DE1520137A1 - Process for the polymerization of isoolefins - Google Patents

Description

Ie. DEER. N AT. V. VO S SITJ S DIPI ... CHEM. MUNICH 88

. PATENTANWALT S = SSUT ""

Pos-4520 Gosei Gomu Jap ", No. 3444/63

JAPAN SYNSHSIIIIO RUBBER CO ₀ , Tokyo »Japan

Process for the polymerization of xaoolefins.

The invention relates to a new method of polymerization of isoolefins with a terminal methylene group, such as isobutylene and 2-methylbutene-1, and for the copolymerization of Isoolefins with Diolefinsiu

The halides of the metals of groups HIA and IVA and IVB of the periodic table, such as the halides of boron, aluminum, titanium, zirconium and tin, have long been known as catalysts for the polymerization of isoolefins. These metal halides "are also known as Friedel-Crafts catalysts. According to the book by H ₀ GUterbock, Polyisobutylen and laobutylenmiechp.polymerisate" Springer 1959 "in which almost all wioh-

909884/1665

POST CHECK ACCOUNT: MÜNCHBW IB 68 07 BANK ACCOUNT: BANKHAUS MAFFBI 4 CO., MÜXCH.If, KTO. NH. S 4OSS

BATH

patents published up to around 1958 on catalysts for the polymerization of isoolefins and for interpolymerization with other olefins or diolefins are listed, Almost all catalysts for the production of high molecular weight polyisobutylene and butyl rubber belong to the class of Friedel-Crafts catalysts and there will be very few Heavy metal! Halide O mentioned as catalysts.

It has recently been known to use organometallic compounds of the metals of groups II and III together with the aforementioned Friedel-Crafts catalysts "Examples are the combination of aluminum triethy1 with titanium tetrachloride (A. Vo Topohier, Doklady 3kad ° Hauk" 3.SoS ₄ R ₀ IU, pages 121 to 124 (1956) “aluminum alkyl compounds and tin tetrachloride (British patent specification No. 867 636), the combination of the reaction products of boron trifluoride and an aluminum alcoholate with titanium tetrachloride ( ₀ Wichterle et al., IUPAC symposium on macromolecules from October 12th to 17th, 1959 in Wiesbaden) and organometallic compounds of the metals of groups II and III with boron trifluoride (Japanese patent specification Hr. 15489/62).

Furthermore, the combination of halides of the metals of groups II and III with organometallic compounds of the me-

909884/1665

All of groups II and III or these combinations and a small amount of compounds of the transition metals of group VIII have proposed all catalysts for the polymerization of isoolefins and interpolymerization of isoolefins with diolefins. These catalyst combinations are very useful with regard to the polymerization activity, the control of the molecular weight and the easy regulation of the polymerization ratio of isoolefin to diolefin.

The advantages of the combination with organometallic compounds are to increase the solubility of the catalyst combinations in poorly-dissolving solvents such as ^{Kohlenwasaer-]} materials, the higher polymerization activity or the higher molecular weight of the polymer obtained in comparison su the Friedel-Crafts catalysts eineein used. However, these catalyst combinations also have disadvantages, see B. they are very sensitive to air and moisture and many. of them react explosively »This is a common characteristic of the organometallic compounds of the metals of the" Groups II and IH _{0 ".} Therefore, the handling of the catalysts and the implementation of the polymerization must be carried out very carefully and special devices are required in order to achieve constant, easily reproducible results to achieve «,

909884/1665 BATH ORIGINAL

· Are carried out in the production of butyl rubber "the copolymer of isobutylene and isoprene, and also occur in the production of high molecular weight polyisobutylene numerous difficulties' aufο example, must implement at very low temperatures below -7O ⁰ C. On the other hand, the reaction proceeds very rapidly and it is generally finished in less than 1 minute "Another problem is the removal of heat from such rapid and approximately XO kcal / Hol exothermic reactions". This problem, however, became more suitable through use Devices solved «so that the polymerization can be carried out on a largely domestic basis.

j When using conventional Friedel-Crafts Katelyeators, impurities are a nuisance! especially olefins, such as the JDimere Triffere or of the isobutylene, the polymerization considerably "It is sohwierig obtained zn reproducible results in terms of a molecular weight and the like. of the polymers. , because oily to dough-like polymers are formed, which worsens the heat exchange in the reactor or clogs the tubes and pumps.

