Vinyl polymer production device and vinyl polymer production method

Abstract

The present invention addresses the problem of providing an apparatus for producing a vinyl polymer, which reduces energy consumption and produces a vinyl polymer at low cost. This vinyl polymer production device (1) is provided with: a polymerization reaction tank (10) for obtaining a vinyl polymer composition; a starting material vinyl monomer supply unit (20) provided with a non-regenerative / non-biological starting material vinyl monomer supply unit (22) and a starting material vinyl monomer supply pump (24); a devolatilization unit (30) for separating a liquid vinyl polymer from a gaseous unreacted vinyl monomer, the devolatilization unit (30) having a vinyl polymer composition introduction port (32), a vinyl polymer discharge port (34), and a first unreacted vinyl monomer discharge port (36) and a second unreacted vinyl monomer discharge port (38); a refiner (40) for separating and removing impurity components; and a circulation unit (50) that circulates the unreacted vinyl monomer to the starting material vinyl monomer supply unit. The regenerated / biological raw material vinyl monomer supply unit is connected to at least one selected from the group consisting of a raw material vinyl monomer supply unit, a polymerization reaction tank, a refiner, a circulation unit, and a third pipe (73).

Description

Technical Field

[0001] This invention relates to a vinyl polymer manufacturing apparatus and a method for manufacturing vinyl polymers, and more particularly, to a vinyl polymer manufacturing apparatus and method particularly suitable for manufacturing vinyl polymers using a mass balance approach. Background Technology

[0002] A representative example of (meth)acrylates contained in so-called vinyl monomers is methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), a vinyl polymer obtained by polymerizing MMA, exhibits excellent transparency and weather resistance. Therefore, PMMA is widely used as a material for constructing automotive parts, signage, display devices, and the like.

[0003] It is known that in the manufacture of such poly(methyl)acrylate, when a monomer mixture with methyl (meth)acrylate as the main component is continuously subjected to bulk polymerization in a fully mixed reactor without the use of solvent, in order to adjust to any monomer conversion rate and achieve stable operation, the dissolved oxygen in the monomer mixture is reduced to less than 1 ppm, an initiator with a specific half-life is used, stirring is performed with a specific power consumption, and the reaction is carried out at a specific temperature and residence time with a specific monomer conversion rate (see Patent Document 1).

[0004] Furthermore, it is known that in the manufacture of poly(meth)acrylate, in order to recover and reuse unreacted (meth)acrylate monomers in a non-self-polymerizing state, a further step (D) is performed in the manufacturing method of the (meth)acrylate polymer having (A), (B), and (C). (A) involves continuously feeding a raw material composition comprising (meth)acrylate monomers containing 50% by mass or more of methyl methacrylate, a free radical polymerization initiator, and a chain transfer agent into a polymerization reactor. (B) involves polymerizing at least a portion of the (meth)acrylate monomers in the polymerization reactor to produce (meth)acrylate polymerized from at least a portion of the (meth)acrylate monomers. In the process of the reaction mixture of the acrylic polymer, step (C) above involves continuously extracting the reaction mixture from the polymerization vessel and performing a devolatilization process to separate and remove volatile components containing methyl methacrylate dimer and unreacted (meth)acrylate monomers to obtain the (meth)acrylate polymer. Step (D) above involves introducing the separated and removed volatile components into a distillation column and recovering the recovered components containing at least a portion of the methyl methacrylate dimer contained in the volatile components and at least a portion of the unreacted (meth)acrylate monomers contained in the volatile components under the condition that the content of methyl methacrylate dimer in the recovered components is 0.1 to 1.0% by mass (see Patent Document 2).

[0005] Furthermore, with the surge in resource prices and increased awareness of environmental issues in recent years, there is a growing desire to recycle and reuse (resource recovery) products (molded bodies) containing poly(meth)acrylate used in the various applications described above.

[0006] Methods for reusing poly(methyl methacrylate) include, for example: material reuse by re-molding the recycled molded body to manufacture a new molded body; heat treatment of the recycled molded body to thermally decompose (depolymerize) the poly(methyl methacrylate) to recover the (methyl methacrylate), and chemical reuse by using the recovered (methyl methacrylate) (sometimes called recycled MMA) to manufacture a new molded body; and thermal reuse by burning the recycled molded body as fuel, using the combustion energy directly as a heat source, and further using the combustion energy to generate electricity and utilize it.

[0007] Poly(methyl methacrylate) can be recovered in high yield by heating at a relatively low temperature of around 300°C, which can reduce impurities. Therefore, it is preferred to reuse it through chemical recycling.

[0008] In addition, from the viewpoint of reducing environmental impact, for example, there are known methods to obtain (recycled) methyl methacrylate as a vinyl monomer by using the thermal decomposition based on chemical recycling as described above, or by using biomass resources as raw materials and utilizing microbial fermentation; furthermore, there are known methods to mix the (recycled) methyl methacrylate as a vinyl monomer (sometimes called recycled / bio-based vinyl monomer) obtained in this way with methyl methacrylate (sometimes called non-recycled / non-bio-based vinyl monomer) that is conventionally used, such as methyl methacrylate produced from fossil fuels as a vinyl monomer (primary vinyl monomer) and is not among the above-mentioned recycled / bio-based vinyl monomers, in a prescribed ratio to produce poly(methyl methacrylate) as a vinyl polymer.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 3-111408

[0012] Patent Document 2: Japanese Patent Application Publication No. 2005-82687 Summary of the Invention

[0013] However, according to the technology of the aforementioned patent documents 1 and 2, and the conventional manufacturing methods of vinyl polymers using recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers, before manufacturing the vinyl polymer, it is sometimes required to perform complex refining processes on both the recycled / bio-based vinyl monomers and the non-recycled / non-bio-based vinyl monomers. These processes require a great deal of energy and therefore sometimes incur higher costs.

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems can be solved by having a vinyl polymer manufacturing apparatus with a specified structure and a method for manufacturing a vinyl polymer using the vinyl polymer manufacturing apparatus, thereby completing the present invention.

[0015] That is, the present invention provides the following [1] to

[14] .

[0016] [1] A vinyl polymer manufacturing apparatus, comprising:

[0017] A polymerization reactor is used to carry out bulk polymerization or solution polymerization of raw vinyl monomers containing recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers to obtain a vinyl polymer composition composed of vinyl polymers and unreacted vinyl monomers.

[0018] A raw material vinyl monomer supply unit is used to supply the vinyl monomer to the polymerization reactor. The raw material vinyl monomer supply unit is connected to the polymerization reactor via a first pipe connected at one end to the polymerization reactor and at the other end to the raw material vinyl monomer supply unit. It includes: a non-renewable / non-biological raw material vinyl monomer supply unit for supplying the non-renewable / non-biological raw material vinyl monomer and a raw material vinyl monomer supply pump for discharging the vinyl monomer to the polymerization reactor.

[0019] The devolatilization section is used to devolatilize the vinyl polymer composition discharged from the polymerization reactor to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer. The devolatilization section is connected to the polymerization reactor via a second pipe connected at one end to the polymerization reactor and at the other end to the devolatilization section. It has: a vinyl polymer composition inlet for introducing the vinyl polymer composition, a vinyl polymer outlet for discharging the vinyl polymer, a first unreacted vinyl monomer outlet for discharging the unreacted vinyl monomer, and a second unreacted vinyl monomer outlet disposed downstream of the first unreacted vinyl monomer outlet.

[0020] A refiner for separating and removing impurities from the unreacted vinyl monomers discharged from the devolatilization section, the refiner being connected to the devolatilization section via a third pipe connected at one end to the first unreacted vinyl monomer outlet and at the other end to the refiner, and also connected to the devolatilization section via a fourth pipe connected at one end to the second unreacted vinyl monomer outlet and at the other end to the refiner; and

[0021] The circulation section circulates unreacted vinyl monomers, after the impurities have been removed by the purifier, to the raw material vinyl monomer supply section. The circulation section is provided in a fifth pipe connected at one end to the purifier and at the other end to the raw material vinyl monomer supply section.

[0022] The recycled / bio-based vinyl monomer supply unit for supplying recycled / bio-based vinyl monomers is connected to at least one of the aforementioned vinyl monomer supply unit, the aforementioned polymerization reactor, the aforementioned purifier, the aforementioned circulation unit, and the aforementioned third piping.

[0023] [2] According to the vinyl polymer manufacturing apparatus of [1], wherein the above-mentioned recycled / bio-based vinyl monomer supply unit is connected to the above-mentioned third piping.

[0024] [3] The vinyl polymer manufacturing apparatus according to [1] or [2], wherein the devolatilization section is a devolatilization extruder.

[0025] [4] The vinyl polymer manufacturing apparatus according to [2] further includes a first cooling section disposed in a region of the third piping connected to the recycled / bio-based vinyl monomer input section that is closer to the devolatilization section than the recycled / bio-based monomer input section.

[0026] The aforementioned first cooling section is a cooling section used to liquefy gaseous unreacted vinyl monomers.

[0027] [5] The vinyl polymer manufacturing apparatus according to any one of [1] to [4] further includes a raw material vinyl monomer blending tank, which is provided in the region of the fifth piping near the raw material vinyl monomer supply section, or connected to the raw material vinyl monomer supply section, for adjusting the composition of the raw material vinyl monomer supplied to the polymerization reactor.

[0028] [6] The vinyl polymer manufacturing apparatus according to any one of [1] to [5], further comprising:

[0029] A first storage tank, located in the region of the fourth piping near the refiner, is used to store unreacted vinyl monomers discharged from the devolatilization section in liquid form; and

[0030] The second storage tank, located in the area near the raw material monomer supply section of the fifth piping, is used to store unreacted vinyl monomers discharged from the purifier in the form of liquid unreacted vinyl monomers.

[0031] [7] A vinyl polymer manufacturing apparatus according to any one of [1] to [6], wherein the raw material vinyl monomer and unreacted vinyl monomer are (meth)acrylates.

[0032] [8] A method for manufacturing a vinyl polymer, comprising, in the method for manufacturing a vinyl polymer using the vinyl polymer manufacturing apparatus described in any one of [1] to [7], the following:

[0033] In the export process, the raw vinyl monomer, which may include non-regenerative / non-biological raw vinyl monomer supplied from the non-regenerative / non-biological raw vinyl monomer supply unit for supplying non-regenerative / non-biological raw vinyl monomer and regenerative / biological raw vinyl monomer supplied from the regenerative / biological raw vinyl monomer supply unit, is exported to the polymerization reactor via the first pipe through the raw vinyl monomer supply pump provided in the raw vinyl monomer supply unit.

[0034] In the preparation process, the raw vinyl monomer supplied from the above-mentioned raw material vinyl monomer supply unit is subjected to bulk polymerization or solution polymerization in the above-mentioned polymerization reactor to obtain a vinyl polymer composition composed of vinyl polymer and unreacted vinyl monomer.

[0035] In the separation process, the obtained vinyl polymer composition is discharged from the polymerization reactor and introduced into the devolatilization section through the second pipe from the vinyl polymer composition inlet. Devolatilization is then carried out in the devolatilization section to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer.

[0036] In the removal process, unreacted vinyl monomers are discharged through the first unreacted vinyl monomer outlet of the devolatilization section and the third pipe and introduced into the purifier for purification, thereby further separating and removing impurity components from the unreacted vinyl monomers.

[0037] In the recycling process, unreacted vinyl monomers, after impurities have been removed, are discharged from the purifier and circulated through the circulation section to the raw material vinyl monomer supply section via the fifth pipe. The discharge process is then repeated.

[0038] In the discharge process, the vinyl polymer after the unreacted vinyl monomers are separated is discharged from the vinyl polymer discharge port of the devolatilization section to obtain the vinyl polymer.

[0039] [9] According to the method for manufacturing vinyl polymers described in [8], wherein the recycled / bio-based vinyl monomer supply unit for supplying recycled / bio-based vinyl monomers is connected to at least one selected from the above-mentioned raw material vinyl monomer supply unit, the above-mentioned polymerization reactor, the above-mentioned purifier, the above-mentioned circulation unit and the above-mentioned third piping.

