Hydrocarbon resin and method for the production thereof

Abstract

Presented and described is a hydrocarbon resin obtainable by thermal polymerization of a cyclic diolefin component comprising a cyclic diolefin compound with an aromatic component comprising indene and / or C1-4-aIkylindene, with the hydrocarbon resin having a polydispersity index (PDI) of 1 to less than 2.3. Further described is a production process for the hydrocarbon resin, wherein a monomer mixture which comprises an aromatic component comprising indene and / or C1-4-alkyIindene and a cyclic diolefin component comprising a cyclic diolefin compound is polymerized by heating to a polymerization temperature of at least 180°C to give a product stream comprising hydrocarbon resin, and oligomers which comprise units originating from the cyclic diolefin compound and / or units originating from the aromatic component are separated from the product stream and returned to the monomer mixture. Lastly described are a hydrogenated hydrocarbon resin, a process for production thereof, and the use of the hydrocarbon resin and of the hydrogenated hydrocarbon resin.

Description

[0001] Hydrocarbon resin and methods for its production

[0002] TECHNICAL AREA OF INVENTION

[0003] The invention relates to a hydrocarbon resin, a process for its production from a cyclic diolefin component containing a cyclic diolefin compound and an aromatic component containing indene and / or Ci-4-alkylindene, its hydrogenation, and a hydrogenated hydrocarbon resin.

[0004] TECHNICAL BACKGROUND OF THE INVENTION

[0005] Hydrocarbon resins are frequently used as tackifiers in hot melt adhesives. Tackifiers are also commonly referred to as tackifiers. Hot melt adhesives have a base polymer that essentially determines their properties. Besides styrene block copolymers (SBC), polyamide, polyurethane, and polyester, metallocene polyolefins (mPO), amorphous polyalphaolefins (APAO), or ethylene vinyl acetate copolymers (EVAC) are frequently used as base polymers in hot melt adhesives.

[0006] Of particular interest are hot melt adhesives that are as light in color as possible and have good processing properties. Essential for good processing properties is a defined compatibility between the tackifier and the base polymer. The tackifiers used are usually only compatible with one base polymer class, such as mPO, APAO, or EVAC, so a separate tackifier is needed for each base polymer class if good compatibility is desired. However, it would be advantageous if the tackifier were compatible with as many base polymer classes as possible. The compatibility of the hot melt adhesive components can be assessed, for example, by determining the cloud point.

[0007] To produce hot melt adhesives that are as light in color and easy to work with as possible, it is important that the at least partially hydrogenated hydrocarbon resins used are as free as possible from undesirable byproducts. These can lead to dark discoloration in the hydrocarbon resin and incompatibilities with other components of the hot melt adhesive. The Gardner color number, yellowness index, or Hazen color number are frequently used to assess discoloration.

[0008] Processes for the production of (hydrogenated) hydrocarbon resins are known. For example, in these processes, a cycloalkene with two conjugated double bonds, such as cyclopentadiene, and an ethylene-unsaturated aromatic component, such as styrene, are copolymerized, and the resulting hydrocarbon resin is at least partially hydrogenated in a further step. The hydrocarbon resin obtained in this way can be used alone or together with other additives as an adhesive for hot melt adhesives.

[0009] Such a process is described in US 5,502,140 A, which uses particularly inexpensive dicyclopentadiene-containing starting materials. However, US 5,502,140 A does not use indene but rather vinyl aromatics such as styrene or α-methylstyrene in the reaction.

[0010] EP 2 251364 Bl describes a process for the production of hydrocarbon resins of the type described above, which have an aromatic compound content of 5 to 25 wt%. In EP 2 251364 Bl, high-quality resins are also achieved only through the use of a pure vinyl aromatic such as styrene as the ethylene unsaturated aromatic component. EP 0936229 Bl describes a process for the production of an aromatically modified aliphatic hydrocarbon resin, in which polymerization feeds comprising olefins, aromatic monomers, and (di)cyclodiolefins are subjected to Friedel-Crafts polymerization. A disadvantage of the process described in EP 0936229 Bl, however, is the use of halogenated catalysts for the production of hydrocarbon resins.

[0011] Byproducts can arise at various stages during the production of hydrocarbon resins for a variety of reasons. For example, during polymerization, low-molecular-weight waxy or high-molecular-weight thermoset-like byproducts can form alongside the desired hydrocarbon resin. These byproducts can impair the quality of the final product and contribute to incompatibility in the hot melt adhesive.

[0012] Undesirable byproducts can also form during purification and / or isolation of intermediates or the final product. For example, both polymerization and hydrogenation are typically carried out in the presence of various inert solvents, meaning that significant amounts of solvent must be removed after both processes. Removing these often high-boiling solvents usually requires heating to high temperatures, which can lead to the formation of byproducts through subsequent reactions.

[0013] To avoid byproducts, various solutions have been proposed. For example, EP 3 124503 Al describes a process for the production of hydrocarbon resins in which, to improve compatibility with an acceptable increase in cost, dicyclopentadiene is reacted with a vinylaromatic compound in a pre-reaction to form a phenylnorbornene derivative, which then serves as an initiator in the subsequent polymerization reaction. The hydrocarbon resin thus obtained is subsequently hydrogenated. A disadvantage of this process is that the pre-reaction adds an extra step, and the temperature in this step must be kept within a narrow range to obtain the phenylnorbornene derivative with high selectivity.

[0014] SUMMARY OF THE INVENTION

[0015] The invention is therefore based on the objective of providing hydrocarbon resins that are as light in color as possible. A further objective of the invention is to provide hydrocarbons that exhibit good compatibility with base polymers, in particular with metallocene polyolefins (mPO), amorphous polyalphaolefins (APAO), and / or ethylene vinyl acetate copolymers (EVAC), and thus serve as tackifiers for hot melt adhesives. Furthermore, the invention aims to provide a process for producing hydrocarbon resins that exhibit the aforementioned compatibility.

[0016] This problem is solved by a hydrocarbon resin obtainable by thermal polymerization of a cyclic diolefin component containing a cyclic diolefin compound with an aromatic component containing indene and / or Ci-4-alkylindene, wherein the hydrocarbon resin has a polydispersity index (PDI) of 1 to less than 2.3.

[0017] The invention further relates to a process for producing the hydrocarbon resin according to the invention, in which a monomer mixture containing an aromatic component containing indene and / or Ci-4-alkylindene and a cyclic diolefin component containing a cyclic diolefin compound is polymerized by heating to a polymerization temperature of at least 180°C in order to obtain a product stream containing hydrocarbon resin, wherein oligomers containing units originating from the cyclic diolefin compound and / or units originating from the aromatic component are separated from the product stream and added back to the monomer mixture.

[0018] The invention also relates to a hydrogenated hydrocarbon resin obtainable by hydrogenation of the hydrocarbon resin according to the invention and / or by the manufacturing process according to the invention.

[0019] The invention further relates to a composition containing

[0020] - a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention, and

[0021] - an adhesive base polymer, for example a metallocene polyolefin or an ethylene vinyl acetate copolymer or an amorphous polyalphaolefin or a styrene block copolymer. The invention also relates to the use of a hydrocarbon resin or a hydrogenated hydrocarbon resin according to the invention as a tackifier in hot melt adhesives, in particular in hot melt adhesives based on metallocene polyolefin, ethylene vinyl acetate copolymer, amorphous polyalphaolefins or styrene block copolymers, and / or in solvent-based adhesives, in particular in solvent-based styrene block copolymer adhesives.

[0022] The invention further relates to the use of a hydrocarbon resin according to the invention as a modifying agent in rubber products, in particular to improve the mechanical and dynamic properties in rubber products, in bitumen, in particular as an additive and / or as a hydrophobizing agent in bitumen, in particular for asphalt, or as a modifying and / or hydrophobizing agent in printing inks.The invention relates to the use of a hydrogenated hydrocarbon resin according to the invention as an additive in paint, in plastics, in particular as a modifying agent in plastics, in rubber, in bitumen, in particular as a hydrophobing agent in bitumen, for example for roofing membranes, in polypropylene films, in particular as a modifying and / or hydrophobing agent in polypropylene films, in particular BOPP films, in cosmetics or as an adhesive in adhesive compositions, in particular for applications in the hygiene products industry and for use in food packaging.

[0023] Surprisingly, a hydrocarbon resin with a PDI of 1 to less than 2.3, obtained by thermal polymerization of a cyclic diolefin component with an indene- and / or Ci-4-Akyii indene-containing component, was found to exhibit excellent properties, in particular good hydrogenation and / or low discoloration. Furthermore, hydrogenation of this resin can yield a hydrogenated resin exhibiting very low color numbers and good compatibility with mPO and APAO, or preferably even with mPO, APAO, and EVAC.

[0024] Fig. 1 shows a schematic representation of the invention.

[0025] Procedure.

[0026] PREFERRED FORMS OF THE INVENTION

[0027] The following section describes first the inventive process for producing hydrocarbon resins and a possible subsequent hydrogenation.

[0028] Preferably, in the process according to the invention, the monomer mixture is essentially a single-phase liquid during heating to a polymerization temperature of at least 180°C and during polymerization. This ensures good mixing. » a shorter reaction time and good heat transfer within the mixture are achieved.

[0029] The cyclic diolefin component contains a cyclic diolefin compound. Preferably, the cyclic diolefin component contains 25% by weight or more. » 30% by weight or more » preferably 35% by weight or more » preferably 50 wt.% or more » even more preferably 60 wt.% or more » even more preferably 70 wt.% or more » based on the total mass of the cyclic diolefin component » the cyclic diolefin compound.

[0030] The cyclic diolefin component can also consist of the cyclic diolefin compound.

[0031] The cyclic diolefin compound preferably contains a cycloalkene with at least two carbon-carbon double bonds. » which may in particular be conjugated. Furthermore, the cyclic diolefin compound preferably consists of one or more cycloalkenes with at least two carbon-carbon double bonds, which may in particular be conjugated.

[0032] A cycloalkene with at least two carbon-carbon double bonds is, according to the invention, referred to as a cyclodialkene. » The compound in which the two carbon-carbon double bonds are conjugated is, according to the invention, referred to as a conjugated cyclodialkene.

