CS233415B1 - Method of selective polymerization of butadiene with c4 fraction - Google Patents

Description

The invention relates to a method for the selective polymerization of butenyl-ene C- fractions not hoeopolyasry e / r ^ Ebo 'tapolyaery' s pteáen designated ^"h in detail tootnneH oaogeinií phase in black light in the angle of the initiators, wherein is used an initiator of a new type .

It is known that butedienes can be peroidized by a number of organdithic compounds. C - fractions selectively. For example, it is known that selectively butadiene or isoprene of bittHithie (JA 73.42 717) can be selectively selected from the C - or C - fraction of pdymerorate. With 100% yield, pdybutedlene having similar properties to pure butediene is obtained.

It is also known to perform organolithic airborne initiators. of the formula R-Li, where R can be alkyl or myl, e.g. n-butyllithium (SOS 2 431 2588. The higher structure content of '1,2' is achieved by adding polar compounds as electron donors before or at the polymereel. The combination of an organic compound with a polar compound yields a betelytic system reacting less with the C * hydrocarbons contained in the mixture as impurities, thus reducing its de-deactivation, so that it may be less propagating. The organic organosilicon compound used is not required to capture the fact that the conversion of butediene is only about 60%. However, the use of these compounds means that it is not possible to obtain polymers having At the two ends of the chain, the functionalized polymers are Αιο ^ Ι ^ in principle only at one end of the chain, and the synthesis of ABA-type block copdymers is problematic.

It is also known from other works that pdicebutyride and copolymers may be prepared from hydrocarbon fractions C. It is important to send acetyls and ЦЗ-Мг ^ го. It is only in this case that the dimensions have properties.

analogous polymers of pure butediene. / R. J. Sornineneld, Am. Chem. Soc. Polym. Chem., Pdymer Preprins 16 (1975) 1, et al. 346 to 350./, * The initiator can be used with 1,4-diylthene (JA 70.01 629, JA 70.01 628,>

JA 70.01 627), as well as 1 lithium adducts having 1 to 7 palms. units (NSR 1 169 674, RAS 1 170 645). Higher functional polyols are generally insoluble in non-polar solvents. The addition of small monomers leads in some cases to the formation of living digomers whose improved solubility in hydrocarbons, while allowing for a newer addition of the given monomers in a homogeneous phase, but the formation of polymers 8, defined by the relative molecular weight, is problematic. Also, the addition of polar solvents improves the solubility of the initiators in the hydrocarbons.

Many initiators are soluble only in the presence of strongly polar solvents. Since polymerization in the presence of such initiator solutions, such as ether ethers, readily decreases the efficiency of the initiators due to ether cleavage. Therefore, in the known methods, it is carried out before polymers. total or partial replacement of the ether with a non-polar solvent (U.S. Pat. No. 3,377,404, 3,388,171, DAS 1,768 ° C, DOS 1,817,479) was not present in the pure 1,3-butyl ether polymer. The presence of hydrocarbonaceous hydrocarbons in the presence of capillary solvents may not require side reactions as long as the raw material corresponding to Matohu. However, the conditions for the removal of the ether often in themselves lead to partial deactivation of the initiators and to an increase in operating costs. Another disadvantage of the known methods is that. The dietary ether is very low in its dietary ether so that it can only be used at high risk on an industrial scale.

It is also known that from pure butedime, eolytes are deactivated by tri- and more polymerization. alketometallic initiators, most of the lithium compounds, to prepare star-shaped radicals with end-functional groups with a fucoconite greater than 2 (US-3 -644 322, 3 602 016, 3 725 368, 3 734 973, 3 862 201, DOS 2 .00 3 384 , 2,063,642, 2,231,908, USA 2,408,696, 2,427,955).

According to these methods, the organdithic compounds are unreacted. can be reacted with fumes of compounds such as O 2 or di-sopropenyl benzene not more than once. metallized compounds useful as polymerization initiators. According to the reaction steps, the pH of the resulting compounds is more or more branched, optionally crosslinked, and forms nitrogels. There may be 1 partially or totally molecular-crosslinked products. These oecrogels are insoluble and, as initiators for enlontic purification, are only slightly impregnable.