[0040] When the aforementioned recycled / bio-based vinyl monomer supply unit is connected to the aforementioned raw material vinyl monomer supply unit, the aforementioned export process is performed using recycled / bio-based vinyl monomers supplied from the aforementioned recycled / bio-based vinyl monomer supply unit to the aforementioned raw material vinyl monomer supply unit.

[0041] When the aforementioned recycled / bio-based vinyl monomer supply unit is connected to the aforementioned polymerization reactor, the aforementioned preparation process is performed using recycled / bio-based vinyl monomer supplied from the aforementioned recycled / bio-based vinyl monomer supply unit to the aforementioned polymerization reactor.

[0042] When the aforementioned recycled / bio-based vinyl monomer supply unit is connected to the aforementioned purifier, the aforementioned removal process is a process performed using recycled / bio-based vinyl monomers supplied from the aforementioned recycled / bio-based vinyl monomer supply unit to the aforementioned purifier, in addition to unreacted vinyl monomers.

[0043] When the aforementioned recycled / bio-based vinyl monomer supply unit is connected to the aforementioned circulation unit, the aforementioned circulation process is a process that uses recycled / bio-based vinyl monomers supplied from the aforementioned recycled / bio-based vinyl monomer supply unit to the aforementioned circulation unit, in addition to unreacted vinyl monomers.

[0044] When the above-mentioned recycled / bio-based vinyl monomer supply unit is connected to the above-mentioned third pipe, the above-mentioned removal process is a process performed using recycled / bio-based vinyl monomer supplied from the above-mentioned recycled / bio-based vinyl monomer supply unit to the above-mentioned third pipe, in addition to the unreacted vinyl monomer exported from the above-mentioned devolatilization unit.

[0045]

[10] According to the method for manufacturing the vinyl polymer described in [9], wherein the above-mentioned recycled / bio-based vinyl monomer supply unit is connected to the above-mentioned third piping.

[0046] The above-mentioned removal process is a process that, in addition to the unreacted vinyl monomers exported from the above-mentioned devolatilization section, also uses the regenerated / bio-based vinyl monomers supplied from the above-mentioned regenerated / bio-based vinyl monomer supply section to the above-mentioned third pipe.

[0047]

[11] The method for manufacturing the vinyl polymer according to

[10] further includes a first cooling section disposed in a region of the third pipe connected to the recycled / bio-based vinyl monomer supply section that is closer to the devolatilization section than the recycled / bio-based monomer supply section.

[0048] After the separation process and before the removal process, a cooling process is further included, in which the unreacted vinyl monomer in gaseous form exported from the devolatilization section is introduced into the first cooling section for cooling and liquefaction.

[0049]

[12] The method for manufacturing a vinyl polymer according to any one of [8] to

[11] further comprises the above-mentioned raw material vinyl monomer blending tank, which is disposed in the region of the fifth pipe near the raw material vinyl monomer supply section, or connected to the raw material vinyl monomer supply section.

[0050] The above-mentioned circulation process is as follows: unreacted vinyl monomers after removing impurities are exported from the above-mentioned purifier, and the unreacted vinyl monomers are introduced into the above-mentioned raw material vinyl monomer blending tank through the above-mentioned circulation section to adjust the composition of the raw material vinyl monomers. Then, the raw material vinyl monomers with adjusted composition are circulated to the above-mentioned raw material vinyl monomer supply section, and then the above-mentioned export process is performed again.

[0051]

[13] The method for manufacturing a vinyl polymer according to any one of [8] to

[12] further comprises a first storage tank disposed in the region near the purifier in the fourth piping and a second storage tank disposed in the region near the raw material vinyl monomer supply section in the fifth piping.

[0052] After the above separation process and before the above removal process, the process further includes the step of storing the unreacted vinyl monomers discharged from the devolatilization section in the first storage tank in the form of liquid unreacted vinyl monomers.

[0053] The above-mentioned recycling process is as follows: the unreacted vinyl monomer after removing impurities is exported from the above-mentioned purifier, stored in the above-mentioned second storage tank in the form of liquid unreacted vinyl monomer, and then recycled to the above-mentioned raw material vinyl monomer supply unit, and then the above-mentioned export process is performed again.

[0054]

[14] A method for manufacturing a vinyl polymer according to any one of [8] to

[13] , wherein the raw material vinyl monomer and the unreacted vinyl monomer are (meth)acrylates.

[0055] The vinyl polymer manufacturing apparatus and the method for manufacturing vinyl polymers using the vinyl polymer manufacturing apparatus according to the present invention can reduce energy consumption with a simplified process and efficiently manufacture vinyl polymers from recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers, especially vinyl polymers using a mass balance method, and can further reduce the manufacturing cost of vinyl polymers. Attached Figure Description

[0056] Figure 1 This is a schematic diagram showing an example of the configuration of a vinyl polymer manufacturing apparatus according to the first embodiment.

[0057] Figure 2 This is a schematic diagram showing an example of the configuration of a vinyl polymer manufacturing apparatus according to the second embodiment. Detailed Implementation

[0058] Hereinafter, embodiments of the present invention will be specifically described with reference to the accompanying drawings. It should be noted that the drawings are only schematic representations of the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited to the following description, and the constituent elements may be modified without departing from the spirit of the invention. In some drawings, repeated descriptions of symbols used for the same constituent element are sometimes omitted.

[0059] <First Implementation>

[0060] 1. Vinyl polymer manufacturing apparatus

[0061] Reference Figure 1 The vinyl polymer manufacturing apparatus of the first embodiment will be described. Figure 1 This is a schematic diagram showing an example of the configuration of a vinyl polymer manufacturing apparatus according to the first embodiment.

[0062] like Figure 1 As shown, the vinyl polymer manufacturing apparatus 1 of the first embodiment includes:

[0063] The polymerization reactor 10 is used to carry out bulk polymerization or solution polymerization of raw material vinyl monomers containing recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers to obtain a vinyl polymer composition mixed with vinyl polymers and unreacted vinyl monomers.

[0064] The raw material vinyl monomer supply unit 20 is used to supply the vinyl monomer to the polymerization reactor 10. The raw material vinyl monomer supply unit 20 is connected to the polymerization reactor 10 through a first pipe 71 connected to the polymerization reactor 10 at one end and at the other end. It also includes a non-renewable / biological raw material vinyl monomer supply unit 22 for supplying the non-renewable / non-biological raw material vinyl monomer and a raw material vinyl monomer supply pump 24 for exporting the vinyl monomer to the polymerization reactor 10.

[0065] The devolatilization section 30 is used to devolatilize the vinyl polymer composition exported from the polymerization reactor 10 to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomers. The devolatilization section 30 is connected to the polymerization reactor 10 via a second pipe 72 connected at one end to the polymerization reactor 10 and at the other end to the devolatilization section 30. It has: a vinyl polymer composition inlet 32 ​​for introducing the vinyl polymer composition, a vinyl polymer outlet 34 for discharging the prepared vinyl polymer, a first unreacted vinyl monomer outlet 36 for discharging the unreacted vinyl monomers, and a second unreacted vinyl monomer outlet 38 disposed downstream of the first unreacted vinyl monomer outlet 36.

[0066] The refiner 40 is used to separate and remove impurity components from the unreacted vinyl monomers discharged from the devolatilization section 30. The refiner 40 is connected to the devolatilization section 30 through a third pipe 73 connected to the first unreacted vinyl monomer outlet 36 at one end and to the devolatilization section 30 through a fourth pipe 74 connected to the refiner 40 through a second unreacted vinyl monomer outlet 38 at one end and to the devolatilization section 30 through a fourth pipe 74 connected to the refiner 40 through a third pipe 74.

[0067] The circulation section 50 circulates unreacted vinyl monomers, after the impurity components have been removed by the purifier 40, to the raw material vinyl monomer supply section 20. The circulation section is provided in a fifth pipe 75 connected at one end to the purifier 40 and at the other end to the raw material vinyl monomer supply section 20.

[0068] The recycled / bio-based vinyl monomer supply unit 60, used for supplying recycled / bio-based vinyl monomers, is connected to at least one of the aforementioned vinyl monomer supply unit 20, the aforementioned polymerization reactor 10, the aforementioned purifier 40, the aforementioned circulation unit 50, the aforementioned third piping 73, and the aforementioned fourth piping 74.

[0069] Explanation of terms

[0070] Here, we will first explain the terminology used in this specification.

[0071] "Vinyl monomers" are monomers containing vinyl groups. Examples of vinyl monomers include methacrylates such as cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and monoglyceride methacrylate; acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and monoglyceride methacrylate; unsaturated carboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; epoxy-containing monomers such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; and styrene-based monomers such as styrene and α-methylstyrene.

[0072] "Vinyl polymer" is a polymer that contains monomer units (residues) derived from the aforementioned monomers having a vinyl group.

[0073] "Vinyl polymer composition" is a composition containing the aforementioned vinyl polymer as a main component and may further contain other components.

[0074] "(Meth)acrylic polymers" are polymers having monomer units derived from monomers having (meth)acryloyl groups.

[0075] "(Meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof.

[0076] "(Meth)acrylic polymer composition" is a composition containing a (meth)acrylic polymer as the main component and may further contain other components.

[0077] "(Meth)acrylates" include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, (2-ethylhexyl) methacrylate, (tert-butylcyclohexyl) methacrylate, benzyl methacrylate, and (2,2,2-trifluoroethyl) methacrylate.

[0078] "(Meth)acrylic polymers" are polymers having monomer units derived from monomers having (meth)acryloyl groups.

[0079] Here, examples of (meth)acrylic polymers include, for instance, (meth)acrylic homopolymers containing only monomer units derived from alkyl (meth)acrylic esters having 1 to 4 carbon atoms; and (meth)acrylic copolymers containing 85% by mass or more but less than 100% by mass of monomer units derived from alkyl (meth)acrylic esters having 1 to 4 carbon atoms, and more than 0% by mass but less than 15% by mass of monomer units derived from other vinyl monomers that can be copolymerized with monomer units derived from alkyl (meth)acrylic esters having 1 to 4 carbon atoms.

[0080] "(meth)acrylate alkyl esters having 1 to 4 carbon atoms" are, for example, compounds represented by CH2=C(CH3)COOR (where R is an alkyl group having 1 to 4 carbon atoms).

[0081] The vinyl monomer that can be copolymerized with alkyl (meth)acrylates having 1 to 4 carbon atoms is a vinyl monomer that can be copolymerized with alkyl methacrylates having 1 to 4 carbon atoms.

[0082] Examples of alkyl methacrylates having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, sec-butyl methacrylate, and isobutyl methacrylate. Alkyl methacrylates having 1 to 4 carbon atoms are preferably methyl methacrylate.

[0083] Examples of vinyl monomers that can copolymerize with alkyl (meth)acrylates having 1 to 4 carbon atoms include methacrylates such as cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, and monoglyceride methacrylate (excluding alkyl methacrylates having 1 to 4 carbon atoms); acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and monoglyceride methacrylate; unsaturated carboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; epoxy-containing monomers such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate; and styrene monomers such as styrene and α-methylstyrene.

[0084] Examples of methods for manufacturing vinyl polymers ((meth)acrylate polymers) include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, which polymerize alkyl (meth)acrylates having 1 to 4 carbon atoms with other vinyl monomers that can be copolymerized with alkyl (meth)acrylates having 1 to 4 carbon atoms as needed.

[0085] The “other components” that may be included in the vinyl polymer composition ((meth)acrylic polymer composition) include, for example, any suitable release agent, polymerization regulator, polymerization initiator, ultraviolet absorber and colorant that may be added in order to produce a molded body with the specified properties.

[0086] "Waste" generally refers to molded bodies manufactured by molding vinyl polymer compositions into various shapes through any suitable injection molding process known in the past, and which are recycled as waste after being used for a specified purpose. It is a molded body that has been adjusted to a shape and size that can be used as a raw material in this invention. In addition, "waste" can be a molded body that has been recycled from defective products during molding and adjusted to a shape and size that can be used as a raw material in this invention, or it can be a molded body that has been recycled from scrap materials generated during molding, grinding, or other subsequent processes and adjusted to a shape and size that can be used as a raw material.

