DE2215237A1 - Controlled high temperature polymerization of butadiene - Google Patents

Description

concerns the u.'e /: i]> erature control at the high,

. ·] * .: is disclosed in the britiscaen Patentee or if t .. 1 143 690 that_ uiu. '. ol ^ mcrization of 1, ^ - Üut ^ dien "at elevated temperatures in the order of" 90 - 'dj> 5 ° G leads to polymers that have a controlled degree of volatility, the Poj. ir '.' Jren a highly desirable improvement in the ¥ ERAR-I) C * nbarkeit, to ^ festigkeic and hot strength in unvulkanisier- ■ _u s state vex'leiht so vie ^ of ^ aItfluß also in unvulkanisierüen state free, if such method to be carried out on a large scale, it has generally proven to be necessary ;; eryiessn to carry out dio polymerisation in the presence of a coal water thinner to regulate the temperature; In the absence of such diluents, the polymerization mass becomes highly vicious and creates very poor heat transfer, so that every temperature rise quickly leads to the fact that the reaction can no longer be controlled, resulting in a risk of explosion and / or degradation of the product. The introduction of hydrocarbon diluents into the polymylation mass enables the reaction to be controlled, but this naturally wastes "heater space" and the result is that the diluent occurs at the very beginning of the reaction.

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must be removed. It should be borne in mind that three or more parts by volume of diluent per part by volume of butadiene must be used for this purpose, since the entire diluent must be purified to a degree that does not interfere with the polymerisation, that ν-poor for the evaporation of the diluent must be added and that it is very difficult to remove the last traces of diluent from the animals, must be recognized, and clici are .also according to British Patent 1 197 - ~ ^ 1, 1, I-pol outadien in the presence of 1,2-butadiene at temperatures other Jiierisiert that intentionally in αen range of 212 ° - 4ü0 ^O 5. (100 - 204 ⁰ G) can be increased. Although it is mentioned in this rate code (page 2, line 49) that the reaction in tjiw. .e can be carried out, was carried out the actual exueL-iiucatelle work in solution systems and fiü <iwi, "-.Icη no indication that the reaction in t.asse in a üroLwon · i <: durchgei itung without loss of temperature control '.'iiiri, v-ev ^ cn may..

Accordingly, the invention is based on the task of better process for lithium-catalyzed rOl, yuti - ;. ei;.: tipu to create butadiene and to create such a process, which can be carried out at high temperatures, with improved cold flow, improved tensile strength and Result in tear strength. Furthermore, such a method is to be created which can be carried out in the substantial absence of carbon, hydrogen diluents without loss of temperature control and without uncontrolled reaction.

The above and other objects are achieved in accordance with the invention in a Process ensured in which 1,3-butadiene or a mixture thereof with one or more copolymerizable therewith Compounds essentially in the absence of solvents by means of a hydrocarbon lithium catalyst in one Large reactor, for example with a capacity of more than 15 gallons (08 liters), can be polymerized, whereby the poly-

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merisa / tionsHiasse 20u - 300U parts per million 1,3-butadiene a 1,2-diene of the formula

Where R contains hydrogen or an alkyl group containing 1-3 carbon atoms, suitable 1,2-dienes are, for example, jrropadiene, (the preferred) 1,2-butadiene, 1,2-pentadiene, 1,2 -iiexadiene and 4-iviethyl-i, 2-pentadiene. The reaction is initially carried out at .venn vergleicrweise moderately high "temperatures, for example -150 ° OEO P (27-66 ⁰ C.) which xteaktion fortscnreitet, the viscosity of the Reaktiönsmasse iiiiaiut 'to and i-'unkt at some it becomes impossible to maintain the temperature at these lower values due to the difficulty of evacuating steam and mrae. However, in contrast to reactions which are carried out without the presence of 1,2-diene, the temperature rise in the practice of the invention is self-limiting and steep tolvinerisationsreaktion the i-iii slowed when the non 4üü ° i '(204 ⁰ C) for about and usually not more than about 2 ^ 0 ⁰ F (121 ⁰ C) addition, iis was found dai 1.2 i Te: nperai; ur increases impermissibly, so that the degree of heat development does not exceed the practical capabilities of a conventional device for removing heat and the reaction is self-limiting and one can prevent it from becoming too violent. unity of 1,2-Jiens slows the reaction rate very quickly with a rise in temperature, for example to temperatures v / o .ji axi of ί'Όΐ. / Mer, as can be seen by the development of i-ia also from the reaction mixture, see above that it is impossible to rapidly absorb the heat of reaction in a reaction apparatus; of any considerable size (for example 6 liters or more) in order to avoid an exponential rise in temperature and reaction rate and consequently a runaway of the reaction. The connection between the reaction and the reaction does not affect the properties of the resulting polymers, which in the unvulcanized state are easy to process and have good tensile strength and tear resistance.

