene homopolymers can be expressed as: A _x B _y C _z , wherein each of x, y, and z is at least 1, and wherein each of A, B, and C has formula (I) , (II), (III), (IV), (V), (VI), (VII) or (VIII), and the formulas of A, B, and C are different. In a further implementation, x, y, z are each greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40 or greater. In some implementations, A, B, and C are joined together in a substantially linear manner, as opposed to a substantially branched or star-shaped manner. In other implementations, A, B, and C are randomly distributed along the farnesene homopolymer chain. In other implementations, A, B, and C form a farnesene homopolymer having a segmental structure, such as AA--A-BB--B-CC--C, in three "segments". In other embodiments, A, B, and C may be alternately distributed along the farnesene homopolymer chain to form a farnesene homopolymer having a variable structure, such as ABCAB, ABCABC, or the like.

In a specific implementation, the polyfarnesene is a farnesene interpolymer. In other embodiments, the farnesene homopolymer is prepared by polymerizing at least one farnesene with a vinyl monomer in the presence of a catalyst suitable for catalyzing the polymerization of an olefin with a vinyl monomer. In a further implementation, the disclosed farnesene interpolymer comprises: (a) one or more constituent units having the formulae (I), (II), (III), (IV) disclosed herein; (b) One or more constituent units having the formula (IX): Wherein p is an integer ranging from 1 to about 5,000, from 1 to about 10,000, from 1 to about 50,000, from 1 to about 100,000, from 1 to about 200,000, from 1 to about 500,000, from 2 to about 10,000, from 2 to about 50,000, Up to about 100,000, 2 to about 200,000 or 2 to about 500,000. And R ⁵ , R ⁶ , R ⁷ and R ⁸ are each hydrogen, an organic group, or a functional group. In certain embodiments, R ⁵ , R ⁶ , R ⁷ and R ⁸ do not contain 4-8 carbons. A monovalent hydrogen group of an atom. In certain embodiments, R ⁵ , R ⁶ , R ⁷ and R ⁸ are not alkyl groups containing from 4 to 8 carbon atoms.

In certain embodiments, the disclosed farnesene interpolymers comprise: (a) one or more constituent units having the formulae (V), (VI), (VII), and (VIII) disclosed herein; (b) One or more constituent units having the formula (IX). In other implementations, the disclosed farnesene interpolymers comprise: (a) one or more constituent units having the formulae (I), (II), (III), (IV) disclosed herein, (V), (VI), (VII), and (VIII); (b) one or more constituent units having the formula (IX).

In certain embodiments, the farnesene interpolymer disclosed herein is a random interpolymer. In other embodiments, the farnesene interpolymer disclosed herein is a random interpolymer in which the vinyl monomer and farnesene composition can be randomly and randomly distributed. In still further implementations, the farnesene interpolymer disclosed herein is a random interpolymer, wherein the vinyl monomer and the farnesene composition are randomly distributed, and the farnesene composition has Formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and (XI) are distributed in a random, alternating or block manner.

In certain embodiments, the farnesene interpolymer disclosed herein is an alternating interpolymer. In other implementations, the farnesene interpolymer disclosed herein is an alternating interpolymer in which the vinyl monomer and the farnesene composition are alternately distributed. In still further implementations, the farnesene interpolymer disclosed herein is an alternating interpolymer, wherein the vinyl monomer and the farnesene composition are alternately distributed, and the farnesene composition has the formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII) and (XI), and are distributed in a random, alternating or block manner.

In a specific implementation, the farnesene interpolymer contains one or more quantities of two inlays The segment component, the constituent unit of the first block component has the formula (I), (II), (III), (IV) or a combination thereof; and the constituent unit of the second block component has the formula (IX). In a further implementation, the farnesene interpolymer contains one or more amounts of two block components, the constituent units of the first block component having formula (V), (VI), (VII), (VIII) Or a combination thereof; the constituent unit of the second block component has the formula (IX). In still further embodiments, there is a first block and a second block, wherein the first block is located between the second blocks. In still further embodiments, each of the second blocks contains a unit composition derived from styrene. In certain embodiments, the farnesene block interpolymer is polystyrene-polyfarnesene-diblock polyfarnesene, polystyrene-polyfarnesene-3 block polyfarnesene or The combination.

In certain embodiments, the formula of the farnesene interpolymer can be expressed as: P _x Q _y , wherein x and y are both at least 1, and wherein P has the formula (IX), Q has the formula (I), II), (III), (IV), (V), (VI), (VII) or (VIII). In a further implementation, x and y are each greater than 1, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40 or greater. In some implementations, Ps and Qs are connected together in a substantially linear manner, as opposed to a substantially branched or star-shaped manner. In other implementations, Ps and Qs are randomly distributed along the farnesene interpolymer chain. In other implementations, Ps and Qs form a farnesene interpolymer having a block structure in the form of two or more blocks or segments, such as PP--P-QQ---Q or PP-- P-QQ---QP---PP. In other implementations, Ps and Qs may be alternately distributed along the farnesene homopolymer chain to form a farnesene interpolymer having a variable structure, such as PQ, PQP, PQPQ, PQPQP or the like. In certain implementations, each Q has the formula A _x B _y or A _x B _y C _z disclosed herein.

In a specific implementation, the polyfarnesene molecule disclosed in the present invention has a content of the formula (I) of up to 85 wt.%, 80 wt.%, 70 wt.%, 60 in the total weight of the polyfarnesene. Wt.%, 50 wt.%. In other embodiments, the composition of formula (III) in the polyfarnesene molecule disclosed herein comprises at least 10 wt.%, 15 wt.%, 20 wt.% of the total weight of the polyfarnesene. 25 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, or 99 wt. %. In a further implementation, the polyfarnesene molecule disclosed in the present invention has a content of the formula (II) in a proportion of 1 wt.% to 99 wt.%, 5 wt% of the total weight of the polyfarnesene. .%-99 wt.%, 10 wt.%-99 wt.%, or 15 wt.%-99 wt.%. In a further implementation, the content of the composition of formula (IV) in the polyfarnesene molecule disclosed in the present invention accounts for up to 0.1 wt.%, 0.5 wt.%, and 1 wt% of the total weight of the polyfarnesene. %, 2 wt.%, 3 wt.%. In certain embodiments, the polyfarnesene disclosed herein is substantially free of compositions of formula (I), (II), (III) or (IV).

In the specific implementation project, the polyfarnesene molecules disclosed in the present invention have the formula (V), (VI), (VII) or (VIII) up to 1 wt.%, 5 wt.%, 10 wt. %, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, or 90 wt.%, depending on the polyfarnesene The total weight depends. In other embodiments, the polyfarnesene molecules disclosed in the present invention have the formula (V), (VI), (VII) or (VIII) up to 1 wt.%, 2 wt.%, 3 wt.%. , 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%. The specific ratio depends on the total weight of the polyfarnesene. In a further implementation, the ratio of the content of formula (V), (VI), (VII) or (VIII) in the polyfarnesene molecule disclosed in the present invention to the total weight of the polyfarnesene is 1 wt.%-99 wt.%, 5 wt.%-99 wt.%, 10 wt.%-99 wt.%, or 15 wt.%-99 wt.%. In certain embodiments, the polyfarnesene disclosed herein is substantially free of compositions of formula (V), (VI), (VII) or (VIII).

In other implementations, the sum of the values of m and n is greater than 250, 300, 500, 750, 1000, or 2000. In a further implementation, the sum of the values of m and l disclosed herein is greater than 250, 300, 500, 750, 1000 or 2000. In a specific implementation, the sum of the values of n and l disclosed herein is greater than 250, 300, 500, 750, 1000 or 2000. In certain implementations, the sum of the values of m, n, l, and k disclosed herein is greater than 250, 300, 500, 750, 1000, or 2000.

In a specific implementation, the polyfarnesene disclosed herein has a number average molecular weight (M _n ), a weight average molecular weight (M _w ), and a viscosity average molecular weight (M _z ) greater than 60,000 Daltons, 100,000 Daltons. 200,000 Daltons, 300,000 Daltons, 500,000 Daltons, 750,000 Daltons, 1,000,000 Daltons, 1,500,000 Daltons or 2,000,000 Daltons. In other embodiments, the present invention is disclosed polyfarnesene of M _n, M _w or M _z value is less than 10,000,000 daltons, 5,000,000 daltons, 000,000 daltons, 750,000 daltons or 500,000 daltons .

In some implementations, the polyfarnesene has a property of at least a glass transition temperature (T _g ) of less than -55 ° C, -60 ° C, -65 ° C, -70 ° C, -75 ° C, measured according to ASTM D7426-08 "Standard Test Method for Assignment of the DSC Procedure for Determining _Tg of a Polymer oran Elastomeric Compound", see the accompanying references of the present invention.

In certain embodiments, the compound of formula (I) comprises up to 80 wt.% of the total weight of the polyfarnesene. In other implementations, the sum of the values of m, n, and l is greater than 300. In a further embodiment, at least a portion of one or more compositions having formula (I), (II), (III), (IV), (IX), (XI), (XII), and stereoisomers The double bond is hydrogenated.

In certain embodiments, the polyfarnesene is a farnesene interpolymer. In a further implementation, the farnesene interpolymer disclosed herein contains one or more composition units derived from farnesene, and the content of these farnesene is at least throughout the farnesene interpolymer. 5 mole percent, 10 mole percent, 15 mole percent, 20 mole percent, 30 mole percent, 40 mole percent, 50 mole percent, 60 mole percent, 70 mole percent, 80 mole percent or 90 mole percent. In still further embodiments, the farnesene interpolymer disclosed herein contains one or more units of the composition derived from a vinyl monomer, and the content of these vinyl monomers is interpolymerized throughout the farnesene At least 5 mole percent, 10 mole percent, 15 mole percent, 20 mole percent, 30 mole percent, 40 mole percent, 50 mole percent, 60 mole percent, 70 mole percent, 80 mole percent or 90 mole percent.

In a specific implementation, the polyfarnesene is composed of one or more polymer molecules, wherein the polymer molecules have the following formula (X'): Wherein n is an integer ranging from 1 to about 5,000, 1 to about 10,000, 1 to about 50,000, 1 to about 100,000, 1 to about 200,000, or 1 to about 500,000; m is an integer ranging from 0 to about 5,000, 0 to about 10,000, 0 to about 50,000, 0 to about 100,000, 0 to about 200,000 or 0 to about 500,000; X is derived from farnesene, and Y is derived from a vinyl monomer.

In certain embodiments, X has one or more of the formulae (I')-(VIII') described below:

In a specific implementation, Y has the formula (IX'): Wherein R ¹ , R ² , R ³ and R ⁴ are the compositions defined in the invention; and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each H, an organic group or a functional group.

Usually, the polyfarnesene contains a mixture of polymer molecules, each of which has the formula (X'), wherein each of m and n is a certain value. The average and distribution of the n or m values disclosed herein depends on various factors such as the molar ratio of the starting materials, the reaction time and temperature, the presence or absence of chain termination reagents, the amount of initiator, and the polymerization conditions. The farnesene interpolymer having the formula (X') may include unreacted comonomer, but even if the density of the comonomer is not extremely small or undetectable, its density is usually small. The degree of polymerization is determined by the values of m and n, which affect the proportion of the polymer product. In certain embodiments, n is an integer ranging from 1 to about 5,000, from 1 to about 10,000, from 1 to about 50,000, from 1 to about 100,000, from 1 to about 200,000, from 1 to about 500,000, not integers, in the range of 0 to about 5,000, 0 to about 10,000, 0 to about 50,000, 0 to about 100,000, 0 to about 200,000 or 0 to about 500,000. In other implementations, the range of n can range from 1 to about 5000, 1 to large, respectively. Approximately 2500, 1 to about 1000, 1 to about 500, 1 to about 100, 1 to about 50; m can range from 0 to about 5000, from 0 to about 2500, from 0 to about 1000, from 0 to about 500, 0, respectively. Up to about 100 or 0 to about 50. One of ordinary skill in the art will recognize that the range of amplification of n and m needs to be well thought out and that its value should be within the scope of the present disclosure.

In certain embodiments, formula (X') includes two terminal groups, as shown below: Wherein the designation (*) in the formula represents a terminal group which may be changed or unchanged in the polymer of different polyfarnesene, depending on various factors, such as the molar ratio of the raw materials. The presence or absence of a chain terminating reagent, the amount of the initiator, and the state of the particular polymerization process at the end of the polymerization reaction.

In certain embodiments, Xs and Ys in formula (X') are linked in a substantially linear manner. In other implementations, Xs and Ys in formula (X') are joined in a substantially branched manner. In a further implementation, Xs and Ys in formula (X') are joined in a substantially star-like manner. In a further implementation, each of Xs and Ys is at least one block distributed along the polymer chain, thereby forming a di-block, a tri-block or a plurality of block farnesene interpolymers, The interpolymer has at least one X block and one Y block. In a further implementation, X and Y are randomly and randomly distributed along the polymer chain, thereby forming a random farnesene interpolymer. In a further implementation, these X and Y groups are alternately distributed along the polymer chain, thereby forming an alternating farnesene interpolymer.

In certain embodiments, the farnesene content of the farnesene interpolymer disclosed in the present invention accounts for more than 1.5 mole%, 2.0 mole%, 2.5 mole% of the total weight of the farnesene interpolymer, 5 mole%, 10 mole%, 15 mole% or 20 mole%. In its In his practice, the farnesene content of the farnesene interpolymer disclosed in the present invention accounts for less than 90 mole%, 80 mole%, 70 mole%, 60 mole of the total weight of the farnesene interpolymer. %, 50 mole%, 40 mole% or 30 mole%.

In certain embodiments, the vinyl monomer content of the farnesene interpolymer disclosed herein is greater than 1.5 mole%, 2.0 mole%, 2.5 mole% of the total weight of the farnesene interpolymer. , 5 mole%, 10 mole%, 15 mole% or 20 mole%. In other embodiments, the farnesene content of the farnesene interpolymer disclosed in the present invention accounts for less than 90 mole%, 80 mole%, 70 mole%, 60% of the total weight of the farnesene interpolymer. Mole%, 50 mole%, 40 mole% or 30 mole%.

In certain embodiments, the molar percentage of farnesene to vinyl monomer is from about 1:5 to 100:1. In other implementations, the molar percentage of X to Y ranges from 1:4 to 100:1, 1:3.5 to 100:1, 1:3 to 100:1, 1:2.5 to 100:1, or 1:2 to 100:1. In certain embodiments, m is a number of one or greater, and the molar percentage of X to Y is from about 1:4 to 100:1.

In a specific implementation, the polyfarnesene molecule disclosed in the present invention has a formula (I') in an amount of up to 85 wt.%, 80 wt.%, 70 wt.%, 60 in the total weight of the polyfarnesene. Wt.%, 50 wt.%. In other embodiments, the composition of the polyfarnesene molecule of the present invention having the formula (III') accounts for at least 10 wt.%, 15 wt.%, 20 wt% of the total weight of the polyfarnesene. %, 25 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.%, 95 wt.%, or 99 wt .%. In a further implementation, the polyfarnesene molecule disclosed in the present invention has a content of the formula (II') in a proportion of the total weight of the polyfarnesene of from 1 wt.% to 99 wt.%, 5 Wt.%-99 wt.%, 10 wt.%-99 wt.%, or 15 wt.%-99 wt.%. In a further implementation, the invention The composition of the disclosed polyfarnesene molecule having the formula (IV') is at most 0.1 wt.%, 0.5 wt.%, 1 wt.%, 2 wt.%, based on the total weight of the polyfarnesene. 3 wt.%. In certain embodiments, the polyfarnesene disclosed herein is substantially free of compositions of formula (I'), (II'), (III') or (IV').

In the specific implementation project, the polyfarnesene molecules disclosed in the present invention have the formula (V'), (VI'), (VII') or (VIII') at most 1 wt.%, 5 wt.%. 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, or 90 wt.%. The specific ratio depends on the total weight of the polyfarnesene. In other implementations, the polyfarnesene molecules disclosed in the present invention have a formula (V'), (VI'), (VII') or (VIII') of up to 1 wt.%, 2 wt.%. , 3 wt.%, 5 wt.%, 10 wt.%, 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, or 60 wt.%. The specific ratio depends on the total weight of the polyfarnesene. In a further embodiment, the polyfarnesene molecules disclosed herein have a formula (V'), (VI'), (VII') or (VIII') in the total weight of the polyfarnesene. The proportion is 1 wt.%-99 wt.%, 5 wt.%-99 wt.%, 10 wt.%-99 wt.%, or 15 wt.%-99 wt.%. In certain embodiments, the polyfarnesene disclosed herein is substantially free of compositions of formula (V'), (VI'), (VII') or (VIII').

Any of the vinyl groups containing a polymer capable of polymerizing with farnesene, i.e., -CH=CH _{2 ,} can be used as the vinyl monomer to prepare the farnesene interpolymer disclosed herein. The vinyl monomers disclosed herein include ethylene, i.e., CH ₂ =CH ₂ . In a specific implementation, the vinyl monomer has the formula (XV): Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each H, an organic group or a functional group.

In certain embodiments, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) is at least one organic group. In a further implementation, the organic group is a hydrocarbyl group, a substituted hydrocarbyl group, a heterocyclic group or a substituted heterocyclic group. In a specific embodiment, R ⁵ , R ⁶ , R ⁷ and R ⁸ having the formula (IX), (IX′) or (XV) may each be hydrogen, alkyl, cycloalkyl, aryl or cycloalkenyl. , alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, aminecarbamyl, alkylamine carbonyl, dialkylamine carbonyl, decyloxy, nitrile or halogen. Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each may be hydrogen, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclic, alkoxy, aryloxy, carboxy, Alkoxycarbonyl, amine mercapto, alkylamine carbonyl, dialkylamine carbonyl, decyloxy, nitrile or halogen. In a specific implementation, R ⁵ having the formula (IX), (IX') or (XV) is an aryl group, and R ⁶ , R ⁷ and R ⁸ are both H. In a further embodiment, R ⁵ having formula (IX), (IX') or (XV) is phenyl, and R ⁶ , R ⁷ and R ⁸ are both H.