[0033] Cyclodialkenes, especially conjugated cyclodiaalkenes, preferably have 5 to 11, and particularly 5 to 7, carbon atoms as monomers. Examples of conjugated cyclodiaalkenes are cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, and ethyltetramethylcyclopentadiene. Cyclodialkenes, especially conjugated cyclodiaalkenes, can dimerize. They can exist as monomers, dimers, or mixtures of monomers and dimers. The dimerization is preferably reversible. For example, cyclopentadiene and cyclopentadiene derivatives tend to dimerize spontaneously at room temperature, with the monomers reforming upon heating in the reverse reaction. If the cyclic diolefin compound contains a mixture of different cyclodialkenes, especially conjugated cyclodialkenes, monomers, dimers and / or codimers may be present.

[0034] The aforementioned examples of conjugated cyclodiaalkenes can exist as monomers, dimers, or mixtures of monomers and dimers, depending on the temperature. Mixtures of different conjugated cyclodiaalkenes can contain not only monomers and dimers, but also codimers. For example, mixtures of cyclopentadiene and methylcyclopentadiene can contain the two monomers cyclopentadiene-cyclopentadiene dimers, methylcyclopentadiene-methylcyclopentadiene dimers, and cyclopentadiene-methylcyclopentadiene codimers.

[0035] According to one embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene and mixtures thereof.

[0036] According to another embodiment, the cyclic diolefin compound contains cyclopentadiene and methylcyclopentadiene.

[0037] According to another embodiment, the cyclic diolefin component consists of the cyclic diolefin compound, and the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene and mixtures thereof.

[0038] According to another embodiment, the cyclic diolefin component consists of the cyclic diolefin compound, and the cyclic diolefin compound consists of a conjugated cyclodialkene selected from the group consisting of cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, and ethyltetramethylcyclopentadiene.

[0039] According to one embodiment of the process according to the invention, a hydrocarbon mixture, for example a petroleum fraction, containing at least 25 wt.%, in particular 30 to 60 wt.%, of conjugated cyclodialkenes as a cyclic diolefin compound, based on the mass of the hydrocarbon mixture, is used as the cyclic diolefin component. The hydrocarbon mixture can also contain aromatic compounds, for example indene, Ci-4-alkylindene and / or ethylene unsaturated aromatic compounds, each with 8 to 15, preferably 8 to 13, carbon atoms independently of one another, preferably in an amount of 10 to 20 wt.%, based on the mass of the hydrocarbon mixture.

[0040] The hydrocarbon mixture may also contain 20 to 40 wt.% non-reactive components, based on the mass of the hydrocarbon mixture.

[0041] The monomer mixture further contains an aromatic component containing indene and / or Ci-4-alkylindene. Ci-4-alkylindene preferably means indene substituted singly or multiply, in particular singly or doubly. Examples of Ci-4-alkylindenes are methylindene, dimethylindene, and ethylindene. An important example of Ci-4-alkylindene is methylindene. Methylindene includes all isomers of methylindene. Examples of isomers of methylindene are 1-methylindene and 3-methylindene. Different methylindene isomers may also be present simultaneously in the aromatic component. The aromatic component may consist of indene and / or Ci-4-alkylindene. The aromatic component can also be an aroniate mixture containing indene and / or C1-4-alkylindene and at least one, in particular at least two, ethylene unsaturated aromatic compounds, each with 8 to 15, preferably 8 to 13, carbon atoms independently of each other.

[0042] According to a preferred embodiment, a petroleum fraction or a component from the tar processing containing at least 25 wt% of indenes and / or Ci-4-alkylindenes and various ethylene unsaturated aromatic compounds, based on the total mass of the petroleum fraction or on the total mass of the fraction from the tar processing, is used as the aromatic component.

[0043] Suitable ethylene-unsaturated aromatic compounds with 8 to 15, preferably 8 to 13, carbon atoms include, in particular, one or more Ci-C4 alkyl-substituted benzene compounds with a carbon-carbon double bond outside the aromatic ring. Examples of such ethylene-unsaturated aromatic compounds are styrene, α-methylstyrene, β-vinyltoluene, μ-vinyltoluene, and / or β-vinyltoluene. These ethylene-unsaturated aromatic compounds are often referred to as vinyl aromatics.

[0044] Accordingly, the aromatic mixture according to one embodiment contains indene and / or methylindene and at least two vinyl aromatics selected from the group consisting of styrene, α-methylstyrene, β-vinyltoluene, μ-vinyltoluene, μ-vinyltoluene, μ-vinyltoluene, or consists thereof.

[0045] According to one embodiment, the aromatic mixture is a mixture containing 50 wt% or less vinyl aromatics such as styrene, α-methylstyrene, β-vinyltoluene, · m-Vinyltoluene and p-Vinyltoluene, 30 wt% or less indene and 15 wt% or less Ci-4-alkylindene, based on the total mass of the mixture, are used. According to a further embodiment, the aromatic mixture is a mixture containing 60 wt% or less indene and / or Ci-4-alkylindene, based on the total mass of the mixture.

[0046] The cyclic diolefin compound and indene and / or Ci-4-alkylindene or the aromatic mixture are preferably the monomers of the monomer mixture or provide them.

[0047] The cyclic diolefin component and the aromatic component can be present in different ratios in the monomer mixture. However, it has been found that better results are obtained when the ratios of the cyclic diolefin component and the aromatic component are adjusted so that the cyclic diolefin compound and indene and / or Ci-4-Alkylindene and the ethylene-unsaturated aromatic compounds are present in specific ratios.

[0048] Advantageously, the cyclic diolefin compound and the aromatic component are defined as above, and the monomer mixture contains 50 to 95 wt.%, preferably 60 to 95 wt.%, or 65 to 90 wt.%, or 65 to 85 wt.%, or 65 to 80 wt.% of the cyclic diolefin compound, based on the total mass of cyclic diolefin compounds, indenes and / or Ci-4-alkylindenes and ethylene unsaturated aromatic compounds.

[0049] According to a preferred embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene and mixtures thereof, and the aromatic component is an aromatic mixture containing indene and / or Ci-4-alkylindene and at least one, in particular at least two, ethylene-unsaturated aromatic compounds, each having independently 8 to 15, preferably 8 to 13, carbon atoms, and the monomer mixture contains 50 to 95 wt.%, preferably 60 to 95 wt.%, or 65 to 90 wt.%, or 65 to 85 wt.%, or 65 to 80 wt.% of the cyclic diolefin compound, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene-unsaturated aromatic compounds.

[0050] According to a further preferred embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene, and mixtures thereof, and the aromatic component is an aromatic mixture, wherein the aromatic mixture is a mixture containing 50 wt.% or less of vinyl aromatics such as styrene, α-methylstyrene, β-vinyltoluene, μ-vinyltoluene, and β-vinyltoluene, 25 wt.% or less of indene, and 10 wt.% or less of Ci-4-alkylindene, based on the total mass of the mixture, or a mixture containing 60 wt.% or less of indene and / or Ci-4-alkylindene, based on the total mass of the mixture, and the monomer mixture contains 50 to 95 wt.%, preferably 60 to 95 wt.%, or 65 up to 90% by weight or 65 to 85% by weight or 65 to 80% by weight-% of the cyclic diolefin compound, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds.

[0051] Advantageously, the cyclic diolefin compound and the aromatic component are defined as above, and the monomer mixture contains 5 to 40 wt.%, preferably 10 to 35 wt.% or 15 to 35 wt.% or 25 to 35 wt.% of indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds.

[0052] According to one embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene and mixtures thereof, and the aromatic component is an aromatic mixture containing indene and / or Ci-4-alkylindene and at least one, in particular at least two, ethylene-unsaturated aromatic compounds, each having independently 8 to 15, preferably 8 to 13, carbon atoms, and the monomer mixture contains 5 to 40 wt.%, preferably 10 to 35 wt.% or 15 to 35 wt.% or 25 to 35 wt.% of ethylene-unsaturated aromatic compounds, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene-unsaturated aromatic compounds.

[0053] According to a further embodiment, the cyclic diolefin compound is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene dimers and mixtures thereof, and the

[0054] The aromatic component is a mixture of aromatics, wherein the aromatic mixture contains 50 wt% or less of vinyl aromatics such as styrene, α-methylstyrene, β-vinyltoluene, μ-vinyltoluene! and p-vinyltoluene, 30 wt.% or less indene and 15 wt.% or less Ci-4-alkylindene, based on the total mass of the mixture, or a mixture containing 60 wt.% or less indene and / or Ci-4-alkylindene, based on the total mass of the mixture, and the monomer mixture contains 5 to 40 wt.%, preferably 10 to 35 wt.% or 15 to 35 wt.% or 25 to 35 wt.% of indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds.

[0055] If a mixture with a low content of cyclic diolefin compound, for example a petroleum fraction, is used as the cyclic diolefin component, a cyclic diolefin compound consisting of one or more conjugated cyclodialkenes, for example cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, and ethyltetramethylcyclopentadiene, can be additionally added to adjust the monomer ratios specified above. The same applies to the aromatic component and indene and / or Ci-4-alkylindene and the ethylenically unsaturated aromatic compounds with 8 to 15, preferably 8 to 13, carbon atoms.

[0056] The monomer mixture may contain a non-polymerizable solvent. Suitable solvents are aromatic and naphthenic solvents or their hydrogenation products. Suitable solvents are, for example, benzene, toluene, xylene, ethylbenzene, cyclohexane, dimethylcyclohexane, ethylcyclohexane, or mixtures thereof. Preferably, the solvent may contain one or more, in particular one or two, alkyl-substituted aromatic compounds with 7 to 10 carbon atoms, for example, o-xylene, m-xylene, p-xylene, and / or ethylbenzene. These preferably have a boiling point above 100°C, in particular above 130°C. If xylene is used as a solvent, it may be present as a pure compound or as a mixture of two or more of the isomers o-xylene, m-xylene, and p-xylene.

