Composition, method for producing composition, scale adhesion inhibitor, reactor, polymer, method for producing polymer

Abstract

To provide a composition, a method for producing the composition, a scale adhesion inhibitor, a reactor, a polymer, and a method for producing the polymer.SOLUTION: A composition includes an addition condensate of aromatic compounds and carbonyl compounds, and thiol compounds. The composition contains, for example, 0.01 pt.mass or more and 100 pts.mass or less of thiol compounds relative to 100 pts.mass of aromatic compounds. In the composition, the addition condensate may include a first type of addition condensate having a first average molecular weight and a second type of addition condensate having a second average molecular weight. In the composition, the first average molecular weight and the second average molecular weight are different.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a composition, a method for producing the composition, an anti-scaling agent, a reactor, a polymer, and a method for producing the polymer. [Background technology]

[0002] Patent Documents 1 and 2 disclose anti-scaling agents for preventing polymer scale from adhering to the inside of a polymerization vessel. (Prior art document) (Patent Documents) (Patent Document 1) Patent No. 5445142 (Patent Document 2) JP 2003-40907 A Summary of the Invention [Means for solving the problem]

[0003] In a first aspect of the present invention, a composition is provided. The composition includes, for example, an addition condensate of an aromatic compound and a carbonyl compound. The composition includes, for example, a thiol compound.

[0004] Any of the above compositions may contain 0.01 to 100 parts by mass of a thiol compound relative to 100 parts by mass of an aromatic compound. In any of the above compositions, the addition condensate may contain a first type of addition condensate having a first average molecular weight and a second type of addition condensate having a second average molecular weight. The first average molecular weight and the second average molecular weight may be different. In any of the above compositions, the ratio of the mass of the second type of addition condensate to the mass of the first type of addition condensate may be 2.3 to 1000. The second average molecular weight may be larger than the first average molecular weight.

[0005] In any of the above compositions, the thiol compound may have a thiol group and at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. In any of the above compositions, the thiol compound may be thioglycerol, thioglycol, or a derivative thereof.

[0006] In any of the above compositions, the aromatic compound may be naphthols. In any of the above compositions, the carbonyl compound may be an aldehyde compound or a ketone compound. In any of the above compositions, the aromatic compound may be 1-naphthol. In any of the above compositions, the carbonyl compound may be formaldehyde. In any of the above compositions, the thiol compound may be 1-thioglycerol or thioglycol.

[0007] In a second aspect of the present invention, there is provided a scale adhesion inhibitor for preventing adhesion of a polymer-containing scale. The scale adhesion inhibitor includes, for example, any of the compositions according to the first aspect.

[0008] In a third aspect of the present invention, a method for producing a composition is provided. The method includes, for example, preparing a mixture of a solvent, an aromatic compound, a carbonyl compound, and a thiol compound. The method includes, for example, reacting the aromatic compound and the carbonyl compound contained in the mixture in the presence of a catalyst and a surfactant to produce a composition containing an addition condensation product of the aromatic compound and the carbonyl compound, and the thiol compound.

[0009] In any of the above methods, the catalyst may be an alkali metal hydroxide.In any of the above methods, the surfactant may be an anionic surfactant.

[0010] In a fourth aspect of the present invention, a reaction apparatus is provided. The reaction apparatus is used, for example, for polymerizing a monomer. The reaction apparatus includes, for example, a reactor configured to be capable of storing a solution containing a monomer. In the reaction apparatus, the reactor has, for example, a coating layer disposed on at least a part of an inner wall surface that is a surface on the side that contacts the solution. In the reaction apparatus, the coating layer includes, for example, an addition condensate of an aromatic compound and a carbonyl compound. In the reaction apparatus, the addition condensate includes, for example, a first type of addition condensate having a first average molecular weight and a second type of addition condensate having a second average molecular weight. In the reaction apparatus, the second average molecular weight is, for example, larger than the first average molecular weight. In the reaction apparatus, the ratio of the mass of the second type of addition condensate to the mass of the first type of addition condensate is, for example, 0.75 to 1000.

