CH635597A5 - Process for the continuous preparation of vinyl chloride homopolymers, copolymers or graft polymers - Google Patents

Description

The invention relates to a method according to claim 1.

It is known to the person skilled in the art that, depending on the type of production of vinyl chloride homo-, co- or graft polymers, differences in the stabilizability of these polymers can be observed using known heat stabilizers. For example, pre-stabilizing emulsion polymers with inorganic, alkaline reacting salts, such as sodium carbonate, can be stabilized quite well with diphenylthiourea, especially if the subsequent processing temperatures are not too high, for example below 200 ° C. In contrast, the stabilizing effect of the di-phenylthiourea in suspension and bulk polymers of vinyl chloride is relatively low.

But even with known metal-containing stabilizers, such as lead or barium / cadmium or tin compounds, such differences are dependent on the type of polymerization (emulsion, suspension, bulk polymerization) as well as within one type of polymerization, for example emulsion polymerization Dependence on the polymerization conditions used, in particular the polymerization auxiliaries used, found. If something is changed in the polymerization recipe in order to improve the stabilizability of the polymer produced in any direction, other disadvantages such as poorer yield, poorer processability, deterioration of the stabilizability with other classes of stabilizers have to be accepted.

In order to avoid a variety of types which confuse the further processor, thereby favoring processing failures, undesirably increasing storage and worsening the cost-effectiveness of production, it is desirable to use only one or at least a few types of polymer which are to be stabilized as universally as possible during further processing to produce as economically as possible. It is the object of the present invention to provide a method for this.

DE-AS 1 223 556 discloses a process for the polymerization of ethylenically unsaturated compounds in the aqueous phase in the presence of catalysts and salts of monocarboxylic acids of the formula

I \

R3 OH

with a total of 11 to 32 carbon atoms in the molecule, where R 1 and R 2 are an alkyl group, R 3 is an alkyl group or a hydrogen atom and two or three of the groups bonded directly to the tertiary or quaternary C atom can be cyclically linked to one another, the designation Alkyl groups also include cycloalkyl groups. The process is said to be particularly suitable for polymerization at temperatures below 10 ° C.

Vinyl chloride is mentioned among a large number of suitable ethylenically unsaturated monomers, and in one example the homopolymerization of vinyl chloride is described by an apparently discontinuous process. The following are used as emulsifiers: Sodium salts of unsaturated aliphatic monocarboxylic acids with 11 to 32 carbon atoms in the molecule, the carboxyl group of which is bonded directly to a tertiary or quaternary carbon atom. A precise indication of which sodium salt was used is missing.

DE-AS 1 645 672 also discloses a process for polymerizing and copolymerizing vinyl chloride in aqueous emulsion using a polymer seed latex in the presence of water-soluble salts aliphatic.

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635 597

tical, saturated monocarboxylic acids branched in the alpha position to the carboxyl group and having at least 8 carbon atoms per molecule as emulsifiers. Suitable monocarboxylic acids correspond to the formula mentioned in DE-AS 1 223 556, but the radicals R 1, R 2 and R 3 have extended meaning compared to DE-AS 1 223 556 in that they can also mean aryl or aralkyl groups. It is advisable to use monocarboxylic acids with 11-28 carbon atoms, especially those with 15-19 carbon atoms.

According to or DE-PS 1 745 561, the process of DE-PS 1 645 672 can also be carried out if, instead of the salts of the monocarboxylic acids described therein, the salts of monocarboxylic acids of the formula

// °

R1-CHR2-C

\

OH

used, where Ri is a branched alkyl group and R2 is a linear or branched alkyl group or a hydrogen atom, at least 50%, preferably at least 80%, of the radical R2 are hydrogen atoms and the sum of the C atoms in Ri and R2, which also form a ring can be connected, is at least 6.

As is evident from the examples, all three known processes relate to batch (batch) emulsion polymerization processes. When the known processes are transferred to the continuous emulsion polymerization of vinyl chloride, there are disadvantages, in particular with regard to the space-time yield to be achieved in connection with the thermostabilizability of the polymer produced with lead, barium / cadmium and tin stabilizers, as described below Comparative experiments emerged.

