DE1570510A1 - Process for the preparation of vinyl chloride-ethylene copolymers - Google Patents

Description

Process for the preparation of vinyl chloride-ethylene copolymers.

The invention relates to a process for the copolymerization of vinyl chloride and ethylene.

Vinyl chloride-ethylene copolymers are made by a number of polymerization processes using a wide variety of catalysts. With a few or even none of the known processes for the preparation of vinyl chloride-ethylene copolymers are obtained products which Due to their physical properties, they are suitable for the manufacture of used items. Recently has been however, found that in the copolymerization of vinyl chloride and ethylene using a polymerization catalyst which is a product of the reaction between an organoborane and either molecular oxygen or a peroxide (or both), copolymers having many desirable properties can be obtained. Certain polymers, which are prepared by bulk polymerization with the above-mentioned catalyst system and a low ethylene content (e.g. less than about 12 wt. £) contain have properties that make them suitable for processing

& 09885 / 16S6

make it suitable for semi-rigid objects. As consumer articles of this type are boxes, cardboard boxes, bottles and Material for transparent packs called. In many applications it is desirable that the plastic material be colorless and transparent. However, even the best vinyl chloride-ethylene copolymers of this type have the disadvantage that the objects made therefrom generally have a rough surface and a matt or cloudy (or have a translucent) appearance. In certain applications this is not a major disadvantage, but it is for Packaging and similar purposes, it is desirable to have copolymers that have a smooth, clear surface. The property of a copolymer that causes a calendered film to have a rough surface and a matte or cloudy (or translucent) in appearance is often referred to as "nerve".

In addition to the ability to use plates, coarse films and foils to form a clear surface are, among other things, the tensile strength, determining the heat resistance and the solvency index for the suitability of a polymeric material for commercial use.

I'm another catalyst system for the copolymerization of Vinyl chloride and ethylene consists of a) an oil-soluble derivative of a transition metal in an oxidation stage, which create a peroxide bond with the formation of free radicals able to reduce, and b) a water-insoluble, but oil-soluble peroxide compound. With this catalyst system vinyl chloride-ethylene copolymers are also obtained which have a number of desirable physical properties exhibit. It has been found, however, that the polymer when made in accordance with the invention has improved properties similar to the copolymer made using the organoborane oxygen catalyst system.

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The invention accordingly provides a method for Manufacture of vinyl chloride-ethylene copolymers, from which objects with a smooth and transparent surface can be produced, and have increased dimensional stability under heat.

According to the invention, semi-hard vinyl chloride-ethylene copolymers prepared by a content of chemically bound ethylene in the range of about 3 to 12 wt.% _$ An intrinsic viscosity of at least 0.9 at 30 ⁰ C (as a solution in cyclohexanone at a Concentration of 0.1 g / 100 cnr) and a smooth surface and clear appearance when used for calendering plates, coarse foils and foils are characterized. In the preferred embodiment, these copolymers are dimensionally stable in the oven for at least 100 minutes at 182 ° C. If a sample of these copolymers with a thickness of approximately 0.15 mm is ^{exposed to a temperature of approximately 166 °} C. for approximately 3 minutes, the surface of this sample will at most shrink

The process for the preparation of the copolymers described above is characterized in that vinyl chloride and ethylene are subjected to the copolymerization until the total use of the comonomers is at least 5% , and the copolymerization is terminated before the conversion reaches 20Ji.

The vinyl chloride-ethylene copolymers according to the invention with about 3 to 12% ethylene (about 3 to 8 % in the preferred copolymer or about 6 to 8% in the particularly preferred copolymer) can conveniently be prepared by polymerizing in bulk at a temperature in the range from about -25 ° C to about 40 ° C at pressures ranging from about 7 to 280 kg / cm. A temperature range of about -20 ⁰ C is preferred to about +20 ⁰ C. The pressure employed will of course depend to some of Unfange

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the size of the reaction vessel and the one used Amount of monomers! Vinyl chloride. The prints can ever according to the desired polymerization rates and the desired molecular weight within a wide range Range vary. However, the molar ratio of ethylene to vinyl chloride will range from about 0.15 to about 1.4 held to produce copolymers with the desired ethylene content.

As already mentioned, the copolymerization can be carried out in bulk. However, it is sometimes advantageous the polymerization in solution in a suitable inert Perform solvent. Suitable solvents are, for example, pentane, hexane, heptane or other inert ones Hydrocarbons.

The most varied of organoboranes can be used for the preparation of the organoborane-oxygen catalyst system used according to the invention. Triorganoboranes, such as trialkylboranes, trioycloalkylboranes, triarylboranes, triaralkylboranes, trialkarylboranes and the like, are well suited, but organoboronhydrides can also be used, for example those of the formula RBH ₂ and RgBH, in which the radicals R can be the same or different and are preferably hydrocarbon radicals, e.g. Alkyl, cycloalkyl, aryl aralkyl and alkaryl. Polymeric forms of borane such as diborane, tetraborane, pentaborane, hexaborane, and dicaborane can also be used successfully. Preferred of the organoboranes are the trialkylboranes, such as triethylborane, tri-n-propylborane, triisopropylborane, such as tributylboranes, trihexylboranes, trioctylboranes and the like.

