DE1420683B1 - Process for the preparation of polyalkylene ether polymers - Google Patents

Description

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So far, various polyalkylene or 4-Aylbenzylrest have been denoted and in which R 'H, ether polymers are prepared, usually by a lower alkyl radical, a chloromethyl radical or polymerization of cyclic ethers, or of polyoxy a lower alkoxymethyl radical denotes the compounds. These polymers formed proportionally is characterized in that the reaction in moderately low molecular weight liquids and oils up to 5 essence of 0.02 to 0.2 mol percent, based on relatively high molecular weight liquids, the total number of moles of the cyclic and solids to be polymerized. However, they did not yield any usable elastomers when they hardened see ether, phosphorus pentafluoride, and antimony pentatation. In addition to these chloride or antimony pentafluoride or 0.01 mol polyalkylene ether polymers, other poly percent of an aryldiazonium hexafluorophosphate was carried out as a catalyst with recurring ether bonds,
posed, namely z. B. the polyurethanes from poly- The preferred, according to the invention

alkylene glycol ethers and organic diisocyanates. The polyalkylene ether polymers obtained by the process can be prepared in a simple manner by means of units which are cured essentially from the following structural polyisocyanates as curing agents:
the. However, they are thermally 15 to some degree

unstable due to groups like (a) - (- CH ₂ -CH ₂ —CH ₂ - CH ₂ —OJ-

Urethane or allophanate groups. The creation
an extremely stable and easy way to / R

known processes to produce valuable elastomers, curable polyether polymers are therefore very desirable. 20 (b) - | -CH

In the German Auslegeschrift 1 027 400 the
Production of oily and waxy, crosslinkable polymers from tetrahydrofuran and olefinic carbon-carbon double bonds ent- wherein the number of (a) units at least containing epoxy compounds using 25 one third of the total number of recurring an ionically acting catalyst, z. B. boron units and the repeating units fluoride described. For many purposes, however, from one carbon atom to one to an acidic polymer of this type are required, in particular substance atoms of the other are bonded, η means polymers with a molecular weight before 0 or 1. The term "inert radical" means crosslinking of at least 30 000. Such polymers 30 have a radical that can be rolled with the polymerization catalyst, which essentially does not react for oils and wax, ie the radical-like substances are impossible. either does not react with the catalyst at all or

It has now been found that when you use it, you get so much slower than the cyclic ether bond, certain catalysts in very small quantities that this does not prevent polymerization rollable sulfur-curable polyalkylene ether polymers 35 is. Such inert R radicals include: with a molecular weight of 30,000 and higher hydrocarbon radicals, halogenated carbons Tetrahydrofuran and epoxy compounds, hydrogen radicals or the corresponding oxa-anates can; these catalysts are phosphorus penta- analogs of these hydrocarbon and halogenated ones fluoride, antimony pentachloride and antimony penta hydrocarbon radicals. If R is a bivalent fluoride, alone or as a mixture. In their place 40 oxa analogs of a hydrocarbon or halo can also aryldiazonium hexafluorophosphate-genetically modified hydrocarbon radical with a free one be turned. If these catalysts are in valence on a terminal oxygen atom, Larger amounts are usually used that can add one carbon atom in a valence to this Desired molecular weight is not achieved while other repeating unit belong so that In practice, concentrations that are too low - 45 a partially crosslinked, millable polymer is obtained, point out are unsuitable and inaccurate results- So that these radicals are inert, i. H. not with the deliver nits. Polymerization catalysts react, they should

The invention relates to a method for containing no active Zerewitinoff hydrogen,

Production of polyalkylene ether polymers with and if they contain an oxygen atom, this molecular weight of at least 30,000 through 50 should be present as acyclic ether oxygen and min reaction of at least 33 ¹ I ₃ mol percent, based at least through 2 carbon atoms from another

on total reactants, tetrahydro-ether oxygen and about in the polymer furan be separated with one or more monomeric cyclic halogen atoms contained. R needs

Ethers of the general formulas: of course not necessarily in every particular poly-

P _RR , 55 mere to be the same in every case, and an un-

IX _x / equality is even preferred.