Thus, one of the purposes of the invention is to provide a catalyst make available for the polymerization of isoolefins, which is very active in small amounts, provides easily reproducible results and is resistant to impurities

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BATH

Hydrocarbons are negligible

Another purpose of the invention is to provide a process for the production of high molecular weight copolymers from an isoolefin and provide a diolefin ssu »

It has been found that vanadium compounds have considerable activity in the polymerization of isoolefins. It is not previously known that vanadium compounds are useful catalysts for the polymerization of isoolefins. Of the isoolefins, isobutylene is particularly preferred because a high molecular weight polymer is easily produced o whole In general, however, isoolefins with a terminal methylene group, eg _o 2-diethylbutene-1, can be used. Diolefins that can be used for copolymerization with the isoolefins can contain conjugated or isolated double bonds and 4 to 8 carbon atoms in the molecule. Examples of preferred diolefins are butadiene, isoprene , 2,3-dimethylbutadiene, piperylene,!, A-pentadiene, vinylcyolohexene and oyclooctadiene »

The catalysts used according to the invention are the halides of vanadium »such as vauadine tetrahaloride, vanadium triohloride, • Vanadium tetrafluoride, yanadine trifluoride and vanadium oxychloride, and organic vanadium compounds such as dicyolopentadienyl vanadium dichloride and dicyolopentadienylvanadinedibromido

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Can be used as catalyst also by mixing a vanadium compound, preferably a Vanadinhalogenide, in an inert solvent _f with the carbonyl compound of a lietalles Group VIII of the Periodic Table precipitate obtained in a hydrocarbon or halogenated hydrocarbon may be used "as carbonyl compounds Z ₀ B. nickel carbonyls or! cobalt carbonyls are used «, the hydrocarbon or the halogenated hydrocarbon can be one of the diluents mentioned below«

The present invention catalysts used may also be used on a carrier "> For the polymerization is allowed to isoolefin in an inert solvent or diluent with the catalyst in contact _α come The reaction is in an inert Gaeatmosphäre such as nitrogen, performed · The catalyst may be in the inert solvents are suspended for the polymerization.

For the polymerization, only a small amount of the catalyst is required example show in the polymerization of isobutylene in Methylendiclilorid with vanadium tetrachloride already 0.01 Get "£ the vanadium compound a remarkable Aktivitätο aluminum trichloride, a typical and conventionally used catalyst, under the same conditions has no activity _o

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BATH

The diluent is usually an inert organic solvent, BoB ₀ a hydrocarbon such as ethylene, propylene, propane, butane, butene-1, butene-2, pentene, pentane, hexane, cyclohexane, heptane, benzene and toluene, a halogenated aliphatic or aromatic hydrocarbon, such as methylene chloride, Hethylendichlorid, Methylendifluorid, ethyl chloride, Äthylondichlorid, Triohloräthylen, tetrachloroethane, hexachloroethane and chlorobenzene or carbon disulfide verwendetο,

In the process according to the invention, the average molecular weight of the polymers obtained can be determined by the type of the solvent used, the reaction temperature, the Easily adjust the catalyst concentration and the like Polymerization is carried out at low temperature using aromatic halogenated hydrocarbons as a solvent, it is easy to obtain polyisobutylene with a molecular weight of over 100,000 or the copolymer a content of several percentages of butadiene or isoprene.

In reducing the catalyst concentration, the average molecular weight increases of the obtained polyisobutylenes or copolymers of isobutylene and the diolefin to _o This phenomenon occurs in the catalytic polymerization of vinyl compounds in the uncommon. If 0.01 itol- # vanadium tetrachloride is used in the process according to the invention, a polyisobutylene with a molecular weight of

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ORIGINAL

1S20137 - θ -

over one million "Am Such hochaolekularee product contains a Kaun In organic solvents such as Beneol, toluene, hexane and derglo soluble gel and it is very good processable ¹ _(bar" high molecular weight polyisobutylene having a iet voraug- * lichee elastomer with high tensile strength, even without the · »use of reinforcementBinitt a, like kiss«

An essential feature of the catalysts used according to the invention is the considerably higher molecular weight of the polyisobutylene obtained, even if the polymerization is carried out at relatively high temperatures, such as -30 ⁰ O Another feature is that very pure monomeric isobutylene is not required as the starting material For example, the C. Praction of cracked gases in the dry state can also be used as a starting material ₀

The Isoolefinpolymerisate and the Mischpolyoerleate from one Isoolefin and a diolefin can be used for the most diverse k purposes are used β.B. as glue, diok agent, putty, Potting »and sealing compounds, binders for paints, insulating material, Insulating oils, lubricating oils, cutting oils, main components of chewing gum, plastic additives (reforming agents) » as rubber and the like "."