[0087] "Impuric components" refers to components whose main components may include low-boiling-point impurities and high-boiling-point impurities.

[0088] "Low-boiling-point impurities" refer to impurities whose main component is an impurity with a boiling point lower than that of the vinyl monomer used. For example, in the case of methyl methacrylate (Mmeth)acrylate, it refers to impurities containing compounds with a boiling point range of, for example, 50°C to 100°C at atmospheric pressure. Specifically, low-boiling-point impurities include, for example, methanol, methyl acrylate, methyl isobutyrate, and methyl propionate.

[0089] "High-boiling-point impurities" refer to impurities whose main component is an impurity with a boiling point higher than that of the vinyl monomer used. This includes impurities containing compounds with a boiling point range of, for example, 102°C to 450°C at atmospheric pressure. High-boiling-point impurities can include, for example, dyes, dimers of vinyl monomers obtained through thermal decomposition, and trimers of vinyl monomers obtained through thermal decomposition. Here, high-boiling-point impurities mainly originate from coloring components contained in waste materials, such as methyl methacrylate in the case of (meth)acrylate. Specifically, high-boiling-point impurities include, for example, styrene, toluene, 1-butanol, dimethyl 2-methylene-5-methylhexanoate, and dimethyl 2-methoxymethyl-2,4-dimethylglutarate.

[0090] Hereinafter, the constituent elements of the vinyl polymer manufacturing apparatus 1 that may constitute this embodiment will be specifically described.

[0091] (1) Polymerization reactor

[0092] The polymerization reactor 10 is a functional part used for bulk polymerization or solution polymerization of raw material vinyl monomers containing recycled / bio-based vinyl monomers, non-recycled / non-bio-based vinyl monomers, and recovered unreacted vinyl monomers to prepare a vinyl polymer composition by mixing vinyl polymers with unreacted vinyl monomers, i.e., unreacted vinyl monomers from any of the recycled / bio-based vinyl monomers, non-recycled / non-bio-based vinyl monomers, and recovered unreacted vinyl monomers.

[0093] As the polymerization reactor 10, for example, a tank-type reactor or a tubular reactor equipped with a stirring section (not shown) can be used. The stirring section is preferably a functional part that can uniformly mix the raw material vinyl monomer and reactants supplied to the polymerization reactor 10.

[0094] Additionally, the polymerization reactor 10 may include a temperature control unit (not shown), which can adjust the temperature (polymerization temperature) within the polymerization reactor 10 to a predetermined temperature as needed by cooling or heating. The temperature control range of this unit can be any suitable range determined, for example, by considering the type of raw material monomers used, the proportions, other components, etc.

[0095] Temperature regulation using this temperature regulating unit can be achieved by any suitable method known in the prior art. As a temperature regulating unit that may be included in the polymerization reactor 10, any suitable configuration known in the prior art can be applied. Specifically, such a temperature regulating unit can be selected from at least one of a sleeve capable of allowing the medium (hot medium, cold medium) to circulate internally, a double-tube heat exchanger, an electric heater, and an insulation material.

[0096] (2) Raw material vinyl monomer supply department

[0097] The raw material vinyl monomer supply unit 20 is a functional unit capable of supplying non-recycled / non-biological raw material vinyl monomers to the polymerization reactor 10. As will be explained in detail later, the raw material vinyl monomer supply unit 20 is configured to supply recycled / biological raw material vinyl monomers, and consequently unreacted vinyl monomers, together with non-recycled / non-biological raw material vinyl monomers, to the polymerization reactor 10.

[0098] The raw material vinyl monomer supply unit 20 includes a non-renewable / non-biological raw material vinyl monomer supply unit 22 and a raw material monomer supply pump 24 disposed in the non-renewable / non-biological raw material vinyl monomer supply unit 22. The non-renewable / non-biological raw material vinyl monomer supply unit 22 and the raw material monomer supply pump 24 can be integrally formed.

[0099] The non-renewable / non-biological raw material vinyl monomer supply unit 22 is a functional unit capable of supplying non-renewable / non-biological raw material vinyl monomer (virgin vinyl monomer) imported from the outside to the raw material monomer supply pump 24. As the non-renewable / non-biological raw material vinyl monomer supply unit 22, any suitable equipment including conventionally known tanks, towers, vessels, containers, etc. can be used.

[0100] The raw material monomer supply pump 24 is a functional unit capable of supplying non-regenerated / non-biological raw material vinyl monomers, subsequently regenerated / biological raw material vinyl monomers, and subsequently unreacted vinyl monomers from the non-regenerated / non-biological raw material vinyl monomer supply section 22 to the polymerization reactor 10. The raw material monomer supply pump 24 can be any suitable conventionally known configuration such as a plunger pump or a diaphragm pump.

[0101] The raw material vinyl monomer supply unit 20 (raw material monomer supply pump 24) is connected to the polymerization reactor 10 through a first pipe 71 that is connected to the polymerization reactor 10 at one end and to the raw material vinyl monomer supply unit 20 at the other end.

[0102] As the first conduit 71, any suitable stainless steel conduit known in the past can be used, for example.

[0103] Here, the vinyl monomers and unreacted vinyl monomers used as raw materials in this invention are preferably (meth)acrylates, and more preferably methyl (meth)acrylates.

[0104] like Figure 1 As shown, the vinyl polymer manufacturing apparatus 1 may further include a polymerization initiator supply unit 26 and a chain transfer agent supply unit 28 connected to the already described raw material monomer supply pump 24.

[0105] The polymerization initiator supply unit 26 is a functional unit that can supply any conventionally known suitable polymerization initiator corresponding to the selected vinyl monomer to the polymerization reactor 10 via the described raw material monomer supply pump 24.

[0106] As the polymerization initiator supply unit 26, any suitable equipment, including conventionally known tanks, towers, vessels, containers, plunger pumps, diaphragm pumps, and other metering pumps, can be used.

[0107] When the vinyl polymer manufacturing apparatus 1 is equipped with a polymerization initiator supply unit 26, the raw material monomer supply pump 24 is configured to supply polymerization initiators to the polymerization reactor 10 in addition to non-recycled / non-biological raw material vinyl monomers, recycled / biological raw material vinyl monomers, and unreacted vinyl monomers.

[0108] In the example shown, a configuration in which the polymerization initiator supply unit 26 is connected to the raw material monomer supply pump 24 is described. However, the polymerization initiator supply unit 26 can also be directly connected to the polymerization reactor 10 in a manner that allows it to supply polymerization initiator to the polymerization reactor 10.

[0109] When the vinyl polymer manufacturing apparatus 1 is equipped with a polymerization initiator supply unit 26 connected to the raw material monomer supply pump 24, when supplying the polymerization initiator, from the viewpoint of preventing the polymerization of vinyl monomers (raw material vinyl monomers and unreacted vinyl monomers) in the raw material monomer supply pump 24, it is preferable to adjust the supply to a condition that prevents the vinyl monomers from polymerizing, that is, a temperature condition, for example, lower than the polymerization temperature.

[0110] The chain transfer agent supply unit 28 is a functional unit that can supply any suitable chain transfer agent, conventionally known to correspond to the selected vinyl monomer, to the polymerization reactor 10 via the described raw material monomer supply pump 24.

[0111] As the chain transfer agent supply unit 28, any suitable equipment, including conventionally known tanks, towers, troughs, containers, plunger pumps, diaphragm pumps, and other metering pumps, can be used.

[0112] When the vinyl polymer manufacturing apparatus 1 is equipped with a chain transfer agent supply unit 28, the raw material monomer supply pump 24 is configured to supply chain transfer agent to the polymerization reactor 10 in addition to non-regenerated / non-biological raw material vinyl monomers, recycled / biological raw material vinyl monomers, and unreacted vinyl monomers.

[0113] In the example shown, a configuration in which the chain transfer agent supply unit 28 is connected to the raw material monomer supply pump 24 is described. However, the chain transfer agent supply unit 28 may also be directly connected to the polymerization reactor 10 in a manner that enables the supply of chain transfer agent to the polymerization reactor 10.

[0114] (3) Deviation section

[0115] The vinyl polymer manufacturing apparatus 1 includes a devolatilization section 30. The devolatilization section 30 is a functional unit that performs devolatilization on the vinyl polymer composition discharged from the polymerization reactor 10, as described above, separating the liquid vinyl polymer from the gaseous unreacted vinyl monomers (which may also contain impurity components). The devolatilization section 30 can be implemented using any apparatus with a suitable conventional configuration, provided it possesses the aforementioned functions.

[0116] Examples of devolatilization section 30 include extruders containing devolatilization extruders, thin-film evaporators, evaporators, multi-tube heat exchangers, and special heat exchangers.

[0117] The devolatilization section 30 is preferably a devolatilization extruder. Suitable examples of devolatilization extruders for the devolatilization section 30 include twin-screw extruders such as co-rotating twin-screw extruders and counter-rotating twin-screw extruders. Specific examples of devolatilization extruders include vented extruders such as the TEX (trade name) manufactured by Nippon Steel.

[0118] The following description uses the structure of a twin-screw extruder as an example to illustrate the structure of the devolatilization section 30.

[0119] In the case of a twin-screw extruder, the devolatilization section 30 includes: a barrel for internally heating while moving the vinyl polymer composition prepared by the polymerization reactor 10 along the extension direction (generally horizontal direction) within the twin-screw extruder, and a screw disposed inside the barrel.

[0120] like Figure 1 As shown, a vinyl polymer composition inlet 32 ​​for supplying the vinyl polymer composition into the interior of the devolatilization section 30 is provided. The vinyl polymer composition inlet 32 ​​is equivalent to the feeder configuration in a twin-screw extruder. The vinyl polymer composition inlet 32, i.e., the feeder, is typically located near the upstream end of the barrel in a manner capable of supplying the vinyl polymer composition into the barrel.

[0121] The devolatilization section 30 is provided with one or more unreacted vinyl monomer outlets for extracting the gas containing unreacted vinyl monomers and unavoidably present impurities generated by the devolatilization process, which separates the vinyl polymer into a liquid state and the unreacted vinyl monomers into a gaseous state, outside the devolatilization section 30. The configuration (location) of the one or more unreacted vinyl monomer outlets is not particularly limited and can be any suitable configuration corresponding to the design. For example, from the viewpoint of improving the extraction efficiency of the gas generated in the devolatilization section 30, the unreacted vinyl monomer outlets are preferably located near the downstream end of the devolatilization section 30, opposite to the vinyl polymer composition inlet 32 ​​described above, and on the upper end side of the devolatilization section 30. When two or more unreacted vinyl monomer outlets are provided, they are preferably arranged at predetermined intervals (e.g., equal intervals) on the upper end side of the devolatilization section 30.

[0122] The devolatilization section 30 is provided with a vinyl polymer outlet 34 for discharging the prepared vinyl polymer outside the devolatilization section 30. The vinyl polymer outlet 34 is typically located near the downstream end of the devolatilization section 30.

[0123] The following, such as Figure 1 As shown, the example described is a devolatilization section 30 having a first unreacted vinyl monomer outlet 36 and a second unreacted vinyl monomer outlet 38 disposed downstream of the first unreacted vinyl monomer outlet 36.

[0124] The first unreacted vinyl monomer outlet 36 is disposed on the upstream side of the devolatilization section 30, that is, on the opposite side of the end portion to the downstream side where the vinyl polymer outlet 34 is disposed. It should be noted that the first unreacted vinyl monomer outlet 36 is sometimes referred to as the upstream unreacted vinyl monomer outlet 36.

[0125] The second unreacted vinyl monomer outlet 38 is located downstream of the devolatilization section 30, i.e., close to the vinyl polymer outlet 34. It should be noted that the second unreacted vinyl monomer outlet 38 is sometimes referred to as the upstream unreacted vinyl monomer outlet 38.

[0126] Here, the gas containing unreacted vinyl monomers discharged from the first unreacted vinyl monomer discharge port 36 located further upstream may contain a greater amount of low-boiling-point impurities as impurity components. On the other hand, the gas containing unreacted vinyl monomers discharged from the second unreacted vinyl monomer discharge port 38 located further downstream may contain a greater amount of high-boiling-point impurities as impurity components.