It has now been found that a selection from the large number of salts of branched monocarboxylic acids which can be used according to DE-AS 1 223 556, DE-PS 1 645 672 and DE-AS 1 745 561 is surprisingly good in the continuous polymerization of vinyl chloride in aqueous emulsion Thermostability of the polymer produced with lead, barium / cadmium and tin stabilizers in conjunction with high space-time yields during the polymerization.

The invention accordingly relates to a process for the continuous production of homo-, co- or graft polymers of vinyl chloride which contain at least 85% by weight, based on the total polymer, of polymerized vinyl chloride and which optionally contain other comonomers and / or graft polymers in copolymerized form in an aqueous emulsion Presence of at least one water-soluble catalyst, 1.5 to 3.5% by weight, based on the monomer used, of at least one water-soluble emulsifier and optionally further polymerization auxiliaries, which is characterized in that at least one water-soluble salt of an aliphatic saturated monocarboxylic acid is used as the water-soluble emulsifier of formula I.

RI (CH2) 3

1 (I)

R2 (CH2) 5-CH-COOH

wherein R 1 and R 2 are the same or different and each represent a saturated, unbranched or branched alkyl having 1 to 5 carbon atoms, or a mixture of a salt mentioned above with at least one sodium, potassium or ammonium salt of a sulfate or effective emulsifier sulfo group-containing organic compound is used.

Preference is given to the water-soluble salts of a monocarboxylic acid of the formula I, in which R 1 and R 2 are the same and mean an alkyl radical having 2 to 4 carbon atoms, both because of the favorable properties during the polymerization and the polymer produced, and also because of the easy accessibility of the monocarboxylic acids .

Particularly good results are achieved with 2-hexyl-decanoic acid (1).

Water-soluble salts of the monocarboxylic acids mentioned are generally those of which at 50 ° C. at least about 0.5% by weight, based on the solution, of the monocarboxylic acid anion dissolves in water. The salts with alkali metals or the salts of ammonium which is optionally substituted with organic groups are preferably used. Suitable organic substituents for ammonium are, for example, one to four of the following groups: alkyl groups with 1 to 6 C atoms, alkylaryl groups with 7 to 9 C atoms; Hydroxylalkyl groups with 2 to 4 carbon atoms, halogenoalkyl groups with 1 to 6 carbon atoms, polyalkoxy groups with 2 and / or 3 carbon atoms in the polymerized alkoxy group formed by reaction with ethylene oxide or propylene oxide. Monocarboxylic acid salts with at least two different monocarboxylic acid anions or with at least two different cations in admixture with one another can also be used. Likewise, at least two water-soluble salts in which both the monocarboxylic acid anion and the cation are different from one another can be used in a mixture with one another.

Of the mixtures described above, 1.5 to 3.5% by weight, based on the monomer used, are used in the polymerization; below 1.5% by weight, no latices which are sufficiently stable for further processing are generally obtained. Above 3.5%, polymers with poorer performance properties such as transparency, sensitivity to water and physiological harmlessness are obtained.

The sodium, potassium and ammonium salts of the monocarboxylic acids are preferably used, in particular the sodium salts.

Particularly good results are obtained if 1.5 to 2.8% by weight, based on the monomers used, of one of the monocarboxylic acid salts described above or a mixture of several such salts are used.

The monocarboxylic acids of the formula I or their salts are prepared, for example, by the reaction of Guerbet (see Angew. Chemie 64th year 1952 pages 213-220), initially using alkaline condensing agents and dehydrogenation catalysts from two straight-chain aliphatic alcohols in general A branched chain high molecular weight alcohol is formed according to the following equation

2 RCH2CH2OH RCH2CH2-CH-CH2OH

(wherein R can be an alkyl; cycloalkyl or arylalkyl radical).

This branched alcohol can now be oxidized to the carboxylic acid using known methods, for example with chromic acid, and the salts can be produced therefrom. The branched acids are formed in the Guerbet reaction

RCH2CH2-CH-COOH R

however, even as by-products, whereby the reaction can be controlled so that about half and half branched alcohol and branched acid are formed [J. At the. Soc. 76 (1954) pp 52-56]. By using alcohols with different radicals R, analogously branched higher molecular alcohols with different radicals R are formed [fats, soaps, paints 71 (1969) pp. 215-218], from which, as mentioned above, correspondingly

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Carboxylic acids with different radicals R and their salts can be produced.

