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
  • C08F10/02—Ethene
• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene

Definitions

• the present invention relates to processes for the production of ethylene homopolymers and copolymers in a tubular reactor at temperatures from 160 ° C to 350 ° C and pressures in the range from 500 to 5000 bar, optionally * r use of molecular weight regulators, characterized in that as Polymerization initiator uses a peroxide mixture which contains 1 to 95 mol%, based on the total amount of the peroxide mixture, of at least one cyclic peroxide of the formula I.
• radicals R being identical or different and being selected from alkyl groups or aryl groups.
• the high-pressure polymerization process is a proven process for the production of low-density polyethylene (LDPE), which is carried out with great success on a large scale in numerous plants worldwide.
• the start of the polymerization in high-pressure polymerization is usually effected by atmospheric oxygen, by peroxides, by other free radical formers or by mixtures of these. In practice, it has proven to be particularly advantageous to start the polymerization reaction at several points within the reactor at the same time and thus to keep the reactor yield high and to keep the product quality at a uniformly high level.
• the radical chain initiators used to start the polymerization must be added to the reaction medium in a suitable manner.
• the reaction is generally carried out such that several peroxides are metered in first at the starting point, that is to say at the start of the reactor, at least one of which decomposes at a comparatively low temperature.
• EP-B 0 813 550 teaches that cyclic peroxo compounds of the general formulas P 1 to P 3 are particularly suitable for polymerizing styrene or acrylates. It also follows that these can also be used for the polymerization of ethylene.
• the radicals R 1 to R 6 are independently hydrogen, C ⁇ -C 2 o alkyl, C 3 -C 2 o cycloalkyl, C 6 * -Co aryl, CC 2 o aralkyl and C-Co alkaryl, the radicals R 1 to R 6 can also carry substituents such as alkyl, aryl alkoxy, aryloxy, hydroxy, carboxyl, hydroxyl, halogen, nitrile or amido.
• P1 P 2 P 3 It has been shown that the conversion using the most important conventional polymerization initiators is still too low.
• the most important conventional polymerization initiators are dibenzoyl peroxide, di-tert-butyl peroxide (DTBP), tert-butyl perpivalate (“TBPP”) and tert-butyl perisononanoate (“TBPIN”). If the turnover is too low, the economy of the high pressure process is impaired.
• the revenue from use of the peroxides of the formulas P 1 to P 3 are for most of these Verb ⁇ ⁇ "*" gen still too low or the amount of initiator to good sales -._- achieve is too high.
• the object was therefore to provide a process by which the conversion in the high-pressure polymerization of ethylene is increased further or the consumption of initiator is reduced.
• a process has now been found for the production of ethylene homopolymers and copolymers in a tubular reactor at temperatures from 160 ° C. to 350 ° C. and pressures in the range from 500 to 5000 bar, if appropriate using molecular weight regulators, characterized in that the polymerization initiator used is a peroxide mixture which contains 1 to 95 mol%, based on the total amount of the peroxide mixture, of at least one cyclic peroxide of the formula I,
• R being identical or different and being selected from alkyl groups or aryl groups.
• R is preferably a C ⁇ -Co linear, branched or cyclic alkyl or a Ce-Ci ⁇ -aryl.
• R is selected from
• Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl, tert.-butyl, n-pentyl, sec.-pentyl, iso-pentyl, n -Hexyl, cyclohexyl, n-heptyl, n-octyl, preferably linear C ⁇ -C 6 -alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-hexyl, particularly preferably linear C ⁇ * -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, very particularly preferred are all three radicals ethyl; and C ⁇ -Ci 4 aryl such as phenyl
• Such trimeric ketone peroxides can be prepared by condensing the corresponding ketones with hydrogen peroxide in the presence of strong mineral acids and is described in the literature (for example R. ⁇ ' gee, in Methods of Organic Chemistry (Houben-Weyl), Vol. 8, p. 6 , Georg-Thieme-Verlag Stuttgart 1952 or in EP-A 0 813 550).
• the polymerization is started in each reaction zone by adding free-radical initiators, the peroxide mixtures according to the invention being used in at least one reaction zone.
• the peroxide mixtures according to the invention are preferably used in several or each reaction zone.
• Any polymerization initiators, such as e.g. free radical, preferably organic, peroxides, air or oxygen are used.
