DE2064498B2 - PROCESS FOR THE PRODUCTION OF THERMALLY STABLE MOLDINGS BY TREATMENT OF VINYL CHLORIDE POLYMERIZES - Google Patents

Description

The invention relates to a process for producing thermally stable molding compositions by treating vinyl chloride polymers.

The vinyl chloride polymers are used for a wide variety of purposes because of their relatively balanced properties. As a typical plastic, its consumption is highest in Japan. However , in the case of the vinyl chloride polymer, since the processing temperature and the decomposition temperature are very close to each other, special care must be taken in processing it, and it is therefore difficult to carry out continuous molding processes over a long period of time.

Because the mechanism of thermal decomposition reduction of the vinyl chloride polymer is extremely complex. is the mechanism for its stabilization so far unexplained. That is why the addition of various stabilizers that were previously mixed in ■ were, ene more or less empirical practice. the Addition of a stabilizer in such large amounts that the polymer against the strict processing boys is effectively stabilized, however, is not a desirable method for various reasons.

It has already been proposed to produce vinyl chloride polymers by polymerization at low temperature, which occur in regular structures. Starting from the viewpoint that the thermal decomposition of the vinyl chloride polymer to the irregular structures in its molecule / ack / ufüh is fen. Such a polymer, which is obtained in regular structures, is, however, more crystalline because of such a !: structure , which has the consequence. that its softening point increases, ie. its processing temperature also rises without any noticeable effect on its thermal stability.

US Pat. No. 2b 71,064 describes the production of a vinyl chloride polymer composition with improved thermal stability by kneading polyvinyl chloride with the cadmium salt of an organic acid and an ester containing epoxy groups. This patent does not contain any information about the use according to the invention of a large amount of alcohol or aqueous alcohol and the technical progress that can be achieved with it.

The aim of the invention is to improve the thermal stability of vinyl chloride polymers in a simple manner without major changes having to be made in the processing process or the shape of the vinyl chloride polymers as are currently available in order to obtain a vinyl chloride polymer which also has a whiteness substantially the same as that of the vinyl chloride polymer before its treatment.

The object according to the invention is achieved by a process for the production of thermally stable molding compositions by treating vinyl chloride polymers with epoxy compounds and carboxylic acid metal salts, which is characterized in that 100 parts by weight of vinyl chloride polymer with a mixture the end

a) 30 to 1000 parts by weight of a one or polyhydric aliphatic alcohol with 1 to 8 carbon atoms, optionally with up to 80 Volume percent water, and

b) 1 to 50 parts by weight of at least one epowd compound and or

c) at least 0.5 part by weight of an aliphatic, aromatic or cycloaliphatic carboxylic acid metal salt of a metal of the I-. II or IV main group of the periodic table, the carboxylic acid having 2 to 20 carbon atoms.

heat-treated at a temperature of 100 to 200C and for a period of 0.5 to 50 hours and then the alcohol, which may contain water, is removed in a customary manner, dissolved.

The term "vinyl chloride polymers" used here relates to both the vinyl chloride homopolymers. as is usually the case with suspension. Emulsion, Bulk or solution polymerization can be obtained, as well as the copolymers of vinyl chloride with ethylenically unsaturated copolymers Monomers. Examples of ethylenically unsaturated monomers which can be used are

the vinylidene halides. z. B.

Vinylidene chloride and vinylidene bromide.

the vinyl esters, e.g. B.

Vinyl acetate. Vinyl propionate, vinyl butyrate,

Vinyl chloroacetate, vinyl chloropropionate.

Vinyl benzoate and vinyl chlorobenzene,

the acrylic acids. alpha-alkyl acrylic acids and

the alkyl esters thereof, e.g. B.

Acrylic acid, chloroacrylic acid, methacrylic acid.

Ethacrylic acid. Methyl acrylate,

Ethyl acrylate, btitylacrylate,

n-octyl acetylate. 2-ethylhexyl acrylate,

n-decyl acrylate. MethyimethaeryUit and

Ethyl methacrylate. Amides such as B.

Acrylamide. N-methyl acrylamide.

