Polymerization modifier for hydrocarbon polymers having high aromaticity and low molecular weight and use thereof

Abstract

This specification describes a hydrocarbon polymer modifier for use in a variety of applications. The hydrocarbon polymer modifier contains cyclic components and has a glass transition temperature and Mn defined by the following two formulas: (1) Tg≧95-2.2 * (% H Ar), and (2) Tg≧-53+(0.265 * Mn); content of aromatic protons (%H Ar) from 12 mole% to 19 mole%; and Mn from 300 g / mole to 450 g / mole, where Tg is the glass transition temperature of the modifier expressed in °C, %H Ar represents the content of aromatic protons in the hydrocarbon polymer modifier, Mn represents the number average molecular weight of the hydrocarbon polymer modifier, and the cyclic component is selected from the group of distillation cuts from petroleum refinery streams, and / or C4, C5 or C6 cyclic olefins and mixtures thereof. Further, the hydrocarbon polymer modifier may be characterized by a Tg from 70°C to 95°C and / or a z-average molecular weight (Mz) of the hydrocarbon polymer modifier less than 1000 g / mole. The hydrocarbon polymer modifier is particularly useful in high Tg applications where low molecular weight is desired.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 141,681, filed January 26, 2021, the disclosure of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates to hydrocarbon polymer resins, and more particularly to novel hydrocarbon polymer polymerization modifiers useful in a variety of applications. [Background technology]

[0003] Background of the Invention Hydrocarbon resins are used in a variety of applications, such as tire components, hoses, belts, footwear components, and vibration isolators. For example, in elastomeric compositions, hydrocarbon resins are used as processing aids and to improve the characteristics of the elastomeric composition. The selection of materials for the commercial design of elastomeric compositions depends on the desired balance of properties, application, and end use for a particular application. Generally, the raw materials and ingredients used in rubber compounds affect performance variables, therefore the materials must be compatible with the rubber, must not interfere with cure, must be easily dispersed in the overall compound, must be cost-effective, and must not adversely affect product performance. For example, in tire applications, rolling resistance, dry and humid traction characteristics, heat storage are important performance attributes, along with the ability to improve the durability of tires used in various conditions. The glass transition temperature ("Tg") in a resin system is defined as the point at which a polymer goes from a rigid to a more flexible state. Tg provides important information about the resin, including the polymer's properties at its use temperature, i.e., whether it is rigid or flexible. At temperatures below Tg, the molecular chains do not have enough energy to allow themselves to move around. Here, the polymer molecules are essentially organized into a rigid, amorphous structure due to short chain lengths, branched molecular groups and their interlocking, and / or rigid backbone structure. When heat is applied, the polymer molecules gain some energy and can begin to move. At some point, the thermal energy transforms the amorphous, rigid state into a flexible state, and the molecules are free to move around each other. This transition point is called the glass transition temperature. Elastomer compositions are amorphous polymers that do not melt (unlike crystalline polymers, which melt when heat is applied); however, they undergo a structural change (from rigid to flexible), resulting in a change in the heat capacity of the resin. Above the Tg, rubbery, flexible polymers have a higher heat capacity. Therefore, for many applications, polymer compositions require a high glass transition temperature.

[0004] High Tg resins can be produced by increasing the molecular weight of the resin. Furthermore, higher molecular weight resins also beneficially affect the impact and chemical resistance of the product, due to the increased strength and stiffness of the resulting resin. However, these resins have limited compatibility with the base polymer. Modifiers can be added to the resin to mitigate polymer incompatibility, but they are not designed to lower the molecular weight of the resin. However, a low molecular weight resin can be important, especially when ease of processing is important. Therefore, hydrocarbon polymer modifiers ("HPMs") with high aromaticity, high Tg, low number average molecular weight ("Mn"), and preferably low z-average molecular weight ("Mz") are promising. Hydrocarbon resins are also useful in adhesive compositions. Styrenic block copolymers are widely used to make hot melt adhesives for a variety of applications, including diaper assembly. These styrenic block copolymers include unvulcanized elastomeric block copolymers, in which the individual monomer moieties are arranged in an alternating sequence with a general ABA structure. In this structure, A is a non-elastomeric block derived from styrene, commonly referred to as a styrene "end-block," and B is an elastomeric polymer block derived from, for example, isoprene and / or butadiene, commonly designated as an isoprene or butadiene "mid-block." This type of block copolymer may be depicted as having polystyrene end blocks at the end of each branch, with a branched polymerized mid-block derived from, for example, isoprene or butadiene. The end blocks provide the necessary cohesive strength and also increase the high-temperature properties of the adhesive. However, it is also known that incorporating low-aromaticity tackifying resins and / or softening oils into hot melt adhesives based on styrenic block copolymers can lead to a decrease in the adhesive's cohesive strength and high-temperature resistance. Therefore, a need exists for hydrocarbon polymer modifiers (“HPMs”) that have high aromaticity, high Tg, low number average molecular weight (“Mn”), and preferably low z-average molecular weight (“Mz”), and that can be used in a variety of applications, including rubber compositions and adhesives. Summary of the Invention

[0005] Summary of the Invention Described herein are hydrocarbon polymer modifiers for use in a variety of applications, which contain cyclic moieties and have a glass transition temperature and aromaticity content defined by the following two equations: (1) Tg≧95-2.2 * (% H Ar), and (2) Tg ≥ -53 + (0.265 *Mn); a content of aromatic protons (%H Ar) of 12 mole% to 19 mole%; and Mn of 300 g / mole to 450 g / mole, where Tg is the glass transition temperature of the hydrocarbon polymer modifier expressed in °C, %H Ar represents the content of aromatic protons in the hydrocarbon polymer modifier, Mn represents the number average molecular weight of the hydrocarbon polymer modifier, and the cyclic component is selected from the group consisting of distillation cuts of petroleum refinery streams, and / or C4, C5, or C6 cyclic olefins and mixtures thereof. Further, the hydrocarbon polymer modifier may be characterized by a Tg of 70°C to 95°C and / or a z-average molecular weight (Mz) of less than 1000 g / mole.

[0006] In one embodiment, the cyclic component is cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene, and / or di(methylcyclopentadiene). In one embodiment, the hydrocarbon polymer polymerization modifier contains the cyclic component in an amount of about 10 wt.% to about 90 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains the cyclic component in an amount of about 25 wt.% to about 80 wt.%. In one embodiment, the cyclic component is selected from the group consisting of dicyclopentadiene, cyclopentadiene, and methylcyclopentadiene. In one embodiment, the cyclic component is cyclopentadiene. In one embodiment, the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount of about 10 wt.% to about 90 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount of about 25 wt.% to about 80 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains methylcyclopentadiene in an amount of about 0.1 wt.% to about 15 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains methylcyclopentadiene in an amount of about 0.1 wt.% to about 5 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier further contains an aromatic component. In one embodiment, the aromatic component is selected from one of olefin-aromatic, substituted benzene, or aromatic distillation cuts. In one embodiment, the aromatic component is an aromatic distillation cut. In one embodiment, the hydrocarbon polymer polymerization modifier contains the aromatic component in an amount of about 20 wt.% to about 75 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains the aromatic component in an amount of about 25 wt.% to about 70 wt.%. Also provided are adhesives containing the hydrocarbon polymer polymerization modifiers provided herein. In one embodiment, the adhesives contain the hydrocarbon polymer in an amount of about 0.1 wt.% to about 99.5 wt.%. Also provided are sealants containing the hydrocarbon polymer in an amount of about 0.1 wt.% to about 99.5 wt.%. Also provided are films containing the hydrocarbon polymer in an amount of about 0.1 wt.% to about 99.5 wt.%. Adhesives, sealants, and films within the scope of the present disclosure do not include those associated with or used on pneumatic and non-pneumatic tires and wheels. Also provided herein is a method for producing the hydrocarbon polymer polymerization modifier of the present invention, which comprises polymerizing a continuous stream of cyclics in the presence or absence of a solvent at a reaction temperature between about 250°C and 290°C for about 1 hour to about 3 hours. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a graph of the relationship between Tg and % H Ar for HPM of the present invention, comparative resins, and prior art elastomer compositions. [Figure 2] FIG. 2 is a graph of the relationship between Tg and Mn for HPM of the present invention, comparative resins, and prior art elastomer compositions. [Figure 3] FIG. 3 is a graph of the relationship between Tg and Mz for HPM of the present invention, comparative resins, and prior art elastomer compositions. DETAILED DESCRIPTION OF THE INVENTION

[0008] Detailed Description of the Invention Provided herein is a hydrocarbon polymer polymerization modifier that contains a cyclic component and has a glass transition temperature and aromaticity content defined by the following two equations: (1) Tg≧95-2.2 * (% H Ar), and (2) Tg ≥ -53 + (0.265 * Mn); further characterized by an aromatic proton content (%H Ar) of 12 mole% to 19 mole%, and an Mn of 300 g / mole to 450 g / mole, where the glass transition temperature ("Tg") of the hydrocarbon polymer modifier is expressed in degrees Celsius (°C), the term "%H Ar" represents the aromatic proton content in the hydrocarbon polymer modifier, "Mn" represents the number average molecular weight of the hydrocarbon polymer modifier expressed in grams per mole ("g / mole"), and the cyclic component is selected from the group of distillate cuts derived from petroleum refinery streams, and / or C4, C5, or C6 cyclic olefins and mixtures thereof. The hydrocarbon polymer modifier may further be characterized by a Tg of 70°C to 95°C and / or a z-average molecular weight (Mz) of less than 1000 g / mole. The subject hydrocarbon polymer modifiers ("HPMs") contain one or more cyclic moieties that are used to prepare one or more complex copolymers described herein. The architecture of the complex copolymers may be controlled by the type and amount of monomers included in the modifier (i.e., the copolymer microstructure). However, the monomer placement in the polymer chain is random, leading to additional complexity in the polymer microstructure.