[0057] According to a preferred embodiment, a celeromer mixture can be used as

[0058] Solvents are used. The Ce isomer mixture preferably comprises a mixture of o-xylene, m-xylene, p-xylene and ethylbenzene.

[0059] Petroleum fractions and components from tar distillation may already contain non-polymerizable components, such as non-polymerizable aromatics like xylenes. Therefore, the addition of a solvent can be omitted if a petroleum fraction is used as the cyclic diolefin component and / or a petroleum fraction or a component from tar distillation is used as the aromatic component. The monomer mixture may contain non-polymerizable components in an amount of 0 to 40 wt.%. The non-polymerizable solvent may also be present in the monomer mixture in an amount of 0 to 40 wt.%, based on the mass of the monomer mixture. Preferably, the monomer mixture contains 5 to 35 wt.%, and particularly preferably 5 to 30 wt.%, for example, approximately 30 wt.%, of non-polymerizable solvent, in each case based on the mass of the monomer mixture.

[0060] It is also conceivable that the monomer mixture contains non-polymerizable solvent and non-polymerizable components together in an amount of 0 to 40 wt.%, preferably 5 to 35 wt.%, more preferably 5 to 30 wt.%, for example about 30 wt.%, based on the mass of the monomer mixture. Finally, it is conceivable that the monomer mixture contains non-polymerizable components in an amount of 0 to 40 wt.%, preferably 5 to 35 wt.%, more preferably 5 to 30 wt.%, for example about 30 wt.%, based on the mass of the

[0061] Contains monomer mixture.

[0062] According to one embodiment, the process is essentially carried out in the absence of oxygen. This reduces the formation of byproducts. In particular, the formation of acid and ester groups in the product can be avoided. This helps in achieving hydrogenated hydrocarbon resins that are as colorless as possible. Preferably, the cyclic diolefin components and / or the aromatic components or the aromatic mixture, especially their storage containers, are inertized with a protective gas such as nitrogen. Advantageously, the hydrocarbon resin and / or the hydrogenated hydrocarbon resin, especially the storage containers for the hydrocarbon resin and / or for the hydrogenated hydrocarbon resin, are also inertized with a protective gas such as nitrogen. In the process according to the invention, the monomer mixture can be rapidly transferred to the

[0063] The polymerization temperature is reached. Preferably, the monomer mixture is heated at a rate of 20°C / minute to 200°C / minute, more preferably 30°C / minute to 200°C / minute, more preferably 35°C / minute to 200°C / minute, even more preferably 35°C / minute to 140°C / minute, and particularly preferably 35°C / minute to 80°C / minute or 35°C / minute to 70°C / minute. In particular, the aforementioned heating rates are used when heating the monomer mixture to the temperature at which the polymerization reaction begins, especially up to a temperature of 180°C to 235°C. Once the monomer mixture has reached a temperature above 180°C or more, subsequent temperatures can also be set using heating rates other than those mentioned above.It was found that at the heating rates according to the invention, the amount of by-products is low and low Mz values ​​can be achieved at a given softening point.

[0064] Although polymerization begins at a temperature of 180°C, the polymerization process according to the invention can also be carried out at higher temperatures. In the process according to the invention, polymerization is carried out at a temperature of 180°C or higher. Thus, polymerization can be carried out at a polymerization temperature of 200°C to 300°C, or from 230°C to 300°C, or from 240°C to 280°C, or from 250°C to 270°C.

[0065] The temperature can be varied during polymerization. For example, the temperature can be increased during polymerization up to a final temperature. These temperature changes can be implemented in various ways. For example, they can be linear or abrupt. According to one embodiment, the aforementioned temperatures are final temperatures reached at the end of the polymerization process. In another embodiment, the temperature is kept essentially constant during polymerization. It has been found that the products exhibit a low softening point and can be waxy if the polymerization is carried out entirely at lower temperatures, particularly below 240°C.

[0066] Polymerization can be carried out at a pressure of 10 bar or more. For example, the pressure can be 10 to 25 bar, particularly 10 to 20 bar or 13 to 18 bar. If polymerization is carried out at less than 10 bar, the end product is of lower quality and the yield is also lower. Furthermore, the aforementioned pressures essentially eliminate the presence of a gas phase. This allows for better control of the reaction and improved heat transfer.

[0067] Polymerization can be carried out continuously or batchwise. Continuous polymerization is preferred. The continuous process has the advantage of better heat transfer compared to the batch process. Furthermore, operating costs are lower with continuous operation, and the process can be carried out more safely.

[0068] The polymerization can be carried out in various reaction vessels. Preferably, the polymerization is carried out continuously in a tubular reactor. This method has proven particularly advantageous for continuous polymerization. In the tubular reactor, the polymerization can be carried out, in particular, during a residence time of 30 to 180 minutes, especially 40 to 120 minutes or 50 to 90 minutes.

[0069] If the properties of the hydrocarbon resin obtained according to the invention are to be modified, the obtained hydrocarbon resin can be partially or completely recycled into the tubular reactor. This measure will be useful, for example, if higher molecular weights of the hydrocarbon resin are to be achieved. Recycling preferably takes place in the raw material feed of the input stream. The material is preferably taken for recycling after the reactor outlet and before the oligomers are separated from the product stream. In the process according to the invention, 0 to 90 wt.% of the product stream, preferably 25 to 75 wt.%, based on the mass of the obtained product stream, can be recycled into the monomer mixture of the input stream. Such recycling can be carried out particularly easily in tubular reactors. In the process according to the invention, oligomers that are removed by the cyclic

[0070] Units originating from the diolefin compound and / or the aromatic component are separated from the product stream and returned to the monomer mixture. Advantageously, the oligomers and the optional non-polymerizable solvent are partially, preferably completely, removed from the product stream after polymerization by batch or, preferably, continuous evaporation. Advantageously, after evaporation, the oligomers are partially or preferably completely separated from the optional non-polymerizable solvent by batch or, preferably, continuous condensation. Advantageously, after condensation, the oligomers are returned to the monomer mixture batch or, preferably, continuously for further polymerization.

[0071] The oligomers can be produced particularly at an absolute pressure of 100 mbar or less, in particular 50 mbar or less, preferably 30 mbar, and at a

[0072] The oligomers boil at a temperature of 80°C or more, preferably from 80°C to 120°C, more preferably from 90°C to 120°C, and even more preferably from 100°C to 120°C. Particularly preferably, the oligomers boil at an absolute pressure of 50 mbar or less, preferably 30 mbar, and at a temperature of 90°C to 120°C, especially from 100°C to 120°C. The aforementioned oligomers can be recycled by operating a partial condenser under the aforementioned conditions, in which the oligomers are separated from lower-boiling components.

[0073] Furthermore, the oligomers preferably have a molecular weight of 100 to 600 g / mol, more preferably of 130 to 600 g / mol, and particularly preferably of 150 to

[0074] have a density of 600 g / mol.

[0075] It has been found that separating the oligomers from the product stream and subsequently adding them to the monomer mixture yields a high-quality hydrocarbon resin. In particular, a hydrocarbon resin with a PDI of 1 to less than 2.3 can be obtained. Furthermore, a hydrocarbon resin containing indene and with a PDI of 1 to less than 2.3 can be obtained. These resins exhibit good compatibility with mPO and APAO, especially with mPO, APAO, and EVAC, particularly after hydrogenation.

[0076] Furthermore, by separating the oligomers from the resulting product stream and subsequently adding them to the monomer mixture in the process according to the invention, the polymerization can also be carried out at a constant temperature without the formation of sparingly soluble products. Additionally, this method can yield hydrocarbon resins that exhibit minimal discoloration. Finally, the yield can be increased by recycling the oligomers.

[0077] The recycled oligomers may also contain non-polymerizable components and / or solvents.

[0078] Unreacted monomers can be thermally separated from the solvent and recycled by adding them back into the feedstock mixture. This further increases the resin yield. The process according to the invention can be carried out effectively by selectively separating oligomers that boil in the aforementioned ranges or have the molecular weights listed above. In particular, the process according to the invention can be carried out with good yields in steady-state operation by selectively separating the oligomers. Furthermore, the feedstock does not need to be adjusted. Dilute feedstocks such as petroleum fractions or fractions from tar processing can also be used.

[0079] Preferably, the polymerization of the monomer mixture to the hydrocarbon resin proceeds via a combination of Diels-Alder reactions and radical linkages of these poly-Diels-Alder products.

[0080] The hydrocarbon resin according to the invention can be obtained using the method described above.

[0081] The hydrocarbon resin according to the invention preferably contains repeating units derived from the cyclic diolefin compound and indene and / or Ci-4-alkylindene units. In particular, the hydrocarbon resin can also contain further units derived from the aromatic component. For example, the hydrocarbon resin can also contain units derived from styrene, α-methylstyrene, β-vinyltoluene, μ-vinyltoluene and / or β-vinyltoluene.

[0082] The above statements regarding the process according to the invention apply accordingly to the cyclic diolefin component, the cyclic diolefin compound and the aromatic component of the hydrocarbon resin according to the invention.

[0083] Preferably, the hydrocarbon resin according to the invention has at least section by section the general structural formula (I)

[0084] where each R 1 and every R 2 independently selected from the group consisting of -H, -CHs, -C2H5, - / 1-C3H7, -CH(CH3)2, -n- C4H9, -CH2CH(CH3)2, -CHCCH3)(C2H5) and -C(CH3)3, each R 3 independently of each other -H, -CH3 or -C2H5, p, q, r, s, t and u are independently of each other integers from 0 to 8, each n, each m and each o are independently of each other integers from 0 to 6, preferably from 0 to 4, more preferably from 0 to 2, and each a, each b, each c and each d are independently of each other integers from 1 to 4, more preferably from 1 to 2, with the proviso that the hydrocarbon resin has a number-average molecular weight Mn of 200 to 600 g / mol, preferably from 220 to 500 g / mol, more preferably from 250 to 400 g / mol, and contains indene and / or C1-4-alkylindene units.

[0085] Accordingly, the resin is preferably a copolymer formed by radical linkage of different units contained in the cyclic diolefin component and the aromatic component, or Diels-Alder reaction products of components of the cyclic diolefin component and / or the aromatic component.