A reaction product of an organoborane is used to produce the organoborane-oxygen polymerization catalyst of the type described above with either molecular oxygen or a peroxide compound. Here a product is obtained in which the atomic ratio of

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elemental boron to elemental oxygen is about 0.25 '· 1 to about 15: 1. To prepare the catalyst, the organoborane and the oxygen and the oxygen-containing material are preferably brought together at a low temperature. To facilitate handling of the catalyst, it can be prepared in an inert solvent such as ether, ester, ketone, hydrocarbon or the like. When using air or oxygen as the oxygen-containing reaction component, the manufacturing process is simplified if an autoclave or a similar closable device, from which all of the air can be evacuated before the use of the organoborane and optionally the solvent, is used as the reaction vessel. Air or oxygen can then be introduced into the system in such an amount that the formation of a catalyst is ensured which contains boron and oxygen in the desired ratio.

When the above-mentioned catalyst system, which consists of the transition metal compound and the peroxide, for the preparation of the new vinyl chloride-ethylene copolymers according to of the invention is used, the transition metal compound can be any oil-soluble derivative which the Has ability to form free radicals when mixed with peroxide compounds. Possible transition metals are the metals of groups I-B, IV-B, V-B, VI-B, VII-B and VIII of the Periodic Table, oil-soluble Rare earth derivatives (lanthanum series) are also effective when used for the purposes of the invention.

As examples of suitable transition metal compounds as constituents of the catalyst for the process according to FIG Invention may be mentioned: Oil-soluble chelates of transition metals, oil-soluble transition metal salts of phenol compounds, oil-soluble transition metal alcoholates and esters as well as other organic compounds which are characterized in that they contain a transition metal and

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have good solubility in organic media. For example, the chelates of transition metals can be used, e.g., the acetylacetonates and alkyl acetoacetates (e.g., the octyl acetacetates of transition metals and the like). Transitions from long-chain metal salts are also suitable Alkyl phenols (e.g. p-nonyl phenol and the like). Further the transition metal alcoholates and esters are suitable "in which the organic part of the molecule has such a carbon content that the compound obtained is organic Media, such as hydrocarbons, is soluble.

Preferred transition metal compounds for the purposes of the invention are the oil-soluble transition metal salts of carboxylic acids. In general, these acid salts contain about 4 to J> 0 carbon atoms in the molecule, and the acids from which they are derived contain 1 to about 4 carboxylic acid groups. However, from the standpoint of cost and availability, oil-soluble transition metal salts of monocarboxylic acids are particularly preferred. These salts are most advantageously made from saturated aliphatic monocarboxylic acids, saturated cycloaliphatic monocarboxylic acids, aromatic monocarboxylic acids and olefinically unsaturated monocarboxylic acids. These acids can be substituted with inert or harmless functional substituent groups (eg with belogens, cyano groups, keto groups, etc.), but are preferably characterized in that apart from the carboxylic acid group they do not contain any functional substituents in the molecule.

Of the transition metal derivatives for the purposes of the invention, the transition metal salts of are particularly preferred Fatty acids with about 5 to 18 carbon atoms in the molecule. These Functionally unsubstituted saturated aliphatic monocarboxylic acids of the fatty acid series are generally sufficient from valeric acids to stearic acids. These compounds have the advantage that they are not only cheap as well are readily available, but also effective from polymers

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exceptionally high quality form when used according to the Invention can be used.

As already mentioned, is suitable as a metallic component this catalyst constituent any transition metal that however, it is generally preferably not used in the highest valence level. For example preferred one the titanium (lll) -, chromium (ll) -, manganese (ll) -, ferro (II) -, Cobalt (II), nickel (H) or copper (I) derivatives, because the corresponding derivatives of the higher valency level under the polymerization conditions used according to the invention are less active. Thus, in the case of the metal salts of the carboxylic acids, the cation is preferably a low-valent one Form of any transition metal, but with the Iron (II), cobalt (II) and nickel (II) cations in general, my be preferred. Particularly good polymerization results are obtained when iron (II) salts of carboxylic acids of the types mentioned above are used,

Examples of suitable salts of aliphatic monocarboxylic acids are ferrocaproate, cobalt (II) caprylate, manganese (II) pelargonate. Chromium (II) laurate, ruthenium (II) palmitate, copper (l) stearate, Molybdenum (III) butyrate, iron (II) -2-ethylhexanoate, Cerium (III) -2-ethyloctanoate, cobalt (II) -3,3 * -dimethylbutanoate, Chromium (lI) -6-isopropyl decanoate, iron (II) laurate, Elsen (II) stearate.

Examples of suitable salts of aromatic monocarboxylic acids are: iron (II) benzoate, cobalt (II) naphthalene-1-carboxylate, Chromium (II) -3-cyanobenzoate, manganese (II) -p-chlorobenzoate, Rhodium (II) -m-methylbenzoate, titanium (II) -4-carboxybiphenyl, Nickel naphthalene-2-carboxylate, ruthenium (II) p-isopropyl benzoate, iron (lI) anthracene-2-carboxylate and ferrous p-nitrobenzoate.

Salts made from unsaturated or substituted monocarboxylic acids or dicarboxylic acids are effective as a component of the process according to the invention

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applied catalyst system. Suitable salts of olefinic Unsaturated monocarboxylic acids are, for example, iron (II) oleate, nickel-4-decenoate, molybdenum (III) -2-dodecenoate, ruthenium (II) -b-octenoate, cerium (HI) -5-decenoate, iron (II) rloinoleate and cobalt (II) ricinoleate.