In a specific implementation, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) is hydrogen. In a specific embodiment, R ⁵ , R ⁶ , R ⁷ and R ⁸ having the formula (IX), (IX') or (XV) are all hydrogen. In a further embodiment, R ⁵ having formula (IX), (IX') or (XV) is a hydrocarbyl group, and R ⁶ , R ⁷ and R ⁸ are both H. In still further embodiments, the hydrocarbyl group is an alkyl group, a cycloalkyl group, or an aryl group. In still further embodiments, none of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) contains or does not contain an alkenyl, cycloalkyl or alkynyl group. In still further embodiments, none of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) has or does not contain a hydrocarbyl group, a substituted hydrocarbyl group, a heterocyclic group or a substituent. Heterocyclic group.

In a specific implementation, at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX′) or (XV) is halogen, O, N, S, P or their Combined functional groups. Examples of suitable functional groups are not limited, and examples include hydroxy, alkoxy, aryloxy, amino, nitro, thiol, thioether, imino, cyano, amino, phosphorylated (-P (=O)(O-alkyl) ₂ ,-P(=O)(O-aryl) ₂ , or -P(=O)(O-alkyl))O-aryl), hypophosphite -P(=O)(O-alkyl)alkyl, -P(=O)(O-aryl)alkyl, -P(=O)(O-alkyl)aryl or -P(=O (O-aryl)aryl], carboxyl, thiocarbonyl, sulfonium (-S(=O) ₂ alkyl or -S(=O) ₂ aryl), sulfonamide [-SO ₂ NH ₂ , -SO ₂ NH(alkyl), -SO ₂ NH(aryl), -SO ₂ N(alkyl) ₂ , -SO ₂ N(aryl) ₂ , or -SO ₂ N(aryl)(alkyl) , keto, aldehyde, ester, carbonyl, amino (primary, secondary or tertiary) -CO ₂ CH ₃ , -CONH ₂ , -OCH ₂ CONH ₂ , -NH ₂ , -OCHF ₂ , -OCF ₃ , -NH(alkyl), -N(alkyl) ₂ , -NH(alkyl), -N(alkyl)(aryl), -N(aryl) ₂ , -CHO, -CO(alkyl) , -CO(aryl), -CO ₂ (alkyl) or -CO ₂ (aryl). In certain embodiments, the functional group is or contains an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an amine carbaryl group, an alkylamino group, a dialkylamino group, a decyloxy group, a nitrile or a halogen. In other embodiments, none of R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) contains or does not contain a functional group. In other embodiments, R ⁵ , R ⁶ , R ⁷ and R ⁸ having formula (IX), (IX') or (XV) are neither or not containing an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, Aminocarboxamyl, alkylamino, dialkylamino, decyloxy, nitrile or halogen.

In certain embodiments, the ethylene monomer is a substituted or unsubstituted olefin such as ethylene or styrene, an alkyl halide, a vinyl ether, an acrylonitrile, an acrylate, a methacrylate, an acrylamide, a methacryl Amine or a combination thereof. In other implementations, the vinyl monomer is ethylene, an alpha olefin, or a combination thereof. Non-limiting examples of suitable alpha-olefins include styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1 , 5-hexadiene and combinations thereof.

In certain embodiments, the vinyl monomer is an aryl group such as styrene, alpha-methyl styrene or 2-vinylbenzene. Additional examples include functionalized vinyl aryl groups such as those disclosed in U.S. Patent No. 7,041,761, which is incorporated herein by reference.

In certain embodiments, the farnesene interpolymer disclosed herein is derived from at least one farnesene and at least one olefin monomer. Olefins refer to unsaturated hydrocarbyl compounds having at least one carbon-carbon double bond. In a particular implementation, the olefin is a conjugated diene. Any olefin can be used in the practice described herein and in accordance with the catalyst selected. Non-limiting examples of certain suitable olefins include C _2-20 aliphatic compounds and C _8-20 aromatic compounds containing unsaturated ethylenic compounds and cyclic vinyl compounds such as butene, cyclopentene, dicyclopentane The dienes and norbornenes, including norbornenes, include, but are not limited to, substituted-C _1-2 hydrocarbyl or cyclic hydrocarbon groups-5, 6-substituted norbornene compounds. Non-limiting examples of olefins suitable for use include these olefins and mixtures thereof with _C4-40 diolefins.

Non-limiting examples of certain suitable olefin or alpha-olefin monomers include styrene, ethylene, propylene, isobutylene, butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosenedioic acid, 3-methyl-1 -butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene, ethylene cyclohexane, Norbornene, ethylbornene, cyclopentene, cyclohexene, dicyclopentadiene, octene, C _4-40 olefins, including but not limited to 1,3-butadiene, 1,3-pentadiene , 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C _4-40 α-olefins and the like. In a particular implementation, the olefin monomer is propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, or a combination thereof.

The farnesene interpolymer disclosed in the present invention may be derived from farnesene and styrene. The farnesene interpolymer may also comprise at least one C _2-20 olefin, at least one C _4-18 diolefin, at least one alkenyl benzene or a mixture thereof. Suitable unsaturated comonomers for the polymerization of farnesene, including ethylenically unsaturated monomers, polyenes (such as conjugated or non-conjugated dienes, alkenylbenzenes and similar compounds) . These comonomers include C _2-20 olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-decene and the like. Other suitable monomers include styrene, halogen or alkyl substituted styrene, vinyl benzene cyclobutane, 1,4 hexadiene, 1,7-octadiene, and cyclic olefins such as cyclopentene, cyclohexene and Cyclooctene.

Some suitable non-conjugated diene monomers may be linear, branched or cyclic hydrocarbon dienes containing from 6 to 15 carbon atoms. Non-limiting examples of certain suitable non-conjugated dienes include linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9- a decadiene, a branched acyclic diene such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1, a mixture of 7-octadiene and dihydromyricene and dihydroocinene, a monocyclic alicyclic diene such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; , 5-cyclooctadiene and 1,5-cyclododediene, and polycyclic alicyclic fusions and bridged dienes such as tetrahydroindene, tetrahydroindene, dicyclopentadiene Bicyclo(2,2,1)-heptabromo-2,5-diene; alkene, alkyl, cycloalkenyl and cycloalkyl norbornene, such as 5-methyl-2-norbornene (MNB) , 5-propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylene-2-nor Norbornene, 5-vinyl-2-norbornene, and norbornene. Among the typical diene compounds used to prepare ethylene propylene propylene rubber (EPDM), the most preferred diene is 1,4-hexadiene. (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and bicyclo Pentadiene (DCPD). In a specific implementation, the diene is 5-ethylidene-2-norbornene (ENB) or 1,4-hexadiene (HD). In other implementations, the farnesene interpolymer is not derived from polyenes such as dienes, trienes, tetraenes, and the like.

In certain embodiments, the farnesene interpolymer is farnesene, styrene, and C _2-20 olefins. Non-limiting examples of suitable olefins include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In certain embodiments, the farnesene interpolymer disclosed herein is not derived from ethylene. In certain embodiments, the farnesene interpolymers disclosed herein are not derived from one or more C _2-20 olefins.

In a specific implementation, the vinyl monomer does not contain terpene. In other embodiments, the vinyl monomer does not contain a terpene selected from the group consisting of isoprene, dipentene, alpha-pinene, beta-pinene, terpinene, limonene (double Pentene, decene, cumene, decene, 3-decene, decene, juniperene, caryophyllene, myrcene, ocimene, cedarene, bisabolene, zingiberene, hop Alkene, citronellol, linalool, geraniol, nerol, dentate, terpineol, D-terpineol-(4), dihydrocarvyl alcohol, nerolidol, gold Acacia alcohol, eucalyptol, citral, D- is citronella, carvone, D-humenone, piperone, carvone, erythrophylline, celery, sandalene, vitamin A, Rosin acids and their compositions. In a further implementation, the vinyl monomer does not contain isoprene.

The farnesene interpolymer can be functionalized by combining with functional groups in at least one polymer structure. Typical functional groups may include ethylenically unsaturated monocarboxylic and dicarboxylic acid groups, ethylenically unsaturated monocarboxylic and biscarboxylic anhydride functional groups and salts thereof ester. Such functional groups can also be transferred to the farnesene interpolymer. Alternatively, the functional group is a copolymerized farnesene having an optional additional monomer to form a farnesene interpolymer, a functional comonomer, and other optional comonomers. The skilled person can apply any known method of transferring functional groups. One of the special functional groups available is maleic anhydride.

In this functionalized farnesene interpolymer, the number of functional groups may vary. In certain embodiments, these functional groups comprise at least 1.0 wt.%, 2.5 wt.%, 5 wt.%, 7.5 wt.%, 10 wt.%, based on the total weight of the farnesene interpolymer. In other embodiments, these functional groups comprise less than 40 wt.%, 30 wt.%, 25 wt.%, 20 wt.%, 15 wt.% of the total weight of the farnesene interpolymer.

Any catalyst which can catalyze the polymerization or copolymerization of farnesene can be used to prepare the polyfarnesenes mentioned in the present invention. Some non-limiting examples of suitable catalysts include organolithium reagents, Ziegler-Natta catalysts, Kaminsky catalysts, and metallocene catalysts. In certain embodiments, the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, or a combination thereof.

In certain implementations, the catalyst can also include a cocatalyst. In a further implementation, the cocatalyst is a hydride, an alkyl or aryl group of a metal, or a combination thereof. In a further implementation, the metal is aluminum, lithium, zinc, tin, cadmium, antimony, magnesium.

In certain implementations, the catalyst is an organolithium reagent. Any organolithium catalyst capable of performing olefin polymerization can be used. Some non-limiting examples of suitable organolithium reagents include n-butyllithium, sec-butyllithium or tert-butyllithium. Some non-limiting examples of suitable Lewis bases include tetramethylethylenediamine (TMEDA), pentamethyldiethylenetriamine (PMDTA) or talonine. Some of the disclosed organolithium reagents can be found in Zvi Rappoport et al. "The Chemistry of Organolithium Compounds", Part 1 (2004) and Volume 2 (2006), both of which are incorporated into the literature references attached to the present invention.

In certain embodiments, the catalyst is a mixture of an organolithium reagent and a Lewis base. Any Lewisine which can depolymerize the organolithium reagent to increase the solubility and activity of the organolithium reagent can be used. The polymeric organolithium reagent typically has a combination of lithium on a plurality of carbon atoms and a carbon combined on a plurality of lithium atoms. Some non-limiting examples of suitable Lewis bases include tetramethylethylenediamine, pentamethyldiethylenetriamine or oleolin. Including 1,2-bis(dimethylamino)ethane (also known as tetramethylethylenediamine or TMEDA), N,N,N',N',N"-pentamethyldiethylenetriamine (PMDTA) And cinnabarin and combinations thereof. In some embodiments, the catalyst is a Ziegler-Natta catalyst. Typically, the Ziegler-Natta catalyst can be heterologous or homologous. In some implementations, The Ziegler-Natta catalyst used in the polymerization of the polyfarnesene disclosed in the present invention is a heterogeneous Ziegler-Natta catalyst. Some useful Ziegler-Natta catalysts can be found in J. Boor "Ziegler-Natta Catalysts and Polymerizations," (Saunders College Publishing, pp. 1-687 (1979); and Malcolm P. Stevens, Introduction to Polymer Chemistry ( Polymer Chemistry, an Introduction ) (Oxford University Press, Third Edition, p. 236-245 (1999)), both of which are incorporated herein by reference.

The heterogeneous Ziegler-Natta catalyst generally comprises (1) a transition metal compound containing an element of Group IV-VIII of the Periodic Table of Elements; (2) an organometallic compound containing a metal element of Groups I-III of the Periodic Table of the Elements. When an organometallic compound is considered as a cocatalyst or agonist, the transition metal compound can be referred to as a catalyst. Transition metal compounds usually contain one Metals with one or more anions and ligands. Some non-limiting examples of suitable metals include titanium, vanadium, chromium, molybdenum, zirconium, iron, cobalt. Some non-limiting examples of suitable anions and ligands include halides, oxyhalides, alkoxy groups, acetoacetone, cyclopentadiene, and benzene.

Any cocatalyst or activator capable of ionizing the organometallic complex to form a living olefin polymerization catalyst can be used herein. Typically, the organometallic cocatalyst is a hydride, an alkane compound or an aromatic metal compound of aluminum, lithium, zinc, tin, cadmium, bismuth, magnesium. Some non-limiting examples of suitable cocatalysts include aluminoxanes (methylaluminoxane (MAO), PMAO, ethylaluminoxane, diisobutylaluminoxane), alkyl aluminum compounds (trimethylaluminum, Triethyl aluminum, diethyl aluminum chloride, trimethyl aluminum, triisobutyl aluminum, trioctyl aluminum), diethyl zinc, di(isobutyl) zinc, di(n-hexyl) zinc, Ethyl zinc (tert-butanol) and the like. Other suitable cocatalysts include acid salts containing non-nucleophilic anions. These compounds generally include large ligands attached to aluminum or boron. Non-limiting examples of such suitable compounds include lithium tetrakis(pentafluorophenyl)boron, lithium tetrakis(pentafluorophenyl)aluminum, aniline tetrakis(pentafluorophenyl)borate, and the like. Some non-limiting examples of suitable cocatalysts include organoboron, including boron and one or more alkyl, aryl or aralkyl groups. Other non-limiting examples of suitable such compounds include substituted and unsubstituted trialkyl and triaryl boron salts such as tris(pentafluorophenyl)borane, triphenylboron, tri-n-octylboroboron. Salt and so on. These and other suitable boron-containing cocatalysts or activators can be found in the disclosures of U.S. Patent Nos. 5,153,157, 5,198,401 and 5,241,025, the disclosure of which is incorporated herein by reference.

In a particular implementation, the Ziegler-Natta catalyst can be impregnated in the support material. Some useful support materials can be found in Malcolm P. Stevens' Introduction to Polymer Chemistry (Oxford University Press, Third Edition, page 251 (1999), see this The accompanying reference to the invention.

The support material is typically a material that is inserted or substantially inserted into the olefin polymerization reaction. Non-limiting examples of suitable support materials include magnesium chloride, magnesium oxide, aluminum oxide such as activated alumina and aluminum microgels, barium, magnesium, diatomaceous earth, fuller's earth, clay, aluminosilicate, porous rare earth halides, and Oxyhalides and compositions thereof. The surface area of the support material is between 5 m ² /g and 450 m ² /g, depending on the surface area inspection described by S. Brunauer, PHEmmett and E. Teller BET (Brunauer-Emmet-Teller), the contents of which can be seen in 1938. Journal of the American Chemical Society [60 (309)], see the references of the present invention. In certain implementations, the support material has a surface area of from about 10 m ² /g to about 350 m ² /g. In a further implementation, the support material has a surface area of from about 25 m ² /g to about 300 m ² /g.

The support material has an average particle size of about 20 to 300 microns, 20 to 250 microns, 20 to 200 microns, 20 to 150 microns, 20 to 120 microns, 30 to 100 microns, or 30 to 90 microns. The compressive bulk density or tamped bulk density of the support material ranges from about 0.6 to 1.6 grams per milliliter, from 0.7 to 1.5 grams per milliliter, from 0.8 to 1.4 grams per milliliter or from 0.9 to 1.3 grams per milliliter.

In a particular embodiment, the catalyst used in the present invention is or contains a Kaminsky catalyst, also referred to as a homologous Ziegler-Natta catalyst. The Kaminsky catalyst can also be used to produce the polyfarnesene of the present invention having specific structural and physical properties. A description of some Kaminsky catalysts or homologous Ziegler-Natta catalysts can be found in Malcolm P. Stevens' Introduction to Polymer Chemistry (Oxford University Press (1999) Third Edition (page 245-251). And John Scheirs and Walter Kaminsky, "Metallocene-Based Polyolefins: Preparation, Properties, and Technology", Volume 1 (Wiley, 2000), both articles can be found in the references attached to the present invention.

In certain embodiments, the Kaminsky catalysts disclosed herein that are suitable for the preparation of polyfarnesene comprise a transition metal atom between the ferrocene ring structures. In other implementations, the formula of the Kaminsky catalyst can be expressed as Cp ₂ MX ₂ , wherein M is a transition metal (such as Zr, Ti, or Hf); X is a halogen (such as Cl), an alkyl group, or a combination thereof; Cp ferrocene group. In a further implementation, the Kaminsky catalyst has the formula (XVI): Wherein Z is an optional divalent bridging group, typically C(CH ₃ ) ₂ , Si(CH ₃ ) ₂ , or CH ₂ CH ₂ ; R is H or an alkyl group; M is a transition metal (eg, Zirconium, titanium or hafnium Hf), X is a halogen (such as chlorine), an alkyl group or a combination thereof.

In some non-limiting examples, the Kaminsky catalyst has the formula (XVI): Wherein M is Zr, Hf or Ti.

In certain embodiments, the catalyst is a Kaminsky catalyst. The cocatalyst can be any of the cocatalysts disclosed herein. In a specific implementation, the cocatalyst is methylaluminoxane (MAO). A MAO oligomeric compound having the general formula (CH ₃ AlO) _n wherein n is 1-10. MAO has several functions: it replaces a chlorine atom with a methyl group to alkylate a metallocene precursor; and produces a catalytically active ion pair Cp ₂ MCH ₃ ⁺ /MAO ^- , in which a cationic group participates in polymerization The reaction, while MAO ^- acts as a weak anion. Some non-limiting examples of MAO include equations (XX) through (XXI):

In a particular implementation, the catalyst used to produce the farnesene interpolymer disclosed herein can be or include a metallocene catalyst. Some metallocene catalysts can be found in the "Modification of a Ziegler-Natta catalyst with a metallocene catalyst and its olefin polymerization behavior" by Tae Oan Ahn et al. From Polymer Engineering and Science, 39(7) , 1257 (1999); and John Scheirs and Walter Kaminsky, "Preparation, Properties, and Related Technologies of Metallocene-Polyolefins," Volume 1 (Wiley, 2000) Both articles can be found in the references attached to the present invention.

