DE1570391B1 - PROCESS FOR THE PRODUCTION OF MIXED POLYMERIZES - Google Patents

Description

ORIGINAL INSPECTED

3 4

the IV., V. and VI. Group with metals or metal turn of analogous terminal dienes ob-

organic compounds of metals of L, II. Gel formation respected if the inventively

and III. Group to be established. used trienes doubly terminally unsaturated

Homogeneous catalyst systems of the latter type are. The infrared spectra of the invention are particularly useful for the production of essentially 5 copolymers have shown that the double-cell amorphous copolymers, which are vulcanized to elastic bonds in the 1,4-position mostly quantitatively in the resilient materials seen, are present in side groups of the polymer chain,
can. As already known, polymerisation can be expected within a wide temperature range, because of the high number of double bonds, the reactions in which these catalysts are used by the trienes according to the invention in the mixing process, could be expected. B. from about -40 to about 200 ° C, carried out that to achieve good properties with respect to. In a similar way, the pressure can be varied from a sulfur cure to the polymerisation of an amount of these trienes, which is required substantially below atmospheric pressure to approximately a little less, 100 atm or more. When using, as in the case of using analogous mono-coordination catalysts, the reactants which are outside the scope of the invention are generally aromatic, saturated ones. It has been shown, however, that the required aliphatic or non-reactive chlorinated amount of the trienes according to the invention is considerably less than the number of carbon dioxide, water or other substances, the remaining double bonds that are formed by them in hydrocarbons with the exclusion of oxygen that can react with the catalyst carried out. 20 mixed polymer are to be expected

The copolymer produced according to the invention was. A rapid development of elastic properties

Sates are particularly easy to harden with sulfur shafts and satisfactory hardening results

and develop their own elastic properties during curing, achieved with copolymers according to the invention,

business very quickly. If the theory is correct that they had an iodine number below 3. Considerable hardness

the sulfur crosslinking through carbon atoms was found at iodine numbers of less than 1

acts, which in the allyl position to an ethylenic and at as high an iodine number as 100 is achieved. Mixed

If there are double bonds, then the outstanding polymers with a higher content of remaining can be used

Properties of these preferred multiolefins on double bonds can be easily made

due to the fact that in the structure the use of large quantities of trienes,

30 which to achieve such high levels of double

I I I I ties are necessary, but does not result in any

- C = C - C - C = C - advantage. Experience has shown that in general

I get usable products when the

Content of the triene in the copolymer is about 0.1

there is a doubly activated position. Other- 35 to about 20 mole percent,

On the other hand, it was also asserted that the place of the The following examples serve to illustrate the

fel attack a carbon atom with a double present invention,

bond is. In this case, the superiority can. -I ₁

this multiolefine is a function of a local example

accumulation of the remaining double bonds, which 40 1.5 1 η-hexane are in a clean, dry

these multiolefins are introduced into the glass mixing 4.5-1 reaction vessel according to the invention, which with

introduce polymers. These theories are just a stirrer, a thermometer, gas conduction

as possible explanations of the observed, unexpected tubes and a rubber injection cap

properties listed. The invention is intended to be provided. The jar is closed and that

but neither bound by these theories nor permeated with argon for 45 minutes by solvent.

they be limited. blow. Then 4.5 ml (3.5 g) are redistilled

The isolated, terminal double bond of the 1,4,9-decatriene is injected, and the reac-

The triene used in the invention was immersed in a dry ice-acetone bath as a bation vessel

particularly reactive with alpha-olefin monomers and therein for 25 minutes at a temperature of

Proven and leads to an effective utilization 50-20 ° C while the solution is kept with propylene

of the present in the polymerization mixture and ethylene is saturated. The influx velocity

Triene monomer. An exploitation of these Triene opportunities of ethylene and propylene are then on

of 25 per cent and more is quite common. 300 or 2400 ml / min. In connection

It has been shown that in the invention to stabilize the inflow velocity

Trienes used an unexpectedly small proportion 55 of the gases become 10.1 ml of a 1.48 molar solution

of the double bonds for polymerization with that of diethylaluminum chloride in n-hexane (0.015 mol

Alpha-olefin is used. This leads to the diethylaluminum chloride) and 15 ml of an O.lmolaren

Formation of a polymerization product, the main solution of which is VOCl ₃ in n-hexane (0.0015 mol VOCl ₃ )

chain only a small number of added with ozone or by injection. The absorption of the

Oxygen vulnerable or fissile double 60 gases begins immediately, and the temperature is 30 mi

has bonds. This small number of double grooves kept between about -18 and -5 ° C,

bonds in the chain, in turn, result in a small number of links

Number of sites that are added to a carbon-carbon 4.5 ml redistilled 1,4,9-decatriene and

