EP1208125A1 - Resines de petrole et leur procede de production par un catalyseur bf 3? - Google Patents

Resines de petrole et leur procede de production par un catalyseur bf 3?

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Publication number
EP1208125A1
EP1208125A1 EP00956267A EP00956267A EP1208125A1 EP 1208125 A1 EP1208125 A1 EP 1208125A1 EP 00956267 A EP00956267 A EP 00956267A EP 00956267 A EP00956267 A EP 00956267A EP 1208125 A1 EP1208125 A1 EP 1208125A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
process according
feed
cocatalyst
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00956267A
Other languages
German (de)
English (en)
Inventor
James Hanley Clark
Jennifer Katie Shorrock
Karen Wilson
Kenneth Lewtas
Maria Leonor Garcia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9916855.1A external-priority patent/GB9916855D0/en
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP1208125A1 publication Critical patent/EP1208125A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/025—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J107/00—Adhesives based on natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention is concerned with the production of petroleum resins and with the improved resins so produced.
  • Petroleum resins are well known and are produced by the Friedel-Crafts polymerisation of various feeds, which may be pure monomer feeds or refinery streams containing mixtures of various unsaturated materials.
  • Typical feeds are C to C 6 or C 8 to C 9 olefin and diolefin feeds and mixtures thereof and a variety of pure olefinic monomers.
  • the resulting hydrocarbon resins can range from viscous liquids to hard, brittle solids with colours ranging from water white to pale yellow, amber, or dark brown depending on the monomers used and the specific reaction conditions. Typically, pure monomer resins tend to be water white, C 9 monomer resins tend to be brown, and C 5 monomer resins tend to be yellow.
  • Hydrocarbon resins are used in adhesives, rubbers, hot-melt coatings, printing inks, paint, flooring, road marking and polymer and other applications.
  • the resins are usually used to modify other materials.
  • Pure monomer hydrocarbon resins can be prepared by cationic polymerisation of styrene- based monomers such as styrene, alpha-methyl styrene, vinyl toluene, and other alkyl substituted styrenes using Friedel-Crafts polymerisation catalysts such as unsupported Lewis acids (e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminium trichloride (AICI 3 ), alkyl aluminium chlorides).
  • boron trifluoride boron trifluoride
  • AICI 3 aluminium trichloride
  • aliphatic C 4 to C 6 hydrocarbon resins can be prepared by cationic polymerisation of cracked petroleum distillates containing C 4 , C 5 and C 6 paraffins, olefins, and diolefins also referred to as "C 5 monomers".
  • These monomer streams are comprised of cationically polymerisable monomers such as 1 ,3-pentadiene which is the primary reactive component, along with butadiene, cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, isoprene, cyclopentadiene, and dicyclopentadiene.
  • the polymerisations are catalysed using Friedel- Crafts polymerisation catalysts such as unsupported Lewis acids (e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminium trichloride (AICI 3 ), or alkyl aluminium chlorides).
  • unsupported Lewis acids e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminium trichloride (AICI 3 ), or alkyl aluminium chlorides.
  • non-polymerisable components in the feed include saturated hydrocarbons, which can be co-distilled with the unsaturated components such as pentane, cyclopentane, or 2-methyl pentane.
  • This monomer feed can be co-polymerised with C 4 or C 5 olefins or dimers.
  • Aromatic C 9 hydrocarbon resins can be prepared by cationic polymerisation of aromatic C 8 , C 9 , and/or C 10 unsaturated monomers derived from petroleum distillates resulting from naphtha cracking and are referred to as "C 9 monomers". These monomer streams are typically comprised of mixtures of cationically polymerisable monomers such as styrene, alpha methyl styrene, beta methyl styrene, vinyl toluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl substituted derivatives of these components.
  • non-polymerisable components include aromatic hydrocarbons such as xylene, ethyl benzene, cumene, ethyl toluene, indane, methylindene, naphthalene and other similar species.
  • unsupported Lewis acids are effective catalysts for cationic polymerisation reactions to produce hydrocarbon resins, they have several disadvantages.
  • Conventional unsupported Lewis acids are single use catalysts, which require processing steps to quench the reactions and neutralise the acids.
  • conventional unsupported Lewis acids also require removal of catalyst salt residues from the resulting resin products. Once the salt residues generated from the cataiyst neutralisation are removed, the disposal of these residues presents an environmental hazard and additional cost. Therefore, it is of particular interest to reduce the amount of catalyst residues, particularly halogen-containing species generated in these reactions.
  • the present invention therefore seeks to overcome these problems and to provide a commercially viable process for the production of petroleum resins, particularly from C 5 to C 6 or C 8 to C 9 refinery feedstreams or mixtures thereof which can tolerate conventional impurities in the feed, reduces catalyst residues in the resin and does not require extensive spent catalyst disposal.
  • the invention employs a supported Friedel-Crafts catalyst. It has been suggested in PCT publication W095/26818 that supported Lewis acid catalysts may be used for hydrocarbon conversion reactions including the polymerisation of unsaturated monomers such as piperylene. More recently, PCT publication W098/130587 is specifically concerned with supported metal halide catalysts useful for the preparation of hydrocarbon resins, WO 98/130587 is primarily concerned with using zinc, zirconium and aluminium halide catalysts.