[0086] The aromatic components are linked together. The unit designated by the variable p in structural formula (I) is formed by single or multiple Diels-Alder reactions of cyclic diolefin compounds with each other. The units designated by the variables q and r in structural formula (I) are formed by Diels-Alder reactions of cyclic diolefin compounds with ethylene-unsaturated aromatic compounds or indenes or Ci-C4 alkylindenes, optionally with the incorporation of further cyclic diolefin compounds via Diels-Alder reactions. The unit designated by the variable s in structural formula (I) is a cyclic diolefin compound incorporated by radical linkage and has not undergone a Diels-Alder reaction.The unit designated by the variable t in structural formula (I) is an indene or Ci-4-alkylindene unit incorporated via radical linkage and which has not undergone a Diels-Alder reaction with a cyclic diolefin compound. The unit designated by the variable u in structural formula (1) is a unit incorporated via radical linkage and derived from the ethylene unsaturated aromatic compound, which has not undergone a Diels-Alder reaction with a cyclic diolefin compound.

[0087] In structural formula (I), the order, presence, and number of units with the variables p, q, r, s, t, and u can differ statistically for individual copolymer molecules of the hydrocarbon resin. The variables n, m, and o indicate whether one or more cyclic diolefin compounds are linked together by Diels-Alder reactions in the respective units. Advantageously, for the unit designated by the variable p in structural formula (I), if p is greater than 1, each n can be an integer from 0 to 6, preferably from 0 to 4, and more preferably from 0 to 2, independently of each other. The same applies to the units designated by the variables q and r in structural formula (!).

[0088] Preferably, the sum of the variables p, q, r, s, t and u is at least 1, more preferably from 1 to 10, even more preferably from 1 to 0.8, and particularly preferably from 2 to 6.

[0089] As shown in the structural formula (I), the various units can be substituted. The aromatic units, in particular, can be multiply substituted. The hydrocarbon resin according to the invention has a PDI of 1 to less than 2.3. Preferably, the hydrocarbon resin has a polydispersity index (PDI) of 1 to 2.1, more preferably of 1.5 to 2.0, and more preferably of 1.5 to 1.95. It has been found that hydrocarbon resins with the aforementioned PDIs exhibit very good compatibility with base polymers of hot melt adhesives, in particular with mPO, APAO, and EVAC.

[0090] Preferably, the hydrocarbon resin according to the invention contains 1 to 20 wt.%, more preferably up to 20 wt.%, more preferably 4 to 16 wt.%, even more preferably 5 to 15 wt.%, and particularly preferably 7 to 13 wt.%, based on the total mass of the hydrocarbon resin, indene and / or Ci-4-alkylindene units. It has been found that hydrocarbon resins with the aforementioned amounts of indene and / or Ci-4-alkylindene units exhibit very good compatibility with base polymers of hot melt adhesives, in particular with mPO, APAO, and EVAC.

[0091] The indene content in the hydrocarbon resin can be determined, for example, by pyrolysis gas chromatography with a flame ionization detector (FID). This method can also be used to determine the content of other units in the hydrocarbon resin.

[0092] Preferably, the hydrocarbon resin contains 40 to 85 wt.%, more preferably 45 to 70 wt.%, further preferably 45 to 65 wt.% units originating from the cyclic diolefin compound, based on the total mass of the hydrocarbon resin.

[0093] If the aromatic component is a mixture containing indene and / or C1-4-alkylindene and at least one, in particular at least two, ethylene-unsaturated aromatic compounds, each with 8 to 15, preferably 8 to 13, carbon atoms independently of one another, the hydrocarbon resin may preferably contain, in addition to indene and / or C1-4-alkylindene units, further units derived from the ethylene-unsaturated aromatic compounds. Preferably, the hydrocarbon resin contains 5 to 25 wt.%, more preferably 10 to 25 wt.%, and further preferably 15 to 25 wt.% indene and / or C1-4-alkylindene units and units derived from ethylene-unsaturated aromatic compounds, based on the total mass of the hydrocarbon resin.

[0094] The hydrocarbon resin preferably has a molecular weight of 800 to 2450 g / mol, more preferably of 800 to 1800 g / mol, more preferably of 800 to 1750 g / mol, and even more preferably of 800 to 1700 g / mol.

[0095] Various molecular weights are known to those skilled in the art. These include the number-mean molecular weight Mn, the weight-mean molecular weight Mw, and the centrifuge-mean molecular weight Mz. In this context, the centrifuge-mean molecular weight Mz is also abbreviated as molecular weight Mz. The ratio Mw / Mn of the number-mean molecular weight Mn and the weight-mean molecular weight Mw is called the polydispersity PDI.

[0096] Methods for determining the molecular weights Mn, Mw, and Mz are known to those skilled in the art. For example, they can be determined by gel permeation chromatography or mass spectrometry, preferably gel permeation chromatography. For measurements with gel permeation chromatography, THF is preferably used as the eluent. Polystyrene is preferably used as the calibration standard. Measurements with gel permeation chromatography are advantageously carried out using linear columns with a porosity of 1000 Å.

[0097] Refractive index and UV detectors are used. In addition to the molar mass, the degree of hydrogenation of a molar mass fraction can also be determined using a UV detector. Furthermore, the hydrocarbon resin preferably has a Mn of 200 to 600 g / mol, more preferably 220 to 500 g / mol, and particularly preferably 250 to 400 g / mol. Advantageously, the hydrocarbon resin according to the invention has a Mw of 300 to 800 g / mol, preferably 400 to 800 g / mol, and particularly preferably 500 to 800 g / mol. As can be seen by those skilled in the art, the values ​​given for the oligomers are

[0098] Molecular weights are not directly comparable to the preferred number-average or weight-average molecular weights specified for the hydrocarbon resins according to the invention. This is primarily because the molecular weights for the oligomers are absolute molecular weights, whereas the preferred molecular weights specified for the hydrocarbon resins according to the invention are not.

[0099] Molecular weights are relative molecular weights in relation to polystyrene standards with the aforementioned molecular weights.

[0100] The hydrocarbon resin preferably has a softening point, determined by the ring and ball method according to standard ASTM D3461, of 80°C to 140°C, preferably of 90°C to 130°C, more preferably of 100°C to 120°C.

[0101] The hydrocarbon resin according to the invention may further exhibit a slight coloration. Preferably, the hydrocarbon resin has a Gardner color number of 14 or less, more preferably 12 or less, and more preferably 11 or less. This results in the hydrocarbon resin according to the invention exhibiting good hydrogenation properties and good compatibility with other components, for example in hot melt adhesives, rubber products, bitumen, and printing inks. The Gardner color number is preferably determined according to ISO 4630, in particular ISO 4630:2015.

[0102] The hydrocarbon resin according to the invention is preferably not hydrogenated. In particular, the hydrocarbon resin according to the invention can be in ! The H-NMR spectrum shows a content of aromatic protons relative to the total amount of protons in the ! H-NMR spectrum, from 1% to 30%, in particular from 2% to 25% or from 3% to 20%. Furthermore, the hydrocarbon resin according to the invention can in particular exhibit in the 1 H-NMR spectrum shows a content of olefinic protons relative to the total amount of protons in the 1 H-NMR spectrum, from 1% to 20%, in particular from 1% to 10% or from 3% to 10%. 1 ¹H NMR spectra are preferably measured in CDCb. Aromatic protons appear in the X The ¹H NMR spectrum in CDCI3 is preferably in the range of 6.01 ppm to 8.00 ppm. Olefinic protons appear in the X H-NMR spectrum in CDCI3 preferably in the range of 5.00 ppm to 6.00 ppm.

[0103] Furthermore, the hydrocarbon resin according to the invention can be readily hydrogenated. In particular, the hydrocarbon resin according to the invention is soluble at room temperature in a mixture of saturated hydrocarbons that are liquid at room temperature, especially aromatic-free refined gasolines. Such mixtures are commercially available under the designation D40, for example Exxsol D40 or Shellsol D40.

[0104] Furthermore, the hydrocarbon resin according to the invention can be hydrogenated within 0.5 to 5 hours, preferably within 0.5 to 3 hours, and particularly preferably within 0.75 to 1.5 hours, to a yellowness index of 5 or less, preferably 3 or less, and particularly preferably 1 or less. The yellowness index is determined according to ASTM 01209-05(2011) or ISO 6271:2015. Hydrocarbon resins that are readily hydrogenable can be hydrogenated more easily and cost-effectively. The resulting hydrogenated hydrocarbon resins are compatible with other components, for example, in hot melt adhesives. Since they exhibit little discoloration, they can also be used for a wide range of applications.

[0105] A high degree of hydrogenation can be achieved during hydrogenation. For example, the hydrocarbon resin according to the invention can be hydrogenated to a residual aromatic content of less than 0.2%, preferably less than 0.15%, and particularly preferably less than 0.09%. Low residual aromatic content results in more stable hydrocarbon resins with regard to discoloration.

[0106] According to one embodiment, the hydrocarbon resin according to the invention is obtained by the method according to the invention, in particular by the method described above.

[0107] The hydrocarbon resin according to the invention can be used directly for the applications mentioned herein, in particular for adhesive applications.

[0108] The hydrocarbon resin according to the invention can be further processed, particularly after removal of solvent, unreacted monomer, and oligomers. In particular, the hydrocarbon resin according to the invention can be functionalized and / or hydrogenated.

[0109] In the process according to the invention, hydrogenation can be carried out following polymerization. Hydrogenation of the hydrocarbon resin yields a hydrogenated hydrocarbon resin. Accordingly, the hydrocarbon resin is preferably partially or completely hydrogenated in a subsequent hydrogenation step to obtain a hydrogenated hydrocarbon resin.

