DE874215C - Process for the production of solid polymers from ethylene or ethylene-rich gases - Google Patents
Process for the production of solid polymers from ethylene or ethylene-rich gasesInfo
- Publication number
- DE874215C DE874215C DEB7335D DEB0007335D DE874215C DE 874215 C DE874215 C DE 874215C DE B7335 D DEB7335 D DE B7335D DE B0007335 D DEB0007335 D DE B0007335D DE 874215 C DE874215 C DE 874215C
- Authority
- DE
- Germany
- Prior art keywords
- ethylene
- production
- solid polymers
- rich gases
- polymers
- 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.)
- Expired
Links
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
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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
Verfahren zur Herstellung von festen Polymerisaten aus Äthylen oder äthylenreichen Gasen 13s ist bekannt, daß man Äthylen oder äthvlenreiche Gase .mit Hilfe von Aluminiumchlorid unter Druck und bei erhöhter Temperatur zu schmierölartigen Erzeugnissen polymerisieren kann. Dabei beobachtet man gelegentlich, daß die höher vish;osen Üle nach der Reinigung von anorganischen Bestandteilen Trübungen und Ausscheidungen fester Stoffe zeigen. Diese kommen wahrscheinlich dadurch zustande, daß höhere feste Kohlenwasserstoffe in feinverteilter Form in dem flüssigen Polymerisat enthalten sind. Es wurde nun gefunden, daß man den Verlauf der Polymerisation derart beeinflussen kann, daß die Bildung flüssiger Polymerisate zugunsten der Bildung höherer fester Stoffe zurückgedrängt wird und diese in größerer Menge gebildet «erden, wenn man als Katalysator Aluminiumchlorid mit einem Zusatz von Titantetrachlorid und gegebenenfalls mit Zusätzen anderer Halogenide aus der Reihe der Friedel-Crafts-Katalvsatoren verwendet. Besonders leicht entstehen diese festen Stoffe, wenn man außerdem noch chlorwasserstoffbindende Metalle, wie Eisen, Zink oder Aluminium, in feinverteilter Form, vorteilhaft Aluminiumpulver, zugibt.Process for the production of solid polymers from ethylene or Ethylene-rich gases 13s it is known that ethylene or ethylene-rich gases can be used Using aluminum chloride under pressure and at elevated temperature to create lubricating oil-like Can polymerize products. Occasionally one observes that the higher vish; osen oil after cleaning of inorganic constituents, cloudiness and excretions show solid substances. These are probably due to the fact that higher fixed Contain hydrocarbons in finely divided form in the liquid polymer are. It has now been found that the course of the polymerization can be influenced in this way can that the formation of liquid polymers in favor of the formation of higher solids Substances are pushed back and these are formed in larger quantities, if one as a catalyst aluminum chloride with an addition of titanium tetrachloride and optionally with the addition of other halides from the Friedel-Crafts range of catalysts. These solid substances are formed particularly easily if one also uses hydrogen chloride-binding substances Metals, such as iron, zinc or aluminum, in finely divided form, advantageously aluminum powder, admits.