Examples of suitable salts of substituted aliphatic monocarboxylic acids are: Eiaen (II) -3-chlorododecanoate, cobalt (III) -4-bromodecanoate, chromium (II) -3-cyanohexanoate, Iron (II) 3-hydroxy octanoate, nickle-2-chlorohexadeoanoate and Copper (I) -2-ethyl-j3-chlorohexanoate.

Suitable salts of cycloallphatic monocarboxylic acids are, for example, iron III cyclohexanecarboxylate, cobalt (H) cyclopentane carboxylate, chromium cyclobutane carboxylate, Iron (II) naphthenate, cobalt (II) naphthenate and manganese (H) naphthenate.

The water-insoluble but oil-soluble peroxide or hydroperoxide component of the catalyst system used according to the invention can generally be selected from the group of acyl peroxides, aroyl peroxides, alkyl hydroperoxides and aralkyl hydroperoxides. For the catalyst system according to peroxides and hydroperoxides suitable for the invention including lauroyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, 1,1-diethylpropyl hydroperoxide, 1,1,2-trimethylpropyl hydroperoxide, 1,1,2,2-tetramethylpropyl hydroperoxide,!,!, ^ iJ-tetramethylbutyl hydroperoxide, α, α-dimethyl-benzyl hydroperoxide, α-methyl-α -äthylbenzylhydroperöxyd, α, α -diphenylethyl hydroperoxide, triphenylmethyl hydroperoxide, Di-t-butyl peroxide, t-butyl-t-amyl peroxide, bis- (m-chlorobenzoyl) peroxide, bis- (p-methoxybenzoyl) peroxide, bis- (p-cyanob6ttäsoyl) -peroxide, bis- (p-nitrobenzoyl) peroxide, ß ^ ß'-iDinaphthöyl ^ foxyd, BIs- (I-hydroxycyclohexyl) peroxide, M6thanhydr © pöroxyd, Bis (l-hydroxyheptyl) peroxide, methyl amyl ketone hydroperoxide, Cylohexanone peroxide and the like.

Other suitable peroxides are, for example, the alkyl percarboxylates, e.g., t-butyl peracetate, di-t-butyl di-perphthalate and t-butyl perbenzoate. 909885/1556

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The "from the transitions tallverbindung and the peroxide compound existing catalyst mixture may, when used for the method according to the invention using a molar ratio of about 0.3 to about 7, O between the catalyst component a) (öllösliehes derivative of a transition metal in an oxidation state that a Able to reduce peroxide bond with the formation of free radicals) and the catalyst component b) (water-insoluble, but oil-soluble peroxide compound) can be produced.

The catalyst mixture must be used in an amount which causes the copolymerization of the vinyl chloride and the ethylene in a reasonable time and in good yield.For example, the catalytic amount of the catalyst base used can be between about $ 0.01 (or less) and about 2.0 % (or more) of the total weight of the monomers used (vinyl chloride + ethylene). In general, an amount of the catalyst mixture of about 0.025 % to about 1.0 % of the total weight of the monomers used is preferred.

The time required to carry out the copolymerization of vinyl chloride and ethylene to form the new copolymers according to the invention depends on a number of factors. The important variables that determine the allowable tent include the one used Pressure, the amount of any diluent present, the catalyst concentration, the molar ratio of the monomers and the temperature at which the Interpolymerization is carried out · It has been found that time is a critically important factor for is the determination of the quality of the copolymer produced according to the invention. The use of vinyl chloride and ethylene to the copolymer under fixed reaction conditions and fixed ethylene / yinyl chloride ratio was found to be directly proportional to that for the Interpolymer allowable time. It was found,

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that by applying a polymerization time in which the tJtasatz of vinyl chloride and ethylene to a value im Range of about 5 to 20 wt. # Is limited, a copolymer of high tensile strength is obtained which is can be processed by stretching, orienting and making orobo films or pollen with a smooth, transparent surface.

So far it has been difficult to precisely limit the conversion of vinyl chloride and ethylene to the mixed polymer if the Polymerization in bulk or in solution is carried out in an autoclave. The time required to blow off of the unreacted ethylene (and sometimes an inert gas, such as nitrogen, necessary to achieve the desired Reaction pressure is used) caused a delay that was sufficient for a significant post-polymerization to be allowed to take place before the polymer product could be freed from the catalyst by war. It was found, that the conversion of vinyl chloride and ethylene to the mixed polymer can be precisely adjusted by a basic compound is blown into the reaction mixture when the desired Utasatz is reached. Oils for The basic compound used to terminate the polymerization is basic in the Lewis sense, i.e. it is a compound capable of releasing electrons during chemical reactions. Further details on Lewis bases can be found in "Electronic Theory of Acids and Bases" by Luder and Zuffanti. For the purposes of the invention are preferred basic nitrogen compounds are used. Here, the basic nitrogen compound should preferably be one for a base characteristic ionization constant of

-12
have at least 1 χ 10, measured in aqueous solution.

In the context of the invention, anhydrous ammonia is preferred as the basic nitrogen compound. This connection is readily available and can easily be sparged into the reaction mixture with nitrogen. Among the preferred basic nitrogen compounds also include AmmoniujB-hydroxyd, which is also easily available and convenient in

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the reaction mixture can be pressed in. Anhydrous Ammonia and ammonium hydroxide stop the copolymerization Preferred by vinyl chloride and ethylene because they are resistant to washing with a number of solvents can be easily removed from the copolymer product.