[0127] The devolatilization section 30 is connected to the polymerization reactor 10 via a second pipe 72, which is connected at one end to the polymerization reactor 10 and at the other end to the devolatilization section 30. The second pipe 72 is used to discharge the vinyl polymer composition prepared by the polymerization reactor 10 from the polymerization reactor 10 and then introduce it into the devolatilization section 30.

[0128] The second piping 72 is not particularly limited in shape, size, or material, provided that it can perform the aforementioned functions. The second piping 72 can typically be equipped with any suitable pump, on / off valve, flow meter, preheater, etc. (not shown) known in the prior art to ensure reliable flow of the vinyl polymer composition. For example, any suitable stainless steel piping known in the prior art can be used as the second piping 72.

[0129] (4) Refining equipment

[0130] The vinyl polymer manufacturing apparatus 1 includes a refiner 40. The refiner 40 is a functional unit for separating and removing impurity components (especially high-boiling-point impurities) other than unreacted vinyl monomers from the unreacted vinyl monomers discharged from the devolatilization section 30, as described above. The unreacted vinyl monomers discharged from the devolatilization section 30 may inevitably contain impurity components in addition to unreacted vinyl monomers.

[0131] As the purification device 40, a distillation column (distillation column) with any suitable configuration known in the past can be used. As an example of a suitable distillation column for the purification device 40, a multi-stage distillation column can be given.

[0132] There are no particular limitations on the shape, size, or material of the distillation column serving as the purifier 40. The shape, size, and material of the distillation column can be selected, for example, by considering the composition, amount, and purification capacity of the unreacted vinyl monomers discharged from the devolatilization section 30 that are being processed. Stainless steel is an example of a preferred material for the distillation column.

[0133] The refining device 40 is connected to the devolatilization section 30 via a third pipe 73 connected at one end to the first unreacted vinyl monomer outlet 36 and at the other end to the refining device 40, and a fourth pipe 74 connected at one end to the second unreacted vinyl monomer outlet 38 and at the other end to the refining device 40.

[0134] The third pipe 73 and the fourth pipe 74 are designed to allow unreacted vinyl monomers to be exported from the devolatilization section 30 and introduced into the refiner 40, and their shape, size, and constituent materials are not particularly limited.

[0135] The third piping 73 and the fourth piping 74 can be equipped with any suitable pump, on / off valve, flow meter, etc. (not shown) to perform the above functions. For example, any suitable stainless steel piping known in the prior art can be used as the third piping 73 and the fourth piping 74.

[0136] Examples of impurity components that can be removed by the purifier 40 include dimers of vinyl monomers, trimers of vinyl monomers, usable chain transfer agents, inactive solvents, and high-boiling-point impurities such as reactants and decomposition products from vinyl monomers.

[0137] (5) Circulation section

[0138] The vinyl polymer manufacturing apparatus 1 includes a circulation unit 50. The circulation unit 50 is a functional unit that circulates unreacted vinyl monomers, after impurity components have been removed by the already described purifier 40, to the already described raw material vinyl monomer supply unit 20 (raw material monomer supply pump 24).

[0139] The circulation unit 50 is not particularly limited in terms of its ability to perform the aforementioned functions, and can be constructed using any suitable configuration known in the prior art. For example, the circulation unit 50 can be a device that includes any suitable tank known in the prior art, and further includes a fixed displacement pump such as a plunger pump or a diaphragm pump, an on / off valve, a flow meter, a thermometer, a temperature regulator such as a cooler, etc.

[0140] A circulation section 50 is provided with a fifth conduit 75, which is connected at one end to the refiner 40 and at the other end to the circulation section 50. The fifth conduit 75 can be made of any suitable stainless steel conduit known in the art. The fifth conduit 75 may have the same (not shown) cooling section as the first cooling section 73a and the second cooling section 74a already described.

[0141] (6) Recycled / Bio-based Vinyl Monomer Supply Department

[0142] The recycled / bio-based vinyl monomer supply unit 60, namely the first recycled / bio-based vinyl monomer supply unit 60a, the second recycled / bio-based vinyl monomer supply unit 60b, the third recycled / bio-based vinyl monomer supply unit 60c, the fourth recycled / bio-based vinyl monomer supply unit 60d, the fifth recycled / bio-based vinyl monomer supply unit 60e, and the sixth recycled / bio-based vinyl monomer supply unit 60f, are functional units capable of supplying recycled / bio-based vinyl monomers introduced from the outside to each of the following components connected to the downstream section: the raw material monomer pump 24 connected to the first recycled / bio-based vinyl monomer supply unit 60a, the polymerization reactor 10 connected to the second recycled / bio-based vinyl monomer supply unit 60b, the third piping 73 connected to the third recycled / bio-based vinyl monomer supply unit 60c, the fourth piping 74 connected to the fourth recycled / bio-based vinyl monomer supply unit 60d, the purifier 40 connected to the fifth recycled / bio-based vinyl monomer supply unit 60e, and the circulation unit 50 connected to the sixth recycled / bio-based vinyl monomer supply unit 60f.

[0143] In the vinyl polymer manufacturing apparatus 1, it is sufficient to provide at least one of the following: a first recycled / bio-based vinyl monomer supply unit 60a, a second recycled / bio-based vinyl monomer supply unit 60b, a third recycled / bio-based vinyl monomer supply unit 60c, a fourth recycled / bio-based vinyl monomer supply unit 60d, a fifth recycled / bio-based vinyl monomer supply unit 60e, and a sixth recycled / bio-based vinyl monomer supply unit 60f.

[0144] From the viewpoint that impurities can be removed using a refining machine, the recycled / bio-based vinyl monomer supply unit 60 is preferably connected to either or both of the third pipe 73 and the fourth pipe 74, and more preferably to the fourth pipe 74. In other words, the vinyl polymer manufacturing apparatus 1 preferably includes the third recycled / bio-based vinyl monomer supply unit 60c and / or the fourth recycled / bio-based vinyl monomer supply unit 60d, and more preferably the fourth recycled / bio-based vinyl monomer supply unit 60d.

[0145] Furthermore, if a fifth recycled / bio-based vinyl monomer supply unit 60e is provided as the recycled / bio-based vinyl monomer supply unit 60, then the cooling unit 74a can be omitted from the fourth piping 74 connected to the devolatilization unit 30, and the continuous operation of the devolatilization unit 30 and the refiner 40 can be carried out with a simpler configuration.

[0146] As the vinyl monomer supply unit 60 for recycled / bio-based raw materials, equipment such as conventionally known suitable tanks, and consequently, metering pumps such as plunger pumps and diaphragm pumps, on / off valves, flow meters, thermometers, pressure gauges, and temperature regulators such as coolers, heaters, and heat exchangers can be used.

[0147] The recycled / bio-based vinyl monomer supply unit 60 can be connected to the specified downstream functional unit, for example, via any suitable stainless steel piping known in the past.

[0148] It should be noted that when the recycled / bio-based vinyl monomer used in the vinyl polymer manufacturing apparatus 1 is, for example, a recycled vinyl monomer that has been regenerated through chemical recycling, a pyrolysis device that manufactures (regenerates) and supplies the recycled vinyl monomer can be connected to the recycled / bio-based vinyl monomer supply unit 60 (details of the pyrolysis device will be described later) via stainless steel piping.

[0149] On the other hand, when the recycled / bio-based vinyl monomer used in the vinyl polymer manufacturing apparatus 1 is, for example, a bio-based vinyl monomer, the bio-based vinyl monomer produced in any conventionally known suitable bio-based vinyl monomer manufacturing equipment can be supplied to the recycled / bio-based vinyl monomer supply unit 60. This can be done in the following manner: for example, by connecting the bio-based vinyl monomer manufacturing equipment to the recycled / bio-based vinyl monomer supply unit 60 through stainless steel pipes, etc., and directly supplying the bio-based vinyl monomer exported from the bio-based vinyl monomer manufacturing equipment to the recycled / bio-based vinyl monomer supply unit 60.

[0150] (7) Storage tanks (first storage tank, second storage tank)

[0151] In this embodiment, the vinyl polymer manufacturing apparatus 1 includes a storage tank 90 (a first storage tank 92 and / or a second storage tank 94).

[0152] Storage tank 90 is a functional unit that can temporarily store a predetermined amount of undecomposed monomers and other components, and further export them to downstream functional units as needed. Specifically, first storage tank 92 is a functional unit that can store raw material vinyl monomers exported from devolatilization unit 30 and liquefied by second cooling unit 74a as needed, and further store regenerated / bio-raw material vinyl monomers supplied from fourth regenerated / bio-raw material vinyl monomer supply unit 60d when a fourth regenerated / bio-raw material vinyl monomer supply unit 60d is provided. Second storage tank 94 is a functional unit that can store undecomposed monomers exported from purifier 40 and imported through fifth piping 75 and circulation unit 50.

[0153] like Figure 2 As shown, in this embodiment, the first storage tank 92 is located in a region closer to the refiner 40 (downstream side) than the second cooling section 74a of the fourth piping 74. Furthermore, the second storage tank 94 is located in a region of the fifth piping 75 near the raw material vinyl monomer supply section 20 (raw material monomer supply pump 24) and closer to the refiner 40 than the first raw material vinyl blending tank 80a.

[0154] The composition, materials, and dimensions of the storage tank 90 are not particularly limited, provided that the aforementioned functions can be performed. For example, the storage tank 90 can be composed of any suitable stainless steel tank known in the past, and further comprising a fixed displacement pump such as a plunger pump or diaphragm pump, on / off valves, instruments such as flow meters, thermometers, and pressure gauges, a cooler, a heater, a heat exchanger, and other temperature regulators.

[0155] Here, as the fourth conduit 74, any suitable stainless steel conduit known in the past can be used, for example.

[0156] (8) Other equipment

[0157] (i) Post-processing equipment

[0158] A post-processing device (not shown) is provided at the vinyl polymer discharge port 34 of the devolatilization section 30. This device may include any suitable conventional equipment such as a stranding cutter, dryer, or silo for drying, preserving, and productizing the manufactured and discharged vinyl polymer in any suitable manner, such as forming strands (filaments), sheets, plates, or granules.

[0159] (ii) Waste gas treatment device

[0160] The purifier 40 is provided with a waste gas extraction section (not shown), which is used to treat and render harmless the waste gas extracted after separation of undecomposed monomers in the purifier 40. This waste gas treatment device (not shown) can be connected, for example, via stainless steel piping. As an example of the waste gas treatment device, it is preferable to use a device that includes at least one selected from acid treatment machines, amine treatment machines, and dehydration and desulfurization machines.

[0161] (iii) Thermal decomposition apparatus

[0162] When the recycled / bio-based vinyl monomer used in the vinyl polymer manufacturing apparatus 1 is a recycled vinyl monomer, a pyrolysis device (not shown) that can be manufactured (recycled) and supplied to the recycled vinyl monomer can be connected to the recycled / bio-based vinyl monomer supply unit 60, for example, via stainless steel piping. Hereinafter, a pyrolysis device for chemical reuse that can be well applied to the vinyl polymer manufacturing apparatus 1 of the present invention will be described.

[0163] A thermal decomposition apparatus comprising a thermal decomposition unit can directly supply the recycled / bio-based vinyl monomer as a recycled / bio-based vinyl monomer to the recycled / bio-based vinyl monomer supply unit 60 of the vinyl polymer manufacturing apparatus 1 of the present invention.

[0164] The thermal decomposition section is designed to thermally decompose waste material from a molded body obtained by molding a vinyl polymer composition containing a vinyl polymer to generate a gas containing vinyl monomers such as (meth)acrylate (and may contain impurity components). Any apparatus with a conventionally known suitable configuration can be used.

[0165] Examples of thermal decomposition units include extruders, kneaders, and fluidized bed heaters.

[0166] The pyrolysis section is preferably an extruder. Suitable examples of extruders for the pyrolysis section include twin-screw extruders such as co-rotating twin-screw extruders and counter-rotating twin-screw extruders.