', C Aliphatic and cycloaliphatic hydrocarbons

(a) HC ₂ CH (b) £ jj / \ £ jj Substance fractions of radicals R can be saturated or

\ / - j / ² \ / ^{2 be} unsaturated, namely e.g. B. alkyl, cycloalkyl

O 60 mixed alkyl / cycloalkyl and the corresponding

Radicals with non-aromatic carbon-carbon

wherein R is an alkyl radical, namely a methyl or fabric double bond. These non-aiomatic an-ethyl radicals, a chloromethyl, cyclopentyl, cyclo parts of the substituents can be divalent, eg. B. hexyl, vinyl, allyl, methallyl, 4-hexenyl, 7-Oc-alkylene radicals, the z. B. with the carbon atoms tenyl, cyclohexenyl, propyloxymethyl, ethyloxy 65 or the carbon atom in the linear polymer methyl, Allyloxymethyl, phenyloxymethyl, 4-pen chain can represent a cyclic structure, e.g. B. tenyloxymethyl, 2,4-diallylphenyloxymethyl, 4-allyl in the 1,2-cyclohexylene radical (obtained by binoxyphenyl, 2-Allyloxybenzyl, allyloxy, 3-butenyl- dation of tetramethylene to neighboring carbon

3 4

Atoms in the linear polymer chain). You can bond in the ring and it is the only heteroatom also the binding of other radicals, e.g. B. of alkene oxygen.

nyl, cycloalkyl, cycloalkenyl, aryl, alkenyloxy, cyclic ethers with 3-membered rings.

Alkyloxy, cycloalkyloxy, cycloalkenyloxy, aryl into the ethylene oxide (epoxy) series and the 4-membered series Oxy, chlorine radicals and the like on the carbon atoms 5 rings belong to the 1,3-propylene oxide (oxetane) take over in the polymer chain. Line. The 3- and 4-membered saturated ether rings

Examples of the aromatic content of these substituted one or more substituents can be preferred cyclic and acyclic-cyclic radicals, however, do not contain more than two, which kale are phenyl, phenylene and substituted phenyl are attached to the ring via carbon and and phenylene radicals, as well as the corresponding radicals, nonaromatic carbon - carbon double kales the naphthalene series. These aromatic radical bonds can contain. The two also wear Kales can sit directly on the carbon atoms in the linear carbon polymer chain connected to the ether oxygen or indirectly via atoms, expediently at least 1 hydrogen carbon each or oxygen to one of the above atoms, and in the oxetanes are useful however be linked to the aliphatic radicals described. 15 doesn't necessarily have these two carbon atoms in The aromatic radical can be so z. B. contain phenyl or methylene groups.

chlorine, alkyl, alkoxyl, alkenyl or alkenyloxy typical functional and non-functional oxetanes

substituted phenyl. On the other hand, this can be inert with respect to the polymerization catalyst aromatic radicals also benzyl, a benzyl homo radicals are trimethylene oxide and its 2-methylloges or one as above for the phenyl grater 20 2,4-dimethyl-, 3-butyl-, 3-phenyl-, 3- (allylphenyl) -, described substituted benzyl or a corresponding 3,3-dimethyl, 3,3-bis (chloromethyl), 3,3-diethyl, of the homologue. The mixed aliphatic / aro- 3-ethyl-3-allyloxymethyl-, 3-vinyl-, 3-allyl-, 3-mematic Radicals can be bivalent, namely thyl-3-crotyl-, 3,3-bis- (ethoxymethyl) - and 3-chlorine. B. o-Phenylenmethyl, as for example in the methyl-3-allyloxymethylderivate. Another typical oxe-1,2-indenylene radical occurs. 25 tanes are compounds like 2-oxaspiro [3,5] nonane

The side chain groups which are a non-aro and 2-oxaspiro [3,4] octane.

The preferred epoxides and oxetanes are the

hold can be referred to as functional groups in the following sense, as they are effective at r>

Handle points are used for curing. The sides- 30 CH ₂ CH-R \

Chain groups without such a double bond can- \ / ^{un <} i / ^

nen regarded as nonfunctional substituents O r '^

will; however, they impart different properties to the polymer

favorable properties, both before as in which R z. B. an alkyl radical such as methyl or even after it has hardened using 35 ethyl, chloromethyl, cyclopentyl, cyclohexyl, vinyl, Sulfur. So z. B. extremely valuable elasto-allyl, methallyl, 4-hexenyl, 7-octenyl, cyclohexenyl, mers with different freezing resistance in propyloxymethyl, ethyloxymethyl, allyloxymethyl, hardened state by regulating the relative phenyloxymethyl, 4-pentenyloxymethyl, 2,4-dialyl number and the nature of these non-functional phenyloxymethyl, 4-allyloxyphenyl, 2-allyloxybenzyl nellen side chains can be obtained. The substituted 40 and 4-allylbenzyl means and where R 'is H, a Alkylene radicals in the chain of the polymer can be a lower alkyl radical or a lower alkoxysomite denotes nonfunctional homologues and isomers of methyl radical.