These disadvantages are solved by a process for the selective polymerization of butadiene from the C-fractions, optionally in the presence of anionic copolynerine-resonable sonors, preferably 1 of supported, styrene, alpha-ethylstyrene, non-homo- and / or copolymers with a predetermined molecular weight of 0. 2. The method of claim 1, wherein said initiator comprises the use of a hydrocarbon solution of the general formula obecného * Я (0Н ₂ ) _п ЖВ ', wherein said initiator is used as initiator.

R, R, R, Η - are CH ₀ · · £ Η- or ² Li -

R, R »8 are Si / ^ ЧсН2 Li is

R -CH ₂ -CH (Li) -CH ₂ -, cured

R ** is alkyl, n-alkyl, cycloacyl, eryl- or aryl-alkyl of 2 to 8 carbon atoms, or

R, R 'are CC ^ _e ^Li

R * and R 'are R ** -CH ₂ -CH (L 1) -CH 2 - or _- - _- -

R is ellyl and R *, R * * * are CH · * ..... \ CH- or * Ы

R-CH ₂ -CH (L 1) -O 4 - or

R and R * are allyl and. ♦ ¹

R * e R * * are CHy · ^ or

Li of R - is CH / - * EH- a.

if;

R @ 1 is R @ 1 --C @ 2 --WLD --C @ 2 -, e - n is 2 and 6, the addition is carried out in a temperature range of 263 and 353 K and under pressure at. It is a mixture of monomers in the liquid phase.

Thus, blocking copolymers of the type B (-A ·) 4 are formed, wherein n is 2,3,4 or statistical copolymers.

Homo-polymers may be dependent upon the use of the eolar polarization initiator: eonorner liquid and solid. It is possible to determine a mean polyolefin molecular weight in the range of 500 to more than 100. 000 g / eol. When the initiators' tetraurnations are used, the calculated e-axis eolecular density, as calculated and found, of the liquid polyesters is calculated in the sequence. ИЧ bFunctional and * triunction. ·

233415 * 4 initiators for polymerization are very likely to proceed by chain building processes under the influence of the free alkyl groups of the initiator. Thus, the values of the molecular weights or the functionalities of the polymers are greater than those calculated.

By adding water or alcohol, the Li-C bonds solvate to give non-functionalized polymers.

By bringing the living polymers into contact with ethylene oxide, butyrolectone, carbon dioxide and the like, polymers having OH, COCH and the like at the chain ends are obtained.

These functionalized polymers can be converted using the corresponding polyfunctional polymers. These include, for example, agents such as isocyanates, epoxides, etc., autocatalysts, i.e., without the addition of other ketelelating compounds, not polymers and dense network. The polymerization of butadiene in the liquid fraction is possible without the addition of non-polar solvents, since the other fraction components act as a diluent.

The microstructure of polymers can be set within wide limits. While polymerization is carried out in non-polar solvents, butadiene polymers are obtained in which the fraction of structures 1.4 is greater than 70%.

At ⁴ can if, before polymerization, a polar solvent, e.g. tetramethylethylenediamine, tetrahydrofuran, or similar compounds, a polymer forms a very high content of structure 1 «2.

The products obtained by the process of the invention have the same properties as those obtained using pure butadiene as raw material. The process of the invention thus provides a convenient method for preparing polybutadiene and butadiene copolymers without the need for a costly butadiene extraction process to be used beforehand.

Synthesis of the initiator system is performed as follows: Monolithiumorganyl, RLi, e alkyl substituted diamine, R ₂ * H (CH _{2) n} NR _2, wherein R is allyl and n is 2 to 6, are reacted in an inert solvent, hydrocarbon, at temperatures between 283 and 373 K, preferably between 323 and 343 K, the reaction time being between 10 min and 16 h, preferably between 1 and 5 h.

