DE1943632A1 - Process for the preparation of copolymers - Google Patents

Description

Patent attorney

Dr.-Ing, from KretsJer T5r.-hg. khönwald _n

fig.Th.Meyar Dr.Fuss Dspl.O'ism.Alijli von Kf «S * l <U 1 9 H- O D 3 2

Dipl.-Ctem. Carola KeÜar Dr.-Ing. KföpKh ■

Cologne. Deichmermheui »

Cologne, £ 7'-August 1969

Ke / Ax

5J-j_ FcIr ¹ P _- Buonapar te _, _ "Ma i 1 and_ j 'Italy ^ _ ^

Process for the preparation of copolymers

The invention relates to a method for producing essentially linear, amorphous, vulcanizable. high molecular weight polymers or copolymers by Cc- Polymerization of ethylene with one -olefin and one Diene using catalysts that have a anionic coordination mechanism are effective,

It is known to carry out the polymerization of ethylene with α-olefins and with a diene in the presence of corinated anionic catalysts in a solvent that dissolves both the monomers and the polymer (ζ = Β = η-hexane ^: and 'n -Heptane alone or in a mixture or their equivalents with other saturated hydrocarbons such as cyelohexane, toluene _, eenzene, carbon ether, chlorobenzenes, etc. and their mixtures *

The applicant also developed the production of amorphous saturated copolymers based on fibers and propylene and the production of amorphous, .unsaturation-containing, essentially linear ones Terpolymers based on ethylene, propylene and a dieq, e.g. cyclooctadiene, methylpentadiene- ".4 .. ethylidene-norbornene. Kethylte-trahydroindene, vinylcyclohexene or an aliphatic pien with a terminal Double bond v / ie hexadiene r'j4 and. Methylpentadiene-1.4

11/1034

- 2 -. ■ '■■ ",. ■.' ■■ -

Proposed, the polymerization of these monomers is in the presence of catalysts based on organometallic compounds of Al and Be and compounds of transition metals of the fifth group of the periodic System carried out so that the polymerization product not. is dissolved in the reaction medium. but in Tom von foamed "particles accumulate, which in the Reaktiönssrediua .. the essentially "" test from the mixture of monomers itself t are 'suspended'.

The latter method has opposite to that in solution ■ procedures carried out have considerable advantages through the this procedure becomes more appropriate. The viscosity of the Reaction system is at least within a certain amount Range of the amount of polymer present per unit volume., Independently, so that much higher polymer concentrations than to be achieved with the solution procedure are = This ■ indicates that it is possible to achieve high sales of the Eonor_eren to achieve without simultaneously having difficulties Stir and diffuse the more reactive Monomers occur. ..;

The last point is of particular interest as it is for the possibility of the composition of the-responsive Phase v / effective to "control or adjust a very -.important requirement is ":" "'" .- ■' .. · '-. \

"If in the present ball, in which one works with ^: " Entrepreneurs of very different relative reactivities: the production of polymers of "-he ^ enogenic -composition desired- v; ird ₃ ^; is the regulation of the ■ concentration of more reactive moaomers such as. Ethylene. and_ sometimes of the third monomer .. (ζ-B- ÄthyiidennorbOr- - ■ neji, -) ;; _; entseheid.enä. important;" , - ....,. .-,.,; ., __._...... ,. -'.-;,

The bus | 3ehslqhsprögess is "by <äas ~ method that Gegeifölahä't% 11alie'nlseH ^ h Patents' .59Q fO3 is. at ':.

009: 836/2034

Ethylene-propylene copolymers are particularly facilitated The process makes it easy to determine the composition of the responsive! hare to control and regulate and a considerable amount of heat per unit of volume and unit of time to dissipate. The polymerization of ethylene with propylene

■ vi < hi; ^: '' - - '' ·. and a conjugated diene in suspension does not always have an advantage over the same polymerization carried out in solution, since it may be more expedient to have the greatest possible conversion of monomers at the reactor outlet and not the r; .a: -: imal concentration Polymers: to be achieved in the total liquidity. This is. Particularly the case when the third ionor is a high-boiling one and a rather expensive one compared to the cost of the solvent and the prepylene

It has now been found that by diluting the Eeak. tic'ust an ethylene, α-olefin and a third conexe res in eiiicra hydrocarbon that is not a solvent for the polymer is. dcqiich is. the more characteristic: Advantages of the Jopolynerization Process on the Elastomers ciu-ocudehr.en. those from /Vtr.ylen, an a-Glefin and eir.e :: i third! -! cnonieren exist.