be each other, e.g. E.g .: 1,2-propylene, 1,2-butylene, 1,3-Bu- The polymerization of the selected mixture cyclic

tylene, 2,3-butylene, 2-methyl-1,3-propylene, cyclo-ether can be used at temperatures of essentially hexylidenedimethylene and 1,2-octylene; related Ra- 45 below room temperature to slightly above usual radicals such as cycloalkylene, e.g. B. 1,2-cyclohexylene; be carried out specifically between -80 and chloro-substituted derivatives of the foregoing radi- 7O ⁰ C and Licher room temperature. Usually the kale, ζ. B. 3-Chloro-l, 2-propylene and 2,2-bis temperature from -20 to 30 ⁰ C. (chloromethyl) -l, 3-propylene radical. You can also use Aryldiazoniumhexafluorophos-

Be members of the aralkylene series, e.g. B. 2-phenyl 50 phaten as catalysts, the polymerization 1,2-ethylene, 3- (o-chlorophenyl) -1,2-propylene and temperature between 0 to 70 ⁰ C, with 20 2- (p- Tolyl) -l, 3-propylene. It can also oxa analog are preferred to 4O ⁰ C.

suppose to be one of the above radicals, e.g. B. The catalysts can be of the cyclic ether

3 - methoxy -1,2 - propylene, 4 - (3 - methoxyphenyl) mixture can be added, or it can also 1,2-butylene, 3-phenoxy-1,2-propylene and 2-methyl-55 reversed the cyclic ethers individually and indiscriminately 2-methoxymethyl-1,3-propylene. be mixed in the presence of the catalyst.

Typical substituted alkylene radicals with non- The polymerisation is exothermic and generally does not require any additional heat in aromatic carbon - carbon double bonds. You can manure are 2-vinyl-1,2-ethylene, 1-allyl and 1-CrotyI- the mixture stand or stir it until the 1,2-ethylene, 1-allyl-1,2-propylene, 2 -Ethyl-2-allyl- 60 desired degree of polymerization has been reached, ie 1,3-propylene, 2- ethyl-2-allyloxymethyl -1,3 -pro until the polyether polymer has an intrinsic molar viscosity, 2-ethyl-2 (4-allylphenyloxymethyl ) - has an act of at least 1.0. A base molar 1,3 - propylene, 1 - allyloxymethyl - 1,2 - ethylene, viscosity of at least 1.0, determined on a 2 - (4 - allylphenyl) -1,2 - ethylene, 3 - (2 - allylphenyl - 0 , 1% solution of the polyether polymer in benzene oxy) - 1,2 - propylene and 3 - (2,4 - diallylphenyloxy) - 65 at 30 ⁰ C, corresponds to an average molecular 1,2-propylene. weight of at least 30,000. To separate dss

The 3 or polymers used as starting materials are first inactivated by the catalyst 4-membered cyclic ethers contain no double or destroyed, and that usually by adding

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of substances that react with it, such as water, aiko- fertilizers are benzoldiazoniumhexafluorophospha ^ o-toholes or amines. It is preferred to use lyl-diazonium hexafluorophosphate and diphenylene water or ammoniacal water in combination 4,4'-bisdiazonium hexafluorophosphate.
nation with an organic solvent for the gaseous phosphorus pentafluoride can be converted directly into polymers. Such a solvent is e.g. B. Tetra- 5 the monomers to be polymerized are dissolved, hydrofuran, dioxane, dimethylformamide and ethyl- whereby the polymerization immediately after the ether must become. The phosphorus pentafluoride which is easy to use for the catalyst can, however, also initially be used in a moderate excess, and the mixture is quickly stirred with only one molar equivalent or more of a cyclic acid. When using a solvent while see ether, z. B. tetrahydrofuran, together inactivation of the catalyst depends on the further brought and then in this mixture for poly work-up on whether the solvent used with merization of a mixture of cyclic ethers is water-miscible or not. If not, we will.

