DE1082414B - Process for the preparation of high molecular weight polymers - Google Patents

Description

GERMAN

The invention relates to the production of high molecular weight polymers that are rubber-like Have properties in the case of alfine catalysts for the polymerization of 1,3-butadiene by themselves or used with substances capable of copolymerization in the presence of impurities.

Cracking and dehydration of mineral oils is one of the most widely used methods of manufacture of 1,3-butadiene, despite the difficulty and cost involved in treating the obtained b-utato low-diene distillate for the production of relatively pure butadiene concentrate brings with it. This one held hitherto indispensable for the preparation of polymers of high molecular weight with a useful Yield.

In the alfine catalyst reactions, the rate of reaction requires rapid distribution of the heat of reaction and for this purpose large amounts of solvents compared to those used Amounts of monomers. Therefore, heretofore, butadiene has been used with a high degree of purity of a multiple its volume is pentane or another inert diluent with an appropriate boiling range diluted before the start of the reaction.

Previous experience teaches the importance of using butadiene with a high degree of purity. For example, A.A.Morton, who developed the alfine catalysts he discovered (Journal of the American Chemical Society, 69, April 1947, pp. 950 to 955), that the intrinsic viscosity of the rubber in large Dimensions would be affected by the purity of the butadiene. The usual technical butadiene could not polymerize easily, and any polymers formed had relatively low molecular weights. In contrast, it has now been found that polymers or copolymers with a high Molecular weight through polymerization of 1,3-butadiene or through its interpolymerization with Styrene by means of an alfine catalyst in a solvent of hydrocarbons on simple and effective type can be obtained if the solvent is a mixture of isobutylene, n-butylenes and butanes as well as hydrocarbon fractions with 3 and 5 carbon atoms.

For example, a mixture of approximately 18 percent by weight 1,3-butadiene, about 81% n-butylene, butanes and isobutylene and about 1% hydrocarbon fractions with 3 and 5 carbon atoms or a mixture of approximately 18 percent by weight butadiene-1,3, about 10% isobutylene, about 71% n-butylene and about 1% hydrocarbon fractions 3 and 5 carbon atoms are used.

It has also proven to be useful in the manufacturing process

of polymers
high molecular weight

Applicant:

Polymer Corporation Limited,
Sarnia, Ontario (Canada)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg,
Munich 27, Pienzenauer Str. 2, patent attorneys

Claimed priority:
Canada November 30, 1951

Harry Leverne Williams ,, Sarnia, Ontario (Canada),
has been named as the inventor

Copolymerization of 1,3-butadiene and styrene in the presence of n-butylenes, butanes and isobutylene to polymerize.

The procedure according to the present invention has the important advantage that the difficulty the handling of butadiene of high purity with it, is avoided.

Another advantage is that the addition of a diluent such as pentane for distribution the heat of reaction is unnecessary. After the polymer formed has been removed, they are not components consisting of butadiene can be recovered, or these components and the remainder can be used Butadiene to the dehydrogenators either directly or through the butylene recovery plant Re-feed in order to prevent the formation of paraffins in the device.

A typical composition of a low-butadiene distillate is shown in the table.

component Weight percent 1,3-butadiene
n-butylenes
Butane 18.1
53.0
18.3
10.0
0.5
0.5 Isobutylene
C ₃ fraction
C ₅ fraction

009 527/357

3 4

In general, the low-butadiene distillate contains laboratory polymerization reactions.

Approximately 18% butadiene, 71% n-butylenes and butanes are injected. The amount of catalog used

10% isobutylene and 1% of C ₃ and C ₅ fractions. lysators swayed slightly what the difference in the

The efficacy of the preparations used in the examples below, and therefore the concentrated alfine catalyst, is produced as follows: It is attributable to the concentration of the active ingredients, but a fine dispersion of sodium metal in xylene was usually between 8 and 15 ecm, which produced that it is carried by stirring with a high of 8 cc corresponding 0.006 moles of active ingredient speed at 110 ⁰ C in finely divided form and then off the highest efficiency notify the Katalysatorzubekühlt. The sand-like sodium thus produced will have maturation. After the addition of the catalyst it was reacted with n-amyl chloride, after which the bottle was shaken to disperse the catalyst to the xylene by n-pentane, whereupon a slimy precipitate of equimolar amounts of amyl sodium and sodium chloride immediately began to appear who get a thick one. Then so much isopropanol is added to the viscous mass of swollen polymer inner mixture that this formed with half of a few minutes. A slight amyl sodium was found with the formation of sodium isopropoxide 15 th temperature increase. After quitting can respond. An excess of propylene is then added to the reaction, 0.15 g of phenyl - /? - naphthyl is added, which reacts with the rest of the amyl sodium under amine as an antioxidant, dissolved in methanol, and forms allyl sodium. The sodium iso and the contents are shaken well. The methanol, zerpropoxyd and the allyl sodium form the active components, the remaining catalyst. Then the stand was opened in the form of a dark green, insoluble sheet and its contents poured into water, in suspension of solid particles in the n-pentane. which the polymer to remove alkali, Na-

The amount of the catalyst is not very important. Trium chloride and n-pentane was kneaded through. That

High, although the proportion required to produce a comparatively tough, white, leather-like polymer was all in one

