US3817953A - Petroleum resins - Google Patents

Petroleum resins Download PDF

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Publication number
US3817953A
US3817953A US00311152A US31115272A US3817953A US 3817953 A US3817953 A US 3817953A US 00311152 A US00311152 A US 00311152A US 31115272 A US31115272 A US 31115272A US 3817953 A US3817953 A US 3817953A
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temperature
stream
hours
catalyst
polymerisation
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US00311152A
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English (en)
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D Younger
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • 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

Definitions

  • ABSTRACT 10 Claims, 1 Drawing Figure PETROLEUM RESINS This invention relates to the production of petroleum resins.
  • the preheating of the C feedstock may be carried out in a continuous or batchwise manner.
  • the present invention is particularly applicable to the continuous process and provides a means whereby the I concentration of monocyclopentadiene in the feed to thepolymerisation is kept as low as possible.
  • a C stream distilled from a cracked naphtha or gas oil is preheated'before conversion to the resin to a temperature of at least 160C fora period of up to 5 hours, and is then held at a temperature between 100 and 160C for a further period of up to 5 hours.
  • the C stream is preheated to a temperature in the range 160 to 250C, more preferably 160 to 200C.
  • the C stream is held at a temperature of between 100 and 160C for 0.05 to 1.5 hours and preferably the temperature is between 130 and 150C.
  • the desired temperature may be achi'eved isothermally or adiabatic conditions may be applied in which case the temperature may vary over a given period of time within the range specified.
  • the monocyclopentadiene which is present at the temperatures .above 160C dimerises to dicyclopentadiene.
  • the C stream is derived from a thermally or steam cracked naphtha or gas oil and-typically boils in the range to 80C. It may contain the following hydrocarbons: isoprene, cis and trans piperylene, npentane,'isopentane, pentene-l, cyclopentadiene, dicyclopentadiene, trans-pentene-2, 2-methylbutene-2, cyclopentene, cyclopentane and benzene. In addition some C hydrocarbons may also be present. If desired this C stream may be further refined before being used in the process of the present invention, e.g.
  • the isoprene may be removed by distillation and/or the monocyclopentadiene may be dimerised by heating at a temperature of 100 to 160C, e.g. at 120C, preferably for up to 5 hours, more preferably for 0.05 to 1.5 hours.
  • the monocyclopentadiene content of the C stream may be reduced by this means the following temperature rise above 160C tends to convert some of the dimer back to the monomer. If the C stream is cooled directly from the temperature above 160C the C stream retains the increased concentration of the monocyclopentadiene and gives an inferior resin. By means of the present invention the concentration of monomer is once more reduced.
  • each tube may be maintained at the desired temperature, i.e. the conditions are isothermal or the system may be maintained under adiabatic conditions in which the heat generated by the reactions taking place may be used to obtain a temperature rise or to maintain a desired temperature.
  • the first stage may be adiabatic with the temperature rising from to 180C
  • the second may be isothermal at 180C
  • the third adiabatic at 100 to 160C, the heat of dimerisation maintaining the temperature within this range,'e.g. at to C.
  • 1f necessary cooling means may be'provided between stages to achieve the desired temperatures;
  • the C stream may be polymerised by meansof a catalyst to produce a resin.
  • Friedel Crafts catalysts are suitable, e.g. inorganic halides and inorganic strong acids.
  • Inorganic halides are generally preferred and include halides of aluminium, iron, tin, boron, zinc, antimony and titanium which may be used in conjunction with a hydrogen halide such as hydrogen chloride. For example,"
  • the Friedel Crafts catalyst is used in an aromatic solvent which is a benzene which is liquid at the temperature of the polymerisation and which is substituted by at least one secondary or tertiary alkyl group or by a cycloalkyl group, e.g. tert butyl benzene, p-cymene, p-isobutyl toluene, p-ethyl-tert amyl benzene or, in particular, cumene.
  • aromatic solvent which is a benzene which is liquid at the temperature of the polymerisation and which is substituted by at least one secondary or tertiary alkyl group or by a cycloalkyl group, e.g. tert butyl benzene, p-cymene, p-isobutyl toluene, p-ethyl-tert amyl benzene or, in particular, cumene.
  • Such catalysts are described in our copending British Patent Application No. 5097/71; (equivalent Belgian Patent No. 779,454) a complex of aluminium chloride, cumene and hydrogen chloride being preferred.
  • the polymerisation of the C feedstock is preferably carried out at a temperature of 100 to-+200C, more preferably 50 to 100C under atmospheric pressure or a positive pressure, e.g. up to 700 p.s.i.g., using a catalyst concentration of 0.05 to 5 percent, preferably 0.5 to 1.5 percent by weight of the C 'stream.
  • the catalyst is'finally broken down and removed from the polymer by treatment, for example with alcoholic ammonia, aqueous alkali or aqueous alcohol followed by one or more washes with water and,