the solvent layer from the aqueous layer 15 While the polyether polymers are separated on the average, a side chain with a non-aromatic carbon vacuum acting as a point of attack for impurities and finally a wetting non-aromatic carbon vacuum can be distilled off from the polymer for complete removal of more soluble ones. Carbon double bond per 10,000 moles - If the solvent is miscible with water, the polymer must contain kular weight units to precipitate the polyether polymer but not all of which are disconnected again. If necessary, the curing may need to take action. Preferred polymers are washed on a rubber roller mill, on average, the polymer does not have to be in order to ensure complete removal including more than about one point of attack for the crosslinking of its water-soluble impurities - 25 per 500 molecular weight units,
Afford. The drying of the polymer can be carried out in the usual manner, e.g. B. in a vacuum, in a desiccator or carbon double bond can also be polymerized by rolling on a rubber mill under cationic catalysts, expulsion of water is done in the form of steam. it is remarkable that the

To achieve polyether polymers with mol- 30 according to the process polymers produced a

Cell weights of at least 30,000 may have the relatively high molecular weight and

monomeric cyclic ether no side chain sub- the unsaturated groups subsequently nor for

have substituents which interfere with the polymerization are available for curing. Polymers

would. These cyclic ethers should not have any groups with molecular weights below 30,000

pen with Zerewitinoff hydrogen atoms contain 35 intrinsic molar viscosities are slightly soft and

d. H. for example no amino groups, hydroxyl sticky and are therefore on common facilities

groups, carboxyl groups, etc. If one of these is difficult to roll and process. All after

Side chain substituents an oxygen or halo process according to the invention produced polyether

Genatom contains, these atoms must be polymeric in common facilities of the chewing

at least 2 carbon atoms from another 40 chuk can be rolled and processed

Oxygen atom be separated. Appropriately, it will also be provided with the usual additives.

Polymerization even under essentially water- You can have essentially linear molecules

however, air will also be branched or networked, namely

excluded during the reaction to one depending on the type of catalyst used and

To avoid autoxidation of the cyclic ethers. 45 the nature of the side chains.

This is expedient by using a so that the polymer can be rolled and turned into elastomers

dry, inert gas, e.g. B. nitrogen, in which is curable, it must not be too branched or

Polymerization vessel reached. to be connected. It is assumed that a branch

During the production of the polyether polymers depends or crosslinking and a subsequent gelation

the 5 ° represented by the intrinsic molar viscosity occurs when a polymer is benzyl ether-like

Degree of polymerization of the polymerization temperature or allyl ether type group in its side chain

temperature as well as of the catalyst used in each case. It can then be sent to the active end of another

and its concentration. In general, active polymer chain is joined, which is benzylic

the molecular weight of the polyether poly- or allyl-like radical formed on the ether oxygen

The higher the concentration, the higher the concentration and even as a branch in its place

of the catalyst and the lower the temperature. occurs. The prospects for such a chain relationship

Of course, the amount of branching you need to take at a given temperature to achieve optimal results

Nisse required respective temperature of the to if more repeating polymer units with

used mixture of cyclic ethers and these allyl ether-like and benzyl ether-like side

on their responsiveness. 60 groups are present and when the catalyst

Suitable aryldiazonium hexafluorophosphates are not available soon after the linear polymers have been prepared including those in which the aryl group is destroyed. The invention also includes here Is phenyl or naphthyl; the aroma of these partially gelled branched or The ring can be formed by crosslinked polymers which are inert during the polymerization and which form extremely Groups may be substituted, e.g. B. by alkyl groups, 65 valuable elastomers are still rollable and curable. Alkoxy groups or halogen. A preferred aryl polyether polymers can be used Diazonium hexafluorophosphate is p-chloro-benzenediazo- are hardened by sulfur. Usually done sodium hexafluorophosphate. Other suitable compounds include curing by heating the polymer

