NO742146L - - Google Patents
Info
- Publication number
- NO742146L NO742146L NO742146A NO742146A NO742146L NO 742146 L NO742146 L NO 742146L NO 742146 A NO742146 A NO 742146A NO 742146 A NO742146 A NO 742146A NO 742146 L NO742146 L NO 742146L
- Authority
- NO
- Norway
- Prior art keywords
- ethylene
- polymerization
- carried out
- type
- compound
- Prior art date
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000012429 reaction media Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 150000003682 vanadium compounds Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 206010039509 Scab Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerisation Methods In General (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
Fremgangsmåte for fremstilling av Method of manufacture of
polyetylen.polyethylene.
Foreliggende oppfinnelse vedrorer en fremgangsmåte for fremstilling av polyetylen som gjennomfores i et reaksjonsmedium som utgjores av flytende etylen i en mengde storre enn 90%. The present invention relates to a method for the production of polyethylene which is carried out in a reaction medium which consists of liquid ethylene in an amount greater than 90%.
Det er kjent at i etylen-polymeriseringsprosesser, er hoved-funksjonen for reaksjonsmediet transport av masse og varme i en reaktor mot dennes vegg, idet det meste av varmen utvikles ved polymeriseringen av etylen. It is known that in ethylene polymerization processes, the main function of the reaction medium is the transport of mass and heat in a reactor towards its wall, as most of the heat is developed during the polymerization of ethylene.
Bruk av dette reaksjonsmedium utgjor en belastning på prosessenUse of this reaction medium places a strain on the process
da det må resirkuleres.as it must be recycled.
Resirkuleringen kan være særlig komplisert og dyr når reaktor-mediet under arbeidet med å rense polymeren for katalysatorrester, er forurenset ved polare forbindelser som ikke er blandbare med katalysatorsystemet for polymeriseringen, slik at det er nodvendig å fjerne dem ved hjelp av dyre rektifiseringer eller ekstraksjoner. The recycling can be particularly complicated and expensive when, during the work to clean the polymer of catalyst residues, the reactor medium is contaminated by polar compounds that are not miscible with the catalyst system for the polymerization, so that it is necessary to remove them by means of expensive rectifications or extractions.
Det er nå funnet at det er mulig å polymerisere etylen uten de ovennevnte mangler ved at det som reaksjonsmedium anvendes etylen i flytende tilstand i nærvær av et katalysatorsystem valgt blant en av de folgende par av forbindelser, It has now been found that it is possible to polymerize ethylene without the above-mentioned shortcomings by using ethylene as a reaction medium in a liquid state in the presence of a catalyst system selected from one of the following pairs of compounds,
A) en overgangsmetallforbindelse tilhorende en gruppe fra IVA) a transition metal compound belonging to a group from IV
til VIII i det periodiske system og en polymeraluminium-forbindelse av polyimin-karakter som inneholder gjentagende enheter av typen (HAI-NR), hvori R er et aryl-, cykloalkyl-eller alkyl-hydrokarbon-radikal. B) en aluminiumforbindelse av typen A1RX2, hvori R er et alkyl, aryl eller cykloalkyl-radikal og X er et halogen, og en vanadium-forbindelse av typen V (NR2)4hvori R har den ovennevnte betydning. to VIII in the periodic table and a polymer aluminum compound of polyimine character containing repeating units of the type (HAI-NR), in which R is an aryl, cycloalkyl or alkyl hydrocarbon radical. B) an aluminum compound of the type A1RX2, in which R is an alkyl, aryl or cycloalkyl radical and X is a halogen, and a vanadium compound of the type V (NR2)4 in which R has the above meaning.
Omsetningen gjennomfores ved polymeriseringstemperaturer lavere enn den kritiske temperatur for etylen, generelt opp til -80°C og ved trykk som tilsvarer eller er litt hoyere enn damptrykket for flytende etylen ved polymeringstemperaturen. The reaction is carried out at polymerization temperatures lower than the critical temperature for ethylene, generally up to -80°C and at pressures that correspond to or are slightly higher than the vapor pressure of liquid ethylene at the polymerization temperature.