[0009] In one embodiment, one or more cyclic components are combined with an aromatic component to provide a hydrocarbon polymer polymerization modifier (also referred to herein as a "polymerization modifier" or "tackifier"), which may include, but is not limited to, olefin-aromatic, substituted benzene and / or aromatic distillation cuts. In one embodiment, the hydrocarbon polymer polymerization modifier of the present invention contains cyclic components in an amount of about 10 wt.% to about 90 wt.% based on the total weight of the hydrocarbon polymer additive. In one embodiment, the hydrocarbon polymer polymerization modifier contains cyclic components in an amount of about 25 wt.% to about 80 wt.% based on the total weight of the hydrocarbon polymer polymerization modifier. In one embodiment, the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount of about 10 wt.% to about 90 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount of about 25 wt.% to about 80 wt.%. In one embodiment, the hydrocarbon polymer polymerization modifier contains methylcyclopentadiene ("MCPD")-derived components in an amount of about 0.1 wt.% to about 15 wt.% and about 0.1 wt.% to about 5 wt.%. In one embodiment, the aromatic component may be an olefin-aromatic, a substituted benzene and / or an aromatic distillation cut. In one embodiment, the total weight of the hydrocarbon polymer polymerization modifier contains the aromatic component in an amount of about 20 wt.% to about 75 wt.% and about 25 wt.% to about 70 wt.% of the total weight of the hydrocarbon polymer additive.

[0010] Before the polymers, compounds, ingredients, compositions, polymerization modifiers, and / or methods are disclosed and described, it is understood that unless otherwise indicated, the teachings are not limited to particular polymers, compounds, ingredients, compositions, reactants, reaction conditions, or the like, as these may vary unless otherwise specified. Furthermore, the terminology used herein is used for the purpose of describing particular embodiments and is not intended to be limiting.

[0011] definition For purposes of this disclosure, the following definitions apply unless otherwise stated: As used herein, the singular forms "a," "an," and "the" include plural referents unless otherwise specified. The molecular weight distribution ("MWD") is expressed as M w / M nEqual to the expression M w / M n is the weight average molecular weight (M w ) number average molecular weight (M n ) as a percentage. The weight average molecular weight is as follows:

number

number

number

[0012] Gel permeation chromatography. Molecular weight distributions and moments (Mw, Mn, Mw / Mn, etc.) were determined using gel permeation chromatography (GPC) on a Tosoh EcoSEC HLC-8320 GPC equipped with a refractive index (RI) and ultraviolet (UV) detector at room temperature (20 °C). Four Agilent PLgels were used in series: 5 μm 50A; 5 μm 500A; 5 μm 10E3A; and 5 μm Mixed-D. Aldrich reagent-grade tetrahydrofuran (THF) was used as the mobile phase. The polymer mixture was passed through a 0.45 μm Teflon filter and degassed using an online degasser before injection into the GPC system. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 200 μL. Molecular weight analysis was performed using EcoSEC software. The concentration (c) at each point in the chromatogram was calculated from the baseline-subtracted IR5 broadband signal intensity (I) using the following formula: c = βI, where "β" is a mass constant determined using polystyrene standards. Mass recovery was calculated from the ratio of the total area of ​​the chromatographic concentration to the elution volume and the injected mass equal to a given concentration multiplied by the injection circulation volume.

[0013] Molecular weight. Molecular weights were determined using a column calibration performed with a series of monodisperse polystyrene (PS) standards of 162, 370, 580, 935, 1860, 2980, 4900, 6940, 9960, 18340, 30230, 47190 & 66000 kg / mole and associated polystyrene calibration. The molecular weight "M" at each elution volume is calculated by the following formula:

number

[0014] The term "dominant compound" refers to a compound that is predominant among compounds of the same type in a composition. For example, a dominant compound is one that represents the greatest weight percentage of compounds of the same type in a composition. Similarly, for example, a dominant polymer is one that represents the greatest weight percentage of the total weight of polymers in a composition. The term "dominant units" refers to units that, within the same compound (or polymer), are predominant among the units forming the compound (or polymer), or that represent the greatest weight percentage of the units forming the compound (or polymer). For example, a hydrocarbon polymer modifier may contain predominant units of cyclopentadiene, with the cyclopentadiene units representing the greatest weight percentage of all units comprising the modifier. Similarly, as described herein, a hydrocarbon polymer modifier may contain predominant units selected from the group consisting of cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof, with the sum of units selected from the group consisting of cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof representing the greatest weight percentage of all units. The term "dominant monomer" refers to the monomer that represents the greatest percentage by weight of the total polymer. Conversely, a "minor" monomer is one that does not represent the largest mole fraction in the polymer. The term "composition based on" refers to a composition containing a mixture and / or product of in situ reactions of the various basic components used, some of which can react and / or are intended to react with each other, at least in part, during various stages of the preparation of the composition or during subsequent curing of the composition, modifying the composition as initially prepared. Thus, the compositions described below may differ in their uncrosslinked and crosslinked states. As used herein, the terms "elastomer" and "rubber" are used interchangeably and refer to elastomer(s) derived at least in part (i.e., homopolymer or copolymer) from diene monomers (monomers containing two conjugated or non-conjugated carbon-carbon double bonds). The terms "adhesive polymer composition" and "adhesive base polymer" are used interchangeably. "Diene elastomer" refers to an elastomer derived at least in part (homopolymer or copolymer) from diene monomers (monomers containing two conjugated or non-conjugated carbon-carbon double bonds). Diene elastomers may be "highly unsaturated" and derived from conjugated diene monomers, the conjugated diene monomers having a molar content of greater than 50% of the constituent units.

[0015] Diene elastomers can be divided into two categories: "essentially unsaturated" or "essentially saturated." "Essentially unsaturated" is generally understood to mean diene elastomers derived at least in part from conjugated diene monomers with a content of diene source (conjugated diene) units of more than 15% (mol %); thus, diene elastomers such as butyl rubber or copolymers of dienes and α-olefins of the EPDM type do not fall within the above definition and can be described, in particular, as "essentially saturated" diene elastomers (with a low or very low content of diene source units, always less than 15%). Within the category of "essentially unsaturated" diene elastomers, "highly unsaturated" diene elastomers are understood to mean, in particular, diene elastomers with a content of diene source (conjugated diene) units of more than 50%. In the present disclosure, when referring to the ratio of the amounts of compound A and compound B or the ratio between the content of compound A and the content of compound B, this is always the ratio in the mathematical sense of the amount of compound A to the amount of compound B. Unless otherwise stated, all indicated percentages (%) are percentages by weight ("wt. %"). Furthermore, any range of values ​​indicated by the expression "between a and b" denotes a range of values ​​that runs from above a to below b (i.e., excluding the limits a and b), while any range of values ​​indicated by the expression "from a to b" means a range of values ​​that runs from a to b (i.e., including the precise limits a and b).

[0016] As used herein, the term "cyclic component" refers to a distillation cut and / or a synthetic mixture of C5 and C6 cyclic olefins, diolefins, dimers, codimers, and trimers. More specifically, cyclic components include, but are not limited to, cyclopentene, cyclopentadiene ("CPD"), dicyclopentadiene ("DCPD"), cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene ("MCPD"), di(methylcyclopentadiene) ("MCPD dimer"), and codimers of CPD and / or MCPD with C4 ring compounds such as butadiene and C5 ring compounds such as piperylene. An exemplary cyclic component is cyclopentadiene. Furthermore, the cyclic component may be substituted. The dicyclopentadiene may be either endo- or exo-converted. The substituted cyclic moiety is C1-C 40 The cyclic components include cyclopentadienes and dicyclopentadienes substituted with linear, branched, or cyclic alkyl groups. In one embodiment, the substituted cyclic components may have one or more methyl groups. In one embodiment, the cyclic components are selected from the following group: cyclopentadiene, cyclopentadiene dimer, cyclopentadiene-C4 codimer, cyclopentadiene-C5 codimer, cyclopentadiene-methylcyclopentadiene codimer, methylcyclopentadiene-C4 codimer, methylcyclopentadiene-C5 codimer, methylcyclopentadiene dimer, trimers and cotrimers of cyclopentadiene and methylcyclopentadiene, and / or mixtures thereof.

[0017] In one embodiment, the hydrocarbon polymer polymerization modifier may further contain an aromatic component. In one embodiment, the aromatic component contains one or more olefinic aromatics represented by formula i: [ka] Formula I In the formula, R1 and R2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an arylalkyl group, such as 1H-indene; 1-methyl-1H-indene; alkylindene; 5-(2-methylbut-2-enyl)-1H-indene; 5,6,7,8-tetrahydro-1H-cyclopentanaphthalene; 4-indene-5-butan-1ol, or a derivative thereof. In one embodiment, the aromatic moiety contains one or more substituted benzene derivatives represented by formula ii: [ka] formula ii wherein R3 and R4 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an arylalkyl group. Alpha-methylstyrene or substituted alpha-methylstyrenes having one or more substituents on the aromatic ring are preferred, particularly those selected from alkyl, cycloalkyl, aryl, or a combination of radicals, each having 1 to 8 carbon atoms per substituent. Non-limiting examples include alpha-methylstyrene, alpha-methyl-4-butylstyrene, alpha-methyl-3,5-di-t-benzylstyrene, alpha-methyl-3,4,5-trimethylstyrene, alpha-methyl-4-benzylstyrene, alpha-methyl-4-chlorohexylstyrene, and / or mixtures thereof.

[0018] In one embodiment, the hydrocarbon polymer polymerization modifier ("HPM") contains an aromatic distillation cut derived from a petroleum refinery stream, such as obtained by steam cracking of the stream followed by separation of the fraction boiling in the range of 135°C to 220°C by fractional distillation. In one embodiment, the aromatic distillation cut component contains styrene, alkyl-substituted derivatives of styrene, indene, and / or alkyl-substituted derivatives of indene. In one embodiment, the aromatic distillation cut component contains from about 4 wt.% to about 7 wt.% styrene; from about 20 wt.% to about 30 wt.% alkyl-substituted derivatives of styrene, from about 10 wt.% to about 25 wt.% indene, from about 5 wt.% to about 10 wt.% alkyl-substituted derivatives of indene, and from about 35 wt.% to about 45 wt.% non-reactive aromatics. In one embodiment, the olefin-aromatic, substituted benzene and / or aromatic distillation cut is from about 20 wt.% to about 75 wt.%, or from about 25 wt.% to about 70 wt.%, of the total weight of the HPM.