N.N-Dime thy! Acrylamide, methacrylamide,

N-methyl methacrylamide and

N, N-dimethyl methacrylamide.

Nitriles, e.g. B.

Acrylonitrile. Chloroacrylonitrile,

Methacrylonitrile and ethacrylonitrile,

the aromatic vinyl compounds, e.g. B.

Styrene, aipha-methylstyrene, monochlorostyrene, Dichlorostyrene and vinyl naphthalene, Maleic acid, fumaric acid and

the alkyl esters thereof,

the vinyl alkyl ethers and ketones, e.g. B.

Vinyl methyl ether, vinyl ethyl ether, Vinyl isobutyl ether, methyl vinyl ketone, Ethyl vinyl ketone and isobutyl vinyl ketone,

the monoolefinic compounds, such as

z. B. vinyl pyridine, N-vinyl carbazole,

N-vinylpyrrolidone, ethylene ethyl malonate,

Isobutylene, ethylene and ethylene trichloride,
as well as other various polymerizable compounds containing an olefinic bond.

Although the vinyl chloride polymer used as starting material may be either in the form as it is obtained as a reaction mixture after completion of fine polymerization reaction or as it: o was a reaction product mixture by a suitable Isulicrungsverfahren and obtain in ungctrocknetem state or after Trocknungsslufe and in the form of a powder , it is preferably in such a state. which does not hinder its complete 2s contact with a lower aliphatic alcohol and! if necessary water.

An aliphatic hydrocarbon with 1 can preferably be used as the lower aliphatic alcohol to b carbon atoms are used. This can be either a primary, secondary, or tertiary Alcohol, and it can also be either a monohydroxy or a polyhydroxy alcohol. if If it is a normally liquid alcohol, it can be used without the js Effects according to the invention are impaired. According to the invention, these alcohols are either used one or in the form of a mixture of two or more thereof. Some of the possible ones Alcohols are methanol, ethanol. Propanol, butanol. Pentanol. Hexanol. Ethylene glycol, propylene glycol and Glycerin.

During the heat treatment, the amount of water in the alcohol is not more than 80 Volume percent. The amount of the above alcohol used and the aqueous alcohol solution is at least 30 parts by weight per 100 parts by weight of vinyl chloride polymer. If the amount of this Reaktanlen used is less than 30 parts by weight, does not become more complete even with stirring Contact between the polymer and the alcohol achieved, which has the consequence. that it will be difficult that To carry out the reaction evenly.

The epoxy compound used in the invention is a compound in its Molecular structure contains at least one oxygen atom (epoxy group) attached to two adjacent carbon atoms the carbon chain is bonded, with the epoxy group either in the main chain or in the Can be side chain. For example, coal can do something hydrogen compounds with a poxy group and with saturated and unsaturated bonds. Halogen-, Hydroxy and nitrile derivatives of such hydrocarbon compounds. Hydrocarbon alcohols with a Epoxy group and with saturated and unsaturated 6s Bonds derived from carboxylic acids and saturated and unsaturated hydrocarbon alcohols Xihpr or ester compounds and the halogen.

Hydroxy and nitrile derivatives of such ether or ester compounds are used.

Some epoxy compounds that can be used are ethylene oxide, propylene oxide, glycide, vinylcyclohexene oxide, glycidyl acrylate and glycidyl methacrylate

The epoxy compound of the type described above is expediently used in an amount of at least 1, preferably at least 3 parts by weight per 100 parts by weight of vinyl chloride polymer. If the amount of the epoxy compound used is less than 1 part by weight, the controlling effect on the discoloration of the treated polymer decreases and it is therefore undesirable. In addition, these epoxy compounds can be added all at once at the beginning , but it is recommended to add them in portions or continuously during the heat treatment , especially when an aqueous alcoholic solution is used.

