NO146155B - MEDICINE TO COMBAT MIDDLE AND LEAVES - Google Patents

Abstract

Remedy for mites and aphids.

Description

Process for the production of deconstructed amorphous ethylene propylene mixture polymers.

Ethylene and propylene can, e.g. under

the use of metal-organic mixture catalysts and the use of the Ziegler low-pressure method are polymerized into high-polymer products, as described in Belgian patent document no. 553 655.

With a suitable content of propylene and

suitable distribution of the two monomers in the polymer, high-molecular, amorphous, rubbery mixed polymers are obtained by this method. They on this one

manner produced mixed polymers have

a reduced solution viscosity of r| ed

> 1 (measured at 135° C in a 0.1% by weight solution in decahydronaphthalene).

But the production of amorphous mixed polymers of ethylene and propylene, which

have low or medium molecular weight, resp. as

has a solution viscosity of t) red < 1,

when using the above-mentioned polymerization method, is very difficult.

Thermal degradation of high molecular weight,

solid olefins to low molecular weight, solid definitions are known from the German patent specification 1 048 415. In this it is described

also thermal degradation of solid high molecular weight mixed polymers of 90%

ethylene and 10% propylene (cf. the examples

12 and 13) so that solid, low molecular weight products are formed which have a molecular weight

of 630-720 and a melting point of approx. 105—

115°C.

From the U.S. patent document no. 2 372 001 is

it is further known that an ethylene-propylene

mixed polymer, which has a molecular weight of 6000 and unknown composition, at a temperature of over 450° C can be degraded into a highly unsaturated (1.04 mol double bonds per molecule) distillable product, which has a greasy consistency and a molecular weight of 501.

It has now been found that it is possible to produce amorphous ethylene-propylene mixture polymers with less than 3% crystalline components which have a solution viscosity of ti red < 1, measured in 0.1% by weight deca hydronaphthalene solution at 135° C. by amorphous, rubbery ethylene-propylene mixture polymers are heated, which in a 0.1% by weight decahydronaphthalene solution at 135° C. have a solution viscosity of t| red > 1, in the absence of air or oxidizing substances, for 3 to 300 minutes, preferably 10—200 minutes, at 260—420° C, preferably 300—360° C.

The method can be carried out continuously or discontinuously. In a discontinuous working method, the high-percentage starting material in a suitable container can gradually be heated to the required reaction temperature, below which it is advantageous to avoid strong overheating in the water zones. In the continuous mode of operation, the high molecular weight starting product is taken to a tubular degradation zone by means of an extrusion device. It is then advantageous to use a fast-moving extrusion device, with the help of which the polymerizate obtains the desired decomposition temperature by the uniform conversion of mechanical work into heat, without the risk of overheating.

The temperature in the degradation zone is regulated so that the degradation products have the desired final viscosity. The lower the decomposition temperature, the higher the viscosity of the final product (compare the examples below). If mixed polymers with different propylene contents are used for the degradation, the polymers with the highest propylene content are degraded the most under otherwise similar degradation conditions.

The length of the residence time in the degradation zone has a very significant influence on the course of the degradation reaction. It has been shown that good breakdown products are obtained especially if the breakdown takes place during a sufficiently long breakdown time. Already with residence times of approx. In 10 minutes, you get high-quality products. If the residence times are longer, e.g. about. 60 minutes, the breakdown products clearly have better mechanical properties at approximately the same viscosity. It is preferable to use a residence time of approx. 15-90 minutes in the degradation zone.

Preferably, mixed polymers containing from 20 to 50 mol% propylene are used for carrying out the method. If the propylene content is lower, the crystallinity of the mixed polymer increases, and if the propylene content is higher, the freezing temperature rises sharply. In particular, mixed polymers containing approx. 25— approx. 45 mol-% propylene, preferably 30-40 mol-%, suitable as starting products for technical implementation of the method according to the invention, as these mixed polymers are practically purely amorphous, i.e. do not contain any crystalline proportions, and because these mixed polymers freezing temperature is at approx. — 60 more

— 70° C. Such mixed polymers can e.g. is produced in the manner described in the above-mentioned Belgian patent no. 553 655. Particularly suitable starting polymers are obtained by the method described in Belgian patent no. 588 764 by polymerization of two olefins in a homogeneous phase using contact agents, which are formed by: 1. at least one ester or acetylacetonate group containing higher-valued compounds of the periodic table system's (Mendelejew's) 4-8 subgroup, where — if it is a vanadium ester — a halogen must be connected at the same time — or hy- drocarbon residue with the vanadium atom, and 2. organometallic compounds thereof periodic table (Mendelejew's) 1-3 main group.

The mixed polymers of ethylene and propylene obtained by the method according to the invention, which have low resp. average molecular weight, differ from the known decomposition products from predominantly crystalline ethylene-propylene mixture polymers, among other things, in that they have no specific melting point. The products are flexible and plastic at temperatures down to approx. — 60 to — 70° C. Also if they give solution viscosity values of r| rode approx. 1.0, these new products already dissolve in the cold in any ratio in the usual non-polar solvents such as e.g. aliphatic and aromatic hydrocarbons and halogenated hydrocarbons. The new, amorphous mixed polymers are also soluble in higher esters, alcohols and ketones. The starting products, on the other hand, are significantly less soluble. They differ from the mixed polymers that can be produced by special polymerization methods in terms of their physical and technical properties. In particular, they are easily processed. For example, the high molecular weight ethylene-propylene mixture polymers used as starting material cannot be melted without splitting, while the decomposition products obtained according to the invention give clear, free-flowing melts.