Das Mengenverhältnis von Aluminiumchlorid zu Titantetrachlorid kann in ziemlich weiten Grenzen schwanken und z. B% i bis io zu i betragen; besonders gute Ergebnisse erhält man bei einem Gewichtsverhältnis von etwa 3 : 1. Man arbeitet bei erhöhter Temperatur, vorteilhaft bei 13o bis i8o°, und bei erhöhten Drücken, vorteilhaft bei 3o bis 8o at oder darüber. Man kann sowohl reines als auch technisches Äthylen verarbeiten. In manchen Fällen ist es vorteilhaft, wenn man das Äthylen oder äthylenreiche Gas von darin enthaltenem Sauerstoff und Schwefel und deren Verbindungen sorgfältig befreit. Auch empfiehlt es sich unter Umständen, mit einem wasserfreien Aluminiumchlorid zu arbeiten, das weniger als 5 °/o, vorteilhaft weniger als 2,5 %, unsublimierbarerRückstände enthält. Oft ist es auch zweckmäßig, für die Polymerisation Gefäße zu verwenden, bei .denen mindestens die mit den reagierenden Stoffen in Berührung kommenden Teile aus Blei, Zinn, Zink, Nickel, Chrom oder mit Nickel und bzw. oder Chrom legierten Stählen bestehen. Die Polymerisation -wird vorteilhaft in Gegenwart von Verdünnungsmitteln, z. B. gesättigten Kohlenwasserstoffen oder niedrigmolekularen Pplymerisaten des Äthylens, durchgeführt. Auch inerte gasförmige iStoffe können anwesend sein, doch soll deren Menge nicht zu groß sein; bei der Verarbeitung von Gasgemischen verwendet man daher solche, die reich an Äthylen sind, z. B. 8o bis 9o % davon enthalten.The quantitative ratio of aluminum chloride to titanium tetrachloride can fluctuate within fairly wide limits and z. B% i to io to i; particularly good results are obtained with a weight ratio of about 3: 1. One works at elevated temperature, advantageously at 130 to 180 °, and at elevated pressures, advantageous at 3o to 8o at or above. You can do both pure and technical Process ethylene. In some cases it is beneficial to use the ethylene or ethylene-rich gas of oxygen and sulfur and their compounds contained therein carefully freed. It may also be advisable to use an anhydrous To work aluminum chloride that is less than 5%, advantageously less than 2.5 %, contains unsublimable residues. Often it is also useful for the polymerization To use vessels, in which at least those with the reacting substances are in contact coming parts made of lead, tin, zinc, nickel, chromium or with nickel and / or Chromium alloy steels are made. The polymerization is advantageous in the presence of diluents, e.g. B. saturated hydrocarbons or low molecular weight Pplymerisaten of ethylene carried out. Inert gaseous substances can also be present, but their number should not be too great; when processing Gas mixtures are therefore used that are rich in ethylene, e.g. B. 8o to 90% of it included.
Bei der Polymerisation bilden sich gelbbraune Massen, die nach Reinigung durch Extraktion ein fast weißes, lockeres Pulver bilden. Eine Bildung schwarzer, asphaltartiger Produkte, wie sie häufig bei solchen Polymerisationen auftreten, wird durch Katalysatoren der obigen Zusammensetzung fast vollständig vermieden.. Als Nebenerzeugnisse entstehen Benzin- und schmierölartige Polymerisate, die als solche verwendet oder bei neuen Ansätzen als Verdünnungsmittel vorgelegt werden können. Die rohen Polymerisate enthalten anorganische Bestandteile, die aus den verwendeten Katalysatoren stammen. Die praktisch völlige Entfernung dieser Bestandteile erreicht man in bekannter Weise, beispielsweise durch Ausschütteln mit verdünnten Säuren, z. B. mit io- bis i5%iger Salzsäure; der man zur Erzielung besseren Netzvermögens geringe Mengen von in Wasser löslichen organischen Lösungsmitteln, wie Äther oder Alkohol, zusetzen kann.During the polymerization, yellow-brown masses are formed, which after cleaning form an almost white, fluffy powder by extraction. An education of black, asphalt-like products, as they often occur in such polymerizations, is almost completely avoided by using catalysts of the above composition. Gasoline and lubricating oil-like polymers are produced as by-products, which are used as these are used or presented as a diluent for new batches can. The raw polymers contain inorganic constituents from the Catalysts used originate. The practically complete removal of these components can be achieved in a known manner, for example by shaking with dilute Acids, e.g. B. with io- to i5% hydrochloric acid; which one to achieve better network capacity small amounts of water-soluble organic solvents such as ether or Alcohol.