  • the catalyst properties can be controlled and the catalyst can be used to produce petroleum resins in high yield including certain novel petroleum resins having particularly desirable properties.
  • the use of the boron trifluoride complex enables better control of the acid strength of the catalyst and allows catalysts of increased strength to be used.
  • petroleum resins produced in this way are used in adhesive formulations for bonding substrates to metal adhesive compositions that are highly resistant to high shear conditions may be obtained.
  • an adhesive with good cohesion may be obtained with a resin of lower molecular weight as compared with resins produced using other conventional catalyst systems.
  • the present invention therefore provides a process for the production of petroleum resins by the polymerisation of C 5 to C 6 and/or C 8 to C 9 unsaturated hydrocarbon feeds wherein the feed is contacted under polymerisation conditions with a supported boron trifluoride cocatalyst complex.
  • This preferred catalyst is a novel form of a supported boron trifluoride complex that exhibits Bronsted and Lewis acid properties that can be tuned by varying the cocatalyst, the nature of the support and the calcination temperature.
  • the catalytic activity of homogeneous boron trifluoride complexes in many organic reactions is dependent on the ability of the complex [H + ][X:BF 3 " j where X is the complexing agent, to act as a proton donor to olefins.
  • the activity of the cocatalyst (HX) in homogenous systems is observed to decrease in the order.
  • Silica is a preferred catalyst support.
  • HX is the complexing Iigand.
  • Bronsted acidity in solid acid catalysts normally arises from polarised ⁇ " 0-H ⁇ + sites.
  • a support such as a support having free surface oxide or hydroxyl groups.
  • additional Bronsted acidity is obtained from the Bronsted complex illustrated above.
  • the pka of the complexing Iigand be between 2.0 and 4.5, ethanol and acetic acid are particularly beneficial complexing agents. If the complexing Iigand is too acidic the system is destabilised, if too basic the catalytic activity is reduced.
  • the choice of solvent (which can also complex with the BF 3 ) used during the preparation of the complex will alter the acidic properties of the catalyst. Protic solvents (alcohols) will result in enhanced Bronsted acidity compared to nonprotic solvents (ethers, aromatic hydrocarbons).
  • the solvent used in the preparation is preferably predried to avoid hydrolysis of the BF 3 complex.
  • BF 3 (H 2 0) 2 (4.1 g, 0.04 mol) was added to a slurry of 100ml of absolute ethanol and 10g of K100 Si0 2 that had been dried at 300°C for 24 hours. The mixture was stirred for 2 hours at room temperature under a N 2 flow of 50ml min "1 . The slurry was then transferred to a rotary evaporator and dried at 50°C for a period of 4 hours to remove all the ethanol.
  • BF 3 (H 2 0) 2 (4.1g, 0.04 mol) was added to a slurry of 100ml anhydrous toluene and 10g of K100 Si0 2 that had been dried at 300°C for 24 hours. The mixture was stirred for 2 hours at 25°C under a N 2 flow of 50ml min "1 . The slurry was then transferred to a rotary evaporator and dried at 50°C for a period of 4 hours to remove all the toluene. c) BF 3 (OEt 2 ) (5.6g, 0.04 mol) was added to a slurry of 100ml toluene and 10g of K100 Si0 2 that had been dried at 300°C for 24 hours.
  • the mixture was stirred for 2 hours under reflux under a N 2 flow of 50ml min "1 .
  • the slurry was then transferred to a rotary evaporator and dried at 50°C for a period of 4 hours to remove all the toluene.
  • BF 3 (OEt 2 ) (5.6g, 0.04 mol) was added to a slurry of 100ml absolute ethanol and 10g of K100 Si0 2 that had been dried at 300°C for 24 hours. The mixture was stirred for 2 hours at room temperature under a N 2 flow of 50ml min "1 . The slurry was then transferred to a rotary evaporator and dried at 50°C for a period of 4 hours to remove all the ethanol.
  • BF 3 (H 2 0) 2 which can exist as [H 3 0] + [BF 3 OH] " .
  • the trend in Bronsted acidity observed between BF 3 .OEt 2 and BF 3 (H 2 0) 2 precursors can thus be explained.
  • Desorption of ethanol from the BF 3 (H 2 0) 2 /Si0 2 catalyst following 200°C calcination lowers the number of Bronsted sites titratable by pyridine. We attribute those remaining to the polarisation of surface hydroxyl groups on the support by the BF X centres.
  • 400°C dehydroxylation of the support further reduces the number of Bronsted sites leaving predominately Lewis acid character which is attributed to the remaining BF X sites.
  • the evolution of HF above 400°C observed by TGIR indicates that these BF X groups start to decompose above this temperature, and by 600°C no titratable acid sites remain indicating complete decomposition of the BF X centres.
  • the present invention provides an improved process to produce conventional resins in a second aspect
  • the invention provides novel petroleum resins.