The addition of a substance that acts as a solvent for the Monomers, but not for the polymer wii-ksaTi is. enables it. css polymers with all associated distributions ·: - in. suspension instead of keeping in solution unc jzl-ichzei t-i £ i eir.e :. higher .. .Umsai-z of the monomers zi; educ-Ιοϊ: Diοs is particularly beneficial in the case of te.-ren Xerccnomercij i :: it low reactivity ..-

The introduction of the decoction for the polymer made possible not only a reduction in the amount of 2er: r.ct: cn: eren used. but also a saving for everyone Workers' walks; and .KaiBnahKen for the separation of the nicr.t J! :: ge se joined · Eermancreersfi vom pöljrnir-en =. this i-.r bei "3-

■. - ÜÜ9B35 / 2 0 3 h

BAD ÖRIGINAU

: .. - 4 - ■ '. ■■■' ■■, '■: "■',

It is wise to use the advantages of polymerization in practice in suspension "and · at the same time ensure the benefits of polymerization in solution, In this way it is possible to have very high concentrations of esters at the reactor outlet and to achieve higher conversions of the monomers. -

As materials that are solvents for the monomers, ater nonsolvents for the polymer are suitable, for example Ethane, propane. Eutan. Pentane and halogenated ^ low molecular weight hydrocarbons such as dichloromethane = ™ The use of propane also makes it possible to use as Terconomere for polymerizing substances in suspension with particularly poor reactivity (vinylcyclohexane. Cyclocctadiene) to use the otherwise they would have to be used in such large quantities, that they are effective as solvents for the polymer would ■ ·.

As polymerization catalysts, the catalyst

s.rsteme used, which are formed by conversion of a compound eir.es transition metal of the 5 group with an Org.ancmetal-lvertincung cdc-r with a hydride of a metal of * groups I to "III. Subgroup A of the periodic system Transition metal compounds that are soluble in hydrocarbons are suitable . ICQI-i VS ^ A ^αΓί ^ ^ snadine triacetylacetonate,. ".

Examples of suitable CrgancT metal compounds are Dialkyl aluminum monochloride, alkyl aluminum sesquichloride and. Alkylaluminum dichloride.

The catalyst components must be chosen so that at least one of the two components contains at least one Kalogenatora =. .. ₇

. ".-. ' Me PolyKerisäit ^ -on * · Can within; a very / wide Ee- ■ - ;. '.. vBizhs "en- iersteratureri ■ -.between -80 ° and +50 ⁰ C ocer

■ 0 0 Β 83 6/2 υ

- % -ΐ- ^: ^ BAD ORIGINAL

_ 5 -

be carried out above, but preferably between -50 ° and + 3Q ⁰ G = The copolymers obtained in this way can be vulcanized to vulcanized elastomers by conventional or unusual processes,

Be i sp i e 1 e _ j _ b i s__ 5.

In a 6 1 stainless steel autoclave, the with a comb stirrer and a wall cooling system with ammonia cooling circuit was provided. five Polymerisatior.sversuche were carried out with and without propane

At the beginning of the experiments, liquid propylene, optionally together with the propane and methylpentadiene-1,4, were added to the autoclave. The temperature was then lowered to -10 ⁰ C and saturated the reaction medium with ethylene up to a certain pressure, the desired ¹ ethylene / propylene Verhältηis urn in the Plüssigphase to ER- "hold Then, the catalyst components were introduced, namely, Al (C. ₂ Hf- _{I 2} Cl as a 15% solution in heptane and vanadium triacetylacetonate as a 5% solution in toluene. The catalyst was added in four portions at intervals of 15 minutes ^ In the course of the experiment, the ethylene was continuously introduced during the pressure in the autoclave was kept constant.

lv ^T ach of the polymerization, the reaction was' addition of 10 ml of methanol and the resulting polymer was cancel the new entnomrcen from the reactor and gewogen-

The working conditions and the results obtained those carried out in the presence and in the absence of propane Experiments are given in Table 1 below.

