DE2732110A1 - MIXED POLYMERS OF AETHYLENE WITH HYDROCARIES AND A METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

I) R. ING. F. AVUKSTIIOFF DR.K. τ. PECHMANN DIi. ING. D. BRIIRKNS DIPL. ING. Ii. GOKTZ PATENT ADVOCATE

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1A-49 638

Applicant: SNAMPROGETTI S.p.A.

Milan, Corso Venezia 16, Italy

Title:

Copolymers of ethylene with polyene hydrocarbons and processes for their production,

709883/1101

DR. ING. F. WtJKSTJIOKK DH. E. τ. PKOlIM ANN DR. ING. D. BEKHKNS DIPL. ING. R. GOKTZ PATENT LAWYERS

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1A-49 638

description

The invention relates to copolymers of ethylene with polyene hydrocarbons and a method their manufacture.

In the process according to the invention, catalyst systems are used on the basis of vanadium compounds used, which have a specific activity in the polymerization of Have ethylene with one or more polyenes, the latter at least one belonging to a polycyclic system have unsaturated bond; according to the invention, copolymers are obtained which are characterized by a high Molecular weight, a statistical distribution of monomer units, the presence of unsaturated bonds in the groups arranged off the main chain, have a high melting point and a high degree of crystallinity.

Such copolymers can be vulcanized with the usual sulfur-based agents and then lead to crosslinking Products similar to high-density polyethylene, but in terms of their mechanical, thermal properties and chemical properties compared to the known copolymers are improved.

It is therefore one of the features of the process according to the invention that copolymers having the properties listed above are obtained in which the remaining vanadium from the decomposition of the catalyst, even if one is from one

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Cleaning, is only available in very small quantities.

This means a considerable simplification of the previous operation, in so far as there is a _possibility% to isolate and dry it immediately, with no washing or cleaning is necessary, the polymer from the reaction mixture.

In the patent applications P 2534493.8 and P 2534497.2 are Process described with the help of which one can produce polyethylenes in good yield that have unsaturation of the trans type; in these processes, activated catalyst systems are used which are in aromatic solvents come into effect.

Surprisingly, it has now been found that copolymers of ethylene with at least one polyene of those described above Art can produce with extremely high yield in the polymerization, it is completely irrelevant whether a aromatic or an aliphatic diluent is present, provided that one has a catalyst system is used, which is composed as follows:

1) One or more vanadium compounds in which the element has a valence of two or more, provided that the compounds are soluble in the reaction medium;

2) one or more aluminum _{compounds of the general formula R 2} AlX, in which R is an alkyl, cycloalkyl, alkylaryl or aryl radical having 1 to 12 carbon atoms, and X is a chlorine or bromine atom;

3) one or more compounds from the following group:

a) organic compounds containing the -CCl ^ group,

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b) hexachlorocyclopentadiene,

c) thionyl chloride.

The following vanadium compounds can be used to produce the catalysts according to the invention:

- halides, such as vanadium tetrachloride or vanadyl chloride,

- alcoholates, such as vanadyl triisopropoxide and

- chelates, such as vanadium triacetylacetonate and vanadyl diacetylacetonate,

as well as all complexes in general.

The hydrocarbyl halides of aluminum serve as the second component of the catalyst system, among which, for example Mention should be made: aluminum diethyl monochloride, aluminum diisobutylmohochloride and aluminum diethyl monobromide.

The third component of the catalyst system is, as mentioned, Hexachloropentadiene or thionyl chloride or one of the organic compounds which have at least one -CCl, group in the molecule contained, as is the case with trichloroacetic acid and its esters or with trichlorotoluene and similar compounds.

Sa is the molar ratio between the Al and V compounds generally high because the vanadium compound is used in a very small amount. The ratio is more than 10: 1 and is usually between 50 and 300: 1.

The molar ratio between the third component of the catalyst system and the other two components can be largely different, the ratio of the third to the second component preferably between 1:20 and 1: 1.

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~ Y

The polymerization is according to the preferred embodiment of the present process in the presence of an or several monomers to be polymerized and as a solvent or diluent in the form of an aliphatic or aromatic hydrocarbon carried out.

