DE1229732B - Process for the polymerization and interpolymerization of olefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C08f

German class: 39 c -25/01

Number: 1229 732

File number: P19691IV d / 39 c

Filing date: November 19, 1957

Opening day: December 1, 1966

It is known that olefins at temperatures below about 26O ⁰ C by contacting with a chromium oxide catalyst in which preferably a substantial portion of the chromium is sechswertfg and also contains at least one oxide from the group Süiciumdioxyd, alumina, zirconia and Thpxiumoxyd polymerize can. A precise description of these catalysts, their preparation, the polymerization conditions and the products that can be prepared in this way can be found in Belgian patents 535 082 and 530 617.

The aim of the invention is a polymerization process using a chromium oxide catalyst with greatly increased productivity.

The invention relates to a process for the polymerization and copolymerization of olefins by means of catalysts supported on silica-alumina gels applied chromium oxides, partly in hexavalent Fprm, and which have been activated by heat treatment, which is characterized in that such catalysts used, which is a silica-alumina gel with an effective surface as a carrier of at least 450 m2 / g and an average pore diameter of at least 65 Å.

The silicon dipoxide-aluminum oxide support materials used according to the invention as the basis for the chromium oxide catalyst are commercially available materials. The alumina content of these materials is generally less than 50 percent by weight, preferably of the order of magnitude from 2 to 30 percent by weight. The remainder is generally composed mainly of silicon dioxide with small amounts of impurities. Other oxides can also be used, for example zirconium oxide, Thorium oxide and / or magnesium oxide. The effective surface area of these catalysts using the method of Br u η a u e r, Emmett and Teller, J. Am. Chem. Soc, 59, P. 1553 (1937), and loc. Cit., 59, p. 2682 (1937). The pore volume is determined by the method described in Analytical Chemistry, 28,332 (1956), was measured. The average pore diameter

4 V
is calculated according to the equation D = - = - , where

P is the pore diameter, V is the pore volume and S is the effective surface, measured by the method of Brunaueretal .; D, V and S are all given in the same unit of length, and D is finally converted into angstrom units. An applied process for the preparation of processes for polymerization and
Interpolymerization of olefins

Applicant:

Phillips Petroleum Company,
Bartlesville, OkIa. (V. St. A.)

ίο representative:

Dr. F. Zumstein and Dr. E. Assmann,
Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:
James Robert Owen,
Bartlesville, OkIa. (V. St. A.)

Claimed priority:
V. St. v. America November 19, 1956
(622 786)

Silica-alumina supports with the above specified properties consists in the acidification of an aqueous solution of sodium silicate to form a hydrosol and gelatinization of the hydrosol, so that a hydrogel is formed, with the addition of a sufficient one Amount of an aqueous aluminum sulfate solution to form the required amount of aluminum oxide, the addition of ammonia making the mixture alkaline, spray drying the precipitated carrier and finally washing with water. Other process using a silica-alumina mass with these particular properties can also be used.

For example, an aqueous solution of a sodium silicate containing 93 g SiO ₂ in 2.325 ml of water is converted into a sufficient amount of aqueous 3.75% NH ₂ Cl solution containing 18.3 g AlCl ₃ (corresponding to 7 g Al ₂ O ₃ ), so that a mixture with a pH of 7.0 is obtained. A clear, translucent sol is obtained which settles into a clear gel within about 5 minutes. At the end of one hour, this gel is cut into cubes 1.778 cm on a side. After 24 hours of aging, these cubes are mixed with 4 parts of an aqueous l% strength ammonium hydroxide solution into contact ^en

