DE1645376A1 - Process for the preparation of hydrolysis products of ethylene / alkenyl ester copolymers - Google Patents

Description

B es ehrei "bu ng, ZM der Patentaniaeidmng

SHELL IHTBRHAOIIONALE RESEARGH MAATS OHAPPIJ N.V. 30 Carel van Bylandtlaan Haag / Netherlands

concerning

Process for the manufacture of TQP hydrolysis products from Ethylene / alkenyl ester copolymers

The invention concerns a process for the production, new hydrolyzed polymers obtained by complete or partial hydrolysis of copolymers of Ithyiens with a or more hydrolyzable yinyl esters were obtained. The invention "also relates to the new hydrolyzed polymers itself, as well as the production of mixtures of the same, also latices, solutions and paints or adhesives, which by means of the new polymers or their Mixtures were obtained, - Finally, the '

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■, ■■ '■' ■■ "'■, - ■' ■ - ■■ '"'> ² - - '■ ^: - - ■ ■■■ - ■■■ "■■

Invention still on the production of shaped counter-', stands, which can also be vulcanized, using the new polymers, their blends or the mentioned! atices, solutions, paints or adhesives «, middle. -

"In-this description 'and in the claims understood ^ one under the name "copolymers" or the more general Designation "polymers" products with an average-borrowed Molecular weight of over 1,000. Furthermore, with • "Copolymers" including the block and graft copolymers meant those obtained from two or more monomers became.

The term "hydrolysis" means alcoholysis as well as hydrolysis with water, and also the

A known technique for the production of hydrolysis products of öopolymeren of ethylene with hydrolysierba- ren Vinylestern such as vinyl acetate, is that subjecting the flexible Öopolymeren a full or partial hydrolysis (cf. the British Patent 60? 911). With complete hydrolysis, the products formed become crystalline thermoplastics, wel-

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■ - 3 -; J645376

before, for example, suitable for the production of threads are. They have good adhesion to metals. Her However, flexibility is poor and so is the stability Insufficient oxidation. With partial hydrolysis the "flexible character of the ethylene / yinylacetate ^ Copolymers in fact partially retained and one still contains elastoplasts, which, however, not only contain a * - have little oxidation stability, but also not sufficiently stable to water and alkali hydroxide are. As a result, these polymers also got a bad G-odor. .

It has been found that a large range of new P _o lymerer can be obtained which, compared with said voXständig or partially hydrolyzed copolymers are less crystalline and therefore more flexible and transparent and also a better stability against over-oxidation and exposure to water or alkalis. According to the invention, the total or partial hydrolysis is subjected to copolymers which, in addition to ethylene and one or more vinyl esters and / or 1-alkyl vinyl esters, of a primary or saturated secondary carbon atom (ester of type 2), also one or more vinyl and / or contain 1-alkyl vinyl esters of such carboxylic acids in

00982071704

which at least one of the carbon atoms attached to the carboxyl group is branched "

As vinyl or 1-alkyl vinyl esters of carboxylic acids in which at least one carbon atom bonded to the carboxyl group is branched, one can use vinyl or alkyl vinyl esters of carboxylic acids with a quaternary or saturated tertiary (X carbon atom (ester of type 1) or use 1-alkyl vinyl ester of type 2..

Co-polymers of Although the hydrolysis products of / esters of type 1

and type 2 is given preference, the hydrolysis according to the invention can already be applied with advantage to copolymers obtained from ethylene and one or more esters of type 2 which have a branch on the carbon atom bonded to the oxyoxygen atom of the carboxyl group. Compared with the non-hydrolyzed Mpolymeren this category, obtained from these esters hydrolyzed products except higher chemical stability also show improved adhesion to Me ₌ metals and a greater hardness and strength.

