DE1033413B - Process for the production of poly (vinyl ethers) - Google Patents

Description

GERMAN

The invention relates to a new process for polymerizing vinyl ethers and producing new poly (vinyl alkyl ethers), which by their high degree of crystallinity and their insolubility in cold water, alcohol and the like. Are marked.

It is known that vinyl ethers are polymerized in bulk or in solution with Friedel-Crafts catalysts can result in the accumulation of polymers, which change the state from viscous liquids to balsamic or possess soft resinous products. Under certain conditions and using boron trifluoride etherates as catalysts it has been possible to use a crystalline type of poly (vinyl methyl ether) and To produce poly (vinyl isobutyl ether). If a solid poly (vinyl ethyl ether) was made, it was but not crystalline. Both the well-known balm-like and crystalline poly (vinyl methyl ether) and poly (vinyl ethyl ether) are entirely in cold water and organic liquids like methanol, ethanol, and acetone Benzene soluble. Because of the unusually high solubility of these polymers, their use has been considerable limited.

It has now been found in accordance with the invention that vinyl ethers can be polymerized by bringing them together of the vinyl ether with a catalyst, which by mixing a metal of groups IVa or Va of the periodic system with an organometallic compound of an alkali or alkaline earth metal, of zinc or aluminum. It has also been found that in many cases, and especially in the In the case of vinyl methyl and vinyl ethyl ethers, the vinyl ether polymers obtained by the process of the invention differ from those previously known in that they are crystalline and very different Have solubility properties compared to the known polymers.

The poly (vinyl methyl ether) obtained according to the invention has a very high degree of crystallinity and a very specific x-ray powder diagram. The crystal lattice spaces and relative intensities the diffraction lines of this new poly (vinyl methyl ether) are as follows:

Method of manufacture
of poly (vinyl ethers)

Crystal lattice Approximate relative inten spaces d sities on a scale of 10 8.0 Ä 4th 5.8 1 4.7 3 4.09 10 3.44 2 3.18 2 2.78 1 2.39 0.5 2.11 1

Applicant:

Hercules Powder Company,
Wilmington, Del. (V. St. A.)

Representative: Dr.-Ing. A. van der Werth, patent attorney,
Hamburg-Harburg 1, Wilstorfer Str. 32

Claimed priority:

V. St. v. America from 20 '. April 5th, 1956

and March 18, 1967

Edwin James Vandenberg, Wilmington, Del. (V. St. A.), has been named as the inventor

This new crystalline poly (vinyl methyl ether) is also characterized by its solubility in that it is insoluble in cold water, methanol and ethanol, but swells only in cyclohexanone and benzene, but generally is soluble in boiling cyclohexanone.

Likewise, the poly (vinyl ethyl ether) of this invention has a very high degree of crystallinity and a very specific x-ray powder diagram. The crystal lattice spaces and relative intensities the diffraction lines of this poly (vinyl ethyl ether) are as follows:

Crystal lattice Approximate relative inten spaces d sities on a scale of 10 10.6 Ä 5 9.9 10 6.06 2 5.68 2 4.92 5 4.57 10 4.15 4th 3.78 5 2.80 2

This new crystalline poly (vinyl ethyl ether) is also characterized by its solubility in that it is in is insoluble in cold water, methanol and ethanol and partially soluble in boiling benzene.

Any vinyl ether, such as B. vinyl alkyl ethers, vinyl cycloalkyl ethers, Vinyl aralkyl ethers or vinyl aryl ethers,

