Method for producing aqueous polymer dispersions from organic waste

Abstract

The invention relates to a method for producing aqueous polymer dispersions by radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein a portion of the monomer M to be polymerized is an ethylenically unsaturated monomer M 'produced from pyrolysis oil as raw material obtained by pyrolysis of plastic waste, in particular selected from the group consisting of mixed plastic waste and waste rubber. In particular, the invention relates to such free-radical aqueous emulsion polymerization of monomer M carried out on an industrial scale.

Description

[0001] The invention relates to a process for producing aqueous polymer dispersions by free-radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein at least a portion of the monomers M to be polymerized are ethylenically unsaturated monomers M′ which have been produced from raw materials obtained by cleavage of organic waste.

[0002] Aqueous polymer dispersions of polymerized ethylenically unsaturated monomers (also called polymer latexes) are fluid systems comprising dispersed polymer particles of chain-grown addition polymers in an aqueous dispersion medium. Depending on the polymer structure of the dispersed polymer particles, polymer dispersions can be used in a variety of technical applications, including binders for paints, architectural and industrial coatings, binders for paper coatings, binders in adhesives, binders for fiber bonding, organic opacifiers, rubbers and impact modifiers for thermoplastics.

[0003] Aqueous polymer dispersions are usually produced by aqueous emulsion polymerization, in particular by free radical aqueous emulsion polymerization of ethylenically unsaturated monomers, including monovinyl aromatic compounds such as styrene or vinyltoluene, monoolefins and dienes such as butadiene, isoprene or ethylene, esters of α,β-ethylenically unsaturated acids, in particular esters of acrylic acid or methacrylic acid, vinyl or allyl ethers and vinyl or allyl esters and combinations thereof. The term "free radical aqueous emulsion polymerization" means that the polymerization of the monomers M is initiated by free radicals, which are formed by the decay of the polymerization initiator, as a result of which free radicals are formed in the polymerization mixture. It is therefore also called "free radical initiated emulsion polymerization". The procedure for the free-radical initiated emulsion polymerization of monomers in aqueous media has been widely described and is therefore sufficiently familiar to the person skilled in the art [see in this regard Emulsion Polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 ff. (1987); DC Blackley, in High Polymer Latices, Vol. 1, p. 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, p. 246 ff. (1972); D. Diederich, Chemie in unserer Zeit, 24, pp. 135 to 142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); DE-A 4003422; and Dispersionen synthetischer Hochpolymerer, F. Springer-Verlag, Berlin (1969), D. Urban, K. Takamura (eds.) "Polymer Dispersions and Their Industrial Applications", Wiley VCH, Weinheim 2002)]. Detailed mechanistic studies have been summarized, for example, by CS Chern, Prog. Polym. Sci. 31 (2006) 443-486; and M. Nomura et al., Adv. Polym. Sci. 175 (2005) 1-128.

[0004] To date, the ethylenically unsaturated monomers used in emulsion polymerization are based on fossil naphtha sources obtained from crude oil refineries. To produce the monomers, the fossil naphtha is first (hydro) cracked to obtain ethylene, propylene, C4 olefin cuts (especially including 1-butene, isobutylene and butadiene), higher olefin cuts (hereinafter also referred to as >C4 olefin cuts, typically C5-C 10 The monomers used for the emulsion polymerization are obtained from the products of the aforementioned (hydro)cracking processes and optionally synthesis gas (see K. Weissermel, H.-J. Arpe, Industrial Organic Chemistry, 4th edition 1994, VCH Verlagsgesellschaft mbH Weinheim). Like the (hydro)cracking products, synthesis gas is usually prepared from fossil sources, for example by steam reforming of methane obtained from gas fields or by gasification of coal.

[0005] Plastic waste is an increasing environmental problem. At present, plastic waste is still mostly landfilled or burned to produce heat. Chemical recovery is the attractive mode that waste plastic material is converted into useful chemicals. The important technology for chemical recovery of plastic waste is cracking. Cracking is the thermal degradation of plastic waste in an inert atmosphere, and produces value-added products such as cracked gas, liquid pyrolysis oil and coke (residue), wherein pyrolysis oil is the main product. Pyrolysis oil can be used as the source of synthesis gas production and / or for example is processed into chemical raw materials such as ethene, propylene, C4 olefin cutting part, >C4 olefin cutting part and aromatic cutting part etc. in (steam) cracker.

[0006] The production of pyrolysis oil and its use as feedstock in (steam) crackers has been frequently described, for example in WO 95 / 03375, EP 713906, WO 2015 / 128033, WO 2020 / 008050 and by Y. Zhang et al., FuelProcessing Technology 206 (2020) 106455 (doi.org / 10.1016 / j.fuproc.2020.106455). WO 2021 / 224287 describes a method for purifying pyrolysis oil obtained by pyrolysis of plastic waste.

[0007] US2021 / 0139620 describes a method for producing polystyrene, which comprises dehydrogenating alkylbenzene obtained directly or indirectly from pyrolysis oil produced by pyrolysis of recovered waste such as waste plastics to obtain styrene, which is then used in the production of polystyrene.

[0008] WO 2022 / 016177 describes the conversion of plastics into monomers by cracking. The method comprises heating a plastic feed stream to a temperature of 300°C to 600°C to crack the waste plastic, subjecting a portion of the low-temperature product stream thus obtained to a second cracking at a temperature of 600°C to 1100°C to obtain a high-temperature product stream, and recovering the monomer from the high-temperature product stream. However, only C2-C4 olefins and styrene can be obtained by this method.

[0009] Unfortunately, the pyrolysis oil obtained from plastic waste contains pollutants that may cause problems in the downstream processing of pyrolysis oil. This is because the polymer contained in the plastic waste is not only composed of carbon and hydrogen usually, but also contains other other elements such as halogen, sulphur, phosphorus, nitrogen and oxygen that are derived from the production of polymer, i.e. monomer, initiator, polymerization catalyst, surfactant and chain transfer agent. However, mixed waste plastics can also contain additives, such as processing aids, stabilizers, dyes, pigments and fire retardants, and this additive has also contributed the amount of organically bound elements in the pyrolysis oil except hydrogen and carbon. Waste plastics may also be polluted in other ways, for example, be polluted by food residues or by product residues in the packaging, for example, in the case of paint cans or building material containers. These pollutants will also contribute the amount of organically bound elements in the pyrolysis oil except hydrogen and carbon.

[0010] Although pyrolysis oil is often purified before further processing, there are still some impurities. Although refineries have carried out multiple cleaning operations, organic sulfur compounds are still found in fossil naphtha, although they are close to the detection limit. Pyrolysis oil contains significantly higher amounts of organic sulfur and elemental sulfur than fossil naphtha, for example, pyrolysis oil based on used tires contains up to 1% sulfur compounds. Although further purification operations have also been carried out at the base product and monomer stage, the monomer produced by pyrolysis oil will likely contain higher traces of sulfur (possibly below the detection limit) and other trace impurities compared to the monomer produced by fossil naphtha. In addition, pyrolysis oil can contain a considerable amount of organically bound oxygen (so-called oxygen-containing compounds), such as aldehydes, ketones, phenolic compounds, quinones and peroxides and nitrogen-containing compounds such as nitroso compounds.

[0011] Free radical polymerization is very sensitive to the smallest traces of impurities. Due to interfacial effects, emulsion polymerization is even more sensitive than single-phase polymerization. It is known that oxygen-containing compounds can accelerate emulsion polymerization (peroxides) or retard emulsion polymerization (aldehydes, ketones). Phenolic compounds and quinones can even inhibit free radical polymerization. Due to the polarity of these molecules, they accumulate preferentially at interfaces and, once introduced, can remain on metal surfaces of reactors, for example, quite permanently (see W. Hübinger: Start behavior of emulsion polymerization, diploma thesis, TU Berlin 1985). Nitroso compounds can be co-stabilizers for inhibitors. Sulfur compounds are also surface-active and have a considerable influence on the polymerization. Even traces below 1 ppm can have a chain regulating effect, but can cause a color change in the product or significantly change the smell of the product. Like oxygen-containing compounds, they can remain on metal surfaces of reactors, for example, quite permanently.

[0012] If such trace impurities are present in the aqueous phase, they will affect the polymerization start, thereby changing particle formation. This may especially affect the properties of polymer dispersions, such as particle size distribution or latex viscosity, which may be problematic in terms of pigment / binder interaction, thereby problematic in terms of the color of architectural coatings, or problematic in terms of the thickener reaction of fast-running adhesives or paper coating dispersions, especially when batch-to-batch variation is large. Although some compounds in the aforementioned compounds are intentionally used as chain regulators to adjust the properties of polymer dispersions, it is generally believed that trace impurities cause trouble during emulsion polymerization, such as flocculation or sediment formation, which is a major problem in polymer dispersion production, resulting in a large amount of cleaning work and may cause spot formation. In addition, it is believed that impurities increase the risk of uncontrolled polymerization and coagulation of polymer dispersions, thereby causing reactor obstruction. These trace materials may be difficult to detect analytically usually, but can still be identified by their influence on the polymerization start behavior (see, for example, DE 4414082). Therefore, it is generally recommended that emulsion polymerization keep the concentration of trace materials as low as possible to avoid trouble during emulsion polymerization. Therefore, it has to be assumed that pyrolysis oils obtained from plastic waste are not suitable raw material substrates for monomers to be polymerized in industrial-scale emulsion polymerization processes.

[0013] Surprisingly, it has now been found that the use of ethylenically unsaturated monomers M, of which at least a portion, in particular at least 20% by weight, preferably at least 30% by weight, more preferably at least 50% by weight, in particular at least 50% by weight or up to 100% by weight, of the monomers M to be polymerized in the free-radical aqueous emulsion polymerization are ethylenically unsaturated monomers M′ produced from pyrolysis oil as raw material obtained by pyrolysis of plastic waste, leads to a reduction in the formation of deposits in their emulsion polymerization, in particular when the free-radical aqueous emulsion polymerization is carried out on an industrial scale.

[0014] The present invention therefore relates to a process for producing an aqueous polymer dispersion by free-radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein a portion of the monomers M to be polymerized are ethylenically unsaturated monomers M′ produced from pyrolysis oils obtained as raw material by pyrolysis of plastic waste, in particular selected from mixed plastic waste and waste rubber. In particular, the present invention relates to such free-radical aqueous emulsion polymerization of monomers M carried out on an industrial scale.

[0015] The present invention is associated with specific benefits. Since the use of ethylenically unsaturated monomers M′ obtained from pyrolysis oil of plastic waste in free-radical aqueous emulsion polymerization leads to reduced sediment formation, the product quality of the polymer dispersion can be improved and the time period between purification cycles of the reaction vessels used in the technical-scale free-radical aqueous emulsion polymerization of ethylenically unsaturated monomers can be extended, leading to an improvement in the space / time yield of such products.

[0016] The present invention therefore also relates to the use of ethylenically unsaturated monomers M′ produced from pyrolysis oil as raw material obtained by pyrolysis of plastic waste, in particular selected from mixed waste plastics and waste rubber, for extending the time period between purification cycles of reaction vessels used in the industrial-scale free-radical aqueous emulsion polymerization of ethylenically unsaturated monomers.

[0017] Without being bound by theory, it is believed that the benefits achieved by the monomers produced from the pyrolysis oil feedstock are generated by trace amounts of impurities, such as organic sulfur compounds, oxygenates and organic nitrogen compounds derived from the pyrolysis oil feedstock, despite many purification and reaction steps. As previously mentioned, such trace amounts of impurities are primarily capable of inhibiting or regulating free radical polymerization, and thus it was assumed in the past that such impurities should not be present in the materials used for emulsion polymerization, if possible, in order to ensure a reaction system that is as limited as possible. However, these impurities appear to accumulate in the interface of the growing polymer particles and prevent uncontrolled overreaction of the monomers there, thereby reducing coagulum formation, thereby reducing deposit formation.

[0018] Hereinafter, the present invention is explained in more detail.

