DE2355320A1 - Non crosslinked unsatd. ethylene vinyl acetate copolymers - prepd. by deacetylation of EVA copolymers - Google Patents

Abstract

High mol. wt. non-crosslinked unsatd. ethylene/vinylacetate(EVA) copolymers or unsatd. polyethylenes are formed by (partial) deacetylation of EVA copolymers or mixts. of EVA copolymers of different vinylacetate content and removing the acetic acid formed immediately after its formation, the deacetylation being effected with continuous stirring of the reactn. mixt. under a permanent vacuum of >=50 torr. The copolymers obtd. are also claimed, contg. a random distribution of double bonds, the latter amountingto is not >10 mole % and the acetate gp. amounting to 0.32.3 mole-%.

Description

Unsaturated E / VA copolymers and unsaturated polyolefins and processes for their preparation by partial or exhaustive deacetylation of Ε / VA-Misehpolynierisaten

E / VA copolymers are copolymers of ethylene and vinyl acetate with statistical distribution of units of vinyl acetate via the polymer chain.

These copolymers are used, for example, as cable insulation compounds, as Hotmelts or in the form of foils, versatile use.

A salient feature is their good thermal stability. For many E / VA copolymers Vererbeitungstemperaturen be specified up to 240 ⁰ C, without giving rise to Zereetzungserscheinungen.

The elimination of acetic acid, e.g. from foils, would also be extremely undesirable as this would damage the packaging and the packaged items Good leads.

On the other hand, a targeted would be partial or exhaustive

509819/093 8

Cleavage of acetic acid from the unshaped polymeric drilling material with the formation of C-C double bonds of great interest because as a result, novel unsaturated E / VA copolymers or Unsaturated polyolefins would be accessible, the starting products for a number of new products or syntheses could.

■ In the following, ^w deacetylation ^{H is} the elimination of acetic acid from the yinylacetate building block - CH ₂ -

-. AZ

of the E / VA copolymers with the formation of a C ^ atom, outgoing double bond, 'without secondary reactions such as oxidation, uptake of an acid residue or white ter atoms or groups of atoms, molecular cleavage or transformation of the macromolecule.

The elimination of acetic acid from E / VA copolymers for the purpose of analytical recording of the E / VA copolymers Polymerized yinylacetate is known. For example, acetic acid was split off by pyrolysis from E / VA copolymers for the analytical determination of the bound vinyl acetate by D. Braun, Mitteilungen the German Plastics Institute, Darmstadt, No. 12, page 3 (1972). This leaves decomposed or highly crosslinked residues.

509819/0938

RC Schulz and co-workers describe an analytical method for the quantitative determination of vinyl acetate in E / VA copolymers by treating these copolymers with an approx. 30-fold excess of molten toluenesulfonic acid at. 16O ⁰ O (Die, Angewandte Makromolekulare Chemie 2 £ (1972) '171-175). Here, too, are the heavily discolored residues

unusable.

In contrast, our own experiments showed that ^undestroyed] - and uncrosslinked macromolecules can be obtained by ^: under certain conditions the de-acetylation in the form of a polymer-analogous conversion without changing the macromolecular structure to unsaturated E / VA copolymers with the formation of double bonds or even can lead to unsaturated, acetate-free polyolefins.

To 300 ⁰ C, a partial deacetylation takes with not very high speed with the formation of double bonds in addition to remaining acetate groups. In the range of

t *

300 to 35O ⁰ C is a rapid partial or complete ι deacetylation without substantial degradation of the macromolecules on.

Above 35O ⁰ C the deaoetylation proceeds faster, but in addition to the acetic acid elimination, conversions can also occur

Macromolecule occur. ·

So is between 350 ° and 400 ⁰ C in addition to the deacetylation a growing integration of the pyrolysis residue. Above 400 ⁰ C occurs a strong destruction of the macromolecules .by. Chain scission a, the average molecular weights

509819/0938

sink sharply and the deacetylated products are brittle and smelly.

The aim of the desired deacetylation, however, is the degree of polymerization of the starting E / VA copolymers and to make changes to the macromolecule exclusively by splitting acetic acid with the formation of double bonds.

Surprisingly, it has now been found that a targeted partial or exhaustive deacetylation of E / VA mixed polymers to unsaturated, high molecular weight and completely or essentially uncrosslinked E / VA copolymers or unsaturated polyolefins is possible in a simple way without the disadvantages mentioned if the cleavage is carried out of the acetic acid catalyzed by compounds having electron holes such as Lewis acids or protonic acids low concentration _r that damage of the products and equipment is excluded.

The invention therefore relates to a process for the production of unsaturated, high molecular weight and uncrosslinked E / VA copolymers or unsaturated polyolefins by partial or exhaustive deacetylation of E / VA copolymers or mixtures of E / YA copolymers of different vinyl acetate content, which is characterized in durchfuhrt that the deacetylation in the presence of a catalyst 'of the Lewis acid type or the proton acid-type "at temperatures of 120-370 ⁰ C.

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It has also been found that it is advantageous to use reaction vessels metal corrosion from released vinegar

i -

■ can exclude acid if you look at its concentration in the Re-, . Action space by evaporation under reduced pressure always

I keep low.

ι According to the invention can -E / VA copolymers with vinyl

j acetate contents of 0.5 to 60 wt .- #, preferably 0.5 to 50

ι Gew .- $, partially or exhaustively deacetylated.