809 559/442

3 4

can be polymerized by the process of the invention. If a compound such as titanium tetrachloride, will. Examples of these polymerizable vinyl ethers are vanadium tetrachloride, vanadium oxytrichloride or vanas Vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl diumoxydichlorid with an organometallic Verbinäther, Vinyl-2-chloroethyl ether, vinyl-2-methoxyethyl- formation of an alkali or alkaline earth metal, zinc or ether, vinyl 2-cyanoethyl ether, vinyl propyl ether, vinyl 5 aluminum is mixed, a reaction takes place, isopropyl ether, vinyl n-butyl ether ", vinyl isobutyl ether, 'which is probably a reduction of the transition metal vinyl tert-butyl ether, Vinyl neopentyl ether, vinyl η compound of one of its higher valence levels too hexyl ether, vinyl 2-ethylhexyl ether, vinyl stearyl one or more of their lower valence levels leads, ether-etc .; dieVinylcycloalkyläther such as vinylcyclohexyl- In general, a compound of a metal is intended to be the ether, vinyl a-terpinyl ether, vinyh'sobornyl ether, etc .; i ° group IVa or Va, which are insoluble or poor the vinyl aralkyl ethers such as vinyl benzyl ether, vinyl p-soluble in the reaction diluent, or a chlorobenzyl ether, vinyl-α, α-dimethylbenzyl ether, etc .; Compound which in this condition through treatment and the vinyl aryl ethers such as vinyl phenyl ether, vinyl p- with an organometallic reducing agent such as methylphenyl ether, vinyl p-chlorophenyl ether, vinyl-α- in the case of vanadium tetrachloride and the like., converted naphthyl ethers, etc. Any mixture of these vinyl ethers 15 will be used.

can be polymerized in the same way. When carrying out the described reaction of titanium

The polymerization of vinyl ethers according to the invention or vanadium tetrachloride or another compound can be carried out in various ways. a metal of groups IVa or Va with an organo-The process can be carried out batchwise or continuously metallic compound prior to its use in and with or without the use of an inert organic 20 polymerization system, any organo-diluent can be carried out. Any inert metallic compound of an alkali or alkaline earth liquid organic diluent can be used for this metal, zinc or aluminum, z. B. aliphatic hydrocarbons. Examples of such organometallic compounds are such as hexane, heptane, etc .; cycloaliphatic carbon alkali alkyls or aryls such as butyllithium, amyl sodium, hydrogens such as cyclohexane; aromatic hydrocarbons, phenylsodium, etc., methylmagnesium, diethyls such as benzene, toluene, xylene, etc., or any mixture of magnesium, diethylzinc, butylmagnesium chloride, such hydrocarbons; halogenated hydrocarbon phenyl magnesium bromide, ethyl magnesium methylate, substances such as ethyl chloride, methyl chloride, methylene chloride, triethyl aluminum, tributyl aluminum, triisobutyl ethylene chloride, chlorobenzene; and aliphatic ethers, aluminum, trioctylaluminum, tridodecylaluminum, cycloaliphatic ethers, aromatic ethers and cyclic dimethylaluminum chloride, diethylaluminum bromide, ethers, e.g. The selection of the equimolecular mixture of the latter two used for the polymerization, known as temperatures and pressures, depends on the activity of the aluminum sesquichloride, dipropylaluminum fluoride, di ^ - used catalyst system, the used - isobutylaluminum fluoride, diisobutylaluminum chloride, thinners, etc. In general, the poly- 35 diethylaluminum hydride, ethylaluminum hydride, di-iso-freezing is carried out at room temperature or a little bit of butylaluminum hydride, ethylaluminum dimethylate, but any temperature between ethylaluminum diisopropylate, ethylaluminum di-tert-about -80 to about 150 ° C, and preferably between about -80 to about 150 ° C Butylate, isobutylaluminum dimethylate, isobutylalu-50 to about + 100 ° C can be used. Miniumdiisopropylat, Isobutylaluminium-di-tert-buty-While normal pressure or a pressure of only a few 40 lat, etc., and complexes of such organometallic Verkg is preferred, the polymerization can also in bonds, eg. Sodium aluminum tetraethyl, lithium over a wide range of pressures, e.g. B. from a partial vacuum aluminum tetraoctyl, sodium aluminum triethylchloride, up to about 70 kg / cm ² and especially from about normal etc. If the organometallic compound used pressure up to about 35 kg / cm ^{2 are} carried out. If it is more insoluble in the reaction mixture, it may be desirable to change the pressure, in general the course of the polymer, its particle size not being noticeable by grinding in a spherical cation. grind before the reaction to decrease. The Molarver-The polymerization of vinyl ethers according to the ratio of the organometallic compound to the titanium, invention is carried out by using a mixture of a compound of one in the reaction as a catalyst for the vanadium or other metal of group IVa or Va polymerization metal of groups IVa or Va of the periodic 50, but usually an amount of organo-system with an organometallic compound of a metallic compound which is the alkali or alkaline earth metal, zinc or aluminum - the desired degree of reduction evokes. Thus miniums is used. All compounds of one are greater proportions of organometallic compound metal of group IVa or Va, that is titanium, zirconium, dung to the transition metal compound for alkali alkyls hafnium, thor, vanadium, niobium or tantalum, can be required 55 than for trialkylaluminum compounds. Im used e.g. B. any inorganic salt, oxide or general, the reaction is made by mixing the organic salt, also complexes of the metal. Examples of transition metal compounds and the organometallic are the halides such as titanium tetrachloride, titanium tri-compound in an inert organic dilution chloride, titanium dichloride, vanadium dichloride, vanadium medium. The insoluble low trichloride, vanadium trifluoride, vanadium oxychloride and 60 shock that forms can be separated from the inert diluent, vanadium oxydichloride etc. or the oxides such as vanadium and then to the polymerization system alone dium trioxide, vanadium pentoxide etc. or organic or together with additional organoaluminum compounds such as Vanadium oxyacetylacetonate, alkyl bond can be added. This separation of the unvanadate, alkyl titanate etc. and the corresponding soluble reaction product from the diluent compounds of zirconium, hafnium, thor, niobium and 65 can be carried out by centrifuging, filtering etc. Tantalum. The reaction products can also be used. Sometimes it is desirable to wash out the insoluble reaction products, which are obtained by mixing a compound such as dukt with additional amounts of the diluent titanium tetrachloride or vanadium tetrachloride with one, in order to remove the soluble by-products completely organometallic alkali or alkaline earth compounds, especially if they are angry. On the other hand, the suspension of the reaction product generated can be obtained from other metals, zinc or aluminum.

