Method for producing an aqueous dispersion of a vinyl chloride-(METH)acrylate copolymer

Abstract

The present invention relates to a method for producing an aqueous dispersion of a statistical vinyl chloride-(meth)acrylate copolymer, comprising the following method steps: (a) producing a mixture of water, at least one (meth)acrylate monomer, at least one emulsifier, optionally one or more further comonomers and optionally one or more auxiliary substances; (b) introducing vinyl chloride, a portion of the mixture produced in step (a), optionally water and optionally one or more auxiliary substances into a reactor; (c) heating the reactor to 40°C to 90°C; (d) adding an initiator to the reactor; (e) adding the rest of the mixture produced in step (a), further vinyl chloride and further initiator to the reactor; and (f) processing the reaction mixture.

Description

[0001] Method for the preparation of an aqueous dispersion of a vinyl chloride (meth)acrylate copolymer

[0002] The present invention relates to a process for producing an aqueous dispersion of a statistical vinyl chloride (meth)acrylate copolymer.

[0003] A dispersion can generally be understood as a multiphase system in which at least one microscopically finely dispersed phase, also called the dispersed phase, is present in a continuous phase. In a polymer dispersion, for example, the dispersed phase comprises spherical plastic particles with a particle diameter typically less than 1 pm, and the continuous phase comprises water. Such aqueous polymer dispersions are usually white liquids and can exhibit viscosities ranging from water-thin to highly viscous. In common parlance, such a dispersion is often also referred to as latex.

[0004] From a thermodynamic perspective, polymer dispersions are not stable systems and therefore tend to agglomerate, coagulate, and settle in order to minimize the internal surface area of ​​the system. The dispersed state can be stabilized for a certain period of time by the addition of surface-active agents, such as surfactants or protective colloids. However, this stabilization can fail under the influence of external factors, resulting in coagulation of the dispersion. These external factors include, in particular, shear (e.g., from shaking, stirring, or pumping), freezing or heating, and the addition of salt.

[0005] Polymer dispersions are often produced on an industrial scale directly from the corresponding monomers using the so-called emulsion polymerization process. However, polymer dispersions are also accessible via other methods. In addition, there are naturally occurring polymer dispersions such as natural rubber latex. Industrially important polymer dispersions typically contain 40–60% polymer in water. Polymer dispersions are produced industrially on a large scale and further processed for a wide variety of applications. Major application areas for polymer dispersions include paints and adhesives. Here, processing from the aqueous phase is common practice. However, static vinyl chloride (co)polymers are rarely found in this market.

[0006] The preparation of vinyl chloride (meth)acrylate copolymers is disclosed, for example, in the following publications: WO 2023 / 180317, CN 102 977 248, US 2023 / 0416433 and Capek et al. Makromol. Chem. 193, 1165-1179 (1992).

[0007] The object of the present invention was the development of aqueous dispersions of statistical vinyl chloride (co)polymers for use in ultrathin coatings and other applications. In many of these applications, e.g., interior wall paints, low-emission and low-odor dispersions with a low residual monomer content are preferred. This object is achieved by the vinyl chloride copolymers according to the present invention, which are suitable for aqueous processing. By using a co-monomer (meth)acrylate and by varying the ratio of vinyl chloride (VC) to (meth)acrylate, the properties can be optimized, enabling use as an aqueous dispersion and serving a broad range of applications. The dispersions produced by this process have a particularly low residual monomer content and are low-odor.Furthermore, the articles produced from these dispersions exhibit inherent flame retardancy due to the halogen contained in the polymer.

[0008] The present invention relates to a process for producing an aqueous dispersion of a statistical vinyl chloride (meth)acrylate copolymer, comprising the following process steps:

[0009] (a) Producing a mixture (emulsion) of water, at least one (meth)acrylate monomer, at least one emulsifier, optionally one or more further co-monomers and optionally one or more excipients;

[0010] (b) placing vinyl chloride, part of the mixture prepared in step (a), water if applicable and one or more excipients if applicable in a reactor;

[0011] (c) Heating the reactor to 40°C to 90°C;

[0012] (d) Addition of an initiator to the reactor;

[0013] (e) Addition of the remaining mixture prepared in step (a), further vinyl chloride and further initiator to the reactor; and

[0014] (f) Work up the reaction mixture.