[0110] The hydrocarbon resin can be partially or completely hydrogenated. The hydrogenation preferably takes place in the presence of a catalyst. Various catalysts are suitable. Nickel-, palladium-, cobalt-, platinum-, and rhodium-based catalysts can be used in the hydrogenation. Advantageously, nickel is used as the catalyst. The aforementioned catalysts can be applied to a support such as aluminum oxide, silicon dioxide, zeolites, clay minerals such as montmorillonite, and silicon carbide. The hydrogenation of the hydrocarbon resin is preferably carried out in the presence of a nickel catalyst. According to a further preferred embodiment, a nickel catalyst is used on an aluminum oxide / silicon oxide support. These catalysts are commercially available. The nickel catalyst can be present, in particular, in heterogeneous form.This allows it to be easily removed by filtration after the hydrogenation process is complete.

[0111] The term "partial hydrogenation" is understood to mean that predominantly olefinic double bonds are hydrogenated, or that some of the aromatic units of the hydrocarbon resin are also hydrogenated. Preferably, the hydrocarbon resin is completely hydrogenated during the hydrogenation process.In complete hydrogenation, at least 70%, preferably at least 90%, more preferably at least 95%, particularly preferably at least 99% of the olefinic double bonds and at least 70%, preferably at least 90%, more preferably at least 95%, particularly preferably at least 99% of the aromatic double bonds are hydrogenated. In partial hydrogenation, at least 70%, more preferably at least 90%, more preferably at least 95%, more preferably at least 99% of the olefinic double bonds and at least 50% or less, more preferably 30% or less, more preferably 10% or less of the aromatic double bonds are hydrogenated.

[0112] Complete hydrogenation has the advantage that fewer byproducts are formed through subsequent reactions, thus largely preventing discoloration in the hydrocarbon resin.

[0113] Whether the hydrocarbon resin has been partially or completely hydrogenated can be determined by NMR spectroscopy, in particular by determining the content of aromatic and / or olefinic double bonds using X H NMR spectroscopy. Preferably, the residual aromatic content indicates the content of aromatic protons, based on the total amount of protons in the 1 ¹H NMR spectrum. The hydrogenation can be carried out in the presence of a solvent, in particular an aliphatic solvent. A mixture of saturated hydrocarbons that are liquid at room temperature can also be used as the solvent, preferably with a boiling point between 155°C and 170°C, more preferably between 160°C and 165°C. Suitable solvents include, for example, refined gasoline. Such mixtures are commercially available under the designation D40, for example Exxsol D40. 'or Shellsol D40. Adding this solvent reduces the viscosity of the hydrocarbon resin. Furthermore, using an aliphatic solvent like D40 can save hydrogen compared to using an aromatic solvent.

[0114] Preferably, 80% by weight or more, in particular 90% by weight or more, or 100% by weight or more, of solvent can be added to the hydrocarbon resin, based on the mass of the hydrocarbon resin. Preferably, a hydrogenation mixture containing hydrocarbon resin and solvent is used. Advantageously, the hydrogenation mixture is a solution. Preferably, the hydrogenation mixture contains 50% hydrocarbon resin.

[0115] Hydrogenation can be carried out batchwise or continuously. Preferably, hydrogenation is carried out continuously. Whether the hydrogenation is continuous or batchwise is independent of the polymerization to the non-hydrogenated hydrocarbon resin. Thus, polymerization can be carried out continuously and hydrogenation batchwise, or vice versa. Furthermore, polymerization and hydrogenation can be carried out continuously. Finally, polymerization and hydrogenation can be carried out batchwise.

[0116] Advantageously, the hydrogenation can be carried out in a loop reactor. The hydrogenation mixture is conveniently circulated during the hydrogenation process. The loop reactor advantageously includes a gas-liquid ejector. By using a loop reactor in conjunction with a gas-liquid ejector, particularly thorough mixing of the hydrocarbon resin to be hydrogenated with hydrogen and any added catalyst can be achieved, thereby reducing the hydrogenation time.

[0117] Preferably, the hydrogenation is carried out at a pressure of more than 60 bar, in particular from 65 bar to 105 bar, or from 65 bar to 100 bar, or from 70 bar to 95 bar. This allows the hydrogenation of the hydrocarbon resin to be adjusted to the desired degree of hydrogenation.

[0118] The hydrogenation is preferably carried out at a temperature of 240°C or higher, in particular from 240°C to 300°C or from 250°C to 280°C. It has been observed that at hydrogenation temperatures below 240°C, the hydrogenation process is slow, and at temperatures above 300°C, increased amounts of byproducts can form again.

[0119] In a conventional large-scale loop reactor, the hydrogenation can be carried out for 50 to 160 minutes, preferably 60 to 150 minutes, and particularly preferably 80 to 150 minutes. This allows the desired degree of hydrogenation of the hydrogenated hydrocarbon resin and its brightness to be adjusted.

[0120] According to a particularly preferred embodiment of the invention, a pressure relief stage is provided both after polymerization and after hydrogenation. The first pressure relief stage after polymerization serves to remove volatile components, in particular solvent and / or unreacted monomer and / or oligomer, from the product stream. By utilizing the pressure differential in the first pressure relief stage, the product stream is flash-fed, thereby removing the more volatile components. Preferably, the product stream containing the hydrocarbon resin can be introduced into the first pressure relief stage at a temperature of 200°C to 300°C, particularly preferably at a temperature of 220°C to 260°C or 230°C to 250°C.

[0121] Preferably, after the first relaxation stage, the hydrocarbon resin contains only 3 wt.% or less, preferably 1 wt.% or less, more preferably 0.5 wt.% or less of solvent and / or unreacted monomer, in each case based on the mass of the hydrocarbon resin.

[0122] In the first pressure reduction stage, the absolute pressure can be reduced to 1 bar or less, preferably 0.1 bar or less, and particularly preferably 0.03 bar or less. This pressure reduction eliminates the need for complex agitated equipment such as thin-film evaporators or water stripping devices. As a result, the process becomes more cost-effective and less prone to failure. However, a thin-film evaporator can be used in the process after polymerization and the subsequent first pressure reduction stage. This allows for a low solvent content in the hydrocarbon resin after polymerization.

[0123] After hydrogenation, a second stress-relief stage can preferably be provided. In the second stress-relief stage, at least a portion of the volatile components, particularly the solvent, can be removed from the hydrogenated hydrocarbon resin without generating a large quantity of byproducts due to additional thermal stress and without deteriorating the resin's color values. Preferably, the hydrogenated hydrocarbon resin after the second stress-relief stage contains 2 wt.% or less, more preferably 0.5 wt.% or less, or 0.03 wt.% or less, of solvent, in each case based on the mass of the hydrogenated hydrocarbon resin.

[0124] The pressure reduction in the second expansion stage can be carried out in two expansion steps. In a first expansion step, the absolute pressure can be reduced to 0.5 bar or less, preferably 0.2 bar or less, more preferably 0.05 bar or less, or particularly preferably 0.01 bar or less. After hydrogenation, the catalyst is preferably removed first. The catalyst can be removed, for example, by filtration. The hydrogenation mixture is preferably introduced into the first expansion step at a temperature of 190°C to 270°C, more preferably 200°C to 260°C, more preferably 210°C to 250°C, more preferably 220°C to 240°C, and even more preferably 230°C.After the first expansion step, the hydrogenation mixture can be introduced into the second expansion step at a temperature of 190°C to 270°C, preferably 200°C to 260°C, particularly preferably 210°C to 250°C, or 220°C to 240°C. In the second expansion step, the absolute pressure can preferably be reduced to 0.1 bar or less, more preferably 0.05 bar or less, more preferably 0.03 bar or less, more preferably 0.01 bar or less.

[0125] Additionally, the hydrogenation mixture, from which any previously added catalyst has been removed, can be introduced into a pre-expansion stage immediately before the second expansion stage. The hydrogenation mixture can have a temperature of 240°C to 300°C, preferably 250°C to 290°C, and particularly preferably 260°C to 280°C. Preferably, the overpressure in the pre-expansion stage can be reduced to 3 bar or less, more preferably 2 bar or less, more preferably 1.5 bar or less, and even more preferably 1 bar or less.

[0126] If a pre-expansion stage is provided, the mixture taken from the pre-expansion stage is preferably introduced into the second expansion stage.

[0127] By carrying out one or more expansion stages, the period during which the hydrocarbon resin and / or the hydrogenated hydrocarbon resin is held at a high temperature can be reduced. This measure can also serve to reduce byproducts. According to one embodiment, two expansion evaporation steps are provided after hydrogenation. These two expansion evaporation steps preferably constitute the second expansion stage. For this purpose, the catalyst is preferably removed first. The catalyst can be removed, for example, by filtration. Subsequently, in the first expansion evaporation step, the preferably catalyst-free hydrogenation mixture is fed into a first pressure vessel. The pressure in the first pressure vessel is lower than the pressure of the hydrogenation mixture.Preferably, the pressure of the hydrogenation mixture in the first pressure vessel is reduced to an absolute pressure of 3 bar or less, preferably 2 bar or less, more preferably 1.5 bar or less, and even more preferably 1 bar or less.

[0128] This allows hydrogen to be removed from the hydrogenation mixture in particular.

[0129] In the second flash evaporation step, the resulting mixture is transferred to a second pressure vessel. The pressure in the second pressure vessel is lower than the pressure of the resulting mixture. Preferably, the pressure of the resulting mixture in the second pressure vessel is reduced to 0.1 bar or less, more preferably 0.05 bar or less, and particularly preferably 0.03 bar or less. This allows for the removal of solvents, in particular. Advantageously, a thin-film evaporator is provided after the second flash evaporation step, which is operated at 0.01 bar or less, more preferably at 0.005 bar or less, and more preferably at 0.003 bar or less. In this way, the solvent can be largely removed from the hydrogenated hydrocarbon resin.

[0130] The hydrogenation mixture is preferably introduced into the first flash evaporation step at a temperature of 190°C to 270°C, more preferably from 200°C to 260°C, more preferably from 210°C to 250°C, more preferably from 220°C to 240°C, and even more preferably from 230°C. After the first flash evaporation step, the hydrogenation mixture can be introduced into the second flash evaporation step at a temperature of 190°C to 270°C, preferably from 200°C to 260°C, and particularly preferably from 210°C to 250°C. » or from 220°C to 240°C. After the second flash evaporation step, the hydrogenation mixture can be introduced into the thin-film evaporator at a temperature of 180°C to 260°C, preferably from 190°C to 250°C, particularly preferably from 200°C to 240°C, or from 210°C to 230°C.