5 6

tes directly in the polymerization system without refer to weight unless otherwise stated prior separation is used. That is responsive.
Product can be used immediately or by standing.

leave the reaction mixture at room temperature Example 1 and 2

for a few minutes to several hours or 5 In two polymerization vessels, from which the air It can be aged longer, or it may have been removed at an elevated temperature and replaced with nitrogen temperatures are heated. 30 parts each of n-heptane, 10 parts of vinyl methyl ether and

In the polymerization of vinyl ethers with the combination 0.40 part of triisobutylaluminum in 1.3 parts of n-heptane nation of a metal compound of group IVa or Vb. In Example 1, 0.16 parts of vanamite were then used an organometallic compound is used io diumtrichlorid added, which in 5 parts of n-heptane in usually the compound of Group IVa metal had been ball milled. To the poly- or Va in finely divided form. Such finely divided merization mixture in Example 2 was the suspension Form is obtained when the compound is added to the organo- an insoluble reaction product, which metallic compound prior to polymerization, such as by mixing 0.041 parts of triethylaluminum described above, is reduced. A finely divided form 15 with 0.19 parts of vanadium tetrachloride in 2.7 parts the compound of a metal of group IVa or Va, n-heptane, allowing this mixture to stand for 2 hours, for example Vanadium trichloride, vanadium oxide dichloride at room temperature, subsequent heating Ride, tantalum pentachloride, etc., are also obtained by recovering them at 90 ° C. for 16 hours. Grinding in the ball mill in the presence of an inert. The polymerization mixtures were stirred and Diluent. In this way, the compound 20 can be kept at 30 ° C. for 19 hours, after which the polymerization obtained in almost any desired particle size. by adding 4 parts of anhydrous ethanol

The organometallic compounds are preferred. The deposited insoluble polymer relatively non-acidic organoaluminum compound was spun off and mixed with 100 parts of a 50:50 like the aluminum trialkyls, which alone wash a vinyl mixture of methanol and ethanol. That do not polymerize methyl ether. 25 polymer was spun off again, with ethanol