It was also found that, in addition to the good properties which the process according to the invention produces and without damage to these properties, the thermostabilizability with tin compounds and the processability (gelling ability) of the polymer produced can be further improved if a part of the water-soluble salts the branched monocarboxylic acids of the formula I are replaced by the sodium, potassium or ammonium salts, preferably the sodium salts, of certain known sulfate- or sulfo-containing organic compounds which are active as emulsifiers. The latter compounds are preferably used in an amount of 25 to 85% by weight, based on the total amount of the emulsifier used. The total amount of the emulsifier is again 1.5 to 3.5% by weight, preferably 1.5 to 2.8% by weight, based on the monomer used.

These sulfo-containing organic compounds known as emulsifiers are, for example:

a) Monoalkylsulfuric acid esters, the alkyl radical of which is saturated, straight-chain or branched and contains 8 to 20 carbon atoms. Monoalkylsulfuric acid esters are preferably used, the alkyl radical of which is straight-chain and contains 10 to 14 carbon atoms or the alkyl radical of which is branched and contains 12 to 18 carbon atoms.

b) a -sulfocarboxylic acid alkyl esters, the carboxylic acid portion of which contains 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms and whose alkyl groups are saturated, straight-chain or branched and contain 1 to 4 carbon atoms.

c) sulfosuccinic acid di-alkyl esters, the alkyl groups of which are identical or different, each alkyl group being saturated, straight-chain or branched and containing 6 to 14, preferably 8 to 12, carbon atoms.

d) sulfosuccinic acid mono-alkyl esters whose alkyl group is saturated, straight-chain or branched and contains 8 to 20, preferably 10 to 16 carbon atoms.

Particularly good results are obtained if the organic compounds containing sulfate or sulfo groups mentioned under a to d and known as emulsifiers are used as their salts in an amount of 35 to 65% by weight, based on the total amount of the emulsifier used.

Of the compounds mentioned under a to d as their sodium, potassium or ammonium salts, only one or more of such salts can be used in a mixture with one another, the constituents of the mixture being found either only in the cation of the salt or only in the sulfo-containing organic anion of the salt or can distinguish both in the cation and in the anion of the salt.

If several of the aforementioned salts are used in a mixture with one another instead of just one salt, the mixture is used in the same amounts described above as if only one salt were used.

The emulsifiers or emulsifier mixtures to be used according to the invention are generally added to the polymerization mixture, dissolved in water, with stirring. To improve solubility, organic solvents, for example lower aliphatic alcohols, can be added to the water.

The polymerization is carried out continuously in aqueous emulsion in the presence of preferably 0.001 to 1% by weight, particularly preferably 0.01 to 0.3% by weight (based on monomers) of free-radical-forming water-soluble catalysts. Peroxidisulfates, peroxidiphosphates, perborates of potassium, sodium or ammonium are suitable for this purpose; Hydrogen peroxide; tert-butyl hydroperoxide or other water-soluble peroxides and also mixtures of various catalysts, these catalysts also in the presence of generally 0.001 to 1% by weight, based on monomer, of one or more reducing substances which are suitable for building up a redox catalyst system , such as Sulfites, bisulfites, dithionites, thiosulfates, aldehyde sulfoxylates, e.g. Sodium formaldehyde sulfoxylate can be used. If appropriate, the polymerization can be carried out in the presence of 0.05 to 10 ppm, based on the metal cation of the salt per monomer, of soluble metal salts, for example of copper, silver, iron, nickel, cobalt or chromium.

In addition to catalysts and emulsifiers, the polymerization can e.g. in the presence of buffer substances, for example alkali acetates, borax, alkali phosphates, alkali carbonates, ammonia or ammonium salts of carboxylic acids and e.g. of molecular size regulators, such as aliphatic aldehydes with 2 to 4 carbon atoms, halogenated hydrocarbons, e.g. Di- and trichlorethylene, chloroform, bromoform, methylene chloride, mercaptans can be carried out.

