DE1645345A1 - Process for the preparation of copolymers of butene-1 and propylene - Google Patents

Description

PATENT ADVOCATE DR. HANS-GUNTHER EGGERT, DIPLOMA CHEMIST

5 KDLN-LINDENTHAL PETER-KINTGEN-STRASSE 2 1645345

Cologne, April 28, 1966 Eg / Ax / st

Sooony Mobil Oil Company, Inc.,

150 East 42nd Street, New York, N.Y. 10017 (V.St.A.)

Process for the preparation of copolymers of butene-1

and propylene

The invention relates to a process for the preparation of new copolymers of 1-butene and propylene.

It is known that butene-1 and propylene can be homopolymerized to give crystalline polymers. These homopolymers are produced with an isotopic index (measured as an amount in% by weight that is insoluble in boiling diethyl ether) on the order of 95-98. However, when these olefins are copolymerized, the copolymer formed is less crystalline. This can be recognized by a lower isotopic index.

Polybutene-1 has two main crystal forms. To Cooling from the melt forms a metastable crystal modification known as "Form II". To - it goes on for a certain period of time, usually several days Form II into a stable modification known as "Form I". The transition from Form II to Form I is accompanied by a change in dimensions in the polymer. This instability of shape in polybutene-1 is common to many Applications disadvantageous. For example, slides that are initially clear lose their visual clarity when that Polymers change their crystal form.

00982 0/1699

It has now been found that crystalline copolymers of butene-1 and propylene have the desired properties of a butene-1 homopolymer, but not the undesirable one Exhibit phase transition and instability of shape characteristic of these homopolymers are, can be prepared by a process in which the choice of the reaction conditions, the quantitative ratios the reactants and the catalyst components are critically important · is the subject of the invention Accordingly, a process for the preparation of copolymers of butene-1 and propylene, which is characterized in that a monomer mixture that 91 -95, in particular 92 mol% Butene-1 and 9-5, in particular 8-6 mol- $ propylene, at a temperature between 54 and 66 ° C, in particular copolymerized at 60 ° C in the presence of a catalyst system, the titanium trichloride, diethylaluminum iodide and contains diethylaluminum chloride, the molar ratio of diethy ^ fenloride to diethylaluminum iodide 4s 1 to 0.5x1, in particular 1.5ϊ1 to 0.5 si and the molar ratio from aluminum to titanium is 3s1 to 6s1.

The products made according to the invention are copolymers of butene-1 and propylene, which, when cooled from the melt, quickly change from the metastable form II to the stable one Form I pass over, a post-crystallization of less than 0.5% by weight and a tensile modulus of more than 1-750 "kg / cm to have.

The copolymers of butene-1 and propylene have the desired ones excellent physical properties of homopolymers of butene-1, namely toughness, high resistance to stress corrosion cracking and high permeability for oxygen. Your X-ray diffraction patterns and infrared spectra are typical of butene-1 homopolymer e * 'in the Crystal modification I. A close look at the X-ray diffraction pattern however, the copolymer shows that the interplanar distance d of the Form I reflection 110 is a Has experienced 8-10 # reduction. This reflects a

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Contraction of the unit cell as a result of the incorporation of the smaller propylene molecules in a polybutene-1 crystal lattice contrary·

When the co-polymers cool from the melt (i.e. from the molten state), they go off extremely quickly form II to stable form I. Indeed, Form II is generally undetectable. As a result are they dimensionally stable and do not experience any further crystal changes, so that only a minimal detailed description ' is detected. The size of the post-crystallization is less than 0.5 Grew .- #, measured over a period of 24 hours.

in
in a density gradient column which measures the percentage change in the density of the polymer as a function of time.