The two catalyst components can be washed as desired and introduced into the polymerization system for 1 hour at room temperature in vacuo. Usually- dried. The polymer obtained in each case was then the organometallic compound and the solutions or suspensions in inert diluents by dissolving in boiling cyclohexanone, to which group IVa or Va metal compound had been added in the form of 0.2% phenyl - /? - naphthylamine cleaned, nitrated the still hot solution and added the polymer. One can both simultaneously or demand of a large excess of 0.2 ° / ₀ mere by the addition of one another, in portions or continuously during polymer ¹ - phenyl enforce / S-naphthylamine containing n-heptane again sation!. The amount of the two catalyst stocks - replenished. The polymer was nitrated and the vacuum part can be changed over a wide range, dried by 4 hours at 80 ° C, but in general the molar ratio of organic 35 a tendency to be highly adherent to glass within the range of about 0.1: 1 to about 20: 1. These polymers were and preferably were insoluble within the range of about 0.3: 1 in cold water (25 ° C), methanol and ethanol, and were about 10: 1. and strongly swellable in cyclohexanone and benzene. That after

It is often desirable that the reaction mixture obtained polymers had a reduced * Complexing agent for the specific viscosity of 1.11 used in the polymerization, determined on a solution To incorporate organometallic compound. Function in cyclohexanone at 135 ° C, and a melting point of the complexing agent is not fully clarified, but is from 150 ° C. The polymer according to Example 2 had a believed to prevent undesirable side reactions reduced specific viscosity of 0.83 in Cyclover, which is otherwise between the organometallic 45 hexanone at 135 ° C and a melting point of 120 ° C. Compound and the monomer or polymer instead- Both polymers were shown to be found by their X-ray powder can. All compounds that have a looser diagram than crystalline. You could after melting Complex (possibly acting as an electron donor) and partially cooled into films and fibers with the organometallic compound, which, when stretched in heat, can become solid films be used, e.g. B. ethers, tertiary amines, esters, 50 and fibers. Ketones, nitroaromatic substances, etc., such as diethyl ether,.

Tetrahydrofuran, triethylamine and ethyl acetate. Often example 3

it is appropriate to use the complexing agent as the larger example 1 was repeated with the modification that.

Component of the 21 parts diethyl ether used for the polymerization process instead of that in this example used inert organic diluents to turn the heptane into the polymerization vessel. were taken. The polymer was made by adding

Of course, the process can be modified to react with a large excess of diethyl ether. For example, it is sometimes desirable to add the ionic mixture after the reaction has been interrupted Add hydrogen to the polymerization system, thereby isolating the reaction mixture, washing it with water, the molecular weight of the polymer is regulated or the ether layer is separated, the ether is removed, and is wrestling. then 200 parts of water were added. The water-

The following examples illustrate the process of insoluble polymers that was collected, once again, invention. The molecular weight of the polymers produced in the examples, washed with water for 16 hours in vacuo in a room, is in each case dried by the reduced temperature, then the specific viscosity is given three times with methanol. The ψρ / c is then dried in vacuo under the name of washing and again 16 hours at room temperature for the »reduced specific viscosity«. It was further purified by understood, determined on a 0.1% solution (0.1 g dissolving in boiling benzene, filtering the still hot polymer to 100 ecm solution) of the polymer in solution, removing the benzene and finally drying cyclohexanone at 135 ° C or in benzene at 25 ° C, unless otherwise stated for the polymer for 22 hours at room temperature. All parts and percentages 70 in vacuum. By pouring out a hot benzene solution

of the polymer on glass and by heating the benzene a clearly tough film was obtained which adhered very strongly to the glass. The X-ray powder diagram indicated crystal structure.