For copolymerization with vinyl chloride, for example, one or more of the following monomers are suitable: olefins such as ethylene or propylene, vinyl esters of straight-chain or branched carboxylic acids having 2 to 20, preferably 2 to 4 carbon atoms, such as vinyl acetate, propionate, butyrate, -2-ethylhexoate; Vinyl halides such as vinyl fluoride, vinylidene fluoride, vinylidene chloride, vinyl ethers, unsaturated acids such as maleic, fumaric, acrylic, methacrylic acid and their mono- or diesters with mono- or dialcohols having 1 to 10 carbon atoms; Maleimide, and its N-substitution products with aromatic, cycloaliphatic and optionally branched aliphatic substituents.

For example, elastomeric polymers obtained by polymerizing one or more of the following monomers can be used for the graft polymerization: dienes such as butadiene, cyclopentadiene; Olefins such as ethylene, propylene; Styrene, unsaturated acids such as acrylic or methacrylic acid and their esters with mono- or dialcohols with 1 to 10 carbon atoms, acrylonitrile, vinyl compounds such as vinyl esters of straight-chain or branched carboxylic acids with 2 to 20, preferably 2 to 4 carbon atoms, and together with at least one of the aforementioned monomers, vinyl halides such as vinyl chloride, vinylidene chloride.

Other suitable polymerization aids are e.g. described in the book “Polyvinylchloride and Vinyl Chloride Copolymers” by H. Kainer, Springer-Verlag, Berlin-Heidelberg / New York, 1965, pages 34 to 59.

After the polymerization, further substances for stabilizing or improving their further processing properties can be added to the polymers obtained as an aqueous emulsion or after drying as a powder.

The polymerization is generally continued at temperatures from 30 to 80 ° C., preferably from 40 to 70 ° C., up to conversions of 87 to 95%, preferably 89 to 91%, based on the monomer used. The percentage conversion can be determined in the continuous emulsion polymerization process as described below.

The pH during the polymerization is generally 7.5 to 10.5.

The ratio of liquor to monomers is expediently chosen so that latices with solids contents of about 40 to 48%, preferably 43 to 46%, are obtained.

After the polymerization has ended and the majority of the unreacted monomers have been removed, the polymer is generally removed by evaporating the water, for example in a spray dryer. If necessary, the latex can be dried by physical Me5

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methods, for example ultrafiltration, are freed from part of the aqueous liquor.

The new process is used to produce vinyl chloride homo-, co- or graft polymers with at least 85% by weight (based on polymer) of polymerized vinyl chloride units. This process is particularly suitable for the production of vinyl chloride homopolymers.

The process according to the invention makes it possible to use a variety of technically important heat and light stabilizers, in particular the known compounds of lead, tin and the mixed barium / cadmium compounds, to stabilize vinyl chloride polymers with the advantages of to produce continuous emulsion polymerization with high space-time yields. The emulsifier mixtures provided according to the invention further improve the stabilizability with tin compounds and improve the processing properties (gelling ability) of the polymer produced.

Known lead, tin and barium / cadmium stabilizers for vinyl chloride polymers are described, for example, in “The Stabilization of Polyvinylchloride” by F. Chevassus and R. de Broutelles; Edward Arnold Pubi. Ltd. 1963, pages 102 to 129 and in “The Stabilization of Plastics Against Light and Heat” by J. Voigt; Springer-Verlag 1966, pages 614-643.

The following examples are intended to explain the invention in more detail.

The stated measured values were determined as follows.

K value: according to DIN 53 726.

Foam weight: Shortly after the discharge opening of the boiler, in which the continuous polymerization takes place, there is a closable outflow opening of 15 mm 0. For the measurement, the latex under pressure is let out, foaming due to its content of unpolymerized monomers. When the foam flow has become uniform, let it flow into a previously weighed metal vessel that contains exactly 2 liters up to the edge. After the vessel has been completely filled, the excess foam is wiped off over the rim of the vessel and the filled vessel is then immediately weighed. The weight gain is the foam weight abbreviated below with S.G. in g.

The turnover is calculated from the foam weight using the following formula:

% Sales =

(S.G. - giVC) x% solid

(S.G. - gjVQx solid / 100% + gì VCxg2VC in which:

giVC =

(2 - S.G. / 1150 g / 1) x 273 ° C x 2.78 g / 1 x p (273 ° C - 8 ° C + t) X 760 Torr

% Solids = solids content in the polymer dispersion in% by weight less the content in% by weight (based on dispersion) of polymerization auxiliaries used which are not volatile at about 100 ° C. with water vapor.

g2VC = In the relaxed, foam-free polymer dispersion, gas chromatography using the «head space» method [Zeitschrift f. analyt. Chemie 255 (1971) pp. 345 to 350] determined content of monomeric vinyl chloride t = polymerization temperature in ° C

p = air pressure in Torr.

