SI8610790A8 - Process for preparing of 1,4-cis-polybutadienes or butadienes copolymers with diolefins with catalytic polymerization or copolymerization of butadien monomer - Google Patents

Description

PROCEDURE FOR OBTAINING 1,4-GIS-POLYBUTADIEN OR BUTADENE COPOLIMERS WITH THE FITTING DIOLEFINS CATALYTIC POLY.MEASIONS OR COPOLYMERIZAGIES.JUT BUTADIEN

This invention relates to the Preparation of 1,4-cis-polibutidlena putem catalytic polymerization of monomer butadiene continuous postupkom when j ⁵ copies in absentia or bitnom odaustvu solvent or diluents, using the procedure described in two sukceaivne phase (first in T ^ 3O ° C and the second at T " or < 5 ° C) in one or more poly merisation reactors, in which the heat of the reaction is distributed by evaporation of the monomers. Practically the same effect is achieved when it is able to do this in two successive phases * the procedure is performed continuously or discontinuously in almost complete or complete absence of solvent or dilute the vial and work. is in the presence of particulate matter which is insoluble in the reaction medium.

ΝΧΡ: C 08 F. 10/08; G 08 F 4/12, 4/18

It is a technical problem to be solved by the invention to provide such a catalytic polymerization process which provides 1,4-c-s-polybutadienes with advantage over the prior art.

Various catalytic processes for the polymerization of butadiene are known in the art, which can yield polybudadenes with a high content of 1,4-c ^; s-components and which are especially suitable for the manufacture of outer tires and other elastomeric products.

- 2 Catalysts generally used for this purpose are derived from the combination of transition metal compounds such as au titanium, cobalt, nickel, uranium and rare earth metals, with alkali and / or hybrid metal derivatives of the Α, IIA and IIIA groups of the periodic system , such as those described in the US for example Patents 3,118,8.64, 3,178,402, and 3,794,6o4 and 4,242,232 and in Belgian Patents 559,676, 573,68ο and 791,7o9Z

According to the methods known in the art, butadiene polymerization is usually performed in a hydrocarbon solution to control the polymerization tem perature ^! is and thus soluble linear polymers are obtained, liberated or substantially released from the gel and controlled molecular weight.

The production of 1,4-cis-polybutadiene by polymerizac ¹ * is by weight, on the other hand, has not found a significant development in industrial practice, despite the evident advantages of the process carried out in the absence or with the substantial absence of solvent or diluent compared to the conventional process solution.

The reasons for this lack of success were found in principle:

•

A) in the absence of suitably defined catalytic systems that satisfy the characteristics required for mass polymerization and are determined:

- which, in the presence of excess monomers, do not lead to side reactions, which are responsible for the production of low molecular weight polymers, which are rarely used;

- which do not cause secondary crosslinking, cyclization and / or branching reactions in the polymer, which is responsible for the formation of piston amounts of gels with very negative effects on the characteristics required in the final product;

- which give high enough activity that the final polymer contains. low level of catalytic residues to avoid washing treatment;

, - which retain high activity and selectivity under the conditions of ⁴ m high temperatures necessary for operation in very viscous systems and with satisfactory kinetics;

B) In the technical, theological, and difficulties of heat exchange with respect to the treatment of highly viscous polymer masses.

An example of a process for the polymerization of butadiene by weight, to obtain 1,4-cis-polybutadiene, is described in U.S. Patent 3,770,710.

U.S. Patent 3,770,710, in fact, relates to a polymerization process for a mass of diolefin monomers with lithium catalysts, which is carried out in a conventional two-stage reactor at different temperatures, by controlling the monomers to control the temperature.

Operation in controlled stages originates solely from the need to prevent, at least reduce, the appearance of foam and to end polymerisation at higher m temperatures. No change in the number of stages in equilibrium takes place as a result of the elevated temperature.

We are further acquainted with the European Patent Application Publication No. 2. 0127236 of December 5, 1984, relating to the process of catalytic polymerization of butadiene to

1,4-cis-polybutadiene, carried out in the absence or substantial absence of a solvent or diluent. According to this method, the catalytic mixture is obtained by contacting, in a hydrocarbon solvent, one or more uumine compounds, one or more halogen compounds, one or more compounds containing hydroxyl groups 1 of an organometallic and / or aluminum hydride compound.

Ova catalytic mixture inlets in contact with the molten ^butad: Female monomer and the resulting mixture is fed continuously to the jednom spot produženog reactor polimerizaciju with piston proticanjem u kojem is played out polymerization butad'ena.

Kao alternative, this reactor the polymerization is supplied continuously with a flow ^katali.t: CKE mixture yields and flow of molten butadiene.

The polymerization heat is removed by partial evaporation of the butadiene monomer, so that by controlling the pressure »

it can sustain at the same time. polymerization temperature within a predetermined interval. By controlling also the composition of the catalyst, the butaditene / catalyst ratio, the polymerisation temperature ⁴ and the residence time in the reactor, it is possible to produce mixtures containing approximately 70% by weight of polymer, which then continuously leaves the polymerization reactor on the other hand.