  • the invention when the invention is performed using a mixed aliphatic/aromatic feed it enables, for a particular feed, the incorporation of higher amounts of aromatic materials into the products produced than when using other catalysts.
  • the catalyst system according to the present invention enables the production of aromatic containing resins of any desired aromatic content up to 100% aromatics. It is believed this may be reflected in the improved adhesive properties obtained when using the resin as a tackifier.
  • the petroleum resins produced according to the present invention are used as tackifiers in adhesive systems such as solvent based adhesives, hot melt adhesives and pressure sensitive adhesives.
  • adhesive systems such as solvent based adhesives, hot melt adhesives and pressure sensitive adhesives.
  • the petroleum resin acts as a tackifier for other polymers and rubbers used in the adhesive system.
  • the choice of the polymer and/or the rubber depends on the nature of the adhesive and its particular application. For example hot melt adhesives frequently are based on ethylene containing copolymers, particularly ethylene/vinyl acetate copolymers.
  • Pressure sensitive adhesives frequently are based on natural or synthetic rubbers such as styrene butadiene copolymer rubbers, solvent based adhesives may be aqueous emulsions or organic solvent based, although for environmental reasons aqueous systems are preferred.
  • solvent based adhesives may be aqueous emulsions or organic solvent based, although for environmental reasons aqueous systems are preferred.
  • polymer systems useful in such aqueous adhesive systems are polyacrylate and polymethacrylate emulsions.
  • the resins of this invention have particularly good shear stability when used in pressure sensitive adhesives, particularly shear on metal and cardboard.
  • the polymerisation conditions are standard conditions for the production of petroleum resins and should be chosen according to the nature of the feed to be polymerised and the ultimate properties required of the resin.
  • the choice of the support for the catalyst, the method of catalyst manufacture and choice of cocatalyst will also depend upon the feed to be polymerised and the resin properties desired.
  • the cocatalyst may be organic or inorganic compounds such as alcohols, carboxylic (preferably acetic) acids, phosphoric acid or water.
  • the ability to choose both the support and the cocatalyst adds flexibility in that by varying the nature of the support, the method of preparation, and the cocatalyst, the ratio of Lewis acidity to Bronsted acidity can be varied producing catalysts suitable for the production of resins with particular desired properties.
  • catalysts can be used in the polymerisation of C 4 to C 6 and/or C 8 to C 9 feeds they are particularly useful in the polymerisation of feeds containing unsaturated aromatic monomers.
  • the monomers may be pure monomers such as alpha-methyl styrene and vinyl toluene or petroleum feeds containing mixtures of the unsaturated aromatic materials.
  • the use of the supported BF 3 /cocatalyst systems according to the present invention enables greater flexibility when polymerising feeds containing monomers that polymerise at different rates such as mixtures of olefins and diolefins.
  • the unsaturated aromatic monomers may be copolymerised with other unsaturated materials, particularly C 4 to C 6 unsaturated materials, which may be petroleum feeds which are mixtures of such materials or pure C 5 monomers.
  • the composition of the feed will be selected according to the use to which the resin is to be put. We have also found that these catalysts are effective without extensively drying the feeds as has been necessary in the past.
  • the solid acid catalysts and/or supports may be treated to remove freely-associated water associated with the solids to maximise catalyst acidity and activity.
  • the catalyst and/or support may be calcined for a sufficient time to remove freely- associated water and/or the catalyst and/or support can be exposed to reduced atmospheric pressure.
  • the calcining may be at a temperature up to 700°C, preferably at a temperature between 50°C and 500°C.
  • the calcining may be under reduced atmospheric pressure for up to 8 hours, preferably between 1 hour to 4 hours.
  • the nature of the support is also important. It must be able to react with the BF 3 and can be chosen according to the nature of the feed, the cocatalyst and the desired resin properties.
  • suitable supports are materials containing surface hydroxyl groups such as silica, synthetic silicas (MCM), hexagonal mesoporous silica (HMS) as described in Nature 1992 359, Page 710 and Science 267 Page 865, and clay supports, including naturally occurring clay mineral such as at least one member selected from the group consisting of kaolinite, bentonite, attapulgite, montmorillonite, clarit, Fuller's earth, hectorite, and beidellite; synthetic clay such as U
  • the preferred supports have surface hydroxyl groups which can react with the boron trifluoride.
  • Mesoporous silica is a particularly preferred support.
  • the support may also include at least one member selected from the group consisting of zeolite ⁇ , zeolite Y, zeolite X, MFI, MEL, NaX, NaY, faujasite, mordenite, alumina, zirconia, titania and alumino silicates.
  • the support may also be calcined and we have found that when using a silica support calcination alters the nature of the surface hydroxyl groups on the silica.
  • the calcination produces isolated as opposed to vicinal hydroxyl groups, which leads to a different interaction with the boron trifluoride which in turn leads to a different polymerisation reaction. Calcination has been found to improve resin yield and decrease the formation of low molecular by-product known as fill.
  • the pore size of the support should be such that the monomer has access to the catalytic species. Furthermore, the pore size should be such that it is not readily clogged with the polymeric resin once formed. We have found that in order to obtain satisfactory resin yields the pore size should be at least 100 A.