To give bare reactions, when enlarging the vacuum dryer at room temperature for removal

Dilution increases slightly. With a low-butadiene mixture of n-pentane and water, dried. The ones with 90 and

starting material containing approximately 20% butadiene, more% yield in a series of experiments in the

an amount of catalyst is sufficient, the 0.0006 mol of the above-mentioned polymers prepared

active ingredient on every gram of butadiene - had internal viscosities between 12 and 19

shows. Lying can be used to achieve optimal results.

the amount of the catalyst to be used to fit 30 Example 2 illustrates a reaction under similar, borrowed conditions like Example 1, but explains it

It was found that the polymerization of the Bu- the polymerization of butadiene, which was present in the form of a tadiene even in the presence of a somewhat larger butadiene-poor feed.
Amount of impurities in low-butadiene starting materials can take place than is normally the case with Example2
is expected. For example, it was found that the

Polymerization with a 97.5% strength butadiene, the use of 9.8 g, the butadiene (44.8 mole percent),

with the impurities of an impure butadiene butane (19.3 mol percent), isobutylene (15.0 mol percent

within concentrations between 475 and cent) and n-butylenes (20.9 mol percent) (as the difference

740 parts by weight calculated on 100 parts of butadiene diluted 40), i.e. it contained 35% by weight of butadiene,

is still taking place. The required catalyst was placed in a bottle of about 250 ecm,

amount that results in comparable conversions, increases the amount of catalyst comparable to Example 1

slightly increases with dilution, while the reaction rate in relation to the amount of buta-

speed decreases. There is also a decrease in the content. The bottle was capped and it

As the internal viscosity of the polymer increased, a solid, white, tough polymer formed immediately

of dilution. This is largely the opposite in 187% yield, based on the butadiene,

was to be ascribed to isobutylene, since the concentration, which is soluble in benzene, is 47% of the total

Represented ions of 0 to 400 parts of isobutylene per 100 parts, had an inherent viscosity of 8.0. the

Butadiene leads to a decrease in the intrinsic viscosity procedure, according to which the catalyst is already

from 19.8 to 13.8, compared to an Ab 50 while the butadiene is being added leads

would take from 21.9 to 18.6, which would result in a partial polymerization of the butadiene _{at a concentration.}

from 0 to 1100 parts of n-pentane to 100 parts of butadiene at the end of the weighing process, which is why butadiene does not

is obtained. was done.

The procedures according to the present invention. .

Findings are found in the following examples

Illustrative, the comparisons with procedures other test series, which under similar condi-

close that under similar conditions, but under conditions as in Example 1 with 10 g of butadiene and 75 g

Use of pure butadiene with an inert n-pentane resulted in polymers

Diluents. with internal viscosities from 9.0 to 16.7.

Example 1 illustrates a control reaction at 60

the technically pure butadiene diluted with n-pentane Example 4

is applied. Another series of experiments, similar to that in

Example 1 Example 1 with 60 to 90 g of an impure butadiene

was carried out, which consists of approximately 20 weight

In a dry bottle of about 250 ecm was 65 percent butadiene and the rest of the normal

the approximately 75 g n-pentane (pure) and 10 g buta impurities in the low-butadiene distillate, as described in

which was briefly brought to vaporization to form the air from the table shown, was composed,

to drive, whereupon the bottle was closed. resulted in a tough and leathery product along with

Then the catalyst suspension was through an intrinsic viscosity of 12 to 18.8. Furthermore,

self-closing seal in the lid in the usual 70 the tests carried out to the possibility of

To show the application of the present invention to copolymers of butadiene.

Example 5

An experiment was carried out similar to Example 3 with the addition of 3.0 g of monomeric styrene to 9.6 g of butadiene in 75 g of n-pentane. A yield of 12.6 g (100 ^{10 10} zo) of a copolymer with an intrinsic viscosity of 11.4 was obtained.

Example 6

An experiment similar to that in Example 4 with the addition of 3.0 g of styrene to 35.9 g of impure butadiene was carried out gave a yield of 8.97 g (96%) of a copolymer with an internal Viscosity of 8.7.

Claims (4)

Patent claims: 1. Process for the production of polymers or copolymers with a high molecular weight by polymerizing a polymerizable reaction mixture using an alfine catalyst, characterized in that a mixture from 1,3-butadiene, isobutylene, n-butylenes and butanes is used. 2. The method according to claim 1, characterized in that that a polymerization mixture is used which contains approximately 18 percent by weight of 1,3-butadiene, about 81% n-butylenes, butanes and isobutylene and about 1% hydrocarbon fractions with 3 and 5 carbon atoms. 3. The method according to claim 1, characterized in that a polymerization mixture is used which is about 18 percent by weight 1,3-butadiene, about 10% isobutylene, about 71% Contains n-butylenes and approximately 1% hydrocarbon fractions with 3 and 5 carbon atoms. 4. mixed polymerization of 1,3-butadiene and styrene according to claim 1, 2 or 3, characterized in that that is polymerized in the presence of n-butylenes, butanes and isobutylene. Considered publications:
Industrial & Engineering Chemistry, 42, p. 95
to 102; U.S. Patent Fr. 2,264,811;
Journal of Polymer Science, 1, p. 275 ff. © 009 5271/357 5.60