[0019] In the context of the present invention, the term "plastic waste" refers to any plastic material discarded after use, i.e., the plastic material has reached the end of its service life. Plastic waste can be pure polymer plastic waste, mixed plastic waste (also referred to as mixed waste plastic) or film waste, including dirt, adhesive material, filler, residue, etc. Plastic waste has nitrogen content, sulfur content, halogen content and optionally heavy metal content. Plastic waste can be derived from any source containing plastic material. Therefore, the term "plastic waste" includes industrial and household plastic waste, including used tires and agricultural and horticultural plastic materials. The term "plastic waste" also includes used petroleum-based hydrocarbon materials, such as used motor oil, machine oil, grease, wax, etc. In the context of the present invention, "plastic waste" to be cracked is preferably mixed plastic waste. The term plastic waste also includes waste rubber, particularly waste rubber generated by tires. The term plastic waste also includes pure polymer plastic waste or film waste, including dirt, adhesive material, filler, residue, etc. In particular, plastic waste includes mixed plastic waste and waste rubber, particularly waste rubber from tires.

[0020] Generally speaking, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics, for example polyolefins, such as polyethylene (HDPE, LDPE) and polypropylene, polystyrene and their copolymers, etc.; and polymers composed of carbon, hydrogen and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, siloxanes, etc., for example chlorinated plastics, such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), etc.; nitrogen-containing plastics, such as polyamide (PA), polyurethane (PU), acrylonitrile butadiene styrene (ABS), etc.; oxygen-containing plastics, such as polyesters, for example polyethylene terephthalate (PET), polycarbonate (PC), etc.), siloxanes and / or sulfur-bridged cross-linked rubbers. PET plastic waste is usually sorted before pyrolysis because PET has a profitable resale value. Therefore, the plastic waste to be pyrolyzed usually contains less than about 10 wt.-% PET, preferably less than about 5 wt.-% PET, based on the dry weight of the plastic material, and most preferably is substantially free of PET. One of the main components of waste from electrical and electronic equipment is polychlorinated biphenyls (PCB). Generally speaking, plastic materials include additives such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives may include elements other than carbon and hydrogen. For example, bromine is mainly associated with flame retardants. Heavy metal compounds can be used as light-resistant pigments and / or stabilizers in plastics; cadmium, zinc and lead can be present in heat stabilizers and lubricants used in plastic manufacturing. Plastic waste may also contain residues. Residues in the sense of the present invention are pollutants adhering to plastic waste. Additives and residues are generally present in an amount of less than 50 wt.-%, preferably less than 30 wt.-%, more preferably less than 20 wt.-%, even more preferably less than 10 wt.-%, based on the total weight of the dry weight plastic.

[0021] In the context of the present invention, the term "cracking" refers to the thermal decomposition or degradation of end-of-life plastics under inert conditions, with the production of gaseous, liquid and solid coke fractions. During cracking, plastics are converted into a variety of chemical substances, including gases such as H2, C1-C4 alkanes, C2-C4 alkenes, acetylene, propyne, 1-butyne, pyrolysis oils with boiling temperatures ranging from 25°C to 500°C, and coke. The term "cracking" includes slow cracking, fast cracking, flash catalytic and catalytic cracking. These cracking types differ in terms of process temperature, heating rate, residence time, feed particle size, etc., resulting in different product qualities.

[0022] In the context of the present invention, the abbreviated notation (steam) cracking includes both thermal cracking such as steam cracking and catalytic cracking such as catalytic hydrocracking and fluid catalytic cracking (FCC). In a similar manner, the abbreviated notation (steam) cracker includes thermal cracking reactors such as steam crackers and catalytic cracking reactors such as catalytic hydrocracking reactors and fluid catalytic cracking reactors.

[0023] In the context of the present invention, the term "sulfur content" relates to the content of sulfur selected from H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur.

[0024] In the context of the present invention, the term "nitrogen content" relates to the content of organic nitrogen determined according to ASTM D 5762-18 and calculated as elemental nitrogen.

[0025] In the context of the present invention, the term "oxygen content" relates to the content of organic oxygen determined according to ASTM D 7423-17 and calculated as elemental oxygen.

[0026] In the context of the present invention, the term "ppm" means 1 part per million by weight, ie 1 ppm = 1 mg / kg.

[0027] In the context of the present invention, the term "pphm" means parts per 100 parts of monomer and refers to the relative amount of a monomer relative to the total weight of the monomers to be polymerized. 1 pphm of a monomer corresponds to 1 wt% of the monomer, based on the total weight of the monomers to be polymerized.

[0028] In the context of the present invention, the term "industrial scale" is used synonymously with the terms "technical scale" and "large-scale". In the context of free-radical aqueous emulsion polymerization, "industrial scale" is understood to mean that the emulsion polymerization is carried out in an internal volume of at least 0.1 m 3 , in particular at least 0.5m 3 For example, between 6m 3 Up to 200m 3 Free radical aqueous emulsion polymerization "on an industrial scale" can be carried out both batchwise (including monomer feed batch processes) and continuously.

[0029] Suitable crude pyrolysis oil comes from the cracking of plastic waste.The plastic material used as the raw material for producing the pyrolysis oil can derive from any source of the plastic material comprising the end of life.The content of sulphur, nitrogen, halogen and (if present) heavy metal of pyrolysis oil can change and depend on the type of processed waste plastic material and the cracking condition adopted.For example, by weight, mixed waste plastics can produce the pyrolysis oil with relatively low sulphur content, for example between 5ppm to 400ppm, the sulphur content in the scope of 50ppm to 300ppm especially, and the pyrolysis oil obtained from waste rubber can have the significantly higher sulphur content that can be between 400ppm to 50000ppm, the sulphur content in the scope of 500ppm to 12000ppm especially.

[0030] Pyrolysis oil is produced by conventional pyrolysis methods known in the art. Pyrolysis methods for waste plastics themselves are known. They are described, for example, in WO 95 / 03375, EP 713906, WO 2015 / 128033 and WO 2020 / 008050. Suitable pyrolysis oils are also commercially available. Generally speaking, pyrolysis includes drying the plastic waste at a temperature of high temperature but less than 400°C, for example at a temperature in the range of 150°C to 380°C, and then pyrolysis at a temperature above 400°C, for example at a temperature in the range of 450°C to 800°C.

[0031] The crude pyrolysis oil obtained from the pyrolysis of plastic waste is usually liquid at 15° C. For the purposes of the present invention, “liquid at 15° C.” means that the pyrolysis oil has a viscosity of at most 1000 mm at 20° C. 2 / s, for example, between 20 mm at 20°C 2 / s to 1000mm 2 / s range at 20 ° C. Kinematic viscosity. As determined according to DIN EN ISO 12185, at 15 ° C and 1013 mbar, the pyrolysis oil generally has a density of up to 1.3 g / mL, for example, a density in the range of 0.7 g / mL to 1.1 g / mL. Typically, the crude pyrolysis oil obtained from the cracking of plastic waste has a boiling temperature greater than 35 ° C and generally up to 500 ° C. Generally speaking, the pyrolysis oil has a wide boiling range. Generally speaking, less than 10% by weight of the pyrolysis oil boils at a temperature below 100 ° C, and less than 10% by weight of the pyrolysis oil boils at a temperature of 360 ° C or higher at atmospheric pressure (1 bar). In particular, at least 80% by weight of the pyrolysis oil boils in the range of 100 ° C to 360 ° C at atmospheric pressure (1 bar). The oil phase of the crude pyrolysis oil generally contains less than 100 ppm of dissolved water. Its pks value (at 20 ° C) is generally in the range of 4 to 8.

[0032] Depending on the waste plastic material subjected to pyrolysis, the crude pyrolysis oil may have varying contents of sulfur (eg in the form of H2S, elemental sulfur and / or organic sulfur), organic nitrogen, organic oxygen, halogens and, if present, heavy metals.

[0033] In the context of the present invention, the term "heavy metal" refers to metals with a density > 4.51 g / cm 3 Examples include arsenic, antimony, bismuth, selenium, tin, cadmium, chromium, iron, copper, mercury, nickel, and lead.

[0034] Crude pyrolysis oil generally has at least one or all of the following properties:

[0035] (a) a content of sulfur selected from H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur, of at least 30 ppm, in particular at least 40 ppm, for example in the range of 30 ppm to 20000 ppm, typically in the range of 40 ppm to 15000 ppm or in the range of 40 ppm to 12000 ppm;

[0036] (β) a content of organic nitrogen of at least 20 ppm, in particular at least 30 ppm, for example in the range of 20 ppm to 40,000 ppm, typically in the range of 30 ppm to 20,000 ppm or in the range of 40 ppm to 10,000 ppm, determined according to ASTM D 5762-18 and calculated as elemental nitrogen; and / or

[0037] (x) a content of organic oxygen, determined according to ASTM D 7423-17 and calculated as elemental oxygen, of at least 50 ppm, in particular at least 70 ppm or at least 80 ppm, for example in the range of 50 to 5000 ppm, typically in the range of 70 to 4500 ppm or in the range of 80 to 4000 ppm.

[0038] In one embodiment, the crude pyrolysis oil has a halogen content of 40 mg / 1 or more, such as 80 ppm or more, or 120 ppm or more, or 400 ppm or more, or 600 ppm or more, relative to the total weight of the crude pyrolysis oil. In another embodiment, the crude pyrolysis oil has a halogen content of 100 ppm to 1000 ppm, typically 120 ppm to 900 ppm, relative to the total weight of the crude pyrolysis oil.

[0039] Organic fluorine, organic chlorine, organic bromine and / or organic iodine compounds are usually the source of the halogen content in the crude pyrolysis oil. Specifically, the halogen content is a bromine and chlorine content of up to 90% or more, such as 95% or more or even 100%. More specifically, the halogen content is a chlorine content of up to 90% or more, such as 95% or more or even 100%.

[0040] In the case where the crude pyrolysis oil also has a heavy metal content, the heavy metal content is at least 1ppm relative to the gross weight of the crude pyrolysis oil. Typically, the heavy metal content is no more than 100ppm relative to the gross weight of the crude pyrolysis oil. In one embodiment, the crude pyrolysis oil has a content of heavy metals other than iron in the range of 1ppm to 4ppm or 1ppm to 3ppm relative to the gross volume of the crude pyrolysis oil. Due to waste processing, 10ppm or even more iron content is usually unavoidable, for example from the residue of the wear of shredder processing and steel equipment such as grinders. Iron salts are usually used to initiate polymerization, and their consumption in subsequent free radical emulsion polymerization can be adjusted.

[0041] The acid number of the crude pyrolysis oil obtained from plastic waste, determined by potentiometric titration to DIN EN 12634:1999, but using tetrabutylammonium hydroxide instead of tetramethylammonium hydroxide, is typically in the range from 1 mg KOH / g to 50 mg KOH / g, in particular in the range from 2 mg KOH / g to 40 mg KOH / g.

[0042] In a preferred embodiment, the crude pyrolysis oil is obtained from mixed waste plastics. In this case, the crude pyrolysis oil generally has at least one or all of the following properties:

[0043] (α.1) a content of sulfur selected from H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur, of at least 20 ppm, in particular at least 30 ppm, for example in the range of 20 ppm to 5000 ppm, typically in the range of 30 ppm to 3000 ppm;

[0044] (β.1) a content of organic nitrogen of at least 20 ppm, in particular at least 30 ppm, for example in the range of 20 ppm to 40,000 ppm, typically in the range of 30 ppm to 10,000 ppm, determined according to ASTM D 5762-18 and calculated as elemental nitrogen; and / or

[0045] (χ.1) A content of organic oxygen, determined according to ASTM D 7423-17 and calculated as elemental oxygen, of at least 50 ppm, in particular at least 70 ppm or at least 80 ppm, for example in the range of 50 ppm to 5000 ppm, typically in the range of 70 ppm to 4500 ppm or in the range of 80 ppm to 4000 ppm.

[0046] The halogen content of the crude pyrolysis oil obtained from mixed waste plastics is generally as described above. Likewise, the acid value of the crude pyrolysis oil obtained from mixed waste plastics is generally as described above.

