DE1268843B - Process for the production of homo- and copolymers of mono- and diolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN # f # PATENT OFFICE

EDITORIAL

Int. Cl .:

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German class: 39 c - 25/01 r: ■ ^! BS, ■

Number: 1268 843

File number: P 12 68 843.6-44

Filing date: March 6, 1965

Open date: May 22, 1968

It is known that olefinically unsaturated compounds, such as -olefins and diolefins, with organometallic Mixed catalysts, which are produced by reacting compounds of the elements of IV. To VI. Subgroup of the periodic table with organometallic compounds from I. to III. Main and subgroups and found their way into technology under the name of »Ziegler catalysts« can be polymerized to high molecular weight, mostly crystalline products.

It is also known that certain heavy metal organyls, such as biscyclopentadienyltitanium diphenyl (U.S. Pat 3,000,870) and methyltitanium trichloride (German Patent 1,026,964) in the presence of Titanium chlorides, are suitable for converting ethylene and butadiene into high-molecular substances. Also trisallyl chrome or diallyl chromium halides (laid out documents of the Dutch patent application 6,409,179) alone have already been used as catalysts for such polymerizations.

However, these pure heavy metal catalysts are - in comparison with many Ziegler catalysts - only slightly active towards ethylene; higher «olefins, ζ. B. Propylene, are in their presence at all not polymerized. Also the additional use of organoaluminum compounds in the process of the laid-out documents of Dutch patent application 6 409 179 does not bring any increase of activity.

There has now been a process for the production of homopolymers and copolymers of mono- and diolefins by polymerizing the monomers, by themselves or as a mixture with one another, in the presence of Catalysts off

(a) Halides, oxyhalides, ester halides or esters of elements from IV. to VIII. Subgroup of the periodic table and

(b) organometallic compounds of elements of subgroups IV to VIII of the periodic table,

optionally with the addition of hydrogen as a regulator, found in which then high molecular weight polymers can be obtained with a high contact time yield if allyl compounds are used as organometallic compounds of chrome can be used.

According to the invention, AUyI compounds are preferably used of chromium trisallyl chromium, diallyl chromium chloride and diallyl chromium iodide are used.

As halides, oxyhalides, ester halides and esters of elements of subgroups IV to VIII especially those of titanium, zircon, van

Process for the production of homo- and
Copolymers of mono- and diolefins

Applicant:

Farbwerke Hoechst Aktiengesellschaft
formerly Master Lucius & Brüning,
6000 Frankfurt

Named as inventor:
Dipl.-Chem. Dr. Walter Herwig,
6000 Frankfurt-Schwanheim;
Dipl.-Chem. Dr. Albert Gumboldt,
6230 Frankfurt-Höchst;
Dipl.-Chem. Dr. Klaus Weissermel,
6233 Kelkheim

diums, chromium, molybdenum, tungsten, iron, uranium or thorium, preferably the halides and oxyhalides, used.

With the catalysts used according to the invention can be ethylene and its aliphatic or aromatically substituted derivatives, e.g. B. propylene, butene (l), pentene (l), 3-methyl-butene (l), 4-methyl pentene- (l), 3,3-dimethyl-5-methyl-hexene (l), styrene, allylbenzene, 4-phenyl-butene (1); Diolefins, ζ. Β. 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-butadiene, 1,4-hexadiene, 1,5-hexadiene, 2,6-dimethyl-octadiene- (2.7), and cyclic diolefins with a carbon bridge, e.g. B. dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, 5-methyl-norbornadiene- (2,6), 5- (2-butenyl) -2-norbornene, 5- (3,5-dimethyl-4-hexenyl) -2-norbornene and 5- (l, 5-dimethyl-4-hexenyl) -2-norbornene, polymerize and copolymerize with one another.