Mixtures of E / VA mixed polymers with different vinyl acetate contents can also be partially or fully deacetylated according to the invention. ■ '

The double bond-containing E / VA copolymers or the unsaturated polyolefins are easily accessible according to the invention if Lewis acids such as aluminum chloride, aluminum bromide, cadmium chloride, beryllium chloride, palladium chloride, gallium trichloride, titanium IV chloride, titanium are used as deacetylation catalysts IV-broaid, zirconium-IV-chloride, zixm-II-chloride, tin-II-bromide, tin-II-iodide, tin-IV-chloride, tin-IV-bromide, antimony-V-chloride, iron-III- chloride, iron (III) bromide, zinc chloride, zinc fluoride, zinc bromide, zinc iodide or uranyl chloride, or, for example, protic acids such as o { -aphthalenesulfonic acid, ß-naphthalenesulfonic acid, o- or p- or m-toluenesulfonic acid, pyrophosphoric acid, meta-phosphoric acid, sulfuric acid, 1 , 3-naphthalenesulfonic acid or 1,7-Naplftlialindisaifon-

509819/0938

acid used. Combinations of two or more of the deacetylation catalysts mentioned, both of the Lewis acid type and of the protic acid type, as well as mixtures of the two types with one another, are possible.

It is not fully understood what kind of effective deacetylation catalysts are, however both are

Lewis acids like protic acid electron acceptors.

A further condition is that the catalyst is at the reaction temperature has little or no volatility. As far as protic acids can have an oxidizing effect at the same time these compounds are not used or only used in low concentrations.

Partial or exhaustive deacetylation is particularly easy, when using zinc chloride as a catalyst. Zinc chloride is highly hygroscopic, but it means Ingress of moisture e.g. from the atmosphere or through Intentional addition of water in amounts up to 4 moles per mole of zinc chloride does not impair the catalytic effectiveness.

The catalysts are available in quantities of 0.01-10% by weight used on the initial quantity of E / VA copolymers.

The partial or exhaustive deacetylation of the EVA copolymers is carried out in the temperature range of 120 ° to 37o C ^0.

509819/0938

Temperatures are preferably between 160 and 35O ⁰ C. increases with increasing temperature with the same starting materials and

: Dwell times the degree of deacetylation. From around 290 ⁰ O, especially. moreover, from 305 ⁰ G, complete deacetylation occurs.

; In the range from about 350 to 370 ⁰ C, to a lesser extent, a _; . Cross-linking occur, which, however, the thermoplastic

'· Not yet affected.

; The melt temperature is decisive for the temperature, hence the

'Temperature of the reaction mixture.

The residence time at the reaction site can be between 20 seconds and

; 2 hours, but need not exceed 1 to 5 minutes with good mixing.

The deacetylation must be carried out in order to avoid undesired oxidation processes take place on the C-C double bonds formed in the absence of atmospheric oxygen.

It is therefore advisable to use a protective gas .; _; during the deacetylation process. Any inert gas can serve as protective gas. Carbon dioxide or nitrogen, optionally also argon or helium, are preferably used. E / VA mixed polymer can be combined with the catalyst by mixing in a mixer, for example a Hensehe mixer or a Papenmeier stirrer. The catalyst can be used both in solid and in liquid form, the E / VA mixed polymer in the form of granules or powder. According to this process, the catalyst is predominantly on the surface of the E / VA mixed polymer granulate or "powder"

S09813 / 0938

distributed.

During the mixing process, the temperature in the mixer is the same to adapt the respective E / VA copolymers and "is usually -30 to 150 ° CE / YA copolymers with a higher When the mixer is stirred vigorously, the vinyl acetate content tends to stick to it due to the heating, which affects the mixing process and in particular the uniform distribution of the catalyst "impaired, so that sufficient heat dissipation by cooling the mixing container must be taken care of. However, the catalyst can also be rolled in on a heated one Roller frame or by kneading in a heated kneader into the E / VA copolymers. Thorough mixing of E / VA copolymer and catalyst is achieved when the two components are mixed in a heated extruder. This procedure is especially for continuous mixing is suitable. According to the methods of rolling in, kneading or mixing E / VA mixed polymer and catalyst in the extruder mix the starting substance and catalyst, the catalyst being particularly finely dispersed in the E / VA copolymer.

The E / VA copolymers in the form of granules or powder can also be impregnated with a catalyst solution. It is advantageous to choose solvents or solvent mixtures which dissolve the catalyst well and easily are taken up by the E / VA copolymers, as is the case with both

509819/0938

- 9 for example ethyl acetate, benzene, toluene, etc.

The solvent or mixtures of solvents become appropriate before the deacetylation process, if necessary by evaporation under reduced pressure, removed, especially if they are larger Amount were applied. Remaining in the copolymer Residues of the solvent, on the other hand, do not interfere with the deacetylation.

Likewise, the E / VA copolymer and the catalyst can be dissolved together in a suitable solvent or solvent mixture, or the solutions of both substances can be combined. Suitable solvents for the polymer are, for example, gasoline, aromatics, especially benzene, toluene or xylene, and chlorinated aliphatics, especially those with 1 and 2 carbon atoms. Evaporation of solvents is advantageously carried out Sm vacuum. -., ...... ........

It is also possible to emulsion or emulsion into the existing solution directly or during the production of the E / VA copolymer To add the catalyst suspension of the polymer, so that in the usual preparation of the polymer by precipitation, Drying etc. an already the deacetylation catalyst in finely divided Porm containing E / VA mixed polymer is obtained »

The introduction of the catalyst in dissolved form into the solid E / VA mixed polymer or the mixing of catalyst and polymer solution leads to a predominantly molecular distribution of the catalyst in the E / VA copolymer.

50981970338.

It is possible to combine the 3 E / VA mixed polymer with the deacetylation catalyst and deacetylation clocks run separately from each other.

It is also possible to combine the E / VA mixed polymer to be carried out with the deacetylation catalyst in the apparatus provided for deacetylation with mixing, where the temperature can be lower than that of the deacetylation, or even temperatures, vacuum etc. such as exist in deacetylation. It is advantageous to mix in continuously deacetylating directly before deacetylation Apparatus, such as heated mixing screws, screw conveyors or preferably one in the first chambers equipped with several chambers vacuum extruder, in which the polymer with Öer or the screws arranged therein under Kneading is conveyed into one of the subsequent vacuum chambers heated to a higher temperature, where the deacetylation is carried out he follows.

