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  • C07C2527/06—Halogens; Compounds thereof
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  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/10—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing cycloaliphatic monomers

Definitions

• the patent relates to a process for the oligomerization of aromatic or alicyclic hydrocarbons at a temperature above 0 °C by means of a complex made up of a boron fluoride catalyst and a cocatalyst.
• the pressure in the oligomerization reaction is adjusted to 1 - 10 bar by means of the gaseous catalyst BF 3 .
• oligomerization and polymerization of hydrocarbons which contain different olefinic groups is coirimonly known technology. These reactions can occur thermally without a catalyst, as a radical reaction with, for example, peroxide catalysts, with coordination polymerization catalysts, through an anionic mech ⁇ anism with basic catalysts, through a cationic mechanism with Friedel-Crafts catalysts, and through polymerization by using molecular sieves, e.g. zeolites.
• the anionic mechanism is mainly used for olefin dimerization reactions, for example for the dimerization of propylene to 4- methyl-1-pentene.
• Coordination polymerization is mainly used for the preparation of various plastics, such as polyethylene, polypropylene and poly-1-butene, in which it is desired to determine in advance very precisely the structure of the prod ⁇ uct to be formed.
• the cationic mechanism and polymerization with molecular sieves produce in the polymerization of olefinic hydrocarbons light oligomers or viscous liquids, so-called liquid polymers.
• the various mechanisms are described, for example, in the books Principles of Polymerization (Odian, G. , J. Wiley & Sons, New York, 2nd ed. , 1981) and Textbook of Poly ⁇ mer Science (Billmeyer, F.W. Jr, J. Wiley & Sons, New York, 3rd ed., 1984).
• the catalysts used in the cationic mechanism have been Lewis acids such as BF 3 , AlCl 3 , AlBr 3 , TiCl ⁇ , SnCl 4 , etc. It is known that Lewis acid catalysts cannot alone initiate a polymeriza ⁇ tion reaction but require a proton donor, i.e. a cocatalyst. Such cocatalysts include water, alcohols, carboxylic acids, inorganic acids, certain alkyl halides, and halogens.
• the oli ⁇ gomerization can be performed in bulk, i.e. without an auxil ⁇ iary solvent, or in the presence of an inert solvent.
• Such inert solvents include alkanes, such as hexane and heptane, and cycloalkanes, such as cyclohexane and cycloheptane, as well as certain aromatic solvents, such as toluene and benzene.
• Marconi et al. (in the Kennedy book mentioned above, pages 194 - 197) polymerized 4-vinyl cyclohexene with acid initiators, in which case the product was a solid, amorphous polymer having a low molar mass and an irregular structure.
• ⁇ -Methyl styrene polymerized by means of a cationic mechanism is used to a limited extent in certain commercial resins.
• Ac ⁇ cording to the literature, ilt is possible to produce from ⁇ - ethyl styrene with A1C1 3 catalyst in suitable conditions (solvent, temperature) polymers the molar mass of which is up to 2*10 g/mol (i.e. degree of polymerization approx. 17000).
• styrene The cationic polymerization of styrene is very well known and investigated in academic research, owing to the relatively easy control and monitoring of its polymerization, in particular with respect to the reaction velocity and the molar mass. How ⁇ ever, because of the relatively poor properties of the product, industrial research has not shown great interest in the said product.
• the molar masses were 45000 - 340000.
• styrene polymerization has been studied using nearly all cationic catalysts, such as Br ⁇ nstedt acids, Lewis acids,- alky1 aluminums, etc.
• Styrene, as well as ⁇ -methyl styrene has been polymerized using BF 3 catalysts.
• the catalyst was a complex formed in a reaction between BF 3 and a cocatalyst.
• the cocatalyst has been water, tetrahydrofuran or ethanol.
• BF 3 etherate as a catalyst for the polymerization of styrene.
• the solvent has in most cases been benzene, carbon tetrachlor ⁇ ide, methyl chloride, or a mixture thereof. 0...30 °C is men ⁇ tioned as the reaction temperature.