Except for the esters of type 1 and / or esters of type 2 can optionally be used in the polymer to be "hydrolyzed" one or more other esters and / or other monomers may be incorporated. Examples of such additional monomers

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are acrylic acid, methacrylic acid, fumaric acid, maleic acid, aeonitic acid. Itaeonic acid, vinylsulphonic acid, metal salts of these acids, vinyl benzoate, acrylonitrile, vinylidenecyanide, vinyl chloride, vinylidene chloride, vinyl methyl ether, horns and orbornadieii ... These additional monomers can have been incorporated by direct copolymerization of all monomers together. It is, however, also possible to prepare the polymers to be hydrolyzed in such a way that copolymers of ethylene with only the esters are first prepared, and these then in one or more of the additional monomers dissolved, the thus obtained solutions in water dispeigiert _t for example by adding a protective colloid, and then polymerized again. · this solution may be further polymerized as such. V

So much for the polymers to be hydrolyzed organic acids that contain OH groups are incorporated are, such as unsaturated carboxylic acids or Vinyl sulfonic acid, or metal salts of these acids, so can the oxygen-containing groups or a part thereof, which is derived from these connections * retrospectively, before, during or after the hydrolysis * via an or several of their oxygen atoms on metals or others

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00820 / 17Oi

Metals are bonded by reacting the polymers with ⁼ one or more metal compounds such as MgO or Eno. Preferably selects one metal compounds such as 2 öew "-fo are soluble to more in water at room temperature, in particular compounds of latrium, potassium, magnesium or zinc, for example in the form of formates, Ace.tate, hydroxides, Methöxyde, Äthoxyde, nitrates, Carbonates or bicarbonates. In this reaction, which can be carried out, for example, at temperatures between 0 and 250 ° C. and using "solutions of the metal compounds in water and / or an alcohol and / or another organic solvent, ionic intermediate bonds are likely to be formed in the solid state are dissolved during melts or under the influence of visual forces during the work-up of the melt, in order to be formed again on cooling and in the absence of shear forces. Such products have particularly good mechanical and optical properties.

Depending on their total ester content and the degree of hydrolysis used, products with different Properties preserved.

The total amount of esters in the to be hydrolyzed

-T-

0Q9820 / 17Q4

The polymers are built in, can be very further within Limits vary and is preferably 2 to 99 wt .-%

Polymers to be hydrolyzed consisting of both types of Esters have been obtained contain the incorporated esters of type 1 and 2 in such an amount as is preferred 99.5 to 5 Gewo- # Ester. «'Of type 1 and 0.5 to

contains

95% by weight of esters of the type .2. Ton these weight ratios is the range in which 95 to 20 wt .- ^ of the built-in esters of both types together from esters of type 1 and 5 to 80 "wt .- ^ consists of esters of type 2, most importantly.

To the extent that this is the case with the method according to the invention 1-Alky! Vinyl esters are polymerized, the isopropenyl esters preferred. ''

The esters of the type I built into the polymers to be hydrolyzed are usually derived from carboxylic acids with up to 28 carbon atoms; if these fermentation acids have a saturated tertiary <X carbon atom, their minimum number of carbon atoms is 4; in the case of quaternary (X carbon atoms, the minimum number of carbon atoms is obviously 5.

0098207 ^ 17

It is preferred to choose type 1 esters of carboxylic acids having 5 to 20 carbon atoms and, among these, preference is usually given to esters of carboxylic acids having 5 to 12 carbon atoms.

Esters of pivalic acid are very particularly preferred (Trimethyl acetic acid), the esters of type 1, which are derived from one or more carboxylic acids with 9 carbons * material atoms, such as 1,1,3,3-tetramethyl-butanecarboxylic acid, 1,2-dimethyl-i-isopropylpropanecarboxylic acid and 1,1,4-trimethylpentanecarboxylic acid, or of one or more carboxylic acids having 10 carbon atoms, and the mixtures of esters of type 1 derived from carboxylic acids with 9, 10 and 11 carbon atoms.

Insofar as more than 1 ester of type 1 in the to hydrolyzing polymer is incorporated, can all of these esters are derived from carboxylic acids having a quarternary ^ carbon atom. You can all from Car- » carboxylic acids with a tertiary C ^ carbon atom, or partly of carboxylic acids with a quaternary 6C carbon atom and derived in part from carboxylic acids with a CC tertiary carbon atom.