The metal salts of carboxylic acids which can be used according to the invention are metal or organometallic salts of carboxylic acids having 2 to 20 carbon atoms. The carboxylic acids can be aliphatic, aromatic or alicyclic. saturated or unsaturated, monobasic or polybasic acids and they can also be those which contain a Substiiuentcnpruppe. The metals are those belonging to groups 1, 11 or IV of the Periodic Table of the Elements, for example Li. Na, K. Mg, Ca, Zn, Sr, Cd, Ba, Sn and Pb. The metal salts are dicarboxylic acids in an amount of at least 0.5. preferably at least 2 parts by weight per 100 parts by weight of vinyl chloride polymer used. A preferred range of amounts is 1 to 50 parts by weight per 100 parts by weight of polymer.

If the heating temperature is below 100 ° C., the temperatures according to the invention do not appear completely, even if the treatment is carried out over a long period of time. Although there is no special upper limit with regard to the heating temperature, treatment conditions in which the polymer to be treated is melted in the heat, which leads to mutual fusion of the powder particles to form a solid product with a high viscosity, are not desirable. Although the treatment time varies depending on the heating temperature, the treatment is preferably carried out for a long period of time at a relatively low temperature. If the treatment is carried out over a prolonged period in a zone with an elevated temperature, this is inexpedient since the effects to be achieved by adding the epoxy compound are weakened and discoloration of the polymer can also occur. The heat treatment is carried out at a temperature within the range of 100 to 200 ^r C over a period of 0.5 to 50 hours, however, from the economic point of 120 to 180 ° C, and preferably 0.5 to 20 hours.

The heat treatment is preferably carried out in an atmosphere of an inert gas or an System carried out from which the oxygen tunnel has been learned, but it is not subject to conditions limited, in which the oxygen must be completely absent.

If the alcohol (and possibly the water) is removed from the treated mixture is removed, one obtains a one

• i

Epoxy compound and / or a metal salt of a carboxylic acid-containing vinyl chloride polymerisais. It is It was expedient to remove these compounds from the polymer, to remove them completely is not required, however, and this can be used for a wide variety of purposes:, without in that it still contains these compounds, disadvantages arise.

Comparative example

A 2-1 stainless steel autoclave provided with a stirrer was charged with the components according to Table A below. After the mixture was cooled, the treated polymer was separated from the reaction vessel by filtration and washed with distilled water and then with methanol. The polymer was then dried under vacuum at 50 ° C. for 20 hours.

An additive of the recipe given in Table B was mixed with 100 parts by weight of the treated resin (Example A or B) or untreated resin (blank test) at room temperature. The resulting mixture was hot-milled at 155 ° C. for 3 minutes in a roll mill and then pressed at 160 ° C. for 3 minutes to obtain test samples.

The test samples were placed in an air bath at 190 ° C and thermal stability was determined by measuring the time (in minutes that elapsed for each sample to appear uniformly black (e).

The results are shown in Table A / u.

Table A. example example Empty- Λ B. attempt Components 300 g 300 g 300 g Polyvinyl chloride 1500 ml 450 ml - Methanol - 1050 ml - water 160 150 - Treatment ^temperature , C C 2 5 - Treatment time (hours) 70 60 30th Thermal stability (min.)

Average degree of polymerisation 800.

Table B.

Weight
share

100
4.0
1.2
0.3

0.2

Treated or untreated

Polyvinyl chloride

Epoxidized soybean oil

(Stabilizer and plasticizer)

Ca-Zn based complex

(Stabilizer)

Zn-based complex

(Stabilizer)

2,2'-methylene-bis (4-methyl-

6-t-butylphenol)

(Antioxidant)

Examples 1 to U

A stainless steel autoclave equipped with a stirrer was charged each with 100 parts by weight of distilled water, methanol or aqueous methanol and 20 parts by weight of a vinyl chloride polymer having an average degree of polymerization of 800, then the autoclave was purged with nitrogen, and then the mixture was subjected to treatment , the conditions of which are given in Table 1 below. 100 parts by weight of the modified polymer obtained were mixed with 3 parts by weight of dibutyltin maleate, 0.5 parts by weight of calcium stearate and 0.2 parts by weight of 2,2'-methylenebis (4-methyl-6-tert-butylphenol) in a roller mill for 7 minutes 155 ° C mixed and then pressed for 8 minutes at 160 ° C. The comparison of the thermal stability of the hard films obtained in this way was carried out in such a way that the time was determined which elapsed until the films had a uniformly black appearance at 190 ° C. in an air bath. The results obtained are shown in Table 1 below.