  • Suitable alcohols are alkanols containing one to four carbon atoms, e.g. isopropanol and suitable alkalis are the alkali metal hydroxides such as sodium hydroxide.
  • the polymerisation is preferably carried out continuously more preferably by passage through a plurality of alternating polymerisation and cooling zones in which catalyst is added to each polymerisation zone.
  • the temperature rises adiabatically in each polymerisation zone only to drop in the next cooling zone preparatory to further polymerisation in the subsequent polymerization zone.
  • the cooling zones may be water cooled.
  • the polymerisation and cooling zones may comprise any vessels in which the desired processes can take place but tubular reactors are particularly suitable. In this case the preheated C feedstock together with catalyst passes through a tube in which its residence time is predetermined and through which the temperature rises due to the heat of polymerisation.
  • the next tube is cooled and the residence time of the hydrocarbon is such that the required drop in temperature takes place during the passage of the hydrocarbon along the tube.
  • the following tubular reactor is a polymerisation zone and additional catalyst is introduced into the hydrocarbon feed. There may suitably be two to eight pairs of such polymerisation and cooling zones, particularly three to five pairs. The amount of catalyst added overall is shared between the various polymerisation zones so as to achieve approximately the same temperature rise and hence the same conversion in each zone.
  • the removal of the catalyst and the final washing of the polymer may also be carried out continuously, e.g. in aseries of mixers and settlers.
  • the polymer is finally stripped of residual C stream hydrocarbons, e.g. by a steam distillation, and is then ready for use.
  • a C stream comprising isoprene, cisand transpiperylene, n-pentane, isopentane, pentene-l, cyclopentadiene, dicyclopentadiene, trans-pentene-2, 2- methylbutene-2, cyclopentene, cyclopentane and benzene is stored in storage tank 1 from which it is fed continuously to three tubular reactors 2, 3 and 4 in series.
  • the temperature of the C stream is allowed to rise adiabatically from 120C to 180C as the exothermic dimerisation of the cyclopentadiene 20 for a repeat of the isopropanol/water washing process, the isopropanol/water being fed in through line 21 and the spent wash liquor being removed via line 22.
  • a third wash with water alone takes place in mixer 23 and settler 24, the water being fed in through line 25 and removed from the mixer via line 26.
  • the washed polymer solution is held in a storage tank 27 from which it is fed to a final steam distillation unit 28 from the base of which is recovered molten resin which is solidified in, for example, pastillated form while the distillate comprising water and unreacted hydrocarbons is sent for recovery.
  • EXAMPLE 8 takes place and is then held at this temperature in the second reactor.
  • the temperature of the stream is decreased to 135C and is then held at this temperature in the third reactor.
  • the residence time of the C stream is each reactor is '5, 20 and 40 minutes respectively.
  • the hydrocarbon stream is cooled to 60C in water cooler 5 and is then fed continuously to a series of tubular polymerisation reactors 6, 7, 8 and .9 interposed with water coolers 10, ll, 12 and 13 respectively.
  • Catalyst is fed from a storage tank 14 to each polymerisation reactor.
  • the catalyst is a liquid complex of aluminium chloride, hydrogen chloride and cumene and is fed to the four polymerisation reactors in such amounts as to give the same temperature rise in each reactor.
  • the temperature of the hydrocarbon stream rises in each reactor to 90 to 100C and is then reduced to 60C in each subsequent cooler. Residence time in each reactor is approximately 3 minutes.
  • the polymerised product is mixed with 10 percent of its weight of a 1:1 mixture of water and isopropanol from line 15 in mixer 16 and then allowed to settle in settler 17.
  • the isopropanol/- water/aluminium chloride is removed from the settler by line 18 for recovery of the isopropanol while the polymer solution is pumped to a mixer 19 and settler 2.5 Kilograms of a C stream was heated to a temperature of 180C in a 5-litre autoclave and washeld at this temperature for 25 minutes.
  • the resin solution resulting from the polymerisation was stirred gently with a 1:1 mixture by volume of isopropanol and water (300 mls.) and allowed to settle. The resin layer was separated and the process repeated. Finally the resin solution was washed'with two separate amounts of water (300 mls. each). The resin was isolated by distillation, firstly at atmospheric pressure with a sidearm take-off and boiler temperature up to 180C to remove unpolymerised constituents of the C stream and lastly at 50 mm. pressure and boiler temperature 200C.
  • the yield of resin was 38% by weight based on the weight of C stream used and was found to have a Gardner colour of l 1 (50% solution in toluene), a softening point (ball and ring) of 108C and melt viscosity 4.1 poise at 200C and 78.4 poise at 130C.
  • f. is. water washed and separated from residual C hydrocarbons by distillation to yield a petroleum resin.
US00311152A 1971-12-15 1972-12-01 Petroleum resins Expired - Lifetime US3817953A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5822571A GB1404580A (en) 1971-12-15 1971-12-15 Synthetic resins derived from petroleum