[0131] The hydrogenated hydrocarbon resin according to the invention is obtainable by hydrogenating a hydrocarbon resin according to the invention and / or by the process described herein.

[0132] Preferably, the olefinic double bonds in the hydrogenated hydrocarbon resin are present to a hydrogenation of at least 70%, preferably at least 90%, 95%, or 99%. Partial or complete hydrogenation of the olefinic double bonds can reduce the formation of discoloration in the hydrogenated hydrocarbon resin. Alternatively or additionally, the aromatic double bonds can be present to a hydrogenation of at least 70%, preferably at least 90%, 95%, or 99%. Partial or complete hydrogenation of the aromatic double bonds can also reduce the formation of discoloration in the hydrogenated hydrocarbon resin, resulting in more stable resins.

[0133] The hydrogenated hydrocarbon resin advantageously has a residual content of olefinic double bonds of less than 0.1%, preferably less than 0.05%, particularly preferably less than 0.01%, and a residual aromatic content of less than 0.2%, preferably less than 0.15%, particularly preferably less than 0.09%. The double bond content can be determined by ¹H NMR spectroscopy. Preferably, the hydrogenated hydrocarbon resin has a molecular weight (Mz) of 800 to 2500 g / mol, more preferably 800 to 1800 g / mol, and further preferably 800 to 1600 g / mol. » The hydrogenated hydrocarbon resin advantageously has a Mn of 200 to 600 g / mol, preferably 220 to 500 g / mol, and particularly preferably 220 to 400 g / mol. More preferably, the hydrogenated hydrocarbon resin has a Mw of 300 to 800 g / mol, further preferably 250 to 700 g / mol, and particularly preferably 300 to 600 g / mol.

[0134] The hydrogenated hydrocarbon resin preferably has a polydispersity index of 1 to less than 2.3, preferably of 1.5 to 2.2, particularly preferably of 1.5 to 2.1.

[0135] The softening point of the hydrogenated hydrocarbon resin according to the ring and ball method according to standard ASTM D3461 is preferably from 80°C to 140°C, preferably from 90°C to 130°C or from 90°C to 125°C.

[0136] Furthermore, the hydrogenated hydrocarbon resin can have a Hazen color number of 40 or less, particularly 25 or less. The Hazen color number is determined according to the standard DIN EN ISO 6271:2016-05. The Hazen color number can also be referred to as the platinum-cobalt color number.

[0137] The hydrogenated hydrocarbon resin advantageously has a yellowness index of 3 or higher, preferably 1 or less. The yellowness index is determined according to ASTM 01209-05(2011).

[0138] The advantages of hydrocarbon resin mentioned above, in particular its good compatibility, low coloration, versatile applicability and good stability, apply accordingly to hydrogenated hydrocarbon resin.

[0139] The invention further relates to a composition comprising - a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention, and

[0140] - an adhesive base polymer, for example a metallocene polyolefin or an ethylene vinyl acetate copolymer or an amorphous polyalphaolefin or a styrene block copolymer.

[0141] A further object of the invention is the use of a hydrocarbon resin according to the invention or a hydrogenated hydrocarbon resin according to the invention as a tackifier in hot melt adhesives, in particular in hot melt adhesives based on metallocene polyolefin, ethylene vinyl acetate copolymer, amorphous polyalphaolefins or styrene block copolymers, and / or in solvent-based adhesives, in particular in solvent-based styrene block copolymer adhesives.

[0142] The invention also relates to the use of the hydrocarbon resin as a modifying agent in rubber products, in particular to improve the mechanical and dynamic properties in rubber products, in bitumen, in particular as an additive and / or as a hydrophobizing agent in bitumen, in particular for asphalt, or as a modifying and / or hydrophobizing agent in printing inks.

[0143] Furthermore, the invention relates to the use of the hydrogenated hydrocarbon resin as an additive in paints, in plastics, in particular as a modifier in plastics, in rubber, in bitumen, in particular as a water-repellent agent in bitumen, for example for roofing membranes, in polypropylene films, in particular as a modifier and / or water-repellent agent in polypropylene films, in particular BOPP films, in cosmetics or as a tackifier in adhesive compositions, in particular for applications in the hygiene products industry and for use in food packaging. EXAMPLES

[0144] The invention is explained in more detail below with reference to an exemplary, non-limiting production of a hydrocarbon resin followed by hydrogenation to produce a hydrogenated hydrocarbon resin. The pressures given are absolute pressures.

[0145] In the continuous polymerization process schematically depicted in Figure 1, storage tank 11 contains a petroleum fraction (available as BN-200 from Dow Chemical, hereinafter referred to as BN-200) rich in dicyclopentadiene, methylcyclopentadiene dimers, and cyclopentadiene-methylcyclopentadiene dimers (hereinafter referred to as the cyclic diolefin compound). BN-200 contains approximately 50 wt% cyclic diolefin compound, approximately 2.5 wt% indene and Ci-4-alkylindene, approximately 6 wt% ethylene unsaturated aromatic compounds, and approximately 41.5 wt% non-reactive components, each based on the total mass of BN-200. Storage tank 12 contains another petroleum fraction (hereinafter referred to as the C9 fraction) rich in styrene, vinyltoluenes, indene, and methylindenes (hereinafter referred to as ethylene unsaturated aromatics). The C9 fraction is a mixture of aromatics. The C9 fraction contains approximately 27% by weight.-% indene and alkylindene derivatives, 1 wt% styrene, 12.5 wt% alkyl derivatives of styrene, and approximately 59.5 wt% non-reactive components. Storage tank 13 contains dicyclopentadiene with a purity of at least 95%. Storage tank 14 contains xylene as an inert solvent. General experimental procedure.

[0146] A monomer mixture is prepared in the receiving vessel 15 from storage tanks 11, 12, 13, and 14. The monomer mixture is mixed by a static mixer upon introduction into receiving vessel 15. Receipt 15 may also be equipped with an agitator for thorough mixing. The components BN-200, C9 fraction, pure dicyclopentadiene, and xylene are withdrawn from storage tanks 11, 12, 13, and 14 in such quantities that the monomer mixture contains cyclic diolefin compounds and ethylene unsaturated aromatics in a ratio of approximately 2:1 to approximately 4:1, based on the mass of the cyclic diolefin compounds and ethylene unsaturated aromatics in the monomer mixture. This ratio can be adjusted, in particular, by adding pure dicyclopentadiene from storage tank 13. The monomer mixture also contains 40% inert components, based on the mass of the monomer mixture.

[0147] From the feedstock 15, the mixture is first fed into the heater 16 at a feed rate of 10 kg / h. In the heater 16, the monomer mixture is heated to a temperature of 195°C and then polymerized in the tubular reactor 20. The temperature of the monomer mixture is increased to 195°C in the heater 16 at a heating rate of approximately 68°C / minute. The monomer mixture is only in the heater 16 during the heating process and is immediately transferred to the tubular reactor 20 afterward. Accordingly, the monomer mixture has a total residence time in the heater 16 of approximately 2.5 minutes. Due to the short residence time, which is less than 20 seconds, especially at a reaction-relevant temperature of 180°C or higher, product-forming reactions do not occur to any significant extent in the heater 16.In tubular reactor 20, the temperature of the monomer mixture is increased to 265°C at a heating rate of approximately 20°C / minute. During this process, the monomer mixture polymerizes, forming the reaction products of the cyclic diolefin compound and the ethylene unsaturated aromatics. The pressure in tubular reactor 20 is 13 bar. The residence time in tubular reactor 20 is 60 minutes. During heating and polymerization, the monomer mixture is essentially a single-phase liquid.

[0148] At the outlet of tubular reactor 20, 10 kg / h are extracted from the outgoing stream and added back to the monomer mixture via line 23 at the inlet of tubular reactor 20. Additionally, 5 kg / h of oligomers, which are later separated from the hydrocarbon resin and the inert solvent, are added back to the monomer mixture. Thus, a continuous supply of 25 kg / h of monomer mixture, including recycled reactor product stream and recycled oligomer, is fed into tubular reactor 20.

[0149] After the removal of the 10 kg / h reactor product stream from the tubular reactor 20, a product stream of 15 kg / h consisting of hydrocarbon resin, solvent, residual monomers, and oligomers is obtained and introduced into the flash evaporator 21. The stream enters the flash evaporator 21 at a temperature of 265°C and a pressure of 13 bar. In the flash evaporator 21, the pressure of the stream is reduced to 30 mbar. This reduces the solvent content as well as the unreacted monomer and oligomer content in the hydrocarbon resin to 0.5 wt% or less. The bottoms product from the flash evaporator 21, which consists essentially of hydrocarbon resin, is fed to the intermediate storage tank 22 as a bottoms product stream of 7 kg / h. A steam stream of 8 kg / h containing solvent, unreacted monomers, and oligomers is discharged overhead from the flash evaporator 21.To further purify the bottom product from the flash evaporator 21, a thin-film evaporator can be used downstream of the flash evaporator 21. The still unhydrogenated hydrocarbon resin can be drawn from the intermediate storage tank 22 via line 22'.

[0150] The vapor stream from the flash evaporator 21 is directed into the partial condenser 24, where the oligomers are separated as the liquid phase and the solvent and unreacted monomers as the vapor phase. The oligomers are fed to the monomer mixture at the inlet of the tubular reactor 20 via line 24' as an oligomer stream of 5 kg / h. Solvent and unreacted monomers are discharged via line 24"". The partial condenser is operated at a pressure of 30 mbar and a temperature of 110°C. This allows oligomers to be selectively recycled back to the monomer mixture, while largely removing non-reactive substances. As a result, the process can be operated stably despite the use of petroleum fractions without adjusting the feedstock.

[0151] Properties of hydrocarbon resins

[0152] Table 1 below shows various monomer mixtures and the resulting hydrocarbon resins.