The deacetylation can be carried out in any suitable reaction vessel, cylindrical or concave, which allows the exclusion of atmospheric oxygen, with a descending distillation tube with a condenser and possibly with a stirrer and a Connection for alternate application of a vacuum or inert gas flow is provided, and the supply of the catalyst skin E / VA mixed polymer as well as the removal of the deacetylated product allowed to be carried out. pre-condition is that the reactor used consists at least on the inside of a material that is released by the acetic acid

509819/0938

or the catalyst is not attacked, 25.B. Glass or enamelled metal, or that in the case of the use of metals as reactor material for a removal of the released Acetic acid is taken care of immediately after its formation.

The Entaeetylierung can at pressures between about 0.2 Torr and Normal pressure can be carried out.

The acetic acid which has been split off is preferably removed from the reaction space by applying a vacuum.

The reactor vessel can, for example, from the cylindrical There are glass flasks with a gas inlet tube and a Claisen attachment for distilling off the acetic acid released is provided. A metal or oil bath, for example, can be used to heat the flask.

The reaction vessel can, for example, also be a heated stirred autoclave with a wall-mounted stirrer and a connection is equipped for alternate supply of an inert gas and application of vacuum.

The applied vacuum ^ which can be generated by a water jet or oil pump and the constant movement of the reaction mass, the released acetic acid can easily be removed from the reaction space, so that corrosion of the inside of the autoclave is avoided.
The use of an autoclave is also advantageous

Bottom drain, as the removal of the deacetylated, mostly viscous Product by applying a slight overpressure

509819/0938

- 12 is easily possible through the bottom opening.

Deacetylation in a vacuum extruder is particularly advantageous made, since then the deacetylation process can be carried out continuously. The partial or exhaustive Deacetylated E / YA copolymer can after exit immediately passed through a cooling bath from the vacuum extruder and then granulated.

Continuous deacetylation is particularly advantageous .in multi-screw vacuum extruders, which have several kneading and conveyor zones, for example, with several kneading disks arranged one behind the other and intermeshing screws and furthermore have several temperature zones that can be heated to different temperatures and several independent vacuum zones. By When using vacuum extruders, the choice of the attached spray head can be made directly after the deacetylation Deformation to the finished shaped body take place, a deacetylation temperature is particularly suitable heated vacuum extruder with two separate dosing devices e.g. dosing scales, one each for the E / VA mixed polymer and the catalyst.

The desired degree of deacetylation of E / VA copolymers can be set through the use of catalysts or catalyst mixtures with different cleavage activity . ·

509819/0938

Furthermore, the degree of deacetylation can be determined by the catalyst concentration, the residence time or the melt temperature at the site of the deacetylation "can be influenced.

Increasing at least one of the aforementioned parameters "means Increase in the degree of deacetylation, while lowering it, lowering the degree of deacetylation.

The degree of deacetylation is the quotient of the amount of acetic acid obtained from a deacetylated E / VA copolymer was split off with a certain yinylacetate content, and that originally present in the E / VA copolymer Total amount of acetic acid understood. With a $ 100 spin-off for acetic acid, the quotient reaches the value 1; if the cleavage does not take place, it has the value 0.

Catalysts with low cleavage activity are ζ.Β.ϊ meta-phosphoric acid, Aluminum tribromide, cadmium chloride, beryllium chloride, uranyl chloride, gallium trichloride and palladium chloride.

Catalysts with medium splitting activity are e.g .: iron (III) chloride, Titanium-lY-chloride, titanium-IY-bromide, aluminum trichloride, Zirconium IV chloride and orthophosphoric acid. Catalysts with higher splitting activity are, for example: tin-IY-chloride, Tin-IY-bromide, mono- and disulphonic acids of naphthalene as well as o- or m- or p-toluenesulfonic acids. Catalysts with an extremely high splitting activity are zinc chloride and zinc bromide,

509819/0938

The degree of deacetylation depends on the amount of cleaved Acetic acid is related to the amount of double bonds formed, since per mole of acetic acid split off exactly or almost exactly one mole of double bonds - measurable by means of the iodine number - arises.

The maximum achievable double bond content in partially or completely deacetylated E / VA copolymers is therefore due to the vinyl acetate content in the starting E / VA copolymer fixed and limited.

The generation of a certain degree of deacetylation of E / VA copolymers by the selection of catalysts with different cleavage activity, the catalyst concentration, the residence time and the melt temperature at the location of the deacetylation as well as the setting of the maximum achievable double bond content via the vinyl acetate content of the starting E / VA copolymer also the subject of the present invention. ·

The content of the double bonds formed was determined using a modified iodine number determination according to Kaufmann. The partially or exhaustively deacetylated samples were dissolved at 6O ⁰ C in hot chlorobenzene and treated with a methanolic set bromine / NaBr solution in excess. Unused bromine was reduced by a KI solution and determined by titration of the released iodine with thiosulphate.

509819/0938

235532 (3

The iodine number is the amount of iodine, expressed in grams, per 100 g of the partially or fully deacetylated E / VA copolymers was consumed.

The acetic acid split off was detected by titration with n / 10 NaOH if the deacetylation took place under normal pressure. In the case of deacetylation in vacuo, the acetic acid split off was determined indirectly via the residual acetate content in the deacetylated product by thermogravimetric analysis. Final temperature: 420 ⁰ C at a heating rate of 8 ° C / min.

Average degrees of polymerization P ^ of the partially or exhaustively deacetylated E / VA copolymers were calculated from the molecular weights determined (number average M), taking into account the residual acetate content and the vinyl units formed. The molecular weight determinations were made in one. Membrane osmometer (Mechrolab) at 85 ⁰ C in o-dichlorobenzene as a solvent.

