DD153880A1 - PROCESS FOR PREPARING BICYCLO [2.2.1.] - HEPTEN-2-BUT-1-EN-COPOLYMERIZATION - Google Patents

Abstract

The invention relates to a process for the preparation of bicyclo (2.2.1) - heptene-2-but-1-ene copolymers, which resulted due to the properties of both comonomers, primarily to relatively low molecular weight products. Targeted catalyst development led to the development of a ZIEGLER NATTA CATALYST based on titanium, which made it possible to obtain bicyclo (2.2.1.) - heptene-2-but-1-ene copolymers through very selective reaction reactions It was found that instead of pure but-1-ene and a but-1,3diene-free C deep 4-hydrocarbon fraction can be used without the copolymers obtained with the pure monomer but-1-en have other properties. Thus, a possibility has been found which, dispensing with costly separation processes, allows the but-1-ene to be polymerized out of the mixture in technical processes of but-1,3-diene extraction as a by-product. It has also been found that bicyclo (2.2.1.) - heptene-2 can be selectively polymerized vinyl analogue, which excludes disadvantages of known methods, especially with regard to processability of the polymer.

Description

A-2

Title of the invention:

Process for the preparation of bicyclo [_2.2.1 .j-heptene-2-but-1-ene copolymers

Field of application of the invention:

The invention relates to a process for the preparation of BicycloJ2.2.1..J-heptene-2-but-i-ene Copolyinerisäten. By suitable selection of the reaction conditions it is possible to obtain different copolymer compositions and molecular weights and thus different product properties.

It is essential that this is a highly selective process. It is possible that instead of pure but-1-ene a but-1,3-dienfreis C ^ -hydrocarbon mixture, which is obtained after but-1,3-diene separation as a technical butene fraction, is used without the product properties deteriorate.

The copolymers are prepared while saving on separation and purification processes and allow the use of the residual fraction for further reactions according to the principle of reactive separation.

Characteristic of the known technical solutions:

Polysaccharides between bicyclic [2.2.1. J-heptene-2 and ^ -olefins are known only in very small numbers in the literature. Thus, in DT-OS 2,532,115 the preparation of a terpolymer consisting of bicyclo [2 <, 2.1.J-heptene-2, ethylene and a ^ Olefin, preferably propene, described. By means of this process it is possible, using vanadium-containing catalysts, to obtain elastomers whose molecular weight is more than 20,000.

According to US Pat. No. 3,667,633, a terpolymer is obtained consisting of bicyclo [2.2.TJ-heptene-2, a non-conjugated diene, preferably hexadiene and an < -olefin, preferably propene and but-1-ene. . By appropriate selection of vanadium-containing catalyst components, it was possible, preferably vinyl-conjugated Bicyclo 2.2.1. to obtain -hepten-2 units;

According to Offenlegungsschrift DT 2,421,838, it is known that bicylol 2.2.1.-heptene-2 can be copolymerized with ethylene on the basis of titanium-containing catalysts. It will, the bicyclo. £ 2.2.1 .j-hepten-2 exclusively vinyl analogue incorporated in the polymer.

WP 217 * 371 describes a process for the reactive separation of hydrocarbon mixtures. Within this process, the preparation of bicyclo [.2.2.1. J-heptene-2-but-1-ene copolymers will also be discussed. The disadvantage of this known process is that pure but-1-ene or an isobutene-free residual fraction must be used for the polymerization. However, this is generally not available in technology «

In addition, the choice of catalyst systems did not allow a purely vinyl-analogous bicyclo [2.2.1.7-hepten-2 polymerization.

Object of the invention:

The aim of the invention is to facilitate effective -a process for the preparation of bicyclo | develop _2.2 _e 1 f] heptene-2-but-1-en-Copolymerisäten.

Due to the properties of both comonomers, preference is given to low molecular weights. Together with a selectively vinyl-analogous bicyclo [2.2.1. J-heptene-2 polymerization and the resulting sufficient aging resistance, a copolymer with good processability can be prepared. , , '·

A further increase in the economic benefits of this process should be achieved by substitution of but-1-ene by a technical butene fraction.