The tensile modulus of the copolymers, determined by ASTM method D638 using a sample D4-12, is greater than 1750 kg / cm and is usually between 1750 and 2450 kg / cm ψ

The polymers have excellent electrical insulation properties, Tenacity and flexibility. Accordingly, they are suitable as such or as a mixture with other polymers as wire and cable insulation, for the production of pipes, foils, coatings, bags for heavy use, packaging for food and other purposes

To produce the copolymers with the properties described above, several must be decisive important factors are carefully considered · These factors are the proportions of the monomers, the composition of the catalyst and the reaction conditions. The copolymerization can be batch or continuous be performed.

The monomers used to make the copolymers are butene-1 and propylene · the molar ratio of the monomers must be kept at 91-95 butene-1 and 9-5 hol ~ 6 propylene will. A ratio of 92 to is preferred

C Γ S 8 2 0/1 6 9?

94 Uol- ^c /> butene-1 to 8-6 mol% propylene. This is illustrated in the following examples,

Comparative Examples A to P and Examples 1 to 3

In a series of experiments propylene and butene-1 copolymerized batchwise in bulk, the molar ratio of propylene to butene-1 being used in each experiment was changed. In each experiment, titanium trichloride (3TiCl, .AlCl,) and a Mixture of 80 mol # diethylaluminum chloride and 20 mol # Diethylaluminum iodide (4 * 1) was used, the molar ratio of aluminum to titanium being 3s1. Every attempt was carried out at 66 ° C. for 1 hour.

5 ¹ Ur each polymer product was determined the percent change in density for a period of 24 hrs., And tensile modulus. The results for each attempt are post-. listed in Table I.

Example insert, mole density tensile modulus, butene-1 propylene change kg / cm ²

Wt .- ^

2124

2882

1.85 2784 1.39 2672

0.96 2572

0.40 2124

0.23 2045

3 92 8 0.21 1800

1500

0 C 9 8 2 0/1 6 9 .-?

Cf. -
example A. 100 0 Comp.-
example B. 99 1 Comp.-
example C. 98 2 Comp.-
example D. 97 3 Comp.-
example E. 96 4th 1 95 5 2 94 6th 3 92 Q Compare -
example P. 90.4 9.6

The curves in the figure are based on the values given in Table I. Curve A shows graphically the relationship between the propylene content in mol # in the feed from butene-1 and propylene, which is polymerized under the conditions according to the invention, and the tensile modulus of the polymer produced from each feed. Curve B concurrently shows the relationship between the propylene content in mole # in this insert and the change in density in weight% (ie the percentage of near-crystallization) for the polymer formed over a period of 24 hours. seen that the tensile modulus of the polymer with increasing amounts of propylene in the use of _Λ 100 ° / o butene-1 up to a maximum rises and then falls. ™ With a propylene content between 8 and 9 i ° , the tensile modulus has fallen to 1750 kg / cm. Above 9 7 propylene, the tensile modulus is well below the acceptable minimum of 1750 cm for heavy use. In addition to a high tensile modulus of at least 1750 kg / cm, the copolymers produced according to the invention must, however, have dimensional stability, which can be recognized by a post-crystallization of less than 0.5% by weight. As can be seen from the figure (curve B), the dimensional stability is only achieved if 5 mol # propylene are used in the monomer mixture. Accordingly, the copolymers with high tensile modulus and high porosity are only produced from monomer mixtures which contain 5 to 9 mol- $ propylene and 95 to 91 mol- $ butene-1. In the preferred embodiment, the feed mixture contains 6 to 8 mole percent propylene and 94 to 92 mole percent 1-butene.

The above-mentioned ranges of the propylene content in the monomer mixture were based on only a combination of reaction conditions determined, but they are also applicable to polymerization reactions, carried out under other conditions within the above ranges. Yfenn within However, these areas of conditions are worked on, there are certain general interrelationships between the

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Conditions to be observed so that the new copolymers according to the invention are formed, which are characterized by high Characteristic of the tensile modulus and high dimensional stability. These relationships are discussed in more detail below

The catalyst system consists essentially of titanium trichloride, Diethyl aluminum iodide and diethyl aluminum chloride. The molar ratio of diethyl aluminum chloride to Diethyl aluminum iodide is between 4 and 0.5, preferably between 1.5 and 0.5. The molar ratio of aluminum to titanium in the catalyst is between 3: 1 and 6: 1.