909884/1665

ORIGINAL

The. , Examples explain the process according to the invention · », example 1

All operations are carried out in a pure nitrogen atmosphere o JBine catalyst storage solution is carried out as follows Manufactured: In a Schlenk tube * which has been dried by heating under reduced pressure, 1.928 g of vanadium tetra chloride and methylene dichloride are added up to a volume of 100 ml presented at room temperature »The vanadium tetrachloride stock solution thus has a concentration of 0.1 mKol / ml *;

In a pressure vessel made of glass, a methylene chloride solution of isobutylene with an isobutylene concentration of 0.1 ml / 40 ml.

In a three-necked flask provided with a good stirrer »a thermometer and a nitrogen inlet tube, 40 ml of Isobutylenlösung and 15 ml methylene dichloride presented · After cooling, the! Solution at -7O ⁰ O in a Trockeneia-methanol, under vigorous agitation 5 nl of the catalyst solution were added. The polymerization starts immediately. After one hour the Reaktionsgemiseh is poured into excess methanol, the phenyl-containing frnaphthylamin obtained 5.46 g (97.5 1 "doth") eisstn a "solid polymers ο The ViskoBitätszahl (? 1) of the polymer * measured at 50 ⁰ O in toluene, is 2.31 »

909884/166 5 BATH ORIGINAL

«Ίο -

Examples 2 bio 5

Isobutylene is polymerized under the same conditions as in Example 1 in methylene dichloride at -70 ⁰ C _o The concentration of vanadium tetrachloride, however varied from 0.25 to 0.01 mmol The results are given in Table I. For comparison, the result of the polymerization is in Presence of aluminum dichloride as a typical polymerization catalyst for isobutylene under the same conditions indicated in Table II

Table I.

at mmol * » ^Υ Polymer! Conversion 2.12 game TOl ₄ “70 duration, h lung, $> 2.22 2 0.25 η 1 100 2.50 3 0.1 Il Il 100 3.08 4th 0.05 Il Il 95.4 5 0.01 Il 61.1

labella II

Ver
euoh aMol
AlCl ₅ T, ⁰ O Polymerisation
duration, h Conversion
lung, 96 0.26
0.31
> 0.71 1
2
3 0.1.
0.05
0.01 -70
H
It 1
It
It 83.3
59i2
15.9

A comparison of Table I with Table II shows that Vanadium tetraobloride has a much higher catalytic activity than aluminum chlorides

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BAD ORlGiNAU

Example 6 . ...

Isobutylene fire is polymerized in Hethylendiohlorld with yanadine tetra chloride under otherwise the same conditions as in Example 1, but 0.05 alfol yanadine tetra chloride is used as a catalyst and the polyamide ion temperature is -30 ⁰ O. A white, white chewable material for single-use polyisobutylene is obtained (Yj ) from 0.54 »

Example 7

Isobutylene is old Yanadintetraohlorid polyaerislert in Methylendiohlorld under otherwise identical Polymerisationebedingungen as in Example 1 '^ edooh be O ₁ I Alfol Yanadintetraohlorid as

Catalyst used and the polymerisation temperature is

liquid 0 0. A white BOB / Eolyisobutylene is obtained in one yield from 89 Jt. (7Y) * 0.21.

Examples 8-10 Isobutylene is converted into trichlorethylene with yanadine tetra chloride

under otherwise identical polymerization conditions as in Example I. 1 polymerized. You will ever yanadine tetrachloride conentratlon dooh varied from 0.5 to 1 millimole. rature is -70 ⁰ C _{0 The} results are given in Table III ^:

909 8 84/1665
BATH ORIGINAL

Table III

at
game mlÄol
VCl ₄ Ί? _Γ ⁰ C Polymerization
duration, h Conversion
lung, $ (T ₂ }. 8th
9
10 0.5
O _s 25
OpI -70
(I.
ti 1
η
I! 100
58 _f 2
10.5 2.34. ^v
2 _F 47
3.07

Example 11 bio 13

iBobutylene is polymerized in ethylene chloride with vanadium tetrachloride under otherwise identical conditions as in Example 1, but the concentration of the vanadium tetrachloride is varied from 0.5 to 0.1 mmol. The polymerization temperature is -30 ⁰ Co The results are given in Table IV

table IV

at
game a-'icl
7oil ₄ -30
II
ti Polymerization
duration, b Umv / and-
lung (fl) 11
12th
13th 0.5
0.25
0.1 1
il
H 100
1"
H Oe 56
0.68
0.47

Example 14

Isobutylene is polymerized in tetrachlorethylene with vanadium tetrachloride under the gloichen conditions as in Example 1. The vanadium tetrachloride concentration is 0.5 rallol and the

Polymerization temperature ~ 30 ^e _{C e} A white, soft, rubber-like polymer is obtained in a yield of 71.6 # _o (7) )

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BATH ORIGINAL

. - 13 "

* 0.76 ° With 2-15ethylbutene ° l one obtains similar results under the same conditions.