Whether you choose one or the other type of solution or Thinner depends on what molecular weight the polymer should have, since the aliphatic solvents cause the formation of higher Favor molecular weights; Of course, other reasons also play a role, such as profitability or the Availability of the solvents in question is a hell of a lot. Optionally, you can also use a mixture of aromatic and use aliphatic hydrocarbons when beneficial.

The polymerization temperature is between O and 12O ⁰ C, operating particularly advantageously between 20 and 8O ⁰ C, that is necessary in a range in which the catalyst system exerts a particularly good effect, and in which the use of a cooling cycle to dissipate the heat of reaction is not is.

The polymerization yield is in the range from 30,000 to more than 1,000,000 g of copolymer per gram of elemental Vanadium in the catalyst.

Two or more monomers are introduced under the conditions described above: namely ethylene and one or several compounds with at least two unsaturated bonds, the latter one to the polycyclic Belonged to system of bicyclo- (2,2, i) -2hepten. The monomers of the last-mentioned class react during the polymerization by splitting the condensed cyclopentene ring, while

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the other unsaturated bond is outside the polymer chain and remains intact.

Examples of such monomers include:

5-ethylidenebicyclo- (2,2,1) -2-heptene (ethylidenorbornene), 8-isopropylidene-tricyclo- (2,2,2,1) -2,6-diene (isopropylidenedicyclopentadiene), 5- (2 ', V-Dimethylpenta-1 ¹ , 3'-dienyl) -bicyclo- (2,2,1) -2-heptene (dimethylpentadienyl-norbornene) and its. Isomers, / ~ bicyclo (2,2, i) -3'-heptenyl_7-3 '' 9 ^1, 5'-trimethylcyclohexadienylmethan) and its. Isomers.

The copolymerization of ethylene with one or more cyclic hydrocarbons of the above type is accelerated of the catalysts according to the invention, leads to novel ones under the conditions of the present process Hydrocarbon polymers, the properties of which are considerable Are interested in practice.

In particular, the above-mentioned copolymers with 99.9 to 95 % ethylene units and 0.1 to 5 % polyene units have some physical properties (e.g. melting point and specific gravity) which differ only slightly from those of a high density polyethylene with the same average molecular weight .

On the other hand, however, one obtains due to the presence of unsaturated bonds in the side chain and their statistical distribution both inside the individual Macromolecule like products crosslinked under several chains, which in terms of their physical-mechanical and their chemical properties as well as their thermal behavior compared to the best types of polyethylene are significantly improved are.

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The mixed or copolymers according to the invention are particularly reactive under the vulcanization conditions known to the person skilled in the art if sulfur and accelerators are used as crosslinking agents be used. For example, a very low content of ethylidene norbornene is sufficient (0.2 to 0.5 mol%) In the copolymer with ethylene, vulcanizates with more than 80% gel are obtained. The content of ethylidene norbornene is 0.5 to 1 mol%, practically 100% gel is obtained.

Such a result, which is a sure sign of a real statistical distribution of the comonomer units is, was previously never obtained when using other comonomers for ethylene than those according to the invention.

In the very special case in which the ethylene is isopropylidenedicyclopentadiene is copolymerized, products are obtained directly from the polymerization in which due to of the branches the molten mass has a high viscosity. On the other hand, however, the product easily crushed in an open device and has the ability to expand in the press, even if no curing agents are present.

The mixed or copolymers according to the invention are not only suitable for the production of expanded products, but they can be used in all areas in which a particularly good impact resistance and Resistance to tearing under load, at the same time with a high mechanical rigidity and a good resistance to heat and chemicals are required.

The examples serve to explain the invention in more detail.

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Example 1_

In a flask equipped with a mechanical stirrer steel autoclave of 22 1, 'which was maintained at 6O ⁰ C, the following reactants were charged in the given order:

Toluene 16 liters

Et ₂ AlCl 100 millimoles (= 13.4 g)

Ethylidene norbornene 12.5 g

Then at an internal temperature of 6O ⁰ C ethylene up to

a pressure of 4.5 kg / cm and then hydrogen up to a total pressure of 5 * 5 kg / cm.

