DD228272A1 - METHOD FOR PRODUCING FUNCTIONAL 1,3-DIENHOMO AND COPOLYMERISATES - Google Patents

Abstract

The invention relates to a process for the homopolymerization of 1,3-dienes, z. As butadiene, isoprene and similar substances, or copolymerization of 1,3-dienes with vinyl monomers, eg. As styrene, alpha-methylstyrene and similar compounds to living homopolymers and copolymers, by functionalization with suitable substances such as ethylene oxide, CO2 u. a. can be converted into multifunctional polymers whose microstructure, depending on the polarity of the solvent, can be characterized by high 1,4- or 1,2-structural proportions. Multilithium compounds from diamines of the type RR1N- (CH2) 2 -N (H) R2 (RR1R2 simple or substituted allyl group), which are predominantly used in a homogeneous phase in non-polar solvents (hydrocarbons), if appropriate with polar additives, serve as initiators.

Description

Title of the invention

Process for the preparation of functional 1,3-diene homopolymers and copolymers

Field of application of the invention

The invention relates to a process for the preparation of homopolymers and copolymers of t.3-dienes or of 1,3-dienes and yinyl monomers _r, for example styrene and alpha-methylstyrene, living polymers of low to medium molecular weight being formed by means of lithium-initiators soluble in hydrocarbons.

The living polymers can be converted into functional polymers with suitable agents such as ethylene oxide, gamma-butyrolactone and carbonyl compounds.

Characteristic of the known technical solutions

It is known that 1,3-dienes can be polymerized with organolithium compounds (H-Id {R = alkyl, aryl)? For example, n-butyllithium is industrially used for the polymerization of styrene, 1,3-butadiene, isoprene and other monomers (US Pat. No. 3,505,304). The polymers shown have a high 1.4-structure content, but are functionalizable only at one end of the chain (J. Pol. Sei. 4t (1959), p. 381). The particular interest in the synthesis of bifunctional polymers having a narrow molecular weight distribution has already been established (US-PS 3 t35 71 S j DB-OS 2 425

ΟΙ.- ¹

924? SIKPS 296 775).

A suitable initiator for this purpose is t-4-dilithium butane (Japanese Pat. No. 7,229,196), Japanese Patent No. 7,001,629, Japanese Patent No. 7,001,628 and Japanese Patent No. 7,001,627.

DD-PS 137 804 and US Pat. No. 3,193,596 describe a process for polymerizing 1,3-diolefins by means of special bi- and multifunctional alkali metal initiators. The initiators are thermal, stable, ether-free and soluble in nonpolar solvents.

The preparation of bi- and multi-functional initiators of polyvinylaromatic compounds, such as diynylbenzene or diisopropenylbenzene and lithium organylene is described in U.S. Patent 4,039,593 and U.S. Patent 3,668,263. The methods described so far have disadvantages, e.g. that

- The solubility of the initiators in nonpolar media is often limited, which requires polar additives, which in turn cause changes in the polymer microstructure in terms of an undesirably strong increase of the 1.2 content

- The use of monofunctional alkali initiators with good solubility in hydrocarbons leads to non-living oligomers, which can be converted after punctionalization in high polymer products

- In certain cases, the adjustability of the molecular weights and the representation of polymers with low molecular weights (1000 - 5000) is not guaranteed.

Object of the invention

The aim of the invention is to develop a process for the homopolymerization of conjugated dienes or for the copolymerization of conjugated dienes with vinyl monomers to living polymers of low to medium molecular weight, which can then be converted by reaction with special Punktionali sungsmitt a multifunctional prepolymers.