It is essential that, according to the invention, a mixture of diethyl aluminum chloride and diethyl aluminum iodide is used as cocatalyst. If diethyl aluminum;) ο did alone with TiCl- is used, a catalyst system with low activity is obtained. ¹ IIeWi only DiäthylaluminiuB_ chloride is used in the catalyst system, the polymers formed have a low tensile modulus. This is illustrated by the following example.

Comparative example G

Batch experiments on bulk polymerization were carried out using mixtures of monomers containing 6 to 7 mole percent propylene and the remainder butene-1. Each experiment was carried out for 1 hr. At 66 ° 0 Ii presence of titanium trichloride and diethylaluminum chloride. The molar ratio of aluminum to titanium was 3: 1. In each pail, the copolymer formed had a tensile modulus between 560 and 700 kg / cm.

The ^ polymerization process according to the invention is carried out at temperatures between 54 and 66 ° C. the Contact time or the mean dwell time in the case of continuous Operation is between 1 hour and 5 hours

Some general considerations are to be neglected when within the above ranges ron conditions

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; is being worked on. When using temperatures of about 66 ° C is an aluminum / titanium molar ratio of 3t 1 for Short-term attempts are preferred. In general, higher molar ratios of diethyl aluminum chloride will be used Diethylaluminum iodide up to 4: 1 under these conditions preferred. Using the low aluminum / titanium molar ratio of 3: 1 and a high molar ratio from diethyl aluminum chloride to diethyl aluminum iodide Temperatures down to 54 ° 0 can be effectively applied. These relationships are illustrated in the following examples .

Examples 3 and 6 and Comparative Examples H-J G

In a series of batch bulk polymerization experiments, a mixture of monomers containing 8 mol- $ Propylene and 92 MoI-Jb butene-1 contained. All attempts were made carried out at 66 ° C. for a period of 1 hour with the exception of example 6, which was carried out at 54 ° C. for a period of 2 hours was carried out - it passed in every attempt Catalyst system made from titanium chloride, diethylaluminum chloride and diethylaluminum iodide, where the molar ratio of aluminum to titanium and the molar ratio of diethyl aluminum chloride to diethylaluminum iodide were varied. The data and results of these experiments are given below mentioned in table II in comparison to example 3

example DEAC /
DEAI (1) Al / Ti (2) Temp.
OC Time
Hours. density
modification
Weight-j6 Tensile module
kg / cm ² 3 4th 3 66 1 0.21 1793 6th 4th 3 60 2 0.25 2110 Comp.-
example H 1.5 6th 66 1 0.27 1448 Il I 2.45 4th 66 1 0.27 1227 Il J 2 4th 66 1 0.29 1364

(1) Col ratio of diethyl aluminum chloride to diethyl aluminum iodide

(2) aluminum / titanium molar ratio.

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-β-

However, if with short reaction times at 60 ° G, a preferred working temperature, lower molar ratios of diethylaluminum chloride can be used to diethyl aluminum iodide. Likewise, it seems any aluminum to titanium molar ratio to be effective. These relationships are in the following Examples illustrated.

Examples 7 to 12

A series of batch bulk polymerization experiments were carried out at 60 ° G for 1 hour. A mixture of 8 Mo1-% was used in each experiment. Propylene and 92 Mpl -? & Butene-1 are used. With every attempt the catalyst system consisted of titanium trichloride, Diethyl aluminum chloride and diethyl aluminum iodide, where the IaO 1 ratio of aluminum to titanium and the oil ratio from diethylaluminum chloride to diethylaluminum iodide were varied. The data and results of these experiments are given in Table III below.