For. wherein said reaction conditions are the reference base molar ratio

R-Li: R * ₂ N (CH ₂ ) _n HR * ₂ · When reacting pure components in a 2: 1 solar ratio under an inert gas in a pure hydrocarbon containing no oxygen or hydrogen at all, eg benzene, bifunctional forms an initiator that is soluble in this solution. A soluble trifunctional initiator is also obtained at a 3: 1 molar ratio. The reaction of the components in a 4: 1 molar ratio yields a somewhat poorly soluble tetrafunctional initiator, but which is later converted to rostoku when more benzene is added so that a homogeneous reaction mixture for polymerization can be achieved without the addition of some conjugated dienes or vinyl-substituted aromatics. The solutions, and in the case of tetrafunctional initiators at high concentrations, also partial suspensions, have a concentration of 10 to 2, in particular 0.2 to 1 mol of active lithium per liter.

The process according to the invention is further illustrated by the following examples.

Example 1 mmol of initiator I dissolved in 200 ml of benzene was used to polymerize 980 mmol of butadiene 1.3 contained in 220 ml of C. fraction. The polymerization was carried out for 150 minutes at 313 K. The initiator I had the composition НН'ЩСНр ^ Н ^ 'ičemž where R was CH ₂ CH-CH ₂ -,

R * and R ** were CH 2 OH-OH and R * was iso-C 1 -C 8 -CH ₂ CH ₂ Li -CH ₂ Li

2 33415

After polymerization. the residue of the C fraction was distilled off and the polymer was precipitated with methanol.

A well-flowable product was obtained which had an anaimetrically determined molecular weight of 2700 and a calculated 1512. This was done regardless of the initiator molecules incorporated into the polymer chains, and in the case of the mono-polymeric polymers, they did not increase the molecular weight due to functionalization. Mtarostructures were 47% 1,4-friction, 32 *

1,4-cis and 27% 1,2-structures. The polymer yield was 95% of theoretical.

Example 2

K 12.5 mmel of initiator II RR ^ CHp ^ V 'where

K 1 was CH 2 and R 1 was iso-C 1 -C 8 -CH 2 -CHCLD-CH 3 - dissolved in 200 ml of benzene. at 313 K, 1.96 asses of butadlene-1.3 contained in the 440 c ol fraction were added. The polymerization was carried out for 150 minutes. The rest. the α-reaction fraction was terminated by precipitation in methanol. A viscosity product with an average molecular weight of 9,620 was obtained, whereby 8,467 were calculated according to the method of Example 1. Mtarostructure was 48% 1,4-trens, 26.1,4-cis and 26% 1,2-structures. The yield was 100%.

Example 3

To 313 mole of the initiator II in 350 ool of benzene at 313 K was added 1.96 mmol of tatadiene 1.3 contained in 440 ml of the C fraction, after which the solution was homogeneous and polymerized for 150 minutes. Then the remainder C - fraction ldeeeStlooel and butadlene - was precipitated in methanol.

A liquid polymer with an average molecular weight of 2,520 was obtained, calculated as in Example 1 of 2117. The morostructure was 48% 1,4-trens, 28% 1,4-cis and 24% 1,2structures. The polymer yield was 95% of theory.

Example 4 * N

The 50 ouoI of the initiator ΙΠ with the composition RRNOHOH1), where R and R 'were ΟΗ ^ ΟΗ- ^ R was

Ы

R was iso-C18-CH2-CH2-CH3-.

and dissolved in 250 ml of benzene at 313 K was added 980 µl of tatadiene-1,3 contained in 220 ml of the C-fraction. After 150 minutes of polymerization, the mixture was cooled to 268 K and 220 vol ethylene oxide was added. The solution solidified to a white solid gel. After distilling off the residue of the C fraction, hydrolysis was carried out with water and the water with HHL salts was centrifuged from the benzene solution. This benzene solution was then dreamed on a vacuum rotary evaporator.

A liquid polymer having an average molecular weight of 3,700 was obtained, with a calculation according to Example 1 'of 1058. The fuccioonlitic rate was 2.9. The polymer had the same structure as in Example 1. The yield was 95% of theory.

233415 б

Ř í cl 0 d 5

К 2.5 mmol of initiator II, dissolved in 200 ml benzene, at 323 К from stirring added 35 g butadiene 1.3 contained in 145 ml fraction and 15 g styrene · The homogeneous solution * was stirred for 300 minutes, then the rest of the fraction distilled off and precipitated in methanol. A random copolymer was formed with a styrene content of 33% and a polybutadiene microetructure of 74% 1,4- and 26% 1,2-structures.