From this mixture, 1,4-cis-polybutadiene is regenerated ⁴ as a final product, by evaporation of ⁴ unreacted butadiene and any solvent used as catalyst medium

- 5 of a polymeric mass containing an agent that prevents tides, stabilizers and stabilizers that prevent thermo-oxidative degradation. This evaporation takes place in a solvent extruder.

However, when operated continuously with the process at an inlet temperature of not less than 50 ° C, _t is generally obtained

1,4-chis-polybutadiene whose Mooney viscosity (ML) value is not constant due to insufficient homogenization of the system composed of monomer and polymer catalysts.

This demonstrates the evident inadequacy of such a product in meeting the prescribed specifications and, moreover, the questionable reproducibility of the results in the designed plant.

We have now found that it is possible to overcome the ^{4 and the} aforementioned disadvantage by obtaining l ₄ 4-c's-polybutadiene of a fully controlled molecular weight i. this avoids changes in the relative values of Mooney vi through the aunt.

It is an object of the present invention to provide a process which, through the combination of a suitable catalytic system and an adequate polymerization process of act ^4, is capable of overcoming the above difficulties and obtaining a high yield of linear 1,4-cis-polybutadiene without gel, with a large and strictly controlled molecular mass, via polymer ⁴ zation performed in the absence of t

hydrocarbon solvents n ⁴ boiling points or such diluents, or in the presence of min ⁴ small quantities of said low-boiling solvents or ⁴ diluents (generally, about 2% or less by weight, relative to the butadiene monomer) and working in two subsequent stages: the first at a temperature below 30 ° C (T <? 0 ° C) and the second at a temperature of ⁴ 30 ° C or ⁴ more (T «or 30 ° C) suitable between 55 ° θ and 90 ° C (50 <I <90 ° ).

- 6 According to Thorne, it was surprisingly found that while polymerization in the mass of butadiene is carried out at 30 ° C and higher in the heterogeneous phase due to the insolubility of the polymer in the monomer, then the same reaction is carried out at low temperature in a homogeneous one-phase system. Under these conditions, no catalyst is separated from the dissolved polymer, the molecular weight is strictly controlled by the physical and chemical parameters of the reaction, and the resulting product is completely homogeneous. However, since there is little need to perform polymerization in mass to high conversion in each viscous phase, due to the high energy consumption required and useful for working with relatively higher kinetics, it is particularly found that it is convenient to work in two successive phases: first at T <.3O ° C (suitable within the interval between 0 * 30 ° C) 'second at T = or / 30 ° θ (suitable between 5θ and 90 ° C).

The first, not scotemperature phase, e.g. at 20 ° C, it can conveniently be carried out to any desired conversion, but it is clear that it is convenient to avoid high v ⁴ through aunts resulting from high conversion, as well as the cgran'ed effect of homogenizing the early separation of a single phase in two phases .

In fact, with the increase of temperature, and as soon as it reaches the level of 3θ-55 ° θ », here separates the polymer, first dissolved, in the solid phase separates from the liquid phase formed by the excess monomer. It is convenient for this to occur when already 5-20% of butadiene is polymerized.

In the case of solid particles insoluble in the reaction medium, polymerization is carried out ^; by continuous or discontinuous procedure. Solid Chastiee used for this purpose are organic in nature as well as inorganic.

The solid organic particles used are high molecular weight polymeric substances, preferably polyethylene and polysilicon powder, and carbon of various nature and origin, such as soot commonly used in the rubber industry.

Inorganic solid particles used ^; ce are oxides and salts, whether natural or lo synthetic, conveniently in finely divided form, such as zinc oxide, ti. tan-d ⁴ oxide, celite, talc, etc.

The amounts of solid particles used are less than 50% of the polymer obtained, preferably in the range of 1-10% by weight.

The presence of solids, as shown above, to a content of several percent, does not modify the properties of polybutadiene. Larger quantities may even prove more suitable for certain polymer characteristics since they act either as components of vulcanization or as a batch for reinforcement.

The solid may be pre-mixed with the monomer to be polymers and / or the catalytic system, or may be added gradually during the polymerization process, especially if the process is carried out discontinuously or in an extended piston flow reactor.

A further advantage obtained by the use of inert solid particles added to the pol ¹ 'measure of the healer is the better control of molecular weights due to the improved contact between the monomers and the catalyst, which results in the preservation of aluminum compounds.

The advantage given by the new ^; a process, a Koja appears homogeneous ML values, ^modest: it resemble tack reactant tora, koji like to višoj temperature is understood in relation to the činjenicu to Nakon separation exists between nabubrelog monomer and polymer, the pre shape paradise male solid Čestice, Koje readily be uklanjaju and transfers mešalicCm ⁴ to aglomerišu u Vece forms only bath odmiče poly mer 'ation. However, This agglomerate has sasvim različitu Konz wall ¹ 'by the koji care onaj

- 8 occurs in the absence of separation (operating at a temperature greater than 30 ° C); it is more paste-like and more closely related to the liquid phase, and is easily homogenized by the mechanical action of the agitator.