DEAC / Table III density Tensile module,
kg / cm ² example DEAI (1 modification, 1793 2.45 ) Al / Ti (2) 0.20 1890 7th 2.45 3 0.30 2123 8th 2.45 4th 0.10 1830 9 2.45 5 0.22 1933 10 2 6th 0.22 2088 11th 2 4th 0.21 12th 6th

(1) Molar ratio of diethyl aluminum chloride to diethyl aluminum j odid

(2) aluminum / titanium molar ratio

If in batch operation with a longer reaction time or with continuous operation with correspondingly longer

C: 9 S 2 0/1 6 9 ';

Residence times are the aluminum / titanium molar ratios between 4s1 and 6: 1 is most appropriate. While polymerization temperatures of 66 ° C can be used, higher tensile moduli will usually be used achieved when working at 60 ° C. These considerations, which are particularly relevant in the case of continuous operation, are illustrated in the following examples.

Examples 13 to 20 and Comparative Example K.

A -Seihe from batch experiments for bulk polymerization was carried out at temperatures of 60 ° 0 and 66 ⁰ C for a period of 4 hrs., Except in Experiment K The polymerization time was 3 hrs.. In each experiment the monomer mixture consisted of 7-8.5 mol # propylene, the remainder butene-1 · The catalyst system consisted in each case of titanium trichloride, diethyl aluminum chloride and diethyl aluminum iodide. The molar ratio of aluminum to titanium and the molar ratio of diethyl aluminum chloride to diethyl aluminum iodide were varied. The data and results of these experiments are given in Table IV.

MoI-Ji
Propylene Tabel IV Temp.
oc density
modification
Grew .- # Tensile module,
kg / cm'2 example K 8 DEAC /
DEAId) Al / Ti
(2) 66 0.62 1497 Comp.-
example 7th 4th 3 66 0.47 2088 13th 7th 4th 6th 66 0.31 2102 14th 7th 1.5 6th 60 0.18 2250 15th 8th 1.5 6th 60 0.24 2291 16 8.5 1.5 6th 60 0.27 1870 17th 8.5 0.67 6th 60 0.27 1870 18th 8th 1.5 4th 60 0 * 18 1800 19th 8th 0.67 4th 60 0.22 2067 20th 0.67 4th

(1) Molar ratio of diethyl aluminum chloride to diethyl aluminum iodide

(2) aluminum / titanium molar ratio

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Example 21

A bulk polymerization experiment was carried out continuously. It was made under absolutely anhydrous conditions worked. The insert consisted of a mixture of 91.5 mol% 1-butene and 8.5 mol% propylene. The catalyst system consisted of titanium trichloride. (3TiCl, .AlCl,) and a mixture of 4-0 mole # diethylaluminum iodide and 60 mole # diethylaluminum chloride. The catalyst components were added so as to maintain a 6: 1 molar ratio of aluminum to titanium. The copolymerization was carried out at 60 ° C. The amounts of the olefin monomers used were such that the average The residence time was 3.7 hours. The copolymer formed was continuously withdrawn. During the entire experiment the copolymer formed had the following properties:

Isotactic index (# insoluble matter

in boiling diethyl ether) 95-98

Tensile modulus (ASTM D638) 1970 - 2246 kg /

Post-crystallization 0.2-0.4 wt .- ^

Density, g / cm- ⁵ 0.905-0.908

Embrittlement temperature ^{-23 0 C}

The product showed the characteristic X-ray diffraction pattern and infrared spectrum of Polybutene-1 Form I.