609 729/407

3 ^: 4 '

brought. Everyone; , Part, of the -aqueous ammonia produced according to ■ crystalline homopolymers. solution corresponds in the "volume to the volume * of the In addition one can also use ethylene with certain Gels, and the contact times are 2, 2, 2 and 2-olefins, such as butene- (2), polymerize. Other 16 hours. The pH value during the final contact olefins, as the ~ 1-olefins. (AHphatic 2-O.leefins-bei = -. period is 11.0. The gel is then with 25 parts 5 for example) can with the invention distilled water, washed, whereby each part in the catalyst is Hömöpö'lymerisiert '"but" sincT " Volume corresponds to the volume of the gel, and in some cases the polymers are predominantly liquid. Dried at 110 ° C for 16 hours. The final The polymerization reaction can be in gaseous form

Gel, which contains 93% _: SiPa and 7% Al ₂ O ₃ , has or liquid phase can be carried out; a detailed description of these methods, ranging in size from 0.80 to 1.5 mm (particle size), the following properties were measured: stated in the above-mentioned patents.

Any kind of polymerization technique known

can be used in the invention

Effective ■ surface, »qm / g (1). ,, ..... -.-.-.- 488 Kätälysätö'ferT "~ are applied": A "test bed particle density, g / ml (2) 0.97 ₁₅ process can be carried out very well. The catalyst

Real density; "g / mL: (3,).; ....... 2.18 can be in the form of a suspension in a gas stream

Average diameter; A (4)., ... 70 of ^the reacting olefin or in the form of a fluid

ized; Bettes-be-turned-around. Height yields aü

(1) Low-temperature Njj adsorption, polyethylene; this is possible if gaseous ethylene is used

- ao with a 'suspended or fluidized catalyst

(2) pycnometric, mercury displacement ^. _{of the} type described above in a polymerization '

(3) pycnometric, water displacement; temperature below the; melting point of the poly-

fA \ λ j χ. τ. -Js-Ί.- '' 4 · · ι "* ϊ ~ j ι. '■""' · j of ethylene, for example ^ below about 12Q ° C, to-

(4) the average particle diameter is ^J , '■■ -J - ^ - "■ <> j · c ν ί ju. ^W Κ. · -"---' · .-- - · *. ' The use of a. Gravity ^

according to the formula D = 6 - calculated, whereby 25 bed catalyst is also possible. "According to a

T ^ - · '- ^■':; Embodiment of the invention includes a suspension

^{aS pore volume of} the Katdyfatdr _Sr derm _e iner -partik _e lsize-von.Q, 833

S ^: ^^ f ^ '. is ground up to -0.175mMvieiter mesh size,

γ γ for example * m cyclohexane suspended pcontaieri

V = - Tr -; - - 3o borrowed to one. Reaction vessel;. "The" with 'a * meena = ·

Tight density real density - ruffled back is provided ^ in. Stream of "ethylene

and A is the effective surface. '"' also flows -m- the reaction vessel that at 12Ö

(, Λ ......, Up to 150 C * and approximately below, one: pressure Ύοη 21

■ - can be held up to 42 "ata". After a "geeigi

A preferred size range of effective dwell time, for example from 2 to 1/2 hours

Surface. _f according to | ß ^ dgr (invention is 450th to '- the reaction mixture is continuously withdrawn

600 qm / g, 'and' a particularly suitable area of the und'um approximately 14 ° C higher than in the reaction vessel

average pore diameter lies between heated, -so "that the greatest possible" solution desrPoIy ^

65 and 150 Ä. "" merenim'KOUenwasserstofflösmittei 'is achieved:

As already mentioned, certain silicon contain 40 Additional solvents can, if desired,

Dioxide-aluminum oxide masses of the above are given: - 'Die "-Polymerkönzerrtration der

Type-relatively low percentage hooked sulfate solution is generally between 1 and 5 weight =

■ as a union; ijrj 'general this should be sulphate ^ per cent during.'. of heating (and "agitation)

content substantially less than 2 percent by weight of the total gas that has not been set can be blown off, so that

ten '· "non-impregnated silica-aluminum 45 the pressure to approximately" .7 ata. falls. The heated one

oxide measurements. Usually there can be excess 'polymer solution containing the' suspended catalyst