QQ9836 / 2034

Facts Experiment no. j 2 3 • ■■ = 4 - ^ °. Propqa, g - 1 O 1540 ■ "5 ^ 9. XÖAO Propylene, g 1450 i / 00 550 55-p ". ' Ke t h y 1 ρ ent ad i e'n, - g 520 580 168 . 168 ' Contact time.HiniAt.en. . " '75 :&O 60 60 2; 85 Al (O ₂ H ₅ V ₂ Cl, g 12C 2.9 3.0 3.0 " 0.96 Vanadium triaeetylace tonate, g 3.8 1.08 1.0 300 Polymer, g. 1.44 500 640 460 80 Yield, g terpolymer /
g catalyst 460 130 160 120 6.5 In-polymerized methyl
pentadienv Gev.-fo 92 5 3.2 4th 36 Polymerized Propy
len; G-eWc-5 « 3.7 50 43 40 2 , 5 Conversion of methylpenta-
cl ie η, Gew -ft 50 4.8 12th 11.5 /.2 Ethylene partial pressure.
Atmospheres. ■ '.- ■ '0.3 I. 0/4 0.4- 0.3

The values in the table above show that the Amount of the third monomer in the batch is reduced to a third, while its conversion is doubled.

With the same device and under the same working conditions as in all of the tests from Example 1 to 2, two comparative tests, i.e., one test with and one test without a diluent in the polymerization phase, were carried out: the diluent used was η-butane verv; endsc Pas terpolyinere was produced by polymerizing ethylene, propylene and methyl tetrahydrofuran - the temperature was lowered to -IO ⁰ O, whereupon the ethylene was reduced to a certain predetermined pressure: was introduced, 'who so chosen what ?; that the desired

OG983β / 2D04 ^{; :}

BhD ORIGiNAt

Ratio of bonded ethylene and bonded propylene was obtained in the terpolymer formed.

Subsequently, Al (C ₂ Kc ^ ₂ C as: 5 / ji £ ü solution in heptane and vanadinoxy chloride as a 5 'solution in heptane were introduced into the autoclave as the catalyst component added YJduring the polymerization, ethylene was continuously added so that the previously set Fartialdrock was kept constant rei Eeeπαigung the polymerization, the reaction was terminated by adding 'C ml of kethanol- Then the suspension was taken from the autoclave and the polymer after evaporation of the not unoccupied monomers

Kit of the same device and using the same I-'newer and the same dilution number, tests 8 and 9 were carried out in the same way, which increased the comparison tests in the case of a cerium. temperature. c-ie us 40 ⁰ C ¹ above the previously applied tempera ^{1 1} Ji lag. represented ::, ph the experiments were carried out at +30 0 The catalyst in this case was a complex formed by reacting vanadium triacetylacetonate with diethylalus monochloride. The working conditions and the results obtained in this two series of comparative experiments sir.G :: given below in Table 2:

0G9 8 3B ^ 20 34

Table 2 Attempt no- 6th _7th 8th- - Έ utan, ml 2000 - - _ 2000 40C0 Propylene, ml 2000 4000 20C0 1.2
Partial
pressure Ethylene, atm .; 0.52
Partial
press ., Ul
Partial -: -
pressure 0.55 400 Ke t hy 11 et rah ydr ο i η de η.
ml 197 405 201 +30 Temperature, ° C -10 -10 +30 60 Contact time. Minutes 60 60; 60 , VfAc ^ ₅ VCCl ₇ 2 _; 56 mmol 2.56 mcol - 2.4 g Al (C ₂ H ₅ J ₂ Cl 1 9.24 "1 9.24 " 2.4 g 110 Polymer, g 520 .480 135 45 Bound propylene,
Gew - ^c , 'i 46; . ■ - 44 46 3.5 Bound Kethyl
tetrahydroinden.
Wt .- 'l 3.5 ■■■■ "■ - ■ '3.4- 3.6 1.5 "■ - ' ΓηJ ■ 4th Austria ^; - 4.6 1.4 2.25 Prox-ylene sales. i> 21 ". 7 9/6 5.65

Kethyltetrahycroinden Urasatz. 4 ..-. 10.3

Yield in Graam Polycerisate / g Eataiysatcr 190

4.5

175

2.8

37/5

1 .07

30. 6

The above results show. that reduction the amount of conofeers propylene and methyl tetrahydro --- '■ incen. in the fieatctlc-n '"from a significant. increase in the ürasatzes of these con-nomers is accompanied byV "■■ -" ■

Je χ sp i e 1 e_ _1 p_ u ηd_ jJ_

In the filial device, and in the same way, v / ie in. the above ■. Examples described. became two comparative tests carried out with and without propane

jvobei: as; j3rittfiS -onomereÄ Oyclöoctaäien-1,5 -vervie-'naet: viuxclev; As a catalyst: the product became bigger

BATH

Reaction of Al (C ₂ HV) ₂ Cl with VCJ .. used.

