DE1570391C - Process for the production of mixed polymers - Google Patents

Description

I 57 U

the IV., V. and VI. Group with metals or organometallic compounds of metals of the I., II. and III. Group to be established.

Homogeneous catalyst systems of the latter type are particularly useful for making essentially amorphous copolymers that are vulcanized to form elastic, resilient materials be able. As already known, polymerization reactions in which these catalysts are used can be used are within a wide temperature range, e.g. B. from about -40 to about 200 ° C will. Similarly, the pressure can range from substantially below atmospheric to about 100 at or more can be varied. When using these coordination catalysts, the reactions generally aromatic, saturated aliphatic or non-reactive chlorinated Hydrocarbons with the exclusion of oxygen, carbon dioxide, water or other substances that can react with the catalyst carried out.

The copolymers produced according to the invention are particularly easy to cure with sulfur and develop their elastic properties on hardening very fast. If the theory is correct that the sulfur crosslinking occurs through carbon atoms which is in the allyl position to an ethylenic Double bond, then the outstanding properties of these preferred multiolefins can be found on it be due to that in the structure

C = C - C - C = C -

there is a doubly activated position. On the other hand, it was also alleged that the site of the sulfur attack is a carbon atom with a double bond. In this case, the superiority can of these multiolefins may be a function of a local accumulation of the remaining double bonds, which introduce these multiolefins into the copolymers according to the invention. These theories are only listed as possible explanations of the unexpected properties observed. The invention aims to however, be neither bound by nor limited by these theories.

The isolated, terminal double bond of the triene used according to the invention has proven to be special Proven to be reactive with alpha-olefin monomers and results in effective utilization of the triene monomer present in the polymerization mixture. An exploitation of this Triene of 25% and more is quite common.

It has been shown that the trienes used according to the invention have an unexpectedly low proportion the double bonds are used for polymerization with the alpha-olefin. This leads to the Formation of a polymerization product, the main chain of which is only a small number with ozone or Has oxygen vulnerable or cleavable double bonds. This small number of kind of double bonds in the chain, in turn, results in a small number of points that form a carbon-carbon crosslinking are accessible between adjacent chains, through which crosslinking the elastomers generally undesirable gels are generated. It has also been shown that the formation of gels then is considerably less than that observed using analogous terminal dienes Gel formation when the trienes used according to the invention are doubly terminally unsaturated are. The infrared spectra of the copolymers according to the invention have shown that the double bonds mostly quantitatively in the 1,4-position in the side groups of the polymer chain.

Because of the high number of double bonds that are formed in the copolymer by the trienes according to the invention are introduced, it could be expected that in order to achieve good properties regarding sulfur hardening requires the polymerisation of a somewhat smaller amount of these trienes is than in the case of the use of analogous monomers, which are outside the scope of the invention. However, it has been shown that the required Amount of the trienes according to the invention is considerably less than solely on the basis of the number of remaining double bonds, which are introduced into the copolymer by them, are to be expected was. A rapid development of elastic properties and satisfactory cures were made achieved with copolymers according to the invention in which the iodine number was below 3. Considerable hardening were achieved with iodine numbers less than 1 and with iodine numbers as high as 100. Copolymers with a higher residual double bond content can be easily made. The use of large amounts of trienes necessary to achieve such high levels of double bonds are necessary, however, there is no advantage. Experience has shown that in general Useful products are obtained when the content of triene in the copolymer is about 0.1 is up to about 20 mole percent.

The following examples serve to illustrate the present invention.

example 1

1.5 liters of η-hexane are introduced into a clean, dry 4.5-1 reaction vessel made of glass, which is provided with a stirrer, a thermometer, gas transfer tubes and a rubber injection cap. The vessel is closed and the solvent is blown with argon for 45 minutes. Thereafter, 4.5 ml (3.5 g) was injected redistilled 1,4,9-decatriene, and ^ is immersed the reaction vessel in a dry ice-acetone bath and held for 25 minutes at a temperature of -2O ⁰ C while the solution becomes saturated with propylene and ethylene. The flow rates of ethylene and propylene are then set at 300 and 2400 ml / min, respectively. After the inflow velocity of the gases has stabilized, 10.1 ml of a 1.48 molar solution of diethylaluminum chloride in n-hexane (0.015 mol of diethylaluminum chloride) and 15 ml of an O.lmolar solution of VOCl ₃ in n-hexane (0.0015 mol VOCl ₃ ) added by injection. The absorption of the gases begins immediately and the temperature is maintained between about -18 and -5 ° C for 30 minutes. An additional 4.5 ml of redistilled 1,4,9-decatriene are then added to the reaction vessel, followed by 10.1 ml of the 1.48 molar diethylaluminum chloride solution in n-hexane and 15 ml of the 0.1 molar solution of VOC1 _S in n-hexane -Hexane. The reaction temperature is then held between about -19 and -17 ° C for an additional 30 minutes. At the