[0015] Furthermore, the present invention relates to an aqueous dispersion of a vinyl chloride (meth)acrylate copolymer produced by the process according to the invention.

[0016] Furthermore, the present invention relates to a vinyl chloride (meth)acrylate copolymer which was produced according to the process according to the invention.

[0017] The production of the vinyl chloride-(meth)acrylate copolymer according to the invention can, after carrying out the process according to the invention for producing an aqueous dispersion of a statistical vinyl chloride-(meth)acrylate copolymer, further comprise a drying step in which the resulting dispersion is dried (e.g., by spray drying). Furthermore, after drying, the product obtained can be further processed (e.g., by screening and milling).

[0018] The vinyl chloride (meth)acrylate copolymer produced according to the invention is particularly suitable for paste applications.

[0019] Preferably, step (a) is carried out in a mixing vessel (premixing vessel). In the process according to the invention, the (meth)acrylate monomer (hereinafter also referred to as (meth)acrylate) used in step (a) is preferably at least one (meth)acrylic acid ester of an alcohol having 1 to 18 carbon atoms. Preferred examples are: n-butyl acrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; with 2-ethylhexyl acrylate being particularly preferred.

[0020] In step (a), an anionic or a nonionic emulsifier, or a mixture thereof, is preferably used as the emulsifier. Particularly preferably, an anionic emulsifier is used in step (a) that is composed of an alkali metal salt or ammonium salt of a fatty acid with 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkylsulfonic acid with 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkylbenzenesulfonic acid with 6 to 20 carbon atoms (e.g., sodium n-alkyl-(C10-C13)benzenesulfonate), or an alkali metal salt or ammonium salt of an alkyl sulfate with 6 to 20 carbon atoms (e.g., sodium n-alkyl-(C10-C13)benzenesulfonate).sodium lauryl sulfate), an alkali metal salt or ammonium salt of an alkyl disulfonic acid diphenyl oxide with 6 to 20 carbon atoms, and an alkali metal salt or ammonium salt of a sulfosuccinate (such as sodium dihexyl sulfosuccinate, ammonium dihexyl sulfosuccinate, sodium dioctyl sulfosuccinate, or ammonium dioctyl sulfosuccinate), or a mixture thereof, is selected.

[0021] The properties of the copolymer produced according to the invention can be modified by using additional co-monomers. Examples of suitable additional co-monomers are itaconic acid, maleic acid, fumaric acid, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, vinyltrimethoxysilane, and vinyltriethoxysilane. These can be used alone or in mixtures. The additional co-monomers are preferably used in an amount of 0.01 to 5% by weight based on the amount of total monomer. Preferably, a pH regulator is added as an auxiliary substance in step (a) and / or step (b). Preferred examples of pH regulators (buffers) are: Na₂CO₃, NaHCCh, NasPC, Na₂HPO₄, NaH₂PO₄, Na₂SiO₃, or mixtures thereof. Na2COs is particularly preferred as a pH regulator.

[0022] Other optional additives include chain regulators (such as propanal) and crosslinking agents (such as diallyl phthalate).

[0023] Preferably, in the process according to the invention, water is additionally added in step (b).

[0024] In step (b), vinyl chloride, a portion of the mixture prepared in step (a), optionally water, and optionally one or more excipients can be placed in a reactor in any order. Preferably, water is first placed in a reactor, optionally mixed with an excipient (e.g., a pH regulator (buffer)), and then a portion of the mixture prepared in step (a) as well as vinyl chloride are added.

[0025] Preferably, in step (b) 0 to 20 wt% of the mixture prepared in step (a) is added; preferably 0.1 to 20 wt%; particularly preferably 10 to 15 wt%.