In den gewöhnlichen organischen Lösungsmitteln sind die erhaltenen festen Polymerisate nicht löslich. Beim Erhitzen unter Druck in chlorierten Kohlenwasserstoffen, z. B. Trichloräthylen, tritt Ouellung unter Bildung gummiartiger Massen ein. Gelöst werden die Polymerisate beim Erhitzen in Mineralöl, Paraffinöl und chemisch verwandten Stoffen. Dabei steigert sich die Viskosität solcher Lösungsmittel schon bei geringen Zusätzen ganz beträchtlich. Beispielsweise ergibt ein Mineralöl mit dem Viskositätsindex 112 mit einem Zusatz von 1,2 % des festen Polymerisats ein Erzeugnis von schmierfettartiger Konsistenz. Die Polymerisate zeigen keinen einheitlichen Schmelzpunkt, sie erweichen vielmehr allmählich unter Bildung zähflüssiger, fadenziehender Massen.In the common organic solvents are those obtained solid polymers not soluble. When heated under pressure in chlorinated hydrocarbons, z. B. trichlorethylene, occurs Ouellung with the formation of rubbery masses. Solved the polymers are chemically related when heated in mineral oil, paraffin oil and Fabrics. The viscosity of such solvents increases even at low levels Additions quite considerable. For example, gives a mineral oil with the viscosity index 112 with an addition of 1.2% of the solid polymer a product of grease-like Consistency. The polymers do not show a uniform melting point, they soften rather, gradually with the formation of viscous, stringy masses.
Beispie1 In einen Rührautoklav aus V2A-,Stahl von :2,31 Inhalt füllt man 30 g Aluminiumchlorid, io g Titantetrachlorid, i g Aluminiumpulver und 5oo ccm (341 g) n-Heptan. Dann wird die Luft durch Spülen mit Äthylen verdrängt und Äthylen unter Erwärmen eingepreßt. Sobald die Reaktion einsetzt, wird laufend so viel Äthylen nachgepreßt, daß die Temperatur 155° beträgt, wobei der Druck bis auf 58 atü steigt. Insgesamt werden 165 at Äthylen eingepreßt. Dann läßt man erkalten. Man erhält eine Rohausbeute von 780 g einer festen benzinfeuchten Masse, aus der durch Waschen mit Äther 145 g eines sehr leichten, fast weißen Pulvers gewonnen werden. Der ätherische Extrakt hinterläßt nach dem Abdestillieren des Äthers und des n-Heptans 194 g eines öligen Rückstandes. Example 30 g of aluminum chloride, 10 g of titanium tetrachloride, ig aluminum powder and 500 cc (341 g) of n-heptane are filled into a stirred autoclave made of V2A steel with a volume of 2.31. Then the air is displaced by flushing with ethylene and ethylene is injected with heating. As soon as the reaction starts, so much ethylene is continuously injected that the temperature is 155 °, the pressure rising to 58 atmospheres. A total of 165 at ethylene are injected. Then let it cool down. A crude yield of 780 g of a solid, gasoline-moist mass is obtained, from which 145 g of a very light, almost white powder are obtained by washing with ether. After the ether and the n-heptane have been distilled off, the ethereal extract leaves 194 g of an oily residue.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB7335D DE874215C (en) | 1943-12-18 | 1943-12-18 | Process for the production of solid polymers from ethylene or ethylene-rich gases |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB7335D DE874215C (en) | 1943-12-18 | 1943-12-18 | Process for the production of solid polymers from ethylene or ethylene-rich gases |
Publications (1)
Publication Number | Publication Date |
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DE874215C true DE874215C (en) | 1953-04-20 |
Family
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Family Applications (1)