Usually preference given to such polymers in which at least a one of a carboxylic acid with

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Quaternary ζ (carbon atom derived esters incorporated is.

In general, the CC carbon atoms are the
Carboxylic acids, the esters of which are derived from type 1, bound to aliphatic and / or cycloaliphatic and / or aromatic hydroearbyl groups.

Type 2 esters are preferably derived from carboxylic acids with 2 to 4 carbon atoms, especially from acetic acid. Type 2 esters of carboxylic acids with more however, 4 carbon atoms are also suitable. In the As a rule, the esters are type 2 esters of saturated carboxylic acids. But you can also use esters of unsaturated carboxylic acids with more than 3 carbon atoms, for example esters of oleic acid.

Are no esters of type 1 in the au hydrolyzing Polymers incorporated, so are the copolymers of ethylene with isopropenyl acetate ^ rmr, in which possibly also Vinyl acetate is polymerized, is preferred.

When using copolymers in which esters from Type 2, which is derived from carboxylic acid containing 2 to 4 carbon atoms can be derived, built-in, the extensive

ooseio / nov ~ ¹⁰ *

Range of possible new products in two categories organize:

1 »Polymers obtained by complete or partial hydrose of copolymers with a total amount of thawed Esters from 2 to 40 weight percent were obtained. These products are hard "to elastic plastics and are not very sensitive to water,

2. Polymers obtained by complete or partial hydrolysis of copolymers with a total amount of built-in Esters of 40 Ms 99 wt. # Were obtained. Compared to the polymers mentioned under 1, these products are more sensitive to water, but they are more sensitive to water More resistant to hydrocarbons. Dependent on. the degree of hydrolysis and the total ester content are these Polymers rubbery, leathery or hard.

The above mentioned limitations of both groups are obvious not sharp · The areas overlap more or less, with the specified »character dominating.

The novel polymers produced according to the invention do not dissolve in cold water and show under moist

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excellent strength. In general, the hardness of the products increases as the hardness increases Degree of hydrolysis.

The polymers to be hydrolyzed are usually at elevated pressure and in the presence of free Catalysts that give off radicals are produced. Representatives of this type of catalyst are: oxygen, Per compounds and azo compounds. These catalysts can also be used in Re doxsy stones. You can also use the well-known «polymerization melitodes, such as emulsion, suspension, solution or precipitation polymerization as well as polymerization in the absence of solvents or diluents, in the grass phase, or use other polymerization methods »The molecular weight of the polymers can be determined by measures regulate the pressure and / or the initiator concentration. M ^ n can also be chain transfer agents such as dodecyl mercaptan, Use acetaldehyde, (DOl ^, CHCl, etc. Alcohols, especially methanol, ethanol, Isopropanol and ter-butanol and aromatic hydrocarbons such as benzene are recommended. Also mixtures of Alcohols with aromatic hydrocarbons and / or Water can be used.

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Furthermore, the polymerizations described above ■. Batchwise in stirred reactors, or continuously, either in a tubular reactor or in one single stirred reactor or in two or more stirred reactors arranged in series Conditions under which the mixture of the reactor components is and remains the same in every reactor, be performed. The conversions of the residence times can be a function of the selected monomers and / or Chain transfer agents vary within wide limits.

Although the polymerization processes are using _a K of free radical taysatoren preferred, the invention is by no means limited to these. Copolymerization · Even organizations using other types of catalysts ^te i elevated or normal pressure are suitable.

The average molecular weight of the polymers to be hydrolyzed is preferably so high that the products obtained are solid. The melt index is a measure of the average molecular weight, and for the rubber-like polymers also the Hoekstra plasticity value. The melt index at 190 ^° C. using a load of 2.16 kg and a standard shape with a length of 8,000 + 0.025 mm 4e * - ¥ "a? Fi" ge and an inside diameter

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_ 13 ■ - ■■
2.095 pounds 0.005 mm is preferably greater than 0.05 dg / min.

