HU192076B - Process for producing terpolymeres based on ethylene-propylene-diene - Google Patents

Abstract

The invention relates to ethylene-propylene terpolymers made from ethylene, propylene, propenylnorbornene and dicyclopentadiene, in a molar ratio between ethylene and propylene of from 1:1 to 5:1 and between propenylnorbornene and dicyclopentadiene of from 5:1 to 1:1, the terpolymers being amorphous polymers of high molecular weight and being sulphur-vulcanisable, having an unsaturation content of from 3 to 15% by weight. The process for the preparation of the terpolymers comprises the polymerisation reaction of ethylene with propylene and with a diene mixture as intermediate in the synthesis of propenylnorbornene, comprising 70-75% of propenylnorbornene and 25-30% of dicyclopentadiene in solvents such as aliphatic, naphthenic and aromatic hydrocarbons or mixtures thereof, in the temperature range from -30 DEG C to +30 DEG C and at a pressure of from 1 to 10 Atm in the presence of a catalyst system comprising soluble vanadium components and halogenated organoaluminium components with or without addition of modifiers, under polymerisation conditions. The terpolymers obtained have the corresponding properties in the crude state and in the vulcanised state.

Description

The present invention relates to a process for preparing ethylene propylene diene based terpolymers.

It is known that the synthesis of ethylene-propylene terpolymers can be carried out in a solution or suspension of bicarbonate (usually using liquid-phase propylene) in the presence of a Ziegler-Natta catalyst.

The third monomer (termonomer) is generally a compound having two double bonds in its molecules, one of which is involved in the polymerisation process of ethylene and propylene and the other does not react under these conditions and can be used in the subsequent vulcanization process. when the crosslinking of the polymer chains takes place.

In order to produce high performance ethylene-propylene terpolymers, a thermonomer is used in which the double bond reactivity is different (thus no polymer crosslinking occurs during the polymerization process) and the free double bond to be vulcanized is located in the side chain rather than in the backbone.

The best results with respect to the properties of the terpolymers were obtained using cyclic endomethylene bonded thermonomers such as dicyclopentadiene or ethylidene norbornene. The double bonds in the endomethylene rings of these thermonomers are highly reactive under polymerization conditions, while the second double bond is passive during polymerization, thus remaining active for the vulcanization process.

A disadvantage of using the above-mentioned thermonomers is that the extraction and refining operations required to prepare them in pure form are complicated and costly.

The range of ethylene and propylene based terpolymers of the present invention has been expanded as follows: they consist of ethylene, propylene, propenyl norbomene and dicyclopentadiene and the molar ratio of ethylene / propylene is 1/1 to 5 µl and the molar ratio of norbornene / dicyclopentadiene is 5/1. -1/1.

These terpolymers are high molecular weight amorphous polymers which can be vulcanized with sulfur and have an unsaturation of 5 to 15% by weight.

The terpolymers of the present invention are prepared as follows: ethylene, propylene, and a diene mixture containing from 70% to 75% propenyl norbomene and 25% to 30% dicyclopentadiene, are polymerized in an aliphatic, naphthenic or aromatic hydrocarbon solvent. , or mixtures thereof, in the temperature range of -30 ° C to + 30 ° C, from 1 to 10 atm. pressure in the presence of a catalyst comprising a soluble vanadium component and a halogenated organic aluminum component with or without the addition of a modifier.

Example 1

With a 2.5 L cooling jacket and stirring, 2 L of freshly distilled n-heptane was poured into the feeder vessel after the air and moisture were displaced using pure nitrogen and the temperature was adjusted to 10 ° C. The solvent was then saturated by bubbling through a mixture of ethylene and propylene (ethylene / propylene molar. After saturation of the solvent, VOCl ₃ (0.5 mol / l) and Al ₃ (C ₂ H _s ) ₃ Cl ₃ (9/1 molar ratio of Al / V) are added via dosing pump to the reaction mixture, followed by g of a mixture of dienes containing 70/30 propylene bromide and dicyclopentadiene. The mixture of ethylene and propylene was then bubbled through for 20 minutes, and the reaction mixture was deactivated by addition of methanol, washed with distilled water, and precipitated with acetone to give 148 g of a polymer having a viscosity of 2.3, and 3.24 g. Composition: 59 mol ethylene, 41 mol% propylene. The polymer had a Moone ViscosityML (1 + 4) of 58.125 ° C.