[0019] The hydrocarbon polymer modifiers ("HPMs") of the present invention can be prepared by different techniques. For example, thermal polymerization of cyclic feed streams in combination with or without olefin-aromatic, substituted benzene, and aromatic distillation cuts can be used. As described in the examples below, various resins were prepared to obtain the desired molecular weight and softening point or glass transition temperature. Specifically, Tables 4 and 5 below list the feed streams, polymerization conditions, and final physical properties of the HPMs of the present invention. Incompatibility with the base polymer can limit the application of high Tg resins where low molecular weight and ease of processing are desirable. The hydrocarbon polymer modifiers of the present invention overcome this drawback through their unprecedented novel combination of %H, Ar, and Mn, and preferably Tg and / or Mz.

[0020] Specifically, the HPM of the present invention is defined as follows: Tg≧95-2.2 * (% H Ar); Tg≧―53+(0.265 *Mn), where Tg is the glass transition temperature of the modifier expressed in °C, %H Ar represents the content of aromatic protons in the modifier, and Mn represents the number average molecular weight of the modifier. More specifically, the HPM of the present invention is defined by an aromatic proton content ("%H Ar") of 12 mol% to 19 mol% and an Mn of 300 g / mole to 450 g / mole. In one embodiment, the HPM of the present invention has a glass transition temperature (Tg) of from 70°C to 95°C, preferably from 70°C to 90°C. In one embodiment, the HPM of the present invention has a z-average molecular weight (Mz) of less than 1000 g / mole. In one embodiment, the hydrocarbon polymer polymerization modifier has at least one, and preferably all, of the following additional characteristics: Tg≧100-2.2 * Glass transition temperature (Tg) expressed as (H Ar) Tg≧-32+(0.265 * Glass transition temperature (Tg) expressed as Mn Number average molecular weight (Mn) from 350g / mole to 420g / mole

[0021] rubber composition Further provided herein is a rubber composition containing at least one elastomer, a reinforcing filler, a crosslinking system, and one or more hydrocarbon polymer modifiers of the present invention. In one embodiment, the rubber composition (also referred to as the "composition" or "elastomer composition") of the present invention contains a hydrocarbon polymer modifier of the present invention having units selected from the group consisting of cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof. In addition, when used in a rubber composition, the HPM of the present invention further contains an aromatic proton content expressed as a percentage and a glass transition temperature, Tg, expressed in °C, wherein Tg is 95-2.2°C or higher. * (% H Ar) and Tg≧-53+(0.265 *The HPM may be further characterized by a %H Ar of 12 to 19 mole percent (mole %) and a Mn of 300 to 450 g / mole, where %H Ar represents the aromatic proton content of the HPM and Mn represents the number average molecular weight of the HPM of the present invention. The HPM may further be characterized by a Tg of 70 to 95°C and / or a z-average molecular weight (Mz) of less than 1000 g / mole. The content of the HPM in the rubber composition may range from 15 to 150 phr, 25 to 120 phr, 40 to 115 phr, 50 to 110 phr, and 65 to 110 phr. If the HPM of the present invention is less than 15 phr, the effect of the HPM of the present invention may be insufficient, and the rubber composition may have grip problems. Above 150 phr, manufacturing difficulties may be presented with regard to readily incorporating the HPM of the present invention into compositions.

[0022] Elastomer The rubber composition of the present invention contains at least an elastomer and a rubber composition based on a specific hydrocarbon polymer polymerization modifier, as described above. The elastomer is further described below. As used herein, the terms "elastomer" and "rubber" are used interchangeably and are well known to those skilled in the art. "Diene elastomer" refers to an elastomer derived at least in part (homopolymer or copolymer) from diene monomers (monomers containing two conjugated or non-conjugated carbon-carbon double bonds). Diene elastomers may be "highly unsaturated" and derived from conjugated diene monomers, the conjugated diene monomers having a molar content of greater than 50% of the constituent units. Diene elastomers can be divided into two categories: "essentially unsaturated" or "essentially saturated." "Essentially unsaturated" is generally understood to mean diene elastomers derived at least in part from conjugated diene monomers with a content of diene source (conjugated diene) units of more than 15% (mol %); thus, diene elastomers such as butyl rubber or copolymers of dienes and α-olefins of the EPDM type do not fall within the above definition and can be described, in particular, as "essentially saturated" diene elastomers (with a low or very low content of diene source units, always less than 15%). Within the category of "essentially unsaturated" diene elastomers, "highly unsaturated" diene elastomers are understood to mean, in particular, diene elastomers with a content of diene source (conjugated diene) units of more than 50%.

[0023] Subject to the above definitions, diene elastomers refer to: (a) All homopolymers obtained by polymerization of conjugated diene monomers having from 4 to 12 carbon atoms; (b) all copolymers obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (c) terpolymers obtained by copolymerization of ethylene and α-olefins having from 3 to 6 carbon atoms with non-conjugated diene monomers having from 6 to 12 carbon atoms, such as, for example, elastomers obtained from ethylene and propylene with non-conjugated diene monomers of the above-mentioned types, such as, in particular, 1,4-hexadiene, ethylidenenorbornene or dicyclopentadiene; (d) Copolymers of isobutene and isoprene (butyl rubber) and halogenated, especially chlorinated or brominated, copolymers of this type. Although the present invention applies to all types of diene elastomers, essentially unsaturated diene elastomers, particularly types (a) or (b) above, are useful in tire applications. The following are particularly suitable as conjugated dienes: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C-C alkyl)-1,3-butadienes such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, aryl-1,3-butadienes, 1,3-pentadiene or 2,4-hexadiene. The following are, for example, suitable as vinyl aromatic compounds: styrene, ortho-, meta- or para-methylstyrene, the commercially available "vinyltoluene" mixtures, para-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinylmesitylene, divinylbenzene or vinylnaphthalene. The copolymer may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units. The elastomer may have any microstructure, depending on the polymerization conditions used, particularly the presence or absence of polymerization control and / or randomization agents and the amount of polymerization control and / or randomization agents used. The elastomers may be, for example, block, random, sequential, or microsequential elastomers and may be prepared in dispersion or in a solvent; they may be conjugated and / or star-branched, or may be functionalized using additional coupling and / or star-branching or functionalizing agents. In this specification, "functional group" is primarily understood to mean a chemical group that interacts with the reinforcing filler of the composition.

[0024] In summary, the diene elastomer of the composition is preferably selected from the group of highly unsaturated diene elastomers consisting of polybutadiene (abbreviated as "BR"), synthetic polyisoprene (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene / styrene (SBR) copolymers. Thus, the present invention preferably relates to a composition in which the aforementioned diene elastomer is selected from the group consisting of essentially unsaturated diene elastomers, in particular from the group consisting of polybutadiene, synthetic polyisoprene, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.

[0025] According to a particularly preferred embodiment of the invention, the elastomer comprises as a main component an elastomer, preferably a diene elastomer, having a glass transition temperature Tg of less than -40°C, preferably between -40°C and -110°C, more preferably between -60°C and -110°C, more preferably between -80°C and -110°C, and even more preferably between -90°C and -110°C. Preferably, the primary diene elastomer is selected from the group consisting of polybutadiene, butadiene copolymers and elastomeric mixtures thereof, more preferably from the group consisting of polybutadiene, copolymers of butadiene and styrene and elastomeric mixtures thereof. According to an embodiment of the present invention, the elastomer, preferably diene-based, having a very low Tg is preferably present in the composition in a content of at least 60 phr, more preferably at least 70 phr and even more preferably at least 80 phr. More preferably, the composition contains 100 phr of the elastomer having a very low Tg as defined above.

[0026] Reinforcement material The composition may contain a reinforcing filler. Any type of known reinforcing filler may be used for its ability to toughen rubber compositions, including, for example, organic fillers such as carbon black, reinforcing inorganic fillers such as silica or alumina, or a mixture of these two types of fillers. As described herein, the reinforcing filler may be selected from the group consisting of silica, carbon black, and mixtures thereof. The reinforcing filler content may be within a range ranging from 5 phr to 200 phr, and from 40 to 160 phr. In one embodiment, the reinforcing filler is silica, and in one embodiment, the content is within a range ranging from 40 phr to 150 phr. The compositions provided herein may also contain small amounts of carbon black, and in one embodiment, the content is within a range ranging from 0.1 phr to 10 phr. All carbon blacks are suitable as carbon black. More particularly, reinforcing carbon blacks of the 100, 200, or 300 series (ASTM grades), such as N115, N134, N234, N326, N330, N339, N347, or N375 blacks, or others, are mentioned below, and, depending on the intended application, more expensive blacks (e.g., N660, N683, or N772) may also be used. The carbon black may, for example, be incorporated into the isoprene elastomer beforehand in the form of a masterbatch (see, for example, applications WO 97 / 36724 or WO 99 / 16600).