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at least 125 ° C with sulfur in the presence of flask was sealed and 48 hours at 0 ⁰ C vulcanization accelerators. Usually kept. A soft, rubber-like polymer was obtained, if about 0.1 to 2.0 parts of sulfur were required on solid polymer, which was dissolved in 2900 parts of tetrahydrofuran to cure 100 parts of the polymer, the 30 parts of concentrated aqueous substance suitable accelerator. Which did not contain enough ammonia and 40 parts of water. With hardened polyethers, the hardening agents can be slowly added to the solution to a large extent and is then stable and the polymer was precipitated until the ice water was poured through and the desired hardening was achieved, which then resulted in 2.5 parts phenyl in 3340 parts. jÖ-naphthylamine usually redissolved by heating for half to several hours on tetrahydrofuran containing it. There is 125 to 16O ⁰ C, storage stable. Of course, different embodiments of the sulfur can be precipitated again by pouring into a large volume of water and hardening can be used on a rubber rolling mill, each dried at 100 ° C. This gave 302 parts depending on the type of polyether used. Displacement of a soft, rubbery polymer with a dene methods and embodiments of the sulfur intrinsic viscosity of 1.40 at 30 ⁰ C warm felhärtung are more accurate in 15 Encyclopedia of Chemical benzene and having an iodine value of 19.1. This Poly-Technology, K irk and O rthmer, published mere rolled out easily on a cold rubber mill from Interscience Encyclopedia, Inc., New York, 1953.

Vol. II, pp. 892 to 927; Principles of High Polymer B. 30 parts of the polymer obtained above

Theory and Practice, Schmidt & Marlies, was published on a 9 part rubber mill by McCraw-Hill Book Co., Inc., 20 abrasion resistant furnace black, 1.5 parts zinc oxide, New York, 1948, pp. 556 and 566; Chemistry and 0.9 parts of sulfur and 0.23 parts tetraethyl Technology of Rubber, Davis & Blake, comparable thioramdisulfid added and the mixture was published under Reinhold Publishing Corp., New York, 2 hours in molding under pressure at 150 ⁰ C vulkani-1937, Chapter VI. sated. The elastomer obtained was elastic and

The polymers obtained according to the invention were rubber-like, it had a tensile strength of seats for the most varied of purposes. So 218 kg / cm ² and an elongation of 340%. Its can be used for the production of tires, pipe made of Yerzley elasticity was 70%, the Shore hardness 67 for clothing, belts, hoses and pipes, as and its permanent deformation (method B, 22 stun wire and cable sheaths, for footwear, den, 70 ⁰ C) 21%. (The Yerzley elasticity is used according to sponges, coated fabrics and for the manufacture of 30 the ASTM method D 945-55 and the permanent multiplier of coated and shaped structures will be used for the ASTM method D 395-55. As already mentioned, draw it is determined by [Method B].) Good thermal stability and durability
against hydrolysis. Example 2

The elastomeric properties of these substances can 35

can be varied by suitable additives. The A. In a dried over a flame and in

The amount and nature of the addition nitrogen-cooled flask were 72 parts fresh depends on the intended use under nitrogen over lithium / aluminum hydride dedes Elastomers. The tetrahydrofuran usually chewed, 39 parts of 3,3-bis (chlorochuk industry for both natural and 40 methyl) oxacyclobutane and 5.7 parts of 1-allyloxysynthetic The additives used in rubber are 2,3-epoxypropane, both of which are freshly consumed suitable for the products according to the invention: were distilled under reduced pressure. The solution ver-es if these include carbon black, chalk, silica, 0.20 parts of antimony pentachloride were added. All esterified silica particles, tallow, zinc and magne additions were made while nitrogen was passed through, siumoxide, calcium and magnesium carbonate, titanium 45 The flask was closed and in dioxide and plasticizer. To achieve certain an ice bath kept. The solid polymer formed Colors can also be inorganic and organic then dissolved in 670 parts of tetrahydrofuran, the Dyes are incorporated, as the natural color is 5 parts of concentrated, aqueous ammonium hydroxide, of these elastomers a light yellow or light amber - 5 parts of water and 0.75 parts of phenyl-ß-naphthylamine is stone yellow. 50 contained. By adding to a large volume

The following examples illustrate the invention. Water was used to precipitate the polymer, which, unless stated otherwise, was washed out on a rubber mill. According to part by weight. The properties of the cured drying also on a rubber mill at elastomers in stress and strain wur- 100 ⁰ C determined soft kauden by the customary in the rubber industry 55 tschukartigen polymers having an intrinsic methods of a received is 77.5 parts. Viscosity of 1.13 in benzene ^{at 30 ° C.} This

. . Polymers settled on a cold rubber mill

^Bei P ^{iel 1} rolled out easily.