[0026] Preferably, in step (b) 0 to 20 wt% of the total amount of vinyl chloride is added; preferably 0.1 to 20 wt%; particularly preferably 10 to 15 wt%.

[0027] The ratio of vinyl chloride to (meth)acrylate monomer in the copolymer produced according to the invention is preferably 90:10 to 10:90 wt%. Particularly preferably, the ratio of vinyl chloride to (meth)acrylate monomer is 70:30 to 30:70 wt%. The ratio of the total amount of vinyl chloride used to the total amount of (meth)acrylate monomer used is preferably 90:10 to 10:90 wt%; particularly preferably 70:30 to 30:70 wt%.

[0028] Preferably, in step (c) the reactor is heated to 60°C to 75°C (preferably to 65°C).

[0029] In the process according to the invention, a sodium, potassium, or ammonium peroxodisulfate, a peroxide, a hydroperoxide, or hydrogen peroxide, either alone or in combination, is preferably used as an initiator. These compounds can also be used in combination with redox catalysts (temperature range 40 to 75 °C). Preferred redox catalysts comprise at least one reducing agent and a transition metal salt. Examples of reducing agents are sodium sulfite or sodium methanesulfinate. Examples of transition metal salts are copper(II) sulfate or ammonium iron(II) sulfate.

[0030] Potassium peroxodisulfate (KPS) is preferably used as the initiator.

[0031] Preferably, in step (d) the addition of the initiator begins at the latest when the polymerization temperature is reached.

[0032] The addition of the initiator is preferably continued in step (e), i.e. the addition of the initiator in step (d) and in step (e) is preferably continuous without interruption.

[0033] Preferably, in step (e), the remaining mixture prepared in step (a) and the additional vinyl chloride are added after the polymerization has begun. The start of the polymerization is indicated by the release of heat of reaction; that is, from the start of polymerization, the reactor must be cooled to maintain a constant internal temperature. Again, preferably, in step (e), the remaining mixture prepared in step (a), the additional vinyl chloride, and the additional initiator are added continuously or (preferably in pulses) in several (preferably equal) portions.

[0034] In step (e) the remaining mixture produced in step (a), the vinyl chloride, and the initiator are preferably added in such a way that the metering pressure (i.e. the pressure established by gaseous monomer at polymerization temperature in the reactor) changes by less than 10% (preferably at any time).

[0035] Preferably, in step (e) the remaining mixture prepared in step (a), further vinyl chloride, and further initiator are added until the target amount of (meth)acrylate emulsion (e.g. the remaining mixture prepared in step (a)) has been added.

[0036] Preferably in step (e) the remaining mixture produced in step (a), the additional vinyl chloride, and the additional initiator are added over a period of 30 to 600 min.

[0037] During the polymerization, the vinyl chloride dosing rate is selected such that the pressure is preferably in the range of the polymerization pressure ±0.2 bar. The polymerization pressure is chosen to preferably allow for high conversion, i.e., polymerization with only a small monomer reservoir. Parallel to the vinyl chloride dosing, the emulsion (i.e., the mixture prepared in step (a)) is dosed from the premixing vessel. The dosing rate is preferably selected such that the vinyl chloride and the monomer(s) in the emulsion are in the same ratio as the polymer is to be built up. Once all the emulsion has been dosed, the vinyl chloride and initiator dosing is also stopped. The preferred polymerization pressure depends on the selected polymerization temperature and is 5 to 8 bar. Preferably, the reaction mixture is degassed in step (f).

[0038] Preferably, in step (f) a radical scavenger, e.g. sodium nitrite or Term-N-ator P, is added.

[0039] Preferably, the particle size of the vinyl chloride (meth)acrylate copolymer in the dispersion is 100 to 800 nm.

[0040] Preferably, the reactor used is a polymerization autoclave.

[0041] Preferably, the described sequence of process steps (a) to (f) is followed in the process.