[0167] As a kneading machine that can be well used as a pyrolysis section, the apparatus described in U.S. Patent No. 10301235 can be cited as an example.

[0168] As a fluidized bed heater that can be well used as a pyrolysis section, the device described in Japanese Patent Application Publication No. 2009-112902 can be cited as an example.

[0169] The following description uses the structure of a twin-screw extruder as an example to illustrate the structure of the pyrolysis section.

[0170] In the case of a twin-screw extruder, the pyrolysis section includes: a barrel for heating the introduced waste material as raw material while moving it along the extension direction within the twin-screw extruder, and a screw disposed inside the barrel.

[0171] The pyrolysis section is provided with an input section, which is equivalent to a hopper (feeder), for supplying waste material as raw material into the interior of the pyrolysis section. In addition, the pyrolysis section is provided with one or more gas extraction sections (exhaust ports) for extracting the gas generated during pyrolysis.

[0172] The pyrolysis apparatus is equipped with a condenser, which can introduce the gas containing vinyl monomers generated by the pyrolysis of the pyrolysis section, and separate the vinyl monomers from high-boiling-point impurities whose main components are impurities (compounds) with boiling points higher than those of the vinyl monomers.

[0173] Specifically, the fractional condenser can liquefy high-boiling-point impurities with boiling points higher than vinyl monomers by staged condensation, thereby removing them from the vinyl monomer-containing gas generated in the thermal decomposition section, resulting in the purification and extraction of the vinyl monomers.

[0174] As a condenser, any conventionally known suitable condenser with a configuration corresponding to the flow rate and composition of the introduced gas containing vinyl monomers can be used.

[0175] Here, we will briefly explain the thermal decomposition and fractionation processes involved in the regeneration of vinyl monomers through the thermal decomposition section, i.e., the manufacture of regenerated / bio-based vinyl monomers.

[0176] There are no particular limitations on the implementation conditions of the pyrolysis process using a twin-screw extruder (e.g., barrel temperature (°C), screw speed (rpm), waste feed rate (raw material feed rate) (kg / hour)). The implementation conditions of the pyrolysis process can be set to any suitable conditions, taking into account the properties and composition of the waste being processed.

[0177] The barrel temperature in the thermal decomposition process is usually 400℃~500℃, for example, when the waste is composed of pure poly(meth)acrylate, it is preferably 450℃~470℃.

[0178] The screw speed in the thermal decomposition process is usually 500 rpm to 1500 rpm. For example, when the waste is composed of pure poly(meth)acrylate, it is preferably 500 rpm to 1000 rpm.

[0179] The waste supply in the pyrolysis process can be adjusted appropriately according to the diameter of the material cylinder of the pyrolysis section, usually from 10 kg / hour to 5000 kg / hour. For example, when the diameter of the material cylinder is 47 mm, it is preferred to be from 40 kg / hour to 90 kg / hour.

[0180] Specifically, the fractional condensation process is a process of fractionally condensing vinyl monomers and high-boiling-point impurities by adjusting the gas containing vinyl monomers to a temperature above the boiling point of the vinyl monomers, which are the main components, and below the boiling point and melting point of the high-boiling-point impurities.

[0181] The temperature in the fractional condensation process can be any suitable temperature corresponding to the composition of the gases produced by the thermal decomposition of vinyl monomers, high-boiling-point impurities, etc., which are being fractionally condensed.

[0182] According to the thermal decomposition apparatus 1 of the present invention, energy consumption can be reduced, and vinyl polymers from recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers can be produced efficiently with high yield and low cost, especially vinyl polymers using a mass balance method.

[0183] 2. Manufacturing method of vinyl polymers

[0184] The method for manufacturing vinyl polymers according to the first embodiment is a method for manufacturing vinyl polymers using the vinyl polymer manufacturing apparatus 1 already described, comprising:

[0185] In the export process, the raw vinyl monomer, which may include non-regenerative / non-biological raw vinyl monomer supplied from the non-regenerative / non-biological raw vinyl monomer supply unit 22 for supplying non-regenerative / non-biological raw vinyl monomer and recycled / biological raw vinyl monomer supplied from the recycled / biological raw vinyl monomer supply unit 60, is exported to the polymerization reactor 10 via the first pipe 71 through the raw vinyl monomer supply pump 24 provided in the raw vinyl monomer supply unit 20.

[0186] In the preparation process, the raw vinyl monomer supplied from the raw material vinyl monomer supply unit 20 is subjected to bulk polymerization or solution polymerization in the polymerization reactor 10 to obtain a vinyl polymer composition composed of vinyl polymer and unreacted vinyl monomer.

[0187] In the separation process, the obtained vinyl polymer composition is discharged from the polymerization reactor 10, and the vinyl polymer composition is introduced into the devolatilization section 30 through the second pipe 72 from the vinyl polymer composition inlet 32. Then, devolatilization is carried out through the devolatilization section 30 to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer.

[0188] In the removal process, unreacted vinyl monomers are discharged and introduced into the refiner 40 for refining via the first unreacted vinyl monomer outlet 36 and the third pipe 73 of the devolatilization section 30, and via the second unreacted vinyl monomer outlet 38 and the fourth pipe 74, thereby further separating and removing impurity components from the unreacted vinyl monomers.

[0189] In the recycling process, unreacted vinyl monomers, after impurities have been removed, are discharged from the purifier 40 and circulated through the circulation section 50 to the raw material vinyl monomer supply section 20 via the fifth pipe 75. Then, the discharge process is repeated.

[0190] In the discharge process, the vinyl polymer after the unreacted vinyl monomers are separated is discharged from the vinyl polymer discharge port 34 of the devolatilization section 30 to obtain the vinyl polymer.

[0191] The following describes in detail the various steps that may be included in the manufacturing method of vinyl polymers.

[0192] (1) Export process

[0193] The export process is as follows: the raw vinyl monomer, which may include non-renewable / non-biological raw vinyl monomer supplied from the non-renewable / non-biological raw vinyl monomer supply unit 22 for supplying non-renewable / non-biological raw vinyl monomer and recycled / biological raw vinyl monomer supplied from the recycled / biological raw vinyl monomer supply unit 60, is exported to the polymerization reactor 10 via the first pipe 71 through the raw vinyl monomer supply pump 24 provided in the raw vinyl monomer supply unit 20.

[0194] The export quantity and export speed of the raw material vinyl monomers in the export process can be set to any suitable conditions, taking into account the type and composition of the selected raw material vinyl monomers.

[0195] It should be noted that when the recycled / bio-based vinyl monomer supply unit 60 is connected to the raw material vinyl monomer supply unit 20, the export process is carried out using the recycled / bio-based vinyl monomer supplied from the recycled / bio-based vinyl monomer supply unit 60 to the raw material vinyl monomer supply unit 20.

[0196] (2) Preparation process

[0197] The preparation process is as follows: the raw vinyl monomer supplied from the raw material vinyl monomer supply section 20 is subjected to bulk polymerization or solution polymerization in the polymerization reactor 10 to obtain a vinyl polymer composition composed of vinyl polymer and unreacted vinyl monomer.

[0198] The conditions (polymerization temperature, polymerization pressure, concentration of vinyl monomers, concentration of additives, polymerization time, etc.) in the polymerization of vinyl monomers in the preparation process (preparation of vinyl polymers (vinyl polymer compositions that may contain partially polymerized vinyl polymers)) can be appropriately determined by taking into account the structure and properties of the target vinyl polymer.

[0199] It should be noted that when the recycled / bio-based vinyl monomer supply unit 60 is connected to the polymerization reactor 10, the preparation process is carried out using the recycled / bio-based vinyl monomer supplied from the recycled / bio-based vinyl monomer supply unit 60 to the polymerization reactor 10.

[0200] (3) Separation process

[0201] The separation process is as follows: the prepared vinyl polymer composition is discharged from the polymerization reactor 10, the vinyl polymer composition is introduced into the devolatilization section 30 through the second pipe 72 from the vinyl polymer composition inlet 32, and then devolatilization is carried out through the devolatilization section 30 to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer.

[0202] Specifically, in the separation process, the gaseous unreacted vinyl monomers (which may contain dimers, chain transfer agents, inactive solvents, methanol, methyl propionate, methyl isobutyrate, methyl acrylate, methyl α-hydroxyisobutyrate, and other impurities) generated by devolatilizing the vinyl polymer composition using the devolatilization section 30 are adjusted to a temperature above the boiling point of the vinyl monomers, which are the main components, but below the thermal decomposition temperature of the vinyl polymer, thereby separating the vinyl monomers from the impurities.

[0203] For example, when the unreacted vinyl monomer is methyl methacrylate, the temperature of the gas containing methyl methacrylate after adjusting it to "above the boiling point of methyl methacrylate and below the thermal decomposition temperature of the vinyl polymer" is preferably 100°C to 300°C, more preferably 150°C to 300°C, and even more preferably 200°C to 290°C.

[0204] The devolatilization process in the devolatilization section 30 can preferably be carried out, for example, by adjusting the exhaust pressure in the first unreacted vinyl monomer outlet 36 to -0.01 to -0.04 MPa (gauge pressure), adjusting the exhaust pressure in the second unreacted vinyl monomer outlet 38 to -0.09 to -0.1 MPa, and setting the temperature to 200 to 290°C, thereby continuously separating and removing unreacted vinyl monomers.

[0205] (4) Removal process

[0206] The removal process is as follows: unreacted vinyl monomers are discharged and introduced into the refiner 40 for refining via the first unreacted vinyl monomer outlet 36 and the third pipe 73 of the devolatilization section 30, and via the second unreacted vinyl monomer outlet 38 and the fourth pipe 74, thereby further separating and removing impurity components from the unreacted vinyl monomers.

[0207] First, the unreacted vinyl monomers after devolatilization in the devolatilization section 30 are discharged to the purifier 40. When discharging unreacted vinyl monomers from the devolatilization section 30, there is a tendency to discharge not only unreacted vinyl monomers but also low-boiling-point impurities such as low-boiling-point impurities as described above from the first unreacted vinyl monomer discharge port (upstream unreacted vinyl monomer discharge port) 36, and there is a tendency to discharge high-boiling-point impurities such as high-boiling-point impurities as described above from the second unreacted vinyl monomer discharge port (downstream unreacted vinyl monomer discharge port) 38.

[0208] Next, the unreacted vinyl monomers discharged from the first unreacted vinyl monomer outlet 36 and the second unreacted vinyl monomer outlet 38 are introduced into the purifier 40 for purification.

[0209] Specifically, from the unreacted vinyl monomers containing impurity components introduced into the already described refiner 40, the impurity components, including low-boiling-point impurities and high-boiling-point impurities, are separated and removed in the refiner 40.

[0210] It should be noted that when the recycled / bio-based vinyl monomer supply unit 60 is connected to the purifier 40, the removal process is carried out using recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit 60 to the purifier 40, in addition to unreacted vinyl monomers.

[0211] In addition, when the recycled / bio-based vinyl monomer supply unit 60 is connected to either or both of the third pipe 73 and the fourth pipe 74, the removal process is carried out using recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit 60 to either or both of the third pipe 73 and the fourth pipe 74, in addition to the unreacted vinyl monomers discharged from the devolatilization unit 30.

[0212] There are no particular limitations on the conditions for implementing the removal process. The temperature, flow rate, pressure, and other conditions in the refining apparatus 40 can be set to any suitable conditions, taking into account the structure, characteristics, and properties of the impurity components of the vinyl polymer being manufactured.

[0213] (5) Cyclic process

[0214] The recycling process is as follows: unreacted vinyl monomers after removing impurities are discharged from the purifier 40, and the unreacted vinyl monomers are circulated to the raw material vinyl monomer supply unit 20 via the fifth pipe 75 through the recycling unit 50. Then the discharge process (and subsequent preparation, separation and removal processes) described above are performed again.

[0215] Specifically, using a metering pump or the like in the circulation unit 50, the unreacted vinyl monomers, after being purified by the purifier 40 and discharged from the purifier 40 to remove impurities, are circulated through pipe 75 to the described raw material vinyl monomer supply unit 20 (raw material monomer supply pump 24). The described discharge process, preparation process, separation process, and removal process are repeated, thereby reusing the recovered unreacted vinyl monomers and manufacturing vinyl polymers.

