DE2234087A1 - Copolymers, process for their production and their use. Elimination from: 2216190 - Google Patents

Description

DR. BERG DIPL.-ING. SfAh ⁹ F

PATENTANWÄLTE β MÜNCHEN eo. MAUERKiRCHERSTR. 48 2 234 0 8 /

June 28 \ m

Attorney's file; 22 591

Esso Research and Engineering Company Linden, New Jersey / USA

"Copolymers, process for their production

and their use "

The invention relates to copolymers, especially high molecular weight, their production and their Use.

The invention relates to copolymers, in particular linear copolymers with high molecular

IV / Kr. -2-

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2234Q87

by weight of ethylene, 2.3-dimethyl-2.5-norbornadiene (hereinafter referred Dimethylnorbornadien) and one or more alpha-olefins of the general formula R-CH = CHp, wherein R is an alkyl group having 1 to ¹ I carbon atoms. The alpha-olefin is preferably propylene or 1-butene. The term dimethylnorbornadiene also includes substituted compounds as indicated by the formula given below. The invention also relates to a process for the preparation of the abovementioned copolymers by means of organometallic catalysts.

Various dienes or trienes have already been described in the literature as possible components of copolymers, these components of the introduction of unsaturation in elastomers based on copolymers of ethylene alpha olefins serve · However is in no case mentioned the use of dimethylnorbornadiene.

The serving monomers useful in the invention and which should have a free double bond for polymerization can be represented by the general formula will

-3-

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2234ObT

wherein the radicals R, which do not have to be the same, are hydrogen and / or alkyl groups, preferably C ^ - to C ^ -alkyl groups are. The connections are highly responsive.

The diene compounds can be prepared by reacting cyclopentadienes or substituted cyclopentadienes with dimethylacetylene, the desired diene compounds being obtained in a one-step process. The one step is carried out in the manner by reacting cyclopentadiene or substituted cyclopentadiene at a temperature of about 150 to 400 ⁰ C. Lower temperatures are possible. Temperatures higher than 400 ° C, in addition to being uneconomical, involve the risk of polymerization. A very suitable temperature range is 200 to 300 ⁰ C. The reaction is preferably carried out in the presence of solvents such as hydrocarbon

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Substance solvents or oxygenated solvents for further heat transfer carried out

The proportions of the reactants can vary within wide limits, but should not be too different from that stoichiometric ratio may vary · Suitable ratios vary from 1 to 10 to 10 to 1 · The reaction can be carried out at various pressures from atmospheric to higher pressures · When the reaction is carried out discontinuously, autogenous pressures or positive pressures can be used.

The dienes can also be in a two-stage process by means of a Diels-Alder condensation of chloroprene and Cyclopentadiene or substituted cyclopentadiene can be produced with subsequent dehydrochlorination. The first stage can be carried out under essentially the same conditions as described for the one-stage process The second stage is then carried out in the presence of a base, such as sodium or potassium hydroxide, performed, taking both the desired Diene as well as an exo-isomer can form · The undesired exo-isomer can be formed by distillation in the presence of a Isomerization catalyst are separated off, which leads to the formation of the thermodynamically more stable dimethylnobornadiene compound will favor

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_κ ■ ■ ■ 223408?

The serving monomers have the particular advantage that the corresponding monomer units have a large number AlIy! -Methyl hydrogen, which leads to a high Vulcanization rate of their copolymers with ethylene and alpha-olefins. The weight percent sat ζ of monomers in the terpolymers can be found in can be varied within wide limits. The content of ethylene can be between 5 and 90 $, of dimethy lnorbornadiene between $ 0.5 and $ 20, with the balance being due alpha-01efin (e) is formed. If an amorphous product if desired, the ethylene content should normally not exceed 75% by weight. Under these conditions are the mixed polymerized in aliphatic, cycloaliphatic, aromatic or chlorinated hydrocarbons, such as η-hexane, n-heptane, cyclohexane, toluene, xylenes, CCl ^, chlorobenzene, tetrachlorethylene, solvable. The molecular weight of the copolymers can vary widely.

The intrinsic molar viscosity number, measured in tetrahydronaphthalene at 135 ° C, for example between 0 ^ 1 and 10 dl / g, without the products according to the invention being restricted to this range.

The distribution of the monomer units in the copolymers is almost statistical (random). The fact,

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that . 3 he unsaturation is homogeneously distributed demonstrated by the possibility of obtaining good vulcanizates, whereby one can use processes that normally used for unsaturated elastomers, "especially those with low levels of unsaturation will. In addition to vulcanization, the double bonds present in the polymer chain can be used for other reactions, "for example oxidation, ozonization, halogenation, etc., whereby one can form "polar groups" which are suitable as such or for subsequent reactions.

Optionally, the double bonds present in the copolymers can be used for grafting on another Monomer or a mixture of monomers can be used on the copolymer.