The invention also relates to unsaturated E / VA copolymers or unsaturated polyethylenes with a statistical distribution of the double bonds and acetate contents from 0 to 59.5 wt. #.

These substances belong to a new class of polymers and surprisingly have exclusively or predominantly double bonds as trans-vinylene double bonds. In the IR spectrogram, the double bond is shown as a chain-related tranä bond "HC, -'CH as a deformation oscillation 8 at ·

\ ·, CH

509819/0 938

965 cm "clearly recognizable, further with the partially acetylated products the stretching vibration V _rt __ of the acetate group at 1745 cm"", while both the vibration cfmr of ^the cis double

binding at 720 om "" ¹ as well as the oscillation cf _CH ■ the vinyl

group at 905 cm "" are missing.

f _CH ■

The new polymers are accordingly polymers which, corresponding to the building blocks of the E / VA copolymers from which they were formed, only have the ethylene group and the vinylene group as building blocks, and in the case of the partially acetylated products, those which are linked to them from the chain Acetate residue. The degree of polymerization is surprisingly the completely or almost completely changed degree of polymerization of the E / VA starting material. Since elastomeric or tough-elastic E / VA copolymers are preferably used as a starting point, the products predominantly have their degree of polymerization, which is approximately in the range of P _n = 200 to 2000, preferably between 500 and 1500.

However, there are also E / VA copolymers with less or less higher P deacetylable.

In the same way, the acetate content of the E / VA starting materials reduced by the degree of deacetylation is possible as the acetate content of the products. Since especially 3.0 to 50 parts by weight J ^ are common in the starting material Acetatgehalte from 0.5 to 60, Acetatgehalte are the product up to 59 "5 _f especially to 49.5 possible. Starting materials with molar ratio genes of ethylene to vinyl

509819/0938

acetate of 1: 1 with acetate contents "to about 75 wt .- $, which tdsher because of its tacky consistency found little acceptance in industry, but may also to products with MS 50 moles i> double bonds, optionally together with acetate contents reacted v / ground . exceeding the value of 50 mol $ double bonds it seems-but _we gen of occurring content of conjugated double bonds or even accumulated only for special purposes sense.

Iodine numbers of the products are from 2 to 120, preferably from 3 to 105 hence the usual, although these iodine numbers have also been exceeded can be.

In general, it is not necessary to remove residues of the catalysts from the products before processing. Processing can be carried out on apparatus customary for thermoplastic polymers according to customary recipes, for example under Addition of fillers, heat and UV stabilizers, etc. to moldings and foils.

The moldings produced can particularly expediently over- ' used wherever "environmentally friendly" as waste Plastics that are easily degradable by natural means should be sought, since the double bond content, especially if they are neglected or specifically used UV stabilization, enable degradation by natural UV radiation.

509819/0938

Example 1 A:;

60 kg Elvax 46O granules (E / VA mixed polymer from the company
Dupont, with a vinyl acetate content of 18.5 wt determined i>) were added in portions of 15 kg with 37.5 g of anhydrous zinc chloride in a 35 1 - mixer (Papenmeier-; mixed at 720 rpm mixer). The mixing time "was 15 minutes. The coolant temperature in the cooling jacket of the mixer was measured by a connected cooling unit (Hokostat, cooling ]

medium methanol) maintained at 5 to 10 ⁰ C. |

After the mixing process, the zinc chloride was firmly adhered to the

Distributed surface of the granules. j

For storage, the mix was wrapped in polyethylene film

filled sacks. '!

Example 2 A: i

120 kg Lupolen V 2524 EX (E / VA mixed polymer from the company
BASi ¹ , with a determined vinyl acetate content of 2.5 wt .- ^) were in portions of 12 kg each with 120 g of anhydrous
Zinc chloride mixed with the mixer described under Example 1 at 1445 rpm. The mixing time was 5 minutes. The coolant was kept at 20 ^° C.

After being removed from the mixer, the material to be mixed was ready for further processing as described under Example 1, stored.

509819/0933

Example 3. A:

-100 kg Alkathene YJP 502 granules (E / VA mixed polymer of 3? Irma IGI, with a determined vinyl acetate content of 8.5 wt Zinc chloride and 6.6 ecm of distilled water in the un-

.1

ter Example 1 "mixed mixer described. The cooling jacket of the mixer was ^{heated with 45 0} C warm water". The mixed:

Duration "was 10 minutes, the mix was his for _resale.:. processing in open Polyäthylenhehältern stored.

Example 1 B to 3 B:

The Ahmisehungen of E / VA mixed polymer with zinc chloride after Examples 1A to 3A were passed successively through a heated vacuum extruder for deacetylation. i For this purpose, a vacuum twin-screw extruder of the type already described was used, which acts as a twin-screw kneading disk screw press is designated (type ZSK 53/14 variable from Pirma Werner and Pfleiderer, Stuttgart) and on one Length of approx. 2.5 meters, several kneading and conveying zones, as well seven temperature zones Z ^ to Z «and the three, partly again subdivided vacuum zones VA-j to VA.

The speed is in the range of. 36 to 300 rpm variable.

509819/0938

The extruder used could operate at a vacuum of approx. 25 Torr (water ring pump) as well as 0.5 - 2.0 Torr (water vapor jet pump) can be operated. The outlet nozzles consisted of Teflon-coated 4 mm round openings. - - ■ The extruder was preceded by an electronically controlled weigh feeder ", via which the material throughput in the extruder (k" g / h) i was regulated. '

The extruder filler neck and the area of the outlet nozzles were gassed with carbon dioxide during operation. The extrudate was immediately after leaving the outlet nozzles over ■ Rolls led through a cooling trough with cold water. ί

finally crushed in a chopper and put into polyethylene-lined paper under a carbon dioxide atmosphere; sacks filled. j

Tables 1 to 3 show the temperatures of the individual

Zones the throughput and the residence times for the substances ^! of Examples 1 to 3 and the partial or exhaustive deacetylation achieved using the respective degree of deacetylation and the iodine number are shown. In addition, the degrees of polymerization and crystalline melting points of the resulting product are listed. ■

The following abbreviations are used in the tables:

T .. to Tr, - inner wall temperatures in ⁰ C in the tempera door—

■ Zones 1 "to 7 of the twin screw extruder, whereby 509819/0938

- 21 - ■ · ■■ - ■■

T ₁ indicates the temperature in zone 1, T ₂ the temperature in zone 2 and so on.