The conversion for vinyl chloride copolymers is to be calculated analogously if VC in the above equations is understood as the sum of the amounts of the monomeric vinyl chloride and the comonomer or comonomers.

Space-time yield:

It is defined by a certain amount of dry polymer (in tons), which in a unit of time (here: 1 month calculated to 658 production hours) continuous, 5 continuous polymerization in a certain closed space available for this polymerization (in m3; e.g. content a polymerization vessel) is generated. The space-time yield (hereinafter abbreviated to R.Z.A.) is given in moto / m3. io measurement: The polymer dispersion formed continuously over the course of 24 hours approximately 3 days after the start of the polymerization is sprayed in a warm air stream at an inlet temperature of approximately 170 ° C. to a residual water content of approximately 0.2% by weight. (based on polymer) 15 dried and weighed. The quantity determined (in t) is multiplied by 658/24 and divided by the content of the polymerization vessel used (in m3).

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Stabilizability:

According to the following recipes:

Lead stabilization abbreviated Pb hard

Vinyl chloride polymer 100 parts of three-part lead sulfate 1.5 parts

25 montanic acid glycol esters 0.5 parts

Polyethylene wax (MW approx. 2000) 0.3 parts soft

Vinyl chloride polymer 100 parts

30 three-base lead sulfate 1.5 parts

Montanoic acid glycol ester 0.5 parts

Polyethylene wax (MW approx. 2000) 0.3 parts

Di-2-hexylethyl phthalate 20 parts

Tin stabilization abbreviated Sn

35

hard

Vinyl chloride polymer 100 parts

Dibutyltin bisthioglycolic acid 2-ethylhexyl ester 1.5 parts montanic acid glycol ester 0.5 parts

Titanium dioxide 2.0 parts

40

Barium / cadmium stabilization abbreviated Ba / cd soft

Vinyl chloride polymer 100 parts

4J Ba / Cd laurate equimolar mixture 1.5 parts

Montanoic acid glycol ester 0.5 parts

Di-2-hexyl ethyl phthalate. 20 parts are each thoroughly mixed 300 g of polymer powder to be tested with the corresponding amounts of the other recipe components and as long as on a rolling mill (roll diameter 150 mm, roll length 350 mm) at 175 ° C rolling temperature, at a speed of 11 RPM rolled without friction until the material turns dark brown and begins to stick. A 0.3 mm thick 55 plate is removed every five minutes and the degree of discoloration is determined by measuring the yellowness index (abbreviated YI; according to ASTM D 1925-70 1970, book of ASTM standards, Part 27). The YI is a measure that indicates the degree of discoloration relative to a defined white standard (magnesium oxide) when wetted by a defined lighting source (normal light type C).

The initial color (abbreviated AF) of the articles made from the polymer powder indicates the lead YI stabilization of the platelet after 30 min and the Bari-65 µm / cadmium of the platelet YI after 15 min rolling time. The long-term stability (abbreviated LZ) in minutes results from the rolling time of the plate, in which the YI is over 150 units for the first time.

635 597

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Fell formation time

The coat formation time is determined as a measure of the plasticizing speed (gelling ability) of the PVC powder: 300 g of polymer powder are mixed with 4.5 g of three-base lead sulfate (eg Naftovin T 3, Metallgesellschaft AG), 1.5 g of mono 5-tanoic acid glycol ester (Wax E, Hoeachst AG) and 0.6 g polyethylene wax (wax PA 520, Hoechst AG) intimately mixed with a spatula. The mixture is then distributed evenly over the 0.1 mm wide nip of a two-roll mill, the rollers of which, rotating in opposite directions and rotating at 11 rpm, have a diameter of 150 mm, a length of 350 mm and a surface temperature of 175 ° C . The pair of rollers is then gradually moved apart up to a gap width of 0.7 mm. The opening of the roller gap should be done in such a way that the thicker rolled skin always seals the roller gap in order to prevent the still unplasticized material from falling through. Rolling is continued until all polymer powder is in the form of fully plasticized rolled skin. The time required for this is the fur formation time. 20th