Due to the low reactivity of cyclooctadiene- '.. 5 had to be used when propane was not used as a light dissolver an amount of 1,5-cyclooctadiene in relation to the propylene is used that the mixture obtained of cyclooctadiene-1.5 and propylene a solvent for the polymer was so that the reaction was not in suspension, but took place in solution,

The conditions and results of each experiment are shown in Table 3 below. The values in this Tables show that the conversion in the experiment with propane of the third monomer is twice as high as in the experiment without propane

It should be noted "that by adding propane in this Case as well as in all cases where the third monomer is not very reactive and must be used in large amounts in relation to the propylene, the amount of third monomers present in the reaction medium, can be greatly reduced, leaving the reaction, which would otherwise have to take place in solution, in suspension takes place with all the associated advantages.

This fact represents another significant advantage of working with propane, as it makes it possible is. the "advantages of working in suspension on such." To extend polymerizations that are excluded from this possibility by the nature and amount of monomers would be.

BATH

00 98 36/2 034

- -ίο -

Table 3 Try Fri _8. " 10 11th Partial pressure of ethylene, atm " 0.3- 1.0 Propane, g ISCO " 0 Propylene, g 275 ¹³⁰⁰ Cyclooctadiene, g. 475 1350 Contact time. Minutes 120 120 VCl ₄ . g ■ 0.72 0.8 Al (C ₂ H ₅ V ₂ Cl, g, 2.2 2.5 Polymer, g 150 160. Yield, g polymer / g catalyst 62 55 Bound cyclooctadiene, Gev /, - $ - \ ./L 1.9 " Bound propylene. Weight, - ^c / o 44 53 Conversion of cyclooctadiene. $ & 0.55 "O ₃ 25 EeisOiel * 2. 13th and 14

In the same device and "in the same Yüeise .. as described in the previous examples three comparative tests carried out = one test was carried out without thinner and in the other tests using pentane or methylene chloride as a diluent for the polymerization process * works, ■ -.

Ethylidene was used as a termonomer in these experiments. norborneη (ElIB) used Due to its high reactivity, the Blffi was partly used at the beginning of the Experimental and .partly supplied during the reaction. " with the amount added constantly on the reaction rate was adjusted so that the G ^ Hg / SIiE ratio would remain approximately constant in the liquid phase

The working conditions and the results obtained

are mentioned in the following table, so that a

equal _: de.r _; ; phtte, and preserved with dilute ^ medium. Results possible. _eating; . : ■ '-...

9 8 3 6/2 0-3 A '' ^

Table 4 Try Mr. 12th 13th 14th Diluent, g 0 Pentane Bi chlorine than ■! 130 23ε υ Propylene, g 1900 950 950 Ethylene partial pressure.
Atmospheric 0.5 J, 5 ElIB. G 26.4 13.5 33 Temperature, ⁰ C -10 -10 -10 Contact part. Minutes 90 so SO Vanadium triacet-ylaceto-
nat. cKol 0.04 0.08 Ο.'ίβ Al (CpH _r ) 'oCl. tnHoi 32.2. 32.2 32 _Γ 2 Polymer c-s. G 1C8 • 48 5CO Bound propylene. ^ 45 43 ; 43 Hardcover EKB. ? * 4.2 5.1 CnJ
Sales of sales. & ro, 5
2.56 8th
7 .. 15 8.2
22.7 EKE turnover. # 17.2 38.8 56.0 Yield in grams of polymer
risat -'f. catalyst 27 57 ■ 25 Yield in grams of polymers
σ vanadium metal γ /
5,000 36000 6 -, - X) O

Ee i

_! 5

/ 6

In a: 2 "C 1 autoclave made of non-rusting steel, the was provided with a Kar.:r,rUhrer and Kühlqantel, - "were two comparisons with and without a diluent in the pelycation phase carried out as dilution; r; ££ - Middle of η-butane is used