In terms of the Hoe / kstra plasticity values is ws advisable that the values that correspond to the information by B.W. Duck and J.A. Waterman, Rubber and Plastics Age 42 (1961) 1079 with a load duration of JO see will be below 50. All melt index values mentioned below in this description and the Hoekstra Plastic Value are based on them Declarations.

The hydrolysis of the ethylene / yinyl ester copolymers is usually carried out in solution. For this purpose, the polymers are first in a hydrocarbon such as Bfnaol, toluene, xylene, <? Or in alcohols such as methanol, ithinol, propanol, butanol, isobutanol, or in mixtures of one or more of these alcohols with one or more of the hydrocarbons or dissolved with pyridine, dioxane, trichlorethylene. Usually a suitable catalyst is used
a base or an inorganic acid is used. It can be partially or fully hydrolyzed depending on the solvent, the amount and type of catalyst, the time and the temperature »

'& O09-2-O / 1.-704

Correspondingly larger amount of hydrolyzable vinyl ester in the copolymer, the hydrolysis is faster. In addition, alkaline hydrolyzing agents lead to higher Rates of hydrolysis, as catalysts derived from inorganic Acids exist.

The hydrolysis of the copolymers can be achieved by direct saponification can be achieved with excess alkali. It can also be done with a small amount of alkaline substance are «Sodium hydroxide is very suitable for this, as well as potassium hydroxide and other alkaline bases, e.g. Lithium hydroxide, tetramethylammonium hydroxide, etc. In certain In cases where a lower rate of hydrolysis is desired, hydrolysis with an acid such as sulfuric acid, Phosphoric acid, p-toluenesulfonic acid or hydrochloric acid can be carried out. ·

Complete hydrolysis can be achieved, for example, by preparing a 5-20% solution of the copolymer in Toluene / alcohol or an alcohol / toluene mixture, adding Add excess sodium or potassium hydroxide in alcoholic solution and reflux for one or more times Hours and subsequent separation of the hydrolyzed products from the solvent by steam distillation or simple filtration. The completely hydrolyzed products can be pressed between heated plates or with the help of suitable solvents to be cast to film. Such films are stiffer and tougher than films of nioiit-hydrolyzed copolymers and

U0882Q / 17Q4.

also generally have higher softening temperatures.

In some cases, partial hydrolysis may be desired. This can, for example, by hydrolysis with sulfuric acid or ethyl or methyl alcohol or using of less than the theoretically required amount Alkali or by a precise choice of the time and temperature of the reaction.

The hydrolysis can also be achieved on solid polymers, for example in the manner that the ethylene / vinyl ester copolymers is moistened with an insufficient amount of alcohol to dissolve. Then · until a homogeneous Mixture kneaded, an alkaline or acidic catalyst added and then until the desired one is obtained Degree of hydrolysis kneaded again. The polymers to be hydrolyzed can also first be converted into a finely divided state bring, for example by grinding.

The partially hydrolyzed products are different of the fully hydrolyzed due to better solubility in organic solvents. They are more flexible and tougher at low temperatures, and soften at slightly lower temperatures and show a higher elongation at break.

Rubbery or elastic copolymers to be hydrolyzed even with a low degree of hydrolysis, the

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is for example 5 # of the hydrolyzable ester groups, Products that give a much higher modulus than the non-hydrolyzed copolymers with white fillers, while the elastic character is retained.

The hydroxyl groups formed by hydrolysis can optionally be further treated with mono- or diisocyanates * carboxylic acids, aldehydes, such as formaldehyde, acetaldehyde, n-buty2faldehyde iind chloral, are converted; also with poly-N-hydroxymethyl compounds, like dihydroxymethylurea and dihydroxymethyluron, with ethers of poly-N-hydroxymethyl compounds, and with diacyl chlorides. The hydrolyzed oil polymers can also with phenol / formaldehyde resins, urea / formaldehyde resins or melamine / formaldehyde resins are treated. The invention. Polymers can easily be used if desired modified by other chemical reactions. she can be chlorinated. They react with chlorosulfonic acid and carbonyl chlorides, such as stearyl chloride and salicylic acid chloride, also with p-toluenesulfonyl chloride or with aliphatic Sulfonyl chlorides, such as suspended in pyridine Butanesulfonyl chloride at low temperature. You surrender. then the corresponding polysulfonates of the polyalcohols. With Oiaphthenic acid chlorides form oil-soluble esters. The sulfonates can be used as alkylating agents for amines, the amino hydrogen included.