In other implementations, the metallocene catalyst comprises a transition metal complex having a core comprising transition metals such as nickel and palladium and a large neutral ligand containing alpha-diimine or diketimine. In a further implementation, the metallocene catalyst has the formula (XXII): Wherein M is nickel or palladium.

In certain embodiments, the catalyst used in the present invention may be or include a metallocene catalyst with a monoanionic bidentate ligand. A non-limiting example of a metallocene catalyst has the formula (XXIII):

In other embodiments, the catalyst used in the present invention may be or include an ion-containing metallocene catalyst with a pyridine located between the two imine groups and which may be given a tricoordinate ligand. A non-limiting example of a metallocene catalyst has the formula (XXIV):

In certain embodiments, the catalyst used in the present invention may be or include a metallocene catalyst comprising a ruthenium catalyst system based on zirconium. A non-limiting example of a metallocene catalyst has the formula (XXV):

In certain embodiments, the farnesene homopolymers disclosed herein can be prepared by the following various steps: (a) the microorganism produces a farnesene using a monosaccharide or non-fermented carbon feedstock; and (b) the polymerization of farnesene in the presence of the catalyst disclosed herein.

In a particular implementation, the farnesene interpolymer disclosed herein can be prepared by the following steps: (a) the microorganism utilizes a monosaccharide or non-fermented carbon feedstock to form farnesene; and (b) disclosed in the present invention In the presence of a catalyst, the farnesene and at least one vinyl monomer are copolymerized.

In certain embodiments, the polyfarnesene disclosed herein is prepared by the polymerization of β-farnesene in the presence of a catalyst, wherein the cis-1,4 microstructure of the polyfarnesene is polycondensed. The proportion of the total weight of the olefin is up to 80 wt.%, 75 wt.%, 70 wt.%, 65 wt.% or 60 wt.%. In certain embodiments, the beta-farnesene will be copolymerized with the vinyl monomer to form a farnesene copolymer. In other implementations, the vinyl monomer is a phenyl group. In a further implementation, the farnesene copolymer is a block copolymer.

In a specific implementation, the polyfarnesene disclosed in the present invention is prepared by polymerization of α-farnesene in the presence of a catalyst, wherein the cis-1,4 microstructure of the polyfarnesene accounts for polyfarnesene. The ratio of the total weight ranges from 1 wt.% to 99 wt.%, 10 wt.% to 99 wt.%, 20 wt.% to 99 wt.%, 30 wt.% to 99 wt.%, 40 wt.% -99 wt.%, 50 wt.%-99 wt.%, 1 wt.%-99 wt.%, 1 wt.%-90 wt.%, 1 wt.%-80 wt.%, 1 wt.% -70 wt.% or 1 wt.%-60 wt.%. In certain embodiments, alpha-farnesene will be copolymerized with a vinyl monomer to form a farnesene copolymer. In other implementations, the vinyl monomer is a phenyl group. In a further implementation, the farnesene copolymer is a block copolymer.

In certain embodiments, the polyfarnesene disclosed herein can be cooked by a skilled person. Any one of the known hydrogenating agents performs a partial or total hydrogenation reaction. For example, a saturated polyfarnesene can be prepared by two aspects (a) in the presence of a catalyst, by the polymerization of farnesene provided by the present invention to form a polyfarnesene; and (b) the presence of a hydrogenation reagent At least a portion of the double bonds in the unsaturated polyfarnesene are hydrogenated. In certain embodiments, farnesene will be copolymerized with the vinyl monomers disclosed herein to form a farnesene copolymer. In other implementations, the vinyl monomer is a phenyl group. In a further implementation, the farnesene copolymer is a block copolymer. In a further embodiment, the farnesene is alpha-farnesene, beta-farnesene or a combination thereof.

In a specific implementation, the hydrogenating agent is hydrogen present in a hydrogenation catalyst. In certain embodiments, the hydrogenation catalyst is palladium, palladium on carbon, platinum, platinum oxide, Ru(PPh ₃ ) ₂ Cl ₂ , Raney nickel, or a combination thereof. In one implementation, the catalyst is a palladium catalyst. In another implementation, the hydrogenation catalyst is 5% palladium on carbon. In a further implementation, the catalyst is 10% palladium on carbon in a high pressure reactor and the hydrogenation reaction can be continued until completion. Typically, after completion of the translation, the reaction mixture is washed with water, concentrated and dried to give the corresponding hydrogenated product. In addition, any reducing agent that reduces the C=C bond to the CC bond is also used. For example, polyfarnesene can be hydrogenated by hydrazine to form the corresponding hydrogenated product in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate. . The disclosure of the reduction reaction with hydrazine can be found in the literature by Imada, which is incorporated in the journal J. Am. Chem. Soc (2005, 127, pp. 14544-14545, see the literature attached to the present invention.

In certain embodiments, at least a portion of the C=C double bond in the polyfarnesene is reduced to the corresponding C-C bond at room temperature and in the presence of a catalyst and hydrogen. In other implementations, One or more of formula (I')-(III'), (V')-(VII'), (XI)-(XIV), and stereoisomers in the presence of a catalyst and hydrogen at room temperature At least a portion of the double bonds in the bulk compound are reduced to the corresponding CC bonds. In a further implementation, the hydrogenation catalyst is 10% palladium on carbon.

In a specific implementation, the vinyl monomer is a phenyl group. In certain embodiments, the farnesene is alpha-farnesene, beta-farnesene, or a combination thereof. In other embodiments, the farnesene is prepared by a microorganism. In a further implementation, the farnesene is prepared by a monosaccharide or non-fermented carbon feed.

Farnesene

The farnesene can be derived from any starting material or prepared by any skilled artisan using any known method. In certain embodiments, the farnesene may be derived from a chemical feedstock such as petroleum or coal or obtained by chemical synthesis. In other implementations, the farnesene can be prepared by fractional distillation of petroleum or coal. In a further implementation, the farnesene is obtained by any chemical synthesis method. Non-limiting examples of suitable chemical synthesis methods include the dehydration of nerolidol using a phosphonium halide in pyridine, and the "(E,Z)-α-, (Z,Z)-α- and (Z) of Anet EFLJ can be seen. ) synthesis of [beta farnesene (synthesis of (E, Z) -α -, (Z, Z) -α-, and (Z) -β-farnesene) "( Journal" Aust.J.Chem ", 23(10) 2101-2108 Page 1970, see the literature attached to the invention.

In some embodiments, farnesene can be obtained or prepared directly from naturally occurring terpenes, and naturally occurring terpenes can be obtained from a variety of plants, such as Copaifera langsdorfii, Euphorbia, insects. Such as swallowtail butterflies, leaf beetles, termites and pine leaf bees; and marine life such as algae, sponges, corals, molluscs and fish.

Cooper gum trees or gum trees are also known as diesel trees and kerosene trees. Become a local language Kupa'y, cabismo, and copaúva. The wood and leaves of the gum tree can produce a large amount of terpene. Typically, gum trees produce 30-40 liters of terpenes per year.

Terpene oils are also available from conifers and eucalyptus plants. Conifers belong to the Cypress or Cypress class of the plant kingdom. They are usually cone-shaped seed plants with vascular tissues. Most of the conifers are trees and some are shrubs. Some non-limiting examples of suitable coniferous plants include cedar, cypress, douglas fir, fir, alfalfa, kauris (Araucaria), larch, pine, redwood, spruce, and yew. Euphorbia or Spurges is a genus of plants that is widely distributed throughout the world and belongs to the Euphorbiaceae family. There are about 2,160 species of Euphorbia, which is one of the largest plant species in the plant kingdom.

The farnesene is a sesquiterpene which is a compound of a larger class among terpenes. Terpenes are a large and diverse class of compounds including semidecene, monoterpene, sesquiterpene, diterpene, sesquiterpene, triterpene, tetradecene and polydecene. Thus, farnesene can be isolated or derived from terpene oil and used in the present invention.

In a specific implementation, farnesene can be prepared from biological materials. In other embodiments, the farnesene can be obtained from a prepared, available renewable carbon feedstock. In a further embodiment, the farnesene is prepared by cells which are capable of producing farnesene using a carbonaceous feedstock under suitable conditions.

Any carbon feedstock capable of being converted to one or more isoprene compounds can be used in the present invention. In certain implementations, the carbon feedstock is a sugar or non-fermented carbon feedstock. The sugar can be any sugar material known to the skilled person. In a particular implementation, the sugar is a monosaccharide, a disaccharide, a polysaccharide, or a combination thereof. In other implementations, the sugar is a single sugar (monosaccharide or disaccharide). Some non-limiting examples of suitable monosaccharides include glucose, galactose, Mannose, fructose, ribose, and combinations thereof. Some non-limiting examples of suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof. In still other embodiments, the single sugar is sucrose. In a specific implementation, the composition of the bioengineered fuel can be obtained from a polysaccharide. Some non-limiting examples of suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.

Sugar substances suitable for the production of farnesene can be found in a wide variety of crops or raw materials. Non-limiting examples of suitable crops or materials include sugar cane, bagasse, miscanthus, sugar beet, sorghum, alfalfa, switchgrass, barley, hemp, nettle, potato, sweet potato, tapioca, sunflower, fruit, syrup, whey or skim milk. , corn, straw, grain, wheat, wood, paper, straw, cotton, various cellulosic waste and other biomass. In particular implementations, suitable crops or materials include sugar cane, sugar beets and corn. In other implementations, the sugar source is sugar cane juice or molasses.

The non-fermented carbon raw material is a carbon raw material in which an organism cannot convert it into ethanol. Some non-limiting examples of suitable carbon materials include acetic acid and glycerin.

In a specific implementation, the farnesene can be prepared in an apparatus capable of biosynthesizing _C15 isoprene. The facility may comprise any construct that utilizes microorganisms to prepare _C15 isoprenoids such as alpha-farnesene, beta-farnesene, nerolidol or farnesol. In certain implementations, the biological production equipment can include one or more of the cells disclosed in the present invention. In other embodiments, the biological production device comprises cells comprising at least one _C15 isoprene, the isoprene content of at least 1 wt.%, 5 wt.% of the total weight of the cell culture. , 10 wt.%, 20 wt.%, 30 wt.%. In a further implementation, the biological production facility includes a fermentation unit containing one or more of the cells disclosed in the present invention.

Any fermenter that can provide a stable, optimal growth and breeding environment for cells or bacteria can be used in the present invention. In certain embodiments, the fermentor can include a cell culture device containing one or more of the cells disclosed in the present invention. In other implementations, the fermentor can include a cell culture device that is capable of biologically producing farnesyl pyrophosphate (FPP). In a further implementation, the fermentor can include a cell culture device that is capable of producing isopentenyl diphosphate (IPP) in a biological manner. In other embodiments, the biological production apparatus comprises a cell culture device containing at least one _C15 isoprene, the isoprene content of at least 1 wt.%, 5 wt.% of the total weight of the cell culture. , 10 wt.%, 20 wt.%, 30 wt.%.

The facility may also comprise any construction that can produce an oil composition or an oil additive from a _C15 isoprene such as alpha-farnesene, beta-farnesene, nerolidol or farnesol. This configuration may comprise a reaction apparatus for hydrogenating α-farnesene, β-farnesene, nerolidol or farnesol. Any reaction apparatus capable of converting ethanol to an olefin under conditions known to the skilled person can be used in the present invention. The reaction unit can include a dehydrogenation catalyst as disclosed herein. In certain implementations, the construction can further comprise a mixer, a vessel, and a mixture of dewatered products obtained from the dewatering step.

The disclosure of the biosynthesis step for the preparation of _C15 isoprene can be found in U.S. Patent No. 7,399,323, U.S. Patent Application Publication No. US 2008/0274523, and International Patent Nos. WO 2007/140339 and WO 2007/139924, all of which are incorporated herein In the references.

--farnesene

The structure of α-farnesene is expressed as follows: It can be found in different biological materials, including ants' Du Fu glands and apple and pear skins, but is not limited to these examples. From a biochemical point of view, α-farnesene is produced by FPP under the action of α-farnesene synthase. Non-limiting examples of some suitable nucleotide sequences encoding the synthetase include (DQ309034, Pyrus communis cultivar d'Anjou) and (AY182241, Malus domestica). See Plantous et al., Planta (2004, 219(1) : pp. 84-94).

--farnesene

The structure of β-farnesene is expressed as follows: It can be found in different biological materials, including aphids, essential oils, and peppermint oil, but is not limited to these examples. In some plants such as wild potatoes, β-farnesene is synthesized as a natural insect repellent. From a biochemical point of view, β-farnesene is produced by FPP under the action of β-farnesene synthase. Some non-limiting examples of suitable nucleotide sequences encoding the synthetase can be found in (AF024615; Mentha x piperita) and (AY835398; Artemisia annua). See Picaud et al., Phytochemistry 66(9) : 961-967 (2005).

Farnesol

The structure of farnesol is expressed as follows: It can be found in different biological materials, including insects and essential oils, of which essential oils are derived from citronella, neroli, cyclamen, lemongrass, tuberose and rose. From a biochemical point of view, farnesol is produced by FPP under the action of a hydroxylase such as farnesol synthase. Some non-limiting examples of suitable nucleotide sequences encoding the synthetase can be found in (AF529266; Zea mays) and (YDR481C; Saccharomyces cerevisiae). See Song, L., Applied Biochemistry and Biotechnology 128 : 149-158 (2006).

Orange flower tertiary alcohol

The structure of nerolidol is expressed as follows: It can be found in different biological materials, including insects and essential oils, of which essential oils come from orange blossom, ginger, jasmine, lavender, tea tree, lemongrass. From a biochemical point of view, nerolidol is produced by FPP under the action of a hydroxylase such as nerolidol synthase. A non-limiting example of some suitable nucleotide sequences encoding the synthetase can be found in the AF529266 sequence in Zea mays (maize, gene gene tps1).

The farnesol and neroliol disclosed in the present invention can be converted into α-farnesene, β-farnesene or a mixture of the two by dehydrogenation with a dehydrogenating reagent or an acid catalyst. Any dehydrogenating agent or acid catalyst capable of converting ethanol to an olefin can be used in the present invention. Some non-limiting examples of suitable dehydrogenating or acid catalysts include phosphonium chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.

General procedure for preparing polyfarnesene

The polymerization of farnesene or the copolymerization of farnesene with an olefin can be carried out at a relatively wide range of temperatures. In a specific implementation, the temperature of the polymerization reaction is -30. °C-280 ° C, 30 ° C -180 ° C or 60 ° C -100 ° C. The partial pressure range of ethylene comonomer is 15 psig (0.1 MPa) - 50,000 psig (245 MPa), 15 psig (0.1 MPa) - 25,000 psig (172.5 MPa), 15 psig (0.1 MPa) - 10,000 psig (69 MPa) , 15 psig (0.1 MPa) - 5,000 psig (34.5 MPa) or 15 psig (0.1 MPa) - 1,000 psig (6.9 MPa).

The density of the catalysts disclosed in the present invention for producing polyfarnesene depends on a number of factors. In certain implementations, the density can range from 0.01 micromoles per liter to 100 micromoles per liter. The length of the polymerization depends on the type of reaction process, the density of the catalyst, and other factors. Usually, the polymerization time is from several minutes to several hours.

A non-limiting example of the polymerization of a farnesene homopolymer in solution is outlined below: a farnesene such as β-farnesene can be added to a solvent such as cyclohexane to form a solution in the reaction apparatus. The reaction device can be placed under a nitrogen or argon atmosphere. The solution can be dried by a drying agent such as a molecular sieve. A catalyst such as an organolithium reagent can be added to the reaction apparatus, and then the reaction apparatus is heated to a certain temperature level until all or most of the farnesene has been reacted. The farnesene homopolymer can be precipitated from the reaction mixture and dried in a vacuum oven.

A non-limiting example of the polymerization of a farnesene interpolymer in solution is outlined below: a farnesene such as β-farnesene can be added to a solvent such as cyclohexane, thereby placing it in a nitrogen or argon atmosphere. A solution is formed in the reaction apparatus in a gaseous environment. The farnesene solution can be dried by a drying agent such as a molecular sieve. In a second reaction apparatus placed under a nitrogen or argon atmosphere, a 10% cyclohexane styrene solution was prepared and dried under a desiccant such as a molecular sieve. After raising the temperature to a certain level, styrene can be polymerized with a catalyst such as an organolithium reagent until all or most of the styrene has been reacted. Then, the solution is dissolved The liquid is transferred to a second reaction unit. The reaction is allowed to proceed until all or most of the farnesene has been reacted. Then, a dichlorosilane coupling agent (for example, dimethyldichloromethane in 1,2-dichloroethane) is added to the second reaction apparatus to form a farnesene interpolymer.

Polyfarnesene

The polyfarnesene can be used to prepare polyfarnesene compositions for various uses. In certain embodiments, the polyfarnesene composition comprises the polyfarnesene disclosed herein and a second polymer or at least one additive. In a specific implementation, the polyfarnesene contains a second polymer. In other implementations, the polyfarnesene composition does not contain a second polymer. The second polymer can be an ethylene polymer or a polyfarnesene, a non-ethylene polymer or a polyfarnesene or a combination thereof. Some non-limiting examples of ethylene polymers and polyfarnesene can be found in Malcolm P. Stevens' Introduction to Polymer Chemistry (Oxford University Press, Third Edition, pages 17-21 and 167-279 (1999), please See the accompanying references to the present invention. Non-limiting examples of suitable second polymers include polyolefins, polyurethanes, polyesters, polyamides, styrenic polymers, phenolic resins, polyacrylates, polymethacryls. Ester or a combination thereof.

In a specific implementation, the ratio of the polyfarnesene to the second polymer ranges from about 1:99 to 99:1, 1:50 to 50:1, 1:25 to 25:1, or 1:10 to 10: 1.