To Eegir.r. of attempts were in '· the. Autoclave des Combine propylene with - butane. (Experiment 16) and that as third 'Ecüo: -eres given Kethyltetrahydroinden used. The temperature was then brought to -f25 G and SeakfioiiS'sriediüni'init Äthylen 'up to the desired Ρε-r-

0 0 9 8 3 6/203 4

BATH ORIGINAL

tialdrüek saturated, -, · .--. Subsequently, as catalyst components Vanadium oxychloride and isobutylalu. niumsesquüichlorid (AlgiBu-zCl,) as a 15 $ solution in Heptane introduced. These components were divided into four Portions added every 15 minutes The reaction lasted 1 hour and was enhanced by adding Methanol canceled - compartment removal of monomers was performed the polymer weighed and examined *

The essential working conditions and the results obtained in the two experiments are shown below Table specified-

Table 5 Diluents 0 16 ral Propylene '1 1000 ral 5500 ral Ethylene partial pressure; Atm-. 1.4 ... 5500 Methyl tetrahydroids. 1100 ral 0/7 1 Temperature. ⁰ G. . +25 550 κ Kcntakzei.t. Minutes 60 +25 VGOl ₃ ./■■■'-. 1> 52 g - . 60 G IsObutylaluminium Seociuichlorid 7; 2 g 1.52 G Polymer. 630 g Bound propylene. Gev / -φ 44 ' 725 g Bound Meth ^ ltetfahydroindeo *
Wt .- ^ 7/5. .. "/ ■■■■" 46 02 y 4th 8.4 PROPYLUM SET '■■' -, 4.6 $ ·: 3.6 ■ Ke tiiy 11 e tr ahyä ro i nd e n-Ümsat ζ II j I , 0 Yield; g polymer / g iCataly-
sator ■■ - ■■ - ■. . 72. ^; ', 2, Ai 84

A) Comparative experiments on terpolymerization using of methyltetrahydroinden as a third conomer with or without propane as a diluent of the

Flow ieen_ Polymer isatipnphase

The first series of experiments was carried out in a stirred autoclave carried out, which had a capacity of 20 1, of which 15 1 were usable. The autoclave was with a stirrer and the one in the Italian patent 598 103 "heat stabilization system described, Propylene, Ethylene, the termonomer, any propane used and the catalysts supplied »Vom Fuß the polymer and the unreacted monomers were removed from the autoclave, that with a gamma ray system regulated liquid level remained constant.

Some of the gases were sucked out through the top of the autoclave and through the bottom of the autoclave blown in to better balance between the To ensure liquid phase and gas phase,

The temperature, the pressure and the composition of the gas phase were precisely measured and regulated. The steadiness of the composition was controlled with the help of the signals of a process gas chromatograph, to which a fraction sucked in from the reactor was fed into the gas phase . The polymer discharged below was in a sump containing at 1QO ⁰ C ,, water kept separated from the monomers "in this vessel, the monomers were distilled off, while the polymer was extracted with Yiasser in the form of a rubber dispersion in Kasser,

To the influence of Anwesenhe.it of propane compared to the normal ■ Try fixed ζ us; share that in Geiaisc / i · der

0 0 9 8 3 _6/2 03 4 BATHROOM ^ "

liquid monomers were carried out. became two Series of comparative tests carried out on both; In the series, the polymer formed proved to be insoluble in the polymerization medium. In the first series of tests " this medium consisted of the mixture of the neat liquid monomers, i.e., propylene, ethylene and methyltetrahydroindene. "* In the second series of tests, the ratio of the monomers was unchanged, but were diluted them with varying amounts of propane, 'the ■ a solvent for the monomers, but not for that Polymers is = ■

; The experiments were all continuously and always - carried out in the same way, the catalyst used as the complex that was formed by reacting aluminum diethyl monochloride with vanadium triacetylacetonate. These two catalyst components were also fed continuously to the autoclave. Discharge was also carried out continuously in such a way that the liquid level in the autoclave was kept constant. so dosed that the contact times were comparable =

The polymerization conditions (temperature and pressure in the reactor. ¹ added amount of monomers and .catalysts, contact time, total contact time of the experiment) and the chemical and physical properties of the polymers obtained are given in the following table. - Experiments 17 to 22 were carried out under normal conditions, which are used in the suspension polymerization of monomers in the liquid state ..-.- ■, -

Experiments 23 to 29 were carried out according to the invention in Present, ν-όη liquid propane as a diluent of the Reaction phase carried out in unte ^ schiealiclaen proportions

00a836 / 2O34

About the series of experiments * those without a diluent have been carried out, note the following p

1) A substantial increase in sales for each Monomers and the total conversion of these monomers is to be determined. "

2) The yield based on the catalyst is higher (higher ratio of polymer formed! in

■ grams per gram of the catalyst used), and this of course partly with the same Kooney viscosity and with the same content of polymerized propylene and methyltetrahydroindene.