The polymers can be etherified with sodium chloroacetate. The anhydrides of maleic acid and phthalic acid

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■ - 17 -

react with the hydrolyzed copolymers and yield good yields of polycarboxylic acids which are ■ soluble in alkalis and are insoluble in water *

The new polymers produced according to the invention are, provided that the hydrolysis is based on copolymers of ethylene with 1-

Type 2 alkyl vinyl esters have therefore been used

without exception -

ädüh are characterized by the presence of the

following two units as a structural element

Units of the formula ^ pCE ₂ - CH ₂ - "J un | similar or different units of the formula η

C- OH ₂ -? - .7

in which R _{5 represents} an alkyl group and X represents a hydroxyl group or a metal alcoholate group.

If the hydrolyzable 1-alkyl vinyl ester incorporated during the polymerization was only partially hydrolyzed, they contained these new polymers are also the same or different Units of the formula

- GH ₂ - Q - J

0 = 0 r

in which E, an alkyl group and H-_a hydrooarbyl group §A primary or saturated secondary to the 90 uruppe bonded carbon atom is *

In these formulas E _{1 and E 1 are} preferably methyl groups.

The number of carbon atoms in the hydrocarby group E. is

by 1 less than the number of carbon atoms of the carboxylic acids that make up the 1-alkyl vinyl ester used are derived from type 2. .

If the new polymers have been obtained by hydrolysis of copolymers of ethylene with vinyl and / or 1-alkyl vinyl esters of type 1 and also vinyl and / or 1-alkyl vinyl esters of type 2, the polymers contain the following units as structural elements
Units of the formula

f CH ₂ - CH ₂ - J \

same or different units of the formula

"3.
C- CH ₂ -C-'J

and also identical or different units of the formula

-Ϊ-J

.0

σ = »ο

in which R ^ and Rt represent hydrogen or alkyl groups

001120/1704

«Sil can be the same or different; X means again a hydroxyl or a metal alcoholate group, and Rp a Hydrocarbyl group, the carbon atom of which is bonded to the GQ group is quaternary or saturated tertiary.

If polymers in this category were only partially hydrolyzed, they also contain the same or different ones Units of the formula

-. :. : ^E 'j.' ■ '■■ . ■■. '

I - CH ₂ - G - _ /,

I-

0 = 0 ■ .. ·. ■

■■. ■■ '' - ♦ ■

in which R ¹ * is hydrogen or an alkyl group and -R. again represent a hydrocarbyl group with a primary or saturated secondary carbon atom attached to the CO group. R ₁ and / or R '--- and / or R ¹ , - are preferably methyl groups. The number of carbon atoms of the hydrocarbyl groups R ₀ and R. is - by 1 less than the number of carbon atoms "of the carboxylic acids, from which the used ones of type 1 and type 2 are derived.

If organic acids with unsaturated QH groups have also taken part in the copolymerization, the resulting Polymers also contain OH-containing acidic groups. Are these polymers are then reacted with a metal compound so are the acidic groups or a part of them

0 098 20/17 04 '

- ■■ - -t— - ~ —-— '-'-- l ^y ^^' - J,

converted into acidic groups bonded to carbon, those via one or more of their oxygen atoms to metal are bound * Such acidic groups bound to metal .sind Also present in the polymers when, during the copolymerization, metal salts of organic acids, the unsaturated QH groups contained, were used, and obviously also when the copolymers obtained in this way with compounds other metals have been implemented.