In certain embodiments, the second polymer is a polyolefin [eg, polyethylene, polypropylene, ethylene/α-olefin interpolymer, copolymer of ethylene and propylene, and ethylene and vinyl acetate copolymer (EVA)], Polyurethane, polyester, polyamide, styrene polymer (eg polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene), phenolic resin, polyacrylic acid Ester, polymethacrylate or a combination thereof. In some embodiments, the second polymer is a copolymer of polyethylene, polypropylene, polystyrene, vinyl acetate and ethylene, Poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene) or a combination thereof. The second polymer can be mixed with the farnesene interpolymer before it is added to the polyfarnesene composition. In some implementations, the second polymer can be added directly to the polyfarnesene composition without mixing with the farnesene interpolymer.

The weight ratio of the polyfarnesene to the second polymer in the polymer composition ranges from 1:99 to 99:1, 1:50 to 50:1, 1:25 to 25:1, 1:10- 10:1, 1:9-9:1, 1:8-8:1, 1:7-7:1, 1:6-6:1, 1:5-5:1, 1:4-4: 1, 1:3-3:1, 1:2-2:1, 3:7-7:3 or 2:3-3:2.

In certain implementations, the second polymer is a polyolefin. Any polyolefin which is partially or completely compatible with the polyfarnesene can be used. Non-limiting examples of suitable polyolefins include polyethylene, polypropylene, polybutene (e.g., polybutene-1), polypentene-1; polyhexene-1; polyoctene-1; polydecene-1 Poly-3-methylbutene-1; poly-4-methylpentene-1; polyisoprene, polybutadiene, poly-1,5 diene; interpolymers derived from olefins, Olefins and other polymers derived therefrom such as polyvinyl chloride, polystyrene, polyurethane interpolymers, and the like, and mixtures thereof. In certain embodiments, the polyolefin is a homopolymer such as polyethylene, polypropylene, polybutene, polypentene-1, poly-3-methylbutene-1, poly-4-methylpentene- 1. Polyisoprene, polybutadiene, poly-1,5 diene, polyhexene-1, polyoctene-1 and polydecene-1.

Non-limiting examples of suitable polyethylenes include ultra low density polyethylene (ULDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE). ), high molecular weight high density polyethylene (HMW-HDPE), ultra high molecular weight polyethylene (UHMW-PE), and combinations thereof. Non-limiting examples of polypropylene phosphonium chloride include low density polypropylene (LDPP), high density polypropylene Alkene (HDPP), refractory hard polypropylene (HMS-PP), and combinations thereof. In certain embodiments, the second polymer is or contains refractory strength polypropylene (HMS-PP), low density polyethylene (LDPE), or a combination thereof.

In certain embodiments, the polyfarnesene compositions disclosed herein comprise at least one additive to achieve improved and/or controlled processability, appearance, physical, chemical, and/or mechanical properties of the polyfarnesene composition. The purpose of the feature. In certain embodiments, the polyfarnesene composition does not contain an additive. Any plastic additive known to those skilled in the art can be used in the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable additives include fillers, graft initiators, tackifiers, slip agents, antiblocking agents, plasticizers, antioxidants, blowing agents, blowing agent activators (eg zinc oxide, stearic acid) Acid zinc, etc.), UV stabilizers, acid scavengers, colorants or pigments, active adjuvants (such as triallyl cyanurate), lubricants, antifogging agents, glidants, processing aids, extrusion aids Agent, coupling agent, crosslinking agent, stability control agent, nucleating agent, surfactant, flame retardant, antistatic agent or a combination thereof.

The total amount of the additive accounts for more than 0-80%, 0.001%-70%, 0.01%-60%, 0.1%-50%, 1%-40% or 10% of the total weight of the polymer composition. -50%. Some of the additives can be found in the Plastics Additives Handbook by Zweifel Hans et al., Hanser Gardner Publications, Fifth Edition (2001), see the literature attached to the present invention.

The disclosed polyfarnesene composition may also contain a release agent. In certain implementations, the disclosed polyfarnesene compositions may not contain a release agent. Release agents can be used to prevent unnecessary bonding of layers of material made from polyfarnesene, especially when stored, produced, and applied with some pressure and heat. Any release agent known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of antiblocking agents include minerals (e.g., clays, chalk, calcium carbonate), synthetic silica gel (e.g., SYLOBLOC ^® available from Grace Davison Company), a natural quartz SUPER FLOSS ^® diatomaceous earth commercially available from Celite Corporation Company), talc (e.g., commercially available from Luzenac company OPTIBLOC ^®), zeolites (e.g., SIPERNAT ^® available from Degussa Corporation), aluminosilicates (e.g., SILTON ^® available from Mizusawa Industrial Chemicals, Inc.), limestone (e.g. CARBOREX ^® available from Omya Corporation), spherical polymer Particles (such as EPOSTAR ^® poly (methyl-methacrylate) particles, purchased from Nippon Shokubai and TOSPEARL ^® , resin particles purchased from GE Silicones), waxes, guanamines (such as erucamide, oleic acid) Indoleamine, stearin, decyl behenate, bis- stearylamine, decyl sorbate, erucamide, and other anti-slip agents, molecular sieves, and combinations thereof. Mineral particles can create a physical separation between the articles to reduce stickiness, but the release agent moves to the surface of the material to limit the viscosity of the surface. In use, the release amount of the polymer composition may exceed 0-3 wt%, 0.0001 wt%, 0.001-1 wt%, or 0.001-0.5 wt% in the total amount of the polymer composition. Some anti-adhesive agents can be found in the Handbook of Plastic Additives by Zweifel Hans et al., Hanser Gardner Publications (2001), 5th Edition, Chapter 7, pages 585-600, see the accompanying documents of the present invention.

The disclosed polyfarnesene composition may also contain a plasticizer. Generally, a plasticizer is a compound that increases the elasticity and lowers the proportional conversion temperature of the polymer. Any plasticizer known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of plasticizers include mineral oils, phthalates, adipic acid, alkylbenzene sulfonates, sebacates, benzoic acid, chlorinated paraffins, citric acid, epoxides, glycol ethers, and Its esters, glutaric acid salts, hydrocarbon oils, isobutyrate, oleate, pentaerythritol Alcohol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleate, fatty acid salts, sulfonamides, trimellitate and pyromellitate, biphenyl derivatives, stearic acid Salts, difurfurates, fluoroplasticizers, parabens, isocyanate adducts, polycyclic aromatic compounds, natural product derivatives, nitriles, decyloxy plasticizers, tar-based products, Thioether and combinations thereof. In use, the release amount in the polymer composition may exceed 0-15 wt%, 0.5-10 wt%, or 1-5 wt% in the total amount of the polymer composition. Some plasticizers are disclosed in George Wypych, Handbook of Plasticizers, published by ChemTec Publishing (2004), see the literature section of the present invention.

In certain embodiments, the polyfarnesene compositions disclosed herein comprise a release agent that prevents oxidation of the polymer and organic additives in the polymer composition. Any antioxidant known to those of ordinary skill in the art can be incorporated into the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable antioxidants include aromatic amines or hindered amines such as alkyl diphenylamines, phenyl-α-naphthylamines, alkyl or aryl alkyl substituted phenyl-α-naphthylamines, alkyl pairs An alkyl or aralkyl group such as phenylenediamine or tetramethyldiaminodiphenyl hydrazine; phenols, 6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tri ( 3',5'-di-tert-butyl-4'-hydroxybenzyl)benzene; tetra[(methylene (3,5 di-tert-butyl-4-hydroxyphenyl)] methane (eg IRGANOX, Ciba Geigy, New York) ^TM 1010 product); acryl nonylphenol, octadec-3,5-di-tert-butyl-4-hydroxystyrene (such as IRGANOXTM 1076 from Ciba Geigy, New York); phosphate and phosphazene; hydroxylamine, benzofuran Ketone derivatives and combinations thereof. In use, the antioxidant in the polymer composition may exceed 0-5 wt%, 0.0001-2.5 wt%, 0.001-1 wt% or 0.001-0.5 wt in the total amount of the polymer composition. %. Some antioxidants can be found in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications (2001), Fifth Edition, Chapter 1, page 1-140, with reference to the literature attached to the present invention.

In other implementations, the polyfarnesene compositions disclosed herein may also comprise a UV stabilizer that prevents or reduces polymer degradation by UV radiation. Any UV stabilizer known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable UV stabilizers include xylene ketone, benzotriazole, aryl ester, oxalic anilide, acrylate, formamidine, carbon black, hindered amine, nickel quencher, hindered amine, phenolic Antioxidants, metal salts, zinc compounds, and combinations thereof. In use, the UV stabilizer in the polymer composition can exceed 0-5 wt%, 0.01-3 wt%, 0.1-2 wt%, or 0.1-1 wt% in the total amount of the polymer composition. Some UV stabilizers can be found in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications (Cincinnati, Ohio, 2001), Fifth Edition, Chapter 2, pages 141-426, with reference to the literature attached to the present invention.

In a further implementation, the polyfarnesene compositions disclosed herein may also comprise a color former or pigment that can alter the macroscopic appearance of the polymer. Any colorant or pigment known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable color formers or pigments include inorganic pigments such as metal oxides (e.g., iron oxide, zinc oxide, titanium dioxide, mixed metal oxides, carbon black), organic pigments such as ruthenium, ruthenium, azo And monoazo compounds, linaloamines, benzimidazolone, BONA lakes, diketopyrrole-pyrroles, dioxazines, bisazo compounds, diarylamine compounds, flavanes, oxime, iso Dihydroazaindol, iso-dihydroazaindole, metal complex, monoazo salt, naphthol, β-naphthol, naphthol AS, naphthol lake, perylene, purple ring ketone Perinones), turnip, dermatan, quinine, Iridone and quinophthalone and combinations thereof. In use, the colorant or pigment content of the polymer composition may exceed 0-10 wt%, 0.1-5 wt%, or 0.25-2 wt% in the total amount of the polymer composition. Some colorants can be found in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications (2001), Fifth Edition, Chapter 15, pages 813-882, with reference to the literature attached to the present invention.

The disclosed polyfarnesene composition may also contain a filler for adjusting the polyfarnesene, particularly a filler which adjusts the volume, weight, cost and/or technical properties of the polyfarnesene. Any filler known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, strontium, glass, gas phase cerium oxide, mica, ash, feldspar, aluminosilicate, calcium citrate, Alumina, hydrated alumina such as aluminum trihydrate, glass microspheres, ceramic microspheres, thermoplastic plastic microspheres, barite, wood flour, glass fiber, carbon fiber, marble dust, cement dust, magnesium oxide, magnesium hydroxide, Cerium oxide, zinc oxide, barium sulfate, titanium dioxide, titanate, and combinations thereof. In certain embodiments, the filler is barium sulfate, talc, calcium carbonate, barium, glass, fiberglass, alumina, titanium dioxide, or combinations thereof. In certain embodiments, the filler is talc, calcium carbonate, barium sulfate, fiberglass, or a combination thereof. In use, the filler content of the polymer composition can be greater than 0-80 wt%, 0.1-60 wt%, 0.5-40 wt%, 1-30 wt%, or 10-40 wt% of the total weight of the polymer composition. %. The disclosure of some suitable fillers can be found in U.S. Patent No. 6,103,803 and the publication of Plastics Additives Handbook by Zweifel Hans et al., Hanser Gardner Publications (2001), Fifth Edition, Chapter 17, page 901-948, with reference to the present invention. Literature.

The polyfarnesene compositions disclosed herein may also comprise a lubricant. Generally, lubricating oils can be used to, inter alia, adjust the rheological properties of the polyfarnesene composition, improve the surface finish of the molded article, and/or promote the dispersion of the filler or pigment. Any lubricant known to those of ordinary skill in the art can be incorporated into the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable lubricating oils include fatty alcohols and their dicarboxylates, fatty acid esters of short chain alcohols, fatty acids, fatty acid guanamines, metal soaps, oligo fatty acid esters, long chain alcohol fatty acid esters, lignite Waxes, polyethylene waxes, polypropylene waxes, natural and synthetic paraffins, fluoropolymers, and combinations thereof. In use, the proportion of lubricant in the polymer composition in the total weight of the polymer composition can be greater than 0-5 wt%, 0.1-4 wt%, or 0.1-3 wt%. A disclosure of some suitable lubricating oils can be found in "Plastics Additives Handbook," by Zweifel Hans et al., Hanser Gardner Publications (2001, Cincinnati, Ohio), 5th Edition, Chapter 5, pages 511-552, with reference to the present invention. Attached literature.

The polyfarnesene compositions disclosed herein may also comprise an antistatic agent. In general, antistatic agents can increase the conductivity of the polyfarnesene composition and prevent static buildup. Any antistatic agent known to those of ordinary skill in the art can be incorporated into the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable antistatic agents include conductive fillers (e.g., carbon black, metal particles and other conductive particles), fatty acid esters (e.g., glyceryl monostearate), ethoxylated alkylamines, diethanolamine, B. Oxylated alcohols, alkyl sulfonamides, hydrocarbyl phosphonates, quaternary ammonium salts, alkyl betaines, and combinations thereof. In use, the antistatic agent content in the polymer composition may be greater than 0 to 5 wt%, 0.01 to 3 wt%, or 0.1 to 2 wt%, based on the total weight of the polymer composition. Some suitable antistatic agents can be found in the description of Zweifel Hans et al., such as "Plastics Additives Handbook", Hanser Gardner Publications (2001, Cincinnati, Ohio), 5th edition, Chapter 10, pages 627-646, please refer to the literature attached to the present invention.

The polyfarnesene compositions disclosed herein may also comprise a blowing agent for making a foam article. The blowing agent may include an inorganic foaming agent, an organic foaming agent, a chemical foaming agent, and a combination thereof, but is not limited to these examples. A description of some of the disclosed blowing agents can be found in "Polymeric Foams And Foam Technology" by Sendijarevic et al., Hanser Gardner Publications (2004, Cincinnati, Ohio), 2nd edition, Chapter 18, pages 505-547, to which the present invention is attached. Literature.

Non-limiting examples of suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium. Non-limiting examples of suitable organic blowing agents include aliphatic hydrocarbons of 1 to 6 carbon atoms, fatty alcohols of 1 to 3 carbon atoms, all and partially halogenated aliphatic hydrocarbons of 1 to 4 carbon atoms. Non-limiting examples of suitable aliphatic hydrocarbons include methane, ethane, propane, butane, isobutane, n-pentane, isopentane, pentane, and the like. Non-limiting examples of suitable fatty alcohols include methanol, ethanol, n-propanol, isopropanol. Non-limiting examples of suitable wholly and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Non-limiting examples of suitable fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1 difluoroethane (HFC-152a), 1,1,1-trifluoro (HFC-143a). 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane , perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane. Non-limiting examples of suitable partially halogenated chlorocarbons and chlorofluorocarbons include methyl chloride, dichloromethane, ethyl chloroform, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethyl Alkane (HCFC-141b), 1-chloro-1,1 fluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro- 1,2,2,2-tetrafluoroethane (HCFC-124). suitable Non-limiting examples of all halogenated CFCs include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1, 1-Trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane. Non-limiting examples of suitable chemical blowing agents include azomethamine, azobisisobutyric acid nitrile, styrene sulfonium, 4,4-phenol sulfonium urea, p-toluenesulfonium sulfonium, hydrazine Nitrogen, N, N'-dimethyl-N, N'-dinitrohalogenated phthalamide and tridecyltriazine. In certain embodiments, the blowing agent is azomethamine-isobutane, carbon dioxide, or a mixture thereof.

The percentage of blowing agent in the polymer composition disclosed herein may be from 0.1 to 20 wt.%, from 0.1 to 10 wt.%, or from 0.1 to 5 wt% of the total weight of the farnesene interpolymer or polymer composition. .%. In other embodiments, the blowing agent is present in an amount of from 0.2 to 5.0 moles per kilogram, from 0.5 to 3.0 moles per kilogram, or from 1.0 to 2.50 moles per kilogram per kilogram of interpolymer or polymer composition.

In certain embodiments, the polyfarnesene compositions disclosed herein comprise a slip agent. In other implementations, the polyfarnesene compositions disclosed herein do not include a slip agent. Slip refers to the slidability between the surfaces of the film or between other substrates. The measurement of the slip properties of the film can be carried out by ASTM D 1894 "Static and Kinetic Coefficients of Friction of Plastic Film and Sheeting", see the literature attached to the present invention. In general, slip agents can produce slip by changing the surface properties of the film; and can reduce friction between the film layers and other surfaces in contact with the film.

Any slip agent known to those skilled in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of slip agents are from about 12 to 40 carbon atoms (e.g., erucyl erucamide, decyl oleate, stearylamine and decyl amide); About 18-80 carbon atoms (such as alkyl erucamide, succinic acid amide, methyl erucamide and ethyl erucamide), secondary-bis-decylamine have about 18-80 carbon Atoms such as ethylene-bis-stearylamine and ethylene-bis-oleic acid decylamine and combinations thereof.

In certain embodiments, the slip agent is a primary amine (eg, stearin and decylamine) containing a saturated fat of 18-40 carbon atoms. In other embodiments, the slip agent is a primary amine having an unsaturated fatty group, wherein the unsaturated fatty group contains at least one carbon-carbon double bond and a carbon atom between 18 and 40 (eg, erucyl erucamide) And oleic acid amide. In a further implementation, the slip agent is a primary amine having at least 20 carbon atoms. In a further implementation, the slip agent is erucamide, oleic acid amide, stearylamine, sulphate, ethylene-bis-stearylamine, ethylene-bis-oleic acid guanamine, stearin Guanidine erucamide, behenic acid erucamide or a combination thereof. In a particular implementation, the slip agent is erucamide. In a further implementation, the slip agent can be purchased from the market, such as the purchase of ATMER ^TM SA (Uniqema, Belgium), ARMOSLIP ^® (Akzo Nobel Polymer Chemicals, USA), KEMAMIDE ^® (Witco, USA) and CRODAMIDE ^® (Croda, USA) Company) These brands of slip agents. In use, the slip agent content of the polymer composition may be greater than 0-3 wt%, 0.0001 wt%, 0.001-1 wt%, 0.001-0.5 wt% or 0.05- in the total weight of the polymer composition. 0.25 wt%. A description of some slip agents can be found in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications (2001), 5th edition, Chapter 8, pages 601-608, see the accompanying documents of the present invention.

