MXPA99011727A - Aromatic modified crude c5 - Google Patents

Abstract

This invention relates to novel resins, blends of the novel resins with base polymers and a process for producing a resin comprising combining a reactor feed blend comprising:(a) at least 2 weight%of isoprene, (b) at least 2 weight%of one or more of dicyclopentadiene, substituted cyclopentadienes and substituted dicyclopentadienes, (c) at least 2 weight%piperylene, (d) at least 1 weight%aromatic olefins, and (e) 0 to 92 weight%of additional aliphatic olefins, based upon the weight of the reactor feed blend, with a polymerization catalyst under polymerization conditions, preferably where the ratio of component (c) to component (b) is less than 8 and the ratio of component (a) to component (b) is less than 5.

Description

RESINS BASED ON C5 AROMATIC, MODIFIED, RAW Field of the Invention This invention relates to resins produced from physical feed mixtures comprising: isoprene; piperylene; aromatic olefins; and one or more of cyclopentadiene, substituted cyclopentadienes, dicyclopentadiene, and substituted dicyclopentadiene-10, and processes for producing these resins, and adhesives made therefrom. Background In general, aliphatic hydrocarbon resins of 5 carbon atoms are synthesized using a current Concentrated piperylene has been fractionated to minimize the levels of cyclopene isoprene and diolefins, such as cyclopentadiene and / or methylcyclopentadienes, as well as dimers and co-dimers of these compounds. It is known that the presence of these components in significant amounts (ie, greater than to about 5 percent) in the physical polymerization feed mixes adversely affect the molecular weight and the properties of the resin produced by cationic polymerization. For example, U.S. Patent No. 2,750,353 discloses that a high content of isoprene (greater than 3.5 weight percent) in the feed supply leads to lower yields and gel formation. In the same way, U.S. Patent No. 2,754,288 teaches that gel formation and poor molecular weight control result from the use of feeds that initially contain more than 2 weight percent cyclopentadiene. Isoprene and / or dicyclopentadienes have traditionally been considered undesirable in high concentrations in physical hydrocarbon resin feed mixtures targeted for catalytic polymerization, due to their tendency to crosslink and form gels or resins of undesirably high molecular weight. The description of the United Kingdom patent No. GB 1,408,870 (ICI), describes the heat soaking of a crude C5 stream, followed by direct polymerization without fractionation. The patent uses a chloride complex of aluminum, and does not mention the incorporation of aromatic olefins. The description of United Kingdom Patent No. 2,044,277A (Sumitomo), describes the copolymerization of cyclopentadiene with a copolymerizable monomer (diolefin or chain-conjugated olefin), using a donor complex of electrons / aromatic solvent containing aluminum chloride / rich oxygen that claims no gel formation. Sumitomo teaches that aluminum chloride powder is not suitable for this type of polymerizations, and discloses the polymerization of physical feed mixtures containing proportions of cyclopentadiene: isoprene from 3: 1 to 1: 3. In addition, Sumitomo does not mention the incorporation of aromatic olefins. U.S. Patent No. 5,516,835 discloses a viscosity comprising an isoprene-based hydrocarbon resin obtained by the cationic polymerization (aluminum chloride) of a physical feed mixture consisting of 40 to 90 weight percent isoprene, and from 10 to 60 percent of an aliphatic mono-olefin (e.g., 2-methyl-2-butene). U.S. Patent No. 5,516,835 also discloses hot melt and pressure sensitive adhesive systems based on amorphous polypropylene, natural rubber, and styrene block copolymers. In addition, the optional use of piperilenes, DCPD and aromatic olefins is disclosed. U.S. Patent No. 4,008,360 discloses a resin produced from a C5 fraction that has been subjected to an adjustment of the weight ratio of the acyclic diolefins to the mono-olefins, and a weight ratio of the cyclic diolefins to the mono-olefins from 0.40 to 0.70, and from 0.07 to 0.035, respectively. The inclusion of aromatic olefins is not disclosed. In the same way, U.S. Patent No. 4,952,639 discloses resins produced from a C5 moiety having aromatic mono-olefin and certain proportions of diolefins and mono-olefins.; however, dicyclopentadiene is absent. Two other patents of the United States of interest are 5 U.S. Patent No. 3,950,453 (Nippon Zeon) and 3,467,632 (Reichold). Both patents disclose the cationic polymerization of physical feed mixes containing up to 30 weight percent isoprene, including the use of isoprene dimers (terpenes) as softening point elevators. Therefore, food supplies with low levels of isoprene and dicyclopentadienes have been preferred in the industry. However, obtaining these food supplies has required expensive purification procedures. Accordingly, there is a need in the art to provide a method for polymerizing the mixture of isoprene-cyclopentadiene / di-cyclopentadiene-piperylene feed feeds into hydrocarbon resins without undesirable gels or very high molecular weights. Brief Description