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DEB7335D Expired DE874215C (en) | 1943-12-18 | 1943-12-18 | Process for the production of solid polymers from ethylene or ethylene-rich gases |
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Cited By (69)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1014744B (en) * | 1955-09-14 | 1957-08-29 | Cassella Farbwerke Mainkur Ag | Process for polymerizing ethylene |
DE1016447B (en) * | 1954-04-05 | 1957-09-26 | Ruhrchemie Ag | Process for the purification of high polymer hydrocarbons |
DE1016442B (en) * | 1955-02-24 | 1957-09-26 | Basf Ag | Process for cleaning film-forming polyethylene |
US2846427A (en) * | 1957-03-14 | 1958-08-05 | Phillips Petroleum Co | Treatment of polymers |
DE1038282B (en) * | 1954-09-01 | 1958-09-04 | Du Pont | Process for the production of ethylene polymers |
DE1042235B (en) * | 1954-11-29 | 1958-10-30 | Ruhrchemie Ag | Process for the purification of high polymer hydrocarbons |
US2868771A (en) * | 1956-07-17 | 1959-01-13 | Ethyl Corp | Polymerization of olefins |
US2878240A (en) * | 1956-12-24 | 1959-03-17 | Universal Oil Prod Co | Polymerization of olefins to solid polymers |
US2884409A (en) * | 1956-04-19 | 1959-04-28 | Rhone Poulenc Sa | Polymerisation of ethylene |
US2891040A (en) * | 1955-08-16 | 1959-06-16 | Du Pont | Ethylene polymerization process |
US2899416A (en) * | 1959-08-11 | Catalyst compositions comprising a | ||
US2899413A (en) * | 1959-08-11 | Aicls | ||
US2899415A (en) * | 1959-08-11 | Coordination polymerization catalysts | ||
US2900374A (en) * | 1956-11-15 | 1959-08-18 | Robert S Aries | Aluminum halide catalysis of ethylene polymerization |
US2912424A (en) * | 1955-11-29 | 1959-11-10 | Eastman Kodak Co | Polymerization of alpha-olefins to solid polymers with catalytic mixtures of aluminum metal, a titanium compound and a tetra substituted ammonium salt |
US2914517A (en) * | 1956-12-24 | 1959-11-24 | Universal Oil Prod Co | Polymerization of olefins to solid polymers |
US2918507A (en) * | 1957-11-29 | 1959-12-22 | Sun Oil Co | Polymerization of propylene using a three component catalyst containing solid metal halides and aluminum |
US2927105A (en) * | 1955-01-05 | 1960-03-01 | Basf Ag | Polymerization of ethylene |
US2928820A (en) * | 1957-10-30 | 1960-03-15 | Grace W R & Co | Polyethylene process |
US2930785A (en) * | 1956-04-05 | 1960-03-29 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
US2933485A (en) * | 1957-10-30 | 1960-04-19 | Grace W R & Co | Polyethylene process |
DE1080303B (en) * | 1954-02-25 | 1960-04-21 | Bayer Ag | Process for the production of solid polyethylenes |
US2935498A (en) * | 1957-07-01 | 1960-05-03 | Eastman Kodak Co | Polymerization of alpha-olefins to solid polymers with a three-component catalyst |
US2938018A (en) * | 1957-11-22 | 1960-05-24 | Universal Oil Prod Co | Production of hard olefin polymers |
US2938890A (en) * | 1957-10-30 | 1960-05-31 | Grace W R & Co | Polyethylene process |
DE973540C (en) * | 1954-12-03 | 1960-06-02 | Ruhrchemie Ag | Process for the production of polyethylene |
US2962490A (en) * | 1955-08-22 | 1960-11-29 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
DE1098204B (en) * | 1955-10-04 | 1961-01-26 | Exxon Research Engineering Co | Process for the polymerization of olefins |
US2970133A (en) * | 1956-01-04 | 1961-01-31 | Ethyl Corp | Polymerization of ethylene with catalyst consisting of aluminum chloride and titanium trihalide |
US2980660A (en) * | 1956-12-28 | 1961-04-18 | California Research Corp | Polymerization of olefins |
US2981726A (en) * | 1958-04-02 | 1961-04-25 | Standard Oil Co | Process for polymerizing propylene with a catalyst of aluminum trialkyl, titanium tetrachloride and metallic iron |