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Lie composition of the batch for the polymerization reaction:

As mentioned above, the charge for the polymerization reaction essentially contains 1,3-butadiene or a mixture thereof with up to 40 ^ other ethylenically unsaturated compounds which can be copolymerized therewith, together with 200 to 3000 parts by weight of a 1,2-jiene per million parts by weight of 1,3-butaiene. Preferably the; .en; e 1,2-diene is 500 to 2000 parts by weight per million parts by weight of 1,3-butadiene. The mixture can also contain smaller proportions of other foreign substances which are soluble in the 1,3-butadiene, provided that they do not intervene in the polymerization reaction and are present in sufficiently small amounts (for example not more than 10/1, based on a weight of 1,3-butadiene), so that the reaction is essentially an iviascepolymerization, ie a polymerization essentially in the absence of solvents, examples of such other constituents that are present in such smaller! In the wer.ont; -liciien inert ^ ohlonwacsorstofJ'e, like i ^J ro:> eu, η-butane ,, 1 -; <uU ii, lGxane etc. j ^ s körmer! there may also be compounds which are able to control the polymerization reaction. For example, it was observed in the case of the ancestor of the invention that sec. it in then i :: narrow.n how the 1,2-JJien is ver.vend.et, and the weight of the when the ¹ ^ rfinduii: /; 1,2-jion.s ¹ M.'η α used are reduced by amounts that are roughly equal to the sec.-but.vl chloride present in aewicat na.

z, s v; ird also decont, da .. ji; -de of the vei-r-cnicclen-like ethylenic unf>: es ^: ittii_; th connection, di.e fiiü α em .butadien cooolymeris'erbar, and the on the Jjitiiiumkatalysauor not t; tö-. rend act, voriiauue. · his köiuie.:, beii; uielswei!; e ..Λ. / rol, ^ - ^ lk.vlstyrenes, like ^ -i..eth.vlstyrene, rin -. ^ alkylated »jt. ' role, boisoie '.ßweise 1-, 2- and 3-i-ethyl- and j. tijylotyrole, other conjugated iJiolefins, such as isoprene, 2,3 -: - 'imethyl-1, 3-butane i «n, Pi.Deryleri and the like. Jiece Vyrbiiidun' en \ öiv tu in ..!; η, : οη bi :; : -; u

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For example 4ü / V of the G-esa'iiügewlchts the checkout en polymerized, ie the 1 ^ - butadiene plus any copolymerisierbarcr konomerer plus per _tonne: - lic-aer .tfreiüdbe constituents as above be addressed, be present ^ s is emphasized that the copolymeri-. sierbaren connections not from the point of Losun; are .anzusehen siiiitteln as they go even polymerization and heat .erzeυ '; eii ane "ü .-' tb the v / ärmeableitung to ^unterafc:. caen as a simple Verdünnunc '; s solvents do

vle iv.atal; 7sators based on iiithiuray:

Of course, there are any compounds in which one or more lithium atoms are bonded to a hydrocarbon component which contains up to 40 carbon atoms and preferably up to 20 carbon atoms, such as hydrocarbon lithium Compounds, including the alkyl lithium compounds, aryl lithium compounds, aralkyl lithium compounds, aryl lithium compounds and the like , n-butyllithium, irropyllithium, n-hexyllithium, n-dodecyllithium and n-octadecyllithium. Examples of other hydrocarbon lithium compounds are isopropylethylthium, tert-octyl lithium, n-decyl lithium, phenyl lithium, naphthyl lithium, 4-butyl phenyl lithium, p-iolyl lithium, 4-phenyl lithium, oyclohexyl lithium, 4-butylcyclohexyl lithium, 4-butyl cyclohexyl lithium, 1,4-bilithiobutane, 1,10-bilithiodecane, 1,20-l) illthioeicosane, 1, ^ -. Uilithiocyclohexane, Λ , 4-dilithio-2-butene, 1,8 ^ · I) ilithio «-5-decene , 1,4-uilithiobenzol, 1,4-dilithionaphthalln, 1,2-dilithio-1,2-diphenylethane, 9, Λ O-dilithio-9,1O-dihydroanthracene, 1,2-dilithio-i, 8-diphenyloctane, 1, ^, ^ - Ti'ili'b-b-iopentan, 1,4,15- »Trillthioeicosan, 1,3, ^ - 'I'rllithlOcyclohexan, 1,2,5-ir ili thi onaphthal in, 1, 5, ^ -'-'- 'i'ilithi oanthracen, 1, j ί 5 ϊ 8-i'etralithiodecan, 1,5., 1O, 20-i ¹ ebralithioeicosan, 1,2,3,5-1 ¹ ^ tralithiocyclöhexan, 1,2,5,5- ^u - ^l etralithio-4-hexylanthrac ^: en, etc. The complex adducts which are produced by the reaction '■'

- ο -

of metallic lithium with polynuclear aromatic compounds, like naphthalene, ajithracen, - chrysene, ßiphen. / l, various ai k; v Li er ten naphthalenes etc. are geoilciet, used werüen. Such catalysts are g.-ev / similar in l.ien ^ en are used which are sufficient to be of the order of 0.1- ' 3.0 'II / iillimol lithium per 100 g of butadiene in the batch. (A iiillimol lithium becomes 0.001 gram-atom active Lithium prepared, i.e. lithium in a sufficiently reduced state to push the water out of the water, to exclude it the lithium halides and other fc> aize used in the catalyst preparation may be present), it goes without saying that the cited quantities of catalyst above such a catalyst menu which are consumed by reaction with moisture or other impurities in the polymerization batch will.

The method of the invention:

The process of the invention is usually carried out in an apparatus of considerable size, for example 68 liters or more, as the difficulty of reaction control becomes acute and the utility of the Jirlind becomes particularly important in those reactors where the ratio of the heat dissipation area and / or des / iaumes for the steam releases to the bulk of the contents for temperature control is inadequate. Usually a closed reaction vessel is used, which is provided with a heating and cooling jacket and has a rotating stirrer, there is also usually a reflux condenser on the left head with sufficient space for aie -liquid release to support the heat dissipation, 1,3-butadiene, optionally copolymerizable monomers and 1,2-diene, are introduced, preferably at ambient temperatures, for example lower temperatures of the order of magnitude, with stirring and the lithium catalyst added. The mixture is then slowly heated to temperatures in the gewünscnten polymerization area, ie, 90 ° - 150 ⁰ J ¹ '(32-66 ⁰ G) is heated while the was-

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me development carefully observed. Once the desired temperature has been reached, the polymerization has already started, ·: it is or will · shortly begin and the temperature of the arm will be transferred; "ungsmediums in the 1st; antel of the heating • set the reflux rate in order to dissipate the heat in such a way that the reaction temperature remains within the desired limits ,>, increases the 'temperature despite all efforts at cooling, but as a result of the .abwesenheit 1, 2-3utadiens this Ansiie _t;. selbsbbegrenzend and the temperature can be herabgearückt a moderate bpitze, for example, do not have 2yo ° i ^{(. 1} (121 ⁰ J). After the tip has sunk and the polymerisation: o far as wished, the luonomers are drained off and the polymer recovered . JJieses kai.n i.iittel happen by purely mechanical or daaurch that one rrodukt to the -LJntfernunr;.. from the .Reaktionsbehälter · in a i.ü.sunf.-smittel Raises sLs is noted here -las ijöfjunvrsmittel there is no special thing about this i-tel-le The high level of leverage is needed, about the polarization reaction, in which impurities can enter, is filled to the end.

Detailed description of the preferred tone .i-ais execution forms:

juie vo'estandce considering the general description, now follow into ^ i-'jzo-lne goaende; 3eir \ .iele f ^: 'r dj, e Jurchf.' introduction of the iirfiiidunf. ..1Ie i'e'.ie and jfrözontwerte bezi-.vheii sie .. ¹ on weight, if it is nicxit amvers specially noted. ■ - ■ -

jja-s in aen 3eis.:iexeji vexw-enaete 1, ^ - had butadiene; the following: · ! Ji certificates.