[0042] Preferably, at least one stabilizer is added during or after step (f). Preferably, an ionic and / or non-ionic surfactant is added as the stabilizer.

[0043] Examples of ionic surfactants include: alkali, alkaline earth or ammonium salts of fatty acids (such as lauric, myristic, palmitic or stearic acid), of acidic fatty alcohol sulfuric acid esters of alkanesulfonic acids (preferably with a hydrocarbon chain of 10-18 carbon atoms), of alkylarylsulfonic acids (such as dodecylbenzene or dibutylnaphthalenesulfonic acid), of dialkyl sulfosuccinic acid esters, as well as alkali and ammonium salts of epoxidized fatty acids (such as epoxystearic acid or epoxidized soybean oil), or of reaction products of peracids (such as peracetic acid) with unsaturated fatty acids (such as oleic, linoleic or ricinoleic acid).

[0044] Examples of non-ionic surfactants include fatty acid esters of polyhydric alcohols, such as glycerol monostearate, sorbitan monolaurate, oleate, or palmitate, as well as various oligo- or polyoxyethyl compounds such as polyoxyethylene esters of fatty alcohols or aromatic hydroxy compounds. A preferred method of the present invention is described in detail below by way of example:

[0045] In a premixing vessel, (meth)acrylate(s), co-monomer(s) (optional), buffer (optional), emulsifier(s), and water are placed and stirred vigorously to emulsify the mixture. The mixture (emulsion) is then stirred moderately (optional).

[0046] In an autoclave equipped with a stirrer and baffle (optional), water is preferably placed in the water, and optionally, a buffer is dissolved in the water while stirring. The autoclave is preferably evacuated (-0.9 bar), and the vacuum is optionally broken with nitrogen. This process can optionally be repeated twice more, and the autoclave then evacuated (-0.9 bar). The pressure specifications refer to ambient pressure.

[0047] Subsequently, a portion of the emulsion from the premixing vessel, along with vinyl chloride, is transferred to the stirred autoclave. The mixture is heated to polymerization temperature, and the addition of an aqueous solution of initiator is initiated (dosing of the initiator is started). During polymerization, the reaction mixture is kept at polymerization temperature via a cooling / heating jacket of the reactor.

[0048] After the polymerization reaction has started, the monomers are added (dosed) in step (e), while the initiator is added continuously: vinyl chloride is added until the pressure rises to the polymerization pressure. During the polymerization, the dosing rate is adjusted so that the pressure is preferably within the polymerization pressure range of ±0.2 bar. Simultaneously with the vinyl chloride addition, the emulsion is added from the premix tank. Once all the emulsion has been added, the vinyl chloride and initiator additions are (optionally) stopped. After a pressure drop (of approximately 0.5 bar), the reaction is stopped with a radical scavenger (optional). The mixture is then depressurized to ambient pressure and subsequently degassed under vacuum. The mixture is cooled to room temperature, the pH is adjusted (optionally), and sieved (optionally).

[0049] The process according to the invention and the dispersion of a statistical vinyl chloride-(meth)acrylate copolymer that can be produced according to the invention are characterized by the following advantages over the prior art:

[0050] State of the art:

[0051] Statistical copolymers of vinyl chloride and (meth)acrylate can be produced using semi-continuous processes (see, e.g., EP 4 032 920 A1 and EP 1 798 244 A1). However, deposits often form in the autoclave during the copolymerization of vinyl chloride and (meth)acrylate. Deposit formation is problematic because a) it hinders heat dissipation during polymerization, b) the deposits must be removed after polymerization, c) high residual monomer content and odor formation in the dispersion promote deposit formation, and d) the deposits can lead to the formation of specks.

[0052] Statistical vinyl chloride (meth)acrylate copolymers with a high solids content (> 50%), low minimum film formation temperature (MFT < 40 °C; this leads to high stickiness) and / or those containing acid-functionalized co-monomers such as itaconic acid (these mediate adhesion to metal surfaces) are particularly critical with regard to deposit formation.