At the end of this time, the catalyst and the polymer are deactivated by adding 15 ml of methanol by pouring the contents of the vessel into an equal volume of a mixture of acetone and methanol coagulates containing a small amount of 2,2'-methylene-bis- (4-methyl-6-t-butyl-phenol) contains as an antioxidant. The coagulated polymer is then separated off, washed with methanol and chopped up in a mixer and dried overnight at room temperature in vacuo. The yield is 69.4 g dry Obtained elastomer polymer. An X-ray analysis shows that the structure of the product is essentially is 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, from which results in about 11.4 weight percent utilization of the multiolefin monomer. The polymer is about 87 percent by weight soluble in η-hexane at room temperature. The one soluble in decalin Part of the polymer has an intrinsic viscosity of 3.03 at 130 ° C, and the Mooney viscosity of 162 (ML-4 at 100 ° C.) shows that the polymer can be successfully extended 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:

Polymer 50

Statex R (carbon black) 25

Hardening base mix 6.75

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 cured polymer at room temperature are:

ίο "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 obtained by tripling the size of the polymer in 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 μΐη 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.

B e i s ρ i e 1 e 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
5

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
5

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 (200 psi)
24 kg / cm ²
41 kg / cm ²

(340 psi)
(580 psi)

1.9 decadia
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 for a particular application of the copolymer according to the invention one essentially amorphous structure is either unnecessary or undesirable, then an essentially crystal-line Structure can be easily obtained by polymerizing according to the conventional methods for the production of crystalline alpha-olefin homopolymers and copolymers. Typical of such well-known processes is the use of a heterogeneous coordination catalyst system, e.g. B. of TiCyDiäthylaluminiumchlorid, at a low temperature in a reaction system using one or more of the present invention Multiolefins and one or more unbranched alpha monoolefins, e.g. B. Ethylene, Propylene or styrene. Such crystalline materials cannot, of course, be used as substitutes for Natural rubber can be used if elastomeric properties are required in this application are. Since their double bonds are essentially in the side chains, they can with Sulfur for the production of ozone- and oxygen-resistant plastics are hardened, which are particularly suitable for use as electrical insulators or protection.

Claims (3)

i o / υ j> y ι 1 2 lead to crosslinking of neighboring chains (gel claims: education) and create places 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 at 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 very large will. Quantities used when a satisfactory 3. The method according to claim 1, characterized in that vulcanization should be possible, and it contains f records that a considerable amount of the vulcanized products is used as triene l-pheny! -L, 4,9-decatriene. 25 of remaining double bonds that lead to that the copolymers have a low resistance against the effects 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 of copolymers against the action of acid-alpha-monoolefins are well known and will be essentially insensitive to substance and ozone, for years in a wide range in many areas. This object is used according to the invention. 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 3 carbon number of remaining double bonds and 4 ° atoms are separated from each other and the third therefore by the conventional sulfur-hardening double bond at a distance of 4 or more (vulcanization), which is present in the rubber carbon atoms of the closest and plastics industry usually used first two double bonds, always ending, is not continuously cured in a satisfactory manner, can react in such an amount. Treatments with 45 have been used so that the resulting copolymer contains 10 to t 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, however, the products obtained in this way do not have the difficulties and expenses associated with such 50 with propylene and ethylene and therefore leads to curing techniques due to polymerizat reacts dp terminal double bond good uptake polyolefin chain consisting of double bonds essentially found commercially. A similar little success is freely borrowed, while the remaining, only achieved with polymers, the double merization of one or more alpha mono bonds separated by mixed poly- 3 carbon atoms essentially in the side groups olefins with a small amount of certain linear 55 and aliphatic dienes made available for vulcanization. Such poly- stand. Therefore, the invention creates new merizates often containing a sufficient amount of and valuable synthetic elastomers, double bonds, so that they can be cured by conventional vulcanization processes which are similar to those of natural or buta. diene styrene rubber can be vulcanized. A commercially satisfactory sulfur 60 The copolymer hardening and oxidation resistance produced according to the invention, however, can only be found in the proportion of the polymer in which the residual double introduced by the olefins and using the aliphatic diene is customary in the polymerization of alpha Catalysts are made, bonds are in the side groups. If both 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 are introduced by reducing the polymer, where they lead to uncontrolled tion of compounds of certain transition metals