• the peroxide mixtures according to the invention are defined in such a way that on the one hand they contain at least one so-called high-decomposition peroxide, which is also called “high-decay”, because it disintegrates only at relatively high temperatures and, on the other hand, contain at least one so-called medium-decaying peroxide, which is also referred to as a "medium-decay” because it disintegrates at medium high temperatures.
• Low decayers have a half-life of 0.1 hours at temperatures below 100.
• Medium decays have a half-life of 0.1 hours at temperatures from 100 to 140 ° C.
• High decay has a half-life of 0.1 hours at temperatures above 140 ° C.
• tert-butyl peroxybenzoate di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2, 5-dimethyl-2, 5-di-tert. -butylperoxyhexane, tert. -Butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert -butylperoxy) -hex-3-in, di-tert. ⁇ butyl peroxide, 1, 3-diisopropyl monohydroperoxide, cumene hydroperoxide or tert. Butyl hydroperoxide.
• the trimeric ketone peroxides of the general formula I can be classified as high disintegrators.
• the half-lives of peroxides are usually determined using a commonly used laboratory method:
• ampoules or test tubes are prepared with a diluted solution of concentration c 0 with less than 0.2 mol / 1, preferably less than 0.1 mol / 1, of the peroxide to be examined, the solvent used being an inert, ie not a Peroxide reacting solvent is chosen; benzene, toluene or chlorobenz are preferred
• ampoules are thermostatted at a defined temperature. At defined intervals, for example 1, 2, 3, 4, 6, 8 hours, one ampoule is removed, quickly cooled and then examined for the residual peroxide content c t . This investigation
• the peroxides B) used are preferably one or more medium breakdowns or mixtures of one or more medium breakdowns and one or more low breakdowns. 25
• Peroxide mixtures consisting of are particularly preferred as the polymerization initiators according to the invention
• B ' 20 to 99% by weight of one or more conventional peroxides as medium disintegrators, preferably 30 to 98 mol% and particularly preferably 40 to 97 mol%.
• Particularly preferred in the first reaction zone is an initiator mixture of 1 to 10 mol% A '), 40 to 60 mol% B') and 40 to 45 60 mol% C), where A '), B') and C ) Result in 100%.
• a mixture of 5 to 40 mol% A ') and 60 to 95 mol% B') is preferably used in the following reaction zones.
• the peroxides which are extremely sensitive to shock and impact in the pure state, are advantageously metered in as a solution in aliphatic hydrocarbons, octane and isododecane being examples of solvents.
• the solutions contain the peroxide mixtures in proportions of 5 to 60% by weight, preferably 15 to 40% by weight.
• the polymerization initiator mixtures according to the invention are fed in according to the invention in amounts in the range from 0.5 to 100 mol / t of polyethylene produced, preferably from 1 to 10 mol / t and particularly preferably from 1 to 5 mol / t of polyethylene produced.
• the polymerization is carried out at pressures of 500 to 5000 bar, pressures of 1500 and 3500 bar being preferred and pressures of 2000 to 3300 bar being particularly preferred.
• the reaction temperatures are above 40 ° C.
• the reaction temperature is 150 ° C. to 350 ° C., preferably 250 ° C. to 330 ° C. and very particularly preferably 270 ° C. to 320 ° C.
• the process according to the invention can be used both for homopolymerization and for the copolymerization of ethylene with other monomers, provided that these monomers copolymerize radically with ethylene under high pressure.
• suitable copolymerizable monomers are ⁇ , ⁇ -ethylenically unsaturated C 3 to Cs carboxylic acids, in particular maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and crotonic acid, ⁇ , ⁇ -ethylenically unsaturated C 3 to cis carboxylic acid esters or anhydrides, in particular methyl methacrylate, methyl methacrylate, n-butyl methacrylate or tert-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, tert-acrylate.
• butyl ester methacrylic anhydride, maleic anhydride or itaconic anhydride and ⁇ -olefins, such as propene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene.
• vinyl carboxylates particularly preferably vinyl acetate, can be used as co-monomers.
• the proportion of comonomer or comonomers in the reaction mixture is 1 to 45% by weight, preferably 3 to 35% by weight, based on the amount of ethylene monomer.
• the flowing reaction mixture according to the invention can contain polyethylene in an amount in the range from 0 to 40% by weight, based on the total weight of the monomers, preferably from 1 to 30% by weight.
• the molar mass of the polymers to be prepared can be controlled as usual by adding molecular weight regulators.
• suitable controllers are aliphatic and olefinic hydrocarbons, such as pentane, hexane, cyclohexane, propene, pentene or hexene, ketones such as acetone, diethyl ketone or diamyl ketone, aldehydes such as formaldehyde or acetaldehyde and saturated aliphatic alcohols such as methanol, ethanol , Propanol or butanol.