[0047] In another preferred embodiment, the crude pyrolysis oil is obtained from waste rubber. In this case, the crude pyrolysis oil generally has at least one or all of the following properties:

[0048] (α.2) a content of sulfur selected from the group consisting of H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur, of at least 300 ppm, in particular at least 400 ppm, for example in the range of 300 ppm to 20000 ppm, typically in the range of 400 ppm to 15000 ppm;

[0049] (β.2) an organic nitrogen content of at least 300 ppm, in particular at least 350 ppm, for example in the range of 300 ppm to 40,000 ppm, typically in the range of 350 ppm to 20,000 ppm, determined according to ASTM D 5762-18 and calculated as elemental nitrogen; and / or

[0050] (χ.2) A content of organic oxygen, determined according to ASTM D 7423-17 and calculated as elemental oxygen, of at least 50 ppm, in particular at least 70 ppm or at least 80 ppm, for example in the range of 50 ppm to 5000 ppm, typically in the range of 70 ppm to 4500 ppm or in the range of 80 ppm to 4000 ppm.

[0051] The halogen content of the crude pyrolysis oil obtained from waste rubber is generally as described above. Likewise, the acid value of the crude pyrolysis oil obtained from waste rubber is generally as described above.

[0052] The crude pyrolysis oil may be purified before it is further processed, for example by stripping, one or more distillation steps, by contact with a collector or by a combination of measures. A specific purification method is described in WO 2021 / 224287, to which reference is made, and which is particularly suitable for purifying crude pyrolysis oil obtained from plastic waste.

[0053] The pyrolysis oil obtained from the purification typically has a sulphur content which is at least 40% lower, more preferably at least 50% lower, than the sulphur content of the untreated crude pyrolysis oil.

[0054] The pyrolysis oil obtained from the purification typically has a nitrogen content which is at least 40% lower, more preferably at least 50% lower, than the nitrogen content of the untreated crude pyrolysis oil.

[0055] The pyrolysis oil obtained from the purification typically has an oxygen content which is at least 40% lower, more preferably at least 50% lower, than the oxygen content of the untreated crude pyrolysis oil.

[0056] The pyrolysis oil obtained from the purification typically has a halogen content which is at least 40% lower, more preferably at least 50% lower, than the halogen content of the unprocessed crude pyrolysis oil.

[0057] If present, the pyrolysis oil obtained from the purification typically has a heavy metal content that is at least 40% lower, more preferably at least 50% lower, than the heavy metal content of the untreated crude pyrolysis oil.

[0058] To produce the monomers M' used in the emulsion polymerization of the process according to the invention, the pyrolysis oil obtained from the pyrolysis of plastic waste is further processed, for example by (steam) cracking or by gasification. For this purpose, the gas fraction formed in the pyrolysis can also be used as a co-feed. The solid fraction obtained in the pyrolysis can also be used as a raw material for gasification to synthesis gas.

[0059] The pyrolysis oil obtained from mixed waste plastic material is particularly suitable as feedstock for a (steam) cracker.A preferred embodiment of the present invention therefore relates to a process wherein the pyrolysis oil obtained from mixed waste plastic material is subjected to (steam) cracking.

[0060] As mentioned above, (steam) cracking includes both thermal steam cracking and catalytic cracking. They are known processes for producing low molecular weight hydrocarbon compounds from naphtha feedstocks (see K. Weis-sermel, H.-J. Arpe, loc. cit., Chapter 3, pages 65-98 and references cited therein) and can be similarly applied to the (steam) cracking of pyrolysis oils obtained from mixed waste plastic materials.

[0061] As mentioned above, (steam) cracking produces C2-C4 olefin fractions, such as ethylene, propylene; C4 olefin fractions, including 1-butene, 2-butene, isobutylene and butadiene; >C4 olefin fractions, in particular C5-C 10 Monoolefins and aromatic fractions, including benzene and / or toluene fractions. These products and optionally synthesis gas are the starting materials for the bulk of the ethylenically unsaturated monomers M which are polymerized in the free-radical aqueous emulsion polymerization.

[0062] The pyrolysis oil obtained from the cracking of mixed waste plastic materials can be used as a feedstock by itself, or can be used in combination with other hydrocarbon feedstocks such as naphtha from fossil sources. In order to achieve a beneficial effect, the amount of pyrolysis oil obtained from the cracking of mixed waste plastic materials is at least 10%, in particular at least 20%, based on the total amount of feedstock subjected to (hydro)cracking.

[0063] The feedstock for (steam) cracking is typically a full range naphtha obtained from pyrolysis oil or a mixture of a full range naphtha obtained from pyrolysis oil and a conventional naphtha feedstock. In the context of the present invention, the term "full range naphtha" refers to a fraction of pyrolysis oil or fossil oil having a boiling temperature in the range of 35° C. to 210° C., in particular in the range of 50° C. to 200° C., at atmospheric pressure (1 bar).

[0064] In particular, the feedstock to be (steam) cracked meets at least one or all of the following requirements:

[0065] (α.3) a content of sulfur selected from H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur, of at least 5 ppm, in particular at least 10 ppm, for example in the range of 5 ppm to 500 ppm, typically in the range of 10 ppm to 400 ppm;

[0066] (β.3) a content of organic nitrogen, calculated as elemental nitrogen, determined according to ASTM D 5762-18, of at least 20 ppm, in particular at least 30 ppm, for example in the range of 20 ppm to 10000 ppm, typically in the range of 30 ppm to 4000 ppm; and / or

[0067] (χ.3) A content of organic oxygen, determined according to ASTM D 7423-17 and calculated as elemental oxygen, of at least 30 ppm, in particular at least 50 ppm or at least 60 ppm, for example in the range of 30 ppm to 3000 ppm, typically in the range of 50 ppm to 2000 ppm or in the range of 60 ppm to 1500 ppm.

[0068] The feedstocks subjected to (steam) cracking generally have a halogen content of at most 20 ppm of halogen.

[0069] The feedstock subjected to (steam) cracking generally has a heavy metal content other than iron of less than 1 ppm.

[0070] Typically, the feedstock subjected to (steam) cracking has a water content of no more than 100 ppm. Its pKs value (at 20° C.) is typically in the range of 4 to 8.

[0071] Pyrolysis oils obtained from the cracking of plastic waste, in particular waste rubber, such as tires or construction rubber, can also be used as feedstock for the production of synthesis gas. Therefore, a preferred embodiment of the present invention relates to a method in which the pyrolysis oils obtained from plastic waste, in particular from waste rubber materials, are gasified in a synthesis gas process. In the synthesis gas process, the mixture of carbon monoxide and hydrogen and optionally the (steam) cracked fractions are subsequently used in the production of ethylenically unsaturated monomers.

[0072] In the context of the present invention, synthesis gas, also known as synthesis gas, is a mixture of gases comprising carbon monoxide (CO) and hydrogen (H2) as the main components. The preparation of synthesis gas has long been known (see K. Weissermel, H.-J. Arpe, loc. cit., Chapter 2.1 and Chapter 2.2, pages 15-30 and references cited therein). In order to produce synthesis gas, the pyrolysis oil obtained from the cracking of plastic waste, in particular the cracking of waste rubber, is partially oxidized with oxygen (O2), air, steam (H2O) or a combination of all gasifying agents at high temperatures, usually in the range of 800° C. to 1000° C. and at a pressure in the range of 1 bar to 20 bar. The synthesis gas obtained is then used in the production of ethylenically unsaturated monomers. In particular, the synthesis gas is then used in the production of methanol, which is then used in the production of ethylenically unsaturated monomers M', for example, by the so-called MTO route (methanol to olefins). A portion of the synthesis gas-based methanol can also be converted into alkanes, olefins, oxygenates and alcohols. These chemicals can be blended into diesel, gasoline and other liquid fuels or used directly as diesel, gasoline and other liquid fuels.

[0073] The pyrolysis oil obtained from the pyrolysis of plastic waste, in particular waste rubber, can be used as a raw material by itself, or can be used in combination with other organic raw materials for synthesis gas production, such as high vacuum residue (HVR) from fossil sources. In order to achieve a beneficial effect, the amount of pyrolysis oil obtained from the pyrolysis of plastic waste, in particular waste rubber material, is at least 10%, in particular at least 20%, based on the total amount of raw materials for synthesis gas production.

[0074] The raw material for synthesis gas production, i.e., pyrolysis oil or a mixture of pyrolysis oil and other organic raw materials, preferably meets at least one or all of the following requirements:

[0075] (α.4) a content of sulfur selected from H2S, elemental sulfur and organic sulfur, determined according to ASTM D 7183-18 and calculated as elemental sulfur, of at least 300 ppm, in particular at least 400 ppm, for example in the range of 300 ppm to 15000 ppm, typically in the range of 400 ppm to 10000 ppm;

[0076] (β.4) an organic nitrogen content of at least 300 ppm, in particular at least 350 ppm, for example in the range of 300 ppm to 40,000 ppm, typically in the range of 350 ppm to 20,000 ppm, determined according to ASTM D 5762-18 and calculated as elemental nitrogen; and / or

[0077] (χ.4) A content of organic oxygen, determined according to ASTM D 7423-17 and calculated as elemental oxygen, of at least 50 ppm, in particular at least 70 ppm or at least 80 ppm, for example in the range of 50 ppm to 5000 ppm, typically in the range of 70 ppm to 4500 ppm or in the range of 80 ppm to 4000 ppm.

[0078] The feedstocks subjected to synthesis gas production generally have a halogen content of at most 20 ppm of halogen.

[0079] The feedstocks subjected to (steam) cracking generally have a heavy metal content of less than 1 ppm.

[0080] Typically, the feedstock for gasification has a higher boiling range than the feedstock for (steam) cracking. In particular, it has a boiling temperature of 200° C. or more, preferably 350° C. or more, at atmospheric pressure. Suitable feedstocks are pyrolysis oils obtained from plastic waste, in particular from waste rubber, or mixtures of pyrolysis oils obtained from plastic waste, in particular from waste rubber, and HVR. In general, the feedstock for synthesis gas production has a water content of not more than 100 ppm. Its pKs value (at 20° C.) is generally in the range of 4 to 8.

[0081] Obviously, the pyrolysis oil obtained from the pyrolysis of plastic waste can be used directly as a feedstock for gasification to obtain CO and H2.

[0082] For (steam) cracking, the pyrolysis oil obtained from the pyrolysis of plastic waste needs to be lowered in upper boiling point and cleaned to obtain the feedstock which provides the starting material for the monomer production:

[0083] - C2-C4-olefin fractions, in particular ethylene, propylene, 1-butene, 2-butene, isobutene and butadiene;

[0084] - aromatic fractions, in particular benzene, toluene, ethylbenzene and xylenes;

[0085] ->C4 olefin fraction, especially C5-C 10 Olefins;

[0086] - the methane fraction, which can also be used to produce synthesis gas;

[0087] In the case of C2-C4-olefin fractions, in particular in the case of butadiene and ethylene, these fractions themselves can be used as monomers, or they can be converted into the desired monomers M′ to produce ethylenically unsaturated monomers.

[0088] In particular, the pyrolysis of waste plastics allows the production of aqueous polymer dispersions via the following sequence of process steps:

[0089] i) providing pyrolysis oil from organic waste selected from mixed waste plastics and waste rubber;

[0090] ii) providing a full range naphtha satisfying in particular the aforementioned properties from the pyrolysis oil obtained in step i), for example by fractionating the pyrolysis oil to obtain feedstocks having a boiling range at atmospheric pressure in the range of 35° C. to 210° C., in particular in the range of 50° C. to 200° C., and by cleaning the pyrolysis oil and / or said fractions;

[0091] iii) subjecting the full range naphtha to steam cracking, wherein a C2-C4 olefin fraction, a >C4 olefin fraction and a benzene and / or toluene fraction are obtained, optionally,

[0092] iv) converting at least one of the fractions obtained in step iii) into ethylenically unsaturated monomers M':

[0093] and / or

[0094] ii. a) subjecting the pyrolysis oil directly, ie without cleaning, to a gasification step to obtain a synthesis gas comprising a mixture of carbon monoxide and hydrogen,

[0095] iii.a) using the synthesis gas fraction obtained in step ii.a) in the production of ethylenically unsaturated monomers M′;

[0096] as well as

[0097] v) carrying out a free-radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein

[0098] Preferably at least 20% by weight, more preferably at least 30% by weight and in particular at least 50% by weight of the monomers M to be polymerized are selected from the monomers M′ obtained in step iv) or in step iii.a)

[0099] and one or more of the C2-C4 olefins obtained in step iii).