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BATH

- 8th - 1,3-butadiene example 1 1,3-butadiene 2215237 7o methane * Technical 1,2-butadiene 0.006 Ethane 0.0001 Propylene 0.077 Propadien "0.0039 n-butane 0.0058 Butene-1 0.7618 trans-butene-2 0.1241 cis-butene-2 0.0213 Methylene ethylene ^ 0.0020 1,3-butadiene 99.0000 50 pounds (22.6 kg.) 114 g

n-butyllithium solution 161 ml

(in hexane; contains
0.01 g carbon-bound
Lithium per ml)

* technical · quality, containing
1,2-butadiene 26.7 /?

6 \ -acetylenes 0.870

Butene rest

The above recipe provides 1,350 parts by weight of 1,2-butadiene per million parts by weight of 1,3-butadiene and 0.00514 grams of active lithium per 100 grams of 1,3-butadiene.

For this experiment it was ^ a 91 liter autoclave that with a rotary stirrer, a ./arm transfer jacket and. was provided with a reflux condenser at the top. There was a valve in the line between the condenser and the reaction vessel arranged, if desired, the degree of steam removal to restrict. There was also an observation window in the upper part of the reaction vessel and a pressure bomb connected for injecting isopropanol into the autoclave in case the reaction gets out of control ",

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or to stop the reaction after completion. The reaction vessel was set to 75 ° ^ . "(24 ⁰ C), evacuated and cleaned once with 1,3-butadiene steam, whereupon the 1,3-butadiene and 1,2-butadiene of the recipe were added and stirred A small sample of the contents of the reaction vessel was taken and titrated with butyllithium to determine the consumption of -butyllithium by impurities in the batch, and an appropriate amount of butyllithium solution (not in the recipe included above) to the reaction vessel to neutralize the impurities in the batch, the circulation in the jacket and condenser started and the temperature raised to 80 ^° F (27 ^° G) at which time the butyllithium In a short period of time, reaction set in and the circulation in the jacket and condenser was regulated in order to keep the temperature at or below 100 F (38 ° C) until an intermittent one Analysis showed a conversion of 48 ^. The contents of the reaction container were observed through the window from time to time to check for dangerous abnormalities. -

At about this point the valve in the conduit to the condenser was partially closed, restricting heat dissipation, so as to emphatically demonstrate the effectiveness of 1,2-butadiene as a reaction control agent a! temperature rise, but with a peak at 238 ⁰ I ¹ (115 ° G) instead of a rise to much higher! temperatures at which the polymer would degrade. After the temperature rise subsided, the isopropanol was injected to stop the reaction, 50 pounds (22.7 kg) of hexane was added and stirring was continued to form a flowable conduit. The unreacted butadiene was then drained off and the sludge was removed from the reaction vessel. A yield of .40 pounds (18kg) polybutadiene (DLV = 1.90, no gel) was obtained from the slurry of Ks. The attempt is recorded for 3 seconds.

tu: EEh, Temp. 0 G. - 10 - , 5 conversion , 0 2215237 ■ Injecting aes : 05 . ⁰ I '. 26th , 7 pressure ( Remarks Catalyst Time 80 (psig. ! 9 0 , 9 - a : 35 32 , 2 , 9 - O : 05 90 40 , 0 ; (atü) 7th - 104 42 40 27 Reaction to the critical O i45 107 51 , 5 50 48 1 125 48 2 - 1 70 3 1 3 4th

1:50 185 85 , 0 1:55 238 115 2:30 120 49 , 0

65

4.6

"table point:

Temperature rise

begins

unpeacted butadiene deflated: 59 lbs. (26.8 kg) of hexane filled in to form a Polymer putty for removal

Example 2

52 lbs. (25.6 kg)

1,3-butadiene n-butyllithium solution

(in hexane, contains 0.01 g

carbon-bound lithium per ml) 193

The recipe above provides 0.0082 g of active lithium per
100 grams of 1,3-butadiene. No 1,2-butadiene is used to
to show the uncontrollable nature of the reaction.