Table 1

example Methanol Treat Treatment Thermal 120 salary in lungstem lungszcit stability 160 the water temperature 240 rigen 140 Methanol 120 (Vol.-o / o) ( ⁰ C) (Hours minutes) 140 1 0 i50 5 160 2 20th 150 5 160 3 80 150 5 240 4th 100 150 5 100 5 80 130 5 mn 6th 80 130 20th 7th 80 130 40 8th 80 170 2 q 80 170 5 H) 80 80 40 11th not hch :! nrlollp ·; Bearing ·. ymonsiit ^

Example 10 is a comparative experiment in which the thermal stability was measured after the

Heat treatment at a low temperature of less than 100 "C for a long period of time had been carried out. Example 11 is also a comparative example in which the thermal stability is reduced Hand measured a vinyl chloride polymer, which was mixed and processed as in Examples 1 to 9 had been. which, however, had not been treated according to the invention.

For example 12 to 19

These tests were carried out in exactly the same way as Examples 1 to 11, but this time they were used Types of alcohol were varied. The thermal stabilities of the products obtained were also compared with the results given in Table II below.

Tabel

example Alcohol used Alcohol content Treat Treat Thermal by doing lung lungs time stability aqueous temperature alcohol ( ⁰ C) (Hours) (Minutes) 12th Ethanol 50 150 5 180 Π isopropyl alcohol 50 150 5 180 14th n-pent \ alcohol 50 150 5 180 15th N eopents! Alcohol 50 150 5 180 16 Ethylene glycol 50 150 5 160 17th Glvcerin 50 150 5 160 18th Ethanol 50 80 20th 100 19th isopropyl alcohol 50 80 20th 100

Examples 18 and 19 were comparative examples where the treatment is carried out at a low temperature for a long period of time \\ urde.

Examples 20-22

A stainless steel autoclave equipped with a stirrer was filled with 200 parts by weight of distilled water. 0.2 part by weight of partially saponified polyvinyl acetate and 0.2 part by weight of dilarnyl peroxide were charged, then the autoclave was trc-flushed with nitrogen. and then 100 parts by weight of vinyl chloride were introduced under pressure, and the polymerization reaction was carried out for 15 hours at 60 "C. The polymer conversion was 94%. and the degree of polymerization of the polymer was 940. The unreacted monomer was removed, followed by 100 parts by weight of methanol and the heat treatment was continued for 5 hours at 150 ° C. to form a modified polymer, the thermal stability of which was measured as in Examples 1 to U (Example 20.) For comparison, the thermal stability of a polymer was measured which was had been treated at 8O ⁰ C (example 21). and it was determined the thermal stability of a non-treated polymer (example 22). the results thus obtained are summarized in the following table Ui.

Table III example

Thermal

stability

(Minutes)

Examples 23 and 24

A stainless steel autoclave equipped with a stirrer was charged with 100 parts by weight of distilled water, 100 parts by weight of methanol and 0.5 part by weight of diisopropyl peroxydicarbonate. The inside of the autoclave was then purged with nitrogen, after which 100 parts by weight of vinyl chloride was added under pressure, and the polymerization reaction was carried out ^{at 50 ° C. for 20 hours.} The polymer obtained was then heat-treated in situ for 3 hours by raising the temperature is increased up to 150 ⁰ C. The polymer treated in this way was examined for its thermal stability as in Examples 1 to 11 (Example 23), and for comparison the thermal stability of a polymer obtained by omitting the 150 ° C. heat treatment stage (Example 24) was determined. The results obtained are shown in Table IV below.

Table IV Thermal
stability
(Minutes) example 120
80 23
24

20th 140 21 100 T> 100

Examples 25-28

The various vinyl chloride polymerizates given in Table V below were under varying conditions also given in Table V below using a methanol / water (50/50) mixture (based on parts by volume) treated as a solvent. The one with it The results obtained are shown in Table V below

6s shown. For comparison are in the same table also the data from Vergletchsproben given in which the various copolymers 10 hours had been treated at 80 ° C for a long time.