  • pore size we mean the narrowest cross-section of the pore. This may be the diameter of the orifice or the neck of the pore, which in some instances is narrower than the orifice.
  • the amount of catalyst that is loaded onto the support also has a significant effect on the properties of the resin obtained. We have found that yield increases with increased catalyst loading with good control of resin molecular weight up to a certain loading level.
  • the optimum level depends upon the nature of the boron trifluoride/cocatalyst complex and the nature of the support however above this particular level the control of molecular weight is lost and resins of too high molecular weight are produced.
  • a boron trifluoride/ethanol complex catalyst supported on K 100 silica yield increases as the catalyst loading increases to about 4 mmole BF 3 /g but at higher loadings this high molecular weight materials are produced. This is believed to be because at these higher loadings there is unsupported catalyst present and the system operates, at least to some extent, as a homogeneous system.
  • the feedstream may include between 20 wt % and 80 wt % monomers and 80 wt % to 20 wt % of solvent.
  • the feedstream includes 30 wt % to 70 wt % monomers and 70 wt % to 30 wt % of solvent. More preferably, the feedstream includes about 50 wt % to 70 wt % monomers and 50 wt % to 30 wt % of solvent.
  • the solvent may include an aromatic solvent.
  • the aromatic solvent may include at least one member selected from the group consisting of toluene, xylenes, and aromatic petroleum solvents.
  • the solvent may include an aliphatic solvent.
  • the solvent may be the unpolymerisable component in the feed.
  • the invention may further include recycling the solvent.
  • the feedstream includes at least C 5 monomers. If desired cyclopentadiene and methylcyclopentadiene components may be removed from the feedstream by heating at a temperature between 100°C and 160°C and fractionating by distillation.
  • the C 5 monomers may include at least one member selected from the group consisting of butadiene, isobutylene, 2- methyl-2-butene, 1-pentene, 2-methyl-1-pente ⁇ e, 2-methyl-2-pentene, 2-pentene, cyclopentene, cyclohexene, 1 ,3-pentadiene, 1 ,4-pentadiene, isoprene, 1 ,3-hexadiene, 1 ,4-hexadiene, cyclopentadiene, and dicyclopentadiene.
  • the feedstream may include at least C 5 monomers.
  • a preferred feedstream includes at least 70 wt % of polymerisable monomers with at least about 50 wt % 1 ,3-pentadiene.
  • the feedstream may contain low levels of isoprene. It generally contains a portion of 2-methyl-2-butene, and may contain one or more cyclodiolefins.
  • the feedstream may further include up to 40 wt % of a chain transfer agent, preferably up to 20 wt % of chain transfer agent.
  • the chain transfer agent may include at least one member selected from the group consisting of C 4 olefins, C olefins, dimers of C olefins, and dimers of C 5 olefins.
  • the chain transfer agent may include at least one member selected from the group consisting of isobutylene, 2-methyl-1-butene, 2-methyl-2-butene, dimers thereof, and oligomers thereof.
  • the feedstream includes 30 wt % to 95 wt % of C 5 monomers and 70 wt % to 5 wt % of a co-feed including at least one member selected from the group consisting of pure monomer, C 9 monomers, and terpenes.
  • the feedstream includes 50 wt % to 85 wt % of C 5 monomers and 50 wt % to 15 wt % of a co-feed including at least one member selected from the group consisting of pure monomer, C 9 monomers, and terpenes.
  • the feedstream includes at least C 9 monomers.
  • the C 9 monomers may include at least one member selected from the group consisting of styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives thereof.
  • the C 9 monomers may include at least 20 wt % polymerisable unsaturated hydrocarbons.
  • the C 9 monomers may include 30 wt % to 75 wt % polymerisable unsaturated hydrocarbons, typically 35 wt % to 70 wt % polymerisable unsaturated hydrocarbons.
  • Pure monomer feedstreams may contain relatively pure styrene-based monomers such as styrene, alpha-methyl styrene, beta-methyl styrene, 4-methyl styrene, and vinyl toluene fractions.
  • the monomers can be used as pure components or as blends of two or more monomer feeds to give desired resin properties.
  • Preferred blends include 20 wt % to 90 wt % alpha-methyl styrene with 80 wt % to 10 wt % of one or more co-monomers, preferably styrene, vinyl toluene, 4-methyl styrene or blends of these components.
  • other alkylated styrenes can be used as monomers in this invention such as t-butyl styrene or phenyl styrene.
  • the feedstream includes 30 wt % to 95 wt % of the C 9 monomers and 70 wt % to 5 wt % of a co-feed including at least one member selected from the group consisting of pure monomer, C 5 monomers, and terpenes.
  • the feedstream includes 50 wt % to 85 wt % of the C 9 monomers and 50 wt % to 15 wt % of a co-feed including at least one member selected from the group consisting of pure monomer, C 5 monomers, and terpenes.
  • the catalyst is added to the feedstream.
  • the feedstream is added to a slurry of the catalyst in a solvent.