[0053] The use of specific surfactant combinations in a batch process has been described as reducing deposits (see US 2013 / 0281621 A1). However, no process has yet been described that enables the production of statistical vinyl chloride (meth)acrylate copolymer dispersions in a steel autoclave with virtually no deposits. Advantages of the present invention over the prior art:

[0054] The process according to the invention enables the production of low-odor, statistical vinyl chloride (meth)acrylate copolymer dispersions with a high solids content and low residual monomer content, without the formation of disruptive deposits during polymerization in the steel autoclave. This applies in particular to copolymers with a low minimum film formation temperature (MFT < 40 °C) and / or copolymers containing acid-functionalized auxiliary monomers. This is primarily due to the provision and use of an aqueous emulsion of (meth)acrylate (step (a)) in the process according to the invention, as well as the reaction control (polymerization at as constant a pressure as possible), as can also be seen from the following examples.

[0055] Examples

[0056] Example 1

[0057] In a premixing vessel, 2-ethylhexyl acrylate (83.2 kg), sodium lauryl sulfate (13.8% solution, 13.3 kg), sodium n-alkyl-(C10-C13)benzenesulfonate (13.0% solution, 3.9 kg), and water (38 kg) were stirred vigorously for 30 minutes to emulsify the monomer. The mixture (emulsion) was then stirred moderately.

[0058] In a 400 L stainless steel autoclave equipped with a stirrer and baffle, soda ash (0.48 kg) was dissolved in water (54.8 kg) under stirring. The autoclave was evacuated (-0.9 bar) and the vacuum was broken with nitrogen. This process was then repeated twice more, and the autoclave was subsequently evacuated (-0.9 bar). A portion of the emulsion from the premixing vessel (17.9 kg) and vinyl chloride (10.0 kg) were then transferred to the stirred autoclave. The mixture was heated to 65 °C, resulting in a pressure of 6.1 bar. Potassium peroxodisulfate (1.8% solution, 18.34 kg) was added at a constant rate (3 L / h) over 6 h. The reaction mixture was maintained at 65 °C via the cooling / heating jacket during polymerization. After 32 minutes, the start of the reaction was indicated by a sharp drop in the cooling water temperature to 30 °C.After the cooling water temperature had risen back to 61 °C, monomer dosing began: vinyl chloride was added until the pressure increased from 5.0 to 6.0 bar (26 min). During the subsequent polymerization, the dosing rate was adjusted to maintain a pressure of 6 ± 0.2 bar. Simultaneously with the vinyl chloride dosing, the emulsion was added from the premix tank. The dosing rate was adjusted to ensure a 1:1 ratio of vinyl chloride and 2-ethylhexyl acrylate. Once the entire emulsion had been added (dosing time approximately 10 h), the vinyl chloride dosing was stopped. After a pressure drop from 6.0 to 5.5 bar, the reaction was stopped with Term-N-ator P (1.6 g). The pressure was reduced to 0 bar within one hour, and the reactor was then degassed under vacuum at 65 °C for 3 h. The mixture was cooled to room temperature and sieved through a 200 pm sieve.

[0059] Characterization: Odorless dispersion, free of specks and coagulate. Solids content: 54.2%, pH = 8.5; surface tension: 40.3 mN / m, shear stability (dissolver, 5000 rpm, room temperature) > 120 s, sieve residue 63 pm < 0.01%, particle size d50 = 288 nm; minimum film formation temperature 1 °C. Residual monomers in the dispersion: vinyl chloride: 1.6 ppm, 2-ethylhexyl acrylate < 20 ppm. In a Teflon dish, a colorless, transparent film 0.7 mm thick was obtained after 12 h at 50 °C.

[0060] Despite the high solids content and low minimum film formation temperature, the reactor wall, baffles and stirrer were free of deposits or had minimal deposits.