[0027] The rubber composition of the present invention may contain one type of silica or a mixture of silicas. The silica used may be any reinforcing silica, in particular a silica having a BET surface area and a CTAB specific surface area of ​​450 m 2 / g, e.g., 30m 2 / g to 400m 2 The silica may be any precipitated or fumed silica having a specific surface area of ​​up to 45 and 400 m / g. Highly disperse precipitated silicas ("HDSs") include, for example, Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol 8715, 8745 and 8755 silicas from Huber, treated precipitated silicas exemplified by the aluminum "doped" silicas described in application EPA-0735088, or silicas with high specific surface areas described in application WO 03 / 16837. Silicas may have a specific surface area of ​​45 and 400 m / g. 2 / g and between 60 and 300m 2 / g. The rubber composition of the present invention may contain (in addition to the coupling agent) a coupling activator, an agent for coating the inorganic filler, and any other processing aids that can improve the processability in the raw state by improving the dispersion of the filler in the rubber matrix and reducing the viscosity of the composition, such as hydrolyzable silanes such as alkylalkoxysilanes, polyols, fatty acids, polyethers, primary, secondary or tertiary amines, or hydroxylated or hydrolyzable polyorganosiloxanes. Silane polysulfides may in particular be used which, depending on their specific structure, are termed "symmetrical" or "asymmetrical", as described, for example, in applications WO 03 / 002648 (or US 2005 / 016651) and WO 03 / 002649 (or US 2005 / 016650).

[0028] Also particularly suitable are the so-called "symmetrical" silane polysulfides, which correspond to the following general formula iii, although the following definition is not intended to be limiting: (iii) ZA-Sx-AZ, wherein: -x is an integer between 2 and 8 (e.g., between 2 and 5); -A is a divalent hydrocarbon radical (e.g., C1-C 18 Alkylene group or C6-C 12 Arylene groups, more specifically C1-C 10 alkylene, in particular C1-C4 alkylene, especially propylene); -Z is represented by the formula: [ka] corresponds to one of the following. (In the formula: -R 1 The radicals may be substituted or unsubstituted, and may be the same or different, and may be C1-C 18 Alkyl, C5-C 18 Cycloalkyl or C6-C 18represents an alkyl group (e.g., a C1-C6 alkyl, cyclohexyl, or phenyl group, in particular a C1-C4 alkyl group, more particularly methyl and / or ethyl), -R 2 The radicals may be substituted or unsubstituted, and may be the same or different, and may be C1-C 18 Alkoxy or C5-C 18 It represents a cycloalkoxy group (for example a group selected from C1-C8 alkoxy and C5-C8 cycloalkoxy, for example a group selected from C1-C4 alkoxy, in particular methoxy and ethoxy). In the case of mixtures of alkoxysilane polysulfides corresponding to formula (iii) above, particularly in the case of typical commercial mixtures, the average value of the index "x" is a fraction of approximately 4, for example between 2 and 5. However, the mixture may conveniently be carried out using alkoxysilane disulfides (x=2). Examples include bis((C1-C4)alkoxy(C1-C4)alkylsilyl(C1-C4)alkyl) polysulfides (especially disulfides, trisulfides or tetrasulfides), such as bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Among these compounds, bis(3-triethoxysilylpropyl)tetrasulfide (abbreviated TESPT) of formula [(C2H5O)3Si(CH2)3S2]2 or bis(3-triethoxysilylpropyl)disulfide (abbreviated TESPD) of formula [(C2H5O)3Si(CH2)3S]2 may be used. Other examples include bis(mono(C1-C4)alkoxyldi(C1-C4)alkylsilylpropyl)polysulfides (in particular disulfides, trisulfides or tetrasulfides), more particularly bis(monoethoxydimethylsilylpropyl)tetrasulfide, as described in patent application WO 02 / 083782 (or US 2004 / 132880). As coupling agents other than alkoxysilane polysulfides, difunctional POS (polyorganosiloxanes) or else hydroxysilane polysulfides (R in the above formula iii) as described, for example, in published patent applications WO 02 / 30939 (or US 6,774,255) and WO 02 / 31041 (or US 2004 / 051210) can also be used. 2 =OH) or else silanes or POS containing azodicarbonyl functional groups, as described, for example, in published patent applications WO 2006 / 125532, WO 2006 / 125533 and WO 2006 / 125534.

[0029] The content of coupling agent in the composition of the present invention may be between 1 phr and 15 phr and between 3 phr and 14 phr. In addition, the fillers may be made of other nature, especially organic reinforcing fillers, provided that the reinforcing fillers may be covered with a silica layer or otherwise contain functional sites, especially hydroxyl sites, on their surface, which require the use of a coupling agent to form a bond between the filler and the elastomer. The physical state in which the reinforcing filler is provided is not critical and may be in the form of powder, micropearls, granules, beads and / or any other suitable densified form.

[0030] cross-linked system Any type of cross-linking system for rubber compositions may be used in the rubber compositions provided herein. The crosslinking system may be based on a vulcanization system, i.e., sulfur (or a sulfur donor) and a primary vulcanization accelerator. To this basic vulcanization system, various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (especially diphenylguanidine), may be added, which are incorporated during the initial non-productive and / or productive phases, as described hereinafter. Sulphur may be used in a content between 0.5 phr and 10 phr, between 0.5 phr and 5 phr, and especially between 0.5 phr and 3 phr. The vulcanization system in the composition may contain one or more additional accelerators, such as compounds from the group of thiurams, zinc dithiocarbamate derivatives, sulfenamides, guanidines or thiophosphates. In particular, any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur may be used, especially thiazole-type and derivative accelerators, thiuram-type accelerators, and zinc dithiocarbamates. These accelerators are selected from the group consisting of 2-mercaptobenzothiazole disulfide (abbreviated as "MBTS"), N-cyclohexyl-2-benzothiazole sulfenamide (abbreviated as "CBS"), N,N-dicyclohexyl-2-benzothiazole sulfenamide (abbreviated as "DCBS"), N-(tert-butyl)-2-benzothiazole sulfenamide (abbreviated as "TBBS"), N-(tert-butyl)-2-benzothiazole sulfenimide (abbreviated as "TBSI"), zinc dibenzyldithiocarbamate (abbreviated as "ZBEC"), and mixtures of these compounds. A sulfenamide-type primary accelerator is used.

[0031] The rubber composition may optionally contain all or some of the usual additives customarily used in elastomeric compositions intended, inter alia, for the manufacture of treads, such as, for example, pigments, antiozonant waxes, protective agents such as chemical antiozonants or antioxidants, plasticizers other than those mentioned above, antifatigue agents, reinforcing resins or methylene acceptors (e.g., novolac phenolic resins) or donors (e.g., HMT or H3M). The rubber composition may also contain a plasticizing system which, in addition to the specific hydrocarbon-based polymers mentioned above, may consist of a hydrocarbon-based resin having a Tg above 20°C and / or a plasticizing oil. Of course, the composition may be used alone or in admixture (ie, mixture) with any other rubber composition that can be used in the manufacture of tires. The rubber compositions described herein may be in both an "uncured" or uncrosslinked state (i.e., before crosslinking) and a "cured" or crosslinked state, or alternatively, in a vulcanized state (i.e., after crosslinking or vulcanization).

[0032] Preparation of Rubber Composition The rubber compositions are produced in suitable mixers using a two-stage process: a first stage is thermomechanical processing or kneading at high temperatures (sometimes referred to as the "non-productive" stage) up to a maximum temperature of between 110°C and 200°C, for example between 130°C and 180°C, followed by a second stage (sometimes referred to as the "productive" stage) of low-temperature mechanical processing at lower temperatures, typically below 110°C, for example between 60°C and 100°C, during which a crosslinking or vulcanization system is incorporated; this stage is described, for example, in applications EP-A-0 501 227, EP-A-0 735 088, EP-A-0 810 258, WO 00 / 05300 or WO 00 / 05301. The first (non-productive) stage is carried out in various thermomechanical steps. During the first stage, at temperatures between 20°C and 100°C and between 25°C and 100°C, the elastomer, reinforcing filler, and hydrocarbon polymer modifier (and possibly coupling agents and / or other materials, excluding the crosslinking system) are introduced into a suitable mixer, such as a conventional internal mixer. After a few minutes, from 0.5 to 2 minutes, and then the temperature is raised to 90°C or 100°C and mixing is continued for 20 seconds to several minutes, all the other materials, excluding the crosslinking system (i.e., the remaining materials if not all the materials were added in the first stage), are added all at once or in stages. In this non-productive stage, the total mixing time is between 2 and 10 minutes, and the mixture is carried out at temperatures of up to 180°C and up to 170°C. After cooling the mixture thus obtained, the crosslinking system is generally introduced further into an external mixer such as an open mill at low temperature (typically below 100°C); the combined mixture is mixed for a further few minutes, for example between 5 and 15 minutes (production stage). The final composition thus obtained is then calendered, for example in the form of sheets or slabs, for evaluation of the physical properties, especially at the laboratory level, or else extruded to form rubber moldings, which are used, for example, for the manufacture of semi-finished products for tires, which may then be used in the manufacture of tires, and which have the advantage of having good adhesion between the individual layers before the tire is cured. Crosslinking (or curing) can be carried out at temperatures generally between 130°C and 200°C, under pressure, for a sufficient time that can vary, for example, between 5 and 90 minutes, as a function, inter alia, of the curing temperature, of the selected crosslinking system, of the crosslinking kinetics of the composition under consideration, or else of the size of the tire.

[0033] adhesive composition One or more HPMs described herein may be used as a tackifying resin (also referred to herein as a tackifier and / or tackifying reagent) in an adhesive composition. The adhesive composition may be a hot melt adhesive composition selected from the group of hot melt pressure sensitive adhesives, hot melt packaging adhesives, and hot melt nonwoven adhesives. Table 9 below summarizes the ranges of the major components of exemplary adhesive compositions described herein. As shown in Table 9 of Example 4 below, the formulated hot melt adhesive compositions of the present invention can contain one or more adhesive base polymers in combination with a tackifying reagent. The amount of base polymer and tackifying reagent may vary depending on the particular type of adhesive formulation. The adhesive composition may contain at least about 15% and up to about 90% by weight of one or more adhesive base polymers, based on the total weight of the adhesive composition.