Sulphate through-wash; removed with water. \ is then used without any significant change in

The starting materials used at the invention temperature or pressure to a filter or in a according to Poiymerisierungsverfahren are transferred in the all-centrifuge and the suspendierte.Katalygemernen-1-olefins Finally the aliphatic 50 sator removed here. You can "the catalyst normal'1-olefins, although certain cyclic olefins, recover and regenerate, "for example by such as vinylcyclohexene ·, "can also be used. Combustion of the" carbonaceous deposits - and A preferred class of olefins are the äli-attached "activation. However, productivity is Phätischen 1-Monoolerine with a maximum of the catalysts used according to the invention so 8 carbon atoms in the molecule and no chain 55 high that regeneration is recovery Branches closer to the double bond than in the 4-position. can be omitted and so the. Catalyst examples For such olefins, ethylene and propylene are kept very low cost per kilogram of polymer Butene- (l), pentene- (l),; J-hexene- (l), 4-methyl-pentene- (l). The filtrate or the clarified liquid and hepten- (l). Conjugated diolefins with a terminal from which the catalyst has been removed permanent double bond, for example 1,3-butadiene 60 then for recovery - the polymers - and for and isoprene, are also treated further in the presence of the recovery of the solvent, inventive catalysts polymerizable. In a particular embodiment of the aforementioned Olefins can also be mixed with one another. A catalyst suspension in cyclo ^ · polymerized or interporymerized. Example hexane in a reaction vessel with a Ethylene can wisely. Propylene, butene- (l) or with 65 mechanical stirrer, at "138 ° C and 1,2-Butadiene are polymerized to keep valuable 31.5 atü.- The catalyst concentration in the Mixed polymers with increased chain branching and cyclohexane 'was 0.07 percent by weight. ■ "ethylene To maintain flexibility, compared with the invention, the reaction vessel was continuously with a

sufficient speed "to" maintain the polymer concentration in the reaction vessel at a maximum of about 2 percent by weight. The duration of each experiment was IV ₂ hours.

Various catalysts were used in these experiments. All catalysts were 'produced by impregnating the aforementioned SiliGiumdioxyd-Alunliniumoxyd-Gründiäge with a Wäßtigen solution of chromium trioxide, followed by drying the impregnated mass at about 12O ⁰ C and 5stündiges heating the dried "ingots an air stream (dew point below -18 ⁰ C) at -Si

On each "trial, the reaction mixture

withdrawn from the reaction vessel, unreregulated gas was drained and the remaining mixture was heated to approximately 150 ° C; after that she was praying at approximately this temperature and a pressure of about "7 ata to remove the - catalyst. The polymer was "decanting" from the filtrate by cooling to room temperature and evaporating the remaining cyclohexane, the

ίο still adhered to the polymer, won.

The results of these tests are shown in the table below.