DE1109372B (en) * | 1956-12-28 | 1961-06-22 | Gelsenberg Benzin Ag | Process for the polymerisation of ethylene or gases containing ethylene |
US3004020A (en) * | 1958-03-31 | 1961-10-10 | Eastman Kodak Co | Ethylene polymerization using a mixture of metals and a halogen as catalyst |
US3006904A (en) * | 1956-04-06 | 1961-10-31 | Basf Ag | Polymerization of monoolefins with alcohol-containing catalyst |
US3007909A (en) * | 1956-09-27 | 1961-11-07 | Henkel & Cie Gmbh | Polymerization of olefins |
US3007907A (en) * | 1955-12-30 | 1961-11-07 | Nat Distillers Chem Corp | Polymerization process, using a catalyst of an alkali metal hydrocarbon, a group ivb metal tetrahalide and aluminum trichloride |
DE1117309B (en) * | 1953-01-27 | 1961-11-16 | Phillips Petroleum Co | Process for the production of high molecular weight polymeric olefinic hydrocarbons or their copolymers |
US3019216A (en) * | 1956-12-24 | 1962-01-30 | Universal Oil Prod Co | Polymerization of olefins into polymers of high melting point |
US3021320A (en) * | 1956-01-30 | 1962-02-13 | Celanese Corp | Polymerization of ethylene with catalysts of alkali metal borohydrides, aluminum halides and group ivb metal halides |
US3032509A (en) * | 1958-02-03 | 1962-05-01 | Exxon Research Engineering Co | Partially-reduced cocrystallized transition metal halide polymerization catalyst |
DE1130171B (en) * | 1954-09-03 | 1962-05-24 | Rohm & Haas | Process for the preparation of a catalyst for the polymerization of olefins |
DE1130170B (en) * | 1954-09-03 | 1962-05-24 | Rohm & Haas | Process for the preparation of a catalyst for the polymerization of olefins |
US3037012A (en) * | 1956-11-14 | 1962-05-29 | Basf Ag | Continuous polymerization of ethylene |
DE1135436B (en) * | 1959-10-21 | 1962-08-30 | Basf Ag | Process for the production of tri- and hexasubstituted benzenes from substituted acetylene hydrocarbons by means of catalysts containing titanium and aluminum |
US3057842A (en) * | 1958-03-17 | 1962-10-09 | Monsanto Chemicals | Alcl3-catalyzed polymerization of ethylene |
US3058972A (en) * | 1957-07-20 | 1962-10-16 | Normande De Matieres Plastique | Polymerization of ethylene |
US3066132A (en) * | 1955-07-11 | 1962-11-27 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
US3066125A (en) * | 1958-06-16 | 1962-11-27 | Shell Oil Co | Diene polymerization and catalysts therefor |
US3075958A (en) * | 1955-06-16 | 1963-01-29 | Basf Ag | Production of polymerization products of olefine hydrocarbons with a catalyst of an alkali metal hydride aluminum, chloride, and titanium chloride |
US3078264A (en) * | 1956-01-30 | 1963-02-19 | Celanese Corp | Polymerization of ethylene and catalyst therefor |
US3079371A (en) * | 1957-05-29 | 1963-02-26 | Rhone Poulenc Sa | Production of ethylene polymers using a catalyst based on titanium tetrachloride and aluminum |
US3086964A (en) * | 1955-11-29 | 1963-04-23 | Eastman Kodak Co | Catalytic polymerization of alpha-olefins to solid polymers with catalyst mixtures of a metal, a metal tetraalkyl, and a titanium tetrahalide |
US3093625A (en) * | 1955-10-28 | 1963-06-11 | Basf Ag | Production of polymers of olefinically unsaturated hydrocarbons with a catalyst of aluminum, aluminum trichloride and a titanium tetrahalide |
US3098828A (en) * | 1957-11-04 | 1963-07-23 | Dal Mon Research Co | Catalyst prepared by grinding zirconium and aluminum chloride |
US3101328A (en) * | 1955-03-23 | 1963-08-20 | Phillips Petroleum Co | Polymerization of olefins and catalysts therefor |
US3107236A (en) * | 1956-12-17 | 1963-10-15 | Sun Oil Co | Preparation of polypropylene |