Example 4

Example 2 was repeated except that 34 parts of tetrahydrofuran were used as the polymerization diluent were used in place of the heptane. At the end of the polymerization, the reaction mixture was used to remove the insoluble inorganic The fabrics were spun, these were washed with 150 parts of tetrahydrofuran and the tetrahydrofuran solutions then united and concentrated. Then 5 volumes of water were added, whereupon the polymer precipitated. The whole The mixture was distilled to remove the n-heptane which was added with the catalyst solutions had been; the insoluble polymer was then filtered off, washed with water and vacuumed for 16 hours

Product added, which was obtained by mixing 0.039 parts of triethylaluminum with 0.19 parts of titanium tetrachloride in 5.4 parts of n-heptane, allowing this mixture to stand at room temperature for 2 hours and then heating to 90 ^° C. for 16 hours. The polymerization mixture was stirred and ^{kept at 30 °} C. for 19 hours, after which the polymerization was interrupted by adding 4 parts of anhydrous ethanol. The reaction mixture

ίο was diluted with a further 120 parts of anhydrous ethanol, the deposited insoluble polymer was centrifuged, washed twice with anhydrous ethanol and then dried in vacuo at room temperature for 16 hours. The polymer thus obtained had determined a reduced specific viscosity of 0.31, in cyclohexanone at 135 ⁰ C. It was purified by dissolving in boiling benzene and filtering the benzene solution and freeze-dried to isolate the polymer, after which the polymer was washed three times with methanol and then

was clearly crystalline as seen from the powder X-ray diagram.

Example 8

dried at room temperature. The polymer was dried for 16 hours at room temperature and finally for 2 hours by dissolving in boiling benzene, filtering the ends at 80 ° C in a vacuum. The product is cleaned of customs and benzene removal by freeze-drying. After washing three times in methanol, the polymer was 4 hours at 8O ⁰ C in
Vacuum dried. The poly (vinylmethyl- 25
ether) had a reduced specific viscosity of

0.38 in cyclohexanone and was in cold water, 13 parts of n-heptane, 10.8 parts of vinyl methyl ether and methanol and benzene insoluble. According to the X-ray powder slide, it was 0.40 parts of triisobutylaluminum in 1.4 parts of n-heptane gram clearly crystalline and had a crystal loaded. After adjusting to 30 ° C, a suspension was

30 pension of 0.15 parts of titanium trichloride in 2.7 parts of n-heptane added, which had been ground in the ball mill for 6 hours. The polymerization mixture was stirred and kept at 30 ° C for 19 hours, after which the polymer was isolated as in Example 7 and purified with 10 parts of n-heptane, 12 parts of vinyl methyl ether and 35. The powder x-ray diagram was equal to -0.40 Parts of triisobutylaluminum in 1.3 parts of n-heptane if crystalline structure is evident. loaded. For Example 5, 0.36 parts of tantalum penta-. .

chloride, in the ball mill in 6.2 parts of n-heptane, for example y to Ib

grind, and for example 6 the polymerization mixture. In each of these examples, an air-free polymer

0.18 parts of vanadium pentoxide, in the ball mill in 40 sationsgefäß with 10.0 parts of the particular vinyl ether ", Grind 2.4 parts of n-heptane, added. The polymer 17.8 parts of n-heptane and 0.80 parts of triisobutylaluminum

melting point of 133 ⁰ C.

Example 5 and 6

Two polymerization vessels from which the air had been removed and replaced with nitrogen became

sation was interrupted after 18 hours at 30 ⁰ C by adding 1.6 parts of butanol. In each case, 150 parts of anhydrous ethanol was added to the polymerization mixture, the separated polymer was washed twice with anhydrous ethanol and dried. The polymer obtained according to Example 5 was extracted with boiling benzene and then with boiling xylene. That after the removal of the xylene

nium charged in 2.7 parts of n-heptane. After adjusting to 30 ⁰ C, the suspension of the insoluble reaction product was added, which was obtained by mixing 0.19 parts of vanadium tetrachloride with 0.04 parts of triethylaluminum in 2.7 parts of n-heptane, allowing this mixture to stand at room temperature for 2 hours and heating for 16 hours at 9O ⁰ C had been obtained, after which a small volume of n-heptane the Ge