• BF 3 -catal ⁇ zed oligomerization has been known at least since 1873, when Butlerov and Gorianov reported the oligomerization of isobutene and propylene with BF 3 treatment at room tempera ⁇ ture.
• the first BF -catalyzed polycondensation was performed by Canizzaro in 1854, at which time he reacted benzyl alcohol with BF 3 , and the product obtained was a resin-like hydrocarbon. (Kennedy, J. , Cationic polymerization of olefins, J. Wiley & Sons, New York, 1975, p. 8).
• the present invention relates to the oligomerization of ali ⁇ cyclic or aromatic hydrocarbons which contain an olefinic group to a liquid product by using as the catalyst a complex formed by boron trifluoride and a cocatalyst.
• the cyclic hydrocarbon may contain a group containing a heteroatom, mainly a hydroxyl or ester group, which may be significant in some uses.
• the product is thus neither solid nor crystalline, and its degree of polymerization is low, clearly below one hundred.
• the cyclic compound which contains an olefinic pend ⁇ ant group is preferably vinyl cyclohexane, vinyl cyclohexene, or various isomers thereof, allyl cyclohexane, or allyl cyclo- hexene or various isomers thereof.
• the aromatic compound which contains an olefinic pendant group is preferably styrene or ⁇ - methyl styrene.
• the catalyst system comprises a complex made up of boron trifluoride and a cocatalyst, which may be an alcohol, a carboxylic acid, water, or an inorganic acid.
• the cocatalyst is preferably a carboxylic acid or an alcohol.
• the oligomeriza ⁇ tion takes place in the presence of an active catalyst complex.
• a catalyst complex may be prepared by a reaction between BF 3 and a cocatalyst, separately from the oligomerization re ⁇ actor or in situ in the reactor.
• the oligomerization temperature is above 0 °C, preferably 10 - 30 °C.
• the pressure is 1 - 10 bar, and it can be adjusted by means of gaseous BF .
• the reaction time is relatively short, in general 0.5-1 hour, at maximum 3 hours.
• the oligomerization process according to the present invention differs from the state-of-the-art techniques in particular with respect to the catalyst complex mentioned above and in that the reactions are performed by using a considerably higher reaction temperature.
• One of the advantages achieved by using a higher reaction temperature is the possibility to use water for the cooling of the reactor as an inexpensive alternative instead of expensive specialized apparatus.
• the oligomers of olefinic hydrocarbons are technologically important intermediates, which can be used for the preparation of highly varied end products.
• the oligomers prepared according to the present invention con ⁇ tain in the polymer chain an olefinic double bond having in ⁇ creased reactivity.
• the properties of the oligomers include resistance to thermal oxidation, a low pour point, a low vola ⁇ tility, and a good temperature-viscosity dependence. The above properties are important, especially if the oligomers are used for the production of lubricants and their additives.
• the process according to the invention can also be used for producing oligomers having a low viscosity index. These oligomers and their derivatives are used mainly for ap ⁇ plications other than lubricants and their additives.
• the oligomers can be used as intermediates in the production of various chemical compounds.
• the oligomers are used, for example, for the preparation of alkyl benzenes, alkyl phenols and alkyl succinic acid anhydride.
• Surfactants are prepared from alkyl benzenes and alkyl phenols by sulfonation.
• the oligomers can be used in the pre ⁇ paration of, for example, sulfonates, phenates, thiophosphon- ates, and ash-free dispersants, alkenyl succinimides. In these compounds, the molar mass of the hydrocarbon component is approx.
• alkenyl succinimide as high as 2500 g/mol.
• Other uses include lubricants in two-stroke spark- ignition engines, as a machining oil in the rolling and drawing of metallurgical materials, in the leather and rubber indus ⁇ tries, and in rendering various surfaces hydrophobic.
• hydro- genation of the oligomers it is possible to prepare high- standard transformer oils, electrical insulation and cable oils, and non-toxic oils and white oils.