Compared to the known amorphous polyisobutylenes, the mixed polymers of ethylene and propylene produced in accordance with the invention - at a comparable numerical average molecular weight - have significantly lower viscosity both in solution and in the melt. Furthermore, solutions of polyisobutylenes have the disadvantage that they have a tendency to "spinning". If, for example, a paper tap is drawn through a solution of polyisobutylene in melted paraffin, in order to coat this paper web with the aforementioned mixture, it will often be found that the polyisobutylene is drawn out of the melt in the form of threads. As polyisobutylenes are partly only partially soluble in resp. miscible with hydrocarbons, the further reprocessing of polyisobutylenes usually requires a large technical performance. The products produced according to the present invention do not have this disadvantage.

The amorphous polypropylenes described in Belgian patent document 616 420 are indeed well soluble, but have, in relation to the amorphous ethylene-propylene mixture polymers produced according to the present invention, the disadvantage that they have a freezing temperature of approx. — 30° C.

By means of the method according to the present invention, a large number of amorphous ethylene-propylene mixture polymers of relatively low resp. medium molecular weight and different consistency, whose solution viscosity in a 0.1% decahydronaphthalene solution at 135° C lies at r\ red < 1. In particular, the method enables the production of valuable semi-solid products, which cannot be obtained by other technical means toads. The products manufactured according to the invention can therefore find use in many different areas of use, e.g. in the rubber industry as a processing aid and to increase the inherent stickiness of certain types of rubber. In the plastics industry they can be used in the production of wrapping wax, in the adhesives industry in the production of hot melt and contact adhesives, in the mineral oil industry for changing the viscosity properties of oils, they can also be used in the production of durable plastic sealing compounds, as well as to improve the properties with bitumen and other substances, as well as in the production of chewing gum. The products below can be processed in a manner known per se on rollers or by extrusion from solution or melt or from aqueous emulsion.

Examples:

In the following, the preparation of two mixed polymers is first described, where products obtained according to examples 1-7 are used as starting materials for the preparation. A. Under the absolute exclusion of water and oxygen, 300 liters of completely dry toluene were saturated with ethylene and propylene under stirring at 40° C to 1 ato, so that the weight ratio between the dissolved gases amounted to 1 part C2H4 per 30 parts C3H«. Then, over the course of 150 minutes, 300 m-mol of vanadium triisobutyl ester and 1200 m-mol of diethyl aluminum chloride were pumped in separately and evenly, both dissolved into 10 liters of toluene solution, and the monomer gas consumed during polymerization was replaced in the volume ratio 2C2H4 : 1C3H6 of in such a way that the overpressure of 1 ato was maintained constant throughout the duration of the polymerization. When cooling the device's jacket, the temperature ket to 40° C, whereby the excess of dissolved monomer gas was released, with stirring, and the catalyst was removed by repeated washings with an equal amount of water. The solvent was removed by steam distillation in a suitable apparatus so that the solvent-free mixed polymer was obtained in the form of crumbs with a diameter of 2-5 mm, which could be easily dried. The yield of colourless, dry mixed polymer was 22 kg, which contained 28 mol% propylene, 2% crystalline products and had a reduced viscosity of 5.2, as well as an ash content of 0.02%. B. 60 liters of hexane were, to the exclusion of water and oxygen, at 50° C and with stirring at 2 atoms, saturated with ethylene and propylene in such a way that the solution contained a weight ratio of 1 part C2H4 per 28 parts CsH6. Then, over the course of 60 minutes, 30 m-mol NOCls and 180 m-mol ethyl aluminum dichloride were pumped in evenly, both separately dissolved in 1 liter of hexane, and the pressure was kept constant at 2 ato by supplying a gas mixture consisting of 2 parts by volume of C2H4 and 1 volume part C3H6. After 1 hour, the work was rescheduled for continuous polymerisation, whereby per hour, 120 liters of hexane, 60 m-mol of VOCls and 360 m-mol of A1(C2H6)C12 were added. The pressure was kept at 2 ato by supplying mixed gas, which contained 38% by volume of C2H4, and the temperature was kept at 50° C by cooling the mantle. Relief of monomers dissolved in excess and removal of the catalyst was carried out continuously, in the manner specified under A. Dividend per hour was 4 kg of ethylene-propylene mixture polymer, which contained 32 mol% propylene, less than 1% crystalline fractions, 0.01% ash, and had a reduced viscosity of 1.8.

Examples 1— 3:

In the following examples 1, 2 and 3, a predominantly amorphous ethylene-propylene mixture polymer, which contained approx. 28 mol% propylene and had a viscosity of t| red 5.2, and which was obtained according to polymerization example A, decomposed by heating for 1 hour at the temperature indicated in the table, whereby the following results were obtained:

Decomposition was carried out in an agitator vessel under a nitrogen atmosphere and

exclusion of air and oxygen.

Example 4— 7:

In the following examples 4, 5, 6. and 7 were of a pure amorphous ethylene-propylene mixture polymerizate, which contained 32 mol% propylene and had a viscosity of t) red 1.8, and which was obtained according to polymerization example B, degraded by heating for 1 hour at the temperatures indicated in the table.

Claims (1)

Method of manufacture of. deconstructed amorphous ethylene-propylene blend polymers containing less than 3% crystalline constituents and which are suitable as self-adhesive coatings and as additives for oils and which have a solution viscosity of r\ red < 1, measured in a 0.1% by weight decahydronaphthalene solution at 135° C, characterized by heating amorphous, rubbery ethylene-propylene -mixed polymer sater,' which in a 0.1% by weight decahydronaphthalene solution at 135° C has a solution viscosity of t) red > 1, in the absence of air or oxidizing substances, for 3 to 300 minutes, preferably 10-200 minutes, at 260- 420° C, preferably 300-360° C.