Example 15

In a dry, nitrogen-filled pressure bottle "300 ml of purified and dry Methylendichlorld, 56 g getrooknetes pure isobutylene and methylene dichloride ground up to a volume of 400 ml given, the concentration of isobutylene in this solution is 0.1 mol / 40 ml ₀ In a similar way, 230 ml of a methylene dichloride solution of butadiene are prepared in which the butadiene concentration is 0.1 mol / 40 ml ο As in Example 1, a three-necked flask is dried and flushed with nitrogen, then 36 ml of the isobutylene solution (isobutylene concentration 0.09 mol) and al (0.01 Hol butadiene concentration) of 4 of the butadiene in the Advertising surface Methylendichloridlöeung under nitrogen * laugh addition ron 4 Uethylendichlorid al, the contents of "cooled in an TrockeneitwMöthanolbad to -70 ⁰ O, the total amount of monomers amounts to 0 | 1 Molo The monoaeraol ratio of isobutylene to butadiene is 9 J 1 · With vigorous stirring of the contents kept at 70 ° O, 5 ml of a vanadium tetrachloride solution (vanadium tetra chloride concentration 0.5 oMol) are added. Currency of an hour "is poured with vigorous stirring into the Heaktionegemiech übereohüesi- gee methanol, FDI phenyl-S-naphthylaain contains" Daa koaguliertβ Polyaer is EUR separation of reetliche "Vanadintetraohlorid and repeatedly washed under reduced

9Q988A / 1665 bad original

Pressure dried, giving a soft, kauteohukartigee polymer in a yield of 4.53 S> The Urav? Andlung is 81.2 $ o [W} «ι Of97ο Dor Isobutylengehalfc is in the copolymer 91.9 i * _t Reot Butadiene

Beis piele 16 _bi_Q JS.

Laobutylene and butadiene are copolymerized in methylene dichloride with vanadium trachloride as a catalyst under the same polymerization conditions as in Example 15 ₀ The concentration of vanadium tetrachloride varies from 0.25 mmol to 0.05 mmol »The polymerization is carried out ^{at -7O 0 O *} The Bind results are given in! Table V.

table V

At"
game iiMol Molar ratio
laobutylene;
Butadiene T _t ⁰ O Polyneri "
station
duration, h Conversion «· (,) Iaobuty-
stop in
Product. ^ 16
17th
18th 0 _r 25
0.1
0.05 9: 1
R.
Il -70
η
H 1
η
N 85.9
81.8
71.3 1.03
1.37
1.78 $ 5.4
100
η

Isobutylene and butadiene are used in methylene dichloride with vanadium trachloride as a catalyst under the same conditions in example 15 a.i post-polymerized to the tanadine tetrachloride concentration is 0.1 adfol and the polymerization temperature

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BATH ORIGINAL

. " _Llf!

door -3O ⁰ Cc A white, soft, rubber-like polymer is obtained The conversion is 70.5 "(7 £)" 0.64 "The isobutylene content of the copolymer is 98.1"

Example 20 Xeobutylene and butadiene are converted into methylene chloride with Vana »

dintetrachloride under the same conditions never in example 15 mixed polymer laiorto JDIe vanadium tetrachloride concentration is 0.25 mmol and the polymerization temperature is O ⁰ C * Man λ It contains a white, liquid polymer. «The conversion is 61.4 flo (?%) ^M O _r 19o The isobutylene content of the Miechpolyerl eats is 94.1 * ο

21

Isobutylene and butadiene are in methylene dichloride bit anadine tetrachloride under the same conditions as in Example 15 ■ isohpolynerized, but the ratio of Zso-

butylene t butadiene 5 ι 5, the vanadine tetrachloride concentration 0.1 waste oil and the working temperature -30 ⁰ O. A wiseeo, flUsBigea polymer is obtained. The conversion is 9 »6 Jt ₀ (φ)« 0.19. The labbutylene content of the copolymer is 77.8 ^ ₀