[0100] According to the invention, the fractions obtained in steps iii) and ii.a), respectively, can be combined with the gaseous fractions obtained in the pyrolysis of plastic waste, i.e. C2-C4 olefins, acetylene, propyne and / or 1-butyne, and used as raw material for producing monomer M′.

[0101] In particular, the following fractions (a) to (e) and combinations of fractions (a) to (e) obtained from steam cracking or gasification are used for the production of ethylenically unsaturated monomers:

[0102] (a) a combination of a C2-C4 olefin fraction and a benzene fraction or a toluene fraction, which is particularly useful for the production of monovinylaromatic monomers such as styrene, vinyltoluene and divinylbenzene and other cyclohexanols, the latter of which can be used in the production of cyclohexyl esters of acrylic acid or methacrylic acid;

[0103] (b) C2-C4 olefin fractions, which are particularly useful for the production of acrylic acid, acrylonitrile, acrylamide, vinyl propionate (via propionic acid) and for the production of higher olefins and >C4 alkanols such as C5-C 10 The production of alkanols, the latter of which is used for the C5-C 10 Alkyl esters and C5-C methacrylate 10 In the production of alkyl esters;

[0104] (c) a synthesis gas fraction which is used in particular for the production of methanol which is itself used for the production of methyl methacrylate;

[0105] (d) C2-C4 olefin fractions and synthesis gas fractions, which are used in particular for the production of methacrylic acid, methyl methacrylate, vinyl acetate, vinyl propionate and vinyl esters of Koch acid;

[0106] (e) >C4 olefin fractions, which are particularly useful for >C4 alcohols, such as C5-C 10 Alkanol and C5-C 10 Production of cycloalkanols, the >C4 alcohols are C5-C 10 Alkyl esters and C5-C methacrylate 10 Necessary for the production of alkyl esters;

[0107] (f) C2-C4 olefin fraction, >C4 olefin fraction and synthesis gas fraction, which are used for C5-C 10 Alkyl esters and C5-C methacrylate 10 Production of alkyl esters.

[0108] Apparently, the following ethylenically unsaturated monomers are readily available from pyrolysis oil obtained by pyrolysis of plastic waste: monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylates, methacrylates, acrylic acid, methacrylic acid, acrylic acid amides, methacrylic acid amides, acrylonitrile, C2-C 12 Vinyl esters of alkanoic acids and mixtures thereof.

[0109] Here and below, the acrylate is in particular selected from acrylic acid C1-C 18 Alkyl esters and acrylic acid C5-C 18 Cycloalkyl esters, and wherein the methacrylate is selected from methacrylic acid C1-C 18 Alkyl esters and methacrylates C5-C18 Cycloalkyl esters.

[0110] The production of ethylenically unsaturated monomers and building blocks for producing monomers M' is further illustrated by way of non-limiting examples.Other monomers such as hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, such as hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid, can be obtained by similar methods.

[0111] Styrene

[0112] Styrene is usually produced from ethylbenzene by gas phase catalytic dehydrogenation in the presence of steam. The catalyst used for this reaction is usually composed mainly of iron oxide. The reaction temperature is generally in the range of 550°C to 630°C. The resulting crude product is distilled to remove unreacted ethylbenzene and by-products such as toluene and benzene. Ethylbenzene used as a starting product can be prepared by Friedel-Crafts alkylation of benzene and ethylene in the presence of aluminum chloride or zeolite as a catalyst. According to the present invention, benzene and ethylene can be obtained by cracking pyrolysis oil, as described herein.

[0113] An alternative commercial procedure for the production of styrene is the so-called propylene oxide / styrene monomer (POSM) process. In the first step of this process, ethylbenzene is peroxidized by treating it with air at a temperature of generally about 145° C. The resulting 1-hydroperoxyethylbenzene serves as an epoxidation agent for converting propylene into propylene oxide in the following step and is itself converted into 1-phenylethanol. This epoxidation reaction is generally continued at a temperature of about 100° C. to 130° C. in the presence of a suitable catalyst such as a soluble molybdenum salt. In a final step, the 1-phenylethanol obtained is dehydrated, which is continued at a temperature of generally about 200° C. in the presence of an acidic catalyst such as aluminum oxide. The propylene used in this procedure can be obtained as a C3 olefin fraction during the cracking of the pyrolysis oil according to the invention.

[0114] Another alternative process for producing styrene is based on the catalytic side-chain alkylation of toluene with methanol, which avoids the need for a dehydrogenation step. This process requires cheaper starting materials and is more energy efficient than conventional processes, but has so far suffered from its low selectivity. Toluene can be obtained from pyrolysis oil according to the invention.

[0115] Divinylbenzene

[0116] Divinylbenzene is generally understood to be a mixture of its meta-isomers and para-isomers, which can be produced from diethylbenzene by gas phase catalytic dehydrogenation, analogously to the procedure described above for the production of styrene. Diethylbenzene or a mixture of its positional isomers can in turn be obtained by ethylating ethylbenzene, benzene or a mixture thereof by means of a Friedel-Crafts alkylation, analogous to the ethylation of benzene described above in connection with the production of styrene. In fact, diethylbenzene is in any case an unintentional by-product of this process. The starting materials benzene and ethylene can be obtained from the pyrolysis oil according to the invention.

[0117] acrylic acid

[0118] At present, the two-step propylene oxidation process is mainly used for the large-scale production of acrylic acid. Both oxidation steps are highly exothermic and use air as the oxidant. In the first step, propylene is oxidized at a temperature of usually about 350° C., usually in the presence of a bismuth-molybdenum oxide catalyst, to obtain propenal (acrolein). In the second step, acrolein is oxidized to acrylic acid, usually over a molybdenum-vanadium oxide catalyst at a temperature of usually about 260° C. The propylene used in this process can be obtained from the pyrolysis oil according to the invention.

[0119] Another method for producing acrylic acid is to use carbon monoxide and ethylene oxide as starting materials, which can be obtained on an industrial scale via the catalytic oxidation of ethylene. In the first step, ethylene oxide is catalytically carbonylated with carbon monoxide to obtain propiolactone, which is converted into acrylic acid in the presence of a suitable catalyst. Alternatively, propiolactone is first catalytically polymerized into polypropiolactone, which is then degraded into acrylic acid by cracking. The ethylene and carbon monoxide used in this method can be obtained from pyrolysis oil or synthesis gas according to the present invention.

[0120] Methacrylic acid

[0121] Analogous to the two-step process for the oxidation of propylene for the production of acrylic acid described above, methacrylic acid can be produced from isobutylene in two catalytic oxidation steps. Thus, in the first oxidation step, isobutylene is converted into methacrolein, which is then oxidized to methacrylic acid. The catalysts used in both steps are generally similar to the corresponding catalysts used in the process for the oxidation of propylene to acrylic acid. The isobutylene used in this procedure can be obtained from the pyrolysis oil according to the invention.

[0122] The methacrolein obtained in the first step of the above-described process can alternatively be produced from propionaldehyde, which can be obtained by hydroformylating ethylene with synthesis gas in the presence of a catalyst such as tetracarbonyl hydride cobalt or a rhodium complex. The propionaldehyde obtained is reacted with formaldehyde and a catalytic amount of dimethylamine to give the corresponding Mannich adduct, which is then subjected to thermal liberation of the amine to give methacrolein. Ethylene obtained from the pyrolysis oil according to the invention and the synthesis gas according to the invention can be used as starting material for this process.

[0123] Methyl Methacrylate

[0124] A fairly new process uses ethylene as a starting material and converts ethylene into methyl propionate via homogeneously catalyzed carboxymethylation with carbon monoxide and methanol. In the next step, methyl propionate is converted into methyl methacrylate by aldol condensation with formaldehyde in the gas phase using a supported catalyst such as cesium oxide on silicon dioxide. The ethylene and carbon monoxide used in this process can be obtained from pyrolysis oil or synthesis gas according to the invention, while methanol can be prepared as described herein below.

[0125] In an even newer process, which is still in the experimental stage, a first methacrolein is produced using one of the processes described above in connection with the production of methacrylic acid. In a later step, the methacrolein is oxidized and esterified simultaneously with atmospheric oxygen and methanol over a nickel-gold catalyst under moderate reaction conditions, such as typically a temperature of about 90° C. and a pressure of about 6 bar, to give methyl methacrylate. The methanol used in this process can be obtained as described herein below.

[0126] Methanol

[0127] The technical production of methanol is carried out by catalytic hydrogenation of synthesis gas, which preferably has a carbon monoxide to hydrogen ratio of about 1:2. Depending on the type of catalyst used, the process is carried out at different pressures and temperatures. In the so-called low-pressure process, which is mainly used at present, the hydrogenation is usually carried out at a pressure of about 50 to 100 bar and a temperature of about 200° C. to 300° C. in the presence of a mixture of copper and zinc oxides supported on aluminum oxide as catalyst. The synthesis gas according to the invention can be used as starting material for this process.

[0128] Methanol can be used for the production of methyl acrylate by esterification with acrylic acid, usually acid-catalyzed. Methanol can also be used to produce olefins, preferably ethylene and propylene, via the methanol to olefin (MTO) pathway (for a review of MTO, see, for example, MR Gogate (2019) Methanol-to-olefins process technology: current status and future prospects. Petroleum Science and Technology, 37: 5, 559-565, DOI: 10.1080 / 10916466.2018.1555589).

[0129] n-Propanol

[0130] n-Propanol is generally produced on a large scale by catalytic hydrogenation of propionaldehyde in the presence of a conventional supported copper-nickel-zinc-chromium catalyst at a temperature of about 110° C. to 150° C. and a pressure of about 1.5 bar to 10 bar. Propionaldehyde in turn can be obtained by hydroformylation of ethylene as described above.

[0131] n-Propanol can be used to produce n-propyl acrylate and n-propyl methacrylate by acid-catalyzed esterification, typically of acrylic acid or methacrylic acid, or by transesterification with methyl acrylate or methyl methacrylate, respectively.

[0132] n-Butanol and isobutanol

[0133] On an industrial scale, n-butyl alcohol and isobutyl alcohol are mainly produced by the following two-step method. The first step is to carry out hydroformylation of propylene with carbon monoxide and hydrogen in the presence of a homogeneous cobalt or rhodium catalyst. In the second step, the mixture of gained n-butyl aldehyde and 2-methyl propanal is hydrogenated into a mixture of corresponding n-butyl alcohol and isobutyl alcohol, and then the mixture of this n-butyl alcohol and isobutyl alcohol is separated into two independent alcohols by distillation. Because the general demand for n-butyl alcohol is higher, the catalyst used in the hydroformylation is especially selected so that the formation of n-butyl aldehyde is better than the formation of 2-methyl propanal. Starting compound propylene can be obtained from pyrolysis oil of the present invention, and synthesis gas according to the present invention can serve as a mixture of carbon monoxide and hydrogen used in this method.

[0134] n-Butanol and isobutanol can be used to produce the corresponding n-butyl (meth)acrylate and isobutyl (meth)acrylate, respectively, by acid-catalyzed esterification of acrylic acid or methacrylic acid, or by transesterification with methyl acrylate or methyl methacrylate.

[0135] Tert-Butanol

[0136] The large-scale production of tert-butanol is carried out by acid-catalyzed hydration of isobutene, usually at temperatures of about 30° C. to 120° C. and pressures of about 5 bar to 12 bar. Acidic ion exchange resins are mainly used as catalysts. The starting compound isobutene can be obtained from the pyrolysis oil according to the invention.

[0137] 2-Ethylhexanol

[0138] A common starting material for the industrial production of racemic 2-ethylhexanol is n-butyraldehyde, which is produced by hydroformylation of propylene, as described above. n-Butyraldehyde is subjected to a self-aldol condensation to give 2-ethyl-hex-2-enal, which is then catalytically hydrogenated to 2-ethylhexanol.