A. 360 parts of freshly under nitrogen over B. 20 parts of the polymer obtained under A.

Lithium / aluminum hydride distilled tetrahydro-60 were placed on a rubber roller mill with 6 parts of furan were placed in a flask, which was dried over highly abrasion-resistant furnace soot, 1 part of zinc oxide, a flame and then 0.6 parts of sulfur and 0.3 parts of tetraethylthiuram were cooled in nitrogen was. Disulfide was then added, and the mass was then vulcanized into 28.5 parts under reduced pressure, freshly distilled molding under pressure at 150 ° C. for 2 hours. l-allyloxy-2,3-epoxypropane too. The flask was 65 The vulcanizate was rubbery and elastic and cooled in ice, and the solution was 0.75 parts had a tensile strength of 158 kg / cm ^a ; a Deh antimony pentachloride added. All additions were made at 380%; a Shore hardness of 65; one with dry nitrogen bubbling through. The Yerzley elasticity of 69% and a permanent one

009582/374

9 10

Deformation (method B, 22 hours at 70 ^° C.) of B. In 30 parts of the polymer obtained under A

38 ° / ₀ . became 9 parts thick on a rubber mill

B e i s D i e 1 3 abrasion-resistant furnace soot, 0.9 parts mercaptob ^ nzo-

thiazole disulfide, 0.6 parts mercaptobenzothiazole,

A. In a flask dried over a flame and cooled in 5 0.21 parts of a mercaptobenzothiazole disulphide / zinc nitrogen, 72 parts of chloride complex, 0.02 part of zinc oxide and 0.15 part of sulfur were added freshly under nitrogen over lithium / aluminum hydride, and the mass was in distilled tetrahydrofuran, 31 parts of 3,3-bis- (chlorine molds under pressure for 30 minutes at 150 ° C vulmethyD-oxetan and 7.8 parts of S-ethyl-S-allyloxymethyl- kanisiert. The rubber-like vulcanizate had a oxacyclobutane, both of which had been freshly distilled under reduced pressure with a tensile strength of 246 kg / cm ² , an elongation of 600%, a Shore hardness of 61, a Yerzley Elastiman with 0.2 parts of antimony pentachloride - Ctity of 77 ° / ₀ , a permanent deformation of 14% took place while nitrogen was passed through (method B, 22 hours, 70 ° C) and did not solidify, the flask was then sealed for 24 hours if it was open for 1 week - Held 20 ° C.

kept in an ice bath. The solid polymer was 15 _n .

Dissolved in 890 parts of tetrahydrofuran, the 5 parts of Example 5

concentrated aqueous ammonia, 5 parts of water A. In a flame-dried and in

and 0.5 part of phenyl - /? - naphthylamine. The nitrogen cooled flask was 15.8 parts

Polymers were made by adding to a large fresh under nitrogen over lithium / aluminum hydride

Volume of water precipitated and tetrahydrofuran, 3.1 parts of 1,2-propylene-

washing roller mill washed out. After drying oxide, freshly distilled over Cylciumhydrid, as well

on a rubber mill at 100 ° C., 1.5 parts of S-EthyM-allyloxymethyloxacyclobutane were obtained

76 parts of a soft, rubber-like polymer under reduced pressure also over calcium

with an intrinsic molar viscosity of 1.40 in 30 ° C hydride had been freshly distilled, introduced. Of the

warm benzene. This polymer settled on a 25 flask was cooled in an ice bath and taking

Lightly roll out the cold rubber roller mill. Passing dry nitrogen over the piston

B. In 20 parts of the polymer neck obtained under A were added 0.19 parts by volume of a 0.14 molar 6 parts strong solution of antimony pentafluoride in dry, abrasion-resistant furnace black, 1 part zinc oxide, 0.6 parts 1,1,2- Trifluorotrichloroethane. The flask was enclosed in sulfur and 0.3 part of tetraethylthiuram disulfide and kept in ice for 3 days. You solved then worked. The composition was then cured for 2 hours at 15O ⁰ C in molding under the solid polymer in 220 parts of tetrahydrofuran, pressure. The resulting aqueous 1.4 parts 28 ° / ₀ ammonia solution, rubbery vulcanizate had a tensile strength .1.5 parts of water and 0.6 parts of 2,2'-methylene-bisvon 91 kg / cm ^2; an elongation of 120%; a Shore (4-methyl-6-tert-butylphenol) contained. The polymer hardness of 62; a Yerzley elasticity of 62% and then a permanent deformation (method B, 22 hours, water and several times with fresh 70 ^° C.) of 27% was achieved by adding a large volume. Washed out water. After drying in