Example 22

Isobutylene and isoprene are mixed in methylene dichloride with vanadium tetrachloride under the same conditions as in Example 15 ■ ieohpolyoerielert «The molar ratio of isobutylene to isoprene

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BATH ORIGINAL

is 9 t 1, the vanadium tetra chloride concentration is O ₉ I nmol and the working temperature "30 ⁰ O ₀ A white, liquid polymer is obtained. The conversion is 38.7 £ * (^)" 0.22 »'

BaiBPlel 25 , '

The isobutylene-containing Ctas obtained in the steam cracking is polymerized with vanadium tetrachloride under the same conditions as in Example 15. 50 ml of the dried Oraokgades the following composition: 27 _v isobutylene 5 # »butadiene 25» 8 i> _t t 15.3 butene, n-butane 10.1 i · and other compounds are introduced into a three sharks flask to -70 ⁰ O cooled and mixed with 5 ml of a vanadium tetrachloride solution (vanadium tetraohioria concentration 0.5 railol). This gives 3) 94 g of a white, rubber-like, elastic polymer · (») ■ 0.64 ·

Example 24

Isobutylene is polymerized in llethylene chloride with vanadium oxychloride (VOOl.) Under the same conditions as in Example 1. When the concentration of vanadium oxychloride is 0.1 mjfol and the working temperature is -7O ⁰ O * A white, rubber-like polymer is obtained

Examples 25 to 26

3 ml of a benzene solution of kickfltetracarbonyl (0.5 mmol / ml) and 3 ml of a heptone solution of vanadium tetra chloride (0 _t 5 mol / ml) are added to 30 ml of benzene and the mixture is allowed to stand for 30 min

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BATH ORIGINAL

5O ⁰ O. aged. After the cooling to 1O ⁰ O precipitation is t>

washed three times with 30 ml of methylene chloride. A catalyst suspension is prepared by adding 30 ml of ethylenediochloride. All operations are carried out under an atmosphere of pure nitrogen. The polymerization of isobutylene is carried out at τ78 and at -30 ⁰ O with 10 ml of the catalyst suspension mentioned under otherwise the same conditions as in Example 1. The results are given in Table VI

table VI

At-"
game I, ⁰ O ^ qlymerieatione-
da'uer, hv Conversion
lung, J6 0.22
0.22 25th
26th -78
-30 0.33
0.53 81
81

Examples 2? and, g 3 ml of a Benaollösung of Hiokeltetraoarbonyl (0.5 ntfol / ml) and 3 ml of a Heptanlöeunfj of Vanudintetrachlorid (0.5 mlfol / ml) are added au 24 · al methylene dichloride and gemäsa Example 25 till 26 at room temperature aged The Gemiach The polymerization of isobutylene is at -78 ⁰ O and at -30 ° 0 with

10 ml of the suspension

In any case / under otherwise the same conditions as in Example 1, the Hrgebniaee and given in Table VII.

ι> ΐ »ti- ', ■ - · \

? ■ · ■ * ■

Table YII

at
game *, ⁰ O FolymeriBätione »
duration ,, h Impeccable
lungi 1 » (71 ) 27
28 -78
-30 0.33
If 84
86 0.10
0.18

Claims

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BAD ORIGINAIU

Claims (9)

Patsntanaprttohe 1 * Process for the polymerization of Iaoolefinon in the presence of a catalyst, which means that the polymerization in Oeeenwart is at least ainer Vanadium halogen compound ala catalyst, and optionally a carbonyl bond of a metal of group VIII · dea Periodic table is carried out 2 * The method according to claim I _{9 is} known that the polymerization is carried out in the presence of a diolefin bit of 4 to 8 carbon atoms in oil. *. ' 3 «Method according to claim 1 o &" Z ₉ daduroh ga - · knows that ala laoolefin a compound is polymerized with a terminal methylene group · 1 4 · The method of claim 1 to 5t daduroh ge "(mark verifiable kind DEJ the Uneeteung is carried out under an inert GaaatHtoaphäre. ' 5 · method naoh claim 1 bia 4, characterized in that the reaction in an inert organic Iiusun & saittel is carried out. '9 0988 4/1665
BATH ORIGINAL 6o method according to claim 1 bio 5 »characterized» that the reaction is carried out at a temperature between 0 and -80 ⁰ O «irdo 9 0 9 8 8 ι, I 1 6 6 5BAD ORIGINAL