Presentation of the nature of the invention:

  The object of the invention is the preparation of bicyclo 12,2.1 .j -] ^) ten-2-Büt-1-en-Copolymeri säten.

Both starting monomers are natural products of petroleum pyrolysis. Bicycloj_2.2.1 .J-heptene-2 can be prepared from the cyclopentadiene or dicyclopentadiene obtained in the C (fraction) and ethylene, but the but-1-ene source can be prepared by conventional methods in the But-1 process. 3-diene separation incurred butene fraction can be used.

According to the invention, the present copolymerization is doubly selective by targeted catalyst tuning. It is selective towards the Bicycloj_2.2.1 7} -hepten-2, which is built exclusively vinylanalog -opened in the polymer chain ein-r and selective to but-1-ene, that in contrast to isobutene, Z-but ~ 2-ene and E-but-2-ene alone in the copolymer! sat is installed. To initiate the copolymerization according to the invention, ZIEGLEK-iTAT'TA-CATALY-SATOEEH, which consist of at least two components, are suitable:

1. A component a, a compound of the. Titans, in particular halides, preferably γ -TiCl- ,, ft -TiCl ₂ , TiCl ,,, TiCl ^, -JAlCl ₇ ; Alkoxy halides, preferably Ti (OR) _? Xp, Ti (OR) ₃ X. For the preparation of TiCl ^ compounds from TiCl ₄

According to the invention, such reducing agents as organoaluminum compounds, organomagnesium compounds or else hydrogen are suitable.

2. A component b, a Metallorganoverbindung, but in particular an aluminum organo compound of the type AlR ₂ X, such as. Al (C ₂ H ₂ O ₂ Ol, Al (O ₂ H ₃ Br, Al (CH) ₂ Cl.

A compound of group 1 is contacted with a compound of group 2 before the beginning of the polymerization. A non-limiting example of the invention is the use of blends of a plurality of layers indicated in FIG. 1 or 2

Links. During the mixing, the organometallic compound is added to the titanium compound (or vice versa) in a ratio of 2: 1 to 15 * 1; the ratios are particularly advantageously 3 * 1 to 6: 1.

In addition, according to the invention, electron donors from the classes of amines, ethers, carbonyl compounds, phosphorus compounds, thiol compounds or cycloalkenes can be added to the catalyst. With donors from the. said classes of compounds is both an increase in selectivity to the butene fraction, as well as a control of the molecular weight possible. According to the invention, the molecular weight control in this reaction can also be achieved by adding hydrogen.

The copolymerizations are carried out in a known manner. Due to the handling of liquefied gases, the polymerization autoclave must withstand pressures up to 1000 kPa. The pressure occurring depends on the polymerization temperature, the composition of the 'butene fraction, the comonomer concentration ratio used and the solvent. '·

According to the invention, cyclojydroxy-2-yl-1-ene copolymerizations can be carried out in aliphatic hydrocarbons such as pentane, hexane, heptane, octane, in cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, in gasoline fractions, in aromatic hydrocarbons such as benzene and toluene, as well as in mixtures of the solvents specified here. Furthermore, it is possible to carry out the said copolymerization without addition of auxiliary solvents. In these cases, the bicycl of 2. 2.1 TJ -hepten-2 dissolved in a liquefied C ^ hydrocarbon cut.

The polymerization temperatures are between 290K and 420K, but preferably between 33OK and 39OK. The bicyclo [2.2.1.J-heptene-2-but-1-ene copolymers obtainable by this process, especially depending on the comonomer concentration ratio and on the reaction temperature, have butene-1 contents of 0-50 mol%. but preferably 5-20 mol%. :.