of the Invention This invention relates to a process for producing a resin, which comprises combining a physical reactor feed mixture comprising: (a) at least 2 weight percent isoprene, 0 (b) at least 2 weight percent of one or more of diclopentadiene, substituted cyclopentadienes, and substituted dicyclopentadienes, (c) at least 2 weight percent of piperylene, (d) at least 1 weight percent of aromatic olefins , and (e) from 0 to 92 weight percent of additional aliphatic olefins, based on the weight of the physical mixture supplying the reactor, with a polymerization catalyst, under polymerization conditions. This invention also relates to adhesive compositions comprising the resins described above. Detailed Description In a preferred embodiment, this invention relates to a process for producing a resin, which comprises combining a physical reactor feed mixture comprising: (a) from 2 to 50 weight percent isoprene, (b) from 2 to 20 weight percent of one or more of 5 diclopentadiene, substituted cyclopentadienes, and substituted dicyclopentadiene, • (c) from 2 to 20 weight percent piperylene, (d) from 1 to 50 percent by weight weight of aromatic olefins, and 0 (e) of 2 to 90 weight percent of additional aliphatic olefins, based on the weight of the physical feed mixture of the reactor, with a polymerization catalyst, under polymerization conditions, in the understood that the ratio of component (c) to component (b) is less than 8, and the proportion of component (a) to component (b) is less than 5, preferably the ratio of component (c) to component ( b) is less than 5, and the proportion component (a) to component (b) is less than 2. Isoprene is preferably present in 2 to 30 weight percent, still more preferably 2 to 20 weight percent. Preferred substituted cyclopentadienes include cyclopentadienes substituted with a linear, branched or cyclic alkyl group of 1 to 40 carbon atoms, preferably one or more methyl groups. Methylcyclopentadiene is a preferred substituted cyclopentadiene. The term "dicyclopentadiene" is defined to include both the endo and exo forms of dicyclopentadiene. Preferred substituted dicyclopentadienes include dicyclopentadienes substituted with a linear, branched or cyclic alkyl group of 1 to 40 carbon atoms, preferably one or more methyl groups. Preferably, one or more of dicyclopentadiene, substituted cyclopentadienes and substituted dicyclopentadienes are present in 2 to 25 weight percent. Preferred aromatic olefins include one or more of styrene, indene, styrene derivatives and indene derivatives. Particularly preferred aromatic olefins include styrene, alpha-methylstyrene, beta-methylstyrene, indene and 1-methylindenes and vinyltoluenes. Aromatic olefins are normally present in 1 to 92 weight percent, preferably from 1 to 50 percent by weight, still more preferably from 1 to 30 percent by weight, and still most preferably from 1 to 10 percent by weight. In a preferred embodiment, the feed comprises from 5 to 90 weight percent of one or more aliphatic olefins, preferably from 10 to 85 weight percent, still more preferably from 50 to 70 weight percent . In a preferred embodiment, the aliphatic olefins are linear, branched or alicyclic non-conjugated olefins or diolefins of 40 to 20 carbon atoms, preferably one or more linear, branched or alicyclic non-conjugated olefins or diolefins of 4 to 7 carbon atoms, and still more preferably a mixture of linear, branched or alicyclic non-conjugated olefins or diolefins of 5 and 6 carbon atoms. In another preferred embodiment, the aliphatic olefins comprise one or more natural or synthetic terpenes, preferably one or more of alpha-pinene, beta-pinene,? -3-carene, dipentene, limonenes and / or isoprene dimers. The aliphatic olefins are preferably present in a proportion by weight percent of conjugated diolefin to the weight percentage of aliphatic olefin of 0.05 to 3.0, preferably from 0.05 to 2.0. Preferably, the piperylene may be present in 5 5 to 70 weight percent, and more preferably 5 to 20 weight percent; component (b) is present in 2 to 25 weight percent; isoprene is present at 2 to 20 weight percent; and the aromatic olefins are preferably • present in 1 to 30 weight percent, and more preferably 2 to 25 weight percent. Preferred resins produced herein have a ring and ball softening point of 10 ° C to 140 ° C, preferably 80 ° C to 120 ° C. In another embodiment, the preferred resins produced herein have a weight average molecular weight (Mw) of 4,000 or less, preferably between 500 and 4,000, more preferably from 500 to 2,500. In another preferred embodiment, the resins produced herein have an Mw / Mn of 3 or less, preferably between 1 and 2.5, still more preferably between 1 and 2. The resins described above can be produced by the methods generally known in the art. the technique for the production of hydrocarbon resins. See, for example, Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Volume 13, pages 717-744. A preferred method for the production of the resins described above is to combine the feed stream in a polymerization reactor with a Friedel-Crafts or Lewis acid catalyst, at a temperature between 0 ° C and 200 ° C, preferably between 0 ° C and 120 ° C, still more preferably between 20 ° C and 80 ° C. Friedel-Crafts 5 polymerization is generally carried out by using known catalysts in a polymerization solvent, and the removal of the solvent and the catalyst by washing and distillation. The polymerization process used for this invention can be • in a batch or continuous mode, using techniques known in this field. The continuous polymerization can be carried out in a single step or in multiple stages, as taught in U.S. Patent Nos. 3,701,760 and 4,276,396. The Friedel-Crafts catalysts to be used as polymerization catalysts are in general Lewis acids, such as halides or metal alkyls, such as aluminum trichloride, boron trifluoride, aluminum tribromide or a mixture thereof, as well as the ternary complexes of the halides, aromatic compounds and hydrogen halides. Possible aromatic compounds include benzene and mono-, di- and poly-alkylbenzenes, such as toluene, xylene, cymene and eumeno. Examples of the hydrogen halides to be used in complex formation include hydrogen chloride, hydrogen bromide, hydrochloric acid, and hydrobromic acid. The amount of Lewis acid to be used in the catalyst is on the 0.3 to 3.0 weight percent scale, based on the weight of the physical feed mix, preferably 0.3 to 3.0 percent, still more preferably from 0.5 to 1.0 weight percent. The aluminum trichloride catalyst is preferably used as a powder. 5 For further description of the derivatization of the feed stream, the monomer composition, the polymerization and hydrogenation methods, see Hydrocarbon Resins, Kirk-Othmer Encyclopedia of Chemical Technology, Volume 13, pages 717-743 (J. Wiley & Sons, 1995); Encyclopedia of Polymer Science and Engineering, Volume 7, pages 758-782 (John Wiley &Sons, 1987), European Patent No. 0 240 253, and references cited in all three. In another preferred embodiment, the resins of this invention may be hydrogenated. The hydrogenation of the hydrocarbon resins can be carried out by means of melt-based or solution-based processes, either by a batch process, or more commonly, a continuous process. The catalysts used for the hydrogenation of hydrocarbon resins are usually monometallic and bimetallic supported catalyst systems based on group 6, 8, 9, 10 or 11 elements. Catalysts, such as nickel on a support (for example, nickel alumina, nickel on carbon, nickel on silica, nickel on silicone, etc.), palladium on a support (for example, palladium on silica, palladium on carbon, palladium or magnesium oxide, etc.), and copper and / or zinc on a support (for example, copper chromite on copper, and / or manganese oxide, copper and zinc on alumina, etc.), are good hydrogenation catalysts in the practice of this invention. The support material is typically comprised of porous inorganic refractory oxides, such as silica, magnesia, silica-magnesia, zirconia, silica-zirconia, titania, silica-titania, alumina, silica-alumina, alumino-silicate, etc., being preferred. much the supports that contain? Preferably, the supports are essentially free of crystalline molecular sieve materials. Mixtures of the above oxides are also contemplated, especially when prepared as homogeneously as possible. Among the support materials useful in the present invention are the supports disclosed in U.S. Patent Nos. 4,686,030, 4,846,961, 4,500,424 and 4,849,093. Preferred supports include alumina, silica, carbon, MgO, Ti02, Zr02, Fe03 or mixtures thereof. Any of the known processes for the catalytic hydrogenation of hydrocarbon resins can be used, in order to hydrogenate the resins of this invention; in particular, the processes of U.S. Patent Nos. 5,171,793, 4,629,766, 5,502,104 and 4,328,090 and WO 95/12623 are suitable. Generic hydrogenation treatment conditions include reactions at the temperature of about 100 ° C to 350 ° C, and pressures between five 0 atmospheres (506 kPa) and 300 atmospheres (30,390 kPa) of hydrogen, for example, from 10 to 275 atmospheres (from 1,013 kPa to 27,579 kPa). In one embodiment, the temperature is in the range of 180 ° C to 320 ° C, and the pressure is in the range of 15,195 kPa to 20,260 kPa of hydrogen. The volume ratio of the hydrogen to the reactor feed under standard conditions (25 ° C, pressure of 1 atmosphere (101 kPa)) can normally be 20-200, and 100-220 is preferable for white water-resins. Another suitable process for the hydrogenation of the resin of this invention is that described in European Patent No. EP 0 082 726. European Patent No. EP 0 082 726 describes a process for the catalytic or thermal hydrogenation of petroleum resins using a nickel-tungsten catalyst on a gamma-alumina support, where the hydrogen pressure is 1.47 x 107 - 1.96 x 107 Pa, and the temperature is in the range of 250 to 330 ° C. Thermal hydrogenation is usually done from 160 ° C to 320 ° C, at a pressure of 9.8 x 105 to 11.7 x 105 Pa, and for a period typically of 1.5 to 4 hours. After hydrogenation, the reactor mixture can be evaporated and further separated to recover the hydrogenated resin. Steam distillation can be used to remove the oligomers, preferably without exceeding a resin temperature of 325 ° C. In a preferred embodiment, the hydrogenation is carried out by contacting the resin in