[0216] It should be noted that when the recycled / bio-based vinyl monomer supply unit 60 is connected to the circulation unit 50, the circulation process is carried out using recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit 60 to the circulation unit 50, in addition to unreacted vinyl monomers.

[0217] (6) Discharge process

[0218] The discharge process is as follows: the vinyl polymer after the unreacted vinyl monomers (and impurity components) are separated is discharged from the vinyl polymer discharge port 34 of the devolatilization section 30 to obtain the vinyl polymer.

[0219] Specifically, the vinyl polymer produced by separating and removing unreacted vinyl monomers and impurities using the devolatilization section 30 is discharged from the vinyl polymer outlet 34 of the devolatilization section 30. Then, it is processed in the described post-processing equipment to produce it in any suitable manner, such as in strand (filament) form, sheet form, flat sheet form, or granules, and is dried, temporarily stored if necessary, packaged, etc., to produce the product.

[0220] The method for manufacturing vinyl polymers according to the present invention can reduce energy consumption with a simple process and produce vinyl polymers from recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers with high yield and low cost, especially vinyl polymers using a mass balance method.

[0221] <Second Implementation>

[0222] 1. Vinyl polymer manufacturing apparatus

[0223] Reference Figure 2 The vinyl polymer manufacturing apparatus of the second embodiment will now be described. It should be noted that the same symbols are used for the same components as in the first embodiment, which has already been described, and detailed descriptions are omitted. Figure 2 This is a schematic diagram showing an example of the configuration of a vinyl polymer manufacturing apparatus according to the second embodiment.

[0224] (1) Polymerization reactor

[0225] The polymerization reactor 10 is a functional part for bulk polymerization or solution polymerization of raw vinyl monomers containing recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers, and further recovered unreacted vinyl monomers, to prepare a vinyl polymer composition mixed with unreacted vinyl monomers (which may be from any of the recycled / bio-based vinyl monomers, non-recycled / non-bio-based vinyl monomers, and recovered unreacted vinyl monomers).

[0226] (2) Raw material vinyl monomer supply department

[0227] The raw material vinyl monomer supply unit 20 is a functional unit capable of supplying non-recycled / non-biological raw material vinyl monomers to the polymerization reactor 10. As will be explained in detail later, the raw material vinyl monomer supply unit 20 is configured to supply recycled / biological raw material vinyl monomers, and consequently unreacted vinyl monomers, together with non-recycled / non-biological raw material vinyl monomers, to the polymerization reactor 10.

[0228] The raw material vinyl monomer supply unit 20 includes a non-renewable / non-biological raw material vinyl monomer supply unit 22 and a raw material monomer supply pump 24 disposed in the non-renewable / non-biological raw material vinyl monomer supply unit 22.

[0229] The raw material monomer supply pump 24 is a functional unit that can supply non-regenerated / non-biological raw material vinyl monomers, which are supplied from the non-regenerated / non-biological raw material vinyl monomer supply section 22, and then the regenerated / biological raw material vinyl monomers described later, and then the unreacted vinyl monomers to the polymerization reactor 10.

[0230] The raw material vinyl monomer supply unit 20 (raw material monomer supply pump 24) is connected to the polymerization reactor 10 through a first pipe 71 that is connected to the polymerization reactor 10 at one end and to the raw material vinyl monomer supply unit 20 at the other end.

[0231] (3) Deviation section

[0232] The vinyl polymer manufacturing apparatus 1 includes a devolatilization section 30. The devolatilization section 30 is a functional unit that performs devolatilization on the vinyl polymer composition discharged from the polymerization reactor 10, as described above, and separates the liquid vinyl polymer from the gaseous unreacted vinyl monomers (which may also contain impurity components).

[0233] Examples of devolatilization section 30 include extruders containing devolatilization extruders, thin-film evaporators, evaporators, multi-tube heat exchangers, and special heat exchangers.

[0234] The devolatilization section 30 is preferably a devolatilization extruder. Suitable examples of devolatilization extruders for the devolatilization section 30 include twin-screw extruders such as co-rotating twin-screw extruders and counter-rotating twin-screw extruders. For example, devolatilization extruders of the vented extruder type, such as the TEX (trade name) manufactured by Nippon Steel, can be cited as examples.

[0235] like Figure 2 As shown, the devolatilization section 30 is provided with a vinyl polymer composition inlet 32 ​​for supplying the vinyl polymer composition into the interior of the devolatilization section 30.

[0236] The devolatilization section 30 is provided with one or more unreacted vinyl monomer discharge ports for extracting the gas containing unreacted vinyl monomers and unavoidably possible impurities generated by the devolatilization process, which is separated into liquid vinyl polymer and gaseous unreacted vinyl monomers, to the outside of the devolatilization section 30.

[0237] The devolatilization section 30 is provided with a vinyl polymer outlet 34 for discharging the prepared vinyl polymer outside the devolatilization section 30. The vinyl polymer outlet 34 is typically located near the downstream end of the devolatilization section 30.

[0238] The first unreacted vinyl monomer outlet 36 is disposed on the upstream side of the devolatilization section 30, that is, on the opposite side of the end portion to the downstream side where the vinyl polymer outlet 34 is disposed.

[0239] The second unreacted vinyl monomer outlet 38 is located downstream of the devolatilization section 30, i.e., near the vinyl polymer outlet 34.

[0240] The devolatilization section 30 is connected to the polymerization reactor 10 via a second pipe 72, which is connected to the polymerization reactor 10 at one end and to the polymerization reactor 10 at the other end.

[0241] (4) Refining equipment

[0242] The vinyl polymer manufacturing apparatus 1 includes a refiner 40. The refiner 40 is a functional unit for separating and removing impurity components other than unreacted vinyl monomers from the unreacted vinyl monomers (which may inevitably contain impurity components in addition to unreacted vinyl monomers) discharged from the devolatilization section 30 as described above.

[0243] As the purification device 40, a distillation column (distillation column) with any suitable configuration known in the past can be used. As an example of a suitable distillation column for the purification device 40, a multi-stage distillation column can be given.

[0244] The refining device 40 is connected to the devolatilization section 30 via a third pipe 73 connected at one end to the first unreacted vinyl monomer outlet 36 and at the other end to the refining device 40, and a fourth pipe 74 connected at one end to the second unreacted vinyl monomer outlet 38 and at the other end to the refining device 40.

[0245] (5) Circulation section

[0246] The vinyl polymer manufacturing apparatus 1 includes a circulation unit 50. The circulation unit 50 is a functional unit that circulates unreacted vinyl monomers, after impurity components have been removed by the already described purifier 40, to the already described raw material vinyl monomer supply unit 20 (raw material monomer supply pump 24).

[0247] The circulation section 50 is provided on a fifth pipe 75 that is connected to the refiner 40 at one end and to the circulation section 50 at the other end.

[0248] (6) Recycled / Bio-based Vinyl Monomer Supply Department

[0249] The recycled / bio-based vinyl monomer supply unit 60, namely the first recycled / bio-based vinyl monomer supply unit 60a, the second recycled / bio-based vinyl monomer supply unit 60b, the third recycled / bio-based vinyl monomer supply unit 60c, the fourth recycled / bio-based vinyl monomer supply unit 60d, the fifth recycled / bio-based vinyl monomer supply unit 60e, and the sixth recycled / bio-based vinyl monomer supply unit 60f, are functional units capable of supplying recycled / bio-based vinyl monomers introduced from the outside to each of the following components connected to the downstream section: the raw material monomer pump 24 connected to the first recycled / bio-based vinyl monomer supply unit 60a, the polymerization reactor 10 connected to the second recycled / bio-based vinyl monomer supply unit 60b, the third piping 73 connected to the third recycled / bio-based vinyl monomer supply unit 60c, the fourth piping 74 connected to the fourth recycled / bio-based vinyl monomer supply unit 60d, the purifier 40 connected to the fifth recycled / bio-based vinyl monomer supply unit 60e, and the circulation unit 50 connected to the sixth recycled / bio-based vinyl monomer supply unit 60f.

[0250] In the vinyl polymer manufacturing apparatus 1, it is sufficient to provide at least one of the following: a first recycled / bio-based vinyl monomer supply unit 60a, a second recycled / bio-based vinyl monomer supply unit 60b, a third recycled / bio-based vinyl monomer supply unit 60c, a fourth recycled / bio-based vinyl monomer supply unit 60d, a fifth recycled / bio-based vinyl monomer supply unit 60e, and a sixth recycled / bio-based vinyl monomer supply unit 60f.

[0251] The vinyl polymer manufacturing apparatus 1 preferably includes a third recycled / bio-based vinyl monomer supply unit 60c and / or a fourth recycled / bio-based vinyl monomer supply unit 60d, and more preferably includes a fourth recycled / bio-based vinyl monomer supply unit 60d.

[0252] Furthermore, if a fifth recycled / bio-based vinyl monomer supply unit 60e is provided as the recycled / bio-based vinyl monomer supply unit 60, then the cooling unit 74a can be omitted from the fourth piping 74 connected to the devolatilization unit 30, and the continuous operation of the devolatilization unit 30 and the refiner 40 can be carried out with a simpler configuration.

[0253] It should be noted that when the recycled / bio-based vinyl monomer used in the vinyl polymer manufacturing apparatus 1 is, for example, a recycled vinyl monomer that has been regenerated through chemical reuse, the described pyrolysis apparatus that can manufacture (regenerate) and supply the recycled vinyl monomer can be connected to the recycled / bio-based vinyl monomer supply unit 60 via, for example, stainless steel piping.

[0254] On the other hand, when the recycled / bio-based vinyl monomer used in the vinyl polymer manufacturing apparatus 1 is, for example, a bio-based vinyl monomer, the bio-based vinyl monomer produced in any conventionally known suitable bio-based vinyl monomer manufacturing equipment can be supplied to the recycled / bio-based vinyl monomer supply unit 60. This can be done in the following manner: for example, by connecting the bio-based vinyl monomer manufacturing equipment to the recycled / bio-based vinyl monomer supply unit 60 through stainless steel pipes, etc., and directly supplying the bio-based vinyl monomer exported from the bio-based vinyl monomer manufacturing equipment to the recycled / bio-based vinyl monomer supply unit 60.

[0255] (7) Temperature control unit

[0256] like Figure 2 As shown, in the second embodiment, the second pipe 72 further includes a temperature regulating section 72a provided in such a way that it contacts its outer surface or penetrates its interior.

[0257] Temperature regulating unit 72a is a functional unit used to regulate the temperature of the vinyl polymer composition discharged from the polymerization reactor 10.

[0258] In this embodiment, the temperature regulating unit 72a is a functional unit that can regulate the temperature of the vinyl polymer composition flowing in the second pipe 72 to a temperature above the softening point of the vinyl polymer mainly contained in the vinyl polymer composition and below the thermal decomposition temperature.

[0259] As the temperature regulating unit 72a, any suitable configuration known in the prior art can be used. Specifically, as the temperature regulating unit 72a, at least one selected from the following can be used: a sleeve, a double-tube heat exchanger, an electric heater, and an insulation material that allows the medium (hot medium, cold medium) to flow inside.

[0260] It should be noted that when the temperature regulating section 72a is constructed from two or more components, such as a combination of a dual-tube heat exchanger and insulation material, it is sufficient for at least one component to contact the outer surface of the second pipe 72. In other words, two or more components can be arranged to be stacked on the outer surface of the second pipe 72. The temperature regulating section 72a can, for example, be arranged to cover the outer periphery of the second pipe 72 without interruption.

[0261] The temperature regulating unit 72a is provided in such a way that the temperature of the vinyl polymer composition flowing in the second pipe 72 can be effectively regulated, and there are no particular limitations.

[0262] In this embodiment, a double-tube heat exchanger is preferably used as the temperature regulating unit 72a. This double-tube heat exchanger is preferably a double-tube heat exchanger that uses steam as the heat medium or a double-tube heat exchanger that uses water as the cold medium.