- _M = melt temperature, measured with a hook probe in zone 6.

VA = vacuum in Torr specifying the lowest to highest values in vacuum ports 1 to 3

ITpM = revolutions of the twin screw per minute DS =. Throughput in kg / h

VZ = dwell time in minutes from the entry of the product into the filler neck of the extruder to the exit from the extruder nozzles.

E = degree of de-acetylation

■ ■ ". ■ 'j

JZ = iodine number according to Kaufmann!

= 'mean degree of polymerisation (membrane osmometer) K ( ⁰ C). = Crystallite melting point (differential thermal analysis). In ⁰ O.

509 8 1 9/09 3-8

Ia part 1
Mixture from example 1

cn ο

OO

co CD

^T 1 φ H rn
A ₁ ^T 5 ^T 6 ^T 7 162 VA -
t. ! Torr ——: - > Rpm DS
kg / h VZ
min E. JZ P. K
( ⁰ C) 1 a 105 130 140 160 165 155 130 201 0.7 to 0.9 115 15.2 3.4 0.10 7th 890 92 1 b " 105 170 190 200 205 190. 180 229 Il It It H Il dd 0.27 15th η η 1 c 105 220 225 230 235 220 215 241 0.7 »« 2.0 dd It dd 0.39 23 dd 93 1 d 110 230 250 250 250 230 220 260 0.7 "1.2 ti » Il 0.44 25th 900 η • 1 e 115 240 255 260 265 255 215 279 ft it tt , 11 It 11 0.52 30th It 94 1 f 115- 250 270 I 285 280 270 215 305 0.9 »1.5 dd It η 0.60 35 890 95 1 g .115 290 295 305 300 285 215 330 1.2 »1.5 ti ! 14.9 η 0.72 ' 42 920 96 1 h 115 318 322 323 320 310 222 1.0 «1.5 ! "
i ! Η
I. ti 1.00 63 dd 102

0.01 <1,935 92

ro ro

Comparative example Elvax 460 without deacetylation catalyst:
MV _t 115 250 268 280 285 268 217 278 1 to 1.5 "η η

The measured value of the degree of polymerization is somewhat dependent on the particular membrane of the osmometer used dependent, so that only the values of the substances of the same example are completely comparable with one another are.

Ta V e 1 1 e

, » T ₂ ¹ y * 4 V
ο « * 6 I ₇ ¹ M. **, σ 120 253 245 . 245 235 230 220 250 Ί20 250 260 270 270 250 220 274 120 250 290 295 290 270 220 301 125. 270 312 325 310 290 220 323 125 293 320 325 318 290 220 335

Mixture from example 2

VA Torir

Rpm DS VZ E. JZ 4th 1070 kg / h min • 4th It 200 20.5 2.5 0.56 5 1060 It W. η 0.61 6th η It η It 0.71 7th η η It η 0.91 η η η. 1.00

στ 2 a

26th

to η

27

Comparative example Lupolen V 2524 EX without deacetylation catalyst:
2 V 125 270 290 295 290 280 220 299 26 to 27 " ^w "

0.00 <1 1070

114

η η η η

ro! νχ

114

cn cn co ro

Table 3

Mixture from example 3

TA
■ Torr

3 c

^T 2 ^Τ 3 ^Τ 4 ^Τ 5
O _n ^Τ 6 φ Φ C. 180 230 250 250 240 240 220 250 135 290 290 295 295 275 220 300 105 315 320 325 320 305 220 330

0.6 to 1.0

Il ft Il

Rpm DS VZ ■ Έ JZ P.
η kg / h min 100 10.6 3.6 0.12 3 920 If It η 0.51 12th 870 It 10.0 It 1.00 26th 890

■ Comparative example Alkathene VJE 502 without deacetylation catalyst:
3V ₁ HO 280 290 295 290 280 220 298 0.5 to 1.0 100 10.0 3.6 0.00 <1

( ⁰ C) V

——— ro

112 ι

113: 115 i

112

cn cn co

Subject to Tables 1 to 3, the degree of deacetylation increases especially with increasing temperature in the extruder. The number of formed corresponds to the respective degree of deacetylation Double bonds, measured by means of the iodine number. With complete deacetylation (E = 1) the number corresponds to formed double bonds the vinyl acetate content of the starting 'substance. The unchanged degree of polymerization shows that Degradation of the macromolecules does not occur. A crosslinking of the polymers during the reaction does not appear to occur, as Measurements of the solubility of the reaction products compared to the starting substances in gasoline, aromatic hydrocarbons such as toluene and chlorinated aliphatics such as hexachlorethylene revealed. ι

Example 4 A:

100 kg each of Lupolen Y 3510 K in granulate form (E / VA mixed polymer from BASF, with an.ermittelten vinyl acetate content of 13 wt .- #) were powdered with so much anhydrous Zinc chloride mixed so that the proportion of zinc chloride in the mix had the following percentages by weight or percent by mole;

509819/0 9 38

abcd e

g zinc chloride / y

kg mixed poly- 1.1 2.3 4.7 9.2 39.0 ί

merisat

Weight # zinc

0.10 0.22 0.46 0.91 3.75 chloride

MoI-Ji Zinc

0.02 0.04 0.10 0.20 0.87 chloride

The individual batches were mixed in 10 kg portions in the mixer described under Example 1 "at 720 rpm.