Another significant advantage of two-stage polymerization at two different temperatures comes from the fact that with equivalent proportions and equivalent conversion, an average lower molecular weight (ML) is obtained than in the case of reactions that are carried out at the second phase temperature completely.

This advantage can be measured in the form of preserved AL-alkyls, which are transfer agents, used to maintain molecular weights. The amount retained relative to the ML value in the first phase conversion is of considerable economic scope, since by reducing the ML at least by ten units (altogether approximately 30 ML units) and the AL-alkyls, the highest prices among the catalytic components are individually represented.

More specifically, according to the present invention:

- the catalytic mixture is obtained by contacting, in an internal hydrocarbon medium:

a) at least one neodymium compound selected from neodymium oxide, alcohols, phenoxides and carboxylates, or mixtures thereof with other rare elements;

b) at least one organic compound containing hydroxyl groups derived from an alcohol or phenol or carboxyl group, with the possible addition of water

c) at least one halogen compound selected from secondary or tertiary alkyl, aryl or alkylaryl halogen fumes, organic acid halides, metal or organometallic halides, hydrohalic acids and halogens;

- 9 d) at least one organometallic compound of aluminum or a relevant hydride derivative;

the amount of compounds a) and b) is such that they are in a ratio of 2/1 to 80/1 between hydroxyl and / or carboxyl groups and neodymium atoms and to keep these components in contact to obtain a catalytic mixture in which the aluminum / atom ratios are retained neodymium from 20/1 to 80/1 'halogen / neodymium ratio from 0.2 / 1 to 3/1; »

- this catalytic mixture and the liquid butomer monomer, preferably pre-mixed, are charged in quantities of 10 ^ to

4x10 moles of butadiene per gram atom of neodymium or discounted into polymer-zac reactor ^; by mixing or continuously in two reactors in series, the first of which is homogeneous, or at one end of an extended reactor in which a semi-merization of the mixture is initiated, which is driven by a piston (piston flow), operating initially in both cases at T-30 ° 0 (first phase) and then at T = or 730 ° C (second phase), the temperature was controlled by partial evaporation of the butadiene monomer or the liquid polymerization phase until a mixture having a polymer content of about 25 to about 25 ° C was obtained. 70% by weight, operating constantly at constant pressure.

- 1,4-cis-polybutadiene is separated by regeneration from this mixture by removal from the reactor.

In any 'case, the poly merit can _e continuously perform a single-phase operation in an apparatus-type extruder equipped with a self-discharge single or double piston, maintaining an inlet temperature of at least 30 ° C and an outlet temperature not v- of 130 ° C. Alternatively, it may be performed continuously in several successive phases, using a multi-temperature extruder type with a single- * m -'V double-piston self-discharge or it may be performed discontinuously in a stirred reactor.

9a The agent used for the catalyst according to the invention may be continued from inert (non-reactive) hydrocarbons, with low or relatively low boiling points, alicyclic, cyclic or branched such as butane, pentane, hexane, cyclohexane and heptane, or mixture. These hydrocarbons · 'c ^; , Birds of prey for the catalyst in the small amount zag sasvim manjoj than 5% by weight proizvedenog polymer is odvajaju of polybutadiene according završetku of the first stage polymer · `· ^zac: is.

According to the second termination cloud, the catalyst agent is composed of a hydrocarbon, a mixture of hydrocarbons, a high molecular weight such as paraffin oil and the like, or hydrocarbon oils required for the formulation of expanded polyhydroxybutadiene.

These hydrocarbons do not require separation and remain united in polybutadiene. It was especially found that when the content

1 ,. p, .r-affine oil of 1 ellic aanji of about half an hour of polysers, to «ad» p .liaer characteristic of fcitnr, aa aanje a ·

No x; iaijuask & compounds, the use of yen λ dabbing 'ο thalie & tor, were selected aedju non-soluble oxide ..a (Nd ^ b ^), neodiMj * a alcohol & tia »alifstakih and ci. at skifa «cycloalif.it skifa & & rua« heavy organic acids «at all above, by · ;; the ratio t is 4ata to the neodiate-kaidu, the "eodiatijus-trib" tilet, the naodinius-trine ftsoatin and the neodytius-tri (2-ethyl-hex; inaatu) ·

It is also possible to refer to one neodymium from other Elenentine rare Menus, apr »didinun, which is approximately 72'i id, lv * La and 8> Pr, neodliijun-versatata or« neo * dehanoata.

rg & naka compounds. which contains * faidroxyl groups (alcoholic or phenolic) or carboxyl groups and selects alif & takia and eiklo & lifatekia alcoholika, fenvlina and substitution of feaolin, alit & taki, eiklealif & tskia and aronatic acids «