[0034] Examples of suitable adhesive base polymers (also referred to as elastomers or adhesive polymer components) include natural rubber (NR); styrene butadiene rubber (SBR); butadiene rubber (BR); nitrile rubber (NR); butyl rubber; isobutylene polymers; isobutylene copolymers; e.g., styrene-isoprene-styrene (SIS) copolymer, styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene-ethylene-propylene-styrene (SEPS) copolymer, styrene-butadiene-butylene-styrene (SBBS) copolymer, styrene-ethylene-ethylene-propylene-styrene (SEEPS), styrene ...butylene-styrene (SEBS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene-ethylene-propylene-styrene (SEPS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene-ethylene-propylene-styrene Polyethylene copolymers; polypropylene copolymers; metallocene copolymers comprising polyethylene, polypropylene, and / or polyolefins; amorphous polyalphaolefins (APAO); olefin polymers and olefin block copolymers (OBC); ethyl vinyl acetate (EVA); acrylic polymers; acrylic copolymers; acrylic block copolymers (ABC); polyamides; polyurethanes; epoxies; polyesters; functional polymers (e.g., functional groups include maleic acid, silane, phenol, etc.); and combinations of one or more of the foregoing polymers. Examples of commercially available base polymers include, but are not limited to, polymers sold under the trade names Kraton (available from Kraton, Houston, TX), Vector (available from TSRC-Dexco, Houston, TX), ENGAGE, DOWLEX, AFFINITY, AFFINITY GA, INFUSE, and VERSIFY (available from Dow Chemical Company, Midland, Mich.); EXCEED, ENABLE, EXCEED XP, ESCORENE, ACHIEVE, EXACT, VISTAMAXX (available from Exxon Chemical Company, Irving, Tex.); EASTOFLEX, AERAFIN (available from Eastman Chemical, Kingsport, TN), VESTOPLAST (available from Evonik, Essen, Germany); REXTAC (available from Rextac, Odessa, Tex.); L-MODU (available from Idemitsu, Japan); and Tafmer (available from Mitsui, Japan).

[0035] The HPM of the present invention can be used in an amount of at least about 1 percent and / or up to 99 percent by weight of the total composition of a finished product. The finished product may be any adhesive, adhesive material, any sealant, any sealant material, any film, any film material, any molding material, any thermoforming material, any carpet, any carpet material, any extrusion molding material, any masterbatch, any masterbatch material, any color concentrate, any color concentrate material, any shoe sole material, any rigid packaging material, any flexible packaging material, any electronic component, any automotive component, and is not limited to any automotive material. Finished products within the scope of this disclosure do not include those associated with or used in pneumatic and non-pneumatic tires and wheels. When present, one or more HPMs may be hydrocarbon resins derived from cycloaliphatic species (e.g., cyclopentadiene, dicyclopentadiene), straight-chain aliphatic species (e.g., piperylene, isoprene, isoamylene), aromatic species (e.g., styrene, indene, vinyl toluene), hydrocarbon resins derived from combinations of cycloaliphatic species, straight-chain aliphatic species and aromatic species, aromatic-modified cycloaliphatic resins, C5 hydrocarbon resins, C5 / C9 hydrocarbon resins, aromatic-modified C5 hydrocarbon resins, C9 hydrocarbon resins, styrene resins, styrene / alf para-methylstyrene copolymer resin, styrene / vinyl toluene copolymer resin, styrene / para-methylstyrene copolymer resin, styrene / indene copolymer resin, styrene / methylindene copolymer resin, styrene / C5 copolymer resin, styrene / C9 copolymer resin, terpene resin, terpene phenolic resin, terpene / styrene resin, rosin, rosin ester, modified rosin ester, modified rosin, liquid resin, fully or partially hydrogenated rosin, fully or partially hydrogenated rosin ester, fully or partially hydrogenated modified rosin / rosin ester, fully or partially hydrogenated rosin alcohol, fully or partially hydrogenated C5 resin, fully or partially hydrogenated C5 / C9 resin, fully or partially hydrogenated cycloaliphatic resin, fully or partially hydrogenated cycloaliphatic / C9 resin, fully or partially hydrogenated C5 / cycloaliphatic / C9 resin, fully or partially hydrogenated aromatic modified C5 resin, fully or partially hydrogenated C9 resin, fully or partially hydrogenated styrene resin, fully or partially hydrogenated styrene / alpha-methylstyrene copolymer resin, fully or partially hydrogenated styrene / vinyl toluene copolymer resin, fully or partially hydrogenated styrene / para-methylstyrene copolymer resin, fully or partially hydrogenated styrene / indene copolymer resin, fully or partially hydrogenated styrene / methylindene copolymer resin, fully or partially hydrogenated styrene / C5 copolymer resin, fully or partially hydrogenated styrene / C9 copolymer resin, fully or partially hydrogenated C5 / cycloaliphatic resin,The resin may be selected from the group consisting of fully or partially hydrogenated C5 / cycloaliphatic / styrene / C9 resins, fully or partially hydrogenated cycloaliphatic resins, fully or partially hydrogenated aromatic-modified cycloaliphatic resins, and combinations thereof.

[0036] In addition to the adhesive base polymer or polymers and the tackifier of the present invention, the formulated adhesive composition may contain one or more additional polymerization modifiers, such as oils, waxes, antioxidants, plasticizers, fillers, endblock polymerization modifiers, endblock polymerization modifier / polymer tougheners, crosslinkers, nucleating agents, clarifying agents, masterbatches, color concentrates, odor masking agents, rheology modifiers, thickeners, and combinations thereof. The type and amount of additional polymerization modifier may vary depending on the specific type of adhesive composition being formulated. For example, if the adhesive composition contains a hot melt packaging adhesive, the composition may contain at least about 1 percent and / or up to 70 percent wax, based on the total weight of the adhesive composition. Examples of suitable waxes can include, but are not limited to, microcrystalline waxes; metallocene-catalyzed waxes, including polyethylene (mPE) and polypropylene (mPP) waxes; paraffin waxes; Fischer-Tropsch waxes; vegetable waxes; highly branched, functionalized (e.g., maleated), low molecular weight petroleum-derived waxes; solid oils; and combinations thereof. The adhesive composition may be a hot-melt pressure-sensitive adhesive or a hot-melt nonwoven adhesive. The adhesive may include one or more oils in an amount of at least about 1 percent and / or up to 50 percent by weight of the total adhesive composition. Examples of suitable oils include, but are not limited to, naphthenic oil, paraffinic oil, hydrogenated oil, mineral oil, white oil, aromatic oil, triglyceride oil, and combinations thereof. In addition, the adhesive composition may include one or more extender oils, examples of which include, for example, liquid paraffin, castor oil, rapeseed oil, mineral oil, and combinations thereof. In addition to the wax and / or oil, the adhesive composition may contain one or more antioxidants (e.g., phenolic and / or phosphite types), plasticizers (e.g., dibutyl phthalate, dioctyl phthalate, non-phthalate plasticizers, benzoate plasticizers, and / or chlorinated paraffins), fillers (e.g., carbon black, calcium carbonate, titanium dioxide and / or zinc oxide), endblock modifiers / polymer toughening agents, crosslinkers, and combinations thereof, as well as any other additives that make the final composition suitable for a particular application.

[0037] In one embodiment, one or more HPMs described above may be added to a polymer system comprising at least one polymeric material to thereby improve the stability, flow, processability, barrier properties, cling, adhesion, clarity, haze, flexibility, shrinkability, molding properties, mechanical properties, and / or thermal properties of the resulting polymer system. As described more fully below, adhesive compositions containing one or more HPMs of the present invention can be prepared using any suitable method (any batch and / or continuous mixing technique; vertical and / or horizontal mixing technique). For example, the components in the adhesive composition can be combined using a Sigma Blade mixer, a Plasticorder, a Brabender mixer, a twin-screw extruder, or an in-can blend (pinto can). The resulting adhesive composition may then be formed into the desired shape by any suitable technique, including, for example, extrusion, compression molding, calendaring, or roll coating techniques (e.g., gravure printing, reverse rolling, etc.). The adhesive can also be applied to a suitable substrate via curtain coating or slot die coating, or sprayed using a suitable nozzle (e.g., for deposition at a suitable rate by conventional nonwoven application equipment).

[0038] The adhesive compositions described herein may be applied to a substrate by melting the mixed composition and applying an appropriate amount (e.g., 0.02 to 100 mils) of the adhesive mixture to the desired substrate (e.g., textile, paper, corrugated glass, plastic, film, nonwoven fabric, and / or metal) to thereby form an adhesive article. Examples of adhesive articles comprised of the adhesive composition include, but are not limited to, tapes such as packing tape, conduit tape, masking tape, invisible tape, electronics tape, adhesive tape, hockey tape, and other specialty tapes; paper labels, beverage labels, smart labels, appliance labels, pharmaceutical labels, graphic arts labels, and other labels; packaging applications including container seals, carton seals, book binders, flexible packaging adhesives, and flexible packaging interlayer adhesives; corrugated box adhesives, folding carton adhesives, glue sticks, and others; and nonwoven applications including diaper construction adhesives, diaper elastic attachment adhesives, stretch film, feminine hygiene molding adhesives (napkin adhesives), adult incontinence product adhesives, disposable bed adhesives, mattress adhesives or pet pad adhesives, small nonwoven laminates, and others; automotive adhesives; construction adhesives; engineering adhesives, and others. The adhesive may be solvent-based, water-based, hot melt, reactive, one-part adhesive, two-part adhesive, moisture-cure, UV / EB-cure, cross-linkable, thermoplastic and / or thermoset adhesive. In addition to adhesive compositions, the HPMs of the present invention and / or combinations of HPMs, including non-hydrogenated, partially hydrogenated, and / or fully hydrogenated HPMs, are also useful in other applications. For example, the hydrocarbon polymer modifiers of the present invention can be used in rubber compositions utilized in one or more tire components (e.g., tire treads and / or sidewalls, frames), one or more belt components, and one or more hose components. The hydrocarbon polymer modifiers can be used in plastic processing (e.g., films; rigid packaging articles such as steins, bottles, containers, and / or flat articles) to improve mechanical properties (e.g., stiffness, toughness, tensile strength, modulus, etc.), barrier properties (e.g., oxygen permeability, water / water vapor permeability, etc.), clarity, adhesion, and / or shrinkage. One or more hydrocarbon polymer polymerization modifiers described herein can be used as a replacement for various types of oils typically utilized in rubber compositions and / or plastic processing to improve the processability of rubber / plastic compositions and / or to improve the miscibility of various polymer systems and / or to provide immiscibility in various polymer systems and / or to improve the final performance and / or mechanical properties (e.g., modulus of elasticity, rolling resistance, wet grip, tensile strength, wear, etc., to name a few). Additionally, other applications or uses of the hydrocarbon polymer polymerization modifiers disclosed herein are contemplated as being within the scope of the present disclosure.