• the lightest oligomers of styrene and ⁇ -methyl styrene can be used to replace in part the monomer in polyester resins and vinyl ester resins.
• the oligomers of hydrocarbons which contain a non- aromatic olefinic group, such as cyclohexane and vinyl cyclo ⁇ hexene can be used, for example, in polyester and vinyl ester resins as inhibitors of shrinkage during hardening, as so- called Low Profile agents, and in part to replace the monomer.
• non-aromatic monomers it is possible to reduce the absorption of UV light by the products prepared and thereby to reduce their yellowing and discoloration.
• oli ⁇ gomerization of alicyclic or aromatic hydrocarbons containing an olefinic pendant group is described in several examples.
• the oligomerization reactions were carried out, unless other ⁇ wise stated, in a steel reactor having a volume of 300 ml. It was cooled internally with a cooling coil and was heated, when necessary, by using an electric bath. The reactor was equipped with a mixer. The temperature of the reaction mixture was moni ⁇ tored by using a thermocouple. The aim was to maintain the temperature of the reaction mixture at the set value with a precision of ⁇ 1.
• the reagents used and their amounts are given in the examples.
• the reactor was first charged with a solvent, if necessary, and the cocatalyst, as well as the aromatic or cyclic hydrocarbon containing a vinylic or aromatic pendant group, mentioned in the examples, as the reactor liquid phase. Thereafter the reac ⁇ tor was pressurized with BF gas, whereupon the catalyst com- plex formed in situ and the reaction started immediately.
• the reactor pressure was maintained constant by means of BF gas. The pressure was sufficient to keep the monomers in the liquid phase.
• the reaction parameters used were as follows: pressure 0...10 bar, indicated as overpressure; reaction tem ⁇ perature 10...70 °C; and reaction time 1...4 hours.
• the reac ⁇ tion was terminated by adding into the reactor an excess of either an NaOH solution or water. The product fraction was washed with an NaOH solution and was neutralized with water after the wash.
• ⁇ -Methyl styrene was oligomerized for i h at a BF 3 pressure of 3.2 bar at 20 °C in toluene solvent.
• the feed of monomer was
• 4-Vinyl-l-cyclohexene was oligo erized for _ h at a BF 3 pres ⁇ sure of 2.0 bar at 20 °C in toluene solvent.
• the feed of mono ⁇ mer was 41.3 g
• the feed of toluene solvent was 100 ml
• the feed of n-valerianic acid as a cocatalyst was 2.7 g.
• the mono ⁇ mer conversion was approx. 95 %
• the molar mass distribution ranged up to a molar mass of 10,000 g/mol.
• 4-Vinyl-l-cyclohexene was oligomerized for 2 h at a BF 3 pres ⁇ sure of 3.0 bar at 20 °C in n-heptane solvent.
• the feed of monomer was 82.3 g
• the feed of n-heptane solvent was 50 ml
• the feed of n-valerianic acid as a cocatalyst was 2.8 g.
• the monomer conversion was approx. 95 %.
• the molar mass distribution ranged up to a molar mass of 100,000 g/mol.
• Table 1 shows the starting materials used in the various ex ⁇ amples, the solvent medium and the cocatalyst, as well as their amounts.
• AMS alpha-methyl styrene
• STY styrene
• VCHA vinyl cyclohexane
• VCHE 4-vinyl-l-cyclo- hexene
• val.acid n-valerianic acid.
• Pentanol stands for 1- pentanol and heptane stands for n-heptane.
• Table 2 shows the reaction conditions in the various examples.
• the table shows the reaction temperature (T, C), reaction pres ⁇ sure (p, bar) indicated as overpressure, and the reaction time (t, h) .
• T, C reaction temperature
• p, bar reaction pres ⁇ sure
• t, h reaction time

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1993
  • 1993-08-31 FI FI933796A patent/FI95239C/fi not_active IP Right Cessation
• 1995
  • 1995-02-27 WO PCT/FI1995/000105 patent/WO1996033147A1/en active Application Filing

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