In certain embodiments, the polyfarnesene compositions disclosed herein include a tackifier. In other implementations, the polyfarnesene compositions disclosed herein are free of tackifiers. In the present invention, any substance which can be added to the elastomer to produce adhesiveness can be used for thickening. Agent. Some non-limiting examples of tackifiers include natural and processed resins, glycerin or natural and synthetic rosin pentaerythritol esters, copolymers or terpolymers of natural terpenes, polyterpene resins or hydrogenated polyterpene resins, phenol Processed terpene resin or hydrogenated derivative thereof, aliphatic or alicyclic resin or hydrogenated derivative thereof, aromatic resin or hydrogenated derivative thereof, aromatically processed aliphatic or alicyclic hydrocarbon resin or hydrogenated derivative thereof or their combination. In other embodiments, the tackifier has a ring and ball softening point equal to or greater than 60 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C or 100 ° C, measured according to ASTM 28-67, see attached to the present invention Literature. In other embodiments, the tackifier ring and ball softening point, determined according to ASTM 28-67, is equal to or greater than 80 °C.

In other embodiments, in the polyfarnesene compositions disclosed herein, the tackifier content ranges from 0.1 wt.% to 70 wt.%, 0.1 wt.% to 60 wt.%, based on the total weight of the composition. 1 wt.%-50 wt.%, 0.1 wt.%-40 wt.%, 0.1 wt.%-30 wt.%, 0.1 wt.%-20 wt.% or 0.1 wt.%-10 wt.%. In other embodiments, the tackifier content of the compositions disclosed herein ranges from 1 wt.% to 70 wt.%, from 5 wt.% to 70 wt.%, from 10 wt.% to 70 wt%, based on the total weight of the composition. %, 15 wt.% - 70 wt.%, 20 wt.% - 70 wt.%, or 25 wt.% - 70 wt.%.

Alternatively, the polyfarnesene composition disclosed herein may comprise a petroleum wax material such as a low molecular weight polyethylene or polypropylene, a synthetic wax, a polyolefin wax, a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or a melting point. An ethylene/α-olefin interpolymer of greater than 25 °C. In other embodiments, the wax is a low molecular weight polyethylene or polypropylene having an average molecular weight of from about 400 to about 6,000 grams per mole. The wax occupies a range of 10% to 50% or 20% to 40% in the total amount of the composition.

Alternatively, the polyfarnesene compositions disclosed herein may be partially or fully crosslinked. When cross-linking is desired, the polyfarnesene compositions disclosed herein comprise a crosslinker that can be used to crosslink the polyfarnesene composition to increase the polyfarnesene composition over other moduli and rigidity. One advantage of the polyfarnesene composition is that cross-linking can occur in the side chains, rather than other polymers such as isoprene and butadiene, where the cross-linking sites are on the backbone of the polymer, and the like. Any crosslinker known to those of ordinary skill in the art can be added to the polyfarnesene compositions disclosed herein. Non-limiting examples of suitable crosslinking agents include organic peroxides (eg, alkyl peroxides, aromatic peroxides, peroxyesters, peroxycarbonates, biguanides, peroxyketals, and loops). Peroxides and decanes (eg vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxy) decane, ethylene triacetate, ethylene methyl dimethoxy decane and 3 - Methacryloxypropoxypropane trimethoxydecane). In use, the proportion of crosslinker content of the polymer composition in the total weight of the polymer composition can be greater than 0-20 wt%, 0.1-15 wt% or 1-10 wt%. A description of some suitable crosslinkers can be found in "Plastics Additives Handbook" by Zweifel Hans et al., Hanser Gardner Publications (2001), 5th edition, Chapter 14, pages 725-812, see the accompanying documents of the present invention.

In certain embodiments, the farnesene interpolymers disclosed herein comprise a farnesene-modified polymer prepared by the copolymerization of one or more farnesenes with one or more ethylene monomers. In a particular implementation, the non-modified polymer derived from one or more ethylene monomers can be any known olefin homopolymer or interpolymer. In a further implementation, none of the one or more ethylene monomers have unsaturated side chains that are reactive with the crosslinking agent. In other implementations, the unmodified polymer derived from one or more ethylene monomers can be any known olefin homopolymer or interpolymer.

In a specific implementation, the farnesene content of the disclosed farnesene-modified polymer accounts for about 1 wt.%-20 wt.%, 1 wt.%-10 of the total amount of the farnesene-modified polymer. Wt.%, 1 wt.%-7.5 wt.%, 1 wt.%-5 wt.%, 1 wt.%-4 wt.%, 1 wt.%-3 wt.% or 1 wt.%-2 Wt.%. In other embodiments, the one or more ethylene monomer content of the disclosed farnesene-modified polymer is about 80 wt.% to 99 wt.%, 90 wt% of the total amount of the farnesene-modified polymer. .%-99 wt.%, 92.5 wt.%-99 wt.%, 95 wt.%-99 wt.%, 96 wt.%-99 wt.%, 97 wt.%-99 wt.% or 98 wt .%-99 wt.%.

The crosslinking reaction of the polyfarnesene composition can also be initiated by a radiation method used in any technique, including electron beam irradiation, calcium irradiation, krypton irradiation, corona discharge irradiation with or without a crosslinking catalyst, And ultraviolet radiation, but is not limited to the examples given. The electron beam irradiation method disclosed in U.S. Patent Application No. 10/086,057 (Disclosure No. US2002/0132923 A1) and Patent No. 6,803,014 can be used in the practice of the present invention.

The preferred method of radiation can be 70 megarads by using high energy, ionizing electrons, ultraviolet light, X-rays, xenon rays, and electrons. The source of radiation can be any electron beam generator that operates at an output power range of about 150 kilovolts to 6 megavolts to meet the desired radiation dose. The voltage can be adjusted to an appropriate level, such as 100,000, 300,000, 1000000, 2000000, 3,000,000 or 6000000 or higher or lower. Many instruments for irradiating polymeric materials are known in the art. Typically, the irradiation dose is in the range of about 3 megarads to 35 megarads, preferably 8-20 megarads. In addition, the irradiation can be carried out very simply at room temperature. Radiation can also be performed at higher and lower temperatures, such as from 0 °C to 60 °C. The preferred radiation operation time after molding or manufacturing. this In addition, in a preferred embodiment, the farnesene interpolymer which has been combined with the pre-irradiation additive should be irradiated with an electron beam of 8-20 megarads.

The crosslinking catalyst can promote crosslinking, and any catalyst having such a function can be used. Suitable catalysts generally include organic bases, carboxylic acids, organometallic compounds (organic titanium salts and their complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin, dibutyl-tin-dilaurate, two Tin bismuth octanoate, dibutyl-tin-diacetic acid, dibutyl-tin-dioctanoic acid, tin acetate, stannous octoate, lead naphthenate, zinc octanoic acid, cobalt naphthenate, etc. Catalyst (or catalyst The amount of catalyst is generally from about 0.015 to about 0.035 phr.

Pre-irradiation additive representative materials include, but are not limited to, azo compounds, organic peroxides, and multifunctional ethylene or propylene compounds such as triallyl cyanuric acid, triallyl isocyanurate, pentaerythritol tetramethacrylate, pentane Dialdehyde, ethylene glycol ethylene, dimethacrylic acid, diallyl maleic acid, dipropargyl maleic acid, dipropargyl monoallyl uric acid, dicumyl peroxide, di-tert-butyl Peroxide, tert-butylperbenzoic acid, benzammonium peroxide, cumene hydroperoxide, t-butyl peroxyoctanoate, methyl ethyl ketone peroxide, 2,5-methyl-2,5-di (ton Butylperoxy)hexane, alkyl peroxide, t-butyl peracetic acid, azobisisobutyl nitrite, and the like, or a combination thereof. Preferred pre-irradiation additives for use in the present invention are compounds having multifunctional (i.e., at least two functional) groups, such as C=C, C=N or C=O.

At least one pre-irradiation additive can be introduced into the farnesene interpolymer using any known method. However, the preferred method of introducing the pre-irradiation additive is by using a mother concentrate containing the same or different basic resin as the farnesene interpolymer. The pre-irradiation additive masterbatch concentrate is preferably of a higher density, such as about 25 weight percent (total weight of the total weight).

At least one effective amount of the pre-irradiation additive is introduced into the polyfarnesene. Preferably, the proportion of the at least one pre-irradiation additive introduced into the total weight of the farnesene interpolymer is from 0.001 to 5% by weight, more preferably from 0.005 to 2.5% by weight, and most preferably from 0.015 to 5%. Wt%.

In addition to irradiation with an electron beam, it is also possible to carry out a crosslinking reaction by ultraviolet irradiation. The method comprises mixing a photoinitiator with a polymer before, during, and after the formation of the fiber, the photoinitiator may be previously mixed with or without a photocrosslinking reactant, and then exposing the fiber together with the photoinitiator The cross-linking reaction of the polymer reaches the desired level under the irradiation of ultraviolet rays. In the present invention, the photoinitiator used is an aromatic ketone such as a benzophenone or a monoacetal of 1,2-dione. The main photochemical reaction of the monoacetal is the homogenization reaction of the alpha bond, thereby producing a mercapto group and a dialkoxyalkyl group. This alpha-fragmentation reaction is known as the Norrish type I reaction, and its description can be found in "Organic Photochemistry: A Comprehensive Treatment," by W. Horspool and D. Armesto, published by Ellis Horwood Limited, UK, 1992; J. Kopecky "Organic Photochemistry: A Visual Approach" published by VCH Publishers, Inc., New York, USA, 1992; NJ Turro et al., in Acc. Chem. Res. (1972 (5): 92) and JT Banks et al., J. Am. Chem. Soc. (1993(115): 2473). The monoacetal synthesis of aromatic 1,2 diketone, Ar-CO-C(OR) ₂ -Ar' can be found in the United States Pharmacopoeia 4190602 and USP 4,190,602 and Ger.Offen. 2,337,813. The preferred compound for this reaction grade is 2,2-dimethoxy-2-phenylacetophenone, and C ₆ H ₅ -CO-C(OCH ₃ ) ₂ -C ₆ H ₅ (City Commercially available from Ciba-Geigy, Inc. under the trade name Irgacure 651. Other examples of aromatic ketones useful as photoinitiators in the present invention are the compounds Irgacure 184, 369, 819, 907 and Irgacure 2959, both available from Ciba-Geigy.

In one embodiment of the invention, a photoinitiator is used in conjunction with a photocrosslinking reagent. Two or more polyolefin molecular backbones can be attached as soon as the radicals are generated, and a photocrosslinking reactant which forms a covalent bond with the molecular backbone can be used. Preferred photocrosslinking reagents should be multiplexed agents, i.e., they contain two or more sites which, upon initiation, form a covalent bond with the polyfarnesene backbone composition. Representative photocrosslinking reactants include, but are not limited to, such as polyfunctional ethylene or propylene compounds (eg, triallyl cyanurate, triallyl isocyanurate, pentaerythritol tetramethacrylate, ethylene). Ethylene glycol dimethacrylate, diallyl maleic acid, dipropargyl maleic acid, dipropargyl monoallyl uric acid, etc. The photocrosslinking reactant preferred for use in the present invention is polyfunctional ( That is, at least two compounds. Particularly preferred photocrosslinking reagents are triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC).

Certain compounds can be used as both initiators and photoinitiators and photocrosslinking reagents. These compounds are characterized by the ability to produce two or more reactants (e.g., free radicals, carbene, nitrene, etc.) under ultraviolet light and further form covalent bond linkages with the two polymer chains. In the present invention, any compound having these two functions can be used, and representative compounds include sulfonium azide.

In another implementation, the polyfarnesene undergoes a secondary crosslinking reaction, i.e., other cross-linking reactions in addition to photocrosslinking. In this embodiment, the photoinitiator may be combined with a non-photocrosslinking reactant such as decane or the polyfarnesene may be subjected to a secondary crosslinking reaction under electron beam irradiation. In the implementation, the photocrosslinking reactant used may be selected according to the actual situation.

At least one photo-additive, ie photoinitiator, can be used with any known technique The photocrosslinking reactant is introduced into the polyfarnesene. The preferred photo additive can be introduced via a masterbatch concentrate containing polyfarnesene. Among the total amount of mother liquor, the preferred masterbatch photo additive concentration is higher than 10 wt.%, 15 wt.%, 20 wt.% or 25 wt.%.

At least one photo-additive is introduced into the polyfarnesene at any effective dose. Preferably, at least 1 photoinitiator is present in a proportion of 0.001 wt.% to 5 wt.%, more preferably 0.005 wt.% to 2.5 wt.%, of the total weight of the polyfarnesene. The ratio is from 0.015 wt.% to 1 wt.%.

The photoinitiator and the disposed photocrosslinking reactant can be added at various stages of the fiber or film manufacturing process. If the photo additive can withstand the extrusion temperature, the polyolefin resin can be mixed with the additive and then passed into the extruder, for example through a masterbatch. Further, the additive can be introduced into the extruder before the strip groove is pushed out, but in this case, it is important to effectively mix the composition before extrusion. In another method, the polyolefin fibers can be withdrawn without the use of photo-additives. The photoinitiator and/or photocrosslinker is then used in the fiber extrusion process by a kiss roll process, spraying, dropping into a solution containing the additive or other post-treatment industrial process. The fibers obtained from the photo-additive are treated by continuous or intermittent electromagnetic radiation. The photo additive is mixed with the polyolefin by using conventional composite equipment such as single and twin screw extruders.

The electromagnetic radiation power and the irradiation time are selected based on the effective cross-linking of the polymer without defects of degradation and/or three-dimensional structure. The preferred process can be found in the description in EP 0 490 854 B1. The photo-additive with sufficient thermal stability is pre-mixed with the polyolefin resin, extruded into fibers, and then continuously irradiated with a source of radiant energy or a series of connecting units. There are several advantages to using a continuous irradiation process, which allows for better processing of fibers or fabrics of fibers than batch processing, which is then collected on a spool.

Radiation can be accomplished using ultraviolet radiation. The preferred radiant intensity for UV is 100 J/cm ² . The source of illumination can be any UV generator with an output power of approximately 50 watts to 25,000 watts to provide the desired dose. The power can be adjusted to an appropriate level, such as 1000 watts, 4800 watts, 6000 watts or more, and lower. There are many instruments in the processing process for use with UV-irradiated polymer materials. The irradiation dose is usually 3 J/cm ^{2 to} 500 J/scm ^{2 ,} and preferably 5 J/cm ^{2 to} 100 J/cm ² . Further, the irradiation can be conveniently carried out at room temperature, for example, at a higher and lower temperature of from 0 ° C to 60 ° C. The higher the temperature, the faster the photocrosslinking process. The preferred radiation operation time after molding or manufacturing. In a preferred embodiment, the polyfarnesene which has been mixed with the photo-additive is irradiated with ultraviolet rays at a dose of 10 J/cm ^{2 to} 50 J/cm ² .

Mixture of ingredients contained in the polymer composition

The components of the polyfarnesene composition are the farnesene interpolymer, the additive, the optional second polymer (for example polyethylene and polypropylene) and the additives (for example crosslinkers), which are known to the skilled person. Method of mixing or stirring. Non-limiting examples of suitable mixing methods include melt mixing, solvent mixing, extrusion, and the like.

In some embodiments, the composition of the polyfarnesene composition can be a melt mixing method as described in U.S. Patent No. 4,152,189 to the name of Guer. First, any solvent is removed from the composition by heating to 100 ° C - 200 ° C or 150 ° C - 175 ° C and at a pressure of 5 torr (667 Pa) - 10 torr (1333 Pa). The desired proportion of the composition is then added to the container and the foam is formed by heating the contents of the container to melt and stirring.

In other implementations, these compositions are treated using a solvent mixing process. First, the desired foam composition is dissolved in a suitable solvent and the resulting mixture is mixed or stirred. Of course After that, the solvent was removed to obtain a foam.

In a further embodiment, in the preparation of the homologous agitating material, a physical stirring device having a method such as dispersing mixing, stirring mixing or dispersing and dispensing combination can be used. Both methods of batch and continuous mixing can be used. Non-limiting examples of batch methods include BRABENDER ^® mixing apparatus (e.g., BRABENDER PREP CENTER ^®, commercially available in the United States CWBrabender Instruments, Inc., Inc.) or BANBURY ^® internal mixing and roll milling (Farrel Company, Ansonia, Conn., Inc.). Non-limiting examples of continuous processes include single screw extrusion, twin screw extrusion, disk extrusion, reciprocating single screw extrusion, needle cylinder single screw extrusion. In some implementations, the additive can be added to the extruder through the feed hopper or feed port during the extrusion of the farnesene interpolymer, the second optional polymer, or the foam. A description of the method of mixing or agitating a polymer by extrusion can be found in "Polymer Extrusion" by C. Rauwendaal, Hanser Publishers, pp. 322-334 (1986), with reference to the accompanying documents of the present invention.

When the polyfarnesene composition requires one or more additives, the desired amount of the additive can be added to the farnesene interpolymer, the second polymer or polymer composition one or more times. In addition, it can be added in any order. In some implementations, the additive needs to be added first, mixed or stirred with the farnesene interpolymer, and then the interpolymer containing the additive and the second polymer. In other implementations, the additive is first added, mixed or agitated with the second polymer, and then the second polymer containing the additive is mixed with the farnesene interpolymer. In a further implementation, the farnesene interpolymer is mixed with a second polymer which is then mixed with the polymer.