The achievable average molecular weights are depending on the reaction temperature, the comonomer concentration ratio, the initiator concentration, the donor / titanium ratio or the hydrogen partial pressure between 700-10 000. The inconsistencies are depending. Molecular weight and reaction conditions between 1.5 and

According to the copolymer composition and molecular weight, the polymers according to the invention also have strongly differentiated thermal properties. So can at the present. Method of melting range of the copolymer between 35OK and 55OK be varied.

Exemplary embodiment.

Example 1 '

In a glass autoclave equipped with a stirrer, thermocouple and tempering jacket of 2 liters capacity, 3OO ml of a technical butene fraction having the composition:

4.7% iso-butane 47.5% isobutene 1: 2.9 % n-butane 8.1% e-but-2-ene 24.7 % but-1-ene 2.1% z-but-2 -en.

and 572 g JBiCyCIp [I ^. Add 1 Γ] -hepten-2 as a 1 liter hexane solution. To this are added 20 mmol / l of pre-reacted catalyst consisting of JpTi (IU and Al (C ₂ H ₁ O ₂ Cl in the ratio 1: 3.

The temperature is set to 353K and kept constant for 24 hours. After precipitation in.salzsaurem methanol and drying to obtain a Bicyclo Γ2.2.1.J-heptene-2 copolymer with a but-1-en content of 20%, an average molecular weight of II50 and a softening point of in 87% yield 38OK. ,

An absolute selectivity of the reaction with respect to the remaining polymerizable monomers isobutene, E- or Z-but-2-ene is determined by means of gas chromatography. By HNMR spectroscopy no double bonds were found in the polymer. This indicates a purely vinyl-analogous bicyclo [2.2.1.3-heptene-2 polymerization.

Beispie12

200 ml of a butene fraction having the composition: 'In a stirrer, thermocouple and tempering jacket made of glass autoclaves of 2 l capacity, 200 ml of a butene fraction having the composition:'

36j6 % n- and iso-butane 42.1 % but-1-ene

9.3 % isobutene, 9.5 % E-Büt-2-ene

2.5 % Z- but-2-ene

and 572 g Bicycloj_2.2.1 .j-hepten-2 was added as a 1 liter of Mr-containing heptane solution. To 20 mmol / 1 pre-reacted catalyst consisting of TiCl ^, and ^ added in the ratio 1: 6.

The temperature is set to 353 K and kept constant for 24 hours. After precipitation in hydrochloric acid methanol and drying to obtain a Bicycloj_2 _t 2.1 .J-heptene-2-but-i-ene copolymer with a but-1-ene content of 13%> a mean molecular weight of 1140 in 92% yield and a softening point of 390 K. Analogously to Example 1, a selective Eeaktionsführung could be detected.

Example 3 '.

Me copolymerization is carried out as described in Example 2, but with the use of 100 ml of 1-butene and a catalyst whose TiCl ^ / Al (CpH ^) ₂ Gl ratio is 1s4 ₅ 5 »The temperature is 35.3 K and kept constant for 24 hours. After precipitation in Saizsaurem methanol and drying to obtain a Bicyclo ~ [2.2.1 · J-heptene-2 copolymer with a but-1-ene content of 15% _{5 of} an average molecular weight of 1050 and a softening point in 79% yield of 390 K.

Example 4

The copolymerization is carried out as described in Example 2, but with the addition of 30 mmol / l of hydrogen. The polymerization temperature is adjusted to 353 K and kept constant for 24 hours. '

After filling and drying is obtained in 93% yield, a bi-cyclo [_2.2.1.J-hepten ~ 2-but-1-ene copolymer with a but-1 ~ en ~ content of 18 %, an average molecular weight of 1020 and a softening point of 375 K.

Analogously to Example 1, a selective Eeaktionsführung could be detected. , ·

Example 5; ·

The copolymerization is carried out as described in Example 2? however, using 10. mmol / l

Catalyst. After a polymerization time of 24 hours at 353 K is obtained in 81% yield, a Bicyclo- [^^. IJ-heptene-butene-i copolymer with a but-1-en-content of 13%, one · Average molar mass of 2360, with a nonuniformity of 3.6 and a softening point of 400 K. The selective reaction procedure was analogous to Example. 1 can be detected.