[0153] Table 1: Monomer mixtures and properties of the hydrocarbon resins obtained

[0154] Explanations for Table 1: CD - Content of cyclic diolefin compound in the monomer mixture in wt.%, based on the mass of cyclic diolefin compound, indene or indene derivatives and ethylene unsaturated aromatics; VA - Content of ethylene unsaturated aromatics in the monomer mixture, based on the mass of cyclic diolefin compound, indene or indene derivatives and ethylene unsaturated aromatics; Indene - Indene content in the resin in wt.-%, based on the total mass of the resin; Mn - number-average molecular weight in g / mol; Mw - weight-average molecular weight in g / mol; PDI - polydispersity index; Mz - centrifuge-average molecular weight in g / mol; EP - softening point according to ASTM D3461 in °C; Gardner - Gardner color number according to ISO 4630; * - comparative example in which the oligomers were not added back to the monomer mixture and pure BN-200 and no C9 fraction were used; ** - comparative example in which the oligomers were not added back to the monomer mixture.

[0155] The molecular weights Mn, Mw and Mz were determined using

[0156] Gel permeation chromatography was used. THF was employed as the eluent, and the process was isocratic at an oven temperature of 40°C. In addition to a linear cross-linked polystyrene guard column, three further linear cross-linked polystyrene columns with a porosity of 1000 Å each were used. A refractive index detector and a UV detector were employed. For calibration, a polystyrene kit (Ready Cal Kit from PSS) containing polystyrene standards from 266 g / mol to 66,000 g / mol, as well as a standard with a mass of 162 g / mol, was used.

[0157] The indene content was determined by pyrolysis gas chromatography with flame ionization detection. The respective hydrocarbon resin was applied to a platinum filament and introduced into a pyrolysis chamber, e.g., the Pyrola 2000 from Porylab. The pyrolysis chamber was connected to a gas chromatograph, e.g., the Thermo Trace GC Ultra, with a 60 m capillary column (e.g., the Optima 1 MS with a 0.25 pm film thickness from Macherey-Nagel), the output of which was coupled to a flame ionization detector. Pyrolysis was induced by rapidly heating the platinum filament to 600°C. The platinum filament was placed directly in the helium carrier gas stream, which transported the pyrolysis fragments to the gas chromatograph for separation.

[0158] Hydri mgdes KoM wa§:ser§taffliärz£g

[0159] From interim storage tank 22, 250 g each of hydrocarbon resins 1 to 5 are taken in five different hydrogenation reactions and dissolved in 250 g of Shellsol D40 with stirring. 500 g of the resulting solution are introduced into an autoclave (1 L autoclave from Parr Instruments, reactor series 4530). A nickel catalyst on silica is then added with stirring (0.75 wt% nickel catalyst, based on the total mass of the resin solution). The reactor is then closed and leak-tested at 50°C with nitrogen at a pressure of 40 bar. After the leak tightness is confirmed, the nitrogen is replaced with hydrogen and the reactor outlet is sealed.

[0160] To start the reaction, the hydrogen pressure is increased to 40 bar. The reaction mixture is then heated to a reaction temperature of 265 to 270°C over 45 to 50 minutes using a heat exchanger powered by heating oil. Once the reaction temperature is reached, the hydrogen pressure is slowly reduced to 85 bar. For hydrogenation, the reaction mixture is maintained at 265°C and 85 bar for a further 3 to 5 hours with continuous hydrogen injection. The hydrogenation is considered complete when the hydrogen consumption in the reactor falls below 0.5 L / h.

[0161] Once the reaction is complete, the hydrogen supply and the heating oil are shut off. The reactor is refilled with nitrogen and cooled to approximately 70°C within about one hour. The resin solution containing hydrogenated hydrocarbon resin is then filtered and transferred to a three-necked flask.

[0162] The resin solution obtained after hydrogenation is distilled by steam distillation. For this purpose, the resin solution in the three-necked flask is heated to 180°C, and steam at a temperature of 360°C is passed through the resin solution via a dip tube. Additionally, the flask is connected to a vacuum pump via a cold trap, allowing the distillation to be carried out gently at a pressure of approximately 10 mbar.

[0163] Typically, the solvent is largely removed after approximately 2 hours of distillation. Before the hot, liquid hydrogenated resin is bottled, 0.5 wt% antioxidant, based on the mass of the hydrogenated resin, e.g., Irganox 1010, is added and homogenized.

[0164] In this way, the hydrogenated hydrocarbon resins 1-H, 2-H, 3-H, 4-H, 5-H, and 6-H are obtained from the hydrocarbon resins 1, 2, 3, 4, 5, and 6. The polymerization described above can also be carried out batchwise. The hydrogenation described above can also be carried out continuously.

[0165] The procedure described in the preceding example can also be carried out essentially in the absence of oxygen.

[0166] Properties of hydrogenated hydrocarbon resins

[0167] The hydrogenated hydrocarbon resins 1-H to 6-H are fully hydrogenated. They have a residual content of olefinic double bonds of less than 0.01% and a residual aromatic content of less than 0.1%. The hydrogenated hydrocarbon resins 1-H to 6-H each have a VOC content of less than 300 ppm. Furthermore, the hydrogenated hydrocarbon resins 1-H to 6-H exhibit the properties listed in Tables 2 and 3.

[0168] The compatibility of the resins was determined by ascertaining the cloud point according to the method described below. For each of the resins 1-H to 6-H, a mixture of 3 g of a base polymer and 3 g of the respective resin was prepared. The mixture was then heated in an oil bath in a test tube with an inner diameter of 16 mm until a clear solution was obtained, with a maximum temperature of 260°C. After heating, the test tube was removed from the oil bath and wiped clean on the outside. The mixture was then allowed to cool in the test tube while being gently stirred with a thermometer with a red, 3 mm diameter end bulb. The end bulb was in contact with the bottom of the test tube during stirring.At regular intervals, the stirring was briefly interrupted, the red liquid sphere in the cylindrical part of the test tube was pressed against the test tube wall, the visibility of the red liquid sphere through the mixture along the diameter of the test tube was checked, and the temperature of the mixture was recorded. The cloud point is then the temperature at which the red liquid sphere is just no longer visible through the mixture along the diameter of the test tube.

[0169] To determine the cloud point more precisely, the temperature range in which the cloud point occurs was determined in a first step. Subsequently, the cloud point was determined as the average of three measurements.

[0170] Resins that are well-tolerated have a cloud point up to 65°C. Resins that are compatible have a cloud point between 66°C and 100°C. Resins that are less compatible have a cloud point between 101°C and 150°C. Resins that are poorly compatible have a cloud point between 150°C and 200°C. Resins that are incompatible have a cloud point above 200°C. Resins with a cloud point of 30°C or less are very well-tolerated.

[0171] The base polymer used for the mixture to determine the cloud point was one typically found in hot melt adhesives. Specifically, a metallocene polyolefin, an ethylene vinyl acetate copolymer, or an amorphous polyalphaolefin typically used in hot melt adhesives were employed.

[0172] Typical metallocene polyolefins used include Affinity GA 1900 and Affinity GA 1950 from the Dow Chemical Company. Typical ethylene vinyl acetate copolymers used include Evatane 18-500, Evatane 28-420, and Evatane 33-400 from Arkema. For the aforementioned Evatane ethylene vinyl acetate copolymers, the first two digits describe the average vinyl acetate content in weight percent, and the last three digits describe the average melt flow index at 190°C and 2.16 kg according to ISO 1133 or ASTM D1238. Typical amorphous polyalphaolefins used include Vestoplast 608, Vestoplast 703, and Vestoplast 750 from Evonik Industries. The resins are used in their current state. If one of the resins is no longer available, it is replaced by another resin (each corresponding to mPO, EVAC, APAO), which is typically used in hot melt adhesives instead.Table 2: Properties of hydrogenated hydrocarbon resins.

[0173] Explanations for Table 2: Yellow - Yellowness Index, measured according to ASTM 01209-05(2011); Mn - number-mean molecular weight in g / mol; Mw - weight-mean molecular weight in g / mol; Mz - centrifuge-mean

[0174] Molecular weight in g / mol; PDI - Polydispersity index; EP - Softening point according to ASTM D3461 in °C; * and ** - hydrogenated resins of the comparison examples, see also explanations for Table 1.

[0175] Table 3: Compatibility Explanations for Table 3: The cloud points shown were determined as described above; * and ** - hydrogenated resins of the comparison examples, see also explanations for Table 1. As can be seen from the data above, it is possible to determine the cloud points by thermal treatment.

[0176] The polymerization of cyclic diolefin compounds and an indene- or Ci-4-alkylindene-containing aromatic component in the process according to the invention yields hydrocarbon resins with a PDI of 2.27 and Gardner color numbers of 14.1 or less. Hydrocarbon resins with a PDI of 1.91 and a Gardner color number of 11.1 were even obtained. The fully hydrogenated hydrocarbon resins are compatible with metallocene polyolefins and amorphous polyalphaolefins typically used in hot melt adhesives. In particular, the fully hydrogenated hydrocarbon resins according to the invention exhibit

[0177] Carbon water resins even exhibit good compatibility with ethylene vinyl acetate copolymers typically used in hot glues.

[0178] REFERENCE MARK

[0179] 11 Storage tank BN-200

[0180] 12 Storage Tanks C9 Faction

[0181] 13 Storage tank pure dicyclopentadiene 14 Storage tank xylene

[0182] 15 Template

[0183] 16 heaters

[0184] 20 tubular reactor

[0185] 21 Relaxation evaporator 22 Intermediate storage tank

[0186] 22' withdrawal

[0187] 23 Product Return

[0188] 24 partial capacitor

[0189] 24' Oligomer recycling 24" Removal of solvent and unreacted monomer

Claims

Patent claims Hydrocarbon resin obtainable by thermal polymerization of a cyclic diolefin component containing a cyclic diolefin compound with an aromatic component containing indene and / or Ci-4-alkylindene, wherein the hydrocarbon resin has a polydispersity index (PDI) of 1 to less than 2.