  • the feedstream may be passed over a fixed bed of the catalyst.
  • the feedstream is co-fed with a slurry of the catalyst into a reactor.
  • the polymerisation is carried out as a continuous process or as a batch process.
  • the reaction time in the batch process is 30 minutes to 8 hours, preferably 1 hour to 4 hours at reaction temperature and at a reaction temperature between -50°C and 150°C, preferably between -20°C and 100°C, and more preferably between 0°C and 70°C.
  • the polymerisation may be stopped by removing the catalyst from the hydrocarbon resin.
  • the catalyst may be removed from the hydrocarbon resin by filtration.
  • the hydrocarbon resin may be removed from a fixed bed reactor which includes the catalyst and may be stripped to remove unreacted monomers, solvents, and low molecular weight oligomers. The unreacted monomers, solvents, and low molecular weight oligomers may be recycled.
  • the feedstream may be chosen according to the desired properties of the hydrocarbon resin.
  • the feedstream may include at least C 5 monomers, wherein the softening point of the resulting hydrocarbon resin is between 50°C and 150°C.
  • the feedstream may include at least C 9 monomers, wherein the softening point of the resulting hydrocarbon resin is between about 70°C and 160°C.
  • the feedstream includes at least pure monomer, wherein the resulting hydrocarbon resin has a number average molecular weight (Mn) ranging from 400 to 2000, a weight average molecular weight (Mw) ranging from 500 to 5000, a Z average molecular weight (Mz) ranging from 500 to 10,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.5 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the feedstream includes at least C 5 monomers, wherein the resulting hydrocarbon resin has a number average molecular weight (Mn) of 400 to 2000, a weight average molecular weight (Mw) of 500 to 3500, a Z average molecular weight (Mz) of 700 to 15,000 and a polydispersity (PD) as measured by Mw/Mn between about 1.5 and 4, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the feedstream includes at least C 9 monomers, wherein the resulting hydrocarbon resin has a number average molecular weight (Mn) of 400 to 1200, a weight average molecular weight (Mw) of 500 to 2000, a Z average molecular weight (Mz) of 700 to 6000, and polydispersity (PD) as measured by Mw/Mn between 1.5 and 3.5, preferably 1.5 and 2.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the supported boron trifluoride cocatalyst complex may involve any combination of a single type or plurality of types of BF 3 on a single type or plurality of types of supports and may be complexed with one or more reagents. It is preferred that the BF 3 be complexed with water or an organic compound, particularly alcohols such as methanol, ethanol and propanol or carboxylic acids such as acetic, propionic or butyric acid.
  • the supported BF 3 cocatalyst complex used in the present invention are most effective in the presence of a small amount of water in the feedstream. Accordingly, they may be used without the need for costly, rigorous drying of the feed.
  • non- polymerisable components in the feed may include saturated hydrocarbons which can be co- distilled with the unsaturated components such as pentane, cyclopentane, or 2-methyl pentane.
  • This monomer feed can be co-polymerised with C 4 or C 5 olefins or dimers as chain transfer agents.
  • Chain transfer agents may be added to obtain resins with lower molecular weight and narrower molecular weight distributions than can be prepared from using the C 5 monomers alone. Chain transfer agents stop the propagation of a growing polymer chain by terminating the chain in a way which regenerates a polymer initiation site.
  • Chain transfer agents Components which behave as chain transfer agents in these reactions include but are not limited to isobutylene, 2-methyl-1- butene, 2-methy!-2-butene or dimers or oligomers of these species.
  • the chain transfer agent can he added to the reaction in pure form or diluted in a solvent.
  • the preferred solvents for the polymerisation are aromatic solvents. Typically toluene, xylenes, or light aromatic petroleum solvents. These solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than 200 ppm water, preferably less than 100 ppm water, and most preferably less than 50 ppm water.
  • the preferred solvents are aromatic solvents. Generally, unreacted resin oil components are recycled through the process as solvent. In addition to the recycled solvents, toluene, xylenes, or aromatic petroleum solvents can be used. These solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than 500 ppm water, preferably less than 200 ppm water, and most preferably less than 50 ppm water.
  • the solvent may also be the non-polymerisable component of the feed.
  • a first important variable is the amount of catalyst which is used. It is preferably used at a level of 0.1 wt % to 30 wt % based on the weight of the monomer.
  • the concentration is preferably 0.1 to 15 wt %, more preferably 0.5 wt % to 10 wt %, and most preferably 0.5 wt % to 8 wt %.
  • the concentration is preferably 0.5 wt % to 30 wt %, more preferably 1 wt % to 20 wt %, and most preferably 3 wt % to 15 wt %.
  • the concentration is preferably 0.5 wt % to 30 wt %, more preferably 1 wt % to 20 wt %, and most preferably 3 wt % to 15 wt %.
  • a second important variable in the reaction is the reaction sequence, i.e., the order and manner in which reactants are combined.
  • the catalyst can be added to a solution of the monomers incrementally while controlling the reaction temperature.
  • the monomer can be added incrementally to a slurry of the catalyst in a solvent.