The temperature in the cooling jacket of the mixer was maintained by water cooling to 2O ⁰ C. The mixing time was a uniform 10 minutes. j

Until further processing, the mixtures were as in the example 1 A described, stored. I.

Example 4Bi j

The mixtures described in Example 4 A were used for deacetylation passed through a heated vacuum extruder. The extruder model and process order were the same, as indicated for Examples 1A to 3A.

509819/0938

Carrying out the de-acetylation ι temperature program (C);

1 ^T 2 3 4th 5 6th 105 282 302 310 310 292

. 310

Throughput DS = 12.0 kg / h dwell time VZ «3.8 minutes at 85 πρΜ Pressure: VA = 26-27 Torr.

Table 4 shows the degree of deacetylation and the iodine number listed depending on the catalyst concentration,

Table 4

Mixture weight-jS Mol- # Entacety- Iodine P _n κ from example zinc chloride degree of lierungsgrad number

4 a

4 b

4 c

4 d

4 e

0.10
0.22
0.46
0.91
3> 75

0.02

0.04 0.10 0.20 0.87

0.27 0.56 0.75 0.86 1.00

( ⁰ C)

10 840 99 22nd Il 101 30th 830 102 36 835 103 42 It 104

Comparative example without deacetylation catalyst 4 V - - 0.00 <1,840

509819/0938

Example 5 A:

350 g each of Alkathene A 6455 in granulate form (E / VA mixed polymer from ICI, with a vinyl acetate content of 14.3 wt g-amounts of the compounds listed there mixed in a 2-liter Papenmeier mixer.

The specified g amounts of the compounds represent in each case 0.11 Mol- #, based on the E / VA-Misehpolymeri-

sat.

The mixing process was carried out in two steps:

Ii roughening the granulate surface for 15 minutes at 600 rpm, Addition of one of the compounds listed in! Table 5 and Mix the components for another 5 minutes with the same

Rpm.

During the mixing process, the temperature in the mixer was kept ^{at 35 ° C. by cooling with water.}

The mixtures were sealed until they were processed further Polyethylene bags kept.

Table 5 A

Compound a zinc chloride b aluminum tribromide c ferric chloride

g / 350 g Alkathene A 6455 1.69 .3.31 • 2.01

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link
d tin-II-chloride-

dihydrate

β palladium chloride f titanium tetrabromide g p-toluenesulfonic acid h ß-naphthalenesulfonic acid i meta-phosphoric acid

Tin tetrachloride

g / 350 g Alkathene A 6455 2.80

2.20 4.56 2.14 2.58 0.99

4.61 g / 500 g A 6455

A slightly different treatment was chosen for K, in that _: 500 g of Alkathene A 6455 were treated in the mixer described above at 600 rpm for 15 minutes. The temperature in the mixer was kept ^{at 25 0 O by cooling with water.}

The superficially roughened granulate was put into a ground glass bottle transferred and 4.61 g of tin tetrachloride was added. After closing the bottle, the mixture was agitated on a shaker for 8 hours.

By this time all of the tin tetrachloride was taken up by the granules.

The product was put in the ground-glass bottle until further processing kept

Example 5 B t

Approx. 30 g each of the mixtures produced in Example 5 A were placed in a 200 ecm reaction vessel made of Pyrex-Glaa

509 819/0938

(Height / diameter = 5/1), which was cut at the top, weighed exactly.

A joint attachment with a gas inlet tube was added to the cut and a distillation tube was fitted exactly.

The gas inlet pipe extended up to about 1 cm above the weighed sample. The lower end of the distillation residue . · ■ - ■

dipped into a template with adjusted 0.1 η sodium hydroxide solution.

While sparging with a brisk stream of nitrogen, it was made Place the reaction vessel as deeply as possible in a heated metal bath (Monell metal) and the time from immersion to later removal was measured.

The bath temperature was kept at 30O ⁰ O + 1 ⁰ C and the residence time in the bath was set uniformly at 20 minutes. During the immersion, the acetic acid which had been split off distilled over into the receiver and was neutralized by the sodium hydroxide solution.

After completion of the de-acetylation process, the nitrogen flow was hold for another 5 minutes. After the reaction vessel had cooled down, the ground joint was attached removed, and the plussiness droplets still adhering in the distillation tube with distilled water in the NaOH template convicted.

By titrating the excess NaOH with 0.1 η HgSO . the amount of NaOH required to neutralize the acetic acid split off was determined.

509819/0938

In Table 5 B are. Degree of deacetylation , iodine number and crystallite melting point are listed. '.. - ...

Table 5 B Zinc chloride Deacetylation 0.85 0.14 iodine K Abmisehung : Deaetylation Aluminum tribromide Degree '0.19 0.57 number ( ⁰ C) sus example catalyst Ferric chloride 0.43 Comparative example without deacetylation catalyst: 39 103 5 a Tin-II-chloride- 0.63 8th 97 5 b. dihydrate 18th 99 5 c .Palladium chloride 0.22 0.00 28 100 5 d. Titanium tetrabromide 0.33 p-toluenesulfonic acid 0.74 9 97 ν 5 β ß-naphthalenesulfonic acid 0.79 14th 98 5 f meta-phosphoric acid 32 102 5 g Tin tetrachloride 34 102 • 5 h 5 97 5 i 25th 100 5 k <Λ 96

Accordingly, with the same amount of addition, calculated in mol- #, the individual catalysts have different levels of effectiveness.

-The extended reaction time is partly due to the lower temperature than in the previous examples as well as to the un ~ neglected movement or kneading of the substance.

509819/0938

Example 6 A:

350 g Levapren 336 in lens granular form (E / VA copolymer from Bayer, with a calculated vinyl acetate content of 33.0 wt .- #) "were plasticized at a roll temperature of 10O ⁰ C on a roll mill and 1.75 g of anhydrous zinc chloride at After cooling, the rolled sheet was cut into cube-shaped pieces with an edge length of approximately 3 mm.