3. Hydrocarbon resin according to claim 1, characterized in that the hydrocarbon resin contains repeating units and indene and / or C 1-4-alkyl indene units originating from the cyclic diolefin compound, and optionally contains further units originating from the aromatic component. Hydrocarbon resin according to one of claims 1 or 2, characterized in that the hydrocarbon resin has a polydispersity index (PDI) of 1 to 2.1, preferably of 1.5 to 2.0, more preferably of 1.5 to 1.

95. Hydrocarbon resin according to any one of the preceding claims, characterized in that the hydrocarbon resin contains I to 20 wt.%, preferably 4 to 20 wt.%, more preferably 4 to 16 wt.%, even more preferably 5 to 15 wt.%, particularly preferably 7 to 13 wt.%, based on the total mass of the hydrocarbon resin, indene and / or Ci-4-alkylindene units.

5. Hydrocarbon resin according to any one of the preceding claims, characterized in that the hydrocarbon resin has a molecular weight of 800 to 2450 g / mol, preferably 800 to 1800 g / mol, more preferably 800 to 1750 g / mol, even more preferably 800 to 1700 g / mol, and / or that the hydrocarbon resin has a softening point determined according to the ring and ball method according to standard ASTM D3461, from 80°C to 140°C, preferably from 90°C to 130°C, further preferably from 100°C to 120°C »exhibits, and / or has a Gardner colour number of 14 or less, preferably 12 or less, more preferably 11 or less.

6. Hydrocarbon resin according to one of the preceding claims, characterized in that the cyclic diolefin component contains 30 wt.% or more, preferably 35 wt.% or more, further preferably 50 wt.% or more, even more preferably 60 wt.% or more, even more preferably 70 wt.% or more, based on the total mass of the cyclic diolefin component, the cyclic diolefin compound.

7. Hydrocarbon resin according to one of the preceding claims, characterized in that the cyclic diolefin compound contains a conjugated cyclodialkene and / or is selected from the group consisting of cyclopentadiene, cyclopentadiene derivatives such as methylcyclopentadiene, ethylcyclopentadiene, pentamethylcyclopentadiene, ethyltetramethylcyclopentadiene and mixtures thereof.

8. Hydrocarbon resin according to one of claims 1 to 7, characterized in that the hydrocarbon resin contains 40 to 85 wt.%, preferably 45 to 70 wt.%, more preferably 45 to 65 wt.% units originating from the cyclic diolefin compound, based on the total mass of the hydrocarbon resin.

9. Hydrocarbon resin according to one of the preceding claims, characterized in that the aromatic component is an aromatic mixture containing indene and / or Ci-4-alkylindene and at least one, in particular at least two, ethylene unsaturated aromatic compounds, each having independently 8 to 15, preferably 8 to 13, carbon atoms.

10. Hydrocarbon resin according to claim 8, characterized in that the aromatic mixture is a mixture containing 50 wt.% or less vinyl aromatics such as styrene, o-methylstyrene, o-vinyltoluene, m-vinyltoluene and p-vinyltoluene, 30 wt.% or less indene and 15 wt.% or less C1-4-alkylindene, based on the total mass of the mixture, or a mixture containing 60 wt.% or less indene and / or C1-4-alkylindene, based on the total mass of the mixture.

11. Hydrocarbon resin according to one of claims 9 or 10, characterized in that the hydrocarbon resin contains 5 to 25 wt.%, preferably 10 to 25 wt.%, more preferably 15 to 25 wt.% indene and / or C1-4 alkylindene units and units derived from ethylene unsaturated aromatic compounds, based on the total mass of the hydrocarbon resin.

12. A process for producing a hydrocarbon resin according to any one of claims 1 to 11, in which a monomer mixture containing an aromatic component comprising indene and / or C1-4-alkylindene and a cyclic diolefin component comprising a cyclic diol compound is polymerized by heating to a polymerization temperature of at least 180°C to obtain a product stream containing hydrocarbon resin, wherein oligomers comprising units originating from the cyclic diolefin compound and / or units originating from the aromatic component are separated from the product stream and returned to the monomer mixture.

13. The method of claim 12, characterized in that the monomer mixture is heated to the polymerization temperature and is essentially single-phase liquid during polymerization, and / or that the polymerization temperature is from 200°C to 300°C, preferably from 230°C to 300°C or from 240°C to 280°C or from 250°C to 270°C, and / or that the polymerization is carried out at a pressure of 10 bar to 25 bar, preferably from 10 bar to 20 bar or from 13 bar to 18 bar, and / or that the polymerization is carried out continuously in a tubular reactor.

14. Method according to one of claims 12 or 13, characterized in that the cyclic diolefin component is defined according to claim 6 and / or the cyclic diolefin compound is defined according to claim 7 and / or the aromatic component is defined according to claim 9 or 10.

15. A method according to any one of claims 12 to 14, characterized in that the cyclic diolefin compound is defined according to claim 7 and the aromatic component is defined according to claim 9 or 10 and the monomer mixture contains 50 to 95 wt.%, preferably 60 to 95 wt.%, or 65 to 90 wt.% or 65 to 85 wt.% or 65 to 80 wt.% of the cyclic diolefin compound, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkyl indene and ethylene unsaturated aromatic compounds.

16. A method according to any one of claims 12 to 15, characterized in that the cyclic diolefin compound is defined according to claim 7 and the aromatic component is defined according to claim 9 or 10 and the monomer mixture contains 5 to 40 wt.%, preferably 10 to 35 wt.% or 15 to 35 wt.% or 25 to 35 wt.% of indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds, based on the total mass of the cyclic diolefin compound, indene and / or Ci-4-alkylindene and ethylene unsaturated aromatic compounds.

17. Method according to any one of claims 12 to 16, characterized in that the monomer mixture comprises a non-polymerizable solvent, preferably containing one or more, in particular one or two, Al cyl- substituted aromatic compounds with 7 to 10 carbon atoms, for example o-xylene, m-xylene, p-xylene and / or ethylbenzene.

18. A method according to any one of claims 12 to 17, characterized in that the oligomers boil at an absolute pressure of 100 mbar or less, in particular 10 mbar or less, preferably 30 mbar, and at a temperature of 80°C or more, preferably from 80°C to 120°C, more preferably from 90°C to 115°C, and even more preferably from 100°C to 110°C, and / or have a molecular weight of 100 to 600 g / mol, preferably from 130 to 600 g / mol or from 150 to 600 g / mol.

19. A method according to claim 17 or 18, characterized in that the oligomers and the optional non-polymerizable solvent are partially, preferably completely, removed from the product stream after polymerization by batch or preferably continuous evaporation and / or the oligomers are removed batch or preferably continuously after evaporation by complete or preferably partial Condensation from the non-polymerizable solvent is partially or preferably completely separated and / or, after condensation, is returned to the monomer mixture in batches or preferably continuously for further polymerization.

20. A process according to any one of claims 12 to 19, characterized in that the hydrocarbon resin is partially or completely hydrogenated in a subsequent hydrogenation step to obtain a hydrogenated hydrocarbon resin.

21. The method according to claim 20, characterized in that the hydrogenation step is carried out in the presence of a solvent, preferably an aliphatic solvent or a mixture of saturated hydrocarbons that are liquid at room temperature, and / or in the presence of a catalyst, in particular a nickel catalyst.

22. Method according to one of claims 20 or 21, characterized in that the hydrogenation step is carried out at a pressure of more than 60 bar, in particular from 65 to 105 bar or from 65 to 100 bar or from 70 to 95 bar, and / or at a temperature of 240°C or higher, in particular from 240°C to 300°C or from 250°C to 280°C.

23. Hydrogenated hydrocarbon resin obtainable by hydrogenating a hydrocarbon resin according to any one of claims 1 to 11 and / or by a method according to any one of claims 20 to 22.

24. Hydrogenated hydrocarbon resin according to claim 23, characterized in that the olefinic components in the hydrogenated hydrocarbon resin are Double bonds are hydrogenated to at least 70%, preferably at least 90% or at least 95% or at least 99%, and / or the aromatic double bonds are hydrogenated to at least 70%, preferably at least 90% or at least 95% or at least 99%.

25. Hydrogenated hydrocarbon resin according to one of claims 23 or 24, characterized in that the hydrogenated hydrocarbon resin has a molecular weight of 800 to 2500 g / mol, preferably 800 to 1800 g / mol, more preferably 800 to 1600 g / mol, further preferably 800 to 1400 g / mol, and / or a softening point, determined by the ring and ball method according to standard ASTM D3461, of 80°C to 140°C, more preferably of 90°C to 130°C, more preferably of 90°C to 125°C, and / or a hazen color number of 40 or less, more preferably of 25 or less, and / or a yellowness index of 3 or less, more preferably of 1 or less.

26. Composition comprising - a hydrocarbon resin according to any one of claims 1 to 11 or a hydrogenated hydrocarbon resin according to any one of claims 23 to 25, and - an adhesive polymer, for example a metallocene polyolefin or an ethylene vinyl acetate copolymer or an amorphous polyalphaolefin or a styrene block copolymer.

27. Use of a hydrocarbon resin according to any one of claims 1 to 11 or of a hydrogenated hydrocarbon resin according to any one of claims 23 to 11. 25 as a tackifier in hot melt adhesives, in particular in hot melt adhesives based on metallocene polyolefin, ethylene vinyl acetate copolymer, amorphous polyalphaolefins or styrene block copolymers, and / or in solvent-based adhesives, in particular in solvent-based styrene block copolymer adhesives.

28. Use of a hydrocarbon resin according to any one of claims 1 to 11 as a modifier in rubber products, in particular for improving the mechanical and dynamic properties in rubber products, in bitumen, in particular as an additive and / or as a hydrophobizing agent in bitumen, in particular for asphalt, or as a modifier and / or Water-repellent agents in printing inks.

29. Use of a hydrogenated hydrocarbon resin according to one of claims 23 to 25 as an additive in paint, in plastics, in particular as a modifier in plastics, in rubber, in bitumen, in particular as a hydrophobic agent in bitumen, for example for roofing membranes, in Polypropylene films, in particular as modifying and / or hydrophobing agents in polypropylene films, especially BOPP films, in cosmetics or as tackifiers in adhesive compositions, especially for applications in the hygiene products industry and for use in food packaging.