Explanation of the essence of the invention

It is an object of the present invention to develop an economical and efficient process for the homopolymerization of conjugated diolefins and copolymerization thereof with vinyl monomers to living polymers of medium to low molecular weight and high 1.4 structural content of the polydiene component, which are reacted with reagents such as ethylene oxide, gamma-butyrolactone, Buren variation of the initiator concentration should be adjustable to a predetermined molecular weight of the polymer, also variable should be the proportion of 1.2-Sinheiten in the polymer by addition of polar solvents , According to the invention, this object is achieved in that the homopolymerization of conjugated dienes or copolymerization of conjugated dienes with vinyl monomers with the aid of multi-lithium initiators, the reaction products of monolithium organyls E, - Id (R * - i-alkyl, n-alkyl, cyclic alkyl, aryl , Arylalkyl having 1 to 20, preferably 3 "to 10 C atoms) and ethylenediamine derivatives of (Cyp

^> H - CH ₂ - CH ₂ - HC ^

(R, R 1, R ₂ = -CHR. -CR. "CHR ₄ , R ₄ = H, n-alkyl, i-alkyl, cyclic alkyl, aryl, arylalkyl) in hydrocarbon solvents and the structure

Li * - CH ₂ - CH ₂ - N <^

H ₅ R ₅

(R ₅ = R, R ^ or R ₂ or -C (Li) R- - CR, = CHR, or -CHR - C (Li) R ₃ - CHR ₅ R ₄ )

in which 2 to 4 Id atoms are contained in the initiator molecule, in gasoline fractions or aromatic hydrocarbons, e.g. Benzen is carried out without or with the addition of a polar solvating agent and leads to the addition of functionalizing agents to multifunctional prepolymers of variable microstructure

 The polymerization is carried out in a known manner at temperatures of 273-373 K, preferably at 303 to 333 K at atmospheric pressure or elevated pressure and after TO min to 6 h, usually after 0.5 to 3 h, completed. Bs arise living homopolymers, which can be converted by the addition of other anionic ρolymeriaierbaren monomers, especially vinyl aromatic compounds in living blocks op polymers or in random copolymers.

According to the invention, it is possible to prepare functionalized polymers with low molar masses, eg 1000 and with high molar masses (20,000-50,000), wherein the desired molar mass can be set by the choice of the initiator concentration}, likewise variable between 90 $> 1.2 and 75 # 1.4 Structural units is the microstructure by suitable solvent additives.

The process according to the invention is distinguished by eliminating the disadvantages of known processes, such as initiator insolubility, low initiator effectiveness in nonpolar solvents, low functionality, and the like

 The ether-free polymerizations take place as far as possible without termination reactions and allow functionalities 2-4, the polymers obtained can be crosslinked, for example with diisocyanates to high polymers

 The examples given are intended to illustrate the process according to the invention without restricting it in any way.

Exemplary embodiments Example 1

50 mmol Tri allyl ethylenediamine (TRIAED) in 50 ml Benaen be reacted with 205 mmol of i-butyllithium in 250 ml of benzene in 3 h at 343 K to a tetralithium. At 313 Σ, the polymerization of 926 mmol butadiene-1 x 3, which is completed after 2 h. After cooling to 268 K, the punctionalization is carried out with 410 mmol of ethylene oxide, resulting in a white solid gel, which can be stirred like a sand. This is destroyed with 30 ml of water and the organic phase separated by centrifuging water and lithium compounds. After drying on a rotary evaporator, a low viscosity polymer of average molecular weight 990 (M ₁₃₈₃ , = 1000 * ') and functionality is obtained

3.4 with a yield of 96 i> d. Th * The microstructure was determined to be 25.5 # 1.4 cis, 46.8 $> 1.4 trans and 27.7 $ 1,2 polybutadiene benzenes.

Example 2

5 mmol of TRIABD in 20 ml of benzene and 21 mmol of i-butyllithium in 20 ml of benzene are formed as in 1) to Tetralithiuminitiator and reacted at 313 K in a known manner with 926 mmol of 1,3-butadiene. After 2 h, the reaction is stopped by precipitation in methanol. Bs results in a polymer having an average molecular weight of 11 800 (M ^ _er = 10,000), and a microstructure similar to 1). The yield is $ 91 > d. Th.

Example 3

From 50 mmol of TRIABD in 80 ml of benzene and 155 mmol of i-butyllithium in 15 ml of benzene, a trilithium-indene is added as in 1).

1) In all examples, the molar mass of the initiator did not enter into the calculation of the molar mass.

illustrated. The polymerization of 926 mmol of 1,3-butadiene is carried out at 313 K. After 2 h, gamma-butyrolactone is reacted at 268 E, whereupon a syrup-like gel is obtained average molecular weight of 1500 (M = 1000) and a functionality of F = 2.6 and the following microstructure is characterized: 26.4 1 ° 1,4-cis, 42.2 $ 1,4-trans and 31, 4 ί * 1,2-PB, the yield was $ 92.0, ie.