Example 7 A:

200 g levapren 400 (E / YA copolymer from Bayer, with a determined vinyl acetate content of 41 | 2 wt .- #) were treated with 1 g of anhydrous zinc chloride, as in Example 6 A described, treated on the roller. The millhead was cut into small cubes.

Example 8 A:

Of a blend of 50 g Lupolen V 3510 K (E / VA copolymer from BASF, with a calculated vinyl acetate content of 13 wt .- _f 0 #), 50 g Alkathene 24-03 (E / VA copolymer ICI, With a determined vinyl acetate content of 24.4% by weight and 0.6 g of anhydrous zinc chloride, a rolled sheet was produced according to the information in Example 6A and this was cut into small pieces. · J

509819/0938 \

Example 9 A:

90 g Alkathene YJG 502 (E / VA mixed polymer from ICI, with a determined vinyl acetate content of 8.4 wt. * - ^) and 10 g Elyax 40 (E / YA mixed polymer from Dupont, with a determined vinyl acetate content of 41 0% by weight were plasticized together on the roller mill described in Example 6A at 15 ° C. and 0.5 g of anhydrous zinc chloride was added
homogeneously distributed in the mixture at a constant temperature. The cooled millhead was cut into small, cube-shaped pieces.

Example 6B to 9Bi

About 20 g of the mixtures produced in Examples 6 A to 9 A were thermally treated one after the other in a glass vessel, as described in Example 5 B «,
In Table 6 are those at certain bath temperatures and
Dwell times reached degrees of deacetylation, iodine numbers,
Shore hardnesses A and crystallite melting points indicated «?

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509819/0938

Example 10.Δ:

6 g of anhydrous zinc chloride were in 7 »5 ecm dry. Dissolved ethyl acetate and mixed with 50 ecm of benzene. The solution was filtered and, together with 300 g of Alkathene A 6455 in granulate form (E / VA mixed polymer from ICI, with a vinyl acetate content of 14.3% by weight determined), poured into a 2 l ground joint bottle (wide neck). The mixture was shaken on a shaker at room temperature for 24 hours. At each time the liquid phase was completely absorbed by the E / VA copolymer. The solvent mixture was then distilled off ^{at 50 ° C. under reduced pressure.}

Example 11 A:

400 g of Alkathene YJF 502 in granulate form (E / VA copolymer from ICI, with a vinyl acetate content of 8.5% by weight) and 2.3 cd-naphthalenesulfonic acid were dissolved in 3800 ecm of toluene at the boiling point and the solvent was then dissolved in a Rotavapor (Büchi) at 60 ⁰ C removed. A powdery residue was obtained.

Examples 10 B and 11 B:

The catalyst described in Examples 10 A and 11 A

509819/0938

j -36-

containing E / VA copolymers were deacetylated as follows:

In a to 29o ⁰ C heated 2 1-pressure autoclave in addition with a close-clearance Schaufe! Stirrer and a vacuum and pressure-resistant filler neck was equipped, 300 g katalysetorhaltiges material were added with vigorous passage of nitrogen, hei not filled to sehneHäufendem stirrer. The filler neck was simultaneously interrupted

closed to the nitrogen supply. The nitrogen supply pipe was connected to a water ring pump and a vacuum of 30 torr was created.

After 15 minutes, heating and stirring were interrupted and the vacuum was again replaced by a stream of nitrogen. After cooling the autoclave to 120 ° 0 1.5 1 gasoline fraction were 140 - 200 ⁰ C charged and heated to 18O ⁰ C by a pressure-resistant closure of the filler neck, the autoclave. After heating for 5 minutes, the stirrer was switched on again and heated with a high-speed stirrer for a further 25 minutes and then allowed to cool to room temperature with continued stirring.

After removal of the suspension, the portion of the polymer dissolved in gasoline was precipitated with an excess of ethanol, the precipitated Sucked off material and dried in a high vacuum. A fine white powder was obtained.

Table 7 shows degrees of deacetylation, iodine numbers and crystallite melting points specified.

509819/0938

Table 7 Material from Entacetylie example 10 0.88 11 0.71 Example 12:

Iodine number K ( ⁰ C) 41 103 18th 114

Alkathene VJP 502 in granulate form (E / VA mixed polymer from Pinna ICI with a determined vinyl acetate content of 8.5% by weight and anhydrous zinc chloride in powder form were under a coblene dioxide atmosphere via two separate weighing scales in the Weight ratio 1000: 2.5 in the examples 1B to 3 B "described vacuum extruder fed. The extruded After cooling, the material was crushed in a chopper and covered with polyethylene film under a carbon dioxide atmosphere filled with lined paper sacks.

The temperatures T ₁ to T ₂ ^{in the} respective heating zones Z ₁ to Z _{7 of} the extruder, the melt temperature T ^ of the E / VA copolymer / catalyst mixture, the vacuum VA in the vacuum nozzle, rpm, material throughput DS; Residence time VZ, degree of deacetylation, iodine numbers, average degrees of polymerization and crystalline melting points of the deacetylated products are in.

• ■ - -

Table 8 summarized.