US3121063A (en) * | 1957-07-01 | 1964-02-11 | Exxon Research Engineering Co | Polymerization catalyst |
DE1163030B (en) * | 1955-06-20 | 1964-02-13 | Shell Int Research | Process for purifying polyolefins |
US3128252A (en) * | 1956-04-16 | 1964-04-07 | Exxon Research Engineering Co | Preparation of partially reduced transition metal halide catalyst compositions |
DE1176868B (en) * | 1956-02-17 | 1964-08-27 | Bayer Ag | Process for the polymerization of ethylene |
DE1179373B (en) * | 1955-08-19 | 1964-10-08 | Hoechst Ag | Process for the polymerization of ethylene by means of a catalyst system consisting of halogen-containing organoaluminum compounds and titanium (ó¶) compounds |
US3172865A (en) * | 1965-03-09 | Process for producing a co-crystal- lized salt consisting essentially of aluminum chloride and titani- um trichloride | ||
DE1191575B (en) * | 1959-04-24 | 1965-04-22 | Saint Gobain | Process for the polymerization of ethylene |
US3219649A (en) * | 1955-07-11 | 1965-11-23 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
DE1208076B (en) * | 1955-04-13 | 1965-12-30 | Phillips Petroleum Co | Process for the polymerization of ethylene |
US3236826A (en) * | 1960-02-03 | 1966-02-22 | Goodrich Gulf Chem Inc | Catalyst solution and process of polymerizing therewith |
US3257332A (en) * | 1953-11-17 | 1966-06-21 | Ziegler | Polymerization of ethylene |
DE1226306B (en) * | 1954-08-13 | 1966-10-06 | Ziegler Karl | Process for the polymerization of ethylene |
DE1268846B (en) * | 1955-04-27 | 1968-05-22 | Basf Ag | Process for the production of polyolefins |
-
1943
- 1943-12-18 DE DEB7335D patent/DE874215C/en not_active Expired
Cited By (72)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2899416A (en) * | 1959-08-11 | Catalyst compositions comprising a | ||
US3172865A (en) * | 1965-03-09 | Process for producing a co-crystal- lized salt consisting essentially of aluminum chloride and titani- um trichloride | ||
US2899415A (en) * | 1959-08-11 | Coordination polymerization catalysts | ||
US2899413A (en) * | 1959-08-11 | Aicls | ||
DE1117309B (en) * | 1953-01-27 | 1961-11-16 | Phillips Petroleum Co | Process for the production of high molecular weight polymeric olefinic hydrocarbons or their copolymers |
US3257332A (en) * | 1953-11-17 | 1966-06-21 | Ziegler | Polymerization of ethylene |
DE1080303B (en) * | 1954-02-25 | 1960-04-21 | Bayer Ag | Process for the production of solid polyethylenes |
DE1016447B (en) * | 1954-04-05 | 1957-09-26 | Ruhrchemie Ag | Process for the purification of high polymer hydrocarbons |
DE1226306B (en) * | 1954-08-13 | 1966-10-06 | Ziegler Karl | Process for the polymerization of ethylene |
DE1038282B (en) * | 1954-09-01 | 1958-09-04 | Du Pont | Process for the production of ethylene polymers |
DE1130170B (en) * | 1954-09-03 | 1962-05-24 | Rohm & Haas | Process for the preparation of a catalyst for the polymerization of olefins |
DE1130171B (en) * | 1954-09-03 | 1962-05-24 | Rohm & Haas | Process for the preparation of a catalyst for the polymerization of olefins |
DE1042235B (en) * | 1954-11-29 | 1958-10-30 | Ruhrchemie Ag | Process for the purification of high polymer hydrocarbons |
DE973540C (en) * | 1954-12-03 | 1960-06-02 | Ruhrchemie Ag | Process for the production of polyethylene |
US2927105A (en) * | 1955-01-05 | 1960-03-01 | Basf Ag | Polymerization of ethylene |
DE1016442B (en) * | 1955-02-24 | 1957-09-26 | Basf Ag | Process for cleaning film-forming polyethylene |
US3101328A (en) * | 1955-03-23 | 1963-08-20 | Phillips Petroleum Co | Polymerization of olefins and catalysts therefor |
DE1208076B (en) * | 1955-04-13 | 1965-12-30 | Phillips Petroleum Co | Process for the polymerization of ethylene |