the presence of hydrogen and hydrogenation catalyst metal compounds supported on porous refractory substrate particles having two points: a) an average maximum diffusion path length less than, or equal to, twice the hydraulic radius; b) a pore volume distribution where: 1) pores that have diameters > 150,000 A (150,000 x 10"10 m) constitute more than 5 approximately 2 percent of the total volume, ii) pores having diameters> 20,000 A (20,000 x 10-10 m) and <150,000 A (150,000 x 10"10 m) constitute more than about 1 percent of the total volume, and iii) pores having diameters > 2,000 A (2,000 x 10"10 m) and <20,000 A (20,000 x 10'10 m) make up more than about 12 percent of the total volume, and c) a total pore volume of approximately 45 percent at 86 percent of the total volume of the substrate particles In a particularly preferred embodiment, the catalyst comprises nickel or cobalt on supports of one or more of molybdenum, tungsten, alumina or silica. In a preferred embodiment, the amount of the zinc oxide and / or cobalt oxide on the support is from 2 to 10 weight percent. The amount of tungsten oxide or molybdenum on the support after preparation is from 5 to 25 weight percent. Preferably, the catalyst contains 4 to 7 weight percent nickel oxide, and 18 to 22 weight percent tungsten oxide. This process and suitable catalysts are described in greater detail in U.S. Patent Application Serial No. 08 / 755,267, filed November 22, 1996, 0 pending, which is incorporated herein by reference. In another preferred embodiment, the hydrogenation can be carried out by the process and the catalysts described in U.S. Patent No. 4,629,766. In particular, nickel-tungsten catalysts over gamma-5 alumina are preferred.

The resins of this invention can be combined with a base polymer to form an adhesive. Typical base polymers include homopolyethylene, ethylene copolymerized with up to 50 percent by weight of one or more α-olefins of 3 to 20 carbon atoms, polypropylene, propylene copolymerized with up to 50 percent by weight of one or more ethylene and / or α-olefins of 4 to 20 carbon atoms, polybutene, ethylene-vinyl acetate, low density polyethylene (density of 0.915 to less than 0.935 grams / cm3) linear low density polyethylene, ultra-low density polyethylene (density from 0.86 to less than 0.90 grams / cm3), very low density polyethylene (density from 0.90 to less than 0.915 grams / cm3), medium density polyethylene (density from 0.935 to less than 0.945 grams / cm3), high density polyethylene (density from 0.945 to 0.98 grams / cm3), EMA, 5 copolymers of acrylic acid, poly-methyl methacrylate, or any other polymers polymerizable by a process of high pressure free radicals, PVC, polybutene-1, isotactic polybutene, elastomers, such as ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, 0 block copolymer elastomers, such as SBS (styrene-butadiene-styrene), SIS (styrene-isoprene-styrene), nylons, polycarbonates, PET resins, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), aromatic monomer polymers, such as polystyrene, copolymers of isobutylene and para-alkylstyrene, poly-1 -esters, high density polyethylene and high molecular weight, high density and low molecular weight polyethylene, graft copolymers in general, homopolymers or polyacrylonitrile copolymers, thermoplastic polyamides, polyacetal, vinylidene fluoride and other fluorinated elastomers, polyethylene glycols, polyisobutylene (PIB) or mixtures thereof. In a preferred embodiment, the base polymer is selected from the group consisting of: block copolymers of styrene and isoprene or butadiene, polyisoprene, butyl rubber, ethylene-vinyl acetate, ethylene-methyl acrylate, amorphous polypropylene , ethylene-propylene-diene monomer rubber, copolymers of ethylene and an α-olefin of 3 to 20 carbon atoms, copolymers of propylene and ethylene or an α-olefin of 4 to 20 carbon atoms, metallocene polyethylenes, metallocene polypropylenes, natural rubber, styrene-5-butadiene rubber, isobutylene and para-alkylstyrene copolymers. Particularly, the preferred polymers are styrene-butadiene-styrene block copolymers, butyl rubber, natural rubber and styrene-butadiene rubber. In a particularly preferred embodiment, the base polymer is a block copolymer SIS (styrene-isoprene-styrene). In another particularly preferred embodiment, the SIS block copolymer has 10 percent by weight or less of diblock present, preferably 5 percent by weight or less. A preferred base polymer is the styrene-5-isoprene-styrene block copolymer, as is commercially available from DEXCO POLYMERS, under the trade name VECTOR®. In another preferred embodiment, the base polymer is a polymer produced using a metallocene catalyst system no. Normally, metallocene homopolymers or copolymers are produced using transition metal catalysts of mono- or bis-cyclopentadienyl, in combination with an activator of alumoxane and / or a non-coordinating anion in solution, paste, high pressure, or in the phase of gas. The catalyst system may be supported or unsupported, and the cyclopentadienyl rings may be substituted or unsubstituted. The metals of «Preferred transition are titanium, zirconium and hafnium. Several commercial products produced with these catalyst / activator combinations are commercially available from Exxon Chemical Company of Baytown, Texas, United States, under the trade names EXCEEDMR and EXACTMR. For more information on the methods and catalysts / activators for producing these metallocene homopolymers and copolymers, see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. 