In addition to thermoplastic homopolymers and copolymers, copolymers with an elastomeric character can also be produced according to the invention from the monomers listed above. Such elastomeric copolymers contain, for example, at least 50 mol percent ethylene in addition to the C ₃ , C ₄ , C ₈ and higher olefins mentioned. In addition, the dienes listed above can optionally also be polymerized into the elastomeric copolymers as a third component.

809 550/463

3 4

The catalysts for the process according to the invention can run off. Drive suitably heated be prepared by reacting the allyl-chromium is, however, for some time to temperatures of connection, for example Trisallylchrom, in a 40 to 130 ⁰ C.

inert solvent, such as η-hexane or benzene, dissolves. The catalysts (contacts) are generally

You can now add the above-mentioned 5 nines to this solution in amounts of 0.1 to 10 mmol - based on cocomponent (a) in substance, or you can add the total metal - per liter of dispersant, the allyl chromium solution is set with a suspension, the polymerization temperatures are between or a solution of the cocomponent in an inert see -20 and + 7O ⁰ C, preferably between +10 solvent, the solvent not being identical and + 55 ° C.

with the solvent of the allyl chromium compound to io An olefin pressure above one atmosphere is generally needs. But one can also think that the cocomponent is not necessary, pressure increases from 1 to 30 atmospheres in the polymerization vessel in an inert solution, however, the polymerization rates Submit the agent in dissolved or suspended form, increase with one part and thereby the profitability of the Verder Provide allyl chromium solution to improve the polymerization process. The dispersants used in the by adding the mono- or diolefin in gear 15 general non-polar, inert hydrocarbons, such as set and then, in the course of the polymerization, saturated aliphatics, for example hexane or continuously or discontinuously further allylchrominated diesel oil, or aromatics, for example benzene, add solution. However, it can also be advantageous, but chlorinated hydrocarbons, the '! allyl chromium compound and the co- such as chlorobenzene and chloroform, and ether, such as add component during the polymerization. 20 Tetrahydrofuran and diglycol dimethyl ether, from Vor-Es can also be of advantage to be part of the catalyst of both.

components only small proportions to initiate the The polymerization can be carried out by blowing in

Combine polymerization and then during the air, adding water or adding alcohol polymerization the two contact components of the pick, such as methanol, iso-propanol or n-butanol, Add reaction fiot. 25 stop.

The polymerisation can also be carried out without solvent and The processing of the polymer fiot takes place after

Dispersants in the liquid monomers themselves known processes, for example by filtration in the be performed. Another preference is to the case of a crystalline, insoluble polymer or see that one is made from an allyl chromium compound and, for example, by steam distillation in the case the said cocomponent is a contact suspension 30 of a polymer dissolved in the reaction medium or prepares the copolymers then used for olefin polymerization.

and by adding again an allyl chromium solution according to the invention with the new catalysts

is activated. thermoplastic polymers obtained are linear

Built up as halides, oxyhalides, ester halides, they are soluble in p-xylene, for example, or esters of the elements of IV. To VTII. Subgroup 35 have easily measurable viscosities with ?? _{rf! £} i-Werdes periodic table (catalyst cocomponents) th, which are particularly mentioned in the areas required by technology: titanium tetrachloride, titanium tri-from about 1 to 20, with the other, of the chloride, titanium tetrabromide, titanium tetraiodide, titanium oxy - Property of the thermoplastic chloride (TiOCl ₂ ), titanium ester halide, as required in practice, as titanium - processability goes hand in hand. Regulations of the chlorodiisobutyrate or titanium dichlorodipropylate, or the molecular weight of the polymer, ester halides with acetylacetone (AAH) as ester can be easily achieved by adding hydrogen to the polymerization component, such as [Ti (AA) ₃ ] [TiCl ₆ ], zirconium tetrachloride. In contrast, a polyethylene made with tris-vanadium oxychloride, vanadium tetrachloride, vanadium trialllylchromium without heavy metal compounds as cochloride, ortho-vanadic acid ester halide, orthocatalyst is not in organic vanadic acid ester, chromyl chloride, chromium trichloride, 45 see solvents, such as p-solvents, such as Comparative molybdenum pentachloride, tungsten hexachloride, iron tri-example) and shows under a load of 5 kg for chloride. 190 ° C according to ASTM D 1238/57 T no measurable