The vulcanizates obtained from the copolymers after the use according to the invention are complete Insoluble in organic solvents and are massively reduced by aromatic solvents Sources brought.

In order to maintain high tensile strengths, reinforcing agents, such as carbon black, are introduced into the copolymers before vulcanization. The mixed polymer "

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can be stretched with oil. You can do this for this purpose aliphatic, cycloaliphatic or aromatic oils be used.

Two uses of the copolymers according to the invention can be used for vulcanization of sulfur and accelerators, as well as peroxide "as is known for the vulcanization of saturated ethylene-propylene copolymers".

The products according to the invention can "for example for the production of tires, tubes, conveyor belts, foils, seals and coatings for electrical wires be used.

The catalysts used in öem manufacturing process of the copolymers used are made by reacting organoaluminum with vanadium compounds manufactured. Non-limiting examples of the organoaluminum compounds are irialkyl aluminum compounds, dialkyl aluminum halides, alkyl aluminum sesquihalides and dihalides such as triethyaluminum, iri-n-propylaluminum, Tri-isohutylaluminum, Tri-n-hexy! Aluminum, Diethyl aluminum chloride, diisohutyl aluminum chloride, diet hy laluminium fluoride, ethyl aluminum dichloride, ethyl aluminum sesquichloride.

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Non-limiting examples of vanadium compounds that can be used in the method of the present invention are halides, alcoholates, halogen alcoholates, acetylaoetonates, haloacetylacetonates such as YOCl ₃ , YOl ₄ , VO (OC ₂ H ₅ ) ₃ , VOC1 (OC ₂ H ₅ ) ₂ , VOCl ₂ (OC ₂ H ₅ ), VOAoaCg, Vacac ^, Preferably at least one of the catalyst components is halogenated. Instead of or in addition to the vanadium compounds, titanium compounds such as halides or alcoholates can also be used. Examples are titanium tetrachloride, titanium tetraisobutoxide, titanium tetraisopropoxide and dicyolopentadienyltitanium oil.

The two catalyst components can be used with one another be reacted outside or inside the polymerization mixture. In the former case, the use is of a diluent attached.

The pre-formed catalyst or the separate catalyst components can be added batchwise or continuously to the monomeric mixture.

The molar ratio between the organoaluminum compound and the vanadium compound can vary within wide limits. In general, a moderate to large excess of organoaluminum is useful as it scavenges for possible Impurities, such as water, oxygen or

209850/1 U6 _ ₉ _

Sulfur compounds, can serve. In general, the Al / V molar ratios are between 1: 1 and 10; 1 satisfactory.

The interpolymerization process can be carried out in the presence or without a solvent. In the former All can be aliphatic ^, cycloaliphatic or aromatic hydrocarbons, such as η-hexane, n-heptane, cyclohexane, Benzene, toluene can be used. Halogenated solvents can also be used provided that they are inert to the catalyst. Not limiting Examples are trichlorethylene, tetrachlorethylene, chlorobenzene, diehlorbenzöle.

In the event that no solvent or a non-solvent is used, the monomer mixture serves as Dispersants. For example, when the propylene is alpha-olefin, the agitation problems arise the insolubility of the copolymer in the reaction mixture, which is then a slurry, reduced. Similar Slurry processes are obtained using inert nonsolvents such as methyl chloride or methylene chloride.

The temperature at which the interpolymerization process can be carried out can vary widely. Temperatures between -50 and +80 ⁰ C are

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generally satisfactory, but the interpolymerization also outside this temperature range can be carried out.

The interpolymerization process can be carried out at atmospheric pressure, but also Pressures above or below atmospheric pressure can be used.

To obtain homogeneous copolymers in terms of composition, the ratios between the The monomers present in the reaction mixture are kept constant as far as possible throughout the reaction Example by continuous charging and removal of a monomer mixture of suitable composition and by vigorous stirring during the polymerization.

The following can be used to produce the diene will.

example 1

2.3 ^ 111 ^ 1 ^ 1-2.5 ^ 0 ^ (^ 1) ^ 16 ^ that also among the more common The name 2.3-dimethylbicyclo- (2.2.1) -2.5-heptadiene is known, can easily be produced by it by contacting cyclopentadiene and dimethylacetylene in the following manner.

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■ * ί · ·

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100 g (1.64 mol) of crude butyn-2 (purity> 90 #), 33 g (0.5 mol) of freshly distilled cyclopentadiene and 2 g. Hydroquinones are introduced into a stainless steel autoclave with a capacity of 300 ml. The mixture is ^{heated to 250 0} O and held at this temperature for 30 minutes. The pressure drops from 68 atm. to 58 atm. during the first 15 minutes and remains constant thereafter.