Examples 1 to 15 and comparative experiments A to H are carried out as follows:

In a vertical autoclave with a content of 500 l, in the upper part of which a blade stirrer rotates, the monomer or monomer mixture, a 2.6% aqueous solution of the emulsifier or emulsifiers and a 2% aqueous solution of potassium persulfate (continuously) introduced. 0.95 kg of emulsifier solution and 0.03 kg of persulfate solution are added per kg of monomers. The temperature of the reaction mixture is kept constant (values see table).

The polymer dispersion formed is removed in the lower part of the autoclave and the foam weight (S.G.) is measured.

The polymer dispersion contains a solids content of approx. 47% by weight, is mechanically stable and is dried by spraying in an air stream heated to approx. 170 ° C. (inlet temperature).

The foam weight is a measure of the degree of conversion in the polymerization. The lower the foam weight, the higher the polymerization temperature for a desired degree of polymerization (K value) can be selected. This in turn means a cheaper space-time yield (R.Z.A.) and thus a more economical manufacturing process.

The following values were measured:

Comparative tests

Stabilizability

Emulsifiers

Amount of Polyme- Pb Sn Ba / Cd related in a way risk-soft hard hard soft Fellbildg.

Monomeric temp. S.G. K value R.Z.A. AF LZ AF LZ AF LZ AF LZ time

% By weight ° C g moto / m3 YI 30 'min YI 30' min YI 30 'min YI 15' min min

A 2.6 iso-octadecanoic acid according to DTPS 1 745 561 50 Example 5

B 2.6 iso-tridecanoic acid according to DTPS 1 745 561 50 Example 1

C 2.6 monocarboxylic acid

"Versatic 1519" according to DTPS 1 645 672 example 1

D 2.6 lauric acid 49

E 2.6 SB ester 48

F 2.6 SBH esters

G 2.6 SF ester 50

140 69-70 33

140 69-70 33

23 150 50 105 48 90 24 165 7.30

24 135 53 105 48 75 56 105 6.00

for a S.G. <160 no polymerization possible

150 69-70 29 27 165 57 150 39 120 38 165 8.00

160 69-70 25 95 75> 100 45 16 90 52 60 5.50

for a S.G. <160 no polymerization possible

140 69-70 33 88 60> 100 45 18 120 40 60 5.25

H 2.0

LS ester

53

115 69-70 48

83 105 99 90 13 150 42

60 6.50

7

Examples

635 597

No emulsifiers

Quantity related on Art

Monomeric

% By weight

Stabilizability

Polyme- Pb Sn Ba / Cd

Quantity risk-soft hard hard soft Fellbildg.

behaves- temp. K value R.Z.A. AF LZ AF LZ AF LZ AF LZ time ° C g moto / m3 YI 30 'min YI 30' min YI 30 'min YI 15' min min ms

1 2.6

2 2.6

3 2.6

4 2.6

5 2.6

6 2.6

7 2.6

8 2.6

9 2.6

10 2.6

11 2.6

12 2.0

13 3.2

14 2.0

15 2.0

2-butyl

octanoic acid

2-hexyl

decanoic acid

2-octyl

dodecanoic acid

HD acid SB ester

HD acid LS ester

HD acid SBH ester

HD acid SF ester

HD acid LS ester

HD acid SF ester

HD acid LS ester

HD acid SF ester

HD acid LS ester

HD acid LS ester

HD acid LS ester

HD acid LS ester

- 51

- 53

- 53 50/50 53 50/50 54 50/50 51 50/50 53 15/85 53 30/70 51 60/40 54 75/25 53 60/40 54 50/50 54 35/65 44 60/40 62

130 69-70 38

115 69-70 48

115 69-70 48

115 69-70 48

110 69-70 53

130 69-70 38

115 69-70 48

115 69-70 48

130 69-70 38

110 69-70 53

115 69-70 48

110 69-70 53

110 69-70 53

115 78 -

115 60 -

32 135 62

30 135 53 24 135 48

24 90 44 29 135 48 29 120 44 26 135 50

31 105 62 22 120 55

25 135 44 36 150 45 21 150 41 18 135 62 28 135 49 24 105 57

120 50 120 51 120 45 75 45 105 41 90 44 105 44 75 20 75 35 120 36 135 55 120 37 105 37 105 31 75 52