To determine the physical and mechanical properties of the polymers, a mixture of the following compositions is prepared:

terpolymer 100 g ZnO 5 stearic 1 Russ FEF 70 Russ SRF 40 192 oils 70 Zinc diethyl dithiocarbamate 2 tetramethyl-dithio-disulfide 0.5 mercapto-benzothiazole 0.5 sulfur 1.5

The above mixture is applied to a laboratory cylinder and vulcanized for 30 minutes at 160 ° C. The results of the measurements are as follows:

tensile strength: 125 kg / Qz; modulus-300%: 114.6 kg / Qz; fracture extensibility: 345% and Shore hardness; 66th

Example 2

The reaction is carried out in a continuous apparatus with a capacity of 6 L and a cooling jacket and a mercury pressure gauge. Toluene solvent in the catalyst system is used following: vanadium triacetyl-acetonate (VAc ₃₎ and A1 (C ₃ H _s) 2C1 mixture of VAc ₃ wherein the concentration 1 mmol / 1 and the molar ratio Al / V 1.15.

Reaction conditions:

C ° temperature and 50 mmHg pressure.

Saturated solutions of VAc ₃ and A1 / C ₃ H ₅ ) ₂ Cl and a solution of diene mixture containing 75/25 by weight of propenyl norbomene and dicyclopentadiene are introduced simultaneously into the reactor (concentration of diene mixture in the reaction space: 20 mmol / l). ). The pressure is maintained using a 70/30 molar mixture of ethylene-propylene. The residence time of the reaction mixture in the reactor is 1.5 hours. Total solvent: 20 1. Thus 1.03 kg of terpolymer (5.1 g% solids) were obtained.

Coherent viscosity: 1.75; propylene content: 30 mol%; degree of unsaturation: 5.2 g% and Mooney viscosity ML (1 * 4): 50, measured at 125 ° C. The physical and mechanical properties of the polymer were tested as in Example 1. The same composition was blended in a Banbury mixer and vulcanized at 160 ° C for 30 minutes. The polymer has the following properties: tensile strength: 119.7 kg / Qz; module 300%: 102.7 kg / Qz; fracture extensibility: 395% and shore hardness: 58.

The terpolymers of the present invention may be prepared by polymerization in the presence of a V-Al catalytic system, with or without the addition of a modifier. As the vanadium component, hydrocarbon solvent-21

192.076 soluble vanadium compounds such as VCI4,

VOClj, vanadium and aluminum as component tríacetilactonát AIjÍCiHj CIJ ^ Al (C _11, Cl ½ compounds. Suitable modiflkátor be a Lewis acid or an oxidizing agent which in reduced bond vanidiumot into active state.

The hydrocarbon solvents used may be aliphatic, naphthenic or aromatic, or mixtures thereof. The reaction temperature ranges from -30 ° C to + 30 ° C, and the pressure used is 0.1 MP-1MP. (SHE

Both continuous and intermittent modes are available.

The results obtained with propenyl norbomene and dicyclopentadiene in the synthesis of ethylene-propylene terpolymers can be explained by the fact that both dienes are able to polymerize at high reaction rates with ethylene and propylene in the presence of a V-Al containing catalyst system. No polymerization of the two dienes takes place and the processing of the diene mixture is easily accomplished, since it contains all of the polymer. u.

The present invention has the following advantageous features:

- significant simplification eliminates the need for separation operations and high purification of individual monomers

- the polymerization process is highly efficient and the diene mixture is well-alkalinized, since both dlenees of the mixture are reacted at high reaction rates during polymerization in the presence of the catalyst used and in the polymer.

- terpolymers, whether crude or vulcanised, have suitable properties.

The terpolymers of the invention can be used in the manufacture of EPDM rubbers.

Claims (1)

Patent Claim CLAIMS 1. A process for the preparation of ethylene-propylene diene-based terpolymers, characterized in that ethylene, propylene is produced in a molar ratio of 1/1 to 5/1 and is produced in the production of propenyl norbomene and 70-75% propylene norbomene and 25-30%. Modifying the diene mixture containing dicyclopentadiene in a catalyst system comprising a vanadium component soluble in an aliphatic, naphthenic or aromatic organic solvent, or a mixture thereof, at a temperature in the range of -30 ° C to +30 ° C and in a pressure range of 0.1 MP-1MP. without figure