5,153,157; U.S. 5,198,401; U.S. 5,240,894; U.S. 5,017,714; 0 CA 1,268,753; U.S. 5,324,800; EPA 129,368; U.S. 5,264,405; EPA 520,732; WO 92/00333; U.S. 5,096,867; U.S. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO 91/09882; WO 94/03506 and U.S. 5,055,438. The metallocene-produced copolymers described above preferably have an amplitude distribution distribution (CDBI) ratio of 50 percent or more, preferably greater than 60 percent, still more preferably greater than 70 percent. In one embodiment, the CDBI is greater than 80 percent, still more preferably greater than 90 percent, and still most preferably greater than 95 percent. In another particularly preferred embodiment, the polyethylene copolymer has a CDBI of between 60 and 85 percent, still more preferably between 65 and 85 percent. The Composition Distribution Amplitude Index (CDBI) is a measure of the distribution of the monomer composition within the polymer chains, and is measured by the method described in PCT publication WO 93/03093, published on February 18. from 1993, including that the fractions having a weight average molecular weight (Mw) 5 less than 15,000 are ignored when the CDBI is determined: The resin may be present in the mixture of 1 to 200 parts per 100 parts of base polymer in the adhesive formulation. In a preferred embodiment, the resin may be present in the mixture of 25 to 200 parts per 100 parts of polymer. In another embodiment, the preferred scale is from 80 to 120 parts of resin per 100 parts of polymer. Adhesive formulations may also contain additives well known in the art, such as anti-blocking agents, anti-static, anti-oxidants, crosslinking agents, silica, carbon black, talc, pigments, fillers, processing aids, stabilizers ultraviolet, neutralizers, lubricants, surfactants and / or nucleating agents. Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium stearate, carbon black and glass beads. The resins of this invention can be formed into pressure sensitive adhesives, hot melt adhesives, or contact adhesives, and can be used in applications such as tapes, labels, paper impregnation, hot melt adhesives, including processing from • wood, packaging, binding of books or disposables, sealants, rubber compounds, tube wraps, underbodies, contact adhesives, road markings or tire construction. In a particularly preferred embodiment, the resins are formulated in a pressure sensitive adhesive application. This pressure sensitive adhesive composition can be applied to any conventional backing layer, such as paper, sheet, polymeric film, release liners, spunbond or non-spun backing material to make, for example, packaging tapes. Examples The feed streams used in the following examples are described in Table I. In the following examples, the concentrate of 2-methylbutene was 92 percent 2-methyl-2-butene and 6 percent 2- methyl-l-butene. The softening point was measured as a ring and ball softening point according to ASTM E-28. The point of cloudiness was the point at which a cloudiness or "cloud" appeared in a mixture of 40 parts of paraffin wax with a melting point of 60 ° C, 20 parts of E3CORENE® UL7750 (ethylene-vinyl acetate) , 28 percent vinyl acetate) from Exxon Chemical Company, and 54 parts of test resin heated to 200 ° C, and allowed to cool in air with agitation. The GPC was calibrated with polystyrene standards. The molecular weight is calculated as equivalents of poly-isobutylene, from the following equation: Record (PIB) = (11.1) (Record (PSmw) -0.517 I Table I (Compositions of the Currents Used in the Examples) • 0 5 • fifteen Examples 1 and 2 The resins produced in Table II were polymerized by means of a continuous process, using a continuously stirred vessel reactor (CSTR), using aluminum chloride as the catalyst, under a nitrogen atmosphere, at about 45 psig (3.2 kg / cm2). The composition of the physical feed mixture of the reactor, indicated in Table I, was continuously added to the reactor, at a speed such as to maintain a residence time of approximately 90 minutes in the reactor. The aluminum chloride catalyst of a particle size distribution of 5-200 mesh was continuously added to the reactor to maintain a catalyst concentration of 0.8 weight percent based on the feed. The polymer was continuously discharged from the reactor, and quenched with a 1: 3 solution of isopropanol and water, followed by washing with water several times to remove the spent catalyst residue. After each wash, the aqueous layer was discarded. The resin was recovered by heating the washed polymer to 250 ° C, while dispersing nitrogen to remove the unreacted components and the low molecular weight oligomers, followed by steam stripping to remove the heavier oligomers (filler). Examples 1 and 2 represent aromatic aliphatic resins produced from a stream of crude C5, such as that shown in Table I (Stream B).