10

Table V Used Amount of Specific Treat Treat Thermal Thermal example Mixed polymer contained Viscosity of the lung lungs time stability Stability eggs Mixed poly Mixed poly temperature Comparison merisats merisats *) sample**) (% By weight) ("C) (Hours) (Minutes) (Minutes) Vinyl acetate 5.4 0.34 150 5 200 120 25th Ethylene 4.2 0.38 150 5 200 140 26th Methyl acrylate 5.2 0.31 130 5 180 120 27 Acetyl vinyl ether 4.3 0.37 150 5 180 100 28

*) Specific viscosity according to Goodrich: The specific viscosity was determined in a solution with a concentration of 0.4S f

measured in 100 ml nitrobenzene at 24 ° C.

**) The test pieces were produced according to the same recipe as in Example 1 and mixed for 7 minutes at 150 "C in a VVaIzwerk and then ^{pressed for 8 minutes at 155 C} C. The thermal stability was determined by measuring the time, the elapsed until the test pieces blackened in an air bath at 170 ° C, with the exception of the vinyl chloride / octyl vinyl ether copolymer sample at which a temperature of 190 ° C was used.

Examples 29 to 3b

A stainless steel autoclave equipped with a stirrer was charged with 500 parts by weight of ethanol and 100 parts by weight of a vinyl chloride polymer having an average degree of polymerization of 800, and after purging with nitrogen, 5 parts by weight of one of the epoxy compounds shown in Table VI below was added, followed by the Heat treatment carried out ^{at 150 c C for 5 hours.} After the ethanol had been removed, the vinyl chloride polymer was extracted for 24 hours with a Soxhlet extractor using methanol, and then dried under reduced pressure.

Using the modified polymer obtained in this way, according to the method described in Examples 1 to 11 given recipe made a mixture that then mix for 5 minutes at 155 ° C in a rolling mill! and then for 3 minutes at 160 ° C was pressed.

The degree of discoloration and the thermal stability (the time it took for the film to become uniform Blackening in an air bath at 190 ° C.) of the film obtained are shown in Table VI below specified.

Treatment was used to add 5 parts by weight of vinylcyclohexene oxide while mixing were to form a mixture corresponding to the mixture according to the invention, which then eberlall has been tested. Example 36, on the other hand, is a control run using a vinyl chloride polymer was used without the treatment according to the invention, using the same recipe as in de present invention a mixture was produced, which is mixed and assessed in the same way became.

Examples 37 to 39

A stainless steel autoclave equipped with a stirrer was charged with 500 parts by weight of an alcohol given in Table VII below by 100 parts by weight of a vinyl chloride polymer with an average degree of polymerization of 801, and after purging the autoclave with nitrogen, the mixture was after addition of: Parts by weight of propylene oxide for 5 hours at 150 ^: (heat-treated. The subsequent treatment to assess the product was carried out as in Examples) 29 to 36, the following! Results given in Table VII were obtained.

Table Vl Table VII

Example used

Epoxy compound

Hue of
pressed foil

Thermal

stability

(Minutes) Example used
alcohol

Color of the pressed film

Ethylene oxide

Propylene oxide

Glycid

Vinylcyclo

hexene oxide

Glycidyl acrylate

Glycidyl

methacrylate

Addition of

Vinylcyclo

hexane oxide

during the

Mixing

not treated

colorless and

transparent

the same

the same

the same

the same
the same

the same

the same

Thermal

stability

(Minutes)

180

180
180
180

180
180

120

100

37 38 39 methanol

sec-butanol

tert-butanol

pale yellowish 160

and transparent

colorless and 180

transparent

also 120

Example 35 is a control experiment in which a vinyl chloride polymer without Examples 40 to 46 according to the invention

An autoclave equipped with a stirrer au; Stainless steel was used with 500 parts by weight ethar and 100 parts by weight of a vinyl chloride polymer! with an average degree of polymerization 800 was charged and then the autoclave was purged with nitrogen. After adding propylene oxide The heat treatment was then carried out in varying amounts at a temperature within the range

/ between 130 and 170 "C and over a period of carried out for about 3 to about 20 hours. The subsequent treatment and assessment of the obtained products were carried out as in Examples 29-36. In doing so, those in the following Results given in Table VIII were obtained.