• Saturated aliphatic aldehydes in particular propionaldehyde or ⁇ -olefins, such as propene or hexene, are particularly preferably used.
• the molecular weight regulator is preferably metered into the reaction mixture before the tube reaction. It can also be metered in together with the polymerization initiator at the different points along the tube reactor.
• polymerization initiator is metered in at 2 to 6 points, particularly preferably at 3 to 5 points, along the tube reactor, so that 2 to 6 reaction zones are formed.
• the entire amount of monomer and, if desired, comonomer is preferably metered in at the reactor inlet.
• the tubular reactor has at least two reaction zones, into each of which additional cold or preheated monomer and / or cold or preheated comonomer is metered in as a fresh gas stream before the start of each reaction zone. At least three successive reaction zones are preferred, the polymerization in each zone having to be restarted by adding the appropriate initiators.
• Tube reactors which are provided with a series of inlet points for the initiator and for the supply of further amounts of monomer.
• Reactors as described in US Pat. Nos. 4,135,044 and 4,175,169 can also be operated using the process according to the invention.
• the tube reactor has a comparatively smaller tube diameter in each reaction zone, from the initiator metering to the maximum temperature, based on the enlarged tube diameter in the subsequent cooling zone (from the maximum temperature to the next initiator metering). This enables a high conversion to be achieved with a relatively low pressure drop over the length of the reactor.
• the tubular reactor can usually be provided with a cooled jacket to remove the heat of reaction.
• a hot water jacket is preferred here, although this can also be segmented.
• the ratio of length to diameter of the tubular reactor is preferably in the range from 10,000 to 50,000, particularly preferably 15,000 to 35,000.
• the average residence time of the reaction mixture in the tubular reactor is between 30 and 300, in particular 30 and 120 seconds.
• the reaction mixture After the last metering in of the polymerization initiator, the reaction mixture is cooled in order to be able to discharge the product from the reactor.
• the reaction mixture is expelled through a suitable high pressure relief valve system at the outlet end of the tubular reactor. Nac. in the discharge of the reaction mixture, the polymer is separated by depressurization of unused ethylene and optionally unused comonomer, after which the monomers are generally returned to the reactor.
• This process according to the invention can also be carried out in an analogous manner with a reactor upstream with backmixing.
• the polymerization mixture together with as yet unused monomers is introduced into the tube reactor through a high-pressure tube, which may also be connected to a heat exchanger, where the process is continued as described above.
• the average residence time of the mixture in the reactor with backmixing is 10 to * 100, in particular 10 to 30 seconds, in the tubular reactor 10 to 200, in particular 10 to 100 seconds.
• Ethylene homopolymers and copolymers with particularly favorable properties can be prepared by the process according to the invention.
• the polymers can furthermore be produced safely and exactly reproducibly using the process according to the invention, without causing an explosive decomposition of the ethylene in the reactors.
• the polymers according to the invention have densities from 918 to 930 kg / m 3 , preferably from 918 to 926 kg / m 3 and particularly preferably from 920 to 925 kg / m 3 .
• the density can be influenced, for example, via the chain regulator and / or the comonomers.
• the melt flow index according to DIN 53 735 (190 ° C / 2.16 kg) is usually less than 50 g / 10 min, in particular less than 10 g / 10 min and particularly preferably less than 5 g / 10 min. In the manner described above, it is possible to produce polymers with densities above 918 kg / m 3 and conversions of more than 25%.
• the process according to the invention makes it possible to significantly reduce the amount of radical chain starter added with the same amount of LDPE (low-density polyethylene) produced, and thus to operate the high-pressure polymerization more economically.
• the polymer prepared by the process according to the invention in particular LDPE, is particularly well suited for the production of films or film products. Films or film products which are produced from the polymers according to the invention have excellent optical and mechanical properties. Films with an elongation at break perpendicular to the machine direction of greater than 750% and a dart drop impact of greater than 100 are preferred.