Example 6 '* ·

In the glass autoclave described in Example 1 , 100 ml of a butene fraction of the following composition are added:

21.3% n- and "iso-butane

13.2 % but-1-ene

43.7 % isobutene · "

10.3% E-but-2-ene 11.5% Z-but-2-ene

For this purpose, 572 g Bicyclo [_2.2.1 / J-hepteii-2 dissolved in 1 1 heptane are added. To this is added 25 mmol / l of pre-reacted catalyst consisting of TiCl 3, Al (C ₂ H) ₂ Cl and pyridene in the ratio 1: 5 * .0.3. The temperature is set to 353 K and kept constant for 4 hours. After precipitation in hydrochloric acid methanol and drying to obtain a Bicyclo [_2.2.1 .J-heptene-2-but-1-ene copolymer with a but-1-en-content of 5%> e-iner in 85% yield average molecular weight of 1770 and a softening point of 480 K.

Claims (7)

Invention entitled; A process for the preparation of Bi cyclop 2.2.1.j-heptene-2-but-1-ene copolymers characterized in that durch.ZIEGLER NATTA-CATALXSATOEEN the monomers bicyclo- [2.2.1 .J-heptene-2 and but-1-ene are selectively converted to a copolymer, the bicyclo [2.2.1] heptene-2 being converted by the. used catalysts exclusively vinyl anal og polymerized, as but-1-en-source a butadiene-free Cn ^ hydrocarbon mixture is used and the other polymerizable η olefins, such as isobutene, E-but-2-ene and Z-but-2-ene remain unreacted and can be fed to other processes. 2. The method according to item 1 characterized .dadurch that as the transition metal component of the ZiEGLER NATTA CATALYST titanium compounds, preferably halogen! de, 'in particular J-TiCl ,, Jb -TiCl ₃ , TiCl ₄₅ TiCl ₃₅ | AlCl _x , alkoxy halides, preferably Ti (OR) ₂ Xo ₅ Ti (OR), Z and that the organometallic compound an aluminum organo compound of the type AlR ₉ X, in particular Al (C ₉ Hj Ci _{9 5} Al (C ₉ H) ₉ Br, AI (CH-J ₉ Cl are used. • 3 · Method according to point · 2 characterized by? that the   Titanium compound and aluminum organo compounds ·   before the beginning of the polymerization, the Ti / Al ratio of 2: 1 to 20: 1, in particular 3: 1 to 7: 1, is contacted. 4. The method according to item 3, characterized in that the catalyst mixture an orLtte component, an electron. Donator, preferably from the class of amines, ethers, carbonyl compounds, phosphorus compounds, thio compounds and cycloalkenes can be added. 5. The method according to item 3, characterized in that hydrogen can be used for molecular weight regulation. , 6. The method according to item 3, characterized in that the copolymerization is carried out in bulk without additional solvents and at such temperatures and pressures that the monomer mixture is in the liquid phase _o '^; 7. The method according to item 3, characterized in that the copolymerization is carried out in solvents and that as a solvent aliphatic, cycloaliphatic or aromatic hydrocarbons _s, in particular hexane, heptane, cyclohexane, benzene or their mixtures are used ,, 8o method according to item 3, characterized in that the copolymerization is carried out at temperatures between 290 K and 420 K, but preferably between 330 K and 390 K. Process according to point 1-8, characterized in that bicyclo [2o2e1]] heptene-2-but-1-ene copolymers have but-1-ene contents of 0-50 mol%, but preferably 5-20 mol%, that by controlling the polymerization conditions molecular weights between. see 700 - 10 000 but preferably between 900 - 2000 and Unheiten of 1,5 -.- 4,5 and highly differentiated thermal properties, such as variation of the melting range corresponding to the copolymer composition between 350 K and 550 K can be achieved «