[0061] Example 2

[0062] In a premixing vessel, 2-ethylhexyl acrylate (61 kg), sodium lauryl sulfate (13.5% solution, 10.8 kg), sodium n-alkyl-(C10-C13)benzenesulfonate (14.0% solution, 3.2 kg), soda (0.54 kg), itaconic acid (1.27 kg), and water (44 kg) were stirred vigorously for 30 minutes to emulsify the mixture. The mixture (emulsion) was then stirred moderately.

[0063] Water (54.8 kg) was placed in a 400 L stainless steel autoclave equipped with a stirrer and baffle and stirred. The autoclave was evacuated (-0.9 bar) and the vacuum was broken with nitrogen. The autoclave was then evacuated (-0.9 bar). Subsequently, a portion of the emulsion from the premix tank (21.1 kg) and vinyl chloride (10.0 kg) were transferred to the stirred autoclave. The mixture was heated to 65 °C. Potassium peroxodisulfate (2.3% solution, 18.43 kg) was added at a constant rate (3 L / h) over 6 h. The reaction mixture was kept at 65 °C via the cooling / heating jacket during polymerization. After 16 min, the start of the reaction was indicated by a sharp drop in the cooling water temperature to 28 °C. Once the cooling water temperature had risen back to 61 °C, the monomer dosing began: vinyl chloride was dosed until the pressure rose to 6.0 bar.During the further course of the polymerization, the dosing rate was selected to maintain a pressure of 6 ± 0.2 bar. Simultaneously with the vinyl chloride dosing, the emulsion was added from the premix tank. The dosing rate was chosen to ensure that the monomers vinyl chloride and 2-ethylhexyl acrylate were added in a 1:1 ratio. Once the entire emulsion had been added (dosing time approximately 15 h), the vinyl chloride dosing was also stopped. After a pressure drop from 6.0 to 5.5 bar, the reaction was stopped with Term-N-ator P (1.3 g). The pressure was reduced to 0 bar within one hour, and the mixture was then degassed for 3 h at 65 °C under vacuum. The mixture was cooled to room temperature, neutralized with NaOH, and sieved through a 200 pm sieve.

[0064] Characterization: Odorless dispersion, free of specks and coagulate. Solids content: 37.7%, pH = 9.1; surface tension: 40.2 mN / m, shear stability (dissolver, 5000 rpm, room temperature) > 120, sieve residue 63 pm < 0.01%, particle size d50 = 180 nm; minimum film formation temperature 9 °C.

[0065] Despite the low minimum film formation temperature and acid functionalization of the polymer, the reactor wall, baffle, and stirrer were only lightly applied. Example 3: Comparative Example

[0066] In a 40 L stainless steel autoclave equipped with a stirrer and baffle, water (13.3 kg), potassium peroxodisulfate (2.2% solution, 4.08 kg), and soda (54 g) were placed and stirred. The autoclave was evacuated (-0.9 bar) and the vacuum was broken with nitrogen. The autoclave was then evacuated (-0.9 bar). The mixture was heated to 65 °C and maintained at this temperature during polymerization via the cooling / heating jacket. Vinyl chloride (9.0 kg), butyl acrylate (9.0 kg), and sodium di(2-ethylhexyl)sulfosuccinate (1.5% solution, 6.75 kg) were added separately over a period of 4 hours. The vinyl chloride was added in such a way that a pressure of 4.5 ± 0.2 bar was maintained during polymerization. The dosage rates of the two remaining components were chosen so that the three dosage rates were added in a fixed ratio to each other. After the dosage was complete, the reaction was stopped with Term-N-ator P (0.2 g).The pressure was reduced to 0 bar, and then the mixture was degassed for 3 hours at 65 °C under vacuum. The solution was cooled to room temperature and sieved through a 200 pm sieve.

[0067] Characterization: Solid content: 43.2%, pH value = 8.5; Surface tension: 45.8 mN / m, particle size d50 = 170 nm.

[0068] With a comparatively low solids content and without acid functionalization of the polymer, the reactor wall, stirrer and baffle were robustly designed.