The ingredients of the polymer composition can be mixed or stirred in any suitable mixing or agitating apparatus known to the skilled artisan. Lower than the temperature at which the blowing agent decomposes In the co-linking agent, the ingredients of the polymer composition can also be mixed to ensure that all of the compositions are uniformly mixed and remain intact. After the polymer composition has been relatively uniformly mixed, it is subjected to a molding treatment, and then placed under conditions such as heat, pressure, shear, etc., to form a foam with a sufficient amount of the starting foaming agent and the crosslinking agent.

Application of a composition containing polyfarnesene

The polyfarnesene or polyfarnesene composition has a very wide range of uses. For example, conventional thermoplastic plastic manufacturing processes can be used to produce useful articles, including at least one film in a single layer film article such as a single layer film; a multilayer film made from a mold, blown film, calendered or extruded adhesive. At least one film; molded articles such as blow molding, injection molding, rotomolded articles; pressed products, fibers, and textiles or non-woven fabrics. Thermoplastic plastic compositions containing the polymers mentioned herein include other natural or synthetic polymers, additives, reinforcing agents, flame retardant additives, antioxidants, stabilizers, colorants, extenders, crosslinkers, A blowing agent and a plasticizer. In particular, fibers of various compositions, such as core fibers/sheath fibers, have at least a portion of one of their outer surfaces containing one or more of the polymers mentioned herein.

Fibers that can be prepared from the polyfarnesene or polyfarnesene compositions disclosed herein include staple fibers, tows, multiple compositions, sleeves/cores, twisted filaments, and monofilaments. Any fiber formation process can be used in the present invention. For example, suitable fiber forming processes include spinning techniques, meltblowing techniques, gel fiber spinning, woven fabrics, and nonwovens. Articles made of such fibers include yarns or fibers with other fibers, polyester, nylon or cotton, thermoformed articles, extrusion molding including picture extrusion and bimetallic extrusion, calendar products, stretching, twisting or embossing . The polyfarnesene or polyfarnesene composition disclosed by the invention can also be used for wire and cable coating operation, as well as vacuum sheet extrusion forming operation, model product forming including injection Plastic, blow molding or rotomolding process. The polyfarnesene or polyfarnesene compositions disclosed herein can also be used in the manufacture of fibrous articles such as the conventional polyolefin processing techniques previously mentioned, i.e., polyolefin processing processes well known to those skilled in the art.

The compositional powders (both aqueous and non-aqueous) can also be shaped using the polyfarnesene or polyfarnesene compositions disclosed herein. The polyfarnesene or polyfarnesene compositions disclosed herein can also be used to make trivial foams. The polymer may be crosslinked by any known method such as hydrogen peroxide, electron beam, decane, azide or other crosslinking techniques. The polymer can also be modified by chemical methods such as grafting (e.g., by maleic anhydride (MAH), decane or other grafting agents), halogenation, amination, sulfonation or other chemical modification methods.

Suitable end uses for the above products include elastic films and fibers such as soft touch goods (toothbrush handles and tool handles), gaskets and frames; adhesives (including hot melt adhesives, pressure sensitive adhesives), footwear (including soles and shoe linings) Automotive interior parts and profiles; foamed products (including open and closed tanks); thermoplastic polymers such as high density polyethylene, polypropylene or other olefin polymer impact modifiers; coated fabrics, hoses Viscosity index modifiers (also known as gel point modifiers) for pipes, windshields, cap liners, floors, and lubricants.

The polyfarnesene compositions disclosed herein can also be used to produce articles for a variety of applications, such as automotive, construction, medical, food and beverage, electronics, home appliances, business machines, and consumer markets. In certain embodiments, the polyfarnesene composition is used in the manufacture of molded parts or articles such as toys, clamps, soft handles, cushion strips, floors, automotive mats, wheels, casters, furniture and electrical pads, labels , seals, static and dynamic gaskets, automotive doors, buffer belts, grille components, rocking plates, hoses, linings, office supplies, seals, gaskets, diaphragms, tubes, covers, plugs, punches, delivery systems, Kitchen utensils, shoes, shoes Skin and sole.

In certain embodiments, the polyfarnesene compositions disclosed herein are used to prepare molded articles, such as films, sheets, and foams using known polymer foam extrusion processes (e.g., extruded sheets and profiles). Molding (eg injection molding, rotational molding and blow molding); spinning, blown film and cast film processing. Generally, extrusion refers to the continuous pushing of a polymer through a high temperature and high pressure region, causing it to melt, compress, and finally pass through a casting trough. The extruder can be a single screw extruder, a multi-screw extruder, a disk extruder or a press. The mold may be a diaphragm mold, a blown film mold, a mold plate, a sleeve mold, a tube mold or a profile extrusion mold. A description of extruded polymers can be found in C. Rauwendaal, "Polymer Extrusion" Hanser Publishers (1986); and MJ Stevens, "Extruder Principals and Operation", Ellsevier Applied Science Publishers (1985), see attached to the present invention. references.

Injection molding is also widely used to manufacture plastic parts for many different applications. Generally, the process of injection molding refers to a process in which a polymer is melted at a high pressure and injected into a mold to form a desired shape to form a part of a desired shape and size. The mold can be made of metal such as steel and aluminum. A description of injection molding of polymers can be found in Beaumont's article "Successful Injection Molding: Process, Design, and Simulation" published by Hanser Gardner Publications, Inc. (2002), see the accompanying references to the present invention.

Molding is usually carried out by melting a polymer and introducing it into a mold to form a desired shape by reversal molding to form a part of a desired shape and size. The mold can be a pressureless or auxiliary pressure mold. A description of the mold of the polymer can be found in Hans-Georg Elias, "An Introduction to Plastics", Wiley-VCH, Germany, pp. 161-165 (2003), with reference to the literature attached to the present invention.

Rotomolding is commonly used to produce hollow plastic products. Through post-processing operations, complex components can also be efficiently fabricated like other types of casting and extrusion processes. Unlike other processing methods, heating, melting, forming, and cooling in the rotational molding process are all performed after the polymer is placed in the mold, so that there is no external pressure during the forming process. A description of the rotational molding of polymers can be found in Glenn Beall, "Rotational Molding: Design, Materials & Processing," Hanser Gardner, (Cincinnati, Ohio, 1998), with reference to the literature attached to the present invention.

Blow molding can be used to make plastic hollow containers. The process involves placing the softening polymer in the center of a mold, inflating the polymer on the mold wall with a blow pin, and then solidifying into a product by cooling. In general, there are three methods of blow molding: extrusion blow molding, injection blow molding, and stretch blow molding. Injection blow molding can be used for polymers that cannot be extruded. Pull-blowing can be used for crystals that are difficult to blow and crystalline polymers such as polypropylene. Blow molding of polymers can be found in the description of Norman C. Lee, "Understanding Blow Molding", Hanser Gardner Publications (Ohio, 2000, USA), with reference to the literature attached to the present invention.

The polyfarnesene compositions disclosed herein can be used as hot melt adhesives or pressure sensitive adhesives. Can be used to make any item that requires or contains hot melt adhesive or pressure sensitive adhesive. Non-limiting examples of suitable articles include paper products, packaging materials, laminated wood panels, kitchen countertops, vehicles, labels, disposable diapers, hospital mats, feminine hygiene napkins, surgical curtains, magnetic tape, cartons, trays, medical equipment, and bandages. . In a further implementation, the adhesive composition can be used in tapes, cartons, trays, medical equipment, and bandages.

In certain embodiments, the compositions disclosed herein are useful as hot melt adhesives. This hot melt adhesive composition can be used in industry, including packaging, especially for low temperature applications such as dairy or freezing. Food packaging, as well as in disposable sanitary items such as diapers, feminine care pads, and napkins. Other suitable applications include bookbinding, woodworking, and labels. Some hot melt adhesives describe "Adhesion and Adhesives Technology, Manufacture and Applications" by A. V. Pocius, published by Noyes Data Corp. (1974), see references attached to the present invention.

In other implementations, the compositions disclosed herein can be used as a PSA. Such PSA gum compositions are useful in sheet products such as decorative, reflective and graphic, self-adhesive labels and tape substrates. The substrate material can be any suitable material, depending on the desired use. In other implementations, the substrate comprises a nonwoven, paper, polymeric film (eg, polypropylene (eg, biaxially oriented polypropylene (BOPP)), polyethylene, polyurea, or polyester (eg, polyester (PET)) or factory. Pipelines (eg 矽Pipe). A description of some PSAs can be found in the AVPocius article Adhesion and Adhesives Technology, Hanser Gardner Publications (2002), 2nd edition, Chapter 9, page number 238-259; and the article by Istvan Benedek, "Technology of Pressure-Sensitive Adhesives and Products", CRC Publishing (2008), see the accompanying references of the present invention.

In other implementations, the composition can also be used to make tape. For example, PSA or hot melt adhesive compositions are at least suitable for the production of one side of tape. The binder composition can be subjected to a crosslinking reaction to further increase its shear strength. Any suitable crosslinking method (for example, a radiation method exposed to ultraviolet rays or electron beams) or a crosslinking agent additive (such as a phenolic and decane curing agent) can be used.

The adhesive compositions disclosed herein may be applied to a desired substrate or attached by any known process, particularly in conventional methods of making tapes, cartons, trays, medical devices, and bandages. . In other implementations, the adhesive composition can be applied through the nozzle or spray head portion of the associated device. In addition to other conventional forms, the adhesive composition can also be used as fine lines, dots or spray coatings and the like.

In certain implementations, the adhesive composition can be applied by melt extrusion techniques. Regarding the application of the adhesive composition, it may be in a continuous or batch manner. An example of a batch application is to place a proportion of the adhesive composition between a substrate to which the adhesive composition is adhered and an outer surface capable of releasing the adhesive to form a combined structure. The continuous forming process involves withdrawing the adhesive composition from the heated film mold and subsequently contacting the extracted composition with a moving plastic web or other suitable substrate.

In other implementations, the adhesive composition can be used as a coating in a solvent process. For example, the solvent-based adhesive composition can be coated by the following methods: knife coating, roll coating, gravure coating, bar coating, curtain coating, air knife coating, and the like. The applied solvent-type binder is dried to remove the solvent. The preferred method is to apply a solvent-based adhesive composition that is prone to warming, for example, supplied by an oven to accelerate drying.

In other implementations, the composition is used as a hot melt pressure sensitive adhesive. A description of some hot melt pressure sensitive adhesives can be found in "Technology of Pressure-Sensitive Adhesives and Products" by Istvan Benedek, CRC Publishing (2008), Chapter 3, see the present invention. Attached references.

In certain embodiments, the composition is used as a rubber or touch adhesive. A description of some rubber or touch adhesives can be found in Adhesion and Adhesives Technology by A.V. Pocius, Hanser Gardner Publications, 2nd ed., Chapter 9, pages 259-265 (2002), please refer to the references attached to the present invention.

The embodiments of the present invention are exemplified below, but are not limited to the specific embodiments of the present invention. All parts and percentages are by weight unless otherwise indicated. All values are approximate. It will be appreciated that while a wide range of content is presented herein, the scope of the invention described herein may still fall within the scope of the invention. In each of the examples, the details of the specific description should not be regarded as a necessary feature of the invention.

Specific example Purification of starting materials

--farnesene includes non-purified hydrocarbons such as zingiberene, sweet myrrhene, farnesene epoxide, farnesene alcohol isomer, E, E farnesol, squalene, ergosolid Alcohol and some farnesene dimers. The cyclohexane was distilled under nitrogen to remove moisture and stored with a desiccant.

Differential scanning calorimetry

The glass transition temperature (Tg) of the polymer samples disclosed herein was determined using a TA Q200 differential scanning calorimeter. The 5 mg sample was placed in an aluminum pan. The quality of the blank control pot and the sample pot were maintained within ±0.01 mg. The sample scanning temperature was approximately from -175 ° C to about 75 ° C and the scanning rate was 10 ° C / min. T _g can be identified during the transitional phase of the heat flow. The transition midpoint value is identified as the T _g of the sample.

Gel permeation chromatography

Gel permeation chromatography (GPC) is used to determine the molecular weight and degree of polymerization distribution of the polymer sample. The Waters 2414 Refractive Index Detector was used with a Waters 1515 Constant Solvent Composition High Performance Liquid Chromatography (HPLC) pump. HPLC gradient tetrahydrofuran was used as a solvent. Gel permeation chromatography collected fractional values for recording the degree of polymerization distribution. The molecular weight of a sample is generally reported as the average molecular weight value (Mn) or the weight ( _Mw ) of the average molecular weight. The peak molecular weight (M _p ) is included when the overlapping peaks that cover the distribution of the degree of polymerization characteristic of each peak appear.

Thermogravimetric analysis

The degradation temperature of the sample was determined by thermogravimetric analysis (TGA). A 20 mg sample was placed in the weighing pan. Then place the weighing pan in the stove. Maintain a balance of air flow. The sample was heated from room temperature to 580 ° C and the heating rate was 10 ° C / min. When the weight lost by the sample was 1% and 5%, the corresponding temperature was recorded separately.

UV-visible spectrum

UV-Vis spectrometers are used to monitor monomer consumption during the reaction. The reaction is continued until all of the monomers have been consumed. A Shimadzu UV-2450 UV-Vis spectrophotometer was used. Five measurements were made with an empty quartz tube to calculate the average of the measured background. An aliquot of the sample was periodically taken from the reaction vessel and placed in a square quartz tube at a distance of 1 cm of beam. The absorbance of the sample is proportional to the monomer concentration. The UV-Vis spectrometer monitors the reaction process and is characterized by a β-farnesene absorption peak of 230 nm.

Tensile Strength

Tensile strength of the samples using INSTRON ^TM tensile tester was measured. The sample is cast into a film and cut to the appropriate size. After the treatment, the thickness and width of the sample were measured. For the measurement, the gauge length is 2.54 cm and the crosshead speed is 25 mm/min.

Lap test

The lap test is used to characterize the adhesion properties of the sample. The two substrates are bonded together with an adhesive. Then, the adhesive is sheared to open the substrate. There are three ways of failure performance in the lap (adhesion) construction. When the substrate adhesion fails, it is called a substrate failure. When the adhesive is separated, it is called adhesion failure. When the interface between the substrate and the adhesive fails, it is called adhesive failure. INSTRON ^TM tensile tester used to test failure force magnitude. An adhesive was used on a 2 cm ² area on the substrate with a crosshead speed of 25 mm/min. Aluminum is used as the substrate. Clean the aluminum with acetone before joining.

¹ H and ¹³ C nuclear magnetic resonance

¹ H and ¹³ C NMR were used to characterize the chemical microstructure of the sample. A Varian Mercury 300 MHz NMR spectrometer was used for the measurements. Chloroform was used as a solvent. Repeated measurements were repeated several times to obtain spectral values.

Example 1 M _n 105,000 1,4-polyfarnesene

n-Butyllithium (1.85x10 ^-3 mol, purchased from Acros, Morris Plains, USA) was added to the reactor as a reaction initiator, and then the reaction vessel was heated at 50 ° C for 19 hours until all β-farnesene was heated. After consumption, the reaction was monitored with a UV-Vis spectrometer. The compound of Example 1 was precipitated from the reaction mixture using 1% ethanol and t-butyl catechol (purchased from Sigma-Aldrich, St. Louis, MO). The mixture was dried under vacuum at 60 ° C for 2 hours, after which the compound of Example 1 was allowed to stand under vacuum for 16 hours. Then, the product of Example 1 was collected in an amount of 89.83 g (yield 97%), and stored in a refrigerator to prevent cross-linking reaction before the test.

The reaction mixture was measured by a UV-Vis spectrometer, and the synthesis of Example 1 was monitored by observing the disappearance state of β-farnesene. Figure 1 shows the ultraviolet visible light of Example 1 and β-farnesene The UV-Vis spectrum of (UV-Vis) shows the characteristic absorption peak of β-farnesene at 230 nm, but the example 1 shown in Figure 1 lacks the UV-Vis ultraviolet spectrum β-farnesene at 230 nm. Characteristic absorption peak.

The molecular weight and degree of polymerization distribution of Example 1 were determined by gel permeation chromatography (GPC). Figure 2 shows the GPC curve of Example 1. The contents shown in Table 1 are the number average molecular weight number (Mn), the weight average molecular weight (M _w ), the peak molecular weight (M _p ), the z average molecular weight (M _z ), and the z+1 average molecular weight (M _{z+ of} Example 1). ₁ ), M _w /M _n (ie, degree of polymerization distribution), M _z /M _w and M _z+1 /M _w . The definitions of M _n , M _w , M _z , M _z+1 , M _p and degree of polymerization can be found in the article "Technical Bulletin TB021" in the article "The definition of MW mean and the distribution of molecular weights (Molecular Weight Distribution and Definitions of MW Averages), published by Polymer Laboratories, see attached literature. Some useful support materials can be found in "Introduction to Polymer Chemistry" by Malcolm P. Stevens (Oxford University Press, Third Edition, pages 35-58 (1999), see the reference attached to the present invention. The number of units of farnesene is about 490.

Figure 3 shows the ¹³ C nuclear magnetic resonance spectrum of Example 1. Peaks at 77.28 ppm, 77.02 ppm, and 76.77 ppm were peaks associated with the collection of ¹³ C NMR spectra of ruthenium chloroform. The characteristic peak of Example 1 is 139.05 ppm.

Figure 4 shows the ¹ H nuclear magnetic resonance spectrum of Example 1. Peaks are at 4.85 ppm and 4.81 ppm, both peaks associated with 3,4-microstructures. Peaks at 5.17 ppm, 5.16 ppm, 5.14 ppm, and 5.13 ppm are peaks associated with 1,4-microstructures and 3,4-microstructures. According to the area under the peak of Figure 4, about 12% of the farnesene units in Example 1 were found to have 3,4-microstructures.

Figure 5 shows the DSC curve of Example 1. The thermal properties of Example 1 were determined by DSC. The _Tg of Example 1 was -76 °C. No other thermal detection values were found to be -175 ° C, -75 ° C.