With the help of two piston pumps, two different pumps gradually became parallel to one another over a period of about 40 minutes Solutions initiated, which were composed as follows:

1.) Toluene 200 ml

Vanadium triacetylacetonate 0.02 mmol (6.96 mg) CCl ₃ COOC ₂ H ₅ 6 mmol

2.) Toluene 100 ml

Ethylidene norbornene 100 g

The polymerization was allowed to take place after introducing the vanadium catalyst

sators 45 minutes under a pressure of 5.5 kg / cm, the was maintained by replacing the used ethylene with new one, after which it can be removed by introducing 200 ml of methanol broke off. The solid polymer was separated from the resulting slurry by centrifugation and dried at 50 ° C in vacuo, whereupon it has the following properties exhibited:

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Ethylidene norbornene units 1.3 mol%

4.48 g / 10 min

₂ j ₆ 4 g / 10 min

Melting point (DSC) 125 ° C

Example 2

In a held at 60 ⁰ C 5-liter stainless steel autoclave equipped with a mechanical stirrer was allowed to a solution of 11.7 mmol of Et ₂ AlCl in 1300 ml of toluene imbibe.

Then one added up to a pressure equilibrium of 4.5 kg / cm Ethylene in and on, up to a total pressure of 5 kg / cm Hydrogen. With the help of two piston pumps, two solutions of the following composition were then produced in parallel within 30 minutes brought in:

1.) toluene 100 ml Vanadium triacetylacetonate 0.019 mmol CCI ₂ COOC ₃ Hc 5.85 mmol 2.) toluene 100 ml Ethylidene norbornene 15 g

During the experiment, the temperature inside the autoclave was kept at 60 ° C. and the total pressure at 5 kg / cm, the ethylene being replaced as it was consumed. 40 minutes after the two pumps had been started, 50 ml of methanol were introduced in order to interrupt the effect of the catalyst, whereupon the polymer thus formed was washed and dried ^{at 50 ° C. in vacuo.}

140 g of dry product were obtained with the following properties:

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Melt flow index at 2.16 kg load

(MFI _{2 16} ,, ASTM-D-1236-65T) 0.47 g / 10 min

Melt flow index at a load of 21.6 kg

(MFI _{21 6} ) - 16.9 g / 10 min

Melting point (differential thermal

Analysis) 120 ° C

£ rfl (in decalin at 135 ° C) 1.79 dl / g

Copolymerized ethylidene norbornene

(Iß analysis) 4.8% by weight

The polymer was then made with the following additives mixed and vulcanized:

Parts per 100 κ polymer

Zinc oxide 5

Stearic acid 1

2,2'-dirnethyl-bis- (4-methyl-tert-butylphenol) 1

N-Oxydiäthylbensthiazol-2-sulfen-

amid (NOBS Special) 1.5

Dibenzothiazyl disulfide

(Vulkacit DM) 0.5

Sulfur 3

The vulcanizing mixture was converted into a completely gelled product under pressure at 180 ° G within 30 minutes, which was completely insoluble in boiling xylene and had an impact resistance of 73.3 kg / cm / cm.

Example 3

The procedure was as in Example 1 in the autoclave that was charged was with:

nor.hexane 1,300 ml

Et ₂ AlCl 11.7 mmol

Ethylidene norbornene 1 g

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At a temperature of 60 ⁰ C, the ethylene pressure was

2 2

5 kg / cm and the hydrogen pressure 1 kg / cm. The solutions, which were then introduced within 20 minutes were composed as follows:

1.) nor.Hexane 100 ml Vanadium triacetyl acetonate 0.013 mmol OCl ₅ CCOC ₂ Hc 5.85 mmol 2.) nor.Hexane 100 moles Ethylidennorbornene 9 g

The experiment was carried out at 60 ^° C. and 6 kg / cm pressure for 30 minutes. 135 g of dry polymer were obtained with the following properties:

, ₁₆ . 1.38 g / 10 min

,. (- 60.4 g / 10 min

Ethylidene norbornene 1.1% by weight

in decalin at 135 ° C 1.38 dl / g

The product was made according to Example 1 with sulfur and accelerators vulcanized, whereupon its gel content 87%

and its impact resistance were 62.7 kg / cm / cm.

example

The procedure was as in Example 1 in the autoclave, into which the following solution was sucked:

Toluene 1,300 ml

Et ₂ AlCl 11.7 mmol

Norbornenyl-trimethylcyclohexadienyl-

methane 1 g

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In a thermostatically maintained at 8O ⁰ C temperature were ethylene up to a pressure of 3.5 kg / cm and then hydrogen to a pressure of 4 kg / cm initiated. The polymerization was initiated by introducing the following solution into the autoclave within 25 minutes:

Toluene 100 ml

Vanadium triacetylacetonate 0.013 mmol

CCl ₃ COOC ₂ H ₅ 5.85 mmol

Simultaneously with the above solution, a solution of 9 g of norbornenyltrimethylcyclohexadienylmethane in 100 ml of toluene was added. After a polymerization time of 30 minutes, 175,6 dry polymer were obtained (corresponds to 264,000 g of polymer per gram of elemental vanadium in the catalyst) which had an A7 ^of 1 * 52 dl / g in decalin at 135 ° C.

_{2 16} 0.281 g / 10 min

MFI ' g. 23.5 6/10 min

Melting point 129 C (DSC)

The polymer can be crosslinked with sulfur and accelerators according to Example 1 and then gives a product that Containing 60.9% gel and an impact strength of 33 kg / cm / cm exhibited.

Example 5

The procedure was as in Example 3, the only difference being that was that the toluene was replaced by an equal volume of nor.hexane.

After a polymerization time of 30 minutes, 120 g of polymer were obtained which had the following properties:

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= 1.06 dl / g in decalin at 135 ^° C.

_{> 16} 2.78 g / 10 min

_{1 6} 140.2 g / 10 min

Melting point (DSC) 127 ^° C

After adding sulfur and accelerators and vulcanizing according to Example 1, a product with 98.5% gel was obtained.

Example 6

In the apparatus described in Example 1, ethylene was copolymerized with dimethylpentadienylnorbornene. In the The solution sucked into the autoclave consisted of:

Toluene 1 JOO ml

Et ₂ AlCl '11, 7 m

Dimethylpentadienylnorbornene 1 g

Then ethylene was passed in at a temperature of 80 ° C until a pressure equilibrium of 3.5 kg / cm was reached, whereupon hydrogen was passed in until the total pressure

ρ
Was 4 kg / cm.

During the experiment ^ was separated and distributed over 20 minutes, initiated the following solution:

Toluene 100 ml

Vanadium triacetylacetonate 0.017 mmol

CCl ₃ COOC ₂ H ₅ 5.85 mmol

as well as a second solution consisting of:

Toluene 100 ml

Dimethylpentadienylnorbornene 9 g

30 minutes after the start, a polymer was obtained which after Drying 125 S weighed. It had the following properties:

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1.74 dl / g in decalin at 135 ° C.

^ ₁₆ 0.079 g / 10 min

₂ ^ ₆ 10.68 g / 10 min

Melting point (DSC) 129 ° C

After crosslinking with sulfur (see Example 1), the polymer had a gel content of 60.8%.

B e is ρ ie 1 7

A solution was poured into a 2 liter stainless steel autoclave equipped with a mechanical stirrer and heating mantle of the following composition:

nor.hexane 900 mmol

Et ₂ AlCl 9 mM

Isopropylidenedicyclopentadiene "2 ml

At a temperature of 90 ° C then ethylene was up to one

Pressure of 6 kg / cm and hydrogen up to a total pressure of ₂

of 8 kg / cm supplied. A solution of the following composition was quickly injected into the autoclave using a piston pump:

nor.Hexan 210 ml

Vanadium triacetylacetonate

(sat. solution in toluene) 0.05 mmol

Immediately thereafter, another solution of the following composition was gradually added over the course of 40 minutes using the same pump pressed in:

nor.Hexane 80 ml

CCl ₃ COOCH ₃ 4.5 mmol

Isopropylidenedicyclopentadiene 4 ml

The experiment was kept constant at 90 ° and 8 kg / cm (pressure by supplying additional ethylene) carried out and 60 min

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terminated after the addition of the vanadium compound. The filtered off from the reaction mixture and in vacuo at dried polymer weighed 63 g. The analysis gave the following results:

1.25 dl / g in decalin at 135 ° C

> ₁₆ 0.08 g / 10 min

Mi ¹ I _{21 6} 18.4 g / 10 min

Melting point (DSC) 122 ^° C

Gel content (insoluble in boiling 40 % SyI en)

The crude copolymer was left in the mold at 180 ° C for 30 minutes vulcanized after the following additives (parts by weight per 100 parts of polymer) had been added:

Zinc oxide 5

Stearic acid 1

2,2'-dimethyl-bis- (4-methyl-tert.-

butylphenol) 1

N-Oxydiethylbenzthiazol-2-sulfen-

amid (KOBS Special) 1.5

Dibenzothiazyl disulfide

(Vulkacit DM) 0.5

Sulfur 3

The gel content of the product thus obtained was 71-3%. Example 8

In the autoclave used in Example 7 were initially a solution of 9 mmol of EtpAlCl and 1 ml of isopropylidene dicyclopentadiene in 900 ml of toluene, whereupon ethylene and hydrogen to a pressure equilibrium at 80 ° C of

2 2

5 kg / cm or then 8 kg / cm total pressure was introduced, whereupon 0.05 mmol of vanadium triacetylacetonate, dissolved

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in 20 ml of toluene was added.

The polymerization also proceeded for the following 48 minutes further, during which a mixture of CCl, COOCH, (4.5 mmol) and isopropylidenedicyclopentadiene (5 ml) diluted with 80 ml of toluene was added. 60 min after adding the Vanadium compound, the polymer slurry was taken out and filtered off; the yield of dried polymer was 58 g.

The polymer had the following properties: 1.47 dl / g in decalin at 135 ° C

₁₆ 0.0415 g / 10 min

J _{1 6} 16.86 g / 10 min

Melting point (DSC) · 126 ⁰ C

Gel content 37 %

The polymer was easy to process in the open device. After a heat treatment in the presence of the ingredients listed in Example 1, its gel content had risen to 75 % .

¹ hour

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Claims (11)

A process for the preparation of mixed or copolymers of ethylene with one or more polyene hydrocarbons, in which at least one unsaturated bond belongs to a polycyclic system, by joint polymerization of the monomers in the presence of an organic solvent or diluent and a polymerization catalyst I denote η et that the polymerization is carried out in the presence of a catalyst system composed of the following components: 1) One or more soluble in the reaction medium Vanadium compounds * in which the valence of vanadium is higher than two; 2) one or more aluminum _{compounds of the general formula R 2} AlX, in which R is an alkyl, cycloalkyl, alkylaryl or aryl radical having 1 to 12 carbon atoms and X is chlorine or bromine; 3) one or more compounds from the group of a) organic compounds which form the -CCl, group contain, b) hexachlorocyclopentadiene, c) thionyl chloride. 2. The method according to claim 1, characterized in that the molar ratio in the catalyst system from aluminum compounds to vanadium compounds is higher than 10: 1 and is preferably between 50 and 500: 1. 709883/1102 -2- ORIGINAL INSPECTED 3. The method according to claim 1 or 2, characterized in that the molar ratio in the catalyst system from component (s) 3) to component (s) 2) is between 1: 1 and 1:20. 4. The method according to any one of claims 1 to 3, characterized in that the polymerization is carried out in an aliphatic or aromatic hydrocarbon as a solvent or diluent. 5. The method according to any one of claims 1 to 4, characterized characterized in that the catalyst system in the presence of at least one of the polymerization involved monomers. 6. A method according to any one of claims 1 to 4, characterized in that the polymerization at a temperature of O to 12O ⁰ C, preferably from 20 to 80 ⁰ C, performs one. 7. Mixed or copolymers of ethylene and 5-ethylidenebicyclo- (2,2,1) -2-heptene (Ethylidene norbornene). 8. Mixed or copolymers of ethylene and 8-isopropylidene tricyclo- (2,2,1) -2,6-diene (Isopropylidenedylcyclopentadiene). 9. Mixed or copolymers of ethylene and 5 (2 ', 4'-dimethylpenta-1, 3'-dienylbicyclo- (2,2,1) -2-heptane. 10. Mixed or copolymers of ethylene and / dicyclo- (2,2,1) -3'-heptenyl_7- (3 ' , £ »', S'-trimethyl-cyclohexa-i', 3'-dienyl) methane (Norbornenyl-trimethyl-cyclohexadienylmethane. -3- 709883/1102 11. Mixed or copolymers according to one of the preceding Claims, characterized in that the copolymerized ethylene units therein are 90 to 99 »9 #, preferably 95 to 99.9 # of the total units present. 709883/1102