Example 4

A tetralithium initiator, formed in 3 h at 343 lb from 50 mmol! THXASD in 50 ml benzene and 205 mmol i-butyl lithium in 200 ml benzene, is reacted with 926 mmol butadiene-1.3 at 313K. After 2 h, the functionalization takes place at 268 Έ. with acetaldehyde. Besides the resulting lithium alcoholate compound, the QH groups formed on the polymer chains are released by hydrolysis.

Example 5

50 mmol of TEIAED in 50 ml of benzene and 205 mmol of n-butyllithium in 150 ml of benzene are used to form the tetralithium initiator at 343 K within 3 h. At 313 E is reacted with 926 mmol of 1,3-butadiene and functionalized after 2 h at 268 K with 410 mmol of ethylene oxidej it forms a white solid gel. After working up in a known Ifeise to obtain a product which is comparable in its properties with that under 1).

Example 6

From 50 mmol of TEIASD in 20 ml of benzene and 105 mmol of i-butyllithium in 70 ml of benzene, a dilithium initiator is formed analogously to 1). After cooling to 293 K, 200 ml of cold

THF, then 926 mmol of 1,3-butadiene. . After 2 Ta is precipitated in methanol, and a polymer product of average molecular weight 1,850 0 ^ _er - 1000) and a Mikrοstruktur containing 86 i 'i 1.2 and 14> 1.4-trans-fractions (yield 96 Si).

Example 7

A lithium lithium initiator, prepared from 5 mmol of TSIAED in 50 ml of benzene and 20.5 mmol of i-butyllithium in 20 ml of benzene, is reacted at 323 lb with 35 g of 1,3-butadiene and 5 g of styrene. After 5 h the product is precipitated in methanol, it results in a random co-polymer with 33 i »PoIystyrenanteil and a microstructure of polybutadiene, similar to 1).

Example 8

With an initiator, formed as described under 7), 35 g of butadiene t.3 are polymerized in 1.5 h at 323 K, followed by another 15 g of styrene in 3 h. The workup results in a block copolymer having a polystyrene content of 32 # and a comparable polybutadiene microstructure with 1).

Claims (2)

Invention claim 1. Examples of homopolymerization of 1,3-dienes for the copolymerization of 1,3-dienes with tinyl monomers, "especially vinylaromatic compounds, for the production of living polymers of low to medium molecular weight, the compounds after addition of special agents, such as ethylene oxide, carbonyl compounds, among others in that functional groups bearing functional groups can be reacted at the chain ends, with microstructures of the diene components which can be varied within the limit of butadiene-1.3 within the limits of $ 75 > 1.4 to $ 90 > 1, ^ structural content, in a mostly homogeneous phase in non-polar paraffinic, olefinic and / or aromatic solvents, optionally with polar additives, at temperatures'from 273 K to 373 K in the presence of multifunctional alkali metal initiators, characterized in that the polymerization and copolymerization is carried out with initiators, the reaction products of Monolithiumorganylen, R , -Li, (R, = i-alkyl, n-alkyl, cyclic alkyl, aryl, arylalkyl with 1 to 20, preferably 3 to 10 C-atoms) and ethylenediamine derivatives of the type R. H R ₁ - CH ₂ - Έ (R, R ₁ , R ₂ = -CHR ₄ -CR ^ = CHR.) R- = H, n-alkyl, i-alkyl, cyclic alkyl, aryl, arylalkyl) in hydrocarbons and the structure Ή - CH ₂ - CH ₂ - Έ R ₅ = R or R ^ or R ₂ or C (Li) R, -CR, = CHR, or CHR-C (Li) R ₃ -CHR ₅ R ₄ ) having 2 to 4 Li atoms in the initiator molecule · 2. Method according to item 1), characterized in that for the preparation of functionalized block copolymers or of functionalized random copolymers all anionically polymerizable monomers, e.g. Styrene, alpha-methylstyrene, can be used as an oomonomer.