Example 6

To 2.5 mmol of initiator II in 300 ml of benzene at 326K was added 35 g of butadiene-1,3 contained in 145 ml of fraction and polymerized for 300 minutes. 15 g of styrene were then added and polymerized for an additional 300 minutes. Then the fraction was distilled off.

49 g of star block copolymers having a styrene content of 33% and a polybutadiene microstructure of 72% 1,4- and 28% 1,2-structures were isolated from the polymer solution.

Example 7

To 50 mmol of Initiator III in 120 mL of benzene was added 200 mL of tetrahydrofuran while cooling. 980 mmol of butadiene-1,3 dissolved in 220 ml of the fraction were then added thereto, then polymerized at 263 K for 180 minutes. The remainder of the fraction was distilled off and the reaction was stopped by precipitation in methanol. A polymer having an average molecular weight of 3,100 was obtained, and 1,058 was calculated according to Example 1. The microstructure was 87% of the 1,2- and 13% of the 1,4-trans structure. The yield was 95% of theory.

Example

To 35 nmol of initiator I in 250 ml of benzene at 31.3 K was added 960 nol of butadiene 1.3 contained in the 220 ml fraction. After 150 minutes of polymerization, the mixture was cooled to 268 K and 220 mmol of game-butyrolactone was added. This resulted in a reddish-red solid gel, which, after distilling off the remainder of the fraction, was treated analogously to Example 4. A well-flowing polymer having an average molecular weight of 3040 was obtained, with a calculation of 1,512 according to Example 1. Functionality was 3.5. The polymer yield was 95%.

Example 9

25 mmol of initiator II dissolved in 175 ml of benzene and 980 mmol of butadiene-1,3 contained in 220 ml of the fraction were added at 313K. After 150 minutes of polymerization, the solution was cooled to 268 K and 220 mmol of ethylene oxide were added.

A solid white gel was obtained, which was processed analogously to Example 4. The liquid polymer had an average molecular weight of 2,500, calculated according to Example 1 of 2,117. The functionality was 3.8. The yield was 95% of theory.

Example 10

To 35 mmol of initiator I, after removal of the benzene solvent in vacuo, 220 ml of a C ₄ fraction containing 980 mmol of butadiene-1,3 were added. The polymerization was carried out for 240 minutes at ca. The living polymer was hydrolyzed with water. A liquid product with an average molecular weight of 2,980 was obtained, the calculated value of Example 1 being 1,512. The microstructure was 70% of the 1,4- and 30% of the 1,2-structure. The yield was 96% of theory.

Claims (1)

SUBJECT MATTER Process for the selective polymerization of butadiene from C C fractions, optionally in the presence of anionically copolyerizable monomers, preferably isoprene, styrene, alpha-ethylstyrene, not homopolymers and / or copolymers, β of a predetermined molecular weight in homogeneous phase in the presence of lithium initiators, characterized in that as initiators, use hydrocarbon solutions of multilithium diterdiaalines of the general formula RR'N (CH ₂ ) _n KR '* R *, where CH R, R *, R **, and R *** are CH 2 R 2 or R ² R, R * and R are and R 'is * Li R * '-CH ₂ -CH (Li) -CH ₂ -, wherein H is isoalkyl, n-alkyl, cycloelkyl, aryl or erylalkyl of 2 to 8 carbon atoms; or R, R * are CH 2 R 2, CH- and * Id R ^zz and t are R -CH ₂ -CH (L 1) -CH ₂ , wherein R ^{zz z} is as defined above, or CH R is allyl e R *, R e R * are CH 2 CH- or Li R ^zzz '-CH ₂ -CH (L1) -CH ₂ -, wherein R ^zzz * has the above exclusion, or R e R * are allyl and <R e R ^z ^ CHk are СНл "'*' in CH- or ² Li R is CH 2 CH 2 and CH 2 R ', R "is -CH ₂ -CH (Li) -CH ₂ - wherein R aa ^ZZZZ abovementioned meaning of E n is 2 Ez 6, wherein pólyaerace carried out in the temperature range 263-353 К and the pressure at the ASCs liquid-phase mixture of aonoaers ·