The quantitative ratio of the chromium allyl compound flow behavior. So you have to go for these products to the heavy metal halide (catalyst-cocompo-crosslinks or branches accept with im nente) depends on the desired optimal physical senses of infinite molecular weight. Polymerization conditions, however, is generally another advantage that is decisive for the technology

the molar ratio of the chromium allyl compound to the process according to the invention is that Heavy metal halide not smaller than 1, often high contact activity of the allylchromium compound according to the invention in one up to ten times turned catalysts. Trisallyl chromium polymerized molar excess applied. For example, ethylene can be used with space-time yields (grams of poly-wise Ethylene in the presence of trisallylchromium and ethylene per liter of dispersant · hour) from 1 to 2 Titanium tetrachloride at a molar ratio of 1: 1 and contact time yields (grams of polyethylene per at high speed at normal pressure poly-millimole contact · hour) of ~ 1, while at merize; However, instead of titanium tetrachloride, the catalyst com vanadium oxychloride according to the invention is used, this means that values of 130 or 160 are easily achieved with an otherwise identical 60 bination. That Conditions good polymerization rates, the next higher -olefin, propylene, can be, as in a three-fold molar excess of chromium, with trisallyl chromium alone no longer a polymeric component. If propylene is polymerized with Tris- sieren, with the addition of titanium trichloride or titanium tetraallylchromium and titanium tetrachloride, in contrast, with chloride one obtains crystalline polypropylene, a two-molar excess of the chromium component 65 The crystallinity of the polymers, but above all good rates of polymerization. the copolymers, can be used within wide limits,

The catalyst mixtures themselves can depend on both the contact and the age tion, which one can vary in the case of Zimmer monomers. Ethylene can be used, for example

with propylene in a volume ratio of 2: 1 to an elastomeric, as already mentioned above, primarily Mix polymerize amorphous product. Furthermore, by copolymerization of the Ethylene with propylene or other Λ-olefins with Used to obtain polymers which are unsaturated. By varying the contact components a shift into more highly crystalline areas can be achieved, creating completely different technological properties of the polymers can result. Similar effects are especially also found with higher «-olefins, for example 4-methylpentene-1 to achieve.

example 1

A solution of 0.8 g of trisallylchromium in 200 ml of hexane is added to a solution of 0.57 g of titanium tetrachloride in 600 ml of η-hexane, which is vigorously stirred in a round bottom flask under a nitrogen atmosphere. The heated at 4O ⁰ C contents are gassed with ethylene. The uptake of ethylene and the separation of solid polyethylene begins after a few seconds. During the polymerization the temperature increases to 6O ⁰ C, external cooling with water is required. After 2.5 hours, 40 ml of n-butanol are added to the thick polymer paste, the polymer is filtered off with suction, washed with acetone, then with 2N aqueous hydrochloric acid, then with water and then again with acetone and dried. Yield = 297 g, η _ϊβ α ~ 19.5.

Example 2

0.4 g of trisallylchromium are dissolved in 500 ml of η-hexane and mixed with 0.25 g of titanium tetrachloride. The deep red solution is discolored within a few seconds, at the same time a black-brown, flaky precipitate separates out. This contact suspension is filled into a glass autoclave and 8 atmospheres of ethylene are injected with stirring. The temperature is kept at 45 ° C. and the polymerization is terminated after 1.5 hours. The work-up is carried out as described in Example 2. 95 g of polyethylene with η red = 14.0 are obtained.