Of these, it is advantageous that this butyl &lt; / RTI &gt; acobel, 2-ethyl-faecanoic acid, a ^ phenic acid and other acids are &quot; these compounds are foot-solved, free-form, or partially or totally in the &apos; or carbokeyls), such as What respects the ratio of sizes * 2/1 to S> / 1 and are related to hydroxyl Syrups (including.! and those of water) and free and / or fused carboxyl groups and nonodiuiine dwellings. by adding limited amounts of water, as a compound that gives a hydroxyl group, preferably in tons, which enhances the activity of the catalysts · more specifically, this effect is condensed when the ratios in the range 1/1 to 5/1 are maintained behind the orthoaa aluaiaijuaa orsunometallic aluainiases. Compounds or corresponding hydride compounds and moles were added to water * whereby approx. 2/1 ·

The halogen compounds used in the preparation of the catalyst are conveniently selected from hydrogen chloride acid, dihydrochloride, ethylaluminum dihydrochloride, aluminum erynlic fricleride3B, tert.butyl chloride, theodyl chloride, benzoyl chloride hydrochloric acid may be introduced in the form of an aqueous solution of hydrochloric kiaeline to debut the desired amount of water · discard the eluainium compounds and the perpetuating feldridal derivatives in eluainium »trialkyls and hydrides aluminum» alkyl »isobutyl and triethyl, butyl and ethyl * aeftohidxidiaa ·

The amount of different catalyst constituents is aerated such that the ratio of the alumina / aluminum ratio is 20/1 to 6- / 1 and that of the halogen / zeodimium co-ethane group O * 2/1 to 5/1.

O suitable "value" of the above pemesutife ratio in the order of 5/1 "> 0/1 for hydroxyl groups (excluding those of water) and / or carboxyl / non-atomic atoms, seda 25/1" 5ϋ / 1 for nluai "nioa etoms / of atoms, and of order 1/1 "2/1 aa halogen atoms / neodymium atoms"

According to the process of the present invention, the catalytic anaaa aa obtains a feed of the gamma soaked catalytic co-components and k a tact in a hydrocarbon medium * at room temperature or at both temperatures ··

Bed and the process of adding catalytic co-constituents are not particularly critical. They are brought into contact with the hydrocarbon solvent in the indicated * r «dvX sequence and with the teap ^ raturi of the antiant or lower (2 / -25 ° 0) and

- neodyssia-alcocholate * feaokaid vili kertoxylate

- org & noaetalao aluainian compounds and / or proper hydride! derivatives • halogenated compounds

- hydroxyl and / or carboxyl compounds * and / or water ·

Press the other · form of boiling one aa contacted in a hydrocarbon solvent in a redbelate nanoclay and at a temperature of $ oea ° Qi

- naodinium-offnid • hydrokail and / or cartookeil organic compound

- halogenated jinning

- water · smaa aa hours «fades to the entperate tenperatures or lower * 2« 25 ° C and adds aa aledecat

- orgsaoaetal compounds of alunini or hydride repellents! derivative ·

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Thus, they receive a catalytic "Bag that will move aa with liquid ao * lioaeroa bufcudieaa, in such quantity as is l-Λ to 4xlv ^ between gr & m-mol of butadiene and ^ r ^ -atoaa naodiaijuac" Throwing ae can be carried out in any apparatus ^ oj £ aaugue well hoao & aaizing, on the prisar pose with a® It is a pity, that., being a smelly polia ration or the first reactor in a zontinualiv procedure · Mixing is carried out at a yearly chosen j J temperature, but ippod Λ in the case of batch polymerization, this temperature then increases (a> or> 5 ° v) in the second phase of the reaction, with the resultant separation of the polymer phase into the Schwartz and the heavy meaomer phase. »The heat of the ec reaction results in evaporation and recycling of butsdieae and constant pressure.

According to another continuous embodiment, the catalytic emeae current and the liquid butadiene stream. are independently introduced into the first poly reactor, following the relationships indicated above *

By settling the temperatures below 2 ° C in the first phase, it poly- ized 5-20 $ of butadiene, yielding a viscous liquid introduced at the crucible of a polymerization reactor operating above 50 ° C and in which the reaction could counter the piston. or mostly with a piston ·

For example, the extruders in which the polymerized maha is moved by the automatic cleaning of the single or double actuator with the bumps are suitable for the eurutilation and the iolioerisation in the latter phase with "no effect at all inlet temperature" 111> 3. ° C 1 outlet temperature does not exceed 13v ° C and at the bottom of the inlet teuporuture Volicine 5v-6-, ° ;; and output vr ^ dmuti which encloses this last value and 30-1.λΛ ;.