[0139] 2-Ethylhexanol can be used to produce 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate by acid-catalyzed esterification of acrylic acid or methacrylic acid, or by transesterification with methyl acrylate or methyl methacrylate, respectively.

[0140] Cyclopentanol

[0141] Cyclopentanol can be produced by a 3-step procedure with 1,3-butadiene as a starter. In the first step, 1,3-butadiene is converted into adipic acid or its ester via dicarbonylation with carbon monoxide in the presence of common homogeneous cobalt or palladium complexes. Then, cyclopentanone can be obtained by ketonization of adipic acid and highly basic such as barium hydroxide or by Dieckmann condensation (Dieckmann condensation) of adipic ester and subsequent decarboxylation. In the last step, cyclopentanone is reduced to cyclopentanol by catalytic hydrogenation or by reacting with a suitable reducing agent such as sodium borohydride. Employed 1,3-butadiene and carbon monoxide in this method can be obtained from cracking oil or synthesis gas according to the present invention.

[0142] Cyclopentanol can be used to produce cyclopentyl acrylate and cyclopentyl methacrylate by acid-catalyzed esterification, typically of acrylic acid or methacrylic acid, or by transesterification with methyl acrylate or methyl methacrylate, respectively.

[0143] Cyclohexanol

[0144] Cyclohexanol can be produced together with pimelinketone by, for example, catalytic oxidation of cyclohexane with atmospheric oxygen in the presence of a cobalt catalyst. This free radical reaction proceeds via unstable intermediate cyclohexane hydroperoxide, which decomposes into a mixture of two mentioned products. Cyclohexanol can be separated from this mixture by distillation. Cyclohexane used as the starting material for the above-mentioned oxidation is conventionally produced on a large scale by catalytic hydrogenation of benzene on a Raney nickel catalyst. Benzene can be obtained from cracking oil according to the present invention in turn.

[0145] Alternatively, cyclohexanol can be produced by hydrogenating phenol in the presence of a nickel catalyst. Phenol in turn can be obtained by the so-called cumene process, which is an industrial procedure for the simultaneous production of phenol and acetone. The process involves converting benzene and propylene into cumene via Friedel-Crafts alkylation and then oxidizing the cumene to cumene hydroperoxide by atmospheric oxygen. After an acidic workup, the hydroperoxide decomposes under rearrangement into phenol and acetone. The benzene used as starting material can be obtained from pyrolysis oils according to the invention,

[0146] Cyclohexanol can be used to produce cyclohexyl acrylate and cyclohexyl methacrylate by acid-catalyzed esterification, typically with acrylic acid or methacrylic acid, or by transesterification with methyl acrylate or methyl methacrylate, respectively.

[0147] Higher oxo alcohols such as isononanol and 2-propyl-1-heptanol

[0148] Higher oxo alcohols are generally produced in a manner similar to that described above for the shorter chain oxo alcohols (see, for example, the production of n-propanol and 2-ethylhexanol outlined above). Thus, the initial reaction is C n Hydroformylation of olefins. n+1 Alkanals are hydrogenated to the corresponding C n+1 The alkanol may first undergo a self-aldol condensation to give the corresponding C 2(n+1) Enaldehyde, the C 2(n+1) Hydrogenation of aldehydes to C 2(n+1) In particular, the C1-C4 olefins obtainable from the pyrolysis oil according to the invention can be used as starting products for this procedure.

[0149] Important higher oxo alcohols are in particular isononanol and 2-propyl-1-heptanol.

[0150] Isononanol is a mixture of branched primary C9 alcohols (main component: 3,5,5-trimethyl-1-hexanol) which can be produced by first hydroformylating a mixture of branched octenes (main component: diisobutylene) and then hydrogenating the resulting C9 aldehydes. The mixture of branched octenes can be obtained by dimerizing isobutylene and 1-butene, both of which can in turn be obtained from the pyrolysis oil according to the invention.

[0151] On the other hand, the production of 2-propyl-1-heptanol is based on n-valeraldehyde, which is formed by hydroformylation of n-butenes. The n-valeraldehyde is subjected to an aldol condensation and the resulting 2-propylhept-2-enal is subsequently subjected to catalytic hydrogenation to give racemic 2-propyl-1-heptanol. The n-butenes used in this procedure can also be obtained from the pyrolysis oil according to the invention.

[0152] Isononyl alcohol and 2-propyl-1-heptanol can be used to produce the corresponding isononyl (meth)acrylate or 2-propyl-1-heptyl (meth)acrylate, respectively, by acid-catalyzed esterification with conventional acrylic acid or methacrylic acid or by transesterification with methyl acrylate or methyl methacrylate.

[0153] Alkyl acrylate

[0154] As mentioned previously, alkyl acrylates such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate can be produced by the acid-catalyzed esterification of acrylic acid with ethanol, n-butanol, isobutanol and 2-ethylhexanol, respectively, wherein acrylic acid and the alcohols are obtainable by the methods previously described herein.

[0155] Alternatively, alkyl acrylates such as those explicitly mentioned above can be prepared from acetylene, carbon monoxide and the corresponding alkanols by Reppereaction. Acetylene and the alkanols ethanol, n-butanol, isobutanol and 2-ethylhexanol can be obtained from the cracking of pyrolysis oils according to the invention, while carbon monoxide can be obtained from the synthesis gas according to the invention.

[0156] Tert-Butyl Acrylate

[0157] Tert-butyl acrylate is produced on a large scale by the acid-catalyzed reaction of acrylic acid with isobutylene at relatively low pressures (usually not exceeding 10 bar). Acrylic acid in turn can be obtained by the above-described process, while isobutylene can be obtained from the pyrolysis oil according to the invention.

[0158] Vinyl acetate

[0159] The main industrial route for the production of vinyl acetate involves the selective gas phase oxidation of acetic acid with ethylene in the presence of oxygen. The conversion is usually carried out in a steam-heated tubular reactor at a temperature of about 150° C. to 160° C. and a pressure of about 8 bar to 11 bar. A bimetallic palladium-gold shell catalyst is usually used as a catalyst. The acetic acid used in this method can be produced by the carbonylation of methanol, which is based on the reaction of methanol with carbon monoxide in the presence of a catalyst such as a rhodium or iridium carbonyl complex. On the other hand, the starting materials ethylene and carbon monoxide can be obtained from a pyrolysis oil or synthesis gas according to the invention, while the methanol can be obtained from the catalytic hydrogenation of the synthesis gas as described above.

[0160] Vinyl Propionate

[0161] The main industrial route for producing vinyl propionate includes the reaction of acetylene with propionic acid in the presence of suitable catalysts such as carbon and zinc salts. Propionic acid can be prepared by gas phase oxidation of propanal in the presence of suitable catalysts such as manganese salts or cobalt salts, such as manganese (II) propionate. Propionic acid can be produced by hydroformylation of ethylene. Alternatively, propionic acid can be prepared by hydrocarboxylation of ethylene with carbon monoxide and water in the presence of a nickel catalyst such as nickel tetracarbonyl. On the other hand, the starting materials ethylene and carbon monoxide can be obtained from pyrolysis oil or synthesis gas according to the present invention, while acetylene can be obtained from the gaseous fraction of the cracking of plastic waste.

[0162] Acrylonitrile

[0163] On an industrial scale, acrylonitrile is produced by catalytic ammoxidation of propylene, also known as the SOHIO process, which involves converting propylene with ammonia and oxygen. The propylene used in this process can be obtained from the pyrolysis oil according to the invention.

[0164] Acrylamide

[0165] The large-scale production of acrylamide is carried out by the hydrolysis of acrylonitrile. The reaction can be catalyzed by aqueous strong acid (usually sulfuric acid), by metal salts or by nitrile hydratase. The starting compound acrylonitrile can be obtained by the SOHIO process described above.

[0166] In order to achieve the specific benefits of the present invention, the relative amount of monomers M′ produced from pyrolysis oil obtained as raw material by cracking organic plastic waste is at least 20% by weight, in particular at least 30% by weight and especially at least 50% by weight, based on the total weight of the monomers M subjected to the free radical aqueous emulsion polymerization. The amount of monomers M′ can also be 100%, based on the total amount of monomers M to be polymerized. Generally speaking, a mixture of monomers M′ produced from pyrolysis oil obtained as raw material by cracking organic plastic waste and monomers M″ produced from other raw materials will be used in the free radical aqueous emulsion polymerization.

[0167] In the free-radical aqueous emulsion polymerization, the monomers M to be polymerized generally comprise at least 80% by weight, for example 80% to 100% by weight or 80% to 99.9% by weight, in particular 85% to 99.9% by weight, based on the total weight of the monomers M, of one or more ethylenically unsaturated monomers M having a limited water solubility, in particular a deionized water solubility, which does not exceed 50 g / L at 20° C. and 1 bar. These monomers are referred to hereinafter as monomers M1.

[0168] Examples of such monomers M1 include in particular

[0169] - Acrylic and methacrylic esters, in particular esters of acrylic acid with alkanols having 1 to 18 C atoms and esters of methacrylic acid with alkanols having 1 to 18 C atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylpentyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, Guerbet acrylate, C 10 Isoamyl acrylate, 1-propylheptyl acrylate, lauryl acrylate and stearyl acrylate. 20 Examples of alkyl esters include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylpentyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, Guerbet C methacrylate, and 2-ethylhexyl methacrylate. 10 Isoamyl methacrylate, 1-propylheptyl methacrylate, lauryl methacrylate, and stearyl methacrylate;

[0170] - esters of acrylic acid and / or methacrylic acid with cycloalkanols having 3 to 8 C atoms, in particular 5 to 10 C atoms, such as cyclopropyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate and 4-tert-butylcyclohexyl methacrylate;

[0171] - monovinylaromatic hydrocarbons, such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene or 4-n-decylstyrene;

[0172] - conjugated dienes, such as butadiene or isoprene;

[0173] - olefins and halogenated olefins, such as ethylene, propylene, vinyl chloride, vinylidene chloride;

[0174] -Saturated C1-C 12 Vinyl and allyl esters of alkanoic acids, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl octanoate, vinyl laurate, vinyl stearate, vinyl versatate, allyl formate, allyl acetate, allyl propionate, allyl butyrate or allyl laurate.

[0175] Preferred monomers M1 are esters of acrylic acid with alkanols having 1 to 10 C atoms, esters of methacrylic acid with alkanols having 1 to 10 C atoms; monovinyl aromatic hydrocarbon compounds, in particular styrene, conjugated dienes, in particular butadiene; saturated C1-C 12 Vinyl esters of alkanoic acids, specifically vinyl acetate, vinyl propionate, and vinyl versatate; and olefins, specifically ethylene; and combinations thereof.

[0176] In particular, the monomer M1 is one of the following monomer combinations (1) to (5):

[0177] (1) at least one monovinyl aromatic monomer, at least one acrylic acid ester and optionally one or more methacrylic acid esters,

[0178] (2) at least one acrylate and at least one methacrylate,

[0179] (3) at least one monovinyl aromatic monomer, butadiene and optionally one or more monomers selected from acrylates and methacrylates

[0180] (4) At least one C2-C 12 Vinyl esters of alkanoic acids;

[0181] (5) At least one C2-C 12A vinyl ester of an alkanoic acid and at least one C2-C4 monoolefin and optionally one of an acrylate and a methacrylate.

[0182] In addition to the monomers M1, the monomers to be polymerized in the aqueous free-radical emulsion polymerization may include one or more ethylenically unsaturated monomers different from the monomers M2, which are in particular selected from the monomers M2, M3 and M4 described below. The total amount of these monomers, based on the total weight of the monomers M, is generally in the range of 0% to 20% by weight, for example in the range of 0.1% to 20% by weight.

[0183] As explained above, the monomers M include monomers M' preferably in an amount of at least 10 wt.-%, in particular at least 20 wt.-%, more preferably at least 30 wt.-%, in particular at least 50 wt.-% or up to 100 wt.-%, based on the total weight of the monomers M. Typically, the monomers M' are selected from the aforementioned monomers M1, but they can also be selected from monomers M2. In particular, the amount of monomers M' is such that the relative amount of carbon atoms originating from pyrolysis oil in the monomers M is at least 20 mol-%, in particular at least 50 mol-%, based on the total amount of carbon atoms in the monomers M.