• the processability of these polymers is also particularly favorable because the build-up of pressure in the extruder is lower shortly before the nozzle.
• the process according to the invention also has the advantage that stable reactor operation can be maintained at unusually high maximum temperatures of up to 320 ° C. without a tendency to decompose.
• Examples 1-3 and comparative experiments A, B, C and D were carried out in a tubular reactor vessel with a length of 560 m and a length to diameter ratio of 33,000.
• the polymerization initiators were dissolved in aliphatic hydrocarbons and fed directly to the feed points of the tubular reactor by means of high-pressure piston pumps.
• the length of the reaction zones in the reaction vessel was determined by the location of the feed points.
• the oxygen-free ethylene was compressed to the respective reaction pressure in several stages, a molar mass regulator was added and the inlet points of the tubular reactor were fed. Propionaldehyde was used as the molecular weight regulator.
• the heat of reaction released during the polymerization was removed from the reaction mixture via a coolant circuit.
• the resulting polymer was separated in a customary and known manner in the separator downstream of unreacted ethylene and other low molecular weight compounds and discharged and packaged using an extruder and granulator. Unreacted ethylene was cleaned in several stages and returned to the suction side of the compressor. The details can be found in Ullman's Encyclopedia of Industrial Chemistry, Volume 19, pp. 169-178 (1980).
• tert-butyl perpivalate TBPP
• Butyl perisononanoate TBPIN
• 3, 6, 9-trimethyl-3, 6, -triethyl-l, 4, 7-triperoxonane TPN
• Ditert. -butyl peroxide DTBP
• methyl isobutyl ketone peroxide MIKP.
• the properties of the resulting polymers were determined using the following methods: the melt flow index (MFI) at a temperature of 190 ° C. and a contact force of 2.16 kp according to ISO 1133 and the density according to ISO 1183.
• MFI melt flow index
• Blown films were produced from the polymers in a customary and known manner (see Ullmans Encyclopedia of Industrial Chemistry, Volume 11, p.673 (1980)), the application properties of which were determined by the following methods: the light scattering of the film in accordance with DIN 53 490 , the gloss of the film according to DIN 67 530, the elongation at break of the film according to ISO 527, the puncture resistance of the film according to DIN 53 373, the "dart drop impact value" according to ASTM D 1709 / A Determined during the tubular film extrusion when pulling and winding the film. The take-off speed was increased gradually by 2 m / min after every 20 s until the film broke.
• the examples according to the invention describe the production (Table 1) and the properties (Table 2) of the polymers or the films produced therefrom, which can be compared directly with the polymers described in the comparative examples.
• TBPP tert-butyl perpivalate
• TBPIN tert-butyl perisononanoate
• TPN 3,6,9-trimethyl-3, 6, 9-triethyl-1,4, 7-triperoxonane
• TPN 7-triperoxonane
• the peak values of the temperature in the 1st, 2nd and 3rd reaction zones for the individual experiments can be found in Table 1.
• the resulting ethylene polymer was freed of ethylene and low molecular weight impurities in a customary and known manner in high and low pressure separators, temporarily stored in bunkers and processed into blown films.
• Table 1 also provides information on the conversion of the reaction, the specific consumption of the highly decomposing peroxides and the total peroxide consumption.
• the physicochemical properties of the ethylene homopolymer and the application properties of the blown film produced from them are summarized in Table 2.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerization Catalysts (AREA)
• Graft Or Block Polymers (AREA)
• Polymerisation Methods In General (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (2)

Family

ID=7634885

Family Applications (1)

Country Status (8)

Cited By (43)

Families Citing this family (15)

Family Cites Families (8)

• 2001
  • 2001-03-13 US US10/221,202 patent/US6844408B2/en not_active Expired - Lifetime
  • 2001-03-13 DE DE50102850T patent/DE50102850D1/de not_active Expired - Lifetime
  • 2001-03-13 CN CNB01809466XA patent/CN1186358C/zh not_active Expired - Lifetime
  • 2001-03-13 EP EP01929431A patent/EP1263812B1/de not_active Revoked
  • 2001-03-13 JP JP2001567811A patent/JP2003527474A/ja not_active Ceased
  • 2001-03-13 AU AU2001256204A patent/AU2001256204A1/en not_active Abandoned
  • 2001-03-13 WO PCT/EP2001/002796 patent/WO2001068723A2/de not_active Ceased
  • 2001-03-13 AT AT01929431T patent/ATE271075T1/de active

Also Published As

Similar Documents

Legal Events