Omsetningen igangsettes ved det av det katalytiske system, fortsetter til den onskede omdannelsesgrad, avhengig av oppholdstiden i reaktoren, temperaturen og mengden av tilsatt katalysator og stoppes til slutt ved hjelp av en enkel avdamping av resterende etylen i en beholder ved et trykk lavere enn damptrykket for flytende etylen ved polymeriseringstemperaturen. The reaction is initiated by the catalytic system, continues to the desired degree of conversion, depending on the residence time in the reactor, the temperature and the amount of added catalyst, and is finally stopped by means of a simple evaporation of the remaining ethylene in a container at a pressure lower than the vapor pressure of liquid ethylene at the polymerization temperature.
Polyetylen som oppsamles i form av skorper er praktisk talt fritt for rester av reaksjonsmediet. Polyethylene that is collected in the form of crusts is practically free of residues of the reaction medium.
En fordel er det faktum at polymeriseringsreaktoren kan være ytterst enkel, f.eks. et ror med regulert utslipping, da termostattemperaturer i reaktoren sikres ved kokende etylen. An advantage is the fact that the polymerization reactor can be extremely simple, e.g. a rudder with regulated discharge, as thermostatic temperatures in the reactor are ensured by boiling ethylene.
Polymerisasjonsvarmen må fjernes mens den fri varme kan gjenvinnes ved hjelp av egnete varmevekslere. The polymerization heat must be removed while the free heat can be recovered using suitable heat exchangers.
Fremgangsmåten i henhold til oppfinnelsen er egnet for polymerisering av etylen til homopolymer, men det er også mulig å fremstille også etylenkopolymerer, hvor da under polymeriseringen den flytende fase i det vesentlige utgjores av etylen, i mengdeforhold tilsvarende de relative reaktiviteter av de tilstedeværende monomerer. The method according to the invention is suitable for the polymerization of ethylene to homopolymer, but it is also possible to also produce ethylene copolymers, where during the polymerization the liquid phase is essentially made up of ethylene, in quantities corresponding to the relative reactivities of the monomers present.
Eksempel 1.Example 1.
966 g etylen ved temperatur -20°C ble innfort i en autoklav med indre volum på 3,2 1, forsynt med roreverk, termometer-uttak og termostat-kappe. Mengden av tilfort etylen beregnes ved hjelp av en passende kalibrert stromningsmåler. 15 cm av n-heptan inneholdende polyiminoalan (PIA) (5,25 mg atom Al), trukket ut fra en liten flaske ved hjelp av nitrogenovertrykk, ble innfort i autoklaven. Den lille flasken ble vasket 966 g of ethylene at a temperature of -20°C was introduced into an autoclave with an internal volume of 3.2 1, provided with agitator, thermometer outlet and thermostat jacket. The amount of added ethylene is calculated using a suitably calibrated flow meter. 15 cm of n-heptane containing polyiminoalane (PIA) (5.25 mg atomic Al), withdrawn from a small bottle by nitrogen overpressure, was introduced into the autoclave. The little bottle was washed
3 3
med 15 cm losningsmiddel.with 15 cm of solvent.
Blandingens temperatur ble bragt sakte til -10°C under omroring. The temperature of the mixture was slowly brought to -10°C with stirring.
Et trykk på 31 kg/cm 2 ble oppnådd.A pressure of 31 kg/cm 2 was achieved.
15 cm<3>n-heptan inneholdende 0,4 millimol VOCl'^ble så innfort ved hjelp av den samme teknikk. 15 cm<3>n-heptane containing 0.4 mmol VOCl'^ was then introduced using the same technique.
Omsetningen begynte umiddelbart med utvikling av varme som frem-bragte okning i temperatur og trykk. The turnover began immediately with the development of heat which produced an increase in temperature and pressure.
Etter 30 minutter ble overskudd av etylen sluppet ut og det ble oppnådd 56,4 g polymer med = 20,7. After 30 minutes, excess ethylene was released and 56.4 g of polymer with = 20.7 was obtained.