The same device as in Example 1 was used. The reaction vessel was set to 50 ϊ (10 ⁰ G), evacuated and cleaned with 1,3-butadiene vapor. Then the 1,3-butadiene of the recipe was poured in, started with clocks and continued during the following experiment. The contents; was titrated and impurities neutralized as in Example 1. The temperature was raised to 95 ⁰ F (35 ° G) and injected the butyllithium solution. Lie xieaktionsmasfae was carefully prepared by the

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Window observed in the reaction vessel. It was observed that red spots were formed in the mass, a sign of dangerous local overheating, and the isopropanol bomb was actuated to stop the reaction, and cyclohexane (80 lbs . = 56 kg) was injected and the temperature to 15O ⁰ F (66 ⁰ C) increases, making flowable supply to the mass m ^ n then dropped from your reaction vessel. The product contained large amounts of gel and degraded polymer.

Example 3

1,3-butadiene .- ■■■ 52 lbs. (23.6 kg)

Technical 1,2-butadiene. 227 g

(26.7 / o as in example '1)
n-butyllithium solution 89 ml

(in hexane, contains 0.01 g of carbon.

bound lithium per ml).

The above recipe provides 2560 parts by weight of 1,2-butadiene each Million parts by weight of 1,3-butadiene and 0.0038 g of active lithium per 100 g of 1,5-butadiene. -

The apparatus of Example 1 was used and the reaction vessel was cleaned, the 1,3-butadiene and 1,2-butadiene of the recipe were charged, it was titrated and neutralized as in Example 1. The temperature was increased to 10O ⁰ F (38 ⁰ O) stated, aw. After about .4 hours, analysis showed a conversion of 47> ό and the temperature was driven up to 120 ° F (49 ⁰ C). The reaction peaked at 140 ^° F (60 ^° C) whereupon the monomers were drained, cyclohexanone (80 lbs. = 36.3 kg) was then added and stirring continued to form a flowable hatch, which one from the iteaktionsb eke keeps he dropped out. The recovered polymer had an Iviooney -vert iviL ^ of> 0 · ^ ^{s is} followed by a recording of the experiment.

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Time l'eicperatur JJrucl: ümwj.n ',. Lunsr ßene r.-kun ^ er

t; tdn. : Min. ° Έ \ ⁰ C. ") sig.atu (, j)

O , 6 catalyst
adorns. in.-ji- 8th , 55 47 Monomers a .. ^ ■; e lan s en

0:00 100 5ö 50 5.5

1; 0ü 2:55 116 46 70 4, y 3: 4-5 4:15 140 60 100?, 0 4:35

Jas rOlymer had an i ^ v of 2, 1S, ei. on L.ooney r, jj-4-of 5 ^, an infrared channel;> ^: se of 35.3 ^ cis-1, 4, 53.4,. ^ tranc-1,4 and. 12 ,; 1, 2-structure.

La ^: polybutadiene, doc in the above becciiricbenen, '/ eise iier: cectel.Lu was, was compared with a ii'-jnaelfrvJbiic'ien lithiura-catalyzed l-olybutadiene, which was polymerized in a. Both polybutadienes were coinoounded according to an otandaru recipe for an i-ieifenlaui'i'lücheiiwerkstofi 'and, v / ie in Jabelle J vorzeich.net, ^ epivi't. ... These vulcanizations were carried out at 300 ° l '(14 ^! ⁰ J) -.välirend the times given in the table. ; 5ε follow the 1-r results. I-: aji sees that the polymer of this jieisoiols the usual ol, yineren quite yleiciivvert?; Ar, uiif.reachGOt of the iiiciitlüsun.csmittiel-I system in which it was produced.

'j-' table 1

Test ^: control product of this example

iiISiOSIS3OlT05 573 ~ 50.5.