15.7 parts were obtained when the 1 4 vacuum was applied over calcium chloride

of a soft, rubbery polymer with a

A. In a flame-dried and 40 intrinsic molar viscosity of 2.65 in 30 ° C warm

Nitrogen-cooled flask was filled with 178 parts of benzene (0.10 g / 100 ecm). This polymer could

lightly roll fresh under nitrogen over lithium / aluminum hydride on a cold rubber roller mill,

brought distilled tetrahydrofuran. The flask B. In 14 parts of the polymer obtained under A.

was cooled in ice, and stirred, working on a rubber mill 4.2 parts

0.44 part of phosphorus penta- 45 mixed with nitrogen, a highly abrasion-resistant furnace black, 0.42 part

fluoride in the solution. Immediately thereafter mercaptobenzothiazole disulfide, 0.28 parts mercapto-

you put the solution in the flask quickly with a benzothiazole, 0.05 part of a mercaptobenzothiazole

Mixture of 56.2 parts of 3,3-diethyloxetane and disulphide zinc chloride complex, 0.07 parts of cadmium

19.7 parts of 3-ethyl-3-allyloxymethyloxetane, both stearate and 0.07 part of sulfur, whereupon the

fresh calcium hydride under reduced pressure over 5 ° mass into molds under pressure for 60 minutes at 150 ⁰ C.

had been distilled. Vulcanized within 10 minutes. The elastomer obtained had a

the solution became too thick to stir. The piston tensile strength of 162 kg / cm ² ; an elongation of

was sealed in an ice bath for 24 hours; 550%; a Shore hardness of 62; a yerzley

keep. The solid polymer was then dissolved in an elasticity of 69%; permanent deformation

3600 parts of tetrahydrofuran, the 36 parts of 28% strength 55 (method B, 22 hours, 7O ⁰ C) of 11% and a

aqueous ammonia, 40 parts of water and 1 part of TR-50 value (solvent hexane) at -24.5 ° C

2,2'-methylenebis (4-methyl-6-tert-butylphenol) ent- (see ASTM method D 1329-58 T).

held. The polymer was made by adding to a. .

large volume of water precipitated and by more- Example 6

repeated soaking washed out with fresh water. 60 A. In a 5-liter flask with a stirrer, which

After drying on a rubber roller mill, dried over a flame and rinsed through

100 to 110 ⁰ C were obtained 209 parts of a rubber that had been cooled with nitrogen, were given

like polymers with an intrinsic viscosity of 907 parts distilled over lithium / aluminum hydride

of 2.62 in benzene at 30 ⁰ C (0.10 g / 100 ecm). Tetrahydrofuran, 84 parts via calcium hydride de-

When repeating the above-described 65 propylene oxide, 87 parts via lithium / aluminum operation, However, the catalyst is in the miniumhydride distilled S-allyloxymethyl-S-methyl mixture all monomeric cyclic ethers are monooxetane and 0.42 parts of p-chlorobenzene diazonium hexa-duct a similar polymer was obtained. fluorophosphate. The concentrations of the reaction

Participants were: 86 mole percent tetrahydrofuran, 9.8 mole percent propylene oxide, 4.2 mole percent allyloxymethyl-3-methyloxetane and 0.01 mole percent catalyst. The solution was stirred and the temperature was kept at 25 ° C. ± 2 ° C. by cooling. After the solution became too thick to stir, the stirrer was removed from the polymer. After about 20 hours, the soft, yellow polymer was dissolved in 9,350 parts of tetrahydrofuran which contained 2.6 parts of phenyl - /? - naphthylamine, 105 parts of concentrated aqueous ammonium hydroxide solution and 105 parts of water. The polymer was then precipitated in a large volume of water and washed out by repeated soaking with fresh water. Drying was carried out on a rubber mill at 100 ⁰ C. 852 parts of a brown colored rubbery polymer was obtained having an intrinsic viscosity of 2.48 in 3O ⁰ C warm benzene having an iodine value of 19.0.