DE1268846B (en) * | 1955-04-27 | 1968-05-22 | Basf Ag | Process for the production of polyolefins |
US3075958A (en) * | 1955-06-16 | 1963-01-29 | Basf Ag | Production of polymerization products of olefine hydrocarbons with a catalyst of an alkali metal hydride aluminum, chloride, and titanium chloride |
DE1163030B (en) * | 1955-06-20 | 1964-02-13 | Shell Int Research | Process for purifying polyolefins |
US3066132A (en) * | 1955-07-11 | 1962-11-27 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
US3219649A (en) * | 1955-07-11 | 1965-11-23 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
DE1208077B (en) * | 1955-07-11 | 1965-12-30 | Phillips Petroleum Co | Process for the polymerization or mixed polymerization of olefins |
US2891040A (en) * | 1955-08-16 | 1959-06-16 | Du Pont | Ethylene polymerization process |
DE1179373B (en) * | 1955-08-19 | 1964-10-08 | Hoechst Ag | Process for the polymerization of ethylene by means of a catalyst system consisting of halogen-containing organoaluminum compounds and titanium (ó¶) compounds |
DE1106076B (en) * | 1955-08-22 | 1961-05-04 | Phillips Petroleum Co | Process for the production of olefin polymers |
US2962490A (en) * | 1955-08-22 | 1960-11-29 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
DE1014744B (en) * | 1955-09-14 | 1957-08-29 | Cassella Farbwerke Mainkur Ag | Process for polymerizing ethylene |
DE1098204B (en) * | 1955-10-04 | 1961-01-26 | Exxon Research Engineering Co | Process for the polymerization of olefins |
US3093625A (en) * | 1955-10-28 | 1963-06-11 | Basf Ag | Production of polymers of olefinically unsaturated hydrocarbons with a catalyst of aluminum, aluminum trichloride and a titanium tetrahalide |
US3086964A (en) * | 1955-11-29 | 1963-04-23 | Eastman Kodak Co | Catalytic polymerization of alpha-olefins to solid polymers with catalyst mixtures of a metal, a metal tetraalkyl, and a titanium tetrahalide |
US2912424A (en) * | 1955-11-29 | 1959-11-10 | Eastman Kodak Co | Polymerization of alpha-olefins to solid polymers with catalytic mixtures of aluminum metal, a titanium compound and a tetra substituted ammonium salt |
US3007907A (en) * | 1955-12-30 | 1961-11-07 | Nat Distillers Chem Corp | Polymerization process, using a catalyst of an alkali metal hydrocarbon, a group ivb metal tetrahalide and aluminum trichloride |
US2970133A (en) * | 1956-01-04 | 1961-01-31 | Ethyl Corp | Polymerization of ethylene with catalyst consisting of aluminum chloride and titanium trihalide |
US3078264A (en) * | 1956-01-30 | 1963-02-19 | Celanese Corp | Polymerization of ethylene and catalyst therefor |
US3021320A (en) * | 1956-01-30 | 1962-02-13 | Celanese Corp | Polymerization of ethylene with catalysts of alkali metal borohydrides, aluminum halides and group ivb metal halides |
DE1176868B (en) * | 1956-02-17 | 1964-08-27 | Bayer Ag | Process for the polymerization of ethylene |
US2930785A (en) * | 1956-04-05 | 1960-03-29 | Phillips Petroleum Co | Process and catalyst for production of olefin polymers |
US3006904A (en) * | 1956-04-06 | 1961-10-31 | Basf Ag | Polymerization of monoolefins with alcohol-containing catalyst |
US3128252A (en) * | 1956-04-16 | 1964-04-07 | Exxon Research Engineering Co | Preparation of partially reduced transition metal halide catalyst compositions |
US2884409A (en) * | 1956-04-19 | 1959-04-28 | Rhone Poulenc Sa | Polymerisation of ethylene |
DE1056374B (en) * | 1956-04-19 | 1959-04-30 | Rhone Poulenc Sa | Process for the polymerization of ethylene |
US2868771A (en) * | 1956-07-17 | 1959-01-13 | Ethyl Corp | Polymerization of olefins |
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