  • substantially lower softening point resins are obtained when the monomer is added to a catalyst slurry.
  • Lower molecular weights and narrow polydispersity (PD), i.e., Mw/Mn, as measured by size exclusion chromatography, are obtained when the monomer is added to the catalyst slurry compared with resins where the catalyst is added to the monomer.
  • the use of the catalyst system in this invention enables much greater control over the catalyst acidity through the ability to vary the nature of the support and the nature and amount of the cocatalyst. This in turn enables better control of resin properties particularly molecular weight and polydispersity, narrow polydispersity is important to ensure compatibility of resin with polymers in end use applications.
  • a third important variable is the reaction temperature.
  • Polymerisation temperatures between -50°C and 150°C can be used, however, more preferred temperatures are between -20°C and 100°C, most preferred between 0°C and 70°C.
  • the temperature is preferably between -50°C and 100°C, more preferably between -20°C and 75°C, and most preferably between -10°C and 60°C.
  • For C 5 monomers it is between -50°C and 100°C, more preferably between -20°C and 75°C, and most preferably between -10°C and 70°C.
  • For C 9 monomers it is preferably between 0°C and 150°C, more preferably between 10°C and 120°C, and most preferably between 20°C and 110°C.
  • Temperature is found to have a significant effect on the properties of the resulting resins. Higher molecular weight and high softening point resins are prepared at lower reaction temperatures.
  • the polymerisation process can be carried out as a continuous, semi-batch, or batch process in such diverse reactors as continuous, batch, semi-batch, fixed bed, fluidised bed, and plug flow.
  • a solution of the monomers can be passed over the catalyst in a fixed bed, or the monomers can be co-fed with a catalyst slurry into a continuous reactor.
  • Fixed bed reactions are preferred as they can improve the colour of the resin as colour formers may be removed by the catalyst system as the feed enters the bed, typically at the top of the bed enabling resins of improved colour to be obtained at the end, typically at the bottom of the bed.
  • the reaction may be stopped by physically separating the catalyst from the products. Physical separation may render the reaction solution neutral. Furthermore, physical separation can be performed by simple filtration or by separation of the resin solutions from a fixed catalyst bed. As a result, acid functionality and catalyst residues are not left in the resin product.
  • any of the known processes for catalytically hydrogenating hydrocarbon resins can be used to hydrogenate the resins of this invention; in particular the processes of US 5,171 ,793, US 4,629,766, US 5,502,104 and US 4,328,090 and WO 95/12623 are suitable.
  • Generic hydrogenation treating conditions include reactions in the temperature range of about 100°C - 350°C and pressures of between five atmospheres (506 kPa) and 300 atm. (30390 kPa) hydrogen, for example, 10 to 275 atm.
  • the temperature is in the range including 180°C and 320°C and the pressure is in the range including 15195 kPa and 20260 kPa hydrogen.
  • the hydrogen to feed volume ratio to the reactor under standard conditions typically can range from 20- 200, for water-white resins 100-200 is preferred.
  • EP 0082 726 describes a process for the catalytic or thermal hydrogenation of petroleum resins using nickel-tungsten catalyst on a gamma-alumina support wherein the hydrogen pressure is 1.47 x 10 7 - 1.96 x 10 7 Pa and the temperature is in the range of 250- 330°C.
  • Thermal hydrogenation is usually performed at 160°C to 320°C, at a pressure of 9.8 x 10 5 to 11.7 x 10 5 Pa and for a period typically of 1.5 to 4 hours.
  • the reactor mixture may be flashed and further separated to recover the hydrogenated resin. Steam distillation may be used to eliminate oligomers, preferably without exceeding 325°C resin temperature.
  • the hydrogenation is carried out by contacting the resin in the presence of hydrogen and a hydrogenation catalyst which is typically metal compounds supported on porous refractory substrate particles having:
  • the catalyst comprises nickel and/or cobalt on one or more of molybdenum, tungsten, alumina or silica supports.
  • the amount of nickel oxide and/or cobalt oxide on the support ranges from 2 to 10 wt %.
  • the amount of tungsten or molybdenum oxide on the support after preparation ranges from 5 to 25 wt %.
  • the catalyst contains 4 to 7 wt % nickel oxide and 18 to 22 wt % tungsten oxide. This process and suitable catalysts are described in greater detail in WO 98/22214.
  • the hydrogenation may be carried out using the process and catalysts described in US Patent 4,629,766.
  • nickel-tungsten catalysts on gamma- alumina are preferred.
  • the resins of this invention may be combined with a base polymer to form an adhesive.
  • Typical base polymers include homopolyethylene, ethylene copolymerised with up to 50 wt % of one or more C 3 to C 20 ⁇ -olefins, polypropylene, propylene copolymerised with up to 50 wt % of one or more of ethylene and/or C 4 to C 20 ⁇ -olefins, polybutene, ethylene vinyl acetate copolymers, low density polyethylene (density 0.915 to less than 0.935 g/cm 3 ) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm 3 ), very low density polyethylene (density 0.90 to less than 0.915 g/cm 3 ), medium density polyethylene (density 0.935 to less than 0.945 g/cm 3 ), high density polyethylene (density 0.945 to 0.98 g/cm 3
  • 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 a C 3 to C 20 ⁇ -olefin, copolymers of propylene and ethylene or a C 4 to C 20 ⁇ -olefin, metallocene polyethylenes, metallocene polypropylenes, natural rubber, styrene butadiene rubber, copolymers of isobutylene and para-alkyl styrene.