Example 3

500 ml of η-hexane are mixed in a round bottom flask under nitrogen with 0.5 g of chromyl chloride, then ethylene is passed in immediately and a solution of 1.2 g of trisallylchromium in 100 ml of hexane is added dropwise over the course of 30 minutes, the temperature rising at the same time 50 ⁰ C is increased. After 3 hours, 26 g of polyethylene with y _r ea = 4.9 can be isolated. in 100 ml of hexane. The experiment is terminated after 1.5 hours. 8.3 g of crystalline polypropylene with η _τβ α = 3.3 can be isolated by filtration. After steam distillation, the mother liquor yields 2.4 g of amorphous polypropylene.

Example 6

A glass autoclave is charged with a solution of 1.6 g of trisallylchromium in 500 ml of hexane and, after the addition of 0.85 g of titanium tetrachloride, the propylene pressure is 6 atmospheres. The autoclave is heated to 45 ° C. for 3.5 hours while stirring. Work- up gave 26.2 g of crystalline _{fyj re} a = 4.05) and 46.6 g of amorphous polypropylene.

B e i s ρ i e 1 7

A contact suspension of 1.0 g of trisallylchromium and 0.46 g of titanium trichloride (produced by the reaction of titanium tetrachloride and ethylaluminum sesquichloride) is prepared in 100 ml of hexane. The suspension is heated to 50 ⁰ C and passed in the course of 3 _^3/4 hour propylene. Work- up yields 22.9 g of crystalline (rjrea = 4.07) and 10.2 g of amorphous polypropylene.

Example 8

A solution of 0.5 g of anhydrous iron (III) chloride in 500 ml of toluene is added with stirring Solution of 0.9 g of trisallyl chromium in 100 ml of toluene.

This contact mixture is gassed at 50 ⁰ C with ethylene and powdered polyethylene after 1.5 hours - after decomposition of the catalyst in the manner described above - was filtered off, washed with dilute hydrochloric acid and dried. Yield = 3.8 g, Vred - 18.2.

Example 9

The iron (III) chloride used in Example 8 is replaced by 0.6 g of cyclopentadiene titanium trichloride. The test procedure corresponds to Example 8. 1.4 g of polyethylene with η _Τ εά = 17.3 were obtained.

Example 4

A prepared in 600 ml hexane solution of 0.35 g Contact Vanadinoxychlorid and 1.0 g Trisallylchrom is gassed at 45 ⁰ C and vigorous stirring with ethylene. After 30 minutes, 34 g of polyethylene with i) ree = 7.9 have formed.

Example 5

1.3 g Trisallylchrom are dissolved in 50 ml of heptane and added dropwise to the cooled to 0 ⁰ C solution under stirring 1.4 g of titanium tetrachloride. After 10 minutes, the mixture is warmed to room temperature and transferred to a round bottom flask in which 500 ml of hexane have been placed. This contact suspension is stirred vigorously, heated to 4O ⁰ C and gassed with propylene. At the same time, a solution of 1.4 g of trisallylchromium is added dropwise over the course of 30 minutes

Example 10

900 ml η-hexane are a suitable reaction vessel made of glass, which is provided with a stainless steel perforated blade stirrer, a ground drop funnel, a reflux condenser with subsequent mercury pressure valve and a gas inlet tube, at 25 ⁰ C with stirring with a gas mixture consisting of 3 parts by volume of ethylene and 7 Parts by volume propylene, saturated. A solution of 0.8 g of trisallylchromium in 100 ml of hexane is then added to the hexane using the dropping funnel, and 0.15 ml of titanium tetrachloride is pipetted into the deep red solution. The polymerization starts immediately, noticeable by the negative pressure occurring in the apparatus. The polymerization gas (ethylene-propylene ratio 2: 1) is introduced to equalize the pressure. The gas supply is regulated in such a way that the mercury pressure relief valve connected to the apparatus does not show fluctuations greater than +5 to - 10 mm of mercury column without exhaust gas escaping. After 2 hours, the batch is terminated by adding 1 liter of water and simultaneously passing nitrogen through. It is heated to 70 ⁰ C and stirred after removal of the first washing water three more times with 11 water at 7O ⁰ C for removal of the catalyst residues. Then the

7 8

Hexane is driven off with steam, the resulting benzene is dissolved and treated with dilute sulfuric acid.

elastomeric, gummy polymerization cakes from wash; one then withdraws from the organic phase in

Hand crushed and in a vacuum at 60 to 7O ⁰ C vacuum the benzene, whereby sticky, colorless

constant weight dried. The yield is polybutadiene that is over 70% off

92 g. 5 consists of 1,2-polybutadiene.