Any remaining polymers were added again mixed in boiling benzene, and the insoluble in hydrocarbons was dissolved, the solution was nitrated and the benzene was separated off by the product. This was removed by freeze-drying with n-Heptaa. The polymer was washed twice with; one set after resuspending in methanol washed and 16 hours at room temperature, 2.7 parts of n-heptane and 0.40 parts of triisobutyl aluminum in 2 hours at 8O ⁰ C in vacuo. 10.9 parts of n-heptane were added and the mixture was allowed to stand for 5 minutes. It was clear from the X-ray powder diagram and was at room temperature. The polymerization mixture had a melting point of 115 ° C. The polymer was stirred and kept at 30 ° C. for 18 hours. Further of Example 6 was by treatment with 10 ° / ₀ methanolic hydrochloric acid and washing with methanol until
Cleaned neutral point, then dissolved in boiling benzene,
filtered off and the benzene removed by distillation, 60
after 4 hours at 8O ⁰ C was dried. The so
poly (vinyl methyl ether) obtained had the typical

Crystal diagram.

Example?

A polymerization vessel was after expelling the air with 10.3 parts of n-heptane, 10.8 parts of vinyl methyl ether and 0.40 parts of triisobutylaluminum in 1.4 parts of n-heptane. After setting to

Information on the vinyl ether polymerized according to each example and the isolation of the polymer produced consequences:

Example 9
Poly (vinyl ethyl ether)

A determination of the solids in an aliquot Teü of the viscous reaction mixture obtained when polymerizing vinyl ethyl ether showed that the Monomers was 100% polymerized and that the tough and rubbery polymer was relatively high Molecular weight and a reduced specific viscosity of 1.2 in benzene at 25 ° C. This polymer

30 ⁰ C, the suspension of the insoluble reaction mixture was 7c, 150 parts of anhydrous ethanol were added.

set; the insoluble polymer was separated off by spinning, washed twice with anhydrous ethanol and then, after the addition of 0.5%, based on the polymer, of a commercially available antioxidant, known under the trade name '»Santowhite« [4,4'-Thiobis- (6 -tert-butyl-m-cresol)], dried in anhydrous ethanol for 16 hours in vacuo at room temperature. Inorganic constituents were removed by treating with 10% hydrochloric acid in methanol at room temperature for 2 hours, after which the polymer was washed again with anhydrous methanol and dried. Purple, film-like, solid substance, clearly crystalline according to the X-ray powder diagram. He was further purified by dissolving in boiling benzene, filtering the still hot benzene solution and washed after ¹ S removal of the benzene by distillation into methanol and dried again. The purified polymer thus obtained was a white film-like solid. This poly (vinyl ethyl ether) was insoluble in cold water, methanol and ethanol and partly soluble in boiling benzene.

Example 10
Poly (vinyl methyl ether)

A determination of the solids in the recovered with vinyl methyl ether the reaction mixture showed 100 ° / ₀ by weight conversion into polymer. Following the procedure of Example 9, this was isolated and purified. The poly (vinyl methyl ether) obtained in this way, insoluble in methanol and ethanol, had the X-ray powder diagram typical for crystal structure and had a reduced specific viscosity of 3.5, determined in cyclohexanone at 135 ° C.

Example 11
Poly (vinyl n-butyl ether)

35

A 100 ° / ₀ by weight conversion into polymer was obtained butylether vinyl n-with. The polymerization was stopped by adding 4 parts of anhydrous ethanol, after which the reaction mixture with n-heptane thoroughly at 3 ° / ₀ methanolic hydrochloric acid, then neutral with water, then neutralized with 5 ° / _o aqueous sodium hydroxide and again with water was washed. The polymer was precipitated by pouring the washed reaction mixture into a large excess of anhydrous ethanol containing 0.2% of an antioxidant, collected and dried to constant weight. The conversion was 75%. This poly (vinyl-n-butyl ether) was a very tough rubbery polymer having a reduced specific viscosity of 1.2 in cyclohexanone at 13O ⁰ C and 3.0 in benzene at 25 ° C.