If both phases of polymerisation, control of the tour 4 era, lifted off the fraction of butadiene auxiliaries of butadiene when pressed with atanine after condensation, this will be recycled into the reaction and will need to be dispensed with. suppress the presence of aunensra butadiene in the weekly fez »2a gm soaked teaperatum intervals of this pressure value are conveniently selected presses next ·« to them from 3 »5 b ^ -ra with the first fez, and from 3» 5 bars to lb bar with the next »iade- and within the opaque sheaths, which are the same as above *, the evaea that inflate the reactor content of the polyether from about * about 25 to about * ojs * with our stay time from 17 to 12j ninut »· f convenient regular · condition with two phases eu in the order of 27-6-ΰ ainut for the sake of growing econoeia, below j>; work ea relatively most brsinan butadi conversion * she to the proper polinar, at Chen and re octor oolaal eneaa with the contents of «polinera of by our ·

Wash one or more of the present invention, the eam that goes with the reactor · polinoriaasis ee is brought into the apparatus by sitting in which agents with interruption of the polyneriaea and stabilizers against temo-okaidative degradation of the polyner are suitable, suitable for «butadlen solution solution» is to use

- 15 water or organic kiaalines such as resin acids, or higher aliphatic alcohols (containing 8 to 18 carbon atoms in the locule; or combinations of irregular treatment jobs in ioiicinuffia which exceed the total sum of catalytic koopanen) * 5-lb times per «ol.

Agentsiaa with Prevention of P? Limerisation To the "kiael" agents, bass agents are conveniently added which are rfcustoms to n J ina, such as aa ^ niac, amines, epoxides, and organic salts (alcoholates and carbokailnts) of alkaline nonhals "

The addition of conventional antioxidant debris, used to preserve polymers, as a hundred-inhibited phenols and foepites, suitable for the addition of hydrocarbon solution and radical-scavenging agents, as well as for secondary anine and sidy * Two solutions are suitable for the foot euTo mock them «

Our knives treated in this way should be sent to a non-adjacent heated appliance and the piston rotate e * (extruder with removal of the creator) in which the volatile substances are removed by evaporation, working at a temperature in the range of iv. C and atosphere "8λ, λι or near atmospheric pressure" · ear treatment is used to remove unconverted butadiene, possibly a low-boiling solvent introduced with the kannalitic sneson, as well as introduced water in excess of the required catalytic system * outadienk -key plugs Solvent solvents are subjected to custom treatments to separate them and say "lick"

- 16 * The smoking press of the process of the present invention typically obtains both dry and stabiliaovanon-shaped olibutadion, aa containing vaporized.iii aupsbanks approximately ipod 1 p-; «Aei.

«Vaj polibutadiea nadel jo iaa content l ^ M — cia- ^ vCpoaeati in general above 9 '/ * and MOone viscosity (» d. 1 * 4, 1 «« · ^ο ό _ζ od> «to above βο · iostupk ^ n this pr. / ballast is possible to c .. be * * a non-soluble polybut & dione bare and aa very high content l, A-oiej the only ca »this poliaer as sabt's wash water« to separate kfltalitidkib residues «axis, step this of the invention is simple and convenient, requiring the energy consumption of 1 nose of ecologically probed nose with respect to waste elimination "

The described procedure with the solos also be used with preference for butadiene copoliaoriaae and other suitable diolofinia such as isoprene, piperylene, debut copoliaero and mainly l, k eis stmkturcau.

X

Rebuttal, teoutlteo «tMtra»

Toflonos first metal plate dysonium 12x55 at the time of the introduction into the glass rage aa solid · sidoviaa, capsules approx. 1 al, Ssg «salt introduced the sweetness of the naphthalene klaolino (acidic brnjedOO) 19,8 g

Bd ^ (£ 95) *, 04g tert · butichloride ^ »25» 1 paraffins; ·;. ·: Oil @ 1

-.; c ·· te a & puM & a naoprenskin perivrirunia krunastia o

ft <4> ears & i transferred to the water cup-tilo teraost «txr« no to tio C.

. .> ostrin inclined ostrin * of the fruit ε ··> triggers · and Jel-. > tiinuta in the reactcioau with & su & $ d that „ _t w8» 1 BC1 in olishite> 7 / »- n>, seaeno ^ of solution · s, J · Mole; at night the aicspray »kr-./S« j «a <sai sapusach. K> alc otpilike dv sinus <> oja suepeasijfc # · translate from lavender «you to hazel-ox * acsi · *

Au aauction ee iivdi total $ cups on Su C * bestali thick reatvor »titrisaa since I stopped ds standing 5 cups aa eobnuj temperature» mow the contents M © d v »> k? nol / 1 ·

- after about 5 minutes, slowly transfer this to the glass p oe udu which k usually contains & c al O »97 aoleric solution (iC ^ H ^ gAlM in paraffin« oils in * aehsnical wear, previously introduced uv,; cu in dry ^ j «Taosieri aaota ·

Thus, the age of the creature is maintained for a period of time at a temperature before use.