29 ⁰

iuoone; y scorch at 129 ⁰ C ^ kognejf _ώθθΓοη_§5_265_ΐ'Λΐ '

• ι '22 17

I ¹ Y _n 40+ 40

V ^ ^v '22.5 23.0

Cepar oclinel extrusion at 99 ° G (Oepar ^ KaOi ^ lxtrusion ^ a ^ llQ ^ i ^^ ". -

.j v // L ratio 64.5 53 »2

(iarvey .i-JOrm- ^ xtrude: '. ^

L ΰ §ΙΎ§-1 - ^J ii§ _ ^? I ^: i? 13-sion) _

Jixtrudier-iueMp. ° i ' ^! ( ⁰ O) 240 (116) 245 (118)

"Ciuell-inüex (g./cm.)" ^ 0.867. 0.692

^> Ltrudiergeschv; indiykeit (g./min.) 93 86

(subjective i: a.; -. stab 16 "'' 16

1-Ib) .. ■,

, tension-JJeiinunpcs-

^ üOyo faiodulTis, psi, (kf ;; / Gm ^ j - -

vulcanized 15 '"" -n / C Ή / ΰ

vulcanized 23 '825 (57.8) 900 (64.0

vulcanized 30 '925 (65.0) 950 (66.8

2 ■ ''

Tensile strength, psi. (k ^ / cm) -.

vulcanized T5 ¹ n / Ö 'S / G

vulcanized 23 '2328 (163.5) 2000 (140.6)

vulcanized 30 2225 (156.4) 2125 (149.4)

BruGh.deIiD.unfi,; -o ■

vulcanized I5 ¹ N / G · Ή / G

vulcanized 23 · '570 500

vulcanized 30 '520 505

KJpannun ^ s-DeJinungs-iiigensclaaf th,

4_'i ¹ a £; e_sealtert__ bei__igg ° G .__ ₌ _____ -

200; -Q modulus, psi. (kg / era ⁶ ")

vulcanized 15 'w / 0 925 (65)

vulcanized 23 "1125 (79) 1175 (82)

vulcanized 30 '1025 (72) IO5O (74)

^ u; ^ fer . υ 1 r ± e iυ, psi. ( k'-y em ¹ "";

viUiiiviLiiiept 1S ¹ "" u / G 1550 (109)

vulAmi.-icrt 23 * 19Ou (1i) 4j 1875 (132)

vulKarii.riort 30 'I7OU (120) 1900 (134)

vul kau is Lo rt 15 ' ia / C 320

vul'-ianLijiorfc 23 '260 260

vulkameter b 30 '2bO ^: - ^:. 260

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'read control. Product of this example *

_iioiiirinf:; REII jprobe, ^vulcanized;

23 _._ iiin.uten

psi at 212 ⁰ K (1UO ⁰ C) 261 (1ö, 4 kpycnip) 319 (2-, 4, k & r / cm§)

psi at 275 ° ϊ. (135 C) 240 (16.9 kg / cm) 265 (18.6 kg / cm »)

tf'ire stone flexometer, vulcanized

70th year 20 20

Running temp. ⁰ K 300 (149 C) 310 (I54 ° ü) "■■

onore ^ at 75 ⁰ K (24 ⁰ C) 60 58

at 212 ⁰ K (IuO ⁰ C) 49 51

Il

;. · S iviodulus index at 1ü psi.

vulcanized 35 minutes ^ l -70 -70

b standing uondon i-i slip test,

average ö-: alenaül3sa; i · .: 35 ₅ O 36.0 index 80 82

In the same distance were two iceifen with treads, which made Each of the above materials was manufactured, constructed and subjected to driving tests. The irüfunsen were at 12 heal aborted because of a break in the sidewall of the tire occurred with a tread made from commercially available polybutadiene. At the end of the x test, the abrasion values were for the commercial polybutadiene and the polybutadiene this Example 100 or 89.

Example 4

1, ^ - butadiene '52 pounds (23.6 kg)

■ i'echii. 1,2-butadiene 40 g

( 2y , 5. '1 _} ' - butadiene)
n-i3ut ;;, - llitniuiiilt3suiig 148 ml

(in -lexan, enbhiilt; 0.01 g
kohlens "
per ml)

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_BATH

■>.

The above recipe provides 500 parts by weight of 1> 2-butadiene per

Λ,

Million filing 1,3-But ad in η and ü, 00S3 π; active lithium pro 10Ό g of 1,3-butadiene.

The working method and arrangement of Example 1 were applied up to the neutralization of impurities. The temperature was set to 87 ° ϊ (31 ⁰ G) and injected the butyllithium. The reaction lasted approximately 6 hours without any special events. At that time, the temperature began to rise. --is - it was possible, however, by kahlening and blowing, to limit the tip temperature to 120 ⁰ I ¹ '(49 ⁰ O). The polymer was dissolved and recovered as in the previous examples, yielding an i-olemer with a., Ooiiey viscosity kL-4 of 55, a record of the experiment follows.