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M o

CM

τ- B

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C τ-

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EH> CM CM U.N. CM O KN KN U.N. KN O O Ε 00 CM O O U.N. KN U.N. Ν ON KN CM CM KN KN CM CM O CM CM KN KN O KN O O C- O O U.N. «* U.N. KN U.N. CM ON KN CM τ— KN CM CM O CM U.N. KN KN O ΚΛ O U.N. ω O O O C- CM 100 KN U.N. CM ON KN O KN • rl CM CM O CM U.N. KN KN O (N
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509819/0938

Xa.belle 9

Mechanical properties of exhaustively deacetylated

E / VA copolymers

Product of iodine number according to tensile strength kp / em elongation at break $>

DIN 53 455, test speed, 125 mm / min, ^aim (test specimen Mr. 4)

114 453

110 41Q

"80 470

76 402

cn
O example Chew CD OO to "^. 2 e 7th O CD
CO 3 c 26th CO 4 e 42 1 h 63

Shore hardness C ι DIN 53 505 VO I. 78 75 73 72

CO K) CD

Example 13 (comparative example);

About 3 g of an E / VA mixed polymer with 18.0 wt .- # vinyl. acetate (Alkathene 18-02, product from ICI) were heated ^{to 375 °} C. in a stream of helium for 15 minutes in an apparatus as described in Example 5B. It was 5.17

- # acetic acid, corresponding to a degree of deacetylation of 0.78, split off.

The product in the reaction vessel was discolored and so highly crosslinked that it in hot gasoline fraction from 140 to 200 ⁰ C could not be resolved.

Example 14 (comparative example) i

About 2 g of an E / VA copolymer with 13.0% by weight vinyl acetate (Lupolen V 3510 K, product from BASF) were ^{heated to 425 °} C. for 5 minutes under nitrogen in the apparatus according to Example 5B.

The acetic acid was split off quantitatively from the E / VA copolymer.

The deacetylated material was very brittle and in hot gasoline boiling range from 80 to 100 ⁰ C slightly soluble. An unpleasant odor adhered to the product.

As a result of the high temperature, acetic acid was also split off severe cracking occurred.

Eb mean molecular weights of about 7000 were measured. The • measurements became significant due to strong diffusion phenomena

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1 . - 41 -

disturbed, i.e. there were also considerable in the thermolyzed material Amounts of very low molecular weight fractions are present. 2.20 mol-ji double bonds were found.

509819/0938

Claims (6)

- 42 claims / j / Process for the production of unsaturated, uncrosslinked, "high molecular weight E / VA copolymers or unsaturated, uncrosslinked, high molecular weight polyolefins by partial or exhaustive deacetylation of E / VA copolymers or mixtures of E / VA copolymers of different vinyl acetate content, characterized in by carrying out the deacetylation in the presence of a catalyst of the Lewis acid type or the proton acid type at temperatures of 120 "to 37o C ^0. 2. The method according to claim 1, characterized in that one E / VA copolymers used are those with a vinyl acetate content of 0.5 to 70 wt .- ^. 3. The method according to any one of claims 1 or 2, characterized in that that the deacetylation catalyst in amounts of 0.01 to 10 wt .- #, based on the copolymers, used. 4. The method according to any one of claims 1 to 3, characterized in that that zinc chloride is preferably used as the deacetylation catalyst. 5. The method according to any one of claims 1 to 4, characterized in that the partial or exhaustive Entacety- 509819/0938 j "- 43 - -regulation of E / VA copolymers between 160 and 35O ⁰ C performs. i - ■ ' 6. The method according to any one of claims 1 to 5 »characterized in that that the partial or exhaustive entacety- ί ■ ■ Γ lation of E / VA copolymers under a protective gas i performs. ; 7 · A method according to any one of claims 1 "to 6, marked thereby, characterized in that one carries out the hot pressing Entacetylierungsprozeß \ .Between 0.2 Torr and atmospheric pressure..; 8. The method according to any one of claims 1 to 7 »characterized in that the union of E / VA mixed polymer. \ ' sat with the deacetylation catalyst by mixing in in a mixer, in a kneader, on a rolling mill, in an 'extruder or in a shaking apparatus and in the '<. Temperature range from -30 ° to + 150 ⁰ C works. 9. The method according to any one of claims 1 to 8, characterized in draws that the E / VA copolymer is as granules or powder, or in plasticized form with the solid Combine deacetylation catalyst by mixing. 10. The method according to any one of claims 1 to 8, characterized. ; It is shown that the E / VA mixed polymer present in solid form is impregnated with a solution of the catalyst 509819/0938. and optionally the solvent under reduced Pressure evaporates. 11. The method according to any one of claims 1 to 8, characterized in that that you have the E / VA mixed polynierisat and the Deacetylation catalyst combined in dissolved form and the solvent evaporated off under reduced pressure. 12. "The method according to any one of claims 1 to 8, characterized in that that the catalyst "during or directly after the polymerization of the E / VA copolymer before it Reconditioning adds. 13. Method according to one of Claims 1 to 12, characterized in that that the union of the E / VA copolymer with the deacetylation catalyst and the deacetylation carried out separately from one another. 14. The method according to any one of claims 1 to 12, characterized in, that the union of the E / VA mixed polymerizates with the deacetylation catalyst and the deacetylation process together at the deacetylation site performs under deacetylation conditions 15. The method according to any one of claims 1 to 14, characterized in that that the deacetylation can be carried out while being cleared, preferably in agitator tanks, "kneaders or very." 509819/0 938 - ♦!? ■ - preferably in a vacuum extruder. 16. Production of unsaturated E / VA copolymers by partial deacetylation according to one of the preceding claims 1 to 15. · ii7 Production of unsaturated polyethylenes by fully I ■. ■ ■. ■ ; permanent deacetylation according to one of the preceding claims 1 to 15. 18. Unsaturated E / VA copolymers or unsaturated polyethylenes with a statistical distribution of the double bonds and acetate contents of 0 "to 59» 5% by weight. 19. Unsaturated B / YA copolymers bew. Unsaturated · Polyethylenes according to claim 18 with chain trans-tynylene double bonds. 20. Unsaturated E / VA copolymers or unsaturated polyethylene with average degrees of polymerisation from 400 to 1800. 21. Unsaturated B / YA copolymers or unsaturated polyethylene with iodine numbers from 2 to 120, preferably 3 "to 105. Dr La/Be 509819/0938