Example 11 Example 15

A 200 ml glass pressure bottle will be like
is charged as follows: Proceed as described in example 13,

1. However, with a ml at 0 ° C in 10 hexane, prepared ¹⁰ applies instead of heptane dry toluene suspension of 3 mmol Trisallylchrom ^and so on. ^at S ^{te "e ™} η. ^τι *? * etrachlori" 145mMol titanium 3 millimoles of titanium tetrachloride tetraiodide, The workup h _e fertl9 ₃ 5g polybutadiene

"." , _TT with 89% 1,4-cis configuration.

2. 60 ml hexane,

3. 15g styrene, ₁₅ example 16

4. 3 mmol trisallyl chromium in 20 ml hexane,

5. 0.15 ml of titanium tetrachloride. ^{In a} 2-1 round bottom flask equipped with winged

stirrer, thermometer, reflux condenser, attached

The sealed bottle is placed in a water bath dropping funnel and gas inlet tube, becomes a Kon-12 Shaken at 50 ° C for hours. Powdery, precipitated 20-cycle mixture of 0.22 g of titanium tetrachloride and 0.5 g Polystyrene is filtered off with suction, washed with acetone, and trisallylchromium is introduced into 850 ml of heptane. Man directs Then, for 3 hours with normal aqueous hydrochloric acid at room temperature, ethylene is used, using the boils, washed halogen-free and dried. From stirring speed an ethylene uptake of prey = 4.7 g. 501 / hour is set. After 5 minutes you start

Example 12 ^{a5 m} ^ ^ ^em dropping ^emer solution of 7 g of butadiene in

100 ml of heptane, the dropping speed being like this

The procedure is exactly as indicated in Example 11, it is regulated that after 40 minutes the entire however, for the polymerization, instead of the styrene solution, the polymerization liquor is added. Wah-4-methylpentene-1 a. The polymer solution obtained at this time is kept at the ethylene uptake is by repeated washing with water from 30 40 to 50 l per hour and the polymerization temperature Freed contact and then steam distilled. by temporarily cooling below 60 ° C. After the A colorless, solid polymer is obtained after polymerization with ethylene alone for 10 minutes Yield of 3.8 g. is continued, is broken by adding 5 ml

". . _Λ „„ n-Butanol and works as indicated in Example 1

Example 13 _{35 on>}

In a round bottom flask equipped with a paddle stirrer, yield = 59 g; η _Τ εα = 6.5. The installation of the buta-

The thermometer, low-temperature cooler and a gas service were mainly configured in 1,4-trans. inlet pipe connected to a supply line for

purified nitrogen, a contact mixture from Example 17

0.8 g of trisallyl chromium and 0.5 ml of titanium tetrachloride in 40

Submitted 500 ml of hexane. The procedure described in Example 10 is added to this mixture, and it is added dropwise

50 g dry butadiene at room temperature. The temperature of the batch, which is a solution during the polymerization, rises in the course of 10 mmol of endo-dicyclopentadiene in 100 ml of hexane from initially 22 to 42 ° C. in the course of 40 minutes, under float. 95 g of polymer are obtained with η _Τ βα - 3.4 with a simultaneous strong increase in viscosity. After 90Mi- 45 and a termonomer content (dicyclopentanutene, the polymerization is practically complete; one dien) of 6.5%. decomposes the contact with the addition of 6 mol of butanol, example 18

previously added 0.3 g of phenyl-ß-naphthylamine at 60 ° C

had been set. The viscous solution is used for a long time

Sam stirred into 21 acetone and the fine flaky polymer which had precipitated out, but instead of trisallyl chromium, was filtered off with suction, several times with acetone chromium chloride. This gives 18.5 g of polyethylene washed with and dried at 40 ° C in a vacuum. Aus r \ _re g, = 12.9. booty 42.5 g. According to IR spectroscopic sub- VprffieiVh ^ atpn