[0011] In a fifth aspect of the present invention, there is provided a method for producing a polymer. The method includes, for example, a step of preparing a reaction apparatus according to any one of the fourth aspects. The method includes, for example, a step of charging a solution containing a monomer into a reactor of the reaction apparatus. The method includes, for example, a step of initiating a polymerization reaction of the monomer in the reactor. The method includes, for example, a step of terminating the polymerization reaction of the monomer in the reactor.

[0012] In a sixth aspect of the present invention, a particulate polymer is provided. In the above polymer, the polymer 200 cm 3 The number of foreign matter particles having a major axis of 250 μm or more contained per unit area is, for example, 2 to 4. In the above polymer, the content of the addition condensation product of an aromatic compound and a carbonyl compound in the foreign matter is, for example, 1 mass % or more. [Brief description of the drawings]

[0013] [Figure 1] An example of a polymerization apparatus 100 is shown diagrammatically. [Diagram 2] An example of a coating device 190 is shown diagrammatically. [Diagram 3] 1 illustrates an example of a method for producing a composition. [Figure 4] 1 illustrates a schematic diagram of an example of a method for producing a polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. In addition, not all combinations of features described in the embodiments are necessarily essential to the solution of the invention. In this specification, when a numerical range is expressed as "A to B", the expression means A or more and B or less.

[0015] In this specification, the ratio of B to A means B÷A. For example, the ratio of the mass My of Y to the mass Mx of X means My÷Mx. The above ratios may be expressed as percentages.

[0016] In this specification, the term compound means the compound and / or a salt of the compound. For example, in this specification, the term thiol compound means the thiol compound and / or a salt of the thiol compound. The term aromatic compound means the aromatic compound and / or a salt of the aromatic compound. The term carbonyl compound means the carbonyl compound and / or a salt of the carbonyl compound. The term aldehyde compound means the aldehyde compound and / or a salt of the aldehyde compound. The term ketone compound means the ketone compound and / or a salt of the ketone compound. Similarly, in this specification, the term addition condensate means the addition condensate and / or a salt of the addition condensate.

[0017] (Overview of Polymerization Apparatus 100) An example of a polymerization apparatus 100 will be described with reference to Fig. 1. The polymerization apparatus 100 is used, for example, for polymerizing a monomer to produce a polymer. The polymerization apparatus 100 may be used for suspension polymerization. Details of a method for producing a polymer using the polymerization apparatus 100 will be described later.

[0018] The above monomer may be an ethylenically unsaturated group-containing monomer. Examples of the above ethylenically unsaturated group-containing monomer include vinyl halides such as vinyl chloride; vinylidene halides such as vinylidene chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, and their esters or salts; maleic acid, fumaric acid, and their esters or acid anhydrides; conjugated diene monomers such as butadiene, chloroprene, and isoprene; styrene; acrylonitrile; and vinyl ether. The above ethylenically unsaturated group-containing monomer may be a vinyl monomer. The above vinyl monomer may be vinyl chloride.

[0019] As described in Patent Documents 1 and 2, when a polymer is produced by polymerizing a monomer inside a reaction vessel, a part of the polymer may adhere to the inside of the reaction vessel as polymer scale. For example, if the degree of adhesion of polymer scale increases with an increase in the number of polymerization batches, the polymer yield and the cooling capacity of the reaction vessel may decrease. In addition, if the polymer scale that has adhered to the reaction vessel peels off from the reaction vessel during the production of the polymer, the quality of the polymer obtained as a product may decrease.

[0020] Specifically, the proportion of foreign matter mixed into the product increases. The above-mentioned polymer scale peeled off from the reaction vessel may be an example of foreign matter. For example, when polyvinyl chloride is produced, the polyvinyl chloride product is obtained as white particles. When a part of the product is sampled and observed visually or under a microscope, colored particles may be found mixed into the white particles. The colored particles are, for example, brown particles.

