CS237359B1 - Processing of bifunctional initiators of polymerization - Google Patents

Description

The invention relates to a process for the preparation of hydrocarbon-soluble bifunctional polymerization initiators with different reactivity of the two metal element bonds by reacting diamines with lithium organyls.

It is known that organodilithium compounds can be prepared by reacting lithium metal with dihalogenoalkanes in the presence of polar solvents, such as ether. the stability of these drugs. The additional removal of the ether required for synthesis fails due to its coordination with lithium, so that its more or less negative effect on the microstructure of polydienes will be manifested ·

Likewise, the synthesis of bifunctional initiators from dienes using lithium naphthalide or other analogous alkali metal transporters is tied to the presence of stronger polar solvents, which can exert their often undesirable effects on the microstructure of polydienes.

t KSR DOS 2,425,964 discloses a process by which organolithium compounds can be prepared by reacting compounds of the type glT (Аг) к | ОНз) g, where Ar is an aryl residue, with butyllithium in aliphatic hydrocarbons. however, the two to five-day reaction time should have the structure, but almost without exception, they are insoluble in non-polar solvents.

Synthesis of defined nitrogen-containing organodilithium compounds, isolated mainly in crystalline form,

237,358 prepared in non-polar solvents such as benzene, toluene, heptane, etc. is described in GDR patent 150,468. ⁰ 2 h the reaction of Nd ^ P-diaryl-N-IP dialkyletylendiaminu lithUumalkylenu from N, N * -H:! - lith-imaryl) -N, N'-dialkyletylendiaminy. The reaction proceeds in boiling hexane or heptane, i.e., in the absence of polar solvents.

A disadvantage of these systems, which give polymers of butadiene with a high content of 1,4 ' the carboxyl $ ont in the orthopole.

These disadvantages are overcome by a process for the preparation of hydrocarbon-soluble bilunctional initiators with different reactivity of the two metal element bonds, by the reaction of diamines with lithium organyls, by reacting diamines of the RN (H) (CH ₂ ) type with R and R are alkyl radicals having 2 to 10 carbon atoms, R is a alkyl radical, n is 1 to 12, preferably 2 to 3, with lithium alkyls, preferably n-buylyllithium, in a molar ratio of 1 2, in non-polar solvents at a temperature of 0 ° to 100 ° C, preferably 50 to 80 ° C, for 1 to 10 hours; preferably 2 to 3 h. R may be preferably equal to R 'and is nC ^H H or isocC ^Hg and R ”-may be a moiety

CH 2 -CH 2 or CH 2 -CH (Li) ii d ^г

-Chg-In-Hg), or · -GH ₂ -GH (Li) -GH ₂ - (iso-G4Hg), wherein n is 2. Also, R may be equal to R ', and mean-η · ^ ΟθΗ

^{CH, and} R 'to be ^with the ^ups and ⁿ -CH ^H' TCH ₂ or -CH? -CH CHHLi ^ -CN-CGH ^ where n be equal to the second nonpolar solvents may · be benzene, toluene, hexane, heptane or cyclohexane.

237 3S9

The reaction may be carried out in a manner known per se under inert conditions in a closed apparatus. The reactants dissolved in the hydrocarbons are allowed to react at the indicated temperature for the indicated time. This results in homogeneous red-brown solutions. The results of gas chromatography, gel permeation chromatography, mass spectroscopy and acidometric determination showed that the reaction described in the following examples proceeded as follows:

RN (H) (CH ₂ ) _n NR * R '+ 2 R' »Li Ш! (Ы) (Οί ^ η ⁰ '(R' (-H) Li) + 2 R» »H where R, R * and R '** are nC ^, * ř' is is -CH ^ * "" CH ₉ and n is 2, or Bl and R 'Θ «CH ₂ , R" (- H) are η-ΟθΗ. ,

R is iso-C.Hg, R je is - CHg-CH «G ^> R ((H) is -

and n

Θ is 2.

In addition, the addition product (NH 2) (CH 2) _n NR '(CH 2 -CH (LiMH 2 R 2) "is formed at a much lower level. Only in a very small region are oligomers present in the reaction chain. initiator.

Removal of the butane formed from the reaction solution from the reaction solution and subsequent hydrolysis and examination of the hydrolyzed mixture by gas chrtmatotgata showed that the butane was no longer practically detectable, indicating that n-butyllithium was recovered after the reaction.