Further basic nitrogen compounds which are suitable for the method according to the invention are, for example Amines, (primary, secondary or tertiary) diamines, hydrazines, imines, heterocyclic nitrogen bases and very generally organic and inorganic nitrogen compounds with one characteristic of a base

-12 Ionization constant of at least 1 χ 10, measured in aqueous solution. The basic organic suitable for carrying out the method according to the invention Nitrogen compounds can be substituted with other functional groups, their number and type only so far are limited than the ionization constant of the organic nitrogen compound must not be lower

1 0

than 1 χ 10. The basic organic nitrogen compounds can thus through functional He groups, such as carbonyl, Carboxyl, hydroxyl, sulfhydryl, halogen, nitro, nitroso, nitrile and other functional groups substituted provided that the organic component

-12 tion has an ionization constant of at least 1 χ 10.

The basic organic nitrogen compounds can Mono- or polyamines, i.e. mono- or polyamino-substituted organic compounds. Furthermore, the basic organic nitrogen compound can be a heterocyclic organic nitrogen base which is one or more heterocyclic Contains nitrogen atoms, in addition, the heterocyclic ring or other parts of the molecule with others Atoms, such as oxygen or sulfur, can be substituted. The main requirement of the basic nitrogen compound is its basic strength, which is reflected in its ionization constant.

In particular, the following basic nitrogen 9 0 9 8 8 5/1556 ' - ~ *

BATHROOM OFIiGINAL

Atoms for the purposes of the invention: 1.) Compounds of the formula

R NR ₁

«2

wherein the molecule contains from 0 to about 22 carbon atoms and the radicals R, R ₁ and R _{2 are} hydrogen or alkyl, alkenyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy or haphthyl with up to 10 carbon atoms. Alkylamines which contain 1 to 5 alkyl radicals with 1 to 6 carbon atoms are preferred.

2.) Compounds of the formula

NR ^ N

in which the whole molecule contains 2 to about 24 carbon atoms, R, R ₁ , R ₂ and R-, which have the meanings given under 1) above, and R ^ is an aliphatic or aromatic divalent hydrocarbon radical. In the preferred compounds, R, R ₁ , R ₂ and R, are alkyl radicals having 1 to 6 carbon atoms or hydrogen and R ^ is phenylene.

5.) Compounds of the formula

RN -NR ₅

where R, R ₁ , R ₂ and R are alkyl radicals with 1 to 6 carbon atoms or aryl radicals with 6 to about 10 carbon atoms or hydrogen.

4.) Compounds of the formula

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R - C - \ CH / -C - R ₂

with 2 to about 22 carbon atoms, in which R, R. and Rq are hydrogen or are alkyl radicals with 1 to 6 carbon atoms and η is a small integer from 0 to 3> is preferably 2 or 3 and the compounds 1 to 3 double bonds in the Ring included.

5 ·) Compounds of the formula

R - NH

where R is a divalent radical, namely lower alkylidene, Clycloalkylidene or aralkylidene with 7 to about 10 carbon atoms »

6.) Heterocyclic nitrogen bases from the group Morpho-Hn, Pyridine and quinoline, these bases being substituted by 1 to 4 lower alkyl radicals.

The compounds mentioned above under 1 to 6, the with functional groups, namely carbonyl, carboxyl, Hydroxyl, sulfhydryl, halogen, nitro, nitroso or nitrile are substituted, can also be used as basic nitrogen compounds can be used in the context of the invention.

As specific examples of suitable basic nitrogen compounds may be mentioned: methylamine, n-butylamine, octylamine, ethylenediamine, diisopropylamine, di- (dodecyl) -amine, Triethylamine, methylethylarain, aniline, N-methylanilirv N, N-Di (deeyl) aniline, o-, m- and p-phenylenediamine, phenyl-ßnaphthylamine, 4-isopropylaminodiphenylamine, Ν, Ν'-di-sec-butyl-p-phenylenediamine, Pyridine, quinoline, N-n-butyl-paminophenol, aconitine, α-alanine, isoaraylamine, anthranilic acid, Apomorphine, benzylamine, benzidine, brucine, isobutylamine, sec-butylamine, caffeine, cinchonldine, cinchonine * cocaine, Coniine, creatine, creatinine, bio-amylauste, diiso-

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butylamine, diethylarain, diethylbenzylamine, dimethylamine, dimethylamino-antipyrine, Dimethylbenzylamine, emetine, ethanolamine, ethylamine, glycine, quanine, hydrastin, hydrazine, hydroquinine. Hydroxylamine, isoquinoline, Lucen, o-methoxybenzylamine, m-methoxybenzylamine, p-methoxybenzylamine, N, N-methoxybenzylamine, o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, Ν, Ν-methylbenzylamine, methyl diethylamine, Morphine, α-naphfchylamine, narcein, narcotine, nicotine, Novocaine, papaverine, p-phenetidine, 5-phenylamylamine, 4-phenylbutylamine, 2-phenylethylamine, 2-phenylmethylamine, Phenylhydrazine, 3-phenylpropylamine, Ν, Ν-isopropylbenzylamine, Physostigmine, pilocarpine, piperazine, piperidine, n-propylamine, Isopropylamine, quinidine, quinine, saroosin, semicarbazide, Solanine, sparteine, strychnine, tetramethylenediamine, Thebaine, o-toluidine, m-toluidine, p-toluidine, triisobutylamine, Trimethylamine, trimethylenediarain, tripropylamine, veratrine, pyrrole, isopyrrole, pyrazole, imidazole, 1,2,4-isotriazole ^ and Mixtures of the above and other basic nitrogen compounds.