The polymer contains 45% 1,4-cis, 50% ergieicnsadiene

1,4-trans and 5% 1,2-configured polybutadiene-55 1.6 g of trisallylchromium were dissolved in nitrogen under nitrogen shares. 500 ml of η-hexane and poured the deep red solution into one

Example 14 Glass autoclave. The contact solution was heated

50 ° C and put it under a pressure of 8 atm

In the apparatus given in Example 13, ethylene is used. The experiment was stopped after 28 hours In 500 ml of absolute tetrahydrofuran 0.7 g of Tris-60 broke, the flaky polyethylene abeallylchrom and submitted 0.44 ml of titanium tetrachloride. vacuums, washed and dried. Were received 23.2 g, which corresponds to a space-time yield, are added to the vigorously stirred solution 60 minutes 65 g of dry butadiene gassed, with (grams of polymer per liter of hexane · hour) of 1.7 the temperature of the batch rises to 54 ° C. Man and a contact time yield (grams of polymer heated to the boil for a further 60 minutes, left to 65 per millimole contact hour) of 0.09. The product Cool to room temperature, the contact was decomposed in p-xylene and decahydronaphthalene at 100 ° C analogous to example 13 and pulls the solvent in only swellable and therefore a viscosity measurement is not Vacuum off. The sticky, tough polymer becomes possible in.

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The following table contains further comparative data, the technical progress of the invention Explain the procedure compared to the state of the art:

Catalyst component (b) catalyst
component (a) Olefin Contact time yield procedure (Grams of polymer each
Response time [in
Hours]) · millimoles Pb (C ₂ H ₅ ), TiCl ₄ Ethylene Ti halide British patent 1.4 font 796 530 (CH ₃ ) ₂ (cyclopentadienyl) ₂ Ti TiCl ₃ Propylene U.S. Patent 0.39 2 992 212 (C ₆ H ₅ ) ₂ (cyclopentadienyl) ₂ Ti TiCl ₃ Ethylene U.S. Patent 0.25 3,000,870 (AlIyI) ₃ Cr Ethylene Documents laid out by the 1.4 *) Dutch patent registration 6 409 179 (Example 2) (AlIyI) ₃ Cr TiCl ₄ Ethylene Method of the invention 39.6 (Example 1) (AUyI) ₃ Cr TiCl ₄ Ethylene Method of the invention 33.4 (Example 2) (AHyI) ₃ Cr TiCl ₄ Propylene Method of the invention 4.65 (Example 6)

*) The information here does not refer to millimoles of Ti halide, but to trisallyl chromium.

Claims (2)

Claims: 35 1. Process for the production of homopolymers and copolymers of mono- and diolefins by polymerizing the monomers, by themselves or as a mixture with one another, in the presence of Catalysts off (a) Halides, oxyhalides, ester halides or esters of elements of IV. to VIII. Subgroup of the Periodic Table and (b) organometallic compounds of elements of subgroups IV to VIII of the periodic table, optionally with the addition of hydrogen as regulator, characterized in that allyl compounds of chromium are used as organometallic compounds. 2. The method according to claim 1, characterized in that the allyl compound of chromium is trisallylchromium is used. Considered publications:
German Patent No. 1,026,964;
U.S. Patent Nos. 2,992,212, 3,000,870; interpreted documents of the Belgian patent
No. 631172; interpreted documents of Dutch patent application No. 6 409 179. 809 550/463 5.68 © Bundesdruckerei Berlin