[0039] Hot melt packaging applications The adhesive compositions disclosed herein can be used in a variety of packaging articles. Examples of packaging articles include cartons, containers, crates, cases, corrugated cases, and trays. More specifically, packaging articles are useful for grain products, cracker products, beer packaging, frozen food products, paper bags, beverage cups, milk cartons, juice cartons, beverage cups, or as containers for shipping produce. Packaging articles are formed by applying an adhesive composition to at least a portion of one or more packaging members. Packaging members may be formed from paper, paperboard, containerboard, tagboard, corrugated board, chipboard, kraft paper, cardboard, fiberboard, plastic resins, metals, alloys, foils, films, plastic films, laminates, sheets, or any combination thereof. In one embodiment, the adhesive composition is used to bond or adhere two or more packaging members together, where the packaging members are formed from the same or different types of materials. Accordingly, the packaging member may be individually formed from paper, paperboard, containerboard, tagboard, corrugated board, chipboard, kraft paper, cardboard, fiberboard, plastic resin, metal, alloy, foil, film, plastic film, laminate, sheet, or any combination thereof. One or more packaging components can also be individually coated with paper, foil, metal, alloys, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyamides, homopolymers thereof, and combinations and copolymers thereof. The adhesive formulations disclosed herein can be used in a variety of woodworking applications, including, but not limited to, furniture, toys, musical instruments, window frames and sills, doors, floors, fences, tools, ladders, sporting equipment, dog houses, gazebos / decks, picnic tables, playground construction, planters, scaffolding boards, kitchen utensils, coffins, church pews / altars, and walking sticks. The adhesive formulations described herein have a high polymer weight and provide a combination of desirable physical properties, such as long-lasting, stable adhesion, a wide application temperature range, and a long open time, and therefore can be used in a variety of woodworking applications. It should be understood that the adhesive formulations disclosed herein are well suited for use with woodworking products, but may find utility in other applications as well. In one embodiment, a woodworking process for preparing a woodworking application includes forming a woodworking article by at least partially applying the adhesive composition to a structural member. The structural member can include various materials, including, but not limited to, wood or plywood or plastic or decorative laminates. For example, the structural member can also include lumber, wood, fiberboard, gypsum board, gypsum, artificial wallboard, plywood, PVC, melamine, polyester, impregnated paper, and sheetrock. The woodworking process can be used to form, for example, indoor furniture, outdoor furniture trim, moldings, doors, window frames, windows, millwork, and cabinetry. As described below, Example 3 illustrates a packaging adhesive composition and evaluation results using the HPM of the present invention. The characteristics of the HPM and compositions comprising HPM of the present invention are illustrated in the following non-limiting examples. The test methods and experimental procedures used in the examples are described immediately below.

[0040] DSC Measurements. The following DSC procedure was used to measure the glass transition temperature (Tg) of HPM. Approximately 6 mg of material was placed in a microliter aluminum sample pan. The sample was placed on a differential scanning calorimeter (Perkin Elmer or TA Instrument Thermal Analysis System) and heated from 23°C to 200°C at 10°C / min and held at 200°C for 3 minutes. The sample was then cooled to -50°C at 10°C / min. The sample was held at -50°C for 3 minutes, then heated from -50°C to 200°C at 10°C / min for a second heating cycle. Tg was determined in TA Universal Analysis using the inflection method in the second heating cycle. The "Glass Transition" menu item in TA Universal Analysis was used to calculate the onset, endpoint, inflection, and signal change of Tg in DSC. The program allows the determination of the onset point, which is the intersection of the first and second tangents, the inflection point, which is the steepest curve portion between the first and third tangents, and the endpoint, which is the intersection of the second and third tangents. The Tg of the HPM is the inflection temperature of the curve. % H Ar. 120 scans were performed on a 500 MHz NMR instrument in TCE-d2 (1,2 dichloroethane) or CDCl3 (chloroform) solvent at 25°C. NMR data for HPM were obtained by dissolving 20 ± 1 mg of sample in 0.7 ml of d-solvent. The sample was dissolved in TCE-d2 / CDCl3 in a 5 mm NMR tube at 25°C until the sample was completely dissolved. No standard was used. TCE-d2 / CDCl3 showed peaks at 5.98 or 7.24 ppm, which were used as reference peaks for the samples. The aromatic protons 1 The H NMR signals are located between 8.5 ppm and 6.2 ppm. Ethylene protons give rise to signals between 6.2 ppm and 4.5 ppm. Finally, the signals corresponding to aliphatic protons are located between 4.5 ppm and 0 ppm. The area of ​​each type of proton is related to the sum of these areas, resulting in a distribution of the areas expressed in % for each type of proton. Softening Point. "Softening point" is the temperature, measured in °C, at which a material flows and is determined according to the ring and ball method and measured by ASTM E-28. Experience has shown that the relationship between Tg and softening point is approximately: Tg = softening point - 50°C. As mentioned above, Mn, Mz and MWD are measured.

[0041] Dynamic properties (after curing) Dynamic Characteristics G * and tan(δ)max are measured on a viscosity analyzer (Metravib V A4000) according to standard ASTM D 5992-96. Response of vulcanized composition samples (cylindrical test specimens 4 mm thick and 10 mm in diameter) subjected to a simple alternating sinusoidal shear stress at a frequency of 10 Hz and at the temperature conditions (23°C) according to standard ASTM D 1349-99 or at another temperature. Deformation sweeps are performed from 0.1% to 50% (forward cycle) and then from 50% to 0.1% (return cycle). On the return cycle, the stiffness value at 10% deformation is recorded. The higher the values ​​of stiffness at 10% deformation and 23°C, the better the load handling of the composition. The results are expressed in terms of a performance base 100, i.e., a value of 100 corresponds to the G at 23°C of the various solutions subsequently tested. * 10% (i.e. stiffness and hence load handling) is arbitrarily assigned to the control. The base 100 value is calculated (G at 23°C of the sample) * 10% of the control value / G at 23°C * 10% value) * 100. Therefore, higher values ​​represent improved load handling performance, while lower values ​​represent worsening load handling performance. The higher the values ​​of stiffness at 10% deformation and 40°C, the better the load handling of the composition. The results are expressed in terms of a performance base of 100, i.e., a value of 100 represents the G at 40°C of the various solutions subsequently tested. *10% (i.e. stiffness and hence load handling) is arbitrarily assigned to the control. The base 100 value is calculated (G * 10% of the control value / G at 40°C * 10% value) * 100. Therefore, higher values ​​represent improved load handling performance, while lower values ​​represent worsening load handling performance.

[0042] Viscosity. The viscosity of the pressure-sensitive adhesive mixtures was measured using a Brookfield viscometer at either about 150°C or about 177°C, as indicated. The viscoelastic properties (rheology) of the adhesive mixtures were analyzed using an Anton Parr rheometer in parallel plate geometry at a strain of 0.1%, a frequency of 10 rad / s, and a heating rate of 2°C / min. Peel Adhesion / Loop Tack / Holding Strength. Selected pressure-sensitive adhesive mixtures were coated onto 2 mil PET film at 177°C using a Cheminstruments HLCL-1000 coater and laminated onto a silicone liner. Peel adhesion (90° peel) was tested according to PSTC-101F (ASTM D3330F) method using a Cheminstruments AR-1000 peel adhesion tester. Tack (loop tack) was tested according to PSTC-16 method B (ASTM D6195B) using a Cheminstruments LT-1000 loop tack tester. Holding strength / static shear was tested according to a modified PSTC-107A (ASTM D 3654A) method using a Cheminstruments RT-30 shear tester. Fiber Tear. Fiber tear refers to the adhesive strength to the substrate and is measured at room temperature ("RT"), 2°C, and -18°C. As used herein, the term "room temperature" refers to a temperature range of about 20°C to about 25°C. Fiber tear is a visual measurement of the amount of paper substrate fibers that adhere to the adhesive after the substrate is torn. 100% fiber tear means that the adhesive is stronger than the substrate and 100% of the adhesive is covered by the substrate fibers. Fiber tear is determined by bonding the substrate to the adhesive. A drop of molten adhesive (150°C to 180°C) is placed on one of the substrates. A second substrate is placed on the adhesive, and a 500g weight is placed on the second substrate to ensure uniform application. The adhesive is allowed to cool at the reference temperature for at least one hour. The substrates are separated, and the adhesive is inspected for fiber tear.