Table VIII at Used Heating Treatment Shade of the pressed Thermal example Propylene oxide mingling management time foil stability temperature (Gcw.-Tcile) ("C) (Hours) (Minutes) 1 150 5 pale yellowish and 180 40 transparent 5 130 20th colorless and transparent 180 41 5 150 10 the same 180 42 5 150 20th the same 180 43 5 170 3 pale yellowish and 180 44 transparent 5 170 5 the same 180 45 50 150 5 colorless and transparent 180 4fa Propylene oxide added, i The heat play 47 bis 49 Mixture was at for 5 hours

A stainless steel autoclave equipped with a stirrer was filled with 500 parts by weight of ethanol, charged with distilled water (varying amounts) and 100 parts by weight of a vinyl chloride polymer, and then the autoclave was purged with nitrogen and then 5 parts by weight

Table IX

treatment of 150 C carried out. During the heat treatment, 5 Parts by weight of propylene oxide introduced under pressure at hourly intervals. The following Treatment and operations were carried out as in Examples 29 to 36, except that those in FIG Results given in Table IX below were obtained.

Example distilled shade of thermal

Water pressed foil stability

(Parts by weight) (minutes)

47 100

48 50

49 25

Examples 50 to 57

A stainless steel autoclave equipped with a stirrer was filled with 500 parts by weight of ethanol, 100 parts by weight of distilled water and 100 parts by weight of a vinyl chloride copolymer. as indicated in Table X below. loaded. After that, the autoclave was filled with nitrogen rinsed, and 5 parts by weight of propylene oxide were added, then the mixture was 5 hours

Table X

colorless and
transparent
desgi.
the same

200

180
170

heat treated at 15O ⁰ C. During the heat treatment, 5 parts by weight of propylene oxide were introduced under pressure at hourly intervals. The subsequent treatment and operations were carried out as in Examples 29-36.

Examples 54 to 57 represent comparative examples in which the polymer used is not according to the invention had been heat treated. The results obtained are summarized in Table X below posed

example Vinyl chloride copolymer Vinyl chloride Specific Hue de ^r pressed Thermal
^ taHility composition (Weight o / b) Viscosity*) foil oldDlllldl 94.6 0.34 colorless and transparent (Minutes) 50 Vinyl chloride / vinyl acetate 95.8 0.38 the same 160 51 Vinyl chloride / ethylene 94.8 0.34 the same 180 52 Vinyl chloride / methyl acrylate *) 5.7 G..s7 de sgl 160 DJ Vinyschterid / OcTylvinyiaThcr 94.6 0.34 the same 54 Vinyl chloride / vinyl acetate 95.8 0.38 the same 120 55 Vinyl chloride / ethylene 94.8 034 the same 140 56 Vinyl chloride / methyl acrylate 95.7 0.77 the same 120 57 Vinyl chloride / octyl vinyl ether 100

* 1 Specific viscosity according to Goodrich.

Examples 58 to 69

A stainless steel autoclave equipped with a stirrer was filled with 540 gcwichistcils of ethanol, 50 parts by weight of distilled water, 100 parts by weight of a vinyl chloride polymer and 3 parts by weight one of the various metal salts of carboxylic acids was charged, then the autoclave was closed, and its interior was purged with nitrogen. The mixture was then under for 5 hours Stirring heated to 150 ° C. The contents have cooled filtered and dried for 24 hours at 50 "C in a vacuum.

The addition of the following standard composition was made with 100 parts by weight of this The modified vinyl chloride polymer obtained was mixed at low temperature, then the mixture was 5 Milled for minutes at I 50 C with heated rollers Then pressed for 3 minutes at 155 ° C to form the test piece.

[3 hue of the thereby obtained test piece and JCreate thermal stability (the time was elapsed until the test piece in an air bath of 180 ⁰ C black) are shown in the following Table XI.