Figure 6 shows the thermogravimetric analysis (TGA) curve measured in the air of Example 1. The decomposition temperature of Example 1 was determined by TGA. In Example 1, the temperature at which the weight was reduced by 1% in air was 210 ° C, and the temperature at which the weight was reduced by 5% in air was 307 ° C.

Figure 7 shows the TGA curve determined in Example 1 nitrogen. In Example 1, the temperature at which the weight was reduced by 1% in nitrogen was 307 ° C, and the temperature at which 5% by weight was reduced in nitrogen was 339 ° C.

Example 1 was observed to be sticky. Figure 8 shows the results of the lap test of Example 1. The adhesion ability of Example 1 was determined by a lap test. The energy of the adhesive of Example 1 was seen to be 11,400 J/m ² and the peak pressure was about 314 N/m ² .

Example 2 M _n 245,000 1,4-polyfarnesene

Example 2 is a M _n of 245,000 g / mol 1,4 polyfarnesene. Example 2 was synthesized in the same manner as in Example 1 except that sec-butyllithium was used as the initiator. The net weight of Example 2 was 83.59 g (yield 71.4%). The yield is lower because there are aliquots of the product used to monitor the progress of the reaction.

The molecular weight and degree of polymerization distribution of Example 2 were determined by gel permeation chromatography (GPC). Figure 9 shows the GPC curve of Example 2. Example shown in Table 2 M _n 2 _{is, M w, M p, M} z, M z + 1, polymerization degree distribution, M _z / M _w and M _{z + 1} / M _w of the individual measured values. The number of farnesene units of Example 2 was calculated to have a value of about 2,000. Since the molecular weight of Example 2 was increased, the winding time and the relaxation time were longer than those of Example 1.

Figure 10 shows the DSC curve of Example 2. The thermal characteristics of Example 2 were determined by DSC. The _Tg of Example 2 was -76 °C.

Figure 11 shows the results of the tensile test of Example 2. The tensile force of Example 2 was measured by a lap test. It was observed that Example 2 was characterized by softness, viscosity, and rapid formation. As shown in Fig. 11, the elongation extreme value of Example 2 reached 6% of the maximum tensile force of 19 psi. The modulus of Example 2 was 4.6 kpsi. Example 2 was continuously prepared as a 40% stretched product.

Example 3 3,4-polyfarnesene

In addition to n-butyllithium (1.71x10 ^-3 mol) was added to N,N,N',N'-tetramethylethylenediamine (TMEDA, 1.71x10 ^-3 mol, purchased from Sigma-Aldrich, St.Louis Example 3 was synthesized in a manner similar to that of Example 1 except for the operation of (US). The net weight of Example 3 was 82.72 g (yield 97%).

The molecular weight and degree of polymerization distribution of Example 3 were determined by gel permeation chromatography (GPC). Figure 12 shows the GPC curve of Example 3. The two peaks of Figure 12 suggest two distinctly distinct components of Example 3. Example 3 shown in Table 3 _{M n, M w, M z} , M z + 1, polymerization degree distribution, M _z / M _w and M _{z + 1} / M _w of the individual measured values. The M _p of the first peak of Calculation Example 12 was about 97,165 g/mol. The M _p of the second peak of Calculation Example 12 was about 46,582 g/mol. The number of farnesene units of Example 3 was calculated to have a value of about 240.

Figure 13 shows the ¹³ C nuclear magnetic resonance spectrum of Example 3. Peaks at 77.28 ppm, 77.02 ppm, and 76.77 ppm were peaks associated with the collection of ¹³ C NMR spectra of ruthenium chloroform. Figure 13 shows that the characteristic peak of Example 1 is at 139.05 ppm, suggesting that Example 3 has a regular microstructure.

Figure 14 shows the ¹ H nuclear magnetic resonance spectrum of Example 3. The peak values were 4.85 ppm and 4.81 ppm, both of which are the microstructure peaks of Example 3. Peaks at 5.17 ppm, 5.16 ppm, 5.14 ppm, and 5.13 ppm are peaks associated with 1,4-microstructures and 3,4-microstructures. According to the under-peak area of Figure 14, about 10% of the farnesene units of Example 3 were found to have a 1.4-microstructure.

Figure 15 shows the DSC curve of Example 3. The thermal characteristics of Example 3 were determined by DSC. The _Tg of Example 3 was -76 °C. No other thermal detection values were found to be -175 ° C, -75 ° C.

Figure 16 shows the thermogravimetric analysis (TGA) curve measured in the air of Example 1. The decomposition temperature of Example 3 was determined by TGA. The temperature at which the weight loss in Example 1 was 1% in air was 191 ° C, and the temperature at which 5% weight loss in air was 265 ° C.

Example 3 was observed to be a highly viscous liquid. Figure 17 shows the results of the lap test of Example 3. The adhesion ability of Example 3 was determined by a lap test. The energy of the adhesive of Example 3 was seen to be 12,900 J/m ² and the peak pressure was about 430 N/m ² .

Example 4 Polystyrene-1,4-polyfarnesene-polystyrene

An argon-dried three-necked reaction flask was taken and a cyclohexane solution containing 12% beta-farnesene preheated solution was added. A second argon-dried reaction flask with three necks was taken and a cyclohexane solution containing 20.65 g of 10% styrene was added. n-Butyllithium (6.88 x 10 ^-4 mol) was added to the styrene solution in the reactor as a reaction initiator, and then the reaction vessel was heated at 50 ° C for 16 hours until all β-farnesene was consumed. The reaction was monitored by GPC. Then, 161.8 g of the β-farnesene solution (i.e., 19.61 g of β-farnesene) was transferred to a reaction apparatus under nitrogen. The reaction was allowed to proceed until the end of 7 hours, and the reaction was monitored by GPC. A three-part dichloromethane coupling agent (3.44 x 10 ^-4 mol, purchased from Acros, Morris Plains (USA)) was added to the reactor, thus obtaining a molar ratio of Li to Cl of the reactant of 1:2, allowing the reaction. The mixture is allowed to finish until the display color changes from yellow to clear. The compound of Example 4 was precipitated from the reaction mixture with a 1% solution of t-butyl catechol ethanol. The mixture was dried under vacuum at 60 ° C for 2 hours, after which the compound of Example 4 was placed under vacuum for 16 hours. Then, the product of Example 4 was collected in an amount of 39.15 g (yield 97%), and stored in a refrigerator to prevent cross-linking reaction before the test.

Figure 18 shows the GPC curve of polystyrene. GPC monitors the synthesis reaction steps of polystyrene. The two peaks of Figure 18 suggest that the polystyrene produced has two distinctly distinct components. Table 4 shows the respective measurements of M _n , M _w , M _z , M _z+1 , degree of polymerization distribution, M _z /M _w and M _z+1 /M _w of polystyrene. Example 18 The first peak M _p of about 59,596 g / mol. Example 20 M _p of the second peak of approximately 28,619 g / mol.

The formed polystyrene is used as a reaction initiator to initiate polymerization of β-farnesene to form a polystyrene-1,4-polyfarnesene diblock copolymer. Figure 19 shows the GPC curve of the diblock copolymer. GPC monitors the synthesis reaction step of the diblock copolymer. The two peaks of Figure 19 suggest that the resulting diblock copolymer has two distinctly distinct components. Table 5 shows the measured values of M _n , M _w , M _p , M _z , M _z+1 , degree of polymerization distribution, M _z /M _w and M _z+1 /M _w of the diblock copolymer. . Example 19, corresponding to polystyrene-1,4-polyfarnesene - polystyrene first peak M _p, of about 141,775 g / mol. Example 19 corresponding to the two second peak block copolymer M _p, of about 63,023 g / mol. The 1.4-polyfarnesene molecular weight in the diblock copolymer is about 35,000 g/mol. FIG 19 corresponding to the third peak polystyrene M _p, of about 29,799 g / mol.

The polystyrene 1,4-polyfarnesene diblock copolymer was further polymerized to form Example 4. Figure 20 shows the GPC curve of Example 4. The molecular weight and degree of polymerization distribution of Example 4 were determined by gel permeation chromatography (GPC). The three peaks of Figure 20 suggest that the resulting coupled product has three distinctly distinct components. Table 6 shows conjugate _{M n, M w, M z} , M z + 1, polymerization degree distribution, M _z / M _w and M _{z + 1} / M _w of the individual measured values. FIG 20 is a first embodiment of a peak corresponding to M _p 4 of about 138,802 g / mol. Example 4 is the 10% coupled product obtained. The unit number of the farnesene monomer of Example 4 was calculated to be about 300. Example 20, corresponding to polystyrene-1,4-polyfarnesene di-block copolymer of the second peak M _p, of about 63,691 g / mol. FIG 20 is a polystyrene corresponding to the third peak M _p, of about 29,368 g / mol.

Figure 21 shows the ¹³ C nuclear magnetic resonance spectrum of Example 4. The peaks at 77.69 ppm and 76.80 ppm are peaks associated with the collection of ¹³ C NMR spectra of ruthenium chloroform. The other peaks shown in Figure 21 are related to 1,4-polyfarnesene and polystyrene. Figure 21 shows that the characteristic peak of 1,4-polyfarnesene is 139.25 ppm, suggesting that Example 1.4 contains 1,4-polyfarnesene.

Figure 22 shows the ¹ H nuclear magnetic resonance spectrum of Example 4. Peaks are at 4.85 ppm and 4.81 ppm, both peaks associated with 3,4-microstructures. The peaks at 5.10 ppm, 5.12 ppm, and 5.14 ppm are peaks associated with 1,4-microstructures and 3,4-microstructures. According to the area under the peak of Fig. 22, about 3% of the farnesene unit of Example 4 was found to have a 3,4-microstructure.

Figure 23 shows the DSC curve of Example 4. The thermal characteristics of Example 4 were determined by DSC. Example 4 1,4-farnesene T _g of -76 ℃. Example 4 T _g of polystyrene was 96 ℃. No other thermal detection values were found to be -175 ° C, -75 ° C.

Figure 24 shows the thermogravimetric analysis (TGA) curve measured in Example 4 air. The decomposition temperature of Example 4 was determined by TGA. In Example 1, the temperature at which the weight was reduced by 1% in air was 307 ° C, and the temperature at which the weight was reduced by 5% in air was 333 ° C.

Figure 25 shows the results of the tensile test of Example 4. The tensile force of Example 4 was measured by a lap test. Example 4 has a rigid character, but it can also be generated. As shown in Figure 25, the elongation fracture value of Example 4 was 425% of the maximum tensile force of 152 psi. The modulus of Example 4 was 31.9 kpsi. The 330% tensile pressure value of Example 4 was 33.4 psi.

Example 4 was observed to be sticky. Figure 26 shows the results of the lap test of Example 4 (because of a bond failure). The energy of the adhesive of Example 4 was found to be 2,928,000 J/m ² and the peak pressure was about 134,000 N/m ² .

Example 5 Polystyrene-3.4-polyfarnesene-polystyrene

An argon-dried three-necked reaction flask was taken and a cyclohexane solution containing 12% beta-farnesene preheated solution was added. A second argon-dried reaction flask with three necks was taken and a solution of 10% styrene in cyclohexane was added. Then, 141.1 g of a styrene solution (i.e., 14.82 g of styrene) was transferred to a reaction apparatus under argon. n-Butyllithium (5.84x10 ^-4 mol) and TMEDA (5.02x10 ^-4 mol) were added to the reactor as a reaction initiator, and then the reaction vessel was heated at 50 ° C for 16 hours until all β-farnesene was consumed. At the end, the reaction was monitored by GPC. Then, 143.07 g of the β-farnesene solution (i.e., 15.74 g of β-farnesene) was transferred to a reaction apparatus under argon. The reaction was allowed to proceed to the end of 16 hours and the reaction was monitored by GPC. A three aliquot of the methylene chloride coupling agent was added to the reactor to give a Li to Cl molar ratio of 1:2. Allow the reaction mixture to proceed to completion time, at which point the display color changes from yellow to clear. The compound of Example 5 was precipitated from the reaction mixture with a 1% t-butyl-catechol-ethanol solution. The mixture was dried under vacuum at 60 ° C for 2 hours, after which the compound of Example 5 was allowed to stand under vacuum for 16 hours. Then, the product of Example 5 was collected in an amount of 28.75 g (yield 96%), and stored under refrigeration to prevent cross-linking reaction before the test.

Figure 27 shows the GPC curve of polystyrene. GPC monitors the synthesis reaction steps of polystyrene. The two peaks of Figure 27 suggest that the polystyrene produced has two distinctly distinct components. Table 7 shows the respective measured values of M _n , M _w , M _z , M _z+1 , degree of polymerization distribution, M _z /M _w and M _z+1 /M _w of the polystyrene. Example 27 The first peak M _p of about 65,570 g / mol. Example 27 The second peak of M _p of about 32,122 g / mol.

The formed polystyrene acts as a reaction initiator to initiate polymerization of β-farnesene to form a polystyrene-3.4-polyfarnesene diblock copolymer. Figure 28 shows the GPC curve of the diblock copolymer. GPC monitors the synthesis reaction step of the diblock copolymer. The two peaks of Figure 28 suggest that the resulting diblock copolymer has two distinctly distinct components. Table 8 shows the respective measurements of M _n , M _w , M _z , M _z+1 , degree of polymerization distribution, M _z /M _w and M _z+1 /M _w of the diblock copolymer. Example 28, corresponding to polystyrene-3,4-polyfarnesene - polystyrene first peak M _p, of about 174,052 g / mol. Example 28 corresponding to the two second peak block copolymer M _p, of about 86,636 g / mol. The molecular weight of 3,4-polyfarnesene in the diblock copolymer is about 54,000 g/mol. FIG 28 is a polystyrene corresponding to the third peak M _p, of about 33,955 g / mol.

The polystyrene 5-polyfarnesene diblock copolymer was further polymerized to form Example 5. Figure 29 shows the GPC curve of Example 5. The molecular weight and degree of polymerization distribution of Example 5 were determined by gel permeation chromatography (GPC). The three peaks of Figure 29 suggest that the resulting coupled product has three distinctly distinct components. M _n shown in Table 5 in Example _{9, M w, M z, M} z + 1, polymerization degree distribution, M _z / M _w and M _{z + 1} / each of M _w measurements. FIG 29 corresponding to Example 5 of the first peak M _p, of about 148,931 g / mol. Example 5 is the 33% coupled product obtained. The number of units of the farnesene monomer in Example 5 was calculated to be about 300. The peak molecular weight of the block in Example 5 was about 32,000-108,000-32,000 g/mol. Example 29, corresponding to polystyrene-3,4-polyfarnesene di-block copolymer of the second peak M _p, of about 81,424 g / mol. FIG 29 is a polystyrene corresponding to the third peak M _p, of about 32,819 g / mol.

Figure 30 shows the ¹³ C nuclear magnetic resonance spectrum of Example 5. Peaks at 77.72 ppm, 77.29 ppm, and 76.87 ppm were peaks associated with the collection of ¹³ C NMR spectra of ruthenium chloroform. The other peaks shown in Figure 30 are related to 3.4-polyfarnesene and polystyrene. Figure 30 shows that the characteristic peak of Example 1.4 is at 139.05 ppm, suggesting that Example 5 has a regular microstructure.

Figure 31 shows the ¹ H nuclear magnetic resonance spectrum of Example 5. Peaks are at 4.85 ppm and 4.81 ppm, both peaks associated with 3,4-microstructures. At 5.15 ppm, the peak at 5.13 ppm is the peak associated with the 1,4-microstructure and 3,4-microstructure. According to the area under the peak of Fig. 31, about 5% of the farnesene unit of Example 5 was found to have a 1.4-microstructure.

Figure 32 shows the DSC curve of Example 5. The thermal characteristics of Example 5 were determined by DSC. Example 5 3.4-polyfarnesene a T _g of -72 ℃. Example 5 T _g of polystyrene was 94 ℃. No other thermal detection values were found to be -175 ° C, -75 ° C.

Figure 33 shows the thermogravimetric analysis (TGA) curve determined in Example 5 air. The decomposition temperature of Example 5 was determined by TGA. Example 5 The temperature at which the weight was reduced by 1% in air was 240 ° C, and the temperature at which the weight was reduced by 5% in air was 327 ° C.

Figure 34 shows the results of the tensile test of Example 5. The tensile force of Example 5 was measured by a lap test. Example 5 has a rigid character, but it can also be generated. As shown in Figure 34, the elongation fracture value of Example 5 was 175% of the maximum tensile force of 768 psi. The modulus of Example 5 was 39.5 kpsi.

Example 5 shows repeated purification four times with n-hexane for further purification. Figure 35 shows the GPC curve after purification of Example 5. GPC evaluated the case of extracting Example 5 from the coupling product. After extraction, the first peak shown in Figure 35 indicates that the extracted product of Example 5 increased by 60%. The polystyrene-3,4-polyfarnesene diblock copolymer shown in Figure 35 was reduced to 30% of the extracted product. The third peak shown in Figure 35 indicates that the polystyrene is reduced to 10% of the extracted product.

Figure 36 shows the GPC curve for extracting hexane solvent. After the extraction, the first peak shown in Fig. 36 indicates that the content of Example 5 in the extraction solvent was very low. The second peak of Figure 36 shows that a significant amount of the polystyrene-3,4-polyfarnesene diblock copolymer was extracted by the extraction solvent. The third peak of Figure 36 shows that the vast majority of the polystyrene is extracted by the extraction solvent.

Figure 37 shows the results of the tensile test after the purification of Example 5. The tensile strength of the purified Example 5 was measured by a tensile test. Example 5 has a soft characteristic and is easy to produce. As shown in Figure 37, the elongated fracture value of the purified Example 5 was 550% of the maximum tensile force of 340 psi. The modulus of the purified Example 5 was 65.9 kpsi. The purified Example 5300% tensile force was 57.1 kpsi.