Sd m »./? ·· g / at on / 1 ,, 1 υ» ό92 ^w

Cl j, U * v · rolnerisation-Reference Test

Poly-aeradia reactor consisting of a steel cylinder mounted horisoatalau, with a capacity of approximately 2 "8 ni" is supplied with a mechanical non-lnion capable of · ds our nsss -elik *

viscose · There will be a transmitting device in the upper part of the reactor

- 18 money won «? raakoijo «to epoxy condenser and aema puspa *

The rakt / r is also a saablevak aa of the ^ usulji-type grouer with a gra ^ anos electric® resistance,

The charge of the rdagenas ee is worth putting the reactor under vHkn- (15 * 52 $ d) 1 nj ^ govia by coupling with a butadiene-containing bocoo, immediately transferring 1 ·. g · and the donkey of thermostation at <k / 'v *

1?, 4 al (equivalent to $ 3 ₉ $ 2 «Sd table) up® description & catalytic solution is introduced into the autoclave ·

The pressure of £ 57 ₉ Gt £ kPa * reaches tersostatization and the resultant internal 'reaiklu'iy of the butedieo * ae maintains a constant «(tseperatnro« rsaksione «« s «) liquid« test * as the vapor is continuously translated «ftieu * dia 4x6 «« * immersed in a bath at -z8 ° C * 1 is collected in cylindrical jars with indicator levels and transferred to the reactor «

The fluid peperature inside the vessels was approximately -15 ^w 3 »bog \ ir> nuae liee in which the r & cooled snela eirculated.

Piaparsia heat react.r «to the atmosphere ae part of lay layman" heat lining "* whose teaperature ee holds about 2 ° 1 isn & d the temperature of the reakoion« ase · neck «aialice is 4 op« ·

The reactor boils 58 «in» starts adding the catalyst introduction »D * f 1 deethyloene and eeriease water» Beisreacted betadie eliminates pressure and settles in the autoclave at 60 ° C for centuries.

Poliner ss does not distinguish between "nestis within reefct" n (axles * sidtvi, etc. ·! 7 «cup ·») and «esMSiti usorsi point of a certain saprenin a« drought · 1 used the separator

Measurer visibility values (1 * 4 »1 ^ v ° j KLj eu next« «

'. · N: / s (maximum n; * djoaa value) 02 sin (maximum u d j one value) 64

RT (value with oeo polymer) / 6 »5

x.on.orsia with respect to half the quantity of butadiene is 46 * 6.

iriagr 2

F linorisaeija butadieaa is performed in the same * plant and aa and Cia reagensiaa as No. · used in the test "bring 1" with tan "painted as polo temoetatiseaa teaperatusa 2 ^ ° C instead of 6k> '^ 0 ·

Seakaija * iaiairena additives * catalysts * lavodl aa 10 «in« at 2u ° C according to the several procedures described * (reeifclovaaje kan * · denaired steam »etc ·« see priaor 1 ·) · žatia sa para prenoanon taped at the top of the reactor * satvori i The oleochemistry was set at 62 ° C. Toke "ten piauta" approximately "internal teaperature reaches 60 ° C and at this time an external circuit of the vapor of the resulting reacions is established.

Fcliaeriaaaija ee interrupts the watery (see pciaer 1 ·) JJ son «after disembarkation» ea mommy vecia strenuous nedaliaa »which expands energy more than three times the fork» Ito ramadane is read aasntra.

obtained poliner »unsorted as if the wave is described by" repent "the following Nosna? viekoaitete *

MX> nax »35» 5

ML «and ·

IK

M

- 20 »

Total conversion reaches up to 5θ, £ 7 · zriaar 3+

Working! transferring gradually the case of 2 ea forgiveness and the realistic son described above, butadiene is polyureaised as before and this is the difference which in a precious feather temperature is set at 5 ^: Λ ua sto what βΛ · Also the first stages continue on 1 / minute ·

The duration of the test is 58 minutes since the introduction of the catalyst. · The resulting polymer gives Fading Ml ®ax 25 values.

Ml «in - 2 *

- 2 *, 5

Butadiene conversion I 40,2 * «

Friaer 4 »

The tasting policy is performed as described in Drawings 2 and 3 of the story, and is the only difference in tone that the temperature of the second heat is? 0®C ·

Se & koij® is sprayed after 4u, 5 »in of debris * and the dry polymer is characterized by its usual action.

The results indicate the following values

HI aax *

MI min · sr s .5

39 »5

Conversion 61% ·

- 24 Butadiene Polymerization - Reference Test

The polymerization reactor consists of ¹ 'horizontally mounted steel cylinders with a capacity of approximately 2.8 1, 5 equipped with a mechanical mixer (shaft and fin) which rotates at 40 opm with a high power motor and a system (placed in the upper part of the reactor) for transfer, cooling and recycling of the reaction vapor. In the reactor, also equipped with one heating liner of the liner type with built-in electrical resistance, the vacuum is achieved by means of a mechanical pump (15.32 Pa), after which it is introduced as follows:

butadiene 1000 g catalytic solution as described above (0.61 mmol Nd) 22.6 ml

Prior to the introduction of the catalyst, the butadiene inside the reactor was thermostatically controlled at 60 ° C. The equilibrium pressure is approximately 657,042 kPa and this pressure is maintained for the duration of the test. In the case of polymer ^; is, the wall temperature is kept a few degrees higher than the one measured internally to compensate for heat losses.