Katalysatoraktiviteten var 2,7 kg polymer/g vanadium.The catalyst activity was 2.7 kg polymer/g vanadium.
Eksempel 2.Example 2.
Ved å anvende apparatet beskrevet i det foregående eksempel ogBy using the apparatus described in the previous example and
med de samme arbeidsbetingelser ble autoklaven tilfort 900 g etylen ved temperatur -20°C, deretter ble det omrort og i samme reaktor ble det innfort 15 cm 3 heptan, inneholdende polyiminoalan (PIA) (5,25 mg atomAl), trukket ut fra en liten flaske ved hjelp av et nitrogenovertrykk. with the same working conditions, the autoclave was fed 900 g of ethylene at a temperature of -20°C, then it was stirred and in the same reactor was introduced 15 cm 3 of heptane, containing polyiminoalane (PIA) (5.25 mg atomic Al), extracted from a small bottle using a nitrogen overpressure.
3 3
Den lille flasken ble vasket med 15 cm heptan.The small bottle was washed with 15 cm of heptane.
Blandingen ble under omroring holdt konstant på temperatur -10°C ved hjelp av termostatvirkning og deretter ble det injisert 15 cm<3>n-heksan inneholdende 0,9 millimol Ti Cl^. The mixture, while stirring, was kept constant at a temperature of -10°C by means of a thermostatic effect and then 15 cm<3>n-hexane containing 0.9 millimoles of Ti Cl^ was injected.
Polymeriseringen begynte umiddelbart og temperatur og trykk steg. Polymerization began immediately and temperature and pressure increased.
Etter 30 minutter ble uomsatt etylen sluppet ut og 145 g polymer med grenseviskositet 12,9 dl/g ble oppnådd. After 30 minutes, unreacted ethylene was released and 145 g of polymer with an intrinsic viscosity of 12.9 dl/g was obtained.
Katalysatoren ga 3,4 kg polymer/g Ti.The catalyst gave 3.4 kg polymer/g Ti.
Eksempel 3.Example 3.
Ved å arbeide på samme måte som i det foregående eksempel bleBy working in the same way as in the previous example
det til autoklaven tilfort 900 g etylen. Deretter ble 15 cm<3>inneholdende 6 millimol Al Et Cl9 innfort i samme autoklav og.. inneholdende 6 millimol Al Et z3i samme autoklav og..". 900 g of ethylene were added to the autoclave. Then 15 cm<3> containing 6 millimoles of Al Et Cl9 was introduced into the same autoclave and.. containing 6 millimoles of Al Et z3 in the same autoclave and..".
en liten flaske som ble vasket med. 15 cm løsningsmiddel. a small bottle that was washed with. 15 cm solvent.
Autoklaven ble så omrort og holdt ved termostat på temperatur -10°C. Autoklavtrykket var 31 kg/cm 2. The autoclave was then stirred and kept at a thermostat at a temperature of -10°C. The autoclave pressure was 31 kg/cm 2.
På dette tidspunkt ble det tilfort 15 cm 3 n-heptan inneholdende 0,15 millimol V (N(CH3)2)4.At this point, 15 cm 3 of n-heptane containing 0.15 millimoles of V (N(CH 3 ) 2 ) 4 was added.
Reaksjonen fortsetter uten særlige variasjoner i trykk og temperatur. The reaction continues without particular variations in pressure and temperature.