Purified Example 5 was observed to have a very high viscosity. Figure 38 shows the results of the lap test of the purified Example 5 (because a bond failure occurred). The adhesion of the purified Example 5 was measured by a lap test. The energy of the purified adhesive of Example 5 was found to be 1,787,000 J/m ² and the peak pressure was about 120,000 N/m ² .

Example 6

Example 6 is the product obtained by vulcanization of Example 1. In order to obtain the formula of the reaction mixture, 62.7 g of Example 1 and 3.20 g of zinc oxide, 1.25 g of stearic acid, 0.94 g of Rubbermakers Sulfur MC-98 substance, 0.13 g of Accelerat or TMTD (dithiotetramethyl thiuram), and 0.63 g of Accelerat or OBTS (N-oxydiethyl-2-benzothiazole sulfoximine) was mixed. Zinc oxide, stearic acid, Rubbermakers Sulfur MC-98 material, 0.13 g Accelerat or TMTD, and Accelerat or OBTS were all purchased from Akrochem Corporation (USA). The compound was placed in a vulcanization mold and the gas was removed at 140 ° C for about 30 minutes. Thereafter, the compound was treated at 170 ° C for 15 minutes. After remolding, 70.4 g of Example 6 elastomeric solid (yield 81%) was obtained.

Figure 39 shows the results of the tensile test of Example 6. The tensile force of Example 6 was measured by a lap test. As shown in Fig. 39, the elongation fracture value of Example 6 was 38% of the maximum tensile force of 16 psi. The modulus of Example 6 was 58 kpsi.

Example 7

Example 7 is the product obtained by vulcanization in Example 2. Example 7 was synthesized in a manner similar to that of Example 6 except that Example 1 was replaced with 60.3 g of Example 2. The net weight of Example 7 was 68.1 g (yield 78%).

Figure 40 shows the results of the tensile test of Example 7. As shown in Fig. 40, the elongation fracture value of Example 7 was 25% of the maximum tensile force of 10 psi. The modulus of Example 7 was 66 kpsi.

Although the invention has been described in terms of a limited number of implementations, the specific features of one implementation of the invention are not applicable to other implementations. Any implementation does not represent all aspects of the invention. In certain embodiments, the compositions or methods may contain some of the compounds or procedures not mentioned in the present invention. In some implementations, mentioned The compositions or methods do not contain or substantially exclude compounds or procedures not mentioned herein. There are also different and adjusted content than those described in the described implementation. Finally, the disclosed digits indicate an approximation regardless of whether the text is expressed as approximately 摂 or approximately 摂. The claims appended hereto are intended to cover all variations and modifications which are within the scope of the invention. The above are only the preferred embodiments of the present invention, and all changes and modifications made to the scope of the present invention should be within the scope of the present invention.

Figure 1 shows the ultraviolet-visible (UV-Vis) spectrum of Example 1 and β-farnesene.

Figure 2 shows the gel permeation chromatography (GPC) curve of Example 1.

Figure 3 shows the C ¹³ nuclear magnetic resonance (NMR) spectrum of Example 1.

Figure 4 shows the H ¹ nuclear magnetic resonance spectrum of Example 1.

Figure 5 shows a differential scanning calorimetry (DSC) curve of Example 1.

Figure 6 shows the thermogravimetric analysis (TGA) curve measured in the air of Example 1.

Figure 7 shows the thermogravimetric analysis (TGA) curve determined in Example 1 for nitrogen.

Figure 8 shows the results of the lap test of Example 1.

Figure 9 shows a gel permeation chromatography (GPC) curve of Example 2.

Figure 10 shows a differential scanning calorimetry (DSC) curve of Example 2.

Figure 11 shows the results of the tensile test of Example 2.

Figure 12 shows a gel permeation chromatography (GPC) curve of Example 3.

Figure 13 shows the C ¹³ nuclear magnetic resonance spectrum of Example 3.

Figure 14 shows the H ¹ nuclear magnetic resonance spectrum of Example 3.

Figure 15 shows a differential scanning calorimetry (DSC) curve of Example 3.

Figure 16 shows the thermogravimetric analysis (TGA) of Example 3.

Figure 17 shows the results of the lap test of Example 3.

Figure 18 shows a gel permeation chromatography (GPC) curve of the formed polystyrene.

Figure 19 shows a gel permeation chromatography (GPC) curve of the formed polystyrene-1,4-polyfarnesene diblock copolymer.

Figure 20 shows a gel permeation chromatography (GPC) curve of Example 4.

Figure 21 shows the ¹³ C nuclear magnetic resonance spectrum of Example 4.

Figure 22 shows the ¹ H nuclear magnetic resonance spectrum of Example 4.

Figure 23 shows a differential scanning calorimetry (DSC) curve of Example 4.

Figure 24 shows the thermogravimetric analysis (TGA) of Example 4.

Figure 25 shows the results of the tensile test of Example 4.

Figure 26 shows the results of the lap test of Example 4.

Figure 27 shows a gel permeation chromatography (GPC) curve of the formed polystyrene.

Figure 28 shows a gel permeation chromatography (GPC) curve of the formed polystyrene-3.4-polyfarnesene diblock copolymer.

Figure 29 shows a gel permeation chromatography (GPC) curve of Example 5.

Figure 30 shows the ¹³ C nuclear magnetic resonance spectrum of Example 5.

Figure 31 shows the ¹ H nuclear magnetic resonance spectrum of Example 5.

Figure 32 shows a differential scanning calorimetry (DSC) curve of Example 5.

Figure 33 shows the thermogravimetric analysis (TGA) of Example 5.

Figure 34 shows the results of the tensile test of Example 5.

Figure 35 shows the gel permeation chromatography (GPC) curve of Example 5 after n-hexane extraction.

Figure 36 shows the n-hexane gel permeation chromatography (GPC) curve after the compound of Example 5 was extracted. line.

Figure 37 shows the results of the tensile test of Example 5.

Figure 38 shows the results of the lap test of Example 5.

Figure 39 shows the results of the tensile test of Example 6.

Figure 40 shows the results of the tensile test of Example 7.

Claims (82)

A polyfarnesene composition comprising one or more polymer molecules having a structure of the following formula (X'): Wherein n is an integer from 1 to about 100,000; m is an integer from 0 to about 100,000; and X has one or more structures encompassed by the following formulas (I')-(VIII'): Y has the structure of the following formula (IX'): Wherein R ¹ has the structure of the following formula (XI): Wherein R ² has the structure of the following formula (XII): Wherein R ³ has the structure of the following formula (XIII): Wherein R ⁴ has the structure of the following formula (XIV): Wherein R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each independently hydrogen, alkyl, cycloalkyl, aryl, cycloalkenyl, alkynyl, heterocyclyl, alkoxy, aryloxy, carboxy, alkane An oxycarbonyl group, an amine carbaryl group, an alkylamine carbhydryl group, a dialkylamine carbhydryl group, a decyloxy group, a nitrile or a halogen; the compound of the formula (I') is present in an amount up to about the total weight of the polyfarnesene The molecular percentage of 80 wt.% and when m is 1 or greater and X to Y is from about 1:4 to about 100:1. The polyfarnesene according to claim 1, wherein the content of the formula (II') is from about 5 wt.% to 99 wt.% based on the total weight of the polyfarnesene. The polyfarnesene according to claim 1, wherein the content of the formula (III') is about 70% by weight based on the total weight of the polyfarnesene. The polyfarnesene according to claim 1, wherein one or more of the formulae (I')-(III'), (V')-(VII') and (XI)-(XIV) or At least a portion of the double bonds of the isomer compound are hydrogenated. The polyfarnesene according to claim 1, wherein m of the formula (X') is 0 and X has one or more structures of the formula (I') to (IV'). The polyfarnesene according to claim 1, wherein m is 0 and X has one or more structures of the formulae (V') to (VIII'). The polyfarnesene according to claim 6, wherein the content of the formulae (V') and (VI') is about a polycondensation method. 1 wt.% to 99 wt.% of the total weight of the olefin. The polyfarnesene according to claim 6, wherein the content of the formula (VII') is from about 1 wt.% to 99 wt.%, based on the total weight of the polyfarnesene. The polyfarnesene of claim 1, wherein m is from about 1 to 100,000, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are both H. The polyfarnesene according to claim 1, wherein m is from about 1 to 100,000, R ⁵ is an aryl group, and R ⁶ , R ⁷ and R ⁸ are both H. The polyfarnesene of claim 10, wherein the aromatic group is a phenyl group. The polyfarnesene of any one of claims 1 to 4, wherein m is about 1 to 100,000, and wherein the polyfarnesene is a random farnesene copolymer. The polyfarnesene according to any one of claims 1 to 4, wherein m is from about 1 to 100,000, and wherein the polyfarnesene is a block farnesene copolymer. The polyfarnesene according to claim 13, wherein the block farnesene copolymer is composed of one block containing X and two blocks containing Y, wherein the block containing X is located in two Between the blocks of Y. The polyfarnesene of any one of claims 1 to 11, wherein the polyfarnesene has a _Mw molecular weight of greater than about 60,000 Daltons. The polyfarnesene of any one of claims 1 to 11 has a _Tg of less than about -60 °C. The polyfarnesene of any one of claims 1 to 11, wherein the sum of the values of m and n is greater than 300. A polyfarnesene obtained by polymerizing β-farnesene in the presence of a catalyst, wherein the poly-farnesene has a cis-1,4 microstructure content of up to 80 wt% of the total weight of the polyfarnesene. %. A polyfarnesene obtained by polymerizing α-farnesene in the presence of a catalyst, wherein the poly-farnesene has a cis-1,4 microstructure content of up to 1 wt% of the total weight of the polyfarnesene. % to 99 wt.%. A polyfarnesene prepared by (a) polymerizing farnesene in the presence of a catalyst to form an unsaturated polyfarnesene; and (b) dissolving the unsaturated polymer in the presence of a hydrogenating reagent At least a portion of the double bonds in the olefin are hydrogenated. The polyfarnesene of any one of claims 18 to 20, wherein the farnesene is copolymerized with a vinyl monomer to form a farnesene copolymer. The polyfarnesene of claim 21, wherein the vinyl monomer is styrene. The polyfarnesene of any one of claims 18 to 20, wherein the farnesene is prepared from a microorganism. The polyfarnesene of any one of claims 18 to 20, wherein the farnesene is derived from a monosaccharide. The polyfarnesene of any one of claims 18 to 20, wherein the catalyst comprises an organolithium reagent. The polyfarnesene of claim 25, wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane. The polyfarnesene of claim 25, wherein the organolithium reagent is n-butyllithium or sec-butyllithium. The polyfarnesene of claim 20, wherein the hydrogenation reagent is hydrogen present in a hydrogenation catalyst. The polyfarnesene of claim 28, wherein the hydrogenation catalyst is 10% palladium on carbon. A method of producing a polyfarnesene according to any one of claims 1 to 11, comprising copolymerizing farnesene and at least one vinyl monomer in the presence of a catalyst, said farnesene and vinyl The molar percentage of monomer is from about 1:4 to about 100:1. A method of making a polyfarnesene comprising: (a) causing a microorganism to produce a farnesene using a monosaccharide; and (b) copolymerizing the farnesene and at least one vinyl monomer in the presence of a catalyst. The method of claim 31, wherein the molar percentage of the farnesene to the vinyl monomer is from about 1:4 to 100:1. The method of any one of claims 30 to 32, wherein the at least one vinyl monomer does not contain a terpene. The method of any one of claims 30 to 32, wherein the at least one ethylene monomer is ethylene, an α-olefin, a substituted or unsubstituted vinyl halide, a vinyl ether, an acrylonitrile, an acrylate, A methacrylate, acrylamide or methacrylamide or a combination of two. The method of any one of claims 30 to 32, wherein the at least one vinyl monomer is a terpene. The method of any one of claims 30 to 32, wherein the catalyst is a Ziegler-Natta catalyst, a Kaminsky catalyst, a metallocene catalyst, an organolithium reagent, or a combination thereof. The method of any of claims 30-32, wherein the catalyst comprises an organolithium reagent. The method of claim 37, wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane. The method of claim 37, wherein the organolithium reagent is n-butyllithium or sec-butyllithium. A polyfarnesene prepared by the method of any one of claims 30-32. A polymeric composition comprising the polyfarnesene of any one of claims 1-11 and 18-20, and at least one additive. The polymer composition according to claim 41, wherein the additive is a filler, a graft initiator, a tackifier, a slip agent, an antiblocking agent, a plasticizer, an antioxidant, a foaming agent, and a foaming agent. Agent activator, UV stabilizer, acid scavenger, colorant or pigment, coagent, lubricant, antifogging agent, flow aid, processing aid, extrusion aid, coupling agent, crosslinking agent, stability Control agent, nucleating agent, surfactant, flame retardant, antistatic agent, or a combination thereof. The polymer composition of claim 41, wherein the additive is a filler. The polymer composition of claim 41, wherein the additive is a crosslinking agent. The polymer composition of claim 41, wherein the additive is a second polymer. The polymer composition of claim 45, wherein the ratio of the polyfarnesene to the second polymer is from about 1:99 to 99:1. The polymer composition of claim 45, wherein the second polymer is a polyolefin, a polyurethane, a polyester, a polyamide, a styrene polymer, a phenolic resin, or a polyacrylic acid. Ester, polymethacrylate or a combination thereof. An article comprising the polyfarnesene of any one of claims 1 to 11 and any one of claims 18 to 20. The article of claim 48, wherein the article is a molded article, a film, a sheet or a foam. The article of claim 48, wherein the article is a molded article selected from the group consisting of a toy, a jig, a soft handle, a cushion rubber strip, a floor, a car mat, a wheel, a caster, a furniture, and an electric foot pad. , labels, seals, static and dynamic gaskets, automotive doors, bumpers, grille components, sills, hoses, linings, office supplies, gaskets, gaskets, diaphragms, tubes, covers, stoppers, punches, Carrying systems, kitchen appliances, shoes, shoe bags and soles. An adhesive composition comprising the polyfarnesene of any one of claims 1 to 11 and a tackifier. The adhesive composition of claim 51, wherein the polyfarnesene is a farnesene homopolymer. The adhesive composition of claim 51, wherein said m is from about 1 to about 100,000, and said polyfarnesene is any random random farnesene copolymer. The adhesive composition of claim 51, wherein said m is from about 1 to about 100,000 and the polyfarnesene is a block of farnesene copolymer. The adhesive composition according to claim 54, wherein the block farnesene copolymer is composed of one block containing X and two blocks containing Y, and the block containing X is located at Between the two blocks containing Y. The adhesive composition according to claim 51, wherein the content of the tackifier is about It accounts for about 5 wt.% to about 70 wt.% of the total weight of the polyfarnesene. The adhesive composition of claim 51 further comprising an additive derived from a plasticizer, an oil, a wax, an antioxidant, a UV stabilizer, a colorant and a pigment, a filler, a glidant, a coupling agent , crosslinkers, surfactants, solvents, and combinations thereof. The adhesive composition as claimed in claim 51 further contains a second polymer. The adhesive composition according to claim 58, wherein the second polymer is natural rubber, synthetic rubber, polyacrylate, polymethacrylate, poly-α-olefin, ethylene homopolymer, ethylene copolymerization. , styrene block copolymer or a combination thereof. An adhesive composition comprising a polyfarnesene and a tackifier prepared according to the method of any one of claims 30-32. The binder composition of claim 60, wherein the farnesene is alpha-farnesene, beta-farnesene or a combination thereof. The adhesive composition of claim 60, wherein the poly-farnesene has a cis-1,4-microstructure content of up to about 80% by weight based on the total weight of the polyfarnesene. The adhesive composition of claim 60, wherein the vinyl monomer is present and the polyfarnesene is a farnesene copolymer. The adhesive composition of claim 60, wherein the vinyl monomer is styrene. The adhesive composition of claim 60, wherein the farnesene copolymer is a block copolymer. The adhesive composition of claim 60, wherein the farnesene is prepared from a microorganism. The adhesive composition of claim 60, wherein the farnesene is prepared from a monosaccharide. The adhesive composition of claim 60, wherein the catalyst comprises an organolithium reagent. The adhesive composition of claim 68, wherein the catalyst further comprises 1,2-bis(dimethylamino)ethane. The adhesive composition according to claim 60, wherein the composition is a hot-melt adhesive composition or a pressure-sensitive adhesive composition. An article, in which all or a portion of the article is coated with the adhesive composition of claim 60. The article of claim 71, which is a paper product, a packaging material, a plywood strip, a kitchen countertop, a vehicle, a label, a disposable diaper, a medical mattress, a female sanitary napkin, a surgical drape, a tape, a box, a carton. , trays, medical equipment or bandages. The article of claim 72, which is a tape, box, carton, tray, medical device or bandage. An adhesive method of adhering a first adherend to a second adherend using an adhesive of the adhesive composition according to any one of claims 51 to 59. The method of claim 74, wherein the first adherend is the same as the second adherend. The method of claim 74, wherein the first adherend is different from the second adherend. The method of claim 74, wherein the first and second adherends are each packaged Including metal, wood, paper, plastic, rubber, glass, stone, granite, marble, masonry, porcelain, ceramic, ceramic tile, porcelain, cement, clay, sand, chalk, fabric, cloth, non-woven fabric, leather or a combination thereof. The method of claim 74, wherein the first and second adherends are each in the form of a sheet, a strip, a tape, a label, a label, a mesh, a magnetic sheet, a sheet, a film, or any molded shape. . An adhesive composition comprising a rubber and a tackifier, and the tackifier comprises the polyfarnesene of any one of claims 1-11. The adhesive composition of claim 79, wherein the polyfarnesene is present in an amount from about 5 wt.% to about 70 wt.%, based on the total weight of the adhesive composition. The adhesive composition of claim 79, wherein the polyfarnesene has a ring and ball softening point of greater than or equal to 80 ° C as determined according to ASTM 28-67. The adhesive composition of claim 79, wherein the rubber has a _{Tg of} less than 20 °C.