[0184] Examples of monomers M.2 are monoethylenically unsaturated acidic monomers M2.a, such as

[0185] - monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms, such as acrylic acid, methacrylic acid or itaconic acid;

[0186] - ethylenically unsaturated sulfonic acids and their salts, such as vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, especially their salts, more particularly their sodium salts and their ammonium salts;

[0187] - ethylenically unsaturated phosphonic acids and ethylenically unsaturated phosphoric acids and their salts, such as vinylphosphonic acid, allylphosphonic acid, ethyl phosphonic acid acrylate, ethyl phosphonic acid methacrylate, propyl phosphonic acid, propyl phosphonic acid methacrylate, phospho-oligo(C2-C3-alkylene ether)acrylate, phospho-oligo(C2-C3-alkylene ether)methacrylate, especially their salts, more particularly their sodium salts and their ammonium salts;

[0188] and monoethylenically unsaturated neutral monomers M2.b, such as

[0189] - primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms, such as acrylamide and methacrylamide;

[0190] - monoethylenically unsaturated monomers carrying ureido or keto groups, such as 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido (meth)acrylate, N-[2-(2-oxo-oxazolidin-3-yl)ethyl]methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2-(acetoacetoxy)ethyl methacrylate, diacetone acrylamide (DAAM) and diacetone methacrylamide;

[0191] - esters of acrylic acid and / or methacrylic acid with alkanediols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate;

[0192] Preferably, the monomer M contains not more than 5 pphm, for example 0.1 pphm to 5 pphm, of monoethylenically unsaturated monomers M2.a having acid groups. 。 Preferably, the monomers M contain no more than 10 pphm of monomers M2b, for example 0 pphm to 10 pphm or 0.1 pphm to 10 pphm of monomers M2.b.

[0193] In addition to the above-mentioned monoethylenically unsaturated monomers M1 and M2, the monomers M may also include a small amount of ethylenically unsaturated monomers M3 with at least 2, for example 2 to 6, non-conjugated ethylenically unsaturated double bonds. These monomers will lead to crosslinking of the polymer chains during polymerization and are therefore referred to as crosslinking monomers M3. Exemplary crosslinking monomers include divinylbenzene, diesters or triesters of diols and triols with monoethylenically unsaturated C3-C6 monocarboxylic acids, for example di(meth)acrylates, tri(meth)acrylates, and tetra(meth)acrylates, for example, alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, and propylene glycol diacrylate, trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate, and vinyl and allyl esters of ethylenically unsaturated acids, such as vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, and divinyl and diallyl esters of dicarboxylic acids, such as diallyl maleate and diallyl fumarate, and methylenebisacrylamide. The amount of said monomer M3 will generally not exceed 3 pphm and, if present, will in particular range from 0.01 pphm to 3 pphm.

[0194] In addition to the above-mentioned monoethylenically unsaturated monomers M1 and / or M2, the monomers M may also include a small amount of a monoethylenically unsaturated monomer M4 having one unsaturated double bond and another reactive group susceptible to post-crosslinking reaction. The monoethylenically unsaturated monomer M4 includes

[0195] - monoethylenically unsaturated monomers containing keto groups, for example acetoacetoxyethyl (meth)acrylate or diacetone acrylamide;

[0196] - monoethylenically unsaturated monomers carrying epoxy groups, such as monoglycidyl allyl ether, glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl acrylate, 4-glycidyloxybutyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-epoxypentan-2-yl acrylate or 4,5-epoxypentan-2-yl methacrylate, preferably epoxy-functional (meth)acrylate monomers;

[0197] - N-hydroxyalkylamides of α,β-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and their esters with alcohols having 1 to 4 carbon atoms, such as N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide

[0198] - unsaturated silane-functional monomers, for example monomers which, in addition to the ethylenically unsaturated double bond, carry at least one mono-, di- and / or tri-C1-C4-alkoxysilane group, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane and mixtures thereof.

[0199] The amount of monomer M4 will generally not exceed 10 pphm and will in particular range from 0.01 pphm to 10 pphm.

[0200] According to the invention, the monomers M are polymerized in a free-radical aqueous emulsion polymerization, in particular in a free-radical emulsion polymerization. This technology has been described in detail in the art and is therefore familiar to those skilled in the art [see, for example, Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659-677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerisation, pp. 155-465, Applied Science Publishers, Ltd., Essex, 1975; DC Blackley, Polymer Latices, 2nd edition, Vol. 1, pp. 33-415, Chapman & Hall, 1997; H.Warson, The Applications of Synthetic Resin Emulsions, pp. 49-244, Ernest Benn, Ltd., London, 1972; J.Piirma, Emulsion Polymerisation, pp. 1-287, Academic Press, 1982; F. Dispersionensynthetischer Hochpolymerer, pp. 1 to 160, Springer-Verlag, Berlin, 1969 and patent specification DE-A 40 03 422].

[0201] Free radical initiated aqueous emulsion polymerization is usually achieved by dispersing ethylenically unsaturated monomers in an aqueous medium, usually with the use of surfactants such as emulsifiers and / or protective colloids, and polymerizing them with the aid of at least one polymerization initiator, in particular a water-soluble free radical polymerization initiator. These surfactants usually contain an emulsifier and provide micelles in which polymerization occurs and which serve to stabilize the monomer droplets and to grow the polymer particles during the aqueous emulsion polymerization. The surfactant used in the emulsion polymerization is usually not separated from the polymer dispersion, but remains in the aqueous polymer dispersion obtainable by the emulsion polymerization of the monomers M.

[0202] The free radical initiated aqueous emulsion polymerization is initiated by a free radical polymerization initiator (free radical initiator). These can be peroxides or azo compounds in principle. Of course, redox initiator systems are also useful. The peroxide used can be an inorganic peroxide in principle, such as hydrogen peroxide or peroxodisulfate, such as a monoalkali metal salt or a dialkali metal salt or an ammonium salt of peroxodisulfate, for example a monosodium salt, a monopotassium salt or a monoammonium salt and a disodium salt, a dipotassium salt or a diammonium salt, or an organic peroxide, such as an alkyl hydroperoxide, for example tert-butyl hydroperoxide, p-menthyl hydroperoxide or cumyl hydroperoxide, and a dialkyl or diaryl peroxide, such as di-tert-butyl or dicumyl peroxide. The azo compound used is basically 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Suitable oxidizing agents for redox initiator systems are essentially the above-mentioned peroxides. Corresponding reducing agents that can be used are sulfur compounds with a low oxidation state, such as alkali metal sulfites, for example potassium sulfite and / or sodium sulfite, alkali metal bisulfites, for example potassium bisulfite and / or sodium bisulfite, alkali metal metabisulfites, for example potassium metabisulfite and / or sodium metabisulfite, formaldehyde bisulfoxylates, for example potassium formaldehyde bisulfoxylate and / or sodium formaldehyde bisulfoxylate, alkali metal salts, in particular potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium hydrogensulfide and / or sodium hydrogensulfide, salts of polyvalent metals, such as iron(II) sulfate, ammonium iron(II) sulfate, iron(II) phosphate, enediols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing sugars, such as sorbitol, glucose, fructose and / or dihydroxyacetone. Preferred free radical initiators are inorganic peroxides, especially peroxodisulfates, and redox initiator systems. Typically, the amount of free radical initiator used, based on the total amount of monomers M, is from 0.01 pphm to 5 pphm, preferably from 0.1 pphm to 3 pphm.

[0203] The amount of free-radical initiator required for the emulsion polymerization M in the process according to the invention can initially be completely charged to the polymerization vessel. However, it is also possible to charge no free-radical initiator or only a portion of the free-radical initiator, for example not more than 30% by weight, in particular not more than 20% by weight, based on the total amount of free-radical initiator required in the aqueous polymerization medium, and then to add the entire amount or any remaining residual amount under polymerization conditions during the free-radical emulsion polymerization of the monomers M, in one or more portions depending on the consumption or continuously at a constant or variable flow rate.

[0204] Preferably, the free radical emulsion polymerization of the monomers M is carried out by the so-called feed method, which means that at least 90%, in particular at least 95% or the total amount of the monomers to be polymerized are metered into the polymerization reaction under polymerization conditions during a metering period P. The duration of the period P may depend on the production equipment, the reactivity of the monomers and the polymerization initiator and the feed rate of the monomers (starved conditions versus flooded conditions) and may vary, for example, between 20 minutes and 12 hours. Typically, the duration of the period P will be in the range of 0.5 hours to 5 hours, in particular 1 hour to 4 hours.

[0205] The term "polymerization conditions" is generally understood to mean those temperatures and pressures at which the free-radical initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. They depend in particular on the free-radical initiator used. Advantageously, the type and amount of free-radical initiator, the polymerization temperature and the polymerization pressure are selected so that there is always a sufficient amount of initiating free radicals to initiate or maintain the polymerization reaction.

[0206] It may be appropriate to establish the polymerization conditions and initially charge at least a portion of the free-radical initiator into the polymerization vessel before metering of the monomers M begins.

[0207] In some cases, it has been found to be advantageous to carry out the free radical emulsion polymerization in the presence of a seed latex. The seed latex is a polymer latex present in the aqueous polymerization medium before the start of metering of the monomers M. The seed latex can contribute to a better adjustment of the particle size of the final polymer latex obtained in the free radical emulsion polymerization of the invention.

[0208] In principle, every polymer latex can serve as a seed latex. For the purpose of the present invention, preference is given to seed latexes in which the particle size of the polymer particles is relatively small. In particular, the Z average particle size of the polymer particles of the seed latex (as measured by dynamic light scattering at 20° C. (see below)) is preferably in the range of 10 nm to 80 nm, in particular 10 nm to 50 nm. Preferably, the polymer particles of the seed latex are made of ethylenically unsaturated monomers containing at least 95% by weight of one or more monomers M1 as defined above, based on the total weight of the monomers forming the seed latex. In the polymer particles of the seed latex, at least 95% by weight of at least one monomer M1 or a mixture of at least two monomers M1, based on the total weight of the monomers forming the seed latex, is particularly included.

[0209] For this purpose, the seed latex is usually charged to the polymerization vessel before the start of metering of the monomers M. Specifically, the seed latex is charged to the polymerization vessel and the polymerization conditions are subsequently established, for example by heating the mixture to the polymerization temperature. It may be useful to charge at least a portion of the free radical initiator to the polymerization vessel before the start of metering of the monomers M. However, it is also possible to meter the monomers and the free radical polymerization initiator into the polymerization vessel in parallel.

[0210] The amount of seed latex calculated in solid form may generally range from 0.01% to 10% by weight, in particular from 0.1% to 5% by weight, based on the total weight of the monomers M to be polymerized.

[0211] The free radical aqueous emulsion polymerization of the present invention can be carried out at a temperature ranging from 0°C to 170°C. The temperature adopted is generally in the range of 50°C to 120°C, often 60°C to 120°C and usually 70°C to 110°C. The free radical aqueous emulsion polymerization of the present invention can be carried out at a pressure less than, equal to or greater than 1 atm (atmospheric pressure), and the polymerization temperature can therefore exceed 100°C and can be as high as 170°C. The polymerization of the monomers is usually carried out at ambient pressure, but it can also be carried out at high pressure. In this case, the pressure can take values ​​of 1.2 bar, 1.5 bar, 2 bar, 5 bar, 10 bar, 15 bar (absolute) or even higher values. If the emulsion polymerization is carried out under reduced pressure, a pressure of 950 mbar, usually 900 mbar and often 850 mbar (absolute) is established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out at ambient pressure (about 1 atm) excluding oxygen, for example under an inert gas atmosphere, for example under nitrogen or argon.

