DE1745405A1 - New partially or fully hydrogenated diolefin copolymers and processes for their preparation - Google Patents

Description

Description
to the patent application

SHELL INTEENATIONALE SESEAECH MAATSCHAPPIJ N ₀ V. 30, Carel van Bylandtlaan, The Hague / Netherlands

concerning

New partially or fully hydrogenated diolefin copolymers and processes for their preparation

The invention relates to a method of manufacture new hydrogenation products of practically arbitrary copolymers from at least two of the monomers 1,3-butadiene, Isoprene and Styrene «The invention also relates to these new products themselves as well as on preparations that contain these, and also on from such preparations manufactured items.

By "substantially random copolymers" is meant copolymers in which over 50 $ of the bound Monomer units are randomly distributed. The copolymers can optionally be conically tapered so-called. tapered block copolymers are telomerized, in which die'Blocks sit at one end of the chain and usually come from the slowest polymeric monomer,

for example styrene.

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In the unhydrated urid, the unvulcanized state is mechanical strength of these essentially random copolymers is very poor.

According to the invention, a process for the production of new polymers is now created in which a copolymer is partially or completely hydrogenated, which was obtained by solution copolymerization of at least two of the monomers 1,3-butadiene, isoprene or styrene in the presence of a lithium hydrocarbon catalyst, a copolymer being formed results in which over 50 <? o of the bound monomer units are randomly distributed and whose intrinsic molar viscosity is between 0.1 and 1.0 dl / g.

In addition to the above-mentioned monomers, small amounts of others can be used in the copolymers to be hydrogenated Be bound by monomers, e.g. divinylbenzolo

The hydrogenation is normally carried out in the liquid phase with the aid of molecular hydrogen. It continues until the number of double bonds is more than 10 "fa below the original number, and preferably

wisely until the number of double bonds / over 30 $> is below the number of double bonds in the copolymers before the hydrogenation.

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■ "■■ ■ - 3 '-

Because the original copolymers are made in solution in the presence of lithium hydrocarbon compounds Hydrogenation is preferred as well

from
takes place in solution, not hindered tm catalyst residues, while interfering compounds, such as emulsifier residues. do not exist at all and therefore do not need to be removed for the time being. If a suitable solvent has therefore been selected for the copolymerization, the hydrogenation can consequently be carried out in the polymer solution obtained during the copolymerization Isolation of the polymer from the medium in which it was produced and / or the removal of substances that hinder hydrogenation.

For the production of the low molecular weight to be hydrogenated Copolymers higher polymer concentrations are permissible than for the production of high molecular weight copolymers, which are also carried out in the presence of lithium hydrocarbons will. This advantage also applies to the hydrogenation if it is carried out directly in the polymer solution, obtained after the end of the copolymerization. At. the process of the invention can adjust the polymer concentration this solution in certain cases even to 25 to 30 Weight $ increase.

Optionally, the hydrogenation can take place in another

Solvents are carried out as the copolymerization ..

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In general, the hydrogenation proceeds very well in cyclohexane, methylcyclohexane, decalin, benzene, toluene, Dioxane, isooctane, isoheptane, n-heptane, tetralin or G-emisohen of these solvents.

If sufficient hydrogenation occurs, thermoplastic, rubber-like substances or elastoplasts are obtained which, surprisingly, not only have good mechanical properties, but are also extremely easy to process. Accordingly, the value for the Hoekstra plasticity (see Rubber and Plastics Age 42 (1961) 1079), which was very low before hydrogenation, increased quite sharply as the hydrogenation increased, while the intrinsic viscosity increased little, if at all . This favorable combination of properties must be attributed to the low intrinsic viscosity of the copolymers prior to hydrogenation. Hydrogenation of random copolymers of higher average molecular weight led to polymers with good mechanical properties, but their flow behavior and thus their processability were poor. The Hoekstra value of these products, which even before the hydrogenation was considerably higher than that of the hydrogenated low molecular weight products used as starting materials in the present invention, had therefore become much too high as a result of the hydrogenation.

The lithium hydrocarbon compounds used in this process have the formula R (Li), where

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H is an aliphatic, cycloaliphatic or aromatic Is a hydrocarbon radical and X is an integer between 1 and 4 mean »R preferably contains 1 to 20 carbon atoms. Examples of such lithium compounds are i.a. Methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, Amyllithium, tert.-octyllithium, 2-ethylhexyllithium, n-decyllithium, phenyllithium, napiihyllithium, 4-butylphenyllithium, p-toluyllithium, cyclohexyllithium, ^ Butylcyclohexyllithium, dilithiomethane, 1,4-dilithiobutane, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,3,5- -Trilithiopentane, 1 ^^

Suitable solvents for the process are benzene, toluene, xy ^ löl, propane, h-butane, n-pentane, isopentane, n-hexane, Isooctane, n-decane, cyclohexane, methylcyclohexane and mixtures this diluent.