Table II Resins from C? S Crudos • fifteen 30 0 • Synthesis of Resins from C? Crude: The examples reported in Tables III and IV resulted from the polymerization by means of a semi-continuous process in a batch reactor, except for Example 7, which was done in a continuous stirred vessel reactor. The physical feed mixture was added in portions for 75 minutes, as well as the catalyst (aluminum chloride powder), in a nitrogen atmosphere and under efficient agitation. The catalyst level was 0.75 weight percent of the total physical feed mixture. The reactor mixture was stirred for a further 15 minutes after all the ingredients had been added to the reactor. Then the total residence time was 90 minutes. The reaction temperature was between 40 ° C and 50 ° C. The content of the reactor was quenched with water, and neutralized with an ammonia solution. The aqueous layer was discarded, and the polymerized was further separated to remove the unreacted monomers (nitrogen separation at 200 ° C) and the low molecular weight oligomers (vapor separation up to 250 ° C). The resin yield was the amount of resin recovered over the total physical feed mixture. Example 7 was polymerized under the same conditions as Example 1. The crude C5 in Tables III, IV and V comprised 12 to 17 weight percent piperylene, 16 to 19 weight percent isoprene, 10% by weight. to 20 weight percent of cyclopentadiene, dicyclopentadiene, substituted cyclopentadienes and substituted 5-dicyclopentadienes, and 21 to 16 weight percent of aliphatic olefins of 4 to 6 carbon atoms. Table III reports examples of lower aromatic modified resins (Example 3 to Example 7), and higher aromatic modified resins (Example 8 to Example 10). For 0 the lower aromatic modified resins, Example 3 and Example 4 are two reference examples made from traditional physical feed mixtures containing piperylene (example 3), or isoprene + piperylene (Example 4) as conjugated dienes, while the Example 5 to Example 7 were made from cut raw 5 C5 ("C5 Crude"), and the physical feed mixture of the reactor comprises three types of conjugated dienes (piperylene, isoprene and cyclopentadiene / dicyclopentadiene). For high levels of aromatic olefins, Example 8 is a reference sample made of physical mixture of traditional feed containing isoprene and piperylene, excluding cyclodiene and dicyclopentadienes. Example 9 and Example 10 are made of cut raw C5, and the physical feed mixture of the reactor contains the three types of conjugated dienes, as indicated in Table III. Table IV reports two examples of resins with a high softening point, with a high level of aromaticity, made of raw C5. t Table III Modified Aromatic Resins 0 • fifty # 0 • Example 3 was polymerized in a continuously stirred vessel reactor.

Table IV Modified Aromatic Resins - High Softening Point Notes for Tables III and IV:. { 1) The piperylene cut was a cut that comprised piperylene (50 weight percent minimum), less than 2 weight percent isoprene, less than 2 weight percent cyclopentadiene / methylcyclopentadiene and the corresponding dimers. (2) IBP-70 was a diolefin / olefin cut that contained essentially 20 to 30 weight percent isoprene, and 15 to 15 weight percent 1,3-cis, trans-pentadiene (piperylene), and less than 3 weight percent cyclopentadie-no / dicyclopentadiene (removed by fractionation). (3) Isomerat was a paraffinic cut comprising paraffins of 4 to 10 carbon atoms, and was used as a diluent. (4) Proportion of diolefins / olefins (% by weight) The diolefins were the total of diolefins in the physical feed mixture The olefins were all mono-olefins. 55) (30/45/25) = (EVA / resin / wax) - EVA was Escorene® UL02528 CC - the wax was a paraffin wax with a melting point of 68 ° C. (6) The aromaticity level was the integration of the aromatic protons in XH-NMR given as percentage by weight of styrene equivalent. (7) GPC: the molecular weights were equivalent to polystyrene. (8) The melt viscosity was measured with a Brookfield • Thermosel, RVT Series, Spindle 21. Examples 13-14 Two products were made in a commercial unit of continuously stirred vessel at 55 ° C, using aluminum chloride powder as a catalyst, in accordance with the feed compositions given in the next Table. The feed composition was completed up to 100 percent with a • non-interfering aliphatic solvent, such as Isomerat, as described in the notes to Tables III and IV. Example 13 was made with a stream of C5, from which the dicyclopentadiene and the alkylcyclodienes were removed by distillation. Example 14 was the product based on crude C5.

Table V Examples of Resin Made in the Continuously Stirred Vessel Reactor Fillers 13 and 14b 120 parts by weight of the resin product of Examples 13 and 14 were mixed with 100 parts by weight of Vector® 4111, 10 parts by weight of Flexon oil, and 1 part by weight of Irganox 1076. The components were mixed in a one liter Z-blade laboratory mixer at a temperature of 150 ° C for 70 minutes. The data is reported in Table V-B. Table V-B Example 14b, made from a physical feed mixture of Crude C5, shows adhesive properties comparable to those of Example 13b, made from a traditional feed, and superior properties with respect to ball viscosity after aging. In Examples 15 to 17, mixtures of resin and base polymer were made in a one liter Z-blade laboratory mixer at a temperature of 150 ° C for 70 minutes. The formulation and properties are reported in Table IV.

Table VI PSA Formulations and Properties • V4111 is a linear triblock copolymer of SIS, with 18 percent by weight of styrene, and an MFR of 12, and an Mn of 120,000, produced by Dexco Polymers of Louisiana, United States, and sold under the trade name VECTORMR 4111.