[0212] The polymerization of monomers M can optionally be carried out in the presence of a chain transfer agent. Chain transfer agents are understood to mean compounds that transfer free radicals and reduce molecular weight or control chain growth in the polymerization. Examples of chain transfer agents are aliphatic and / or aromatic aliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic mercaptans, such as ethanethiol, n-propyl mercaptan, 2-propyl mercaptan, n-butyl mercaptan, 2-butyl mercaptan, 2-methyl-2-propyl mercaptan, n-pentyl mercaptan, 2-pentyl mercaptan, 3-pentyl mercaptan, 2-methyl-2-butyl mercaptan, 3-methyl-2-butyl mercaptan, n-hexyl mercaptan, 2-hexyl mercaptan, 3-hexyl mercaptan, 2-methyl-2-pentyl mercaptan, 3-methyl-2- pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and isomeric compounds thereof, n-octanethiol and isomeric compounds thereof, n-nonanethiol and isomeric compounds thereof, n-decanethiol and isomeric compounds thereof, n-undecanethiol and isomeric compounds thereof, n-dodecanethiol and isomeric compounds thereof, n-tridecanethiol and isomeric compounds thereof, substituted thiols (e.g. 2-hydroxyethanethiol, aromatic thiols such as benzenethiol, o-, m- or p-methylbenzenethiol), mercaptoacetic acid (mercaptoacetic acid The chain transfer agents described herein are preferably alkyl esters of thioglycolic acid, such as 2-ethylhexyl thioglycolate, alkyl esters of mercaptopropionic acid, such as octyl mercaptopropionate, and further sulfur-containing compounds as are also described in the following document: Polymer Handbook, 3rd edition, 1989, J. Brandrup and E. H. Immergut, John Wiley & Sons, Section II, pages 133 to 141, as well as aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane, or hydrocarbons with easily abstracted hydrogen atoms, such as toluene. Alternatively, it is possible to use mixtures of the abovementioned chain transfer agents, which do not destroy each other. The total amount of chain transfer agents optionally used in the process according to the invention will generally not exceed 1% by weight, based on the total amount of monomers M. However, it is possible that the amount of chain transfer agent added to the polymerization reaction during a particular period of the polymerization reaction may exceed the value of 1 wt. %, based on the total amount of monomers that have been added to the polymerization reaction.

[0213] The free-radical emulsion polymerization of the present invention is generally carried out in an aqueous polymerization medium which comprises, together with water, at least one surface-active substance (surfactant) to stabilize the emulsion of monomers and the polymer particles of the polymer latex.

[0214] The surfactant may be selected from emulsifiers and protective colloids. In contrast to emulsifiers, protective colloids are understood to mean polymeric compounds with a molecular weight above 2000 Daltons, whereas emulsifiers generally have a lower molecular weight. The surfactant may be an anionic surfactant or a nonionic surfactant or a mixture of a nonionic surfactant and an anionic surfactant.

[0215] Anionic surfactants usually carry at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups. Anionic surfactants carrying at least one anionic group are usually used in the form of their alkali metal salts, especially their sodium salts, or in the form of their ammonium salts.

[0216] Preferred anionic surfactants are anionic emulsifiers, in particular those with at least one sulfate or sulfonate group. Likewise, anionic emulsifiers with at least one phosphate or phosphonate group can be used as the sole anionic emulsifier or in combination with one or more anionic emulsifiers with at least one sulfate or sulfonate group.

[0217] Examples of anionic emulsifiers with at least one sulfate or sulfonate group are

[0218] -Alkyl sulfates, especially C8-C 22 - salts of alkyl sulfates, in particular alkali metal and ammonium salts,

[0219] - Sulfate monoesters of ethoxylated alkanols, in particular ethoxylated C8-C60 alcohols preferably having an ethoxylation level (EO level) in the range of 2 to 40 22 - salts of sulfuric acid monoesters of alkanols, in particular alkali metal and ammonium salts,

[0220] - Sulfate monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 Salts of sulfuric acid monoesters of alkylphenols (EO level preferably 3 to 40), especially alkali metal and ammonium salts,

[0221] -Alkyl sulfonic acids, especially C8-C 22 - salts of alkylsulfonic acids, in particular alkali metal and ammonium salts,

[0222] - dialkyl esters of sulfosuccinic acid, especially di-C4-C 18 - salts of alkyl esters, in particular alkali metal and ammonium salts,

[0223] -Alkylbenzenesulfonic acid, especially C4-C 22 - salts of alkylbenzenesulfonic acids, in particular alkali metal and ammonium salts, and

[0224] - mono- or di-sulfonated alkyl-substituted diphenyl ethers, e.g., with C4-C 24 -alkyl groups, especially alkali metal salts and ammonium salts. The latter are known, for example from US Pat. No. 4,269,749, and are commercially available, for example as 2A1 (Dow Chemical Company).

[0225] Mixtures of the abovementioned salts are also suitable.

[0226] Preferred anionic surfactants are anionic emulsifiers selected from the group consisting of:

[0227] -Alkyl sulfates, especially C8-C 22 - salts of alkyl sulfates, in particular alkali metal and ammonium salts,

[0228] - Sulfate monoesters of ethoxylated alkanols, in particular ethoxylated C8-C60 alcohols preferably having an ethoxylation level (EO level) in the range of 2 to 40 22 - salts of sulfuric acid monoesters of alkanols, especially alkali metal salts,

[0229] - Sulfate monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 - sulfuric acid monoesters of alkylphenols (EO level preferably 3 to 40),

[0230] -Alkylbenzenesulfonic acid, especially C4-C 22 - alkylbenzenesulfonic acid, and

[0231] - mono- or di-sulfonated alkyl-substituted diphenyl ethers, e.g., with C4-C 24 - bis(benzenesulfonic acid) ethers of alkyl groups;

[0232] Examples of anionic emulsifiers with phosphate or phosphonate groups include, but are not limited to, the following salts selected from the group consisting of:

[0233] - monoalkyl phosphates and dialkyl phosphates, especially C8-C 22 - salts of alkyl esters, in particular alkali metal and ammonium salts,

[0234] - Phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably with an alkoxylation level in the range from 2 to 40, in particular in the range from 3 to 30, for example ethoxylated C8-C3-alkoxylated alkyl alcohols, preferably with an ethoxylation level (EO level) in the range from 2 to 40 22 Phosphoric acid monoesters of -alkanols, preferably propoxylated C8-C8-C10-hydroxy-1-ols having a propoxylation level (PO level) in the range of 2 to 40. 22Phosphoric acid monoesters of C8-C12-alkanols and ethoxylated-co-propoxylated C8-C12-alkanols preferably having an ethoxylation level (EO level) in the range of 1 to 20 and a propoxylation level of 1 to 20 22 - salts of phosphoric acid monoesters of alkanols, in particular alkali metal and ammonium salts,

[0235] - Phosphoric acid monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 Salts of phosphoric acid monoesters of alkylphenols (EO level preferably 3 to 40), especially alkali metal and ammonium salts,

[0236] -Alkylphosphonic acid, especially C8-C 22 - salts of alkylphosphonic acids, in particular alkali metal and ammonium salts, and

[0237] -Alkylbenzenephosphonic acid, especially C4-C 22 Salts of alkylbenzenephosphonic acids, especially the alkali metal and ammonium salts.

[0238] Other suitable anionic surfactants may be found in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Volume XIV / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme-Verlag, Stuttgart, 1961, pages 192-208.

[0239] Preferably, the surfactant comprises at least one anionic emulsifier with at least one sulfate or sulfonate group. At least one anionic emulsifier with at least one sulfate or sulfonate group can be a unique type of anionic emulsifier. However, a mixture of at least one anionic emulsifier with at least one sulfate or sulfonate group and at least one anionic emulsifier with at least one phosphate or phosphonate group can also be used. In such a mixture, the amount of at least one anionic emulsifier with at least one sulfate or sulfonate group is preferably at least 50 weight % based on the total weight of the anionic surfactant used in the method of the present invention. Specifically, the amount of the anionic emulsifier with at least one phosphate or phosphonate group is no more than 20 weight % based on the total weight of the anionic surfactant used in the method of the present invention.

[0240] The surfactants may also include, together with the above-mentioned anionic surfactants, one or more nonionic surface-active substances, in particular selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, aromatic aliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO level: 3 to 50, alkyl groups: C4-C10 ), long chain alcohol ethoxylates (EO level: 3 to 100, alkyl group: C8-C 36 ) and polyethylene oxide / polypropylene oxide homopolymers and copolymers. These may contain alkylene oxide units copolymerized in random distribution or in block form. Very suitable examples are EO / PO block copolymers. Preferred are ethoxylates of long-chain alkanols, in particular those in which the alkyl groups are C8-C 30 Those ethoxylates having an average ethoxylation level of 5 to 100, and particularly preferred are those having a linear C 12 -C 20 alkyl groups and those ethoxylates having an average ethoxylation level of 10 to 50 as well as ethoxylated monoalkylphenols.

[0241] Preferably, the surfactant is used in such an amount that the amount of surfactant is in the range from 0.2% to 5% by weight, in particular in the range from 0.5% to 3% by weight, based on the monomers M to be polymerized.

[0242] The aqueous reaction medium in the polymerization may in principle also comprise small amounts (generally up to 5% by weight) of water-soluble organic solvents, such as methanol, ethanol, isopropanol, butanol, pentanol and acetone, etc. Preferably, however, the process of the invention is carried out in the absence of such solvents.

[0243] It is usually advantageous to carry out an aftertreatment of the aqueous polymer dispersion obtained on completion of the polymerization of the monomers M in order to reduce the residual monomer content. This aftertreatment is carried out chemically, for example by using more effective free radical initiator systems to complete the polymerization reaction (known as afterpolymerization), and / or physically, for example by stripping the aqueous polymer dispersion with steam or an inert gas. The corresponding chemical and physical methods are familiar to the person skilled in the art, see for example EP-A 771 328, DE-A 196 24 299, DE-A 196 21 027, DE-A 197 41 184, DE-A 197 41 187, DE-A 198 05 122, DE-A 198 28 183, DE-A 198 39 199, DE-A 198 40 586 and DE-A 198 47 115. The combination of chemical and physical aftertreatment has the advantage of removing not only unconverted ethylenically unsaturated monomers but also other disruptive volatile organic constituents (VOCs) from the aqueous polymer dispersion.

[0244] In a preferred set of embodiments the aqueous emulsion polymerisation is carried out by the procedure described in EP917545.

[0245] In a preferred set of embodiments the aqueous emulsion polymerisation is carried out by the procedure described in EP 3157992.

[0246] In yet another preferred group of embodiments, the aqueous emulsion polymerization is carried out by the procedure described in EP 3523382.

[0247] In yet another group of preferred embodiments, the aqueous emulsion polymerization is carried out by the procedure described in WO 2020 / 002102.

[0248] In yet another group of preferred embodiments, the aqueous emulsion polymerisation is carried out by the procedure described in WO 2001 / 014426.

[0249] In yet another group of preferred embodiments, the aqueous emulsion polymerization is carried out by the procedure described in WO 2020 / 249406.

[0250] The free radical aqueous emulsion polymerization can be carried out by a single-stage or multistage emulsion polymerization of the monomer composition M, in particular an aqueous free radical emulsion polymerization. In the case of aqueous emulsion polymerization, the term "multistage" is fully understood to mean that the relative concentrations of the monomers in the monomer composition M added to the polymerization reaction are changed at least once during the aqueous emulsion polymerization. Such a procedure produces at least two polymer populations with different monomer compositions in the polymer particles of the latex. For example, it is possible to change the monomer composition so that the multistage latex polymer is characterized by having different glass transition temperatures or glass transition temperatures (T g It is also possible to vary the monomer composition so that a graded latex polymer is characterized by having a population with different concentrations of polymerized acidic monomers such as monomer M2.a or a concentration gradient of monomer M2.a.

[0251] During the addition of monomers M, the type of monomers and / or their relative amounts may be changed continuously or stepwise. However, it is also possible for the type and relative amount of monomers M added to the polymerization reaction to remain constant. For example, it is possible for the ratio of monomers M1 and M2 to increase or decrease during the addition.

[0252] Preferably, the aqueous polymer latex of the carboxylated polymer is prepared by a so-called feed method, by free-radical aqueous emulsion polymerization, wherein during the feeding of the monomer composition M, wherein at least 90% of the monomer composition M to be polymerized is metered into the polymerization reaction under polymerization conditions during a metering period P, and wherein the composition of the part of the monomer composition M metered into the polymerization reaction under polymerization conditions changes at least once during the metering period P.