The reaction vessel is cooled and the reaction product is stripped off under Vatrasan to remove the unreacted Remove materials. This procedure gives 34.7 g of product which is distilled under vacuum will.

A first fraction (56 to 9O ° O / 61! Dorr) corresponding to 31.4 wt. I * of the distillation subjected! Product was obtained and subjected to analysis.

One isolated in the pure state by preparative GIiC Sample was determined by mass spectrometry and nuclear magnetism Checked resonance (60 Me).

The mass spectral analysis shows an original one Peak at 120 m / e.

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-1S-

Nuclear magnetic resonance analysis indicates the presence of the following protons;

Proton types P.P. M. Number of protons; d 8.4- 6th C. 8.2 2 b 6.9 2. a 3.45 2

corresponding to the structure of 2.3-Mmethylbicyclo- (2.2 »1) · 2.5-heptadiene.

(c) H- ^ H (c)

CH ₃ (d)

(Ah

CH ₃ (d)

2.3-Diraethylbicyclo ~ (2.2.1) -2.5-heptadiene has the following Characteristics:

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Boiling point: 42 ° C / 25 Torr

: 1.4648

Elemental analysis C. H Calculated 89.95 05/10 Found 89.70 9.95 Example 2

348 g (5.79 moles) of crude dimethylacetylene (purity = 90 $), 191 g (2.89 moles) of freshly distilled cyclopentadiene and 1 g of hydroquinone are placed in a 1-1 stainless steel autoclave. The mixture is ^{heated to 250 0} O and held at this temperature for 2 hours, the pressure from 80 atm to 62 atm. falls off.

The reaction mass is cooled down and the reaction product under vacuum to remove unsaturated materials stripped. 253.5 g of product are obtained, which is distilled under reduced pressure to reduce the amount to separate boiling products from the bottom of the reaction. The distillate (54.7 g), the 17.4 wt. ^ 2.3-Dimethylbicyclo- (2.2.1) -2.5-heptadiene contains, is distilled again under reduced pressure (60 Torr) and provides the the following three factions:

(1) 57.5 - 61 ⁰ C - 9.24 g with a content of 78.4 # 2.3-

Dimethylbicycio- (2.2.1) -2.5-heptadiene

(2) 61 - 69.5 ° C-2.48 € with a salary of 27.4 # 2.3-

Dimethylbicyclo- (2.2.t) -2.5-heptadiene

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(3) 69.5 - 73.5 ⁰ C - 1.68 g with a content of 2.5j6 2.3-

Dimethylbicyclo- (2.2.1) -2.5-heptadiene

From the ]? Action (1) can be a pure sample (purity $ 99.9) by preparative G.L.G. can be obtained.

The invention is explained below by way of example.

Example 3

This example and the following illustrate the preparation of a terpolymer containing ethylene, propylene and 2,3-dimethylnorbornadiene contains.

The reaction device is a 250 ml flask with a stirrer with Teflon blades, inlet and outlet tubes Gases and two dropping funnels for the catalyst components, with a nitrogen cushion.

The catalyst components are AlIt ₂ Cl, 0.5 H in heptane and YOGI ,, 0.1 M in heptane.

100 ml of dry n-heptane is introduced into the reaction vessel which is then cooled to -20 ⁰ G. Ethylene and propylene are fed to the reaction vessel below the surface of the heptane at rates of 1000 and 4000 l / h. 0.5 ml of 2,3-dimethylnorbornadiene are added. 1 mole of AlAt ₂ Cl and 0.2 mole of VOCl ₅ are added. The reaction takes place immediately, as can be seen from an increase in the viscosity of the reactor content.

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After 10 minutes there will be 0.5 KoI AlAt ₂ Gl and 0.1 KoI VOQl ^ tue © ♦ _% . · '".' ■ '" ·. ■ <■

Minutes after the start, the reaction is increased by adding Methanol onßobelton * The product is diluted with Benaol and in a separate funnel with diluted Bd and donn lait wcssor shaken, 1 »Kothanol koaguliojrt and under Vökuuo gotrocloiot the weight is 5.1 g *

Analysis by lofrarotapoktrockopio zoi ^ t, öoss der longohdlt ungQirühr 57 Hol «jS botrSgt« Bio K «H» R * -AQ3lyse * seigt «2aa Yorlie ^ on of

Kino P ^ obo dos Torpoljaoricatö is in oinoa Wolrcnoiocher ait don the following Bostandtailea ßooiccht »where dio Toilo Gowicbtstoilo per 100 rope · Terpolycori & ot are ι

- ΪΪ3? Soot. 110

. - OX 8 173 x 70 _;

- stearic acid * * · 2 ^:

- ZnO 5

- M or ca pt ob en sot bio sol 1 «5.