Claims

Patent claims 1. A process for producing an aqueous dispersion of a statistical vinyl chloride (meth)acrylate copolymer, characterized in that it comprises the following steps: (a) Producing a mixture of water, at least one (meth)acrylate monomer, at least one emulsifier, optionally one or more further co-monomers and optionally one or more excipients; (b) placing vinyl chloride, part of the mixture prepared in step (a), water if applicable and one or more excipients if applicable in a reactor; (c) Heating the reactor to 40°C to 90°C; (d) Addition of an initiator to the reactor; (e) Addition of the remaining mixture prepared in step (a), further vinyl chloride and further initiator to the reactor; and (f) Work up the reaction mixture.

2. The method according to claim 1, characterized in that at least one (meth)acrylate ester of an alcohol having 1 to 18 carbon atoms is used as the (meth)acrylate monomer in step (a); preferably n-butyl acrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, butyl methacrylate, or 2-ethylhexyl methacrylate.

3. A method according to claim 1 or 2, characterized in that an anionic or a nonionic emulsifier, or a mixture thereof, is used as the emulsifier in step (a); preferably an anionic emulsifier; in particular an anionic emulsifier comprising an alkali metal salt or ammonium salt of a fatty acid having 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkylsulfonic acid having 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkylbenzenesulfonic acid having 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkyl sulfate with 6 to 20 carbon atoms, an alkali metal salt or ammonium salt of an alkyl disulfonic acid diphenyl oxide with 6 to 20 carbon atoms, and an alkali metal salt or ammonium salt of a sulfosuccinate, or a mixture thereof.

4. Method according to one of the preceding claims, characterized in that in step (a) itaconic acid, maleic acid, fumaric acid, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, vinyltrimethoxysilane, or vinyltriethoxysilane, alone or in mixture, are used as a further co-monomer.

5. Method according to one of the preceding claims, characterized in that a pH regulator is added as a further auxiliary substance in step (a) and / or (b); preferably Na2CO3, NaHCOs, NasPC, NaaHPC, NaH2PO4, Na2SiC>3, or mixtures thereof.

6. A method according to any of the preceding claims, characterized in that in step (b) 0 to 20 wt% of the mixture prepared in step (a) is presented; preferably 10 to 15 wt%; and / or that in step (b) 0 to 20 wt% of the total amount of vinyl chloride is presented; preferably 10 to 15 wt%.

7. A method according to any of the preceding claims, characterized in that the ratio of the total amount of vinyl chloride used to the total amount of (meth)acrylate monomer used is 90:10 to 10:90 wt%; preferably 70:30 to 30:70 wt%.

8. Method according to one of the preceding claims, characterized in that a sodium, potassium or Ammonium peroxodisulfate, a peroxide, a hydroperoxide, or hydrogen peroxide, each used alone or in combination; optionally in combination with redox catalysts, wherein preferred redox catalysts comprise at least a reducing agent and a transition metal salt; in particular characterized in that potassium peroxodisulfate (KPS) is used as the initiator.

9. Method according to one of the preceding claims, characterized in that the addition of the initiator in step (d) begins at the latest upon reaching the polymerization temperature and is continued in step (e).

10. Method according to one of the preceding claims, characterized in that in step (e) the addition of the remaining mixture produced in step (a) as well as the further vinyl chloride takes place after the polymerization has begun.

11. Method according to one of the preceding claims, characterized in that in step (e) the addition of the remaining mixture produced in step (a), further vinyl chloride and further initiator is carried out in such a way that the pressure in the reactor changes (preferably at all times) by less than 10%.

12. Method according to one of the preceding claims, characterized in that in step (e) the addition of the remaining mixture produced in step (a) together with further vinyl chloride and initiator is carried out continuously or in several (preferably equal) portions.

13. A method according to any one of the preceding claims, characterized in that the reaction mixture is degassed in step (f); and / or that a radical scavenger is added in step (f), and / or that Following step (f) a stabilizer is added; preferably an ionic and / or non-ionic surfactant.