[0043] Set Time. Set time is the minimum time interval after bonding two substrates for the cohesive strength of the adhesive to become stronger than the bond stress. It represents the time required for the adhesive composition to cool and obtain a good bond. Set time is determined by dropping a drop of molten adhesive (150°C-180°C) onto one of the substrates with a dropper and then bonding the substrates together. A second substrate is placed on top of the adhesive, and a 500g weight is placed on the second substrate to ensure a uniform application. After a predetermined time interval, the second substrate is removed and checked for fiber tear. If no fiber tear is observed, a longer time interval is tested. This continues until fiber tear is observed. This length of time is reported as the set time in seconds. Peel Adhesion Failure Temperature (“PAFT”). PAFT refers to the temperature at which the adhesive bond of a composition fails. The PAFT of hot melt adhesive compositions is tested according to the standard PAFT test per ASTM D-4498. PAFT is an important factor for storing boxes in above-ambient temperature environments, such as warehouses. PAFT is measured in degrees Celsius (“°C”). Each adhesive was also subjected to a Shear Adhesion Failure Test (SAFT), also per ASTM D-4498. The following examples are intended to highlight various aspects of the present invention, but it should be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the invention, unless otherwise stated. [Example]

[0044] Example 1 Analysis of Prior Art Hydrocarbon Polymer Additives Prior art resins containing at least one elastomer and a prior art hydrocarbon polymer additive were evaluated for Tg and %H Ar. A first set of prior art additive samples (PA1, PA2, PA3, PA4, and PA5) each had the following: (a) a dicyclopentadiene, cyclopentadiene, and methylcyclopentadiene content of about 40 wt.% to about 80 wt.% of the total weight of the hydrocarbon polymer additive; (b) a weight average molecular weight of about 100 g / mole to about 800 g / mole; and (c) a softening point, determined according to ASTM D6090, of about 110°C to about 150°C. These dicyclopentadiene resins further contained aromatics such as styrene, xylene, alpha-methylstyrene, vinyltoluene, and indene, and non-aromatics such as the linear C4-C6 fraction or its isomers. Dicyclopentadiene-based additives and combinations with elastomers have been shown to improve tire performance characteristics such as high wet traction and low rolling resistance applications. The hydrocarbon polymer additives used in these elastomer compositions had the properties shown in Table 1. [Table 1] The properties provided in Table 1 were taken from US 2015 / 0065655, and the glass transitions were taken from the literature.

[0045] A second set of prior art samples (PA6, PA7, PA8, PA9, and PA10) were investigated, consisting of thermally polymerized resins prepared from feedstocks primarily containing vinyl aromatics, cyclic diene components, and optionally non-cyclic components. The vinyl aromatic stream was described as containing styrene, alkyl-substituted derivatives of styrene, indene, and alkyl-substituted derivatives of indene. The cyclodiene component contained monomers, dimers, and codimers of cyclopentadiene and alkyl-substituted derivatives of cyclopentadiene. The non-cyclic diene component contained C4-C6 olefins and diolefins. The resins were prepared by thermal polymerization of the above feedstocks at 275°C, preferably for 2-3 hours. The resulting resins had moderate softening points but very broad molecular weight distributions. The glass transition temperatures (Tg) and % aromaticity (%H Ar) of these prior art ("PA") resins with additives were as shown in Table 2. [Table 2] A third set of prior art samples (PA11, PA12, PA13, and PA14) were investigated, which contained hydrocarbon polymer modifiers having piperylene, aromatic, and cyclic pentadiene components. The cyclic pentadiene components contained dicyclopentadiene and dimethylcyclopentadiene fractions and had number average molecular weights (M n ) is greater than 400 and the z-average molecular weight (M z ) was less than 15000 g / mole and had at least 8% H Ar. Reported resin physical properties are provided in Table 3. [Table 3] Regarding the process for manufacturing prior art additives, hydrocarbon polymer additives were prepared by thermally polymerizing a mixture consisting essentially of about 5% to 25% by weight of styrene or an aliphatic or aromatic substituted styrene and about 95% to 75% by weight of a cyclic diolefin component containing at least about 50% by weight of dicyclopentadiene, based on the total monomer content. (See, e.g., U.S. Patent No. 6,825,291.) This sequential addition of a series of monomers has been used to control the molecular weight of hydrocarbon resins. This process is not only tedious but can also result in broad polydispersities in the hydrocarbon resins. Table 4 summarizes additional commercially available resins used in the prior art and in the comparative examples below. [Table 4] The rubber compositions containing the aforementioned hydrocarbon-based resins contained units of cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, and mixtures thereof as a major component. Furthermore, as taught, these hydrocarbon resins had a Z-average molecular weight (Mz) of less than 2000 g / mole and a Tg of 80-200 g / mole. * (%HA) (%HA represents the aromatic proton content of the resin). In developing these compositions, the focus of the problems and solutions was on improving the adhesion and rolling resistance of the elastomer compositions. In addition, the stiffness at low temperatures (dynamic properties G * ) was measured in a low strain sweep.

[0046] Example 2 Analysis of the HPM of the present invention HPM Sample Nos. B, C, D, E, G, and H were prepared by varying the feed stream in a thermal polymerization unit known to achieve the softening point or Tg and molecular weight of the particular tackifier. After processing in the thermal polymerization unit, the tackifier was nitrogen stripped at 200°C. The physical properties of the hydrocarbon polymer modifiers are given in Tables 5A, 5B, 6A, and 6B below. The modifiers described herein can be prepared by known techniques. (See, for example, the Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., Vol. 13, pp. 717-744.) One technique is the thermal polymerization of petroleum fractions. Polymerization can be batch, semi-batch, or continuous. Thermal polymerization is often carried out at temperatures between 160°C and 320°C, e.g., about 260°C to 280°C, for 0.5 to 9 hours, and often 1.0 to 4 hours. The thermal polymerization is usually carried out in the presence or absence of an inert solvent. The inert solvent may have a boiling point ranging from 60°C to 260°C and may be isopropanol, toluene, heptane, Exxsol TM or Varsol TM or from 2 wt.% to 50 wt.% of white spirit solvent. The solvents may be used individually or in combination. The HPM produced is, for example, Exxsol TM or Varsol TM The feed may optionally be dissolved in an inert, dearomatized or non-dearomatized hydrocarbon solvent, such as white spirit solvent, in proportions varying from 10% to 60%, and for example 30% polymer by weight, and then hydrogenated in a fixed-bed continuous reactor in either upflow or downflow liquid phase, or trickle-bed operation. Hydroprocessing conditions generally involve reactions at temperatures ranging from about 100°C to about 350°C, from about 150°C to about 300°C, and from about 160°C to about 270°C. The hydrogen pressure in the reactor should not exceed 2000 psi, for example, not more than 1500 psi and / or not more than 1000 psi. The hydrogenation pressure is a function of the purity of the hydrogen, and the overall reaction pressure should be increased to provide the desired hydrogenation pressure if the hydrogen contains impurities. Typically, the optimum pressure used is between about 750 psi and 1500 psi and / or between about 800 psi and about 1000 psi. The volume ratio of hydrogen fed to the reactor at standard conditions (25°C, 1 atmosphere) may typically range from about 20 to about 200. Further exemplary methods for preparing the HPM described herein are generally found in U.S. Pat. No. 6,433,104.

[0047] As shown in the following examples, various polymerization modifiers were prepared to obtain desired softening points or Tg and molecular weights. Tables 5A and 5B below include the feed streams, polymerization conditions, and physical properties obtained for exemplary hydrocarbon polymer polymerization modifiers. [Table 5A] [Table 5B] Tables 6A and 6B below include the feed streams, polymerization conditions, and physical properties obtained for the comparative hydrocarbon polymer polymerization modifiers. As shown in Tables 6A and 6B, Comparative Example B * , C * and D * was prepared using a vinyl aromatic feed stream consisting of styrene and vinyl toluene. * was prepared using a substituted benzene stream and a distillation cut of aromatics, but had a low Tg and high % H Ar. Comparative Examples A, F, and G *was prepared using an olefinic aromatic stream, but the %H, Ar, and / or Tg were outside the range of the HPM of the present invention. Under the reaction conditions of the present invention, the relative reaction rate of the vinyl aromatic homo-oligomerization reaction is higher than the copolymerization of cyclic and vinyl aromatics. The homo-oligomers formed exhibit higher Mn than is ideal for an optimal HPM. To minimize homopolymerization to form undesirable high molecular weight polymers, it is desirable to fully react substantially all of the stoichiometric amount of vinyl aromatic monomer with the cyclic feedstock. The HPM may be hydrogenated cyclopentadiene or hydrogenated cyclopentadiene derivatives with or without aromatic components (olefin-aromatic, substituted benzene and aromatic distillation cuts). [Table 6A] [Table 6B] Figure 1 is a graph showing the relationship between Tg and %H Ar for the HPM of the present invention, a comparative resin, and a prior art elastomer composition. Figure 2 is a graph showing the relationship between Tg and Mn for the HPM of the present invention, a comparative resin, and a prior art elastomer composition. Figure 3 is a graph showing the relationship between Tg and Mz for the HPM of the present invention, a comparative resin, and a prior art elastomer composition.

[0048] Example 3: Exemplary Rubber Compositions The rubber composition is prepared by introducing all compounding ingredients into an internal mixer, except for the vulcanization system, which is introduced into an external mixer at low temperature (the mixer's construction roll is at 30°C). The purpose of the examples presented in Table 7 is to compare various rubber properties of control compositions (T1-T3) with those of compositions containing the hydrocarbon resin HPM H (C1 and C2) of the present invention. The properties measured after curing are presented in Table 8. In Table 7, the values ​​of the ingredients are expressed in phr (parts by weight per hundred weight of rubber). [Table 7] (1) A non-functionalized SBR having 26.5% by weight of styrene units relative to the total weight of the copolymer and 24 mol% of 1,2 butadiene units relative to the butadiene moieties, and having a glass transition temperature Tg of -48°C. (2) BR: Lanxess polybutadiene CB24; 96% 1,4-cis; Tg = -107°C (3) Carbon black, ASTM N234 grade (4) Silica, Solvay Zeosil 1165MP, HDS type (5) Flexis' N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (Santoflex 6-PPD) and 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ) (6) Coupling agent: Si69 from Evonik-Degussa (7) Diphenylguanidine, Perkacit DPG from Flexis (8) Stearin, Pristerene 4931 from Uniqema (9) Zinc Oxide, Industrial Grade - Umicore (10) N-Cyclohexyl-2-benzothiazole sulfenamide (Flexis Santocure CBS) [Table 8] Regarding the control compositions, it should be noted that compositions T1 and T2, each of which does not incorporate the hydrocarbon polymer modifiers described herein, serve as a base 100 for comparison of the performance of other compositions. It can be seen that only compositions C1 and C2, which are in accordance with the present invention, enable improved load handling performance.