Example 22

A continuous bulk polymerization experiment was carried out in the manner described in Example 21 with the exception that the insert 8 M0I-9 & propylene and 92 MoI-Ji butene-1 contained. The polymer formed had the following average characteristics:

Isotactic index (# insoluble matter

in boiling diethyl ether 95

Tensile Modulus (ASTM D638) 2004

00 9 820 / 169Q

Nachkristallieation 0.3 wt -.%

Density, g / cm ⁵ 0.9072

Comparative example L

A continuous bulk polymerization experiment was carried out in the manner described in Example 22, but at a temperature of 66 ° C, an aluminum / titanium molar ratio of 3s 1 and a "diethylaluminum chloride / diethylaluminum iodide molar ratio of 4 was worked · The tensile modulus of the polymer formed was only 1188 kg / cm, although the post-crystallization 0.4-5 wt .- ^ was

As with any stereospecific polymerization process of this type, anhydrous conditions must be maintained and air and oxygen are excluded. This is achieved in the usual way by carrying out the process under inert gas, such as nitrogen. If the molecular weight of the copolymer is to be adjusted, can conventional materials for this purpose including hydrogen and carbon dioxide can be added to the reaction system.

The deactivation and removal of catalyst components from the reactor product and the deposition of what is formed Copolymers are carried out by customary methods.

Those described in the previous embodiments Tests were carried out in bulk, i.e. without the use of solvents or suspending agents other than those used 1-olefins carried out both batchwise and continuously. The new polymers can in the presence of a Solvent or suspending agent are prepared. Typical solvents and suspending agents are hexane, heptane, Octane, benzene, toluene, various paraffinic and aromatic hydrocarbon fractions and halogenated Hydrocarbons. An experiment which was carried out using a solvent is shown in the following example described

CC9820 / ieSv

Example 23

A polymerization experiment was carried out in a 1 liter glass reactor. 600 ml of n-heptane were put into the reactor given with careful exclusion of moisture. Then butene-1 was raised to a pressure of 873 mm Hg at 66 ° pressed, whereupon 125 ml more n-heptane were added to the reactor and propylene was introduced until the Equilibrium pressure at 66 ° 0 was reached. The feed contained 7.4 mol% propylene and 92.6 mol% butene-1. A Catalyst system, which consists of 0.247 g of titanium trichloride and 1.9 ml of a mixture of diethylaluminum chloride and Diethylaluminum iodide in the molar ratio of 4s1, was then flushed into the reactor with 75 ml of n-heptane. The reaction mixture was then vigorously stirred at 66 ° C. for 2 hours. During this time the pressure in the reactor dropped to 392 mm Hg. By introducing nitrogen into the reactor the pressure was increased to 403 mm. The reaction was continued for an additional 40 hours at 66 ° C. after which the reaction mixture was quenched with methanol. The copolymer was separated in the usual way. It had post-crystallization of 0.3 wt .- ^. Differences in properties between the copolymer of this example and a copolymer obtained by bulk polymerization a comparable monomer mixture was produced, could not be determined.

0C9R20 / 16S

Claims (1)

Claims 1.) Process for the preparation of copolymers from butene-1 and propylene, which crystallize from the melt in the stable crystal form I, characterized in that that a monomer = mixed, which is about 91 to 95 mol # Contains butene-1 and about 9-5 mol- $ propylene, at a temperature of about 54 to 66 ° C in the presence of a catalyst system is copolymerized, which consists essentially of titanium trichloride, diethyl aluminum iodide and diethyl aluminum chloride and in which the molar ratio of diethyl aluminum chloride to diethyl aluminum iodide ™ about 4: 1 to 0.5: 1 and from aluminum to titanium about 2: 1 to 6: 1. 2.) The method according to claim 1, characterized in that is the molar ratio of diethyl aluminum chloride to diethyl aluminum iodide 1.5: 1 to 0.5: 1. 5.) Method according to claim 1 or 2, characterized in that that a monomer mixture is copolymerized, the 92 contains up to 94 mol- # of butene-1 and 8 to 6 mol- $ propylene. 4.) Process according to one of claims 1 to 5j characterized denotes overall j that the copolymerization is carried out at a temperature of 60 ⁰ C. 5.) Method according to one of claims 1 to 4, characterized in that that the catalyst system has a molar ratio of diethyl aluminum chloride to diethyl aluminum iodide of 1.5 s 1 and from aluminum to titanium of 6: 1. 009820/16 99