The amount of the basic nitrogen compound to be blown into the autoclave depends on the amount of the for the copolymerization catalyst used, the blown amount of the basic nitrogen compound in mol £ should be at least the same as the amount of catalyst used in MoIJi. Preferably the basic Excess nitrogen compound, e.g. in the 2-edema * 5-> times the amount of the catalyst used.

In addition to the basic nitrogen compounds mentioned above, the organophosphines or organophosphites, which are basic in the Lewis sense, are also suitable for the purposes of the invention for terminating the copolymerization. Phosphines of the formula PUP, in which R is alkyl, aryl, substituted alkyl and substituted aryl, are suitable. Examples · ^l of this are tributylphosphine and Triphenylphöspfiinv Suitable phosphites are of the formula (RO), P wherein R is alkyl,

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Is aryl, substituted alkyl, or substituted aryl. Examples are tributyl phosphite and triphenyl phosphite.

While some of the above-mentioned basic nitrogen compounds are effective ^{M terminating agents M} for the catalyst system composed of transition metal and peroxide compound, it has been shown that compounds such as the substituted mononuclear phenols, bisphenols, styrenes, conjugated dienes χχηά quinones are particularly effective agents for regulating the rate of vinyl chloride and ethylene when this catalyst system is used. Suitable terminating agents are the alkylphenols, for example 2,6-di-t-butylphenol, 2-methyl-6-t-butylphenol, α-methyl-ot-amylphenol, 2-ethyl-6-t-butylphenol, 2-n-propyl -6- (2-hexyl) phenol, 2-n-propyl-6- (1,1-dimethylheptyl) phenol, 2-n-butyl-6-t-butylphenol, 2-isopropyl-6-t-butylphenol, 2 -Isopropyl-6-t-amylphenol, 2,6-diisopropylphenol, 2,6-di- (2-amyl) phenol, 2,6-di-sec-butylphenol and 2,6-di-t-amylphenol (see U.S. Patent 2,856,577). the nitro-substituted alkylphenols are also very effective: 4-nitro-2,6-di-t-butylphenol, ^ -nitro ^ -isopropyl-et-butylphenol, 4-nitro-2- (2-decyl) -6-t-araylphenol, 2 , 4-Dinltrophenol and 4-Nitro-2,6-Diisopropylphenol) see USA-Patent 2,866,844). The effective bisphenol compounds include 1,1-BIs- (J, 5-di-t-butyl-4-hydroxyphenol) methane, 1,1-bis- (5-t-butyl-5-t-amyl-4-hydroxyphenyl) methane , 1, l-bis (3,5-di-t-amyl-4-hydroxyphenyl) methane, l, l-bis- (3,5-di- (l # l # 3 # 3-tetramethylbutyl) 4- hydroxyphenyl) methane and 1,1-bis (3-t-butyl-5- (1,1,2,2-tetramethylpropyl) -4-hydroxyphenyl) methane (see U.S. Patents 2,900,417 and 2,944,086). Effective quinone compounds are the ^ »^ 'iS ^ S'-tetraalkyldiphenoquinones and p-benzoquinones.

Another particularly effective class of terminating agents are the styrenes, e.g., styrene, 2-methylstyrene or 4-methoxystyrene. They are also very effective as terminating agents

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conjugated dienes, e.g. 1,3-butadiene, isoprene or piperylene.

Preferred as a terminating agent when using the one consisting of the transition metal and the peroxide compound Catalyst systems are styrene or 2,4-dinitrophenol.

To illustrate the implementation and the advantages of the invention, a large number of attempts have been made Copolymerization of vinyl chloride and ethylene carried out Various methods were used here. Some of these methods are described below «.

Procedure A

The copolymerization was carried out in a 1-liter autoclave equipped with means for stirring the reaction mixture. A catalyst solution was prepared by adding the appropriate amount of air was added to a solution of Triäthylboran in JO cnr heptane at a temperature of -78 ⁰ C to obtain a catalyst mixture was obtained in which the ratio of borane to oxygen was 4: 1. The catalyst mixture was allowed to stand for 0.5-0.75 hours, after which the cylinder containing the mixture was evacuated to ensure removal of any unreacted oxygen. The catalyst solution was then added to the autoclave containing the monomeric vinyl chloride. Then ethylene was added to the autoclave in such an amount that the ethylene / Vinylchlorld ratio had the value given in Pussnote a) of Table I. The temperature at the time of addition of the catalyst mixture was approximately Hess polymerization for said in Table I Duration proceed -10 ⁰ C. Man. The reactor was then vented and the polymer filtered and washed with methanol in a Waring blender crushed and then dried at 50 ⁰ C.

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Procedure B

Oils same procedure as described above under A, was used with the exception that unconverted oxygen before the introduction of the catalyst In the autoclave was not removed from the cylinder that contained the catalyst.

Procedure C

The same work cycle as under A was used with with the exception that vinyl chloride and ethylene were placed in an autoclave that already contained the desired amount of oxygen. The reactor and its contents were cooled to the stated reaction temperatures, whereupon the stated amounts of diethylborane as a solution in 30 cnr heptane were placed in the autoclave.