3 * 3 *
Etter 30 minutter ble det innfort 30 cm aceton ved hjelp av .nitrogen-dvertrykk. Overskudd av etylen ble sluppet ut og det ble oppnådd 5,4 g polyetylen med fZJ 23,2. After 30 minutes, 30 cm of acetone was introduced by means of nitrogen underpressure. Excess ethylene was released and 5.4 g of polyethylene with fZJ 23.2 was obtained.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25394/73A IT989189B (en) | 1973-06-15 | 1973-06-15 | PROCESS FOR THE PRODUCTION OF POLYETHYLENE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO742146L true NO742146L (en) | 1975-01-13 |
Family
ID=11216573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO742146A NO742146L (en) | 1973-06-15 | 1974-06-13 |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5036583A (en) |
| BE (1) | BE816218A (en) |
| CA (1) | CA1028449A (en) |
| CH (1) | CH603703A5 (en) |
| CS (2) | CS183750B2 (en) |
| DD (1) | DD111914A5 (en) |
| DE (1) | DE2428561A1 (en) |
| DK (1) | DK135457B (en) |
| FR (1) | FR2233341B1 (en) |
| GB (2) | GB1442465A (en) |
| HU (1) | HU169265B (en) |
| IT (1) | IT989189B (en) |
| LU (1) | LU70328A1 (en) |
| NL (1) | NL7408089A (en) |
| NO (1) | NO742146L (en) |
| SE (1) | SE7407990L (en) |
| ZA (1) | ZA743819B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1015582B (en) * | 1974-07-01 | 1977-05-20 | Snam Progetti | PROCESS FOR THE POLYMERIZATION OF ETHYLENE |
| EP0001186B1 (en) | 1977-09-14 | 1981-08-12 | BP Chemicals Limited | Process for producing polyisobutenes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1369866A (en) * | 1962-09-25 | 1964-08-14 | Snam Spa | Process for the catalytic polymerization of mono-olefins and di-olenes |
| NL125866C (en) * | 1965-02-03 |
-
1973
- 1973-06-15 IT IT25394/73A patent/IT989189B/en active
-
1974
- 1974-05-24 GB GB2347374A patent/GB1442465A/en not_active Expired
- 1974-05-24 GB GB837876A patent/GB1466848A/en not_active Expired
- 1974-06-05 CH CH769574A patent/CH603703A5/xx not_active IP Right Cessation
- 1974-06-10 FR FR7419954A patent/FR2233341B1/fr not_active Expired
- 1974-06-12 BE BE145324A patent/BE816218A/en unknown
- 1974-06-13 NO NO742146A patent/NO742146L/no unknown
- 1974-06-13 DD DD179148A patent/DD111914A5/xx unknown
- 1974-06-13 JP JP49066635A patent/JPS5036583A/ja active Pending
- 1974-06-14 LU LU70328A patent/LU70328A1/xx unknown
- 1974-06-14 HU HUSA2659A patent/HU169265B/hu unknown
- 1974-06-14 DK DK319574AA patent/DK135457B/en unknown
- 1974-06-14 CA CA202,689A patent/CA1028449A/en not_active Expired
- 1974-06-14 DE DE19742428561 patent/DE2428561A1/en active Pending
- 1974-06-14 ZA ZA00743819A patent/ZA743819B/en unknown
- 1974-06-17 NL NL7408089A patent/NL7408089A/xx not_active Application Discontinuation
- 1974-06-17 SE SE7407990A patent/SE7407990L/xx unknown
- 1974-06-17 CS CS7600007840A patent/CS183750B2/en unknown
- 1974-06-17 CS CS7400004253A patent/CS183741B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1442465A (en) | 1976-07-14 |
| DE2428561A1 (en) | 1975-01-09 |
| DK319574A (en) | 1975-02-10 |
| CA1028449A (en) | 1978-03-21 |
| SE7407990L (en) | 1974-12-16 |
| AU6963174A (en) | 1975-12-04 |
| NL7408089A (en) | 1974-12-17 |
| BE816218A (en) | 1974-09-30 |
| FR2233341B1 (en) | 1977-09-30 |
| FR2233341A1 (en) | 1975-01-10 |
| DK135457C (en) | 1977-10-17 |
| HU169265B (en) | 1976-10-28 |
| CS183750B2 (en) | 1978-07-31 |
| IT989189B (en) | 1975-05-20 |
| GB1466848A (en) | 1977-03-09 |
| DK135457B (en) | 1977-05-02 |
| LU70328A1 (en) | 1974-10-17 |
| ZA743819B (en) | 1975-06-25 |
| CH603703A5 (en) | 1978-08-31 |
| CS183741B2 (en) | 1978-07-31 |
| DD111914A5 (en) | 1975-03-12 |
| JPS5036583A (en) | 1975-04-05 |
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