75 18 165 7.00

75 23 165 7.75

75 26 165 8.25

75 35 75 4.00

90 33 90 28 90 30 105 10 120 25 75 24 75 53 90 14 75 25 120 21 75 26

105 2.75

90 3.75

105 3.45

45 6.50

60 4.25

90 4.00

105 4.50

105 4.30

90 2.75

90 3.75

75 4.00

In the table mean:

Column 4: quantitative ratio in parts by weight on the total emulsifiers = 100 parts

Column 3: Short description of the emulsifiers: the Na salt was used in each case HD acid = 2-hexyldecanoic acid SB ester = diisodecyl sulfosuccinic acid ester LS ester = mono-lauryl sulfuric acid ester SBH ester = mono-idodecyl sulfosuccinic acid ester SF ester = Lauryl-a-sulfofatty acid methyl ester v

Claims (7)

635 597 1. Process for the continuous production of homo-, co- or graft polymers of yinyl chloride which contain at least 85% by weight, based on the total polymer, polymerized vinyl chloride and which optionally contain other comonomers and / or graft polymers copolymerized in aqueous Emulsion in the presence of at least one water-soluble catalyst and 1.5 to 3.5% by weight, based on the monomer used, of at least one water-soluble emulsifier, characterized in that at least one water-soluble salt of an aliphatic saturated monocarboxylic acid of the formula is used as the water-soluble emulsifier I. Ri (CH2) 3 I (I) R2 (CH2) 5-CH-COOH wherein R 1 and R 2 are the same or different and each represent a saturated, unbranched or branched alkyl having 1 to 5 carbon atoms or a mixture of a salt mentioned above with at least one sodium, potassium or ammonium salt of a sulfate or sulfo group-containing emulsifier organic compound is used. 2. The method according to claim 1, characterized in that at least one water-soluble salt of a monocarboxylic acid of the formula I, in which R 1 and R 2 are the same and are an alkyl radical having 2 to 4 carbon atoms, is used. 2nd PATENT CLAIMS 3. The method according to claim 2, characterized in that 2-hexyl-decanoic acid (1) is used. 4. The method according to any one of claims 1 to 3, characterized in that in addition to at least one water-soluble salt of a saturated aliphatic monocarboxylic acid of the formula I at least one sodium, potassium or ammonium salt of a monoalkylsulfuric acid ester, the alkyl radical of which is saturated, straight-chain or branched and 8 contains up to 20 carbon atoms, in an amount of 25 to 85, preferably 35 to 65,% by weight, based on the total amount of the emulsifier used. 5. The method according to any one of claims 1 to 3, characterized in that in addition to at least one water-soluble salt of a saturated, aliphatic monocarboxylic acid of the formula I at least one sodium, potassium or ammonium salt of an α-sulfocarboxylic acid alkyl ester, the carboxylic acid content of 8 to 20 Contains carbon atoms and whose alkyl group is saturated, straight-chain or branched and contains 1 to 4 carbon atoms, in an amount of 25 to 85, preferably 35 to 65,% by weight, based on the total amount of the emulsifier used. 6. The method according to any one of claims 1 to 3, characterized in that in addition to at least one water-soluble salt of a saturated, aliphatic monocarboxylic acid of formula I at least one sodium, potassium or ammonium salt of a sulfosuccinic acid di-alkyl ester, the alkyl groups of which are the same or are different, each alkyl group being saturated, straight-chain or branched and containing 6 to 14 carbon atoms, in an amount of 25 to 85, preferably 35 to 65,% by weight, based on the total amount of the emulsifier used. 7. The method according to any one of claims 1 to 3, characterized in that in addition to at least one water-soluble salt of a saturated, aliphatic monocarboxylic acid of formula I at least one sodium, potassium or ammonium salt of a sulfosuccinic acid monoalkyl ester, the alkyl group of which is saturated, straight-chain or branched and contains 8 to 20 carbon atoms, in an amount of 25 to 85, preferably 35 to 65,% by weight, based on the total amount of the emulsifier used.