Values that say ¹ 'paradise from the reaction ^; those masses are transferred from the reactor circuit to a 4 x 6 mm diameter steel wire immersed in cold ethyl alcohol at - 78 ° C and connected to a collection vessel having a level indicator. Inside the vessel, in which the lower layer of butadiene is maintained from the beginning, there is a second cell wire (tube) in which it is placed to circulate cold fluid to maintain the fluid present at approximately - 15 ° C. The measuring pump draws the liquid out of the vessel and returns it to the reactor to maintain a constant level in the vessel.

- 22 expends energ ⁴ yes from the side mirrors koji pokreča osovinu mixers are washed ammetrom; it is kept constant for the first approximately 10 minutes, after which it begins to slowly decrease to approximately 24 minutes, indicating the formation of a polymer mass of such quantity and consistency that this impedes the movement of the agitator, whose speed of movement is reduced.

'The polymerization is terminated after 26.75 minutes from start, by introducing 0.5 l of distilled and deaerated water into the reactor. Unreacted butadiene is removed first by lowering the pressure and then applying an autoclave vacuum, the coating of which is maintained at a starting temperature (60 ° C).

The polymer is taken from an open reactor in specified volumes, taken from various points (7 in total) that are separately dried under vacuum at 50 ° C. Mooney viscosity values (1 + 4, 100 °) ML, measured for specific volumes, give the following results:

ML max (maximum value found) = 52

ML min (minimum above yen) - 34

ML (average value for the whole polymer) 4-2.5

I.

The resulting product weighs a total of 591 g (59.1% conversion).

The content of 1,4-cis units, determined by infrared spectroscopy, is 98 * 2%; the internal v ⁴ throughput, which was tilled in tetrahydrofuran at 25 ° C, was 3.6; no gel or microgel is present.

Examples 2-4

Three polymerization tests were performed in the same plant and following the same procedures as described in Example 1,

- 23 with the only difference being that, before shutting down the reactor and introducing butadiene, different amounts of polyethylene (Pe) are introduced as powders, of which 80% of the particles have dimensions between 5θ and 25 x 10 " ⁶ m.

The results are given in Table 1 in which the conversion (%) is expressed by the polybutadiene obtained by excluding the relative mass to PE.

Z

Table 1

PE wt% Conv.% ML max ML min delta ML ML 2.5 63 58 5o 8 54,8 5, o 61 59.5 56 5.5 57.5 9, o 65 41 4o 1 41

Examples 5-7

Working as described in Example 1 and using the same equipment, tests were carried out with reagents and quantities as indicated, but with the addition of different weights to celite (silicate, specific surface area 1-3 m / g) for each test. Celite is placed in the reactor before shutting down and vacuuming.

The principal results obtained are shown in Table 2

- 24 Table 2

Celite wt% Conv.% ML max Ml min delta ML ML 1.6 65,6 53; 5 ' 4o 13.5 5o 4.7 65Λ 56.5 48.5 8 53 8.5 6o, 5 .47 43.5 3.5 45

Examples 819

In a manner similar to that described in Example 1, two butadiene polymerization tests were performed, using procedures and quantities as indicated, but operating in the presence of 15 g of TiO 2 and, respectively, 50 g of talc ("medium") introduced into the autoclave before butadiene and catalysts.

After 26.75 minutes of reaction, the sample was quenched with water according to the procedure described previously (see Example 1) and the resulting polymer was evaluated. The results are shown below:

Additive Conv ..% • ML max Ml min delta ML ML 7 Ti0 ₂ 15 g 46,2 * 65 58 7 ⁶⁰ Talk 50 g 52,1 42 36 6 37,8

PATENT APPLICATION

Claims (27)