5) There is also some increase in the reactivity of the third monomer with the other two monomers (Determine ethylene and propylene, Eei are alike Ratio of propylene to methyl tetrahydroindene in the Plüs ^ inphase the content is bound! Methyitetrahydrornaen higher than he can achieve without the use of propane is Kit in other words "at lower ratios ".vcn methyltetrahydroinden to propylene in the liquid phase is a content of bound, Kethyltetrahydroinden eriialteö-, which with that at higher ratios, but in "absence." from propane obtainable content is comparable

0 0 9 8 3 S / 2 0

-16- \ ■■ .- ■■. ■ '. -

J7J [8J920

Temperature. C -5 -5 -5 -5: -5 -5 Pressure. 'Atnu 5.2 5-75.8 5.8 5.8 5.8 Ethylene insert.

kg / hour '0.7 0.72 0.85 0.8 0, -71- 0.68 Propylene insert.

■ kg / hour. V 5.05 5.37 4 _f 5.4.8 5.04 4 * 74

'Ter Konorner use.

kg / hour '0.84 ■ ..!. · 09 0.9 0.96 0.91 0.79

Fropan insert.

kg / hour '0 0 0 .0 0 0 V-acetylacetonateK ■

g / S tu n'd e ° .3, 2 2.1- 4.7 ^ 3.1. 4.0 1.4

Al (C ₂ H ₅ ) ₂ Cl, g / h, 8.6 5.-7 12.5 '8.3 10 3.75 ,, • Contact time.Kin · 90 78 93 86 84 95

Total sales of

Monomers ~, % '- 13.1 7.3 26.9 18.4 12.8 15.0:

Mooney viscosity

(HL ⁴ +4 at ICO ⁰ C). 105 100 49 31.5 2'O ^ 220

£ η ~ ί ^ 2 _; 1 .2.4 1.6 1.4 3.0 3.1

GetundeneG Fropy- '■ ...' -

Len, Wt - $: - 43 47.6 46 44.7 4.1.7 46.7

Tied up. Terßono-. .

meres _; Wt .- ^ 5 4.4 4 _f 6 5.0 4 '4.8

Ausceute: g- FoIy- '_ ■ ■. . '"'. ■■.

"" jneres / ß uesamtkata- '.
analyzer 73 67 62 90 52 178

Concentration ara. -

Exit. Gev / - ^ 13.1 7.3 26.9. ' 18.4 1.2.8 15.0 G ₂ sales, $ 64 34.9 62 63 56 65 C ₃ sales ₎ ^ 7.35 4.64 10.9 9.6 6.05 9

Conversion of ethyl "■. ■. ,. ■■" ■ ·.

tetrahydroinden, $ 5-15 .Z ₁ ' 5.45 5.3 3.2 5.6

Try no _-1 23 24 25 __.._ 26 _._ 27_ 28__ _ 29

Temperature;. C -5 -5 -5 -5 -5 -5 -5

Pressure. Atm »5 _r 6 5.2 4.8 4.5 4.5 4.2 4 ₅ 5

Ethylene insert,

kg / hour, 0.85 0.75 '0.75 0.9 0.88 0.85 1.1

Propylene insert,

kg / hour 2.82 2.81 1.6.1 2.85 1.37 1.37 1.49

Termonomer A

rate, -kg / h O; 453 0.254 0.196 0.47 ■ 0.22 O ₅ 22.- 0.248

Propane use =

kg / hour '2.84 2.3 4.0 2.4 4.0 4.0 6.2

V (acetylaceto- "~

nat) ₅ , g / hour 0.92 2.85 '3.06 3.8 4.2 1.21 3 _r 9

Al (O ₂ Hc) ₀ Cl, '

g / StaV "2.46 7.64 8.1 10.7 3.14 3.26 10 _s 7

Contact time, min. 90 90

Total turnover of the monomers, ^ 29.6 35.6

Mooney viscosity

(ML 1 + 4 b, 100 ° C) 147 102

DlJ I ³⁵ 2.5 2..3

Bound propylene, wt- ^ 36.5 44.5 45.6 38.7 29.7 37 42.2

Bound ter-

monoraeres,

Gewc-5 * '5 3.6 4.1 3.7 3 _f 1 2 _S 3 4.0

Yield: -

g polymer / ■

g total lataly-

sator 359 129 130 104 256 195 130

Concentration at the exit.