O ₉ S

- Tellurium diitbylditrhiooacbaoate

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Vulcanization is ^{long at 160 0} O 20 ilinutoQ

goXübxt »,; ■ ■ '

been the following aochoniDohon Eigenehft a go- '

ZußfOBtigkoifc 46.9 Stretching am sua Bruoh

Module 29 »7 kß / co ²

Boinplol 4

The dialing device is oia 1-1 old oinoa Toflon stirrer, svoi Sropftrichtorn and I, iQ and for Godo.

500 dl n-heptane% r @ rdon poured into the device and ouf -20 ⁰ C goküblt «Atbylsn and Bm & floa wordon« ait 1000 bsw »4,000 1 / hour ßußoführfc iiaa ö» 5 oil 2 _e 5 ~ Diaothylnorboxa3-dione cugoccbon. 2 al ο in or 0.5 H solution of AIlLt ^ Gl in heptane (1 kaol) and 2 al oiüor Löcunc »äio osn obtained by Lcsea from Q _t 09 Pl VOCl, (1 cmol) in 10 al Hopton, ucrdon sugogoben · £ a occurs o viclotto preliminary preparation cuf ■ I * ach 10 MiautQO becomes oino gloicbo Mongo KofcoIycator zuccsebQQ · 20 Kiautou Qocb. Bogian is added to methanol, the phen ^ l-botaouthillt _f

The product is v; io in vorauagohouden Bolepiel G & rolnib "t · lake weight doe dry polyaorioate is ?% Z g.

2 0 9 8 5 0/1148

The ία -ifung by infrared dpotrocrupbio follows that dat-Propylenengoholti 43 Hol # is · organic Κ »Μ · Η ·· Αοο1? Ββ doa template voq

iilno Irobö becomes volkanlcicrt, vobol dio gXolcbo Ho2Gptur wlo ia voreus ^ ohoadon Boiepiol vorwendot uircl.

ßio Xolgondoa Qoch ^ nischo »Bigonochafton wordon

- ZuGXoatigkoit 82

- Dobnuag Bua break

- 500 ^ module 76 »3

«PötjontoDoprücho · *

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Claims (12)

Patent claims: 1. linear copolymers with a high molecular weight of ethylene, 2,3-dimethyl-2,5-norbomadiene and one or more alpha-olefins of the general formula R-CH = OHq, in which R is an O ₁ -alkyl radical. 2. Copolymer according to claim 1, characterized in that the alpha-olefin is propylene or 1-butene. 3. _t copolymer characterized according to claim 1 or 2dadurch that the amount of polymerized ethylene in the range of 5 to 90 wt. ^, The amount of 2.3-dimethyl-2.5-norbornadiene in the range of 0.5 to 20 wt. I »is and the alpha-olefin or the alpha-olefins form the balance residue. 4. Copolymer according to any one of claims 1 to 3, characterized in that the baseline viscosity, as defined above, is in the range from 0.1 to 10 dl / g. 5. Copolymer according to one of claims 1 to 4, characterized in that the Copolymer is amorphous, the amount of polymerized Ethylene does not exceed 75% by weight. - 19 -209850 / 1U6 ~ ¹⁹ " 187 6. Process for the production of a copolymer according to one of claims 1 to 5, characterized in that that the reactants are polymerized in the presence of a catalyst by Reaction of organoaluminium with vanadium compounds produced is, in the presence of an inert diluent, which is either a solvent or a Uicht solvent for the polymer can be under the polymerization conditions. 7. The method according to claim 6 characterized in that aluminum compounds than organoaluminum compounds [Drialky!, Dialkyl! Aluminum halides, alkylaluminum dihalides and such as ¹ Iriäthy! Aluminum, iri-n-propyl-aluminiuiij triisobutylaluminum, Iri-n-hexy! Aluminum, Diethylaluminum chloride, biisobutylaluminum chloride, diethylaluminum fluoride, ethylaluminum dichloride and ethylaluminum sesquichloride are used. 8. The method according to claim 6 or 7, characterized that, as vanadium compounds, for example halides, alcoholates, halogen alcoholates, Acetylacetonate and Haloacetylacetonate are used. 9. The method according to any one of claims 6 to ?? ■ thereby gekennze rejects that at least one of the catalyst components used is halogenated. - 20 - 209850 / 1U6 10. The method according to any one of claims 6 to 9, characterized in that instead of vanadium compounds or in addition to them, titanium compounds are used. 11. The method according to any one of claims 6 to 10, characterized in that as Titanium compounds used halides or alcoholates. 12. The method according to any one of claims 6 to 11, characterized in that one Molar ratio of aluminum to vanadium (or titanium or vanadium plus titanium) in the range of 1: 1 to 10: 1 is used. 13 · Use of the copolymer according to one of the preceding together with sulfur and accelerators and / or peroxide and optionally reinforcing agents for the production of vulcanizates. H. Use according to claim 13, thereby characterized in that the copolymer is used in the oil-extended state. 209850/1146