Influence of the effective surface on the productivity

SiO ₂
[Ge
weight
Per-
cent] Silica-Alumina Foundation sulfate
salary
[Ge
weight
Per-
cent] Really
same
Upper
area Pores
volume By
cut
licher
Pores
by
knife Schütt
density Total catalyst sulfate
salary
[Ge
weight
Per-
cent] Polymerization of ethylene Polymer Notch
impact
tenacious
ability ** [qm / g] [ccm / g] [A] [g / ccm] Enamel
index* Ver
search
No. 87 Al ₂ O ₃
[Ge
weight
Per-
cent] 0.12 548 0.69 50 0.59 Cr-
salary
[Ge
weight
Per-
cent] Production
swiftly
ability [g PoIy-
meres / g
Catalyst/
Hours] 11.0 87 0.12 548 0.69 50 0.59 - 0.32 9.9 53+ 87 13th - 519 0.63 49 .—. 1.6 - 540 0.39 10.7 57+ 87 13th 0.20 529 0.88 67 0.47 1.6 0.08 530 0.29 7.5 61+ 87 13th - 451 0.82 73 .—. 2.4 - 580 0.36 8.6 45 87 13th 0.01 529 0.88 67 0.47 3.4 0.06 680 0.54 - 51 87 13th 0.21 529 0.88 67 0.47 2.4 0.14 670 ■ - ■ - 47 87 13th 0.37 529 0.88 67 0.47 2.24 - 670 - - 49 87 13th 0.68 529 0.88 67 0.47 2.17 - 700 - - 62 87 13th 1.99 529 0.88 67 0.47 *** 0.90 730 - - 63 87 13th 0.39 520 0.86 66 0.54 *** - 690 - 6.7 50 87 13th 0.39 520 0.86 66 0.54 2.27 - 600 0.50 - 29 87 13th 0.39 520 0.86 66 0.54 2.6 • - ■ 820 • - · 5.2 58 87 13th - 458 0.78 68 0.55 2.2 - 760 0.93 9.8 66 87 13th - 458 0.78 68 0.55 2.2 - 770 0.33 8.5 46 87 13th 0.05 458 0.78 68 0.55 1.8 .—. 700 0.55 - 52 87 13th 0.17 458 0.78 68 0.55 1.8 0.09 660 - - 54 87 13th 0.17 458 0.78 68 0.55 *** - 660 - - 56 87 13th 0.4 458 0.78 68 0.55 *** - 660 - - 60 87 13th 0.66 458 0.78 68 0.55 *** 0.28 640 - - 64 87 13th 1.99 458 0.78 68 0.55 *** - 640. - - 59 75 13th - 442 0.86 78 *** - 660 - 10.7 67 87 13th .—. 450 1.15 100 .— *** - 620 0.35 9.1 55+ 89 25th - 305 0.48 63 ■ - · 2.2 - 610 0.55 - 75 13th 1.7 670 - 97+ 11 2.5 210

* ASTM D-1238-52T.
** ASTM D-256-54T.

*** Approximately 2 percent by weight. + Comparison tests.

The results show the following: If the silica-alumina base an effective surface area of at least 450 m² / g and an average pore diameter of at least 65 Å, in most cases polymer production rates of at least are obtained 650 g of polyethylene per gram of catalyst per hour. On the other hand, the effective surface is less than 450 qm / g and the average pore diameter less than 65 Å, so become considerable get lower production speeds. The data also indicate that it is desirable to use the Sulphate content of the non-impregnated silica-alumina base keep well below 2 weight percent.

The polymers produced in the above experiments have molecular weights in the order of 40000, densities of approximately 0.96 g / cc at 20 ⁰ C, tensile strengths in the order of 281 kg / ccm, and crystallinity, which are above 90%. These polyethylenes are tough and stiff. They can be pressed into liquid containers, extruded into tubes, hoses or foils, expanded into films or shaped into threads by extrusion and cold drawing.

The molecular weight given here is an average molecular weight calculated on Due to the inherent viscosity of the polymer. Unless otherwise stated, this is the one used here Molecular weight the inherent viscosity,

multiplied by 24500. The inherent viscosity is measured in a solution of 0.2 g of the polymer in 50 ecm of tetrahydronaphthalene at 130.degree. This type of molecular weight determination is described by Kemp and Peters in the journal Ind.Eng.Chem., 35, S.IJOS (1943), and by Dienes and Klemm in the journal I. Applied Phys., 17, p. 458 (June 1946 ).

Claims (1)

Claim: Process for the polymerization and copolymerization of olefins by means of catalysts, which are supported on silica-aluminum oxide Gels contain chromium oxides, some of them in hexavalent form, and are made by Heat treatment have been activated, characterized in that such Catalysts are used, the support a silica-alumina gel with a Effective surface area of at least 450 qm / g and an average pore diameter of at least 65 Å. Considered publications:
German Patent No. 725 OBO;
Belgian Patent Nos. 535 082, 530 617;
U.S. Patent No. 2,698,305. 609 729/407 11.66 © Bundesdruckerei Berlin