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US3817953A true US3817953A (en) 1974-06-18

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US (1) US3817953A (de)
JP (1) JPS5855163B2 (de)
AU (1) AU471498B2 (de)
BE (1) BE792517R (de)
DE (1) DE2259972C3 (de)
FR (1) FR2163628B2 (de)
GB (1) GB1404580A (de)
IT (1) IT1045028B (de)
SE (1) SE401498B (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929736A (en) * 1973-04-17 1975-12-30 Nippon Oil Co Ltd Process for preparing resin for printing ink use
US3960823A (en) * 1971-11-24 1976-06-01 Nippon Zeon Co., Ltd. Hydrocarbon resins and compositions thereof
US3987123A (en) * 1974-03-04 1976-10-19 Exxon Research And Engineering Company Petroleum resins
US4068062A (en) * 1975-07-30 1978-01-10 Exxon Research And Engineering Company Polymerizing C5 and C6 olefins and diolefins with 3° hydrocarbyl halide to produce narrow molecular weight petroleum resins having low softening points
US4072808A (en) * 1976-12-29 1978-02-07 Gulf Research & Development Company Process for preparing elastomers for pressure-sensitive adhesive application
US4078132A (en) * 1975-08-13 1978-03-07 Andre Lepert "Process for preparing petroleum resins having low softening points and narrow molecular weight ranges"
US4156762A (en) * 1977-05-26 1979-05-29 Sumitomo Chemical Company, Limited Process for producing light-colored clear petroleum resins
US4187362A (en) * 1976-03-24 1980-02-05 Imperial Chemical Industries Limited Synthetic resins derived from petroleum
US4250272A (en) * 1979-05-11 1981-02-10 Shell Oil Company Adhesive compositions
US4342850A (en) * 1980-10-27 1982-08-03 Eastman Kodak Company Process for the preparation of hydrocarbon resins
US4419503A (en) * 1982-05-24 1983-12-06 Exxon Research & Engineering Co. Catalytic process for the production of petroleum resins
US4870146A (en) * 1987-07-08 1989-09-26 Tosoh Corporation Process for producing a light color high softening point hydrocarbon resin