• DPX-511 is a linear triblock copolymer of SIS, with 18 percent by weight of styrene, and an MFR of 15, and an Mn of 110,000. • Flexon 876 is a processing oil. Resin: • The ring and ball softening point was measured in accordance with ASTM E-28. • The melt viscosity was measured according to ASTM D-3236. • The point of wax nebulosity was the temperature at which a cloudiness or "cloud" occurs, in a mixture of paraffin wax parts, Escorene, and the test resin heated to 200 ° C, and allowed to cool in air with stirring. • Molecular weight was measured by Gel Permeation Chromatography against polystyrene standards, with molecular weights of 162 to 66M. Block Copolymer: • The MFR was measured by ASTM D-1238. • Molecular weight was measured by gel permeation chromatography, using the method described by J.R. Runyon et al., J. Polym. Sci. 13.2359 (1969). Adhesive: • 180 ° separation (N / cm) was measured on steel according to AFERA TM-4001. • Lamella viscosity (N / 25mm) on steel was measured according to FINAT TM9. • Ball viscosity (cm) was measured according to PSTC6. • The tear was measured according to PSTC7, except that the sample was 25 millimeters by 12.5 millimeters, weighing 1 kilogram. • SAFT (Tear Adhesion Failure Temperature) was measured by adhering a 25 mm wide polyethylene coated strip to stainless steel by press lamination with a contact area of 12.5 millimeters by 25 millimeters, hanging the samples in an oven to 24 ° C, and suspending a weight of 500 grams from the bottom of the strip. The temperature rises to 0.4 ° C / minute, and the temperature of the link failure is measured. The SAFT is the average of three test samples. • Viscosity was measured according to ASTM D-3236. EXAMPLES 18 v 19 - Crude Cc Based Resin Hydroxide: Example 18 is the result of the hydrogenation in a continuous reactor, of a solution of the resin product of Example 14 in a hydrocarbon solvent (Varsol 1), with a Ni-W catalyst on alumina (5 weight percent nickel oxide, 21 weight percent Tungsten oxide). The catalyst was used at a feed rate of 1.5 volumes of resin solution per volume of catalyst per hour (VVH), and had the properties described in Table VIII. Example 19 resulted from the hydrogenation in a batch reactor of a solution of the product of Example 14 in Exxsol D 40, with a palladium on carbon catalyst (5 weight percent of Pd on carbon, and 15 weight percent of catalyst load, based on the weight of the solution) under the autoclave conditions of Table VII. Example 20 was run according to the same procedure as Example 18, except that a nickel-tungsten catalyst on gamma-alumina was used. Example 21 was run according to the same procedure of Example 20, except that the catalyst was used at a feed rate of one volume of resin solution per volume of catalyst per hour (VVH).

Table VII Examples of Resin Hydrogenation [*) A solution of 50 weight percent resin and 50 weight percent toluene was analyzed spectrophotometrically in a Hunterlab Ultrascan Spectrophotometer. The total transmission mode was used, and the Yellowness Index YID1925 was recorded.

Table VIII * S = configured particle support; R = cylindrical particle support + = below the detectable level. For purposes of the present, all references, test procedures, and priority documents are incorporated herein by reference. As can be seen from the above general description and specific embodiments, although some forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. In accordance with the foregoing, it is not intended that the invention be limited by the same.

Claims (26)

1. CLAIMS 1. A process for producing a resin, comprising combining a physical reactor feed mixture comprising (a) at least 2% by weight of isoprene, (b) at least 2% by weight of one or more of dicyclopentadiene, substituted cyclopentadienes and substituted dicyclopentadienes, (c) at least 2% by weight piperylene, (d) at least 1% by weight aromatic olefins, and (e) 0 to 92% by weight additional aliphatic olefins, based on the weight of the physical feed mixture of the reactor, with a polymerization catalyst, under polymerization conditions, with the proviso that the ratio of component (c) to component (b) is less than 8 and the ratio of component (a) component (b) is less than 5; and the resin has a heavy average molecular weight of 4,000 or less, and an Mw / Mn ratio of 3 or less.
2. 2. The process of claim 1, wherein the polymerization conditions comprise a temperature between 0 and 200 ° C.
3. 3. The process of claim 1, wherein the polymerization occurs in one or more continuous or batch reactors.
4. 4. The process of claim 1, wherein the physical reactor feed mixture comprises additional diolefins.
5. 5. The process of claim 1, wherein the aliphatic olefin is one or more of linear, branched or alicyclic C4 to C20 olefins.
6. The process of claim 4, wherein the diolefin is a linear, branched or cyclic conjugated diene.
7. The process of claim 4, wherein the diolefin is selected from the group consisting of butadiene, 1,3-pentadienes and cyclopentadiene.