The arbitrary copolymers to be hydrogenated can with the help of lithium hydrocarbon catalysts known processes are produced. For example, the conversion can be kept low by using the Polymerization according to British patent specification 903 331 can proceed, after which the monomers are introduced into the reaction vessel at a slower rate than the normal rate of polymerization of the system under the respective conditions, or one can according to of British patent specification 994 726, according to which j the fastest during the polymerization process; polymerizing monomers is gradually added, and

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either intermittently or continuously.

Another process consists in allowing the copolymerization to proceed in the presence of polar solvents, for example in the presence of tetrahydrofurans. With this process, diene copolymers with a relatively high proportion of vinyl groups can be produced. Preferably, more than 70% of the bound monomer units should be randomly distributed in the copolymers to be hydrogenated.If the copolymers consist essentially of so-called blocks, the rubber-like or elastoplastic character of the hydrogenation products is insufficiently pronounced.

In general, hydrogenation products of essentially random copolymers in which over 60 $> of the units of these dienes are attached by 1,4-addition are preferred.

Although low molecular weight copolymers of 1,3-butadiene With isoprene it is very useful to use it as a starting material for the hydrogenation, but copolymers are still used either or both of these dienes are preferred with styrene. The proportion of bound styrene is in the Hegel between 2 and 50% by weight, but it can also be use lower or higher styrene / diene ratios.

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The low intrinsic viscosity of the Copolymers can be "for example" by using relatively high catalyst concentrations during achieve the copolymerization.

The hydrogenation can be carried out very favorably with the aid of catalysts of the Ziegler type, and indeed preferably with those that "arise in the reaction of metal hydrocarbon compounds, such as aluminum trialkyls, dialkyl aluminum halides, Monoalkylaluminum dihalides, dialkylaluminum hydrides and monoalkylaluminum dihydrides, with organic compounds of base metals of group VIII of the periodic table, especially of Uickel- and cobalt compounds. If the hydrogenation in liquid phase carried out, so are particularly compounds of metals of Group VIII, which are in the are easily soluble in organic medium, for example nickel, cobalt and iron carboxylate enolates or phenolates, which can be dissolved in the medium in a concentration of at least 10 mg metal per liter. In particular This subheading includes nickel-3,5-di / & ^ opropyl-5-salicylate, nickel -2-ethylhexoate, nickel naphthenate, cobalt-3,5-diisopropylsalicylßfc and cobalt 2-ethylhexoate.

However, the hydrogenation can also be carried out in the presence of others Catalyst systems take place, as with the help of nickel acetylacetonate together with an aluminum alkyl compound or by using metallic nickel on a suitable one Carrier, such as diatomaceous earth.

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Preparations can be made from the hydrogenation products manufacture that can be processed into molded articles that are either vulcanized or unvulcanized, such as strips, tapes, tubes, rods, "threads, films, sheets, hoses, skins, coatings and cellular or porous materials. The vulcanized items are usually obtained from the partially hydrogenated ones Productsβ

example

1,3-butadiene copolymerized with styrene using sea -Lithiumbutyl as a catalyst in the presence of cyclohexane as solvent at 50 ⁰ C. 26% by weight of the monomer feed was butadiene and 74% by weight styrene. The total monomer concentration rose to 40% by weight, while 3 mmoles per liter of solvent were used as the catalyst. In order to obtain a sufficiently random copolymer, the polymerization was stopped at a conversion of 25 #, which was reached after a polymerization time of about 1 hour. The polymerization was terminated by adding 3 mmol of isopropailol per liter of solvent. Was then stripped of unreacted monomer from the ReaktionsgefäJB at 4O ⁰ C under reduced EXR \ print "The polymer solution thus obtained contained about 10 wt .- ^ copolymer having a Iiitrinsic viscosity (IV) of 0.65 dl / g. Infrared analysis of the copolymer indicated 21.4 wt .-% bound styrene, 42.5 wt .-% trans-1,4-bound C. units, 28.9 wt .-% cis-1,4-bound G. Units and 7.2 wt. $ 1,2-linked C. units. Consequently

1 Q 9 8 3 & / 1 1 5 0 ⁴

were $ 90.8 of the total C. units by 1,4-eddion bound. The Hoekstra plasticity value became

determined by 2, determined according to the method / B.W. Duck .and yes. Watermann, described in Rubber and Plastics Age 42 (1961) 1079 * and with that in Proceedings Rubber Technology Conference, London 1938, p. 362. Measurements of the stiffness of the copolymer showed if this was subjected to a torque as a function of the temperature according to Clash and Berg (ASTM D 1053-61 T), that over 70% by weight of the bound monomer units were randomly distributed in the copolymer.