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951928A (en) 1972-12-04 1976-04-20 Imperial Chemical Industries Limited Petroleum resins

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2750359A (en) * 1953-01-08 1956-06-12 Exxon Research Engineering Co Resins from steamcracked c5 distillate fractions
US2775576A (en) * 1952-10-01 1956-12-25 Exxon Research Engineering Co Polymers from steam cracked distillate streams of 18 deg.-54 deg. c. boiling range
US2817647A (en) * 1953-07-03 1957-12-24 British Petroleum Co Thermal polymerization of petroleum hydrocarbon fraction
US3709854A (en) * 1970-09-07 1973-01-09 Ici Ltd Petroleum resins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2775576A (en) * 1952-10-01 1956-12-25 Exxon Research Engineering Co Polymers from steam cracked distillate streams of 18 deg.-54 deg. c. boiling range
US2750359A (en) * 1953-01-08 1956-06-12 Exxon Research Engineering Co Resins from steamcracked c5 distillate fractions
US2817647A (en) * 1953-07-03 1957-12-24 British Petroleum Co Thermal polymerization of petroleum hydrocarbon fraction
US3709854A (en) * 1970-09-07 1973-01-09 Ici Ltd Petroleum resins

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960823A (en) * 1971-11-24 1976-06-01 Nippon Zeon Co., Ltd. Hydrocarbon resins and compositions thereof
US3929736A (en) * 1973-04-17 1975-12-30 Nippon Oil Co Ltd Process for preparing resin for printing ink use
US3987123A (en) * 1974-03-04 1976-10-19 Exxon Research And Engineering Company Petroleum resins
US4068062A (en) * 1975-07-30 1978-01-10 Exxon Research And Engineering Company Polymerizing C5 and C6 olefins and diolefins with 3° hydrocarbyl halide to produce narrow molecular weight petroleum resins having low softening points
US4078132A (en) * 1975-08-13 1978-03-07 Andre Lepert "Process for preparing petroleum resins having low softening points and narrow molecular weight ranges"
US4187362A (en) * 1976-03-24 1980-02-05 Imperial Chemical Industries Limited Synthetic resins derived from petroleum
US4072808A (en) * 1976-12-29 1978-02-07 Gulf Research & Development Company Process for preparing elastomers for pressure-sensitive adhesive application
US4156762A (en) * 1977-05-26 1979-05-29 Sumitomo Chemical Company, Limited Process for producing light-colored clear petroleum resins
US4250272A (en) * 1979-05-11 1981-02-10 Shell Oil Company Adhesive compositions
US4342850A (en) * 1980-10-27 1982-08-03 Eastman Kodak Company Process for the preparation of hydrocarbon resins
US4419503A (en) * 1982-05-24 1983-12-06 Exxon Research & Engineering Co. Catalytic process for the production of petroleum resins
US4870146A (en) * 1987-07-08 1989-09-26 Tosoh Corporation Process for producing a light color high softening point hydrocarbon resin

Also Published As

Publication number Publication date
IT1045028B (it) 1980-04-21
DE2259972A1 (de) 1973-07-12
DE2259972C3 (de) 1979-05-17
JPS5855163B2 (ja) 1983-12-08
AU471498B2 (en) 1976-04-29
AU4982772A (en) 1974-06-13
GB1404580A (en) 1975-09-03
BE792517R (fr) 1973-06-08
JPS4866604A (de) 1973-09-12
SE401498B (sv) 1978-05-16
FR2163628A2 (de) 1973-07-27
DE2259972B2 (de) 1976-09-23
FR2163628B2 (de) 1979-03-02

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