The high proportion of the metal-exchange reaction in the overall reaction process, as well as the extremely short reaction time, indicate that n-butyllithium is activated by the formation of com- bines. plexus with an ethylenediamine derivative. Even after. storing such initiator solutions. there is no loss of activity. These polymers have butadiene in the poly

- 4 initiator efficiency close to 1 ·

237 359

The advantage of the process according to the invention is that in many ways it is no longer necessary to use unsuitable polar solvents in the synthesis of the initiator, that it allows the preparation of bifunctional initiators which are well soluble in completely non-polar media. - and have high efficiency, p. with which - homopolymers - and - diene copolymers i - with different groups at the chain ends, eg long chain amines having a secondary amino group at one chain end, can be prepared. The initiators according to the invention dovooují -Preparation of Polymer G ^H mooekulovou mo ° Noot from. 1000 and ^{Z d} - ¹⁰⁰ g ООО MUL ^_ l.

In addition, the synthesis time is extremely shortened compared to the synthesis of other dilithic initiators (20 to 120 hours), thereby overcoming the further disadvantage of these methods. The initiator yield is almost quantitative.

The invention is further illustrated by the following examples of specific embodiments, which do not limit the invention in any way. In these examples, well purified, anhydrous reagents and solvents were run under the purest argon atmosphere.

Example 1

In a glass autoclave with a - Ar - atmoofér ou were given 50 mmol of N, ^N, -di-n - Butyl-N-alkyOetylonnUадinu - in 100 ml benzenu'a 103 Moo1. - n-buutllithium in benzene at room temperature. There was - a slight heating and a dark yellow color - of the solution. This was heated for 2.5 h at 70 ° C. Then - the solution of the initiator system noavoёe: rve'oohoedd color. After cooling to 40 ° C, 980 mol of butadiene were condensed. At this temperature - polymerized for 2.5 hours. After cooling to - about 5 ° C and e -. 200 mol of ethylene oxide was added and the resulting gel was quenched with water. - After removal of benzene, liquid polybutadiene was obtained with - a median molecular weight of 1,250 g / mol with OH-ffuOcCoolooline 2.05 ·

- 5 Example 2 237 359

50 mmol were reacted in 100 ml of toluene

N, N ^, -di-n-octyl-N-allyl-ethylenediamine with 105 mmol of n-butyllithium, dissolved in 80 ml of toluene, under inert conditions at 65 ° C for 3 h. To a red-brown initiator solution cooled to 45 ° C 1 mol of butadiene 1.3 was added, followed by stirring at this temperature for an additional 2.5 h. Polybutadiene isolated after hydrolysis with water had a microstructure of 73%

1.4 and 27% of 1.2 units and a mean molecular weight of 1350.

Example 3

Analogously to Example 1, 50 mmol of N, N'-di-iso-butyl-N-monoallylethylenediamine was reacted with 105 mmol of isobutyllithium. The dark reddish brown solution of the initiator system stored for weeks without loss of activity has comparable polymerization activity to butadiene-1,3, isoprene and styrene using the system described in Example 1 as well as similar initiator activity.

Claims (4)

Object of the invention 237 359 Process for the preparation of bifunctional polymerization initiators dissolved in hydrocarbons with different reactivity of both metal element bonds by reaction of diamines with lithium organyls, characterized in that RH (H) (CHg) NR * R * * diamines are reacted, wherein R a H * are alkyl radicals having 2 to 30 carbon atoms, R 1 is an alkyl radical, n is 1 to 12, preferably 2 to 3, with lithium alkyls, preferably with n-butyllithium in a molar ratio of 1: 2 in non-polar solvents at temperature 0 to 100 ° C, preferably 50 to 80 ° C, for 1 to 10 h, preferably 2 to 3 h 2. A method according to claim 1, wherein R is equal to R 'and is η-Ο ^ Ηθ or iso-C ^ Hg and R ** - !! is -CH ^ bu5 4cHg, or -CH ₂ -CH (Ii) ₂ -SH, - (nC ₄ H _9), or-CH₂-CH (Li) -Chg- (iso-C ₄ H ₉₎ and n is equal to 2 · 3. The method of clause 1, wherein R is equal to R * and represents p-С _я Н, ₇ and R "Li is a group CH · ^lf -City * ₂ or CH-CH₂-CH (Li) -Chg- (nC ₈ H ₁₇₎ n Li equals 2 · 4. The process of claim 1 wherein the non-polar solvent is benzene, toluene, hexane, heptane, or cyclohexane. Printed by Moravian Printing Works, Price: CZK 2,40 with operation 12, cl. Lidove milici 3, Olomouc