[0263] In addition, if the temperature regulating unit 72a includes insulation material, the insulation material is preferably selected from at least one of rock wool, glass wool, calcium silicate and waterproof perlite.

[0264] According to the vinyl polymer manufacturing apparatus 1 of this embodiment, the second piping 72 is equipped with a temperature regulating unit 72a, which can compensate for the temperature drop caused by the latent heat of vaporization in the devolatilization process. As a result, the equipment load in the devolatilization process caused by the temperature drop can be suppressed, and the devolatilization treatment in the subsequent devolatilization unit 30 can be carried out more efficiently.

[0265] (8) First cooling section and second cooling section

[0266] In the second embodiment, the third pipe 73 further includes a first cooling section 73a disposed in a manner that contacts its outer surface or penetrates its interior. When the third recycled / bio-based vinyl monomer supply section 60c is connected to the third pipe 73, the first cooling section 73a is preferably disposed in a region of the third pipe 73 that is closer to the devolatilization section 30 than the third recycled / bio-based monomer supply section 60c.

[0267] Cooling section 73a is a functional section used to cool and liquefy the gas (gaseous unreacted vinyl monomer) discharged from devolatilization section 30.

[0268] As the first cooling section 73a, a double-tube heat exchanger is preferably used. As this double-tube heat exchanger, for example, a double-tube heat exchanger that uses water as the cooling medium is preferred.

[0269] In addition, if the first cooling section 73a includes insulation material, the insulation material is preferably selected from at least one of rock wool, glass wool, calcium silicate and waterproof perlite.

[0270] In the second embodiment, the fourth pipe 74 further includes a second cooling section 74a disposed in such a manner that it contacts its outer surface or penetrates its interior. When the fourth recycled / bio-based vinyl monomer supply section 60d is connected to the fourth pipe 74, the second cooling section 74a is preferably disposed in a region of the fourth pipe 74 that is closer to the devolatilization section 30 than the fourth recycled / bio-based monomer supply section 60d.

[0271] The function and manner of the second cooling section 74a are the same as those of the first cooling section 73a, which has already been described, so their description is omitted.

[0272] The vinyl polymer manufacturing apparatus 1 according to the second embodiment is equipped with a first cooling section 73a and / or a second cooling section 74a, so that liquefied unreacted vinyl monomers can be supplied to the purifier 40, resulting in more efficient purification in the purifier 40.

[0273] (9) Raw material vinyl monomer blending tank

[0274] In the second embodiment, the vinyl polymer manufacturing apparatus 1 includes a raw material vinyl monomer blending tank 80 (a first raw material vinyl monomer blending tank 80a and / or a second raw material vinyl monomer blending tank 80b).

[0275] The raw material vinyl monomer blending tank 80 has the following functions: in order to make the composition and characteristics of the raw material vinyl monomer supplied to the polymerization reactor 10 within a suitable range, for example, a specified vinyl monomer can be added, or additives such as antioxidants, ultraviolet absorbers, and release agents can be added in addition to the polymerization initiator and chain transfer agent that have been described, for blending.

[0276] like Figure 2 As shown, the first raw material vinyl monomer blending tank 80a is configured to introduce unreacted vinyl monomers circulated through the circulation section 50 into the fifth pipe 75, and then introduce the aforementioned additives for mixing (blending), and introduce the mixture into the raw material vinyl monomer supply section 20 (raw material monomer supply pump 24). The second raw material vinyl monomer blending tank 80b is configured to be supplied to the raw material vinyl monomer supply section 20 (raw material monomer supply pump 24) through any conventionally known suitable stainless steel pipe or the like.

[0277] Here, thiols, particularly butyl mercaptan, octyl mercaptan and dodecyl mercaptan, can be cited as examples of usable chain transfer agents.

[0278] In addition, examples of initiators include azo compounds such as 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylpentanonitrile), and 2,2-azobis(2-methylbutyronitrile), as well as organic peroxides such as 1,1-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane, tert-butylperoxyisobutyrate, benzoyl peroxide, and lauroyl peroxide.

[0279] like Figure 2 As shown, in this embodiment, the first raw material vinyl monomer blending tank 80a is located in the fifth piping 75 in a region near the raw material vinyl monomer supply section 20 (raw material monomer supply pump 24). Additionally, the second raw material vinyl monomer blending tank 80b is connected to the raw material vinyl monomer supply section 20.

[0280] The composition, materials, and dimensions of the raw material vinyl monomer blending tank 80 are not particularly limited, provided that the aforementioned functions can be performed. The raw material vinyl monomer blending tank 80 may, for example, consist of any suitable stainless steel tank known in the past, an agitator installed within the tank, a metering pump such as a plunger pump or diaphragm pump, on / off valves, instruments such as flow meters, thermometers, and pressure gauges, a cooler, a heater, a heat exchanger, and a temperature regulator.

[0281] Specifically, the blending in the raw material vinyl monomer blending tank 80 can be carried out, for example, by taking out a portion of the raw material monomers supplied to the raw material vinyl monomer supply section 20 and before being supplied to the polymerization reaction tank 10, and analyzing the composition and characteristics of the taken-out raw material monomers using any suitable method known in the past to evaluate whether the composition and characteristics of the raw material monomers are within a suitable range. If the evaluation results show that, for example, a specific component is insufficient or does not meet the specified characteristics, additives or the like are blended in the raw material vinyl monomer blending tank 80 to improve the insufficient components and characteristics, and the composition and characteristics of the raw material monomers are adjusted to a suitable range in the raw material vinyl monomer supply section 20.

[0282] The vinyl polymer manufacturing apparatus 1 according to the second embodiment is equipped with a raw material vinyl monomer blending tank 80, so it can manufacture vinyl polymers with desired composition, polymerization rate, molecular weight and other desired properties, weather resistance and other desired characteristics more accurately and efficiently.

[0283] (10) Storage tanks (first storage tank, second storage tank)

[0284] In the second embodiment, the vinyl polymer manufacturing apparatus 1 includes a storage tank 90 (a first storage tank 92 and / or a second storage tank 94).

[0285] Storage tank 90 is a functional unit that can temporarily store a predetermined amount of undecomposed monomers and other components, and further export them to downstream functional units as needed. Specifically, first storage tank 92 is a functional unit that can store raw material vinyl monomers exported from devolatilization unit 30 and liquefied by second cooling unit 74a as needed, and further store regenerated / bio-raw material vinyl monomers supplied from fourth regenerated / bio-raw material vinyl monomer supply unit 60d when a fourth regenerated / bio-raw material vinyl monomer supply unit 60d is provided. Second storage tank 94 is a functional unit that can store undecomposed monomers exported from purifier 40 and imported through fifth piping 75 and circulation unit 50.

[0286] like Figure 2As shown, in this embodiment, the first storage tank 92 is located in a region closer to the refiner 40 (downstream side) than the second cooling section 74a of the fourth piping 74. Furthermore, the second storage tank 94 is located in a region of the fifth piping 75 near the raw material vinyl monomer supply section 20 (raw material monomer supply pump 24) and closer to the refiner 40 than the first raw material vinyl blending tank 80a.

[0287] The composition, materials, and dimensions of the storage tank 90 are not particularly limited, provided that the aforementioned functions can be performed. For example, the storage tank 90 can be composed of any suitable stainless steel tank known in the past, and further comprising a fixed displacement pump such as a plunger pump or diaphragm pump, on / off valves, instruments such as flow meters, thermometers, and pressure gauges, and temperature regulators such as coolers, heaters, and heat exchangers.

[0288] Here, as the fourth conduit 74, any suitable stainless steel conduit known in the past can be used, for example.

[0289] According to the vinyl polymer manufacturing apparatus 1 of the second embodiment, a storage tank 90 is provided. Therefore, when the fourth pipe 74 is provided, unreacted vinyl monomers flowing in the fourth pipe 74, which are particularly easy to liquefy due to the presence of high-boiling-point impurities, can be temporarily stored in the first storage tank 92 and introduced into the refiner 40 for purification more easily and efficiently. In addition, when the fifth pipe 75 is provided, before introducing the raw material vinyl monomers into the raw material vinyl monomer blending tank 80, the raw material vinyl monomer supply unit 20, and then the polymerization reaction tank 10, for example, a portion of the composition containing unreacted vinyl monomers and raw material vinyl monomers temporarily stored in the second storage tank 94 can be extracted and its composition, properties, etc. can be checked. For example, the insufficient components can be supplemented by the raw material vinyl monomer blending tank 80. Therefore, vinyl polymers with the desired composition, properties, and characteristics can be manufactured more accurately and efficiently.

[0290] (11) Other equipment

[0291] The (i) post-processing equipment, (ii) waste gas treatment equipment, and (iii) pyrolysis equipment that the vinyl polymer manufacturing apparatus 1 of the second embodiment may include are the same as those of the apparatus of the first embodiment, and therefore detailed descriptions are omitted.

[0292] 2. Manufacturing method of vinyl polymers

[0293] The method for manufacturing the vinyl polymer according to the second embodiment uses the manufacturing method of the vinyl polymer manufacturing apparatus 1 of the second embodiment, which has already been described. The exporting step, preparation step, separation step, removal step, recycling step, and discharge step involved in the method for manufacturing the vinyl polymer according to the second embodiment are the same as those in the manufacturing method of the first embodiment, so the differences will be specifically described below.

[0294] (1) In the case that the vinyl polymer manufacturing apparatus 1 further includes a first cooler 73a provided in a region closer to the devolatilization section 30 than the recycled / bio-based vinyl monomer supply section 60 in a third pipe 73 connected to the recycled / bio-based vinyl monomer supply section 60, and / or a second cooling section 74a provided in a region closer to the devolatilization section 30 than the recycled / bio-based vinyl monomer supply section 60 in a fourth pipe 74 connected to the recycled / bio-based vinyl monomer supply section 60, a cooling process is further included after the separation process and before the removal process, in which the unreacted vinyl monomer in gaseous form discharged from the devolatilization section 30 is liquefied by introducing it into the first cooling section 73a and / or the second cooling section 74a for cooling.

[0295] When the manufacturing method of vinyl polymers includes a cooling process, liquefied unreacted vinyl monomers can be supplied to the refiner 40, thus enabling more efficient and effective refining in the refiner 40, reuse of unreacted vinyl monomers, and even manufacturing of vinyl polymers.

[0296] (2) In the case where the vinyl polymer manufacturing apparatus 1 further includes a region located near the raw material vinyl monomer supply section 20 in the fifth pipe 75, or a raw material vinyl monomer blending tank 80 connected to the raw material vinyl monomer supply section 20, the previously described circulation process is as follows: unreacted vinyl monomers after removing impurity components are exported from the purifier 40, the unreacted vinyl monomers are introduced into the raw material vinyl monomer blending tank 80 through the circulation section 50 to adjust the composition of the raw material vinyl monomers, and then the raw material vinyl monomers with adjusted composition are circulated to the raw material vinyl monomer supply section 60, and then the export process is performed again.

[0297] If the recycling process is set as described above using the raw material vinyl monomer blending tank 80, vinyl polymers with the desired composition, properties, and characteristics can be manufactured more accurately and efficiently.

[0298] (3) In the case where the vinyl polymer manufacturing apparatus 1 further includes a first storage tank 92 located in the region near the purifier 40 in the fourth piping 74 and a second storage tank 94 located in the region near the raw material vinyl monomer supply section 20 in the fifth piping 75, after the separation process and before the removal process, a process is further included in which the unreacted vinyl monomers exported from the devolatilization section 30 are stored in the first storage tank 92 in the form of liquid unreacted vinyl monomers. The recycling process is as follows: the unreacted vinyl monomers after removing impurity components are exported from the purifier 40, stored in the second storage tank 94 in the form of liquid unreacted vinyl monomers, and then recycled to the raw material vinyl monomer supply section 20, and then the export process is performed again.