Method D

1 ·) air corresponding to an amount of 0.05 mol of oxygen, 2.) 6.4 mol of vinyl chloride and 3.) 8.4 mol of ethylene were placed in a 1 liter stirred autoclave. The temperature of the reactor and contents was brought to about 1 ^° C. while the contents were stirred. The pressure in the reactor at this temperature was 77 to 84 kg / cm ^2. A solution of 0.0173 mol of triethylborane (0.12 mol. Based on total monomer) was then forced into the autoclave with nitrogen Introduction of the catalyst was 210 kg / cm. After the mixture had been stirred for the desired length of time, 10 g of liquid anhydrous ammonia was forced into the autoclave with nitrogen. After brief stirring, the reactor was vented, the product filtered and then crushed in a Waring blender with methane ©} and dried at 50 ⁰ C.

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9SSI / S88606 Temp. ° (

attempt

Triethylborane Conc, _b)

Table I.

Influence of sales on the heat resistance process sales,

C ₂ H ₄ im

Triethyl process conversion, Grenzbor an / 0 _o % ViSkO- ©, o "« «» «.

nls c)

Heat resistance, min at 182 ° C d)

• 9.5 to -9

• 11 "-8

-11 "-6

-9.5 ^w

-8.5 ^w

• 11
• 10
-10

-8th

-5 8

-6.5

-7

7.5

2.5

0.10 0.12 0.12 0.12

0.15 0.20 0.20 0.20 0.20

4 2

4 8 4 4 8 8 4

C C C C C B A A C

5.0 0.97 5.2 8.9 1.39 5.9 12.9 1.12 6.8 17.1 1.12 35.1 0.71 9.0 12.5 1.29 6.4 1 ^ 4.2 1.08 7.7 29.9 ^e ' 1.11 8.1 39.3 0.77 9.5

135 135 135 135 75 135 120

90 60

a) reaction time 2 hours, unless otherwise stated. Ethylene-vinyl chloride ratio 0.75 pressure- 10.5 to 35 kg / cm ² .

b) Based on total monomers (10 mol).

c) Intrinsic viscosity in cyclohexanone (0.1 g / LOO CNP) at 30 ⁰ C.

d) Samples for determining the heat resistance were produced by kneading the sample with 2 t Thermolit 35 and 0.5 wt. # stearic acid and pressing the mass into plates from which the test specimens for determining the heat resistance were cut. Duration of this test ι 135 minutes.

e) reaction time ^ gstands. - "i ^ - -

L / S88606 D. Table II 2.7 with or without in the polymer I. 9SS D. Influence of time on sales 4.6 13.0 VO Attempt procedure D. NH, addition. 6.0 Green viscosity 12.4 I. E. 10.0 b) 11.8 1 E. ^a 'Temp., ⁰ C time, minutes conversion, % 12.0 0.45 4.5 2 E. 16.3 0.59 8.3 3 0.5-1.0 30 0.64 8.1 4th 0.5-1.0 60 1.20 5 0.6-1.6 72 1.20 6th 0.5-1.0 30 1.23 0.5-1.0 60 0.6-1.6 72

a) Total pressure (ethylene + nitrogen) = 210 kg / cm, triethylborane concentration = 0.12

of the total monomers, B / 0 ₂ = 4 (mole ratio), CgHjj / VCl molar ratio = 1.20, b) Intrinsic viscosity in cyclohexanone j0,1 g / 100 cm ^) at 30 ⁰ C.

- 20 - I \. 7 0 5 -1 0

Method E

The same procedure as under D was used with the exception that the autoclave was used according to the desired tent vented and no anhydrous ammonia was added at the end of the experiment.

Method F

The same procedure as for D was used except that the oxygen concentration was adjusted as needed to keep the organoborane / oxygen ratio at about 4. About 5.5 to 5.7 moles of vinyl chloride were used along with about 4.0 to 4.4 moles of ethylene. The autoclave pressure at 0 ^° C. was 21

2
to 22.4 kg / cm before the addition of the catalyst mixture. The amount of triethylborane in JO cnr of the heptane used is given in Table III. The final pressure in the autoclave after the addition of the catalyst mixture was 91 kg / cm,

909885/1556

Table III

9331/888606

Ververaperatur, ⁰ C

search

Influence of the termination of the polymerization on the polymer quality . Time, total con- NHy ^C 2 ^H i | / triethyl t * ¹ - limit % CgH ^

Addition of VCl ^ ' f ^tZ * g £ _ in the poly.

did

Min

printed

kg / cm

travel

meren

Appearance of a rolled film

0.6-1.6

210

2 0-0.5 45 210 3 0 ^ 5-6.0 72 210 4th 1 * 5-2 _S 5 60 210 5 o, 5-i, o 60 210 6th 1 ^ 5-2.5 120 91 7th -G, 5 to 1.5 62 91 8th -1.0 to 0 120 91 9 0 to 4 * 5 78 133

no

1.29 0.12

E. no 1.29 0.12 E. no 1.29 0.12 E. no 1.30 0.12 E. no 1.29 0.12 P. Yes 0.8 0.06 F. Yes 0.8 0.06 P. Yes 0.7 0.05 G Yes 0.8 0.05

16.3 1.23 8.1

9.8
16.6

22.9
12.0
10.6

1.19
1.24

1.13
1.20

0.91

6.9 1.04
6.5 0.99
12.8 1.17

6.5 7.2 7.2

8.3 6.3

7.6 4.9 8.6

rough and dull

dto. dto. dto. dto.

smooth and transparent dto. "

dto. \ dto.

a) Greasiness in cyclohexanone at 30 ⁰ C (0.1 g / 100 cm ⁵ )

- 22 - ί / O 5 i Ü

Procedure O

The same procedure as under D was used with the exception that the oxygen concentration was adjusted as required so that the ratio of orgahoborane to oxygen was about 4. 8.0 moles of vinyl chloride were added to the reactor along with 6.4 moles of ethylene and 100 cnr of heptane. The pressure in the autoclave at ⁰ ° C. before the addition of the catalyst was 42 kg / cm. The final pressure after the addition of the catalyst was 133 kg / cm. It can be seen from the values in Table I that the heat resistance of the copolyroeren is impaired when the temperature of the comonomers approaches 30% . In order to produce a copolymer of vinyl chloride and ethylene with good heat resistance, the total conversion of the comonomers to the copolymer must therefore be limited to about 20 to 25 #.