PATENT APPLICATION 1. A process for the preparation of 1,4-cis-polybutadiene or butadiene copolymers with other suitable diolefins by catalytic polymerization or copolymerization of butadiene monomers, in the absence of a solvent or diluent, comprising the following steps: - obtaining a catalytic mixture by contacting it with an inert hydrocarbon solvent: a) at least one neodymium compound selected from neodymium oxide, alcoholates, phenoxides and carboxylates, or mixtures thereof with other elements; b) at least one organic compound containing a hydroxyl group derived from an alcohol or phenol or carboxyl group, with the possible addition of water; c) at least one halogen compound selected from secondary or tertiary alkyl, aryl or alkylaryl halides, organic acid halides, metal or organometallic halides, hydrohalic acids and halogens; d) at least one organometallic aluminum compound or relative hydride derivative; wherein the amount of compounds a) and b) is such that the ratio 2/1 to 80/1 is between the hydroxyl and / or carboxyl groups and the neodymium atoms so that the catalytic mixture retains the aluminum / neodymium atom ratio from 20/1 to 80/1 and the ratio halogen / neodymium 0.2 / 1 to 3/1; - catalytic mixture and liquid butadiene monomer, 10 ^ to 4 × 10 moles of butadiene per gram atom of neodymium discontinuously in a polymerization reactor or continuously in two reactors in series, the first of which is homogeneous, or at one end of an extended piston driven reactor controlling the tem- peraturv. partial evaporation of the butadiene monomer or liquid phase polymerization until a mixture with a polymer retention of from about 25 to about 70% by weight exiting the other end of the reactor is obtained; - 1,4-cis-polybutadiene is separated and regenerated from this mixture by removal from the reactor; and characterized in that the polymerization is carried out in two phases, the first at a temperature below 30 ° C (T <30 ° C) and the second at a temperature of 30 ° C or higher (T => 30 ° C). Process according to claim 1, characterized in that the first polymerization phase is conveniently carried out at a temperature between 0 and 30 ° C (0 <T <30 ° C). The process according to claim 1, wherein the second polymerization step is conveniently carried out at a temperature between 50 and 90 ° C (50 <T <90 ° C). The method of claim 1, wherein the first phase is interrupted when 5-20% butadiene conversion is achieved. 5. The process according to claim 1, characterized in that the reaction is carried out in the presence of solid particles insoluble in the reaction medium, such as polyethylene, polystyrene, carbon black, gas black, titanium dioxide, zinc oxide, celite or talc. 6. The process of claim 5, wherein the amount of particulate matter is less than 50% by weight relative to the obtained phtimer. 7. The method according to the preceding claim, on the basis that the amount of particulate matter is suitable between 1 and 10% of the obtained polymer. A process according to claim 1 or 5, characterized in that the hydrocarbon solvent for the catalyst is chiral between butane, pentane, hexane, cyclohexane and heptane, or mixtures thereof, paraffin oil or hydrocarbon oils suitable for the formulation of oil-extended polybutadienes. 9. The process according to claim 1 or 5, wherein the neodymium compounds are selected from neodymium oxide (Iid ₂ O) by neodymium tributylate, neodymium trinaftenate, tri- (2-ethylhexanoate) and the corresponding didymium compounds. A process according to claim 1 or 5, wherein the organic compounds containing hydroxyl or carboxylic groups are selected from butyl alcohol, 2-ethylhexanoic acid and naphthenic acids. A process according to claim 1 or 5, wherein the halogenated compounds are selected from hydrochloric acid, diethylaluminum chloride, tert-butyl chloride, benzyl chloride and benzoyl chloride. A process according to claim 1 or 5, wherein the organometallic aluminum compounds and hydrohydride derivatives are selected from trialkylaluminum and alkylaluminum hydrides. Process according to claim 1 or 5, characterized in that the aluminum compounds are selected from triethylaluminum, triisobutylaluminum and diisobutylaluminum monohydrate. A process according to claim 1 or 5, characterized in that water is added to the catalyst in such an amount that the ratio of aluminum atoms of the organometallic aluminum compound or the corresponding hydrohydride derivatives to moles of water is 1/1 to 5/1. 15. The process of claim 14, wherein the ratio of aluminum atoms from organometallic compounds or hydrohydride derivatives to moles of added water is 2/1. 16. The process according to claim 1 or 5, wherein in the catalyst is the ratio of hydroxyl groups (including those in water) and / or carboxyl groups / neodymium atoms of order 3 / 1-30 / 1, the ratio of aluminum atoms / neodymium atoms of operation 25 / 1-50 / 1 and the ratio of halogen atoms / neodymium atoms of order 1 / 1-2 / 1. 17. The method of claim 1 or 5, wherein the polymerization is carried out in the first phase at a pressure of less than 3.5 bass and in the second phase at a pressure of from 3.5 to 18 absolute bars. 18. The process of claim 1 or 5, wherein the total polymerization time in both phases is between 10 and 120 minutes. 19. The method of claim 18, wherein the polymerization time is 20-60 minutes. 20. The method of claim 1, wherein the polymerization is carried out continuously in the first phase in a homogeneous startup reactor and in the second stage in a self-discharge and single or double piston extruder. t 21. The process according to claim 1, n denoted track e, which polymerization is carried out discontinuously in the stirred reactor, at two successive stages and at two different operating pressures. 22. The process according to claim 1 or 5, wherein the butadiene monomer is opened during polymerization, condensed and recycled. 23. The method according to claim 1 or 5, characterized in that the polymerization discontinuing agents and stabilizers against terra-oxidative degradation are added to the leaving mixture of continuous polymerization. 24. The process according to claim 23, characterized in that the polymerization is terminated by discontinuing the polymerization with water «, ohanic acids and C _Q - 0 _χθ aliphatic alcohol 25. The process of claim 24, wherein water and alcohols are added to the base agents selected from among ammonia, amines, epoxides and organic salts of alkali metals (alcohols and carboxylates). 26. The method of claim 25, wherein the polymerisation interrupting agents are associated with antioxidants and radical trapping agents such as secondary amines and epoxides. 2 ?. The process according to claims 23 to 26, wherein the polymerisation interrupting agents and antiradicals are introduced in the form of an emulsion in the presence of liquid butadiene. 28. The method of claim 1 or 5, wherein the additive reaction mixture is released from low-boiling substances at temperatures of 100 to 180 [deg.] C. at atmospheric pressure.