The products according to the invention can with substances are mixed, which affect the properties, such as Pigments, plasticizers, wax or other ^ water-repellent Preparations, dyes, resins and fillers.

Examples

There have been a number of copolymers of ethylene with one or more esters produced in a horizontally rotating autoclave with a capacity of 2 liters as follows:

The autoclave was made with the in the table below stated amounts of tert-butanol, esters and azo-bis-isobutyronitrile (AIBIi) related. The latter connection had previously been dissolved in the ethers. The atmospheric oxygen was previously duroh from the autoclave Durophilization of practically oxygen-free nitrogen, and Also removed after the autoclave was poured into the ground by repeated pressing.

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Then using a diaphragm compressor, ethylene was injected from a cylinder which contained this gas at a pressure of 60-70 atm. The introduction of ethylene under pressure was continued until a pressure of about 200 atm was reached in the autoclave. The autoclave was then set in rotation, after which the pressure decreased considerably by dissolving the ethylene in the liquid phase. Then the rotation of the autoclave was interrupted in order to inject ethylene again, now up to a pressure of about 230 at. After the autoclave was set in rotation again, the pressure dropped again, now to 155-185 at The contents of the rotating reaction ^{vessel were heated to 65 0} O in about 3 minutes, after which the pressure rose accordingly, in order to decrease again, now as a result of the copolymerization used.

This drop in pressure was monitored over the entire duration of the polymerization. The temperature of the autoclave was measured with the aid of a thermocouple and carefully regulated to 65-3 ° ö by gas heating and air cooling. After 24 hours, the copolymerization was terminated by cooling the contents of the autoclave to room temperature. The nioht-polymerieierte ethylene was allowed to flow out, the autoclave was opened and the - Polymerisationeprodukt repeatedly washed with methanol, filtered, under vacuum at 45 - 50 ⁰ O dried and weighed. The oxygen content of the resulting oil was determined by element analysis. '.-. ■' ■

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Furthermore, it was pressed by "a small amount of the polymer a film between Teflon loiien at 160 ⁰ O and taken up by this, the infrared spectrum. Using this data, the amount was determined on engebauten esters. Tyrolian was the Sehmelzindex and / or the Hoekstra plasticity value determined in the aforementioned manner.

The following table 1 shows further data as well the results of the copolymerization carried out.

Table 1 follows

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1 Ester from Ij
link 2_I Table 1 a D II AlBIiT "
g. Amount of
tert. -Butanol
G attempt 2 * Vinyl pivalate lot
G Ester from * g lot
G 1 291 Ιο. the same 86 link 93 1 275 4 ■ "■ ' the same 88 * Vinyl acetate 92.5 * 1.5 - ■ .. _{5 /} . ■ ..: ■ the same 298 the same 47 1.1 138 ^: ·:, 6 ^; ■■■■■ «- 85 the same 323 0.7 390 ta also * 92 1.1 138 ¹ * ■ ·. Isopropenyi-
acetate 380 Vinyl acetate

* 19 g of horbontadiene was reorganized as the fourth monomer from Öopolyjieri.

Pressure during at
after
Oh 65 ⁰ C
after
24 hours yield Table 1 b Total- t attempt Polymerization 410 117 after 24 h
S. Co ^ olj paere ester
salary
Weight - $> Ester content Ho At first
pressure at
Room temp. 425 300 300 Enamel Hoekstra- 29 Type II 155 423 110 140 index,
190 ° C
(2.16 kg)
dg / min Plasticity
value
100 ⁰ C 27 15th 1 182 425 92 416 20th - 40.9 14th 2 162 445 243 545 80 - 48 5.6 3
ο 155 420 106 115 - ■ 6th 12th 38 ° 4
CD ^ 185 460 - 17th 45 12th KJ 5
ο 161 80 - 45 Hey
O 3.0 16
I.

16A5376

The copolymers obtained in Table 1 became one Subjected to hydrolysis. The polymers were "at 100 C in the form of a 5% by weight solution; saponified in toluene. the Saponification was achieved by adding potassium hydroxide solutions in methanol and then refluxing. Table 2 lists further characteristics of hydrolysis.