Crosslinking between neighboring chains is then accessible from 10.1 ml of the 1.48 molar

are through which crosslinking the elastomers 65 diethylaluminum chloride solution in n-hexane and 15 ml

generally undesirable gels are generated. the 0.1 molar solution of VOCl ₃ in n-hexane. the

Furthermore, it has been shown that the formation of gels reaction temperature is then a further 30 minutes

is then considerably less than that at which the demand is kept between about -19 and -17 ° C. At the

At the end of this time, the catalyst is deactivated by adding 15 ml of methanol and the polymer is coagulated by pouring the contents of the vessel into an equal volume of a mixture of acetone and methanol containing a small amount of 2,2'-methylenebis (4-methyl -6-t-butyl-phenol) as an antioxidant. The coagulated polymer is then separated off, washed with methanol, chopped up in a mixer and dried in vacuo at room temperature overnight. The yield obtained is 69.4 g of dry elastomer polymer. An X-ray analysis shows that the structure of the product is essentially amorphous. The IR spectra show a propylene content of the polymer of 56 mol percent. The iodine number of 4.1 corresponds to a 1,4,9-decatriene content of about 1.1 percent by weight, which results in a utilization of about 11.4 percent by weight of the multiolefin monomer. The polymer is soluble in η-hexane to an extent of about 87 percent by weight at room temperature. The soluble fraction of the polymer in decalin has an intrinsic viscosity of 3.03 at 130 ⁰ C, and the Mooney viscosity of 162 (ML-4 at 10O ⁰ C) shows that the polymer can be stretched with success with oil.

Example 2

The product obtained in Example 1 is heated at 153 ° C (307 ° F) for 60 minutes according to the cured following recipe, in which the individual proportions are given in parts by weight:

Polymerisat., 50

Statex R (carbon black) 25

Hardening base mix 6.75

35

The composition of the hardening base mixture is in parts by weight:

Vistanex L-100 (polyisobutylene) 100

Zinc oxide 100

Thionex (tetramethylthiurammono-

sulfide) 30

MBT (mercaptobenzothiazole) 10

Sulfur 30

The physical properties of the hardened Polymer at room temperature are:

100% module 33 kg / cm ² (470 psi)

200% modulus 112 kg / cm ² (1600 psi)

300% modulus 183 kg / cm ² (2610 psi)

Tensile strength up to

Breakage 212 kg / cm ² (3020 psi)

Elongation at break 330%

Shore A hardness 61

Example 3

A similar, rubber-like copolymer can be made by tripling the size of the example 1 used proportions of 1,4,9-decatriene are produced. The IR absorptions of the trans and vinyl double bonds at wavelengths of 10.34 and 11 μm show that the remaining double bonds of the triene are present in the uncured polymer almost quantitatively in the side chains and approximately the same number of internal and terminal double bonds are present.

Examples 4 to 6

The development of the elastic properties of a similarly produced elastomeric copolymer of ethylene, propylene and a third monomer was measured at room temperature after the copolymer had been ^{cured at 153 °} C. for 5 minutes according to the recipe given in Example 2.

example

Third monomer

Weight percent of the third monomer

Iodine number

100% modulus

200% module

300% modulus

* Without significant hardening.

1,4,9-decatriene

1.3

19 kg / cm ² (270 psi) 43 kg / cm ² (610 psi) 71 kg / cm ² (1010 psi) 1,4-hexadiene
4.1
12.8

14 kg / cm ²
24 kg / cm ²
41 kg / cm ²

(200 psi) (340 psi) (580 psi)

1.9 decadiene 2.0 3.6

Example 7

The procedure of Example 1 was modified by the equimolar replacement of diethylaluminum chloride by triisobutylaluminum, increasing the flow rate of ethylene 400 ml / min., Lowering the propylene flow rate to 800 ml / min, and replacing of 1,4,9-decatriene by 25 g of l-phenyl-1,4,9-decatriene. Here, too, was the dried, coagulated The product is more than 50% soluble in η-hexane at room temperature. It essentially had one amorphous structure and could be hardened with sulfur in a satisfactory manner.

If a substantially amorphous structure is either unnecessary or undesirable for a particular application of the interpolymer of the present invention, then a substantially crystalline structure can readily be obtained by carrying out the polymerization according to conventional methods for making crystalline alpha-olefin homopolymers and copolymers will. Typical of such well-known processes is the use of a heterogeneous coordination catalyst system, e.g. B. of TiCl ₄ / diethylaluminum chloride, at a low temperature in a reaction system that contains one or more multiolefins according to the invention and one or more unbranched alpha-monoolefins, e.g. B. ethylene, propylene or styrene contains. Such crystalline materials cannot, of course, be used as a substitute for natural rubber if elastomeric properties are required in that application. Since their double bonds are essentially in the side chains, they can be hardened with sulfur to produce ozone- and oxygen-resistant plastics, which are particularly suitable for use as electrical insulators or protective coatings.