[0049] Example 4 Several types of hot melt adhesive compositions containing the HPM of the present invention were formulated and evaluated. Hot Melt Pressure Sensitive Adhesives The pressure-sensitive adhesives can be used in tape, label, and / or nonwoven (diaper, feminine hygiene, or adult incontinence) applications. Pressure-sensitive adhesive mixtures were prepared using a Brabender mixer, roller blader, and Sigma blader at temperatures between about 130°C and about 180°C. Antioxidants were added to the adhesive base polymer, and the resulting mixture was first kneaded in the Brabender mixer. After several minutes, tackifiers and / or other HPMs and oils were added, and the combined mixture was kneaded for about 20 to about 45 minutes until the torque of the mixer stabilized. Tables 9A and 9B below summarize the specific compositions and evaluations of pressure-sensitive adhesives using various HPMs described herein. [Table 9A] [Table 9B] As can be seen from the data provided above, pressure-sensitive adhesive mixtures containing HPM exhibit an excellent balance of rheology, peel, tack, and shear performance for use in the various applications described herein.

[0050] Hot melt packaging adhesives (also referred to herein as "adhesives") were prepared in pint-sized cans using a paddle-type mixer / kneader. The adhesive base polymer and antioxidant were combined in a pint-sized can. The resulting mixture was stirred with a paddle-type mixer controlled by a variable speed motor and heated to about 150°C to about 180°C with a rotating shaft / heating element while under a nitrogen blanket. After the polymer was melted, the wax and tackifier were introduced into the can, and the resulting mixture was stirred for an additional 30 minutes until a uniform mixture was obtained. Table 10 below summarizes the specific compositions and performance analysis results of packaging adhesives using HPMs of the present invention. [Table 10] As can be seen from the data provided above, packaging adhesive mixtures containing HPM exhibit an excellent balance of rheology, adhesion, SAFT, fiber tear and set time performance for use in the various applications described herein.

[0051] In the specification and claims, the terms "comprise" and "containing" are open-ended terms and should be interpreted to mean "including, but not limited to." These terms encompass the more restrictive terms "consisting essentially of" and "consisting of." It should be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly indicates otherwise. Similarly, the terms "a" (or "an"), "one or more," and "at least one" can be used interchangeably herein. It should also be noted that the terms "comprise," "include," "characterized by," and "having" can be used interchangeably. Another aspect of the present invention may be as follows. [1] A hydrocarbon polymer polymerization modifier containing a cyclic component, wherein the hydrocarbon polymer polymerization modifier has a Tg of 95-2.2 or more. * (% H Ar) and Tg≧-53+(0.265 * and a glass transition temperature and number average molecular weight expressed in °C, wherein the aromatic proton content (%H Ar) is from 12 mol % to 19 mol % and Mn is from 300 g / mol to 450 g / mol, Tg being the glass transition temperature expressed in °C, %H Ar being the aromatic proton content of the hydrocarbon polymer modifier, Mn being the number average molecular weight of the hydrocarbon polymer modifier, and the cyclic component being a distillation cut from a petroleum refinery stream, and / or C 4 、C 5 or C 6 A hydrocarbon polymer polymerization modifier selected from the group of cyclic olefins and mixtures thereof. [2] The hydrocarbon polymer polymerization modifier according to [1] above, wherein the hydrocarbon polymer polymerization modifier is further characterized by a Tg of from 70°C to 95°C. [3] The hydrocarbon polymer polymerization modifier further has a z-average molecular weight (M) of less than 1000 g / mole. z The hydrocarbon polymer polymerization modifier according to [1] or [2] above, characterized by: [4] The hydrocarbon polymer polymerization modifier according to any one of [1] to [3] above, wherein the cyclic component is cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene, and / or di(methylcyclopentadiene). [5] The hydrocarbon polymer polymerization modifier according to any one of [1] to [4], wherein the hydrocarbon polymer polymerization modifier contains cyclic components in an amount of between about 10 wt.% and about 90 wt.%. [6] The hydrocarbon polymer polymerization modifier according to any one of [1] to [4], wherein the hydrocarbon polymer polymerization modifier contains cyclic components in an amount of between about 25 wt.% and about 80 wt.%. [7] The hydrocarbon polymer polymerization modifier according to any one of [1] to [6] above, wherein the cyclic component is selected from the group consisting of dicyclopentadiene, cyclopentadiene, and methylcyclopentadiene. [8] The hydrocarbon polymer polymerization modifier according to any one of [1] to [7] above, wherein the cyclic component is cyclopentadiene. [9] The hydrocarbon polymer polymerization modifier according to any one of the above [1] to [8], further comprising an aromatic component.

[10] The hydrocarbon polymer polymerization modifier according to [9], wherein the aromatic component is selected from one of olefin aromatics, substituted benzenes, or aromatic distillation cuts.

[11] The hydrocarbon polymer polymerization modifier according to

[10] above, wherein the aromatic component is an olefin aromatic.

[12] The hydrocarbon polymer polymerization modifier according to [7], wherein the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount between about 10 wt.% and about 90 wt.%.

[13] The hydrocarbon polymer polymerization modifier according to [7], wherein the hydrocarbon polymer polymerization modifier contains dicyclopentadiene, cyclopentadiene, and / or methylcyclopentadiene in an amount between about 25 wt.% and about 80 wt.%.

[14] The hydrocarbon polymer polymerization modifier according to [7], wherein the hydrocarbon polymer polymerization modifier contains methylcyclopentadiene in an amount between about 0.1 wt.% and about 15 wt.%.

[15] The hydrocarbon polymer polymerization modifier according to [7], wherein the hydrocarbon polymer polymerization modifier contains methylcyclopentadiene in an amount between about 0.1 wt.% and about 5 wt.%.

[16] The hydrocarbon polymer polymerization modifier according to [9] above, wherein the aromatic component contains an olefin aromatic compound of formula i:

change

[17] The hydrocarbon polymer polymerization modifier according to [9] above, wherein the aromatic component contains a substituted benzene derivative compound of formula ii:

change

[18] The hydrocarbon polymer polymerization modifier according to [9], wherein the aromatic component comprises an aromatic distillation cut containing styrene, alkyl-substituted derivatives of styrene, indene, alkyl-substituted derivatives of indene, and / or mixtures thereof.

[19] The hydrocarbon polymer polymerization modifier according to any one of [9] to

[11] and

[16] to

[18] , wherein the hydrocarbon polymer polymerization modifier contains an aromatic component in an amount of between about 20 wt.% and about 75 wt.%.

[20] The hydrocarbon polymer polymerization modifier according to any one of [9] to

[11] and

[16] to

[18] , wherein the hydrocarbon polymer polymerization modifier contains an aromatic component in an amount of between about 25 wt.% and about 70 wt.%.

[21] The hydrocarbon polymer polymerization modifier has the following additional characteristics: Tg≧100-2.2 * Glass transition temperature (Tg) expressed as (H Ar) Tg≧-32+(0.265 * Glass transition temperature (Tg) expressed as Mn Number average molecular weight (Mn) between 350 and 420 g / mole Or, Tg between 70°C and 90°C The hydrocarbon polymer polymerization modifier according to any one of the above [1] to

[20] , which comprises at least one, and preferably all, of the following:

[22] An adhesive composition containing the hydrocarbon polymer polymerization modifier according to any one of [1] to

[21] above, wherein the adhesive composition contains the hydrocarbon polymer polymerization modifier in an amount between about 0.1 wt.% and about 99.5 wt.%.

[23] A method for producing a hydrocarbon polymer polymerization modifier according to any one of [1] to

[21] above, comprising the step of polymerizing a feed stream containing cyclic components in the presence or absence of a solvent at a reaction temperature between about 250°C and 290°C for about 1 hour to about 3 hours.

Claims

1. A hydrocarbon polymer polymerization modifier containing a cyclic component and an aromatic component, wherein the hydrocarbon polymer polymerization modifier has a Tg of 95-2.2 * (% H Ar) and Tg ≧ −53 ​​+ (0.265 * and a glass transition temperature and number average molecular weight represented by a percentage of cyclic moiety in the hydrocarbon polymer modifier, wherein the aromatic proton content (% H Ar) is from 12 mole % to 19 mole % and Mn is from 300 g / mole to 450 g / mole, Tg being the glass transition temperature expressed in °C, % H Ar being the aromatic proton content of the hydrocarbon polymer modifier, Mn being the number average molecular weight of the hydrocarbon polymer modifier, and the cyclic component being a distillation cut derived from a petroleum refinery stream, and / or C 4 , C 5 or C 6 and the aromatic moiety is selected from the group consisting of cyclic olefins and mixtures thereof, and the aromatic moiety is represented by the formula i 【Chemistry 1】 Formula I (In the formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an arylalkyl group. wherein the hydrocarbon polymer polymerization modifier contains an aromatic component in an amount of between 25 wt. % and 70 wt. %, based on the total weight of the hydrocarbon polymer polymerization modifier, and further characterized by a Tg of from 70°C to 95°C.

2. The hydrocarbon polymer modifier further has a z-average molecular weight (M z 2. The hydrocarbon polymer polymerization modifier of claim 1, characterized by:

3. 3. The hydrocarbon polymer polymerization modifier according to claim 1, wherein the cyclic component is cyclopentene, cyclopentadiene, dicyclopentadiene, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, methylcyclopentadiene, and / or di(methylcyclopentadiene).

4. 4. The hydrocarbon polymer polymerization modifier of claim 1, wherein the hydrocarbon polymer polymerization modifier contains cyclic components in an amount between 10 wt. % and 90 wt. %.

5. An adhesive composition containing the hydrocarbon polymer polymerization modifier according to any one of claims 1 to 4, wherein the adhesive composition contains the hydrocarbon polymer polymerization modifier in an amount between 0.1 wt. % and 99.5 wt. %.

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