Example 12
Poly (vinyl isobutyl ether).,

95% conversion to polymer was obtained with vinyl isobutyl ether. The polymerization was interrupted and the reaction mixture was washed as in Example 11 with methanolic hydrochloric acid and water. The polymer produced in this case, insoluble in n-heptane, was separated off and washed with n-heptane and anhydrous ethanol containing 0.5% antioxidant, based on the polymer. After drying, the poly (vinyl isobutyl ether) was a white, tough, stretchable solid which was found to be highly crystalline when examined by X-rays. It was insoluble in n-heptane and benzene at room temperature and had a reduced specific viscosity of 1.3 in cyclohexanone at 135 ° C. A sample obtained after further purification by dissolving in boiling xylene, filtering the solution and reprecipitation in methanol, washed and drying gave the theoretical content of carbon and hydrogen in the analysis. The heptane soluble fraction of poly (vinyl isobutyl ether) was isolated by concentrating the heptane filtrate and washings and then precipitating in anhydrous 0.1% antioxidant ethanol. After collection and drying, a tough, gel-like, rubber-like solid substance with a reduced specific viscosity of 1.1 in cyclohexanone at 135 ^° C. was obtained.

Example 13
Poly (vinyl stearyl ether)

100% conversion was obtained with vinyl stearyl ether. The poly (vinyl stearyl ether) insoluble in n-heptane and the n-heptane soluble poly (vinyl stearyl ether) were isolated according to the procedure of Example 12. The heptane-insoluble polymer was a hard solid having an X-ray powder diagram similar to that of a crystalline straight chain hydrocarbon. The heptane-soluble polymer was a hard, waxy, opaque solid with a reduced specific viscosity of 0.5 in benzene at 25 ^° C.

Example 14
Poly (vinyl tertiary butyl ether)

A conversion of 88% was obtained with vinyl tert-butyl ether. The reaction mixture was washed with methanolic hydrochloric acid and water as described in Example 11, with 5% strength aqueous sodium hydroxide and again with water, after which the polymer which was insoluble in n-heptane was isolated as described in Example 11. The poly (vinyl tert-butyl ether) thus obtained was a white powdery solid, insoluble in n-heptane, benzene and cyclohexanone at room temperature, but soluble in boiling cyclohexanone. The X-ray examination showed it to be highly crystalline and had a melting point of more than 238 ^° C. The analysis showed theoretical carbon and hydrogen content. Reduced specific viscosity of 0.2, determined on a 0.04% solution in cyclohexanone at 135 ° C.

Example 15
Poly (vinyl isoborny lather)

A 62% conversion was obtained with vinyl isobornyl ether. Treatment of the reaction mixture and the isolation of the polymer soluble and insoluble in n-heptane was carried out according to the procedure of the example 12. The poly (vinyl isobornyl ether), which was insoluble in n-heptane, was crystalline according to X-ray examination. This in Heptane soluble polymers was a white powder with a reduced specific viscosity of 0.02 in benzene at 25 ° C.

Example 16
Poly (vinyl-a-terpinyl ether)

A 62% conversion to polymer was obtained with vinyl a-terpinyl ether. Both one insoluble in heptane such as a poly (vinyl-a-terpinyl ether) soluble in heptane were obtained when the reaction mixture according to Example 12 treated and the polymers isolated.

Example 17

Vinyl benzyl ether was polymerized by following the procedure of Examples 9 to 16 except that Toluene was used as the diluent, which was added to the polymerization vessel in place of n-heptane was given. Determination of solids in the reaction mixture after 18 hours indicated conversion

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of 95%. Both one soluble in toluene and one insoluble Poly (vinylbenzyl ether) were obtained when the reaction mixture was treated according to Example 12 and the polymers were isolated.