[0299] In the method for manufacturing vinyl polymers, when the storage tank 90 is provided in the fourth pipe 74, unreacted vinyl monomers flowing in the fourth pipe 74, which are particularly prone to liquefaction due to the presence of high-boiling-point impurities, can be temporarily stored and more easily and efficiently introduced into the refiner 40 for purification. In addition, when the fifth pipe 75 is provided, before introducing the raw material vinyl monomers into the raw material vinyl monomer blending tank 80, the raw material vinyl monomer supply unit 20, and then the polymerization reaction tank 10, for example, a portion of the temporarily stored composition containing unreacted vinyl monomers and raw material vinyl monomers can be extracted and its composition and properties can be checked. For example, the insufficient components can be supplemented through the raw material vinyl monomer blending tank 80. Therefore, vinyl polymers with the desired composition, properties, and characteristics can be manufactured more accurately and efficiently. Energy consumption can be reduced with a simplified process, and vinyl polymers from recycled / biological raw material vinyl monomers and non-recycled / non-biological raw material vinyl monomers can be manufactured efficiently with high yield and low cost, especially vinyl polymers using the mass balance method.

[0300] Symbol Explanation

[0301] 1 Vinyl polymer manufacturing apparatus

[0302] 10 polymerization reactors

[0303] 20 Raw Material Vinyl Monomer Supply Department

[0304] 22 Non-renewable / non-biological raw material vinyl monomer supply department

[0305] 24 Raw Material Vinyl Monomer Supply Pump

[0306] 26 Polymerization Initiator Supply Department

[0307] 28 Chain Transfer Agent Supply Department

[0308] 30% of the volumetric oscillator

[0309] 32 Vinyl polymer composition inlet

[0310] 34 Vinyl polymer discharge outlet

[0311] 36. First unreacted vinyl monomer outlet (upstream unreacted vinyl monomer outlet)

[0312] 38 Second unreacted vinyl monomer outlet (downstream unreacted vinyl monomer outlet)

[0313] 40 Refiners

[0314] 50 Circulation Section

[0315] 60 Recycled / Bio-based Vinyl Monomer Supply Department

[0316] 60a First Regenerated / Bio-based Vinyl Monomer Supply Department

[0317] 60b Second Regenerated / Bio-based Vinyl Monomer Supply Department

[0318] 60c Third Regenerated / Bio-based Vinyl Monomer Supply Department

[0319] 60d Fourth Regenerated / Bio-based Vinyl Monomer Supply Department

[0320] 60e Fifth Recycled / Bio-based Vinyl Monomer Supply Department

[0321] 60f Sixth Regenerated / Bio-based Vinyl Monomer Supply Department

[0322] 71 First Piping

[0323] 72 Second Piping

[0324] 72a Temperature Control Unit

[0325] 73 Third Piping

[0326] 73a First Cooling Section

[0327] 74 Fourth Piping

[0328] 74a Second Cooling Section

[0329] 75 Fifth Pipeline

[0330] 80 Raw material vinyl monomer blending tank

[0331] 80a First Raw Material Vinyl Monomer Blending Tank

[0332] 80b Second Raw Material Vinyl Monomer Blending Tank

[0333] 90 storage tanks

[0334] 92 First Storage Tank

[0335] 94 Second Storage Tank

Claims

1. A vinyl polymer manufacturing apparatus, comprising: A polymerization reactor is used to carry out bulk polymerization or solution polymerization of raw vinyl monomers containing recycled / bio-based vinyl monomers and non-recycled / non-bio-based vinyl monomers to obtain a vinyl polymer composition mixed with vinyl polymers and unreacted vinyl monomers. A raw material vinyl monomer supply unit is used to supply the vinyl monomer to the polymerization reactor. The raw material vinyl monomer supply unit is connected to the polymerization reactor via a first pipe connected at one end to the polymerization reactor and at the other end to the raw material vinyl monomer supply unit. It also includes a non-renewable / non-biological raw material vinyl monomer supply unit for supplying the non-renewable / non-biological raw material vinyl monomer and a raw material vinyl monomer supply pump for discharging the vinyl monomer to the polymerization reactor. A devolatilization section is used to devolatilize the vinyl polymer composition discharged from the polymerization reactor to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer. The devolatilization section is connected to the polymerization reactor via a second pipe connected at one end to the polymerization reactor and at the other end to the devolatilization section. It has: a vinyl polymer composition inlet for introducing the vinyl polymer composition, a vinyl polymer outlet for discharging the vinyl polymer, a first unreacted vinyl monomer outlet for discharging the unreacted vinyl monomer, and a second unreacted vinyl monomer outlet disposed downstream of the first unreacted vinyl monomer outlet. A refiner for separating and removing impurities from the unreacted vinyl monomers discharged from the devolatilization section, the refiner being connected to the devolatilization section via a third pipe connected at one end to the first unreacted vinyl monomer outlet and at the other end to the refiner, and also connected to the devolatilization section via a fourth pipe connected at one end to the second unreacted vinyl monomer outlet and at the other end to the refiner; and A circulation section is provided to circulate unreacted vinyl monomers, after the impurities have been removed by the purifier, to the raw material vinyl monomer supply section. The circulation section is provided in a fifth pipe connected at one end to the purifier and at the other end to the raw material vinyl monomer supply section. in, The recycled / bio-based vinyl monomer supply unit for supplying recycled / bio-based vinyl monomers is connected to at least one of the following: the raw material vinyl monomer supply unit, the polymerization reactor, the purifier, the circulation unit, and the third piping.

2. The vinyl polymer manufacturing apparatus according to claim 1, wherein, The recycled / bio-based vinyl monomer supply unit is connected to the third piping.

3. The vinyl polymer manufacturing apparatus according to claim 1 or 2, wherein, The devolatilization section is a devolatilization extruder.

4. The vinyl polymer manufacturing apparatus according to claim 2, wherein, The system further includes a first cooling section, located in a region of the third piping connected to the recycled / bio-based vinyl monomer input section, closer to the devolatilization section than the recycled / bio-based monomer input section. The first cooling section is a cooling section used to liquefy gaseous unreacted vinyl monomers.

5. The vinyl polymer manufacturing apparatus according to claim 1 or 2, wherein, The system further includes a raw material vinyl monomer blending tank, which is located in the region of the fifth piping near the raw material vinyl monomer supply section, or connected to the raw material vinyl monomer supply section, for adjusting the composition of the raw material vinyl monomer supplied to the polymerization reactor.

6. The vinyl polymer manufacturing apparatus according to claim 1 or 2, wherein, Further features include: The first storage tank, located in the region of the fourth piping near the refiner, is used to store unreacted vinyl monomers discharged from the devolatilization section in the form of liquid unreacted vinyl monomers. as well as The second storage tank, located in the area near the raw material monomer supply section of the fifth piping, is used to store unreacted vinyl monomers discharged from the refiner in the form of liquid unreacted vinyl monomers.

7. The vinyl polymer manufacturing apparatus according to claim 1 or 2, wherein, The raw material vinyl monomer and unreacted vinyl monomer are (meth)acrylates.

8. A method for manufacturing a vinyl polymer, comprising, using the vinyl polymer manufacturing apparatus of claim 1 or 2, a method for manufacturing a vinyl polymer, including: In the export process, the raw vinyl monomer, which may include non-regenerative / non-biological raw vinyl monomer supplied from the non-regenerative / non-biological raw vinyl monomer supply unit for supplying non-regenerative / non-biological raw vinyl monomer and regenerative / biological raw vinyl monomer supplied from the regenerative / biological raw vinyl monomer supply unit, is exported to the polymerization reactor via the first pipe through the raw vinyl monomer supply pump of the raw vinyl monomer supply unit. In the preparation process, the raw vinyl monomer supplied from the raw material vinyl monomer supply unit is subjected to bulk polymerization or solution polymerization in the polymerization reactor to obtain a vinyl polymer composition composed of vinyl polymer and unreacted vinyl monomer. In the separation process, the obtained vinyl polymer composition is discharged from the polymerization reactor, and the vinyl polymer composition is introduced into the devolatilization section through the second pipe from the vinyl polymer composition inlet. Then, devolatilization is carried out through the devolatilization section to separate the liquid vinyl polymer from the gaseous unreacted vinyl monomer. In the removal process, unreacted vinyl monomers are discharged and introduced into the purifier for purification via the first unreacted vinyl monomer discharge port of the devolatilization section and the third pipe, thereby further separating and removing impurity components from the unreacted vinyl monomers. In the recycling process, unreacted vinyl monomers, after impurity components have been removed, are discharged from the purifier and circulated through the fifth pipe to the raw material vinyl monomer supply unit via the recycling section; then the discharge process is repeated. In the discharge process, the vinyl polymer after the unreacted vinyl monomers have been separated is discharged from the vinyl polymer discharge port of the devolatilization section to obtain the vinyl polymer.

9. The method for manufacturing the vinyl polymer according to claim 8, wherein, The recycled / bio-based vinyl monomer supply unit for supplying recycled / bio-based vinyl monomers is connected to at least one of the following: the raw material vinyl monomer supply unit, the polymerization reactor, the purifier, the circulation unit, and the third piping. When the recycled / bio-based vinyl monomer supply unit is connected to the raw material vinyl monomer supply unit, the export process is performed using recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit to the raw material vinyl monomer supply unit. When the recycled / bio-based vinyl monomer supply unit is connected to the polymerization reactor, the preparation process is performed using the recycled / bio-based vinyl monomer supplied from the recycled / bio-based vinyl monomer supply unit to the polymerization reactor. When the recycled / bio-based vinyl monomer supply unit is connected to the purifier, the removal process is a process performed using recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit to the purifier, in addition to unreacted vinyl monomers. When the recycled / bio-based vinyl monomer supply unit is connected to the circulation unit, the circulation process is a process that uses recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply unit to the circulation unit, in addition to unreacted vinyl monomers. When the recycled / bio-based vinyl monomer supply unit is connected to the third piping, the removal process is a process performed using recycled / bio-based vinyl monomer supplied from the recycled / bio-based vinyl monomer supply unit to the third piping, in addition to the unreacted vinyl monomer discharged from the devolatilization unit.

10. The method for manufacturing the vinyl polymer according to claim 9, wherein, The recycled / bio-based vinyl monomer supply unit is connected to the third piping. The removal process is a process that, in addition to the unreacted vinyl monomers exported from the devolatilization section, also uses the recycled / bio-based vinyl monomers supplied from the recycled / bio-based vinyl monomer supply section to the third pipe.

11. The method for manufacturing the vinyl polymer according to claim 10, wherein, The system further includes a first cooling section, located in a region of the third piping connected to the recycled / bio-based vinyl monomer supply section that is closer to the devolatilization section than the recycled / bio-based monomer supply section. The process further includes a cooling step after the separation step and before the removal step, in which unreacted vinyl monomers in gaseous form exported from the devolatilization section are liquefied by being introduced into the first cooling section for cooling.

12. The method for manufacturing the vinyl polymer according to claim 8, wherein, The fifth piping further includes a raw material vinyl monomer blending tank, which is located in the region near the raw material vinyl monomer supply section, or connected to the raw material vinyl monomer supply section. The circulation process is as follows: unreacted vinyl monomers after removing impurities are exported from the purifier, and the unreacted vinyl monomers are introduced into the raw material vinyl monomer blending tank through the circulation section to adjust the composition of the raw material vinyl monomers. Then, the raw material vinyl monomers with adjusted composition are circulated to the raw material vinyl monomer supply section, and then the export process is performed again.

13. The method for manufacturing the vinyl polymer according to claim 8, wherein, It further comprises a first storage tank located in the region of the fourth piping near the refiner, and a second storage tank located in the region of the fifth piping near the raw material vinyl monomer supply section. After the separation process and before the removal process, the process further includes a step of storing the unreacted vinyl monomers discharged from the devolatilization section in the first storage tank as liquid unreacted vinyl monomers. The recycling process is as follows: unreacted vinyl monomers, after impurities have been removed, are exported from the purifier and stored in the second storage tank as liquid unreacted vinyl monomers. They are then recycled to the raw material vinyl monomer supply unit, and the export process is repeated.

14. The method for manufacturing the vinyl polymer according to claim 8, wherein, The raw material vinyl monomer and unreacted vinyl monomer are (meth)acrylates.

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