For comparison, the following Table Xl also shows the results obtained when using a

Test piece were obtained, which was obtained from a lYlischun of 100 Gewichlsieilen an unmodified vinyl chloride polymer with an addition of the following standard composition (Example 64). as well as the results obtained when using residual pieces obtained from mixtures of 100 (lew! setting of an unmodified vinyl chloride polymer, the addition of the following standard composition and 3 parts by weight of a metal salt of a carboxylic acid were (examples h to 6 ^L i).

Addition of the standard composition (to 100 parts by weight of vinyl chloride polymer)

Plasticizer and stabilizer.

composed of epoxyglycends 4.Ί

Stabilizer composed of a complex from the base of

Ca and Zn i.2

Stabilizer, composed of

a complex based on Zn o. i

Antioxidant, composed of 2,2'-meth \ ien-bis (4-methyl-

6-tert-butylphenol) 0.2

Stearyl alcohol (lubricant) l.o

Table Xl example

During treatment
used carboxylic acid metal salts

Composition of the additive hue of the pressed film

Siubslii.il

(Minutes)

58 Lithium stearate Standard composition colorless and transparent IbO 59 Caleium acetate the same the same 160 fco Zinc stearate the same the same 160 t>! Zinc benzoate the same the same 160 t> 2 Lead stearate the same the same IbO fo3 Di-n-buivlzin dilaurate the same the same In O 64 unmodified resin the same the same SO b5 the same Standard composition + slightly reddish and 160 Lithium stearate (3 parts) transparent bb the same Standard composition ■ + · white and opaque 120 Calcium stearate (3 parts) 167 the same Standard composition: -i- desel. 30th Zinc stearate (3 parts) to & the same Standard composition + the same 30th Zinc benzoate 69 the same Standard composition + colorless and transparent 120

Di-n-butyltin dilaurate (3 parts)

Examples 70 to 72 results given in Table XIl below th were.

An autoclave provided with a stirrer from Table XIl

Stainless steel was one of the to

Alcohols given in the following Table XIl, 50 cicw; right: lcfr äesiiinerieni water, 100 üewiciKSieilen of a vinyl chloride polymer and 3 parts by weight of zinc stearate charged After rinsing the interior

example

With nitrogen in the autoclave, the mixture became 5 65 Heat-treated at 150 ° C for hours The following Mixing, milling, and judging were carried out as in BeisDtelen 58 to 69, with those in

71 72 During the
r3 "only: ii; i!" ~ alcohol used

Color of the Thermiscl

geprcStcn Ξ one ^: αε · ϋϊ = ι

(Minutes)

Methanol

sec-butanol
tert-butanol

colorless and transparent like. like.

160

160 140

Examples 73 to 76

A stainless steel autoclave equipped with a stirrer was charged with 300 parts by weight of aqueous methanol of various concentrations as shown in Table XIII below, 100 parts by weight of a vinyl chloride polymer and 3 parts by weight of salicylate. After purging the autoclave with nitrogen, the mixture was heat-treated at 150 ° C for 5 hours .

Table XlIl

The sample was developed and assessed as in Examples 58 to 69.

For comparison, a test piece was tested which was obtained from a mixture consisting of 100 parts by weight of an unmodified vinyl chloride polymer, an addition of those mentioned above Standard composition and 3 parts by weight of zinc salicylate (Example 76). The received The results are compiled in Table XIII below

Example concentrates Hue of Thermal tration of the pressed foil stability Methanol in that aqueous Methanol (% By volume) (Minutes)

73 100

74 80

75 40 7b -

Examples 77 to 87

colorless and

transparent

the same

the same

white and opaque 160

160

140

60

A stainless steel autoclave equipped with a stirrer was charged with 450 parts by weight of methanol. 50 parts by weight of distilled water and 100 parts by weight of a vinyl chloride polymer were charged, then the autoclave was flushed with nitrogen. Thereafter, zinc lactate was added in varying amounts and the heat treatment of the mixture was at a temperature within the range from 130 to 170 ¹ C over a period

35 carried out between 3 and 20 hours. In carrying out the subsequent treatment and the judgment of the product obtained Proceeding as in Examples 58 to 69th

For comparison, a from a mixture of 100 parts by weight of a non-modified vinyl chloride polymer, which an additive of the above-described standard composition and zinc lactate were added in varying amounts, Herge notified test piece was investigated. The results obtained are summarized in Table XIV below.