  • preferred polymers are styrene-butadiene-styrene block copolymers, butyl rubber, natural rubber and styrene-butadiene rubber.
  • the base polymer is a SIS (Styrene-lsoprene-Styrene) block copolymer.
  • the SIS block copolymer has 10 wt % or less diblock present, preferably 5 wt % or less.
  • a preferred base polymer is styrene- 2 ⁇
  • isoprene-styrene block copolymer as commercially available from DEXCO POLYMERS under the trade name VECTOR®.
  • the base polymer is a polymer produced using a metallocene catalyst system.
  • the metallocene homopolymers or copolymers are produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-co-ordinating anion in solution, slurry, high pressure or gas phase.
  • the catalyst system may be supported or unsupported and the cyclopentadienyl rings may be substituted or unsubstituted. Titanium, zirconium and hafnium are preferred transition metals.
  • the metallocene produced copolymers described above preferably have a composition distribution breadth index (CDBI) of 50% or more, preferably above 60%, even more preferably above 70%.
  • CDBI composition distribution breadth index
  • the copolymer is polyethylene and has a CDBI between 60 and 85%, even more preferably between 65 and 85%.
  • Composition Distribution Breadth Index is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 93/03093, published 18 February 1993. Fractions having a weight average molecular weight (Mw) below 15,000 are ignored when determining CDBI.
  • the resin may be present in the blend from 1 to 200 parts per 100 parts of base polymer in the adhesive formulation. In a preferred embodiment, the resin is present in the blend from 25 parts to 200 parts per 100 parts of polymer. In another embodiment, the preferred range is 80 to 120 parts resin per 100 parts polymer.
  • the adhesive formulations may also contain additives well known in the art such as anti-block, anti-static, antioxidants, UV stabilisers, neutralisers, 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 may be formed into pressure sensitive adhesives, hot melt adhesives or contact adhesives and used in applications such as tapes, labels, paper impregnation, hot melt adhesives including woodworking, packaging, bookbinding or disposables, sealants, rubber compounds, pipe wrapping, carpet backing, contact adhesives, road-marking or tyre construction and polymer additives.
  • the resins are formulated into a pressure sensitive adhesive application.
  • a pressure sensitive adhesive composition may be applied to any conventional backing layer such as paper, foil, polymeric foil, release liners, woven or non- woven backing material to make for example, packaging tapes.
  • the resins of the current invention can also be used as modifiers in adhesives, sealants, printing inks, protective coatings, plastics, polymer films, construction applications such as road markings, flooring, paper additives and as dry cleaning re-texturising agents.
  • a particularly important use of these petroleum resins is as tackifiers in adhesive systems such as solvent based adhesives, hot melt adhesives and pressure sensitive adhesives.
  • the petroleum resin acts as a tackifier for other polymers and rubbers used in the adhesive system.
  • the choice of the polymer and/or the rubber depending on the nature of the adhesive and its particular application.
  • hot melt adhesives frequently are based on ethylene containing copolymers, particularly ethylene/vinyl acetate copolymers.
  • Pressure sensitive adhesives frequently are based on natural or synthetic rubbers such as styrene copolymer rubbers, solvent based adhesives may be aqueous emulsions or organic solvent based, although for environmental reasons aqueous systems are preferred.
  • Examples of polymer systems useful in such aqueous adhesive systems are polyacrylate and polymethacrylate emulsions.
  • the acid sites are an integral part of the catalyst, contamination of the resin products or solvents with catalyst residues is minimal. As a result, the catalysts do not impart undesirable colour to the hydrocarbon resins. If pure styrene-based monomers are used, the resulting resins can be water white. Furthermore the resins are substantially free of fluoride impurities.
  • the catalysts used in the present invention are robust, are predicted to have long life and can generally be regenerated and recycled to thereby minimise waste disposal of spent catalyst.
  • the unsupported Lewis acids are generally single use catalysts.
  • the catalysts of the present invention are non-hazardous when compared with traditional unsupported Lewis acid catalysts such as BF 3 and AICI 3 .
  • the catalysts of the present invention generally do not generate corrosive or hazardous liquid or gaseous acids on exposure to moisture.
  • Aromatic C 8 to C 9 feed containing:
  • the catalyst used was prepared as follows:
  • the reaction which was exothermic was performed at ambient temperature.
  • the resin was then obtained by stripping.
  • the resin had an Mn of 580, Mw 1380, Mz 7400 and a softening point of 81 °C.
  • Pressure sensitive adhesive formulations were prepared by blending 90 parts by weight of the resin with 100 parts of a solution of 10% Ivory Coast Natural Rubber of Mooney 50 in 90 parts DSP, 9 parts toluene and 1 part methanol.