Table 2 -

Vers. To hydroly-Ho. sierendes

Polymer, obtained according to experiment no.

Boil under a lot of methanolic KOH reflux solution per 50 g of polymer

8th 1 9 2 10 2 11 5 12th 4th 13th 4th 14th 3 15th 6th

10

20th

10

20th

24

mi;

ml)

ml 'ml

ml mg mg y51 mg

In solution

s ο vie I ⁴ IKOH In? Dissolved methanol that a volume ratio of this solution: polymer solution in toluene

⁵²²⁰

The built-in vinyl pivalate remained unchanged even with the use of excess KOH in terms of vinyl acetate and vinyl pivalate built into the polymer and a boiling time under reflux of 20 hours. ■.

BAD ORiQiNAL

- 99 -

The polymerized vinyl acetate on the other hand was under under these conditions quantitatively converted into built-in vinyl alcohol.

By infrared analysis before and after hydrolysis, the

Percentage of esters of the type incorporated in the polymers that had been converted into alcohol groups. These percentages are listed in the following table.

This table also compares some mechanical properties as well as the nature of the hydrolysis products with those of the non-hydrolyzed polymers.

Table 3 follows

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Table 3

Ver Composition of the non-hydrolyzing <? <> Polymerized tensile tensile properties "at, nature of the

sought copolymers, expressed in terms of mono-tes vinyl (or 20 ° C and a tensile rate of polymer

mers from which it has thawed - isopropenyl acetate speed 3 cm / min 'j

- "* ■ -— converted to *" * ""' ^: ~ "

lthy- vinyl- isopro- vinyl- urorbor- polymerized stretch / tensile strength 'breaking modulus

len acetate penyl- pivalate Nadien · vinyl (or iso _gre nze stigkeit / Elong. $ 300

.2 p
co

12th
13th

3
14th

Gtow

Gw.-

71
71
71

15th
15th
15th

H H H

69 14th 69 14th 69 14th

13 13 13

5 σ 88 12th * «· ■ 11 II
Il CO
Il 00
I I
I I I
I I 11 ro
M I
Il I

38

52
52

38 ·
38

10

10 10

59.1 5.6
59.1 5.6

45 ^;
J5— 15—

35.3 35.3

kg / cm ² kg / cm

* kg / cm

20th
46
63

172 256 219-

1034 675 447,

50 123

144

22nd
42
62

165 264 224

1010 7.10 465

43 110 146

5 * 140 *

164 * 186 *

36 * 43 *

1080 * 820 *

elastoplastic

tough, pise- '

table desgl.

rubber-like tough-plastic * "♦» the same

0 60 80 95 - flexible, plastic 44 tough, plastic

1,800 * 10 * rubber-like 630 * 33 * the same

. 620 * 40 * the same.

125

1700

* kau tsc hukart i ι H * 'desgl.

kauts chukar t i

/ stiff, -,. . plastic

-ar- 1645378

From Table 3 it follows that the original polymers have been converted into products of higher modulus by hydrolysis. On the other hand, the intermolecular Forces weakly decreased as a result of the presence of pivalate groups. The flexibility of the hydrolyzed polymers is therefore determined by the balance between the forces which increase the modulus, and the forces which lower the modulus * The hydrolyzed products could easily films and threads are processed and showed good adhesion to metals. In addition, each of the obtained new products showed its own merits.

A number of the polymers obtained in the experiments mentioned were vulcanized both before and after hydrolysis and determines the properties of the vulcanizates. The vulcanization was carried out according to the following recipe, in which the specified Parts by weight are:

Polymer x 100

Stearic acid 1

Antioxidant (1,5,5-trimethyl-2,4,5-tri (3,5-ditert-

butyl-4-hydroxybenzyl benzene) 0.5

Polyethylene glycol (mole weight 400) 4

white reinforcing filler, based on
Silicic acid {"UltrasÜ VN3") 50

Dicumyl peroxide on a weight-based carrier ("Dicup 40 ö",

containing 40 $ peroxide, 3

Triallyl cyanurate / i 2

After rolling at 60 ⁰ O mixtures at 150 ⁰ C were
vulcanized.