5 Examples 18 and 19

The polymerization procedure used in these examples to polymerize vinyl n-propyl ether in Example 18 and vinyl isopropyl ether in Example 19 was the same as that of Examples 9-16 except that 21.8 parts of n-heptane were used instead of 17.8 Parts were added to the polymerization vessel and 0.58 parts of monoisobutyl aluminum dimethylate in 5.4 parts of n-heptane were used in place of 0.80 parts of triisobutyl aluminum in 2.7 parts of heptane according to these examples. After 17 hours at 30 ⁰ C, the total content of solids showed a conversion of 97% and 92% of the Vinylpropyläthers to the Vinylisopropyläthers in polymer. The polymerization was terminated and the polymers insoluble in heptane were isolated and dried by distilling off the heptane from the filtrate after adding 0.5% antioxidant, based on the polymer. The poly (vinyl n-propyl ether) soluble in heptane had a reduced specific viscosity of 1.3 in benzene at 25 ° C and the poly (vinyl isopropyl ether) soluble in heptane had a viscosity of 0.2 in benzene at 25 ° C The poly (vinyl isopropyl ether), which was insoluble in heptane, was a highly crystalline polymer, as the X-ray powder diagram indicated, and had a reduced viscosity of 0.6, determined on a 0.05% strength solution in cyclohexanone at 135 ° C. and a melting point of 191 ⁰ c.

The new crystalline produced according to the invention Poly (vinyl methyl and ethyl ether) are unlike the previously known poly (vinyl methyl and ethyl ethers) insoluble in cold water and in methanol. Hence, they can be used for many purposes, for which the previously known products are unsuitable. As can be seen from the above examples, poly (vinyl methyl ether) has a relatively high crystal melting point and can be deformed into threads and films which result in tough films and threads when stretched. The new poly (vinyl ethyl ether) is also an excellent one fihn-forming plastic. The films can be oriented uniaxially and biaxially by stretching. These polymers are also useful for making tough plastic articles. For many purposes It is desirable to add antioxidants, pigments, fillers, plasticizers, etc. to the polymers prior to manufacture to incorporate. ■

As can be seen from the preceding examples, the process of the invention enables recovery new crystalline poly (vinyl ether). It also enables the production of high molecular weight amorphous poly

Claims (12)

PATENT CLAIM: 1. A process for the production of poly (vinyl ethers), characterized in that a vinyl ether is brought together with a catalyst, which by mixing a compound of a Metal of group IVa or Va of the periodic table with an organometallic compound an alkali or alkaline earth metal, zinc or aluminum. 2. The method according to claim 1, characterized in that the vinyl ether is a vinyl alkyl ether. 3. The method according to claim 1, characterized in that the vinyl ether is a vinyl cycloalkyl ether is. 4. The method according to claim 1, characterized in that the vinyl ether is a vinyl aralkyl ether. 5. A method for producing a poly (vinyl ether) according to claim 1, characterized in that that a vinyl ether is brought into contact with a catalyst which is obtained by mixing a compound a metal of group Va of the periodic table with an organometallic compound of an alkali or alkaline earth metal, zinc or aluminum, and thus produced Product with an organometallic compound of an alkali or alkaline earth metal, of zinc or of Aluminum is brought together. 6. The method according to any one of the preceding claims, characterized in that the metal of Group Va is vanadium. 7. The method according to claim 5 or 6, characterized in that the vinyl ether is vinyl methyl ether is. 8. The method according to claim 5 or 6, characterized in that the vinyl ether is vinyl tert-butyl ether is. 9. The method according to any one of the preceding claims, characterized in that it is in the presence a complexing agent for the organometallic compound is carried out. 10. The method according to claim 9, characterized in that the complexing agent diethyl ether, tetrahydrofuran, Is triethylamine or ethyl acetate. 11. The method according to any one of the preceding claims, characterized in that it is in the presence an inert liquid organic diluent is carried out. 12. The method according to any one of the preceding claims, characterized in that hydrogen for Regulation of the molecular weight of the polymer formed is added. Considered publications: German Patent Nos. 634 295, 837 928, 846 794 (vinyl ether) at normal temperatures. An an- 55 (especially paragraph 1), 854 705, 906 517, 907 462; whose advantage of the method of this invention is British Patent No. 378,544; in that, in addition to the usual amorphous polymers, Swiss Patent No. 263,984 (see Example 4); and the new crystalline polymers include poly (vinyl U.S. Patent No. 2,231,231; can be produced ether, which in its properties Industrial and Engineering Chemistry, Vol. 41, No. 9, lie between rubbers and plastics. 60 pp. 1998 to 2004 (1949). ® 809 559/442 6.58