Ga \ '! .- $' 15..8 20.3 18.3 21.7 13, θ "10.1 19-, 8 C ₂ -UmS at z,? 5 84 83.5 97 97 - 85 62.5 93 C ₃ -U: i: sentence, fo 15.7 21.4 41 r 20.5 24 25.5 '. 53.5

Sales of.

Methyltetra- '

hydroinden, / ₅ 13.4 18.7 31 11.9 15.6 9.1 30.5

BADORIQINAi.

009836/2034 '. ''

90 90 90 90 90 59 37.5 46 35-, 6 67 76 85 .31 - 300 120 1.8 2 1.1 3.3 2.5

-is - ■; ■■ ■■■■■.

B) Comparative experiments on terpolymerization pit and without Propane as a diluent in the polymerisation phase when using ethylidene norbornene as the third

Using the same apparatus as for the above series of comparative experiments, a series of normal experiments without diluent for the polymerization phase (experiments 30 to 33) and a further series of experiments (experiments 34 to 36; using the diluent) were carried out as Ψ the third I-ionomer in these two series of experiments was ■ ethylidene norbornene and propane as a diluent- '. "'. '.' ■ -. ■ -.- ■■

The experiments were carried out in the same way as the series of experiments described above continuously _f in suspension, etc. - The working conditions, the amounts of monomers and diluent used and the results are shown in the table below. indicated = In this case, too, it should be noted that the use of the non-dissolver for the polymer leads to a; significant increase in the conversion of the monomers with a simultaneous certain increase in the yields based on the catalyst.

BATH

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00983.3 / 2034

BATH ORIGINAL

: - 20 -; ■; ■■; . ■.

Be isme le_ 37 _ u n, d_ 38_ Comparison of polymerization experiments in solution and in

With the same apparatus as was used for experiments 17 "to 36 _; two terpolymerization experiments were carried out continuously, using ethylene, propylene and methyltetrahydroindene as monomers and the complex formed by reaction of aluminum diethyl conochloride with vanadium triacetylacetonate as catalyst lasted 15 hours each. " In both experiments the reaction medium was diluted with a material which did not take part in the reaction but which completely dissolved the monomers. For this purpose cyclohexane and propane were used.

Ira first case, the thinner is a good solvent both for the monomers and for that formed Polymers so that the polymerization takes place entirely in solution. In the second case the polymerization takes place in suspension, since propane is a solvent only for the monomers.

The working conditions and the results of these two: Experiments are given in Table 8 below: Experiment 37 was carried out in solution using cyclohexane and Experiment 38 with propane,

BATH ORIGINAL

9836/2 0 3 ^

~ 21 Table 8.

Jä- £ SB £ b ^^ s. ^ - 37,

Temperature., C

Pressure, Atmα

Ethylene, kg / hour

Propylene, kg / hour Termonomeres, g

Cyclohexane, g

Propane, g

Vanadium triaeetylacetonate, g / hour Al- (O ₂ Hc) ₂ Cl, g / hour contact time, minutes total conversion of the monomers.fi ethylene conversion, $

Propylene conversion, fo

Methyltetrahydroindene conversion, ^ Mooney viscosity (ML 1 + 4 at 100 ^Q C)

Bound propylene, wt, - ^

Bound methyltetrahydroindene, weight - <»

Yield: g polyamide / g total catalyst

Concentration at the outlet, Wt = - $

In the experiment with cyclohexane it was not possible to go beyond a concentration of 80 g of polymer per kg of solution in the reactor, because it was impossible due to the very high viscosity achieved, which was considerably above 1000 cS, the synthesis conditions, z ₌ B, the To regulate the temperature, the uniform distribution of the freshly supplied monomers and the catalysts or the discharge of the solution from the reactor in such a way that there is no risk of constant clogging of the outlet