[0253] The concentration of the polymer contained in the aqueous polymer dispersion is generally in the range from 20 to 70% by weight, in particular in the range from 30 to 65% by weight, especially in the range from 40 to 65% by weight, based on the total weight of the aqueous polymer dispersion.

[0254] In the aqueous polymer dispersion obtained by the method of the present invention, the dispersed polymer is in the form of polymer particles. The polymer particles generally have an average diameter in the range of 30nm to 1000nm, particularly in the range of 40nm to 900nm and especially in the range of 50nm to 800nm. The average particle size mentioned herein relates to the Z average particle size as measured by photon correlation spectroscopy (PCS) (also referred to as quasi-elastic light scattering (QELS) or dynamic light scattering (DLS)). The measuring method is described in ISO 13321:1996 standard. A high performance particle size analyzer (HPPS) can be used for determination. For this purpose, a sample of an aqueous polymer latex is diluted and the dilution is analyzed. In the case of DLS, the water dilution can have a polymer concentration in the range of 0.001% by weight to 0.5% by weight, depending on the particle size. In most cases, a suitable concentration is 0.01% by weight. However, higher or lower concentrations can be used to obtain an optimal signal-to-noise ratio. Dilution can be achieved by adding the polymer latex to an aqueous solution of water or a surfactant to avoid flocculation. Typically, the dilution is carried out by using a 0.1 wt. % aqueous solution of a nonionic emulsifier, such as ethoxylated C16 / C18 alkanol (degree of ethoxylation 18) as diluent. Measurement configuration: HPPS from Malvern, automated, equipped with continuous flow cuvette and Gilson autosampler. Parameters: measurement temperature 20.0°C; measurement time 120 seconds (6 cycles of 20 s each); scattering angle 173°; laser wavelength 633 nm (HeNe); refractive index of the medium 1.332 (aqueous); viscosity 0.9546 mPa·s. The measurement gives the average value (fitted average value) of the second-order cumulant analysis, i.e. the Z average value. The "fitted average value" is the average intensity-weighted hydrodynamic particle size in nm.

[0255] Depending on the desired purpose, the polymer in the polymer dispersion can have a unimodal particle size distribution (including narrow and broad unimodal particle size distributions) as well as a multimodal particle size distribution. The particle size distribution is characterized by a polydispersity index, which is a dimensionless number calculated by a simple 2-parameter fit to the correlation data of the cumulant analysis. The calculation is usually performed as described in ISO 13321: 1996. Typically, the range of PDI will be from 0.1 to 5.

[0256] Depending on the desired use, the polymer dispersions can have a glass transition temperature within a very wide range, for example within the range of -60°C to 150°C. They may have more than one stage, for example 2, 3 or 5 different stages with the same or different glass transition temperatures. The glass transition temperature can be determined by the DSC method (differential scanning calorimetry, 20 k / min, midpoint measurement) according to DIN 53765: 1994-03 or ISO 11357-2, while the sample preparation is preferably according to DIN EN ISO 16805: 2005.

[0257] The pH of the polymer dispersion may be in the acidic to basic pH range, and typically in the range of pH 2 to pH 10, or may be even higher, for example up to pH 12, depending on the intended purpose.

[0258] The polymer dispersion obtained by free radical aqueous emulsion polymerization of monomers M can be adapted to the desired purpose by selecting an appropriate composition of monomers M. In particular, the polymer dispersion obtained by free radical aqueous emulsion polymerization of monomers M can be used as a binder in coating compositions (including masonry paints, interior paints, paints for wood coatings and wood stains, and coating compositions for concrete and cement fiberboards), as a binder in paper coatings, as a modifier in hydraulically bonded building materials such as concrete, plaster and mortar, as a binder in waterproof membranes, as a binder in flexible roofing, as a binder for fiber bonding, and in adhesives (including, for example, pressure sensitive adhesives, construction adhesives and laminating adhesives).

[0259] Particular examples of polymer dispersions that can be produced by using monomers M are described in EP 917545, EP 3157992, EP 3523382, WO 2020 / 002102, WO 2001 / 014426 and WO 2020 / 249406, in particular the production examples described therein, in particular when the examples are carried out on an industrial scale.

[0260] The polymer was prepared on a production scale (e.g. 50 m3) by using 2-ethylhexyl acrylate and methyl methacrylate obtained from a pyrolysis oil feedstock (= approximately 95 wt.% of the polymer was based on recycled material). 3 The emulsion polymerization described in Example E2 of WO 01 / 14426 was carried out in a reactor) to produce an aqueous polymer dispersion having properties similar to those of the polymer latex of Example E2. In addition, by using a pyrolysis oil feedstock to produce these monomers, the number of batches between necessary maintenance and cleaning cycles can be increased from an average of 20 to an average of 24, which is an average increase of about 20% compared to the process with these monomers from classic fossil naphtha feedstocks.

[0261] By using butadiene and styrene obtained from pyrolysis oil feedstock (= approximately 95 wt.% of polymer is based on recycled materials) on a production scale (e.g. 60 m 3 The emulsion polymerization described in Example 1 of WO 2020 / 249406 was carried out in a reactor) to produce an aqueous polymer dispersion having properties similar to those of the polymer latex of Example 1. In addition, by using pyrolysis oil feedstocks to produce these monomers, the number of batches between necessary maintenance and cleaning cycles can be increased from an average of 90 to an average of 105, which is an increase of about 15% compared to carrying out the process with these monomers from classic fossil feedstocks.

[0262] By using styrene and n-butyl acrylate obtained from pyrolysis oil feedstock (= approximately 83 wt.% of polymer is based on recycled material) on a production scale (e.g. 50 m 3 The emulsion polymerization described in Example 1 of EP 3157992 was carried out in a reactor) to produce an aqueous polymer dispersion having properties similar to the polymer latex of Example 1. Furthermore, by using pyrolysis oil feedstocks to produce these monomers, the number of batches between necessary maintenance and cleaning cycles can be increased from an average of 26 to an average of 31, which is an increase of about 20% compared to carrying out the process with these monomers from classic fossil feedstocks.

[0263] By using styrene obtained from pyrolysis oil feedstock (= approximately 78 wt.% of polymer is based on recycled material) on a production scale (e.g. 25 m 3 The emulsion polymerization described in the examples of EP 3523382 was carried out in a reactor) to produce an aqueous polymer dispersion having properties similar to those of polymer dispersion C1 of Example 3. Furthermore, by using pyrolysis oil feedstocks for the production of styrene, the number of batches between necessary maintenance and cleaning cycles can be increased from an average of 8 to an average of 10, which is an increase of about 25% compared to carrying out the process with these monomers from classic fossil feedstocks.

Claims

1. A process for producing aqueous polymer dispersions by free-radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein a portion of the monomers M to be polymerized are ethylenically unsaturated monomers M′ produced from pyrolysis oils obtained as raw material by pyrolysis of plastic waste.

2. The method of claim 1, wherein the pyrolysis oil has at least one of the following properties: (a) a sulfur content of at least 5 ppm selected from H2S, elemental sulfur and organic sulfur, calculated as elemental sulfur, as determined in accordance with ASTM D 7183-18; (β) an organic nitrogen content of at least 20 ppm as determined in accordance with ASTM D 5762-18 and calculated as elemental nitrogen; and / or (x) an organic oxygen content of at least 50 ppm, calculated as elemental oxygen, as determined in accordance with ASTM D 7423-17.

3. The method according to any one of the preceding claims, wherein the pyrolysis oil is obtained from mixed waste plastic material.

4. The process according to claim 3, wherein the pyrolysis oil is subjected to steam cracking, wherein a C2-C4 olefin fraction, a >C4 olefin fraction and a benzene and / or toluene fraction are obtained, which fractions are converted into the desired monomers M'.

5. The method according to any one of claims 1 or 2, wherein the pyrolysis oil is obtained from waste rubber, in particular from waste tire material.

6. The process according to claim 5, wherein the pyrolysis oil is subjected to a gasification step, wherein a synthesis gas fraction comprising a mixture of carbon monoxide and hydrogen is obtained, said synthesis gas fraction being used in said production of said ethylenically unsaturated monomers M'.

7. The process according to claim 6, wherein the synthesis gas fraction is converted into methanol which is subsequently used in the production of the ethylenically unsaturated monomers M'.

8. The method according to any one of claims 4, 6 or 7, comprising the following steps: i) providing a pyrolysis oil form of an organic waste selected from mixed waste plastics; ii) providing full range naphtha from said pyrolysis oil obtained in step i), iii) subjecting the full range naphtha to steam cracking, wherein a C2-C4 olefin fraction, a >C4 olefin fraction and a benzene and / or toluene fraction are obtained, optionally, iv) converting at least one of the fractions obtained in step ii) into ethylenically unsaturated monomers M′; and / or ii.a) subjecting the pyrolysis oil to a gasification step to obtain a synthesis gas comprising a mixture of carbon monoxide and hydrogen, iii.a) using the synthesis gas fraction obtained in step ii.a) in the production of ethylenically unsaturated monomers M′; as well as v) carrying out a free-radical aqueous emulsion polymerization of at least one ethylenically unsaturated monomer M, wherein at least 20% by weight of said monomer M to be polymerized are selected from the group consisting of: One or more of the monomer M′ obtained in step iv) or step iii.a), the C2-C4 olefin obtained in step iii), and combinations thereof.

9. The process according to one of claims 4 and 6, 7 or 8, wherein at least one of the following fractions (a) to (f) or a combination of fractions (a) to (f) obtained from steam cracking or gasification is used in the production of the ethylenically unsaturated monomers: (a) a C2-C4 olefin fraction and the benzene fraction or the toluene fraction; (b) C2-C4 olefin fraction; (c) the synthesis gas fraction; (d) a C2-C4 olefin fraction and said synthesis gas fraction; (e)>C4 olefin fraction; (f) C2-C4 olefin fraction, >C4 olefin fraction and the synthesis gas fraction.

10. The process according to any one of the preceding claims, wherein the ethylenically unsaturated monomer M′ is selected from the group consisting of monovinyl aromatic monomers, divinyl aromatic monomers, butadiene, acrylates, methacrylates, acrylic acid, methacrylic acid, amides of acrylic acid, amides of methacrylic acid, acrylonitrile, C2-C 12 Vinyl esters of alkanoic acids, C2-C 12 Allyl esters of alkanoic acids and mixtures thereof.

11. The process according to any one of the preceding claims, wherein at least 20% by weight of the monomers M are selected from ethylenically unsaturated monomers M' produced from pyrolysis oil obtained as raw material by pyrolysis of organic plastic waste.

12. The process according to any one of the preceding claims, wherein the monomers M to be polymerized comprise at least 80% by weight, based on the total weight of the monomers M, of one of the following monomer combinations (1) to (5): (1) at least one monovinyl aromatic monomer, at least one acrylic acid ester and optionally one or more methacrylic acid esters, (2) at least one acrylate and at least one methacrylate, (3) at least one monovinyl aromatic monomer, butadiene and optionally one or more monomers selected from acrylates and methacrylates (4) At least one C2-C 12 Vinyl esters of alkanoic acids; (5) At least one C2-C 12 A vinyl ester of an alkanoic acid and at least one C2-C4 olefin.

13. The method according to claim 10 or 12, wherein the acrylate is selected from acrylic acid C1-C 18 Alkyl esters and acrylic acid C5-C 18 Cycloalkyl esters, and wherein the methacrylate is selected from methacrylic acid C1-C 18 Alkyl esters and methacrylates C5-C 18 Cycloalkyl esters.

14. The process according to any one of the preceding claims, wherein the relative amount of carbon atoms in the monomers M originating from the pyrolysis oil is at least 20 mol%.

15. The process according to any one of the preceding claims, wherein the free-radical aqueous emulsion polymerization of the ethylenically unsaturated monomers M is carried out on an industrial scale.

16. Use of ethylenically unsaturated monomers M′ produced from pyrolysis oil obtained as raw material by pyrolysis of plastic waste, in particular selected from mixed waste plastics and waste rubber, for extending the time period between purification cycles of reaction vessels used in the industrial-scale free-radical aqueous emulsion polymerization of ethylenically unsaturated monomers.