The polymer solution was hydrogenated at 40 ⁰ C and atmospheric pressure with the aid of 1.5 mmol per liter MckelnaplräBnat, ■ which had been Aluminiumtriäthylaktiviert 6 millimoles per liter. A completely hydrogenated product was obtained within 6 hours in the form of a 5% strength by weight solution which, after isolation, proved to be a free-flowing powder with a Hoekstra plasticity of 29. Isolation of the product was carried out as follows% to deactivate the hydrogenation catalyst, the hydrogenated polymer solution was first treated with 20 ml of ethanol containing 0.8 ml of a 38 G ew .- # contained -HCl solution. Extraction was then carried out with a solution of 2 ml

one after the other 38 Gewy- $ iger HCl per liter of water and washed aHöOkü-eÄ-eiKl with water ^ a 0.2 G-Ew .- $ igen HaCO, solution and again with water »Finally the solvent was removed by stripping with Eamspf - removed at 10O ⁰ C and dried the hydrogenated copolymer at 60 C in vacuo. . '· .--.

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Plates were pressed of 1.5 mm thickness at 150 ⁰ C and in accordance with ASTM 412-62 Ό T (die D) for determining a number of tensile elongation at a pulling speed of 50 cm per minute used in the hydrogenated copolymer. The results are shown in the table below. For comparison, the corresponding values for 3 other hydrogenation products were included in the table. These products were obtained by complete hydrogenation of the following random butadiene-styrene copolymers with comparable styrene proportions: 1. a high molecular weight copolymer produced in solution with a lithium hydrocarbon bond, 2. a likewise high molecular weight copolymer which is produced by emulsion polymerization according to the 1500 sulfoxylate specification by Duck and Waterman and La Heije, described in J. Appl. Chem. 12 (1962) 469-4-78, and which had been brought into the form of a pure, easily hydrogenatable solution by the process described in British Patent 1 018 376, and 3. a low molecular weight emulsion copolymer which Had been prepared in a similar manner, but for which a larger amount of modifier was used, and which had also been brought into solution.

Tabel

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According to the invention 65 Hydrogenated, Hydrogenated Hydrogenated lirlii hydrogenatedV never » 136 high molecular hoehmsle ^ mole d er mo 1 ekul ar e s, 272 lares, want kulares, kulares, willh Arbitrary 323 natural arbitrariness- , Emulsion Copolymer 460 Copolymer, lijshies copOlymer 46 manufactured. Emalsions.- 89 in solution in copolym ^: he outstanding present of Lithium carbon hydrogen S. © ehalt sn bound Styrene Sew. -96 21.5 22nd 23.5 24 Hoekstra-Wiert before the Hydrogenation 2 20th 35 2 Hoekstra-Üert after the Hydrogenation 29 83 ' 80 40 IV before hydrogenation ;, dl / g 0.65 1.7 2.1 0.6 17 after hydrogenation, dl / g 0.7 1.8 2.2 0.7 100 $ * Ηοφαΐ »kg / cm ² 45 25.5 20.7 300 t ^ module, kg / cm ² 116 52.7 32.8 500 $> Mödiil, kg / cm - 90.1 51 Drawability, kg / cm 295 228 270 Ermehaehmtng> fo 365 726 1400 cn Siiöre ^ hardness 1 40 - 22nd O Shore hardness A 84 - 68 cn Liability in the bad bad useful Mill

Although the tensile elongation properties listed in the last column are not bad, it must be stated that the latex of the low molecular weight
Emulsion copolymer (similar to the latex of the high molecular weight emulsion copolymer) was first subjected to treatments as described in the British patent
108,776 are given before it could be hydrogenated.

Claims

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Claims (7)

DR. ING. F. WUESTIIOFF “MUNICH OO DIPL. ING. G. PULS SCHWEIGERSTHASSE IiK.E.ν.PECHMANN ",". Κ SSO6 51 PATENTANWÄLTE. j% TKtBOBAMMADBBBSBl & m0 PBOTBOTPATBHT ttÜXOHJCX 1A-33 418 claims 1. New partially or fully hydrogenated diolefin copolymers consisting of units of at least 2 of the monomers 1,3-butadiene, isoprene or styrene, in which over 50 % of the bound monomer units are randomly distributed, and which are produced by solution polymerization in the presence of lithium hydrocarbons Compounds have been made and have an intrinsic viscosity between 0.1 and 1.0 dl / g. 2. New polymers according to claim 1, characterized in that the number of double bonds of hydrogenated products is over $ 30 less than the pre-hydrogenation copolymers. 3. New polymers according to claim 2 and 3 _f, characterized in that over 60 f £ of the units come from dienes bound by 1,4-addition. 4. A process for the preparation of novel copolymers, characterized gekennz ei seframe that a copolymer of partially or fully hydrogenated, in which more than 50 ° / o of bonded monomer units are distributed randomly, and an intrinsic viscosity between 0.1 and 1.0 dl / g, and by copolymerization in solution of at least the monomers 1,3-butadiene, isoprene or styrene in counter- 109836/1150 was obtained from a lithium hydrocarbon catalyst became. 5. The method according to claim 4, characterized in that the catalyst is the reaction product of a metal hydrocarbon compound and an organic compound of a base metal of Group VIII of the periodic table. 6. The method according to claim 4 and 5, characterized in that the hydrogenation is carried out in the solution the
makes in which / copolymers were made. 7. The method according to claim 4 to 6, characterized in that the polymer concentration of the solution, in which the hydrogenation takes place, is 25 to 30 wt .- #. 109836/1150