B. In 100 parts of this polymer, 50 parts of highly abrasion-resistant furnace black, 3 parts of 2,2'-dithio-bis-benzothiazole, 2 parts of 2-mercaptobenzothiazole and 0.7 parts of a 1: 1 molar complex of zinc chloride with 2, Incorporated 2'-dithio-bisbenzothiazole, 0.7 parts of zinc oxide and 0.7 parts of phenyl- / 3-naphthylamine. The material provided with the additives was cured at 150 ° C. for 30 minutes, and a cured elastomer having the following physical properties was obtained: tensile strength 180 kg / cm ² , elongation 310 ° / ₀ . Modulus at 300%, elongation 173 kg / cm ^2, elasticity of 67% and compression set 12 ° / ₀ (Method B, 22 hours 7O ⁰ C).

Water-soaked and dried for 10 minutes on a rubber mill at 100 ⁰ C. Here, parts of a soft yellow product with an intrinsic viscosity of 2.31 was obtained in 30 ⁰ C warm benzene and having an iodine value of 16.6.

B. In 100 parts of the uncured polymer obtained under A, 10 parts of highly abrasion-resistant furnace black, 0.60 part of 2,2'-dithio-bis-benzothiazole, 0.40 part of 2-mercaptobenzothiazole, 0.14 part of a 1: Imolar zinc chloride-2,2'-dithio-bis-benzothiazole complex, 0.014 part zinc oxide, 0.10 part sulfur and 0.15 part phenyl- / 3-naphthylamine incorporated. The material provided with the additives was ^{cured at 150 °} C. for 1 hour. The rubber-like vulcanizate obtained had the following properties:

Tensile strength to break (25 ° C) .. 204 kg / cm ²

Elongation at break (25 ° C) 400 ° / ₀

Modulus at 300% elongation (25 ° C) 139 kg / cm ²

Yerzley elasticity (25 ° C) 68 ° / ₀

Shore hardness 70

Permanent deformation (70 ⁰ C) 14%

Claims (1)

Claim: Process for the preparation of polyalkylene ether polymers with a molecular weight of at least 30,000 by reacting at least 33 V ₃ mol percent, based on the total reactants, of tetrahydrofuran with one or more monomeric cyclic ethers of the general formulas: Example 7 35 A. Into a 2 liter flask equipped with a stirrer and continuously purged with nitrogen 189 parts of tetrahydrofuran distilled over lithium / aluminum hydride, 12 parts over Calcium hydride distilled biallyl monoepoxide and 16.3 parts propylene oxide distilled over calcium hydride brought in. The concentrations of the reactants were as follows: tetrahydrofuran 86.7 mole percent; Biallyl monoepoxide 4.0 mole percent and propylene oxide 9.3 mole percent. This mixture was with stirring at 23 ° C with 0.086 parts of p-chlorobenzene diazonium hexafluorophosphate offset. The mixture was then stirred at about 23 to 25.5 ° C. for 2 hours and 20 minutes. While during this time the viscosity increased. The mixture was then left at room temperature for about 16 hours stand. The resulting soft polymer readily dissolved in about 1332 parts of tetrahydrofuran, which is 1 percent by weight concentrated aqueous ammonia, 1 weight percent water and 0.025 weight percent Phenyl - /? - naphthylamine contained. The clear, viscous, yellow solution obtained was poured into water. The precipitated polymer was then repeated using (a) HC ₂ CH (b) ^R \ _c / ^R ' CH ₂ , CH ₂ where R is an alkyl radical, namely a methyl or ethyl radical, a chloromethyl, cyclopentyl, Cyclohexyl, vinyl, allyl, methallyl, 4-hexenyl, 7-octenyl, cyclohexenyl, propyloxymethyl, Ethyloxymethyl, allyloxymethyl, phenyloxymethyl, 4-pentenyloxymethyl, 2,4-diallylphenyloxymethyl, 4-allyl-oxyphenyJ-, 2-allyloxybenzyl, allyloxy-, 3-butenyl or 4-allylbenzyl radical and wherein R 'is H, lower alkyl, chloromethyl or lower alkoxymethyl means, characterized in that the reaction in the presence of 0.02 to 0.2 mol percent, based on the Total number of moles of cyclic to be polymerized Ether, phosphorus pentafluoride, antimony pentachloride or antimony pentafluoride or 0.01 mole percent an aryldiazonium hexafluorophosphate is carried out as a catalyst.