Time • ± 'e sip at ur Ji-uck . atii ■ Üaiwaudluii ;; Remarks Ot (II ,. L. • Or psig 2.9 / - ■> 0: 0 ,, 87 30.6 42 i. at al js at or inji 2, ö adorns 1: Oü & 7 '30.6 4u 3.2 6.27. 1:50 B7 30.6 46 2, ö 10.6 ' ; ^; :: rx 90 . 32.2 40 3.5 15.0 2:50 1Uü 37.5 SO 2.6 - 3 · po 94 34.4 4u 26.6 4: 1 \ " - - 4.2 35.0 4:45 1Uö 42.α 6o - >: 2u Hu 43.0 - .4 ^, 0 b: Ul) 120 49. ο 6:35 49. υ Lonomer aoeelass

• ius aei "preliminary general discussion; 5 and the detailed special examples show that the .drfinaung a new and easily controllable process for high temperature -1-polymer is ation of butadiene in! .Lasse in a device from;? roi:> eiJ «refreshment; from delivers. Yes procedure avoids. the Complications that the Verwenäurti: from kohlenwasserstoffvereln to the extent of the polymerization reaction

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BATH ORIGINAL

"brings about and leads to products that have a!, iikrο structure and Have molecular weight distributions, which are in the oil. von ivalOfluss, in the tensile strength, £ er.: 'i. strength and uniform Processing properties in a polymeric product demonstrate.

Bringing in 200-3000 ropes per million of a 1,2-diene in bulk polymerization or copolymerization of 1,5-butadiene with catalysts based on Lithiuiafirundlage allows that the reaction in a Gröl device without loss of Temperacurkoiitroile can be carried out.

209844/1040

Claims (6)

Patent to pri cu.e 3y. Leading to the iJurcM '^ hrmiy of a polymerization process, characterized by ■. (l) a lol.yitieri s ati ons batch, which essentially "consists of (a; 1,3-butadiene 60-100; o) (b) with 1,3-Butaai-eii οουοί, γ- 4-0- - Ο / σ ) based on-the merisi'ez'ez'bare Verbi.-cun-) weight gen) from (a) + (b) + (c) ^ c) inert Ilonlenwas & er 0-10; » ) fabrics. . "■ - -) zui --- airjfuort with (rl) a 1, ^ - x. the 200-3000 weight parts per _: Million weight. share 1,3-butadiene (x) wobsi the 1,2-i) ie: i the formula '' UH ₂ = C = üii- ii has, wherein -R denotes hydrogen or an alkyl group with 1-3 carbon atoms (.11.) A heating container of at least 68 liters i``assunp; sverr / iÖgen. (.LH) the presence of a catalytic converter jüithiumgrundlage. (TY) Temperatures initially in the range 27 ° - 66 ⁰ U, where (a) 'temperatures are kept in this area by increasing V'iskosität makes it impossible _r the ./arme dissipate fast enough (b) The temperature is then allowed to stiffen Cc) the presence of the 1,2-die mentioned under I, (d): serves to stop the temperature rise at a temperature rise that is not higher than about 204 ⁰ O ^ (V) the production of polymers with a desirable branched microstructure »which is in (a) freedom from ivaltflub \ (b) good tensile strength) ^ ^^^ (c) good tear resistance j "bein: / Sustand (d; put; en Veraroei-Gunt-s- \ rh cia characteristics -y BATH 2. Procedure according to. Claim 1, characterized in that the 1,2-diene is 1,2-butadiene. 3. The method according to claim 2, characterized in ;, daü the i, 2-butadiene in amounts up to 5 ^ 0-2000 parts by weight per Million parts by weight of 1,3-butadiene is present. ^L V. A method according to claim 3, characterized in that daL no copolymerizable compound is present. 5. The method according to ^ nsuruch 1-3 »characterized in that that the copolymerizable compound is otyrene. 6. The method according to claims 1-5 »daaurch gekeniiZeicaai: G, that the lithium-based catalyst is butyllithium 98A4 / 1040