Claims (10)

1 2 Establish cross-links between neighboring chains (gel claims: formation) and create sites for oxidative cleavage. These difficulties can be partly 1. Process for the production of essentially bypassed in that for the Polymerisalichen amorphous, unsaturated mixed polymerisation reaction an aliphatic diene is used, sowed by polymerization of ethylene and in which one of the double bonds through the inner one Propylene with an aliphatic, open-chain position or proximity to a bulky substituent Trien, characterized in that it is disabled. Such a disability diminishes one propylene, ethylene and a triene, of which, however, clearly the curing rate of the Double bonds two by three carbon atoms in the polymer. are separated from each other and the third double It is also known to use copolymers by the bond in ■ a distance of 4 or more Polymerization of alpha monoolefins with 1,3,6-Oc- Generate carbon atoms from the closest of the tatriene or 3-methyl-1,4,6-heptatriene. at first two double bonds and these trienes always have two conjugated double bonds is terminal, in such an amount to react, which are both active and therefore with the alpha tion brings that the copolymer obtained monoolefin can react. In this way 10 to 80 mole percent propylene, up to 80 mole long double bonds in the polyolefin chain, and percent ethylene and 0.1 to 20 mol percent of the side groups are generated that only have a double Contains Triens. binding included. The application of such trienes 2. The method according to claim 1, characterized in that 20 leads to copolymers which are vulcanized, that allows 1,4,9-decatriene used as triene sation, but they must be in very large. Quantities are used when a satisfactory ^ 3. The method according to claim 1, characterized thereby vulcanization should be possible, and contain it draws that as triene l-phenyl-1,4,9-decatriene, the vulcanized products a considerable amount is used. 25 of remaining double bonds that lead to that the copolymers have a low resistance to the action of oxygen and ozone to have. In contrast, the invention has the task The invention relates to a method for the basis, a method for the production and manufacture of essentially amorphous, unsaturated alpha-monoolefin polymers Copolymers by polymerizing fen, which are easily hardened with sulfur Ethylene and propylene with an aliphatic, open can without them an excessively large proportion chain trienes. must contain trienes. Furthermore, these Homopolymers and copolymers from 35 copolymers against the effects of Sauer-Alpha-Monoolefinen are well known and will be essentially insensitive to matter and ozone, For years in a wide range in many fields This object is achieved according to the invention used. The use of these polymers is solved by propylene, ethylene and a triene, but limited by the fact that they contain a small number of its double bonds two by three carbon atoms of remaining double bonds and 40 atoms are separated from each other and the third is therefore separated by the conventional sulfur-curing double bond first two double bonds is present at a distance of 4 or more methods (vulcanization), the advertising usually employed in the rubber carbon atoms from the nearest of and plastics industries, always final Λ the not hardened satisfactorily constantly can become a reaction in such an amount. Treatments with 45 have been used so that the resulting copolymer contains 10 to organic peroxides and irradiations with 80 mol percent propylene, up to 80 mol percent ethylene, and with some success, contains essentially len and 0.1 to 20 mol percent of triene,
to cure saturated alpha monoolefin polymers, depending on the mixture produced according to the invention however, the products thus obtained have the terminal double bond reacted due to polymerizate of the difficulties and expense involved with such 50 with the propylene and ethylene and therefore leads to a Hardening techniques are linked, no good absorption polyolefin chain, which consists of double bonds essentially Trade found. A similar minor hit is borrowed freely while the rest, just by was achieved with polymers, which are separated from each other by mixed poly- 3 carbon atoms of one or more alpha mono bonds essentially in the side groups olefins with a small amount of certain linear 55 exist and are available for vulcanization aliphatic dienes. Such poly- stand. Therefore, the invention provides new merisate often contain a sufficient amount of and valuable synthetic elastomers created, Double bonds so that they can be cured by conventional which in a manner similar to natural or buta vulcanization can be hardened. diene styrene rubber can be vulcanized. A commercially satisfactory sulfuric polymer hardening produced according to the invention and shows resistance to oxidation, however, only sate can in the polymerization of Alphader Proportion of the polymer in which the olefin customary manner and using the aliphatic diene introduced remaining double catalysts customary for this are produced, bindings are in the side groups. Typical catalysts of this type are the Friedel double bonds of the diolefin for copolymerization 65 Crafts catalysts, such as. B. aluminum chloride, are used with the monoolefins, anionic catalysts such. B. Sodium, and the remaining double bonds in the main chain coordination catalysts, which by Redukdes Polymerisats introduced where they lead to uncontrolled tion of compounds of certain transition metals