8. The process of claim 1, wherein the aliphatic olefin comprises one or more natural or synthetic terpenes.
9. 9. The process of claim 1, wherein the aliphatic olefin preferably comprises one or more of alpha-pinene, beta-pinene,? -3-carene, dimers of isoprene, dipentene and limonenes.
10. The process of claim 1, wherein the aromatic olefins comprise styrene and / or indene and / or alkylated styrene derivatives and / or alkylated indene derivatives.
11. The process of claim 1, wherein the aromatic olefins comprise one or more of styrene, alpha-methyl-styrene, beta-methyl-styrene, indene, methyl-indenos and vinyl toluenes.
12. The process of claim 1, wherein component (b) is present at 2-25% by weight.
13. 13. The process of claim 1, wherein the polymerization conditions comprise a temperature between 0 and 80 ° C and the polymerization catalyst is present at 0.5 to 1.0% by weight, based on the weight of the physical feed mixture.
14. The process of claim 1, wherein the piperylene is present in 5 to 70% by weight.
15. The process of claim 1, wherein the piperylene is present in 5 to 20% by weight, the component (b) is present in 2 to 25% by weight, the isoprene is present in 2 to 20% by weight, and the aromatic olefins are present in 1 to 30% by weight.
16. 16. The process of claim 1, wherein the aromatic olefins are present up to 50% by weight.
17. The process of claim 1, wherein the aromatic olefins are present in 2 to 25% by weight.
18. 18. The process of claim 1, further comprising hydrogenating the resin produced by the polymerization.
19. The process of claim 18, wherein the catalyst used to hydrogenate the resin produced by the polymerization is one or more metal compounds supported on porous refractory substrate particles having: a) a maximum, average length of diffusion path lesser or same as twice the hydraulic radius; b) a pore volume distribution where: i) pores having diameters 150,000Á (150,000 x 10"10 m) constitute more than about 2% of the total volume, ii) pores having diameters> 20,000Á (20,000 x 10"10 m) and < 150,000Á (150,000 x 10"10 m) constitute more than about 1% of the total volume, and iii) the pores having diameters 2,000Á (2,000 x 10 ~ 10 m) and - <; 20,000Á (20,000 x 10 ~ 10 m) constitute more than about 12% of the total volume; and c) a total pore volume of about 45 to 86% of the total volume of the substrate particles.
20. The process of claim 1, wherein the polymerization catalyst is a Friedel-Crafts catalyst.
21. The process of claim 1, wherein the polymerization catalyst is aluminum trichloride, boron trifluoride, aluminum tribromide, or a mixture thereof.
22. 22. An adhesive comprising a base polymer and the resin produced by a process for producing a resin, comprising combining a physical reactor feed mixture comprising: (a) at least 2% by weight of isoprene, (b) at least 2% by weight of one or more of dicyclopentadiene, substituted cyclopentadienes and substituted dicyclopentadienes, (c) at least 2% by weight of piperylene, (d) at least 1% by weight of aromatic olefins, and (e) 0 to 92% by weight of additional aliphatic olefins, based on the weight of the physical feed mixture of the reactor, with a polymerization catalyst, under polymerization conditions; and the resin having a heavy average molecular weight of 4,000 or less, and an Mw / Mn ratio of 3 or less; and wherein the ratio of component (c) to component (b) is less than 8 and the ratio of component (a) to component (b) is less than 5.
23. 23. The adhesive of claim 22, wherein the base polymer is selected from the group consisting of block copolymers of styrene and isoprene or butadiene, polyisoprene, butyl rubber, ethylene vinyl acetate, ethylene methyl acrylate, amorphous polypropylene, monomeric ethylene propylene diene rubber, copolymers of ethylene and a C3 alpha olefin C20, copolymers of propylene and ethylene or a C4 to C20 alpha-olefin, metallocene polyethylenes, metallocene polypropylenes, natural rubber, styrene butadiene rubber, and copolymers of isobutylene and para-alkylstyrene.
24. 24. The adhesive of claim 22, wherein the base polymer is a styrene-isoprene-styrene tri-block copolymer.
25. The adhesive of claim 22, wherein the resin is present in 25 to 200 parts by weight per 100 parts by weight of the base polymer.
26. 26. A resin having a ring and ball softening point of 10 to 140 ° C, a heavy average molecular weight of 4,000 or less, and an Mw / Mn ratio of 3 or less, comprising the polymerization product of a polymerization catalyst and a physical reactor feed mixture, comprising: (a) at least 2% by weight of isoprene, (b) at least 2% by weight of one or more of dicyclopentadiene, substituted cyclopentadienes and substituted dicyclopentadienes, ( c) at least 2% by weight of piperylene, (d) at least 1% by weight of aromatic olefins, and (e) 0 to 92% by weight of additional aliphatic olefins, based on the weight of the physical feed mixture of reactor, with a polymerization catalyst, under polymerization conditions, with the proviso that the ratio of component (c) to component (b) is less than 8 and the ratio of component (a) to component (b) is lower of 5.