  • the coating weight was 20 to 22 grams per square metre.
  • the 1800 peel adhesion on steel was measured by the AFERA Test Method 4001.
  • the loop tack on steel was measured by the FINAT Test Method 9.
  • the ball tack was measured by PSTC 6.
  • the shear on steel was measured and on cardboard by PSTC 7.
  • the yield of the resin of the invention was 16% whereas that obtained using a supported AICI 3 catalysed resin from the same feed was 5%.
  • the resin of the invention contained 42.8% aromatics compared to 31.5% for the AICI 3 resin, the resin of the invention had a softening point of 81 °C compared to 77°C for the AICI 3 resin and an Mn of 580 compared to 820.
  • the adhesive properties of the resin of the invention were compared with similar adhesives but containing the resins obtained from the same feed and with a supported AICI 3 catalyst.
  • the catalyst was prepared as follows:
  • Example 2 In this example the process of Example 2 was repeated using 5 gms of catalyst. In one experiment the drying of the feed was omitted.
  • This example compares the use of supported and unsupported (homogeneous) catalyst, using dried feed and the polymerisation conditions of Example 2.
  • Example 1 The process of Example 1 was repeated except that only feed C was used so the polymerisables in the feed were all aromatics. 100% conversion of unsaturates was achieved.
  • the stability of the boron trifluoride/ethanol complex catalyst supported on silica was evaluated by conducting ten sequential polymerisations in each of which in polymerisation catalyst and the total aromatic feed used in Example 5 were added to the reactor.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des résines de pétroles obtenues grâce à un complexe cocatalyseur BF3 supporté. Ce cocatalyseur est organique de préférence, tel qu'un alcool ou un acide carboxylique. L'utilisation du catalyseur supporté et du cocatalyseur permet de réguler l'acidité Bronsted et Lewis afin d'assurer un meilleur contrôle des propriétés des résines. L'invention permet aussi de résoudre les problèmes liés à l'élimination des déchets et à la manipulation du catalyseur.
EP00956267A 1999-07-20 2000-07-19 Resines de petrole et leur procede de production par un catalyseur bf 3? Withdrawn EP1208125A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9916855 1999-07-20
GBGB9916855.1A GB9916855D0 (en) 1999-07-20 1999-07-20 Petroleum resins and their production with BF3 catalyst
US15366399P 1999-09-14 1999-09-14
US153663P 1999-09-14
PCT/EP2000/007084 WO2001005857A1 (fr) 1999-07-20 2000-07-19 Resines de petrole et leur procede de production par un catalyseur bf¿3?

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EP1208125A1 true EP1208125A1 (fr) 2002-05-29

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CN101412786B (zh) * 2007-10-18 2011-04-06 中国石化上海石油化工股份有限公司 一种碳九馏份制取环戊二烯生产废液的利用方法
WO2011112729A1 (fr) 2010-03-11 2011-09-15 Soltex, Inc. Oxydes métalliques inorganiques activés
US8829105B2 (en) 2012-01-18 2014-09-09 Eastman Chemical Company Low molecular weight polystyrene resin and methods of making and using the same
CN103319659B (zh) * 2012-03-23 2015-09-09 天津德兰玮诚科技有限公司 多元共聚石油树脂及其制备方法
CN103319660B (zh) * 2012-03-23 2015-07-01 天津鲁华化工有限公司 加氢多元共聚石油树脂及其制备方法
AU2013277339B2 (en) 2012-06-18 2015-08-27 Petrochemical Supply, Inc. Polyisobutylene composition having internal vinylidene and process for preparing the polyisobutylene polymer composition
CN111790443B (zh) * 2020-07-17 2022-11-04 万华化学集团股份有限公司 一种负载型催化剂及其制备方法和应用
CN115212922A (zh) * 2021-04-15 2022-10-21 中国石油天然气股份有限公司 一种α-烯烃聚合的催化剂组合物及其制备与应用

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US4394296A (en) * 1979-12-17 1983-07-19 Gulf Research & Development Company Boron trifluoride-water-silica catalyst
GB2169614A (en) * 1984-12-31 1986-07-16 Mobil Oil Corp Producing alpha-olefins and their conversion into lubricants
US5268520A (en) * 1987-07-30 1993-12-07 The Lubrizol Corporation Lower alkene polymers
JP2944229B2 (ja) * 1991-02-01 1999-08-30 出光石油化学株式会社 オレフィンオリゴマーの製造方法
EP0936229B1 (fr) * 1998-02-12 2004-04-28 Eastman Chemical Resins, Inc. Procédé de préparation de résines hydrocarbonées aliphatiques modifiées aromatiquement présentant un équilibre excellent entre les caractéristiques d'adhésion et cisaillement
GB9819456D0 (en) * 1998-09-07 1998-10-28 Univ York Synthesis of a new supported bf-complex solid acid catalyst

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BR0013176A (pt) 2002-04-02
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MXPA02000651A (es) 2002-07-02
AU6827500A (en) 2001-02-05
CN1451021A (zh) 2003-10-22

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