The values in Table II show very clearly that post-polymerization of vinyl chloride takes place if none Termination agent is used at the end of the reaction time. Although the autoclave after the same period of time as the Attempts 2 and 3 blown off resulted in homopolymerization of vinyl chloride in experiments 4, 5 and 6 take place, recognizable by the higher rate, the higher viscosity and the lower ethylene content of the copolymer in comparison to experiments 1, 2 and 3 If no terminating agent is used, the Uhis rate in percent, the limiting viscosity of the copolymer and the ethylene content in the copolymer by the time it takes to remove the unreacted vinyl chloride and the suspended polymer required from the autoclave is greatly affected. This makes it very difficult to produce successive batches of vinyl chloride-ethylene copolymers with the same properties to manufacture.

Processing properties and physical properties.

The processing properties and some physical
Properties of the copolymers produced according to the invention were determined in order to determine the suitability of these? Mixed poly

909885/1566 '_. . _ *

- 23 - ■; ■ ■ · ο ■; ^: ο

to evaluate mers for commercial use. Some of the more important processing properties of the copolymers are 1.) Kettability on the mixing mill, 2) "nerve", recognizable by the appearance of the rolled foil, 3.) Heat resistance, determined by stability tests in the heating cabinet. For these tests, 100 parts of the copolymer were combined with a stabilizer consisting of 2.5 parts of Thermolite 35 (an organotin-sulfur compound, prepared according to the method of US Pat. No. 2,648,650) and a lubricant mixture consisting of 0.25 parts Stearic acid and 0.25 part of a paraffin wax ("Advawax 28o"). The mixture was dry blended on a Henschel mixer and then kneaded on a roller mixer at about 150 ° C for 8 to 10 minutes. The behavior during the kneading, the stability and the appearance of rolled sheets were observed during the processing by the visual inspection. Sikalische phj measurements were taken on the finished films. The heat resistance was measured by were laid from the foil test piece cut in a held at 185 ⁰ C convection oven .. The specimens were taken in from 15 minutes from the oven and aiii 'checked color.

The data for copolymerizations of vinyl chloride and Ethylene for different periods of time, different molar ratios of ethylene su vinyl chloride and verseliie = those catalyst concentrations are made in Table III. The copolymers obtained were dry in a mixer mixed with the stabilizers and the lubricant. Each Product was then rolled on a plate on a roller mixer under the same conditions. The rolled film was then examined visually and determined their appearance. In every EaIl in the ammonia at the end of the experiment had been blown into the autoclave. «had the rolled film of the copolymer had a smooth surface, and it was due to " sighted. In all other cases where the autoclave

9098857 1558 -

was only blown off and emptied, had the tarpaulin of the copolymer has a rough, cloudy surface.

In Table IV the conversion and intrinsic viscosity of juxtaposed two attempts. In one of these attempts, ammonia was blown into the autoclave. The rest Conditions were kept constant.

BAD 909885/1556

IuS IO

Table IV

Influence of the ΝΗ, addition on the UFO rate and the limiting viscosity.

Temperature, ° CN _o pressure, kg / cm C ₂ H ^ pressure, kg / cm time, minutes C ₂ H ₄ , moles of ViCl, moles of monomers, moles

Triethylborane concentration triethylborane / Og Utasatz, %

Orenz viscosity ΟλΗιι. , Qe w. %

Trial Attempts 2 "' 0.6 to 1.6 0.6 to 1.6 210 210 84 78 72 72 8.3 8.4 6.4 6.4 14.7 14.8 1.29 1.30 0.119 0.117 4th 4th 16.3 6.0 1.23 0.64 8.1 11.8

a) Orenzviskosität in cyclohexanone at 30 ⁰ C (0.1 g / 100 cmr).

b) NHy addition

BATH

909885/155

The physical properties of samples made from a vinyl chloride-ethylene copolyraerene prepared according to the invention were compared with the physical properties of samples of the vinyl chloride-ethylene copolymer, which has been produced without using a basic nitrogen compound to suppress post-polymerization was. The results of these tests are shown in Table V.

Table V "

Physical properties of vinyl chloride-ethylene copolymers.

Production Production of the copolymer without merging with breaking means breaking means

"Nerve" ^a ^ ; oriented 28.5 % ^l) 13.5 % ² ^ Color ^b ^ dark bright Tensile strength ^c
kg / cm2 700 1400 Elongation ^c ' 640 # at
76 ⁰ C IO6O
at 96 ⁰ C

Permeability to moisture

and vapors according to ASTM E 96-53 T 1.6 2.2

Resistance to light good good

a) Percentage shrinkage of the surface of the sample.

b) After kneading and pressing to form a film.

c) Oem according to ASTM D 882-56 T, but carried out at 5 mm / minute.