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The results are shown in Table 4 below.

Follows! Table 4 .

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Tabel

Polymer produced according to vers.

not hydrolyzed hydrolyzed not hydrolyzed hydrolyzed 3 14 4 12 13,

Wt .- ^ esters

35.3 25th 10 · - ^v 25th Vinyl pivalate 161 Vinyl pivalet 25th 5.6 510 38 210 212 ^ Vinyl "dot at 105 Vinyl acetate 220 207 ⁺ 6th 160 17th 189 ⁺ min 20th 119 20th - 41 2
kg / cm 134 51 210 40 48 610 23 541 49 23 2
kg / cm 50 57 21st kg / cm 90 173 / β 165 81 kg / cm 45 41 19th 20th

JJ Hoeketra placidity score **> Vulcanization time ο

^ Tensile strength
«4 Elongation at break
^ Module, 300 ^

Module, 500JS

■ set at breakt

Heat strength, "angle" ¹ )

"Delft" ■)

*) Module,

*) ASTM: D62 ^ -5 ^, page 363, form "C" ·) JM Bulst and H. Geldof, India Subber World 122 (1950), No.

CO

cn co ■ <] CO

Claims (8)

Claims 1. Process for the production of hydrolysis products by at least partial hydrolysis of copolymers of ethylene and alkenyl esters and optionally further comonomers, by g e k e η denoting that one those copolymers are used which, as the alkenyl ester, are a mixture of one or more vinyl and / or 1-alkyl vinyl esters of carboxylic acids in which at least one of the carbon atoms attached to the carboxyl group is branched, (Type I ester) and one or more vinyl and / or i-alkyl vinyl esters τοη a primary or saturated secondary carboxylic acids containing flt carbon atoms (esters of type II) included. 2. The method according to claim 1, characterized in that g e k e η η draw t that copolymers are used which, as type I esters, are those of a quaternary or saturated tertiary Carboxylic acids containing OC carbon atoms contain. 3. The method according to claim 1, characterized in that g e k β η η, that such copolymers are used which contain, as esters of type I, 1-alkyl vinyl esters of type II. * 009820/1704 4. The method according to claim 2 or 3, characterized in that such copolymers are used whose built-in mixture of vinyl and / or 1-alkyl vinyl esters 99.5 to 5 wt .- # of esters of type I and 0.5 to 95 % By weight of esters of type II, preferably 95 to 20% by weight Esters of type I and 5 to 8% by weight of esters of type II. 5. The method according to claim 1 to 4, characterized in that copolymers are used as 1-alkyl vinyl ester contains isopropenyl ester. 6. The method according to claim 2 to 5 »characterized in that copolymers are used as Type I esters contain those of carboxylic acids having 5 to 25 carbon atoms. 7. The method according to claim 2 to 6, characterized in that mäh copolymers used as Ester of the type. I contain at least one such which is derived from a carboxylic acid with a quaternary OC carbon atom. 8. The method according to claim 7, characterized in that copolymers are used as Type I esters contain pivaiic acid esters. 00S820 / 1704 9i method according to claim 1 to S ^ thereby g e k β η n ζ e i c h η e t that jfman uses copolymers as lstei of type II those from Gai? bönsäü £ eri with 2 Ms 4 Koh « v-ö £ 2possibly Eösigsäiii? ei contain 10 »Partial abilities according to claim 1» daduEoh gg ke η η - zeiöhneti that one iSopölymefe tan. Ethylene used with IööpEöpenylaeetät * - 11 * Procedure riaoh 4nsp £ uüh 1 to 1Q _f daduaieh geke η η- draws »that one Öopölymeif.ö veswendeti as further gomönomea? E one or ¹ several unsaturated OB> -G groups ätil-showing 02? · Contain polymerized * • 8538 ORtGJNAL