00 98 36/2 0 3 k BAD ORIGWAL

37 _ 38 -5. ' -5 2.8 4.5 0.85 0.86 1.65 1.39 0.27 0.22 5 0 0 4.24 4.8 1.2 13.2 5.24 90 90 20.2 44.6 33 74 15.8 30.6 7.3 18.5 75 85 1.8 2 46.5 38th, 7th 3.5 3.7 -31 248 7.8 17.5

The high viscosity and the resulting low Rates of diffusion of the monomers and the Penetration of the solution of the catalyst components is responsible for the very low yields, which at the test carried out in solution obtained the limit value of the viscosity at which the work was carried out. and not exceeded because of the general mechanical and physical difficulties described above could be, was therefore responsible for the low concentration at the outlet of the reactor »

A comparison of the two attempts reveals the 'advantages des Arbeitc "in suspension very clearly: The conversion of the monomers is higher, and so are the yields and concentrations of the polymer at the exit of the reactor are much higher ■

It should also be emphasized that the concentration of 7, S ^ in the case of the solution already represents an upper limit that is not excessive, at which the operation as a result of the Difficulties of discharge and the very bad ones Distribution of monomers and catalysts completely is unstable and insecure, yes, the opposite must be the fc ■ value of 17? 5/3 in the case of suspension as absolutely normal and easy to increase with further completely smooth Operation to be viewed. ' The one formed in experiment 38 Polymers also proved to be perfectly homogeneous and had good mechanical properties, while the Run 37 polymers formed poor homogeneity because it was partly made of polyethylene and polypropylene duration. Because of these properties, this was polymer completely useless for practical purposes /

00 9836/2034

Claims (11)

patent claims 1. "Process for the production of copolymers from ethylene ur.d an α-clef in and possibly an elen in Presence of a catalyst, which eir.er by reaction Connection of a transition ring of the V group with ' an organometallic compound or with a hydride of a metal from I. to III. Subgroup A of the Periodic Table has been established., Thereby characterized in that the monomers mentioned are in flow: 'ecm a state which dissolves the monomers, the polymers but adds non-reading diluent and saturated aliphatic hydrocarbons as diluents, chlorinated low molecular weight aliphatic hydrocarbons or mixtures thereof are used. 2. _{t The} method according to claim 1, characterized in that iraa as a diluent propane. Eutan. Fentan and / or ϊ ic hl or-rre t hau verwer.de t .. . "5. Process according to claim 1 or 2, characterized in that ethylene, propylene and an iron are crystallized. k.) Method na: h claims 1 to 3, characterized. -.ia3 ran a.1 s Copolymeri :: a * Icnskcmponente a cyclic ~> en used, 5. ': The method according to claim 1 to. 4. characterized by that rr.an as cyciisches Tien Cyclocctadiene .. Kthylidenncy'c; ::: en, vethyltetrahyircir.ien or Vinylcyclchexen ver * .: er.i5er. ' 6. "The method according to claim 1 to 3, characterized in that ΐΓΛη as Tien an aliphatic diene ^: verv with at least one Vinyldcppelbünden ends. 009836/203 C ORIGINAL BATHROOM r · "rf - ■■ 24 - 7.) The method according to claim6, characterized in that one as aliphatic diene methylpentadiene-1/4 or Kexadiene-1,4 used. 8.) Process according to Claim 1 to J _3, characterized in that a polymerization catalyst is used which is produced by reacting a vanadium compound with an organometallic compound or an aluminum hydride. 9.) Method according to claim 1 to 8, characterized in that ^) that one uses catalysts in their manufacture at least one halogen-containing component is used - that is. ". * 10.) Method according to claim 1 to 9j, characterized in that that the vanadium compound used is vanadiurotriacetylacetonate, Vanadium oxide tetrachloride or vanadium oxychloride is used. 11.) The method according to claim 1 to 10, characterized in that that the organometallic aluminum compounds are dialkyl aluminum moncchicridej alkylalurainium sesquichloride or Alkylaluminum dichlorides are used. | l 12.) The method according to claim 1 to 11, characterized in that .that Iran, as an organometallic aluminum compound, diethyl ; aluminum monocloride used> Λ- Λ-; ■ '; = .-.; -; - ^: - ν :. BAD 009S3S / 2034