1) Pronounced surface structure, kantengekraus © It and wrinkled.

2) Very little surface change.

909885/1556 W.

From the values in Table V it can be seen that the vinyl chloride-ethylene copolymer made using a terminator had considerably less "nerve" than the sample produced without this additive. The inventive pleasure Copolymers tend to shrink much less than the copolymers produced by the known processes, A significant increase in the tensile strength of the oriented sample from that made according to the invention Copolymers is achieved. Probably the most striking The difference is the increased strength in the case of the copolymer according to the invention after the copolymer has been oriented is attainable at elevated temperature. That in well-known Copolymers prepared in this way had only half the elongation compared to the copolymer according to the invention at a much lower temperature.

In order to numerically express the contrast between the rough, matt and translucent surface of the old polymer produced without a terminator and the new copolymer produced with a terminator, measurements of the light transmittance were made on samples of each of the two copolymers. A sample of each copolymer was prepared from 0.15 mm thick film and mounted in a Beckman DK-2 spectrophotometer to determine the percent light transmission of each sample. The samples were then placed on the lower platen of a heated press, separated from the upper platen by a 1.25 mm thick shim, and held at 166 ° C for J5 minutes. After heating, the samples were again clamped in the spectrophotometer. In Table VI, the measured values for the percentage transmittance of light at a wavelength of 556 m λι are given.

909885/1556

- 28 - ι /.;5

Table VI

Light permeability of copolyiner samples .

Copolymers without copolymers with a terminating agent

Percentage Translucent 77 5 6o 5 sweetness 1, 33 » before the Heat after this Heat

Change in light transmission, % 75.5 26.5

From these measurements it is readily apparent that the polymer produced according to the invention, by action is much less affected by heat than the copolymer made without the addition of the terminator will. The heat treatment used in these tests corresponds to the conditions that a film of the copolymer is subjected to vacuum deformation or blow deformation. It is evident that with the copolymer according to the invention a material is obtained that has a. has better clarity and a smoother surface than that Material made from the copolymer, which is produced without the addition of a terminating agent will be produced.

A series of copolymerization experiments were carried out using the catalyst system consisting of the transition metal compound and the peroxide compound. The values and results of these tests are summarized in Table VII. All experiments were carried out in a 1 liter autoclave fitted with facilities for stirring the reacting mixture. The amount of vinyl chloride (5.9 moles) and ethylene (4.0 moles) was the same in all experiments. A pressure of 17.5 atmospheres was used in all experiments. At the end of each experiment, 2.4 dinitrophenol in a benzene solution (0.50% by weight) was forced into the autoclave. After brief stirring, the reactor was blown off, the product was filtered and then poured into

909885/1556 _ _

BATH ORIGINAL

- 29 - ι W U S Ü

a Waring blender with methanol crushed and dried at 50 ⁰ C. The resulting copolymer was excellent in heat resistance. A sheet rolled from the copolymer was clear and had a smooth surface.

BATH 309885/1556

Table VII

Vinyl chloride-ethylene copolymers, produced using a catalyst system composed of a transition metal compound and a peroxide compound.

Ver Tempe Time, Lauroyl search rature, NIn. Mon ⁰ C 0.025 1 0-7 13b ¹ 0.025 2 0-7 120 0.025 3 0 315 0.025 4th 0 244 0.025 5 0-2 247

Catalyst turnover, $ limit viscosity

cyd + iron (II) caproate sity

MoIJt

a)

^ 2 ^ 4

in the copolymer

0.01

0.125

0.021

0.125 ^C)
0.250

b)

14.1
15.1
13.7
13.3
6.2

1.42
1.45
1.70
l, 7ö
0.97

4.5 6.3 6.9 5.1 7.9

a) Qrenzviskosität in cyclohexanone at 30 ⁰ C (0.1 g / cnr ⁵⁾

b) Addition in two servings.

c) Manufactured in situ from iron (II) sulfate and sodium caproate in an aqueous medium, then followed Addition of vinyl chloride and lauroyl peroxide.

as ο to 00

ι 00

cn

απ cn cn

Claims (7)

Claims 1. A process for the preparation of vinyl chloride-ethylene copolymers, characterized in that vinyl chloride and ethylene are copolymerized up to a total conversion of the comonomers of at least 3% and the polymerization is terminated before the conversion reaches $ 20. 2 «The method according to claim 1, characterized in that one the polymerization is terminated by introducing a Lewis base into the reaction mixture. 3. The method according to claims 1 and 2, characterized in that that basic nitrogen compounds are added as Lewis bases. 4. The method according to claims 2 and 3, characterized in that that basic nitrogen compounds with ionization -12 constant of at least 1 χ 10, measured in aqueous solutions, is added and the copolymerization aborts wen.i the copolymer about 3 to 12, preferably, about 3 to β, in particular 6 to 8 wt.% Comprises ethylene. 5 * Method according to claims 1 to 4, characterized in that that the polymerization at temperatures from -25 to + 40 ° C and pressures in the range of about 7 to 280 kg / cm performs. 6. Process according to Claims 1 to 5 *, characterized in that that ammonia or ammonium hydroxide are added as basic nitrogen compounds. 7. The method according to claim 1 to 2, characterized in that substituted mononuclear phenols are used as bases of the Lewis type, Bisphenols, styrenes, conjugated dienes or quinones. 909885/155 6