Table XIV example

Zinc lactate
(Parts by weight)

Heating temperature

5
5
5
5

5
5

20th

150

130 150 150 150

170 170

150

Treatment time (hours) 5

20 5

10 20

3 5

non-modified PVC + addition of the standard composition ■ + ■ / incl + Addition of the standard composition + zinc acetate (2 parts by weight) shade of the pressed film

Thermal

stability

(Minutes)

pale yellowish and 140

transparent

colorless and transparent 100

also 160

also 180

pale yellowish and> 200

transparent

also '160

also 140

also 160

colorless and transparent 30

white and opaque <30

the same. <20

Examples 88 to 100

A flask equipped with a stirrer autoclave o-free steel was charged with 900 parts by weight of methanol, 100 parts by weight of distilled water, 3 parts by weight of zinc stearate and 100 parts by weight of a given in the following table vinyl chloride polymer, and then the mixture was treated for 5 hours at 150C. The following

Treatment and assessment of the product obtained was as in Examples 58 to carried out

For comparison, test pieces were prepared from mixtures composed of 100 parts by weight of an unmodified Vinyl chloride copolymer passed, the addition of the standard composition given above and 3 parts by weight of zinc stearate had been added (Examples 92, 94, 97 and 99). Further, a test piece was prepared from a mixture composed of 100 parts by weight of a modified one Vinyl chloride copolymer obtained by heat treating 100 parts by weight of a vinyl chloride copolymer with 900 parts by weight of methanol

Table XV

and 100 parts by weight of distilled water and the addition of the above Standard composition had been added (Example 96), and test pieces made from mixtures that of 100 parts by weight of a modified vinyl chloride copolymer obtained by heat treatment from 100 parts by weight of methanol and 100 parts by weight of distilled water and to which the addition of the standard composition specified above had been added, and 3 parts by weight of zinc stearate (Examples 93, 95, 98 and 100). These test pieces were evaluated. The results obtained are summarized in Table XV below.

example

Vinyl chloride copolymer resin Composition Color of the pressed film

Vinyl chloride

salary

(% By weight) Specific
Viscosity*)

Thermal stability!

(Minutes)

& 8 vinyl chloride / vinyl acetate 94.6

89 vinyl chloride / ethylene 95.8

90 vinyl chloride / methyl acrylate 94.8

91 vinyl chloride / octyl vinyl ether 95.7

92 vinyl chloride / vinyl acetate 94.6

93 and 94.6

94 vinyl chloride / ethylene 95.8

95 same as 95.8

96 same as 95.8

97 vinyl chloride / methyl acrylate 94.8

98 the same "94.8

99 vinyl chloride / octyl vinyl ether 95.7 100 the like '"95.7

ii) 4
0.34
0.38
0.38
034
0 34
0.34
0.37
0.37

colorless and transparent

the same

the same

the same

white and opaque

slightly brownish and opaque

white and opaque

slightly brownish and opaque

the same

white and opaque

slightly brownish and opaque

white and opaque

slightly brownish and opaque

100 180 100 180

30 30 30 30 160 30 30 30 30

Specific viscosity according to Goodrich.

Claims (1)

Claim: Process for the production of thermally stable molding compounds by treating vinyl chloride polymers with epoxy compounds and carboxylic acid metal salts, characterized in that 100 parts by weight of vinyl chloride polymer with a mixture of a) 30 to 1000 parts by weight of a monohydric or polyhydric aliphatic alcohol with 1 to 8 Carbon atoms, optionally with up to 80 percent by volume of water, and b) 1 to 50 parts by weight of at least one epoxy compound and / or c) at least 0.5 part by weight of an aliphatic, aromatic or cycloaliphatic carboxylic acid metal salt of a metal der [-. Fl or! V main group of the periodic table, the carboxylic acid having 2 to 20 carbon atoms. at a temperature of 100 to 200 ° C and for a period of 0.5 to 50 hours heat-treated and subsequently the alcohol, optionally containing water, in the usual way Will get removed.