[0021] Therefore, when polymer scale adheres to a reaction vessel, work is carried out to remove the polymer scale. When removing polymer scale adhered to a reaction vessel, various work is carried out while protecting the worker from the unreacted monomer contained in the polymer scale. Since the removal of polymer scale requires a lot of labor and time, various scale adhesion inhibitors have been developed for the purpose of reducing the labor and time required for the removal work.

[0022] The present inventors have found that, depending on the type of scale adhesion inhibitor, when the scale adhesion inhibitor is applied to a reaction vessel, the scale adhesion inhibitor does not provide the scale adhesion prevention effect expected from the results of laboratory experiments. In this regard, when the scale adhesion inhibitor is applied to the inner surface of a reaction vessel, the scale adhesion inhibitor is often introduced into the reaction vessel using steam (see, for example, Patent Document 2). As a result of intensive research, the present inventors have found that the active ingredient in the scale adhesion inhibitor is reduced by heating the scale adhesion inhibitor with steam. It was presumed that the above-mentioned active ingredient is reduced by, for example, thermal decomposition.

[0023] Based on the above findings, the present inventors adjusted the composition of the scale adhesion inhibitor, and found that, depending on the composition of the scale adhesion inhibitor, when the scale adhesion inhibitor is introduced into the interior of a reaction vessel using steam, the active ingredient of the scale adhesion inhibitor may be thermally decomposed, making it difficult to use the agent as a scale adhesion inhibitor. As a result of intensive research, the present inventors found that the thermal decomposition of the active ingredient can be suppressed by adding a thiol compound to the solvent of the scale adhesion inhibitor.

[0024] The present inventors have also found that by applying the above composition to the inside of a reaction vessel, the formation of a coating film and polymer scale buildup can be suppressed even when the number of polymerization batches using the reaction vessel is increased. This suppresses the inclusion of foreign matter in the product. As a result, a polymer with a small amount of foreign matter is obtained. An example of the reaction vessel is a reaction vessel for producing a polymer by polymerizing a monomer. An example of the monomer is a monomer having an ethylenic double bond.

[0025] (Overview of each part of the polymerization apparatus 100) 1 is a schematic cross-sectional view of a polymerization apparatus 100. In this embodiment, the polymerization apparatus 100 includes a reaction vessel 110, a stirrer 120, one or more (sometimes simply referred to as one or more) baffles 130, one or more cooling pipes 140, a jacket 170, a reflux condenser 180, and a coating apparatus 190.

[0026] In this embodiment, the reaction vessel 110 has a body 112 and a scale prevention layer 116 formed on at least a portion of an inner surface 114 of the body 112. In this embodiment, the agitator 120 has an agitation shaft 122, an agitation blade 124, and a power mechanism 126. In this embodiment, the baffle 130 has a body 132 and one or more supports 134. In this embodiment, the jacket 170 has a heat medium flow path 172. In this embodiment, the reflux condenser 180 has a heat medium flow path 182.

[0027] In this embodiment, the stirring shaft 122 and the stirring blades 124 are disposed inside the reaction vessel 110. In this embodiment, each of the one or more baffles 130 is disposed inside the reaction vessel 110. In this embodiment, each of the one or more cooling tubes 140 is disposed inside the reaction vessel 110.

[0028] In this embodiment, the power mechanism 126 is disposed outside the reaction vessel 110. In this embodiment, the jacket 170 is disposed outside the reaction vessel 110. In this embodiment, the reflux condenser 180 is disposed outside the reaction vessel 110.

[0029] In this embodiment, the reaction vessel 110 is configured to be capable of storing raw materials for a synthesis reaction (e.g., a polymerization reaction). An example of a synthesis reaction is a polymerization reaction for producing a polymer by polymerizing a monomer. When the polymerization apparatus 100 is used for producing a polymer, the reaction vessel 110 stores a solution containing a monomer.

[0030] When the polymerization apparatus 100 is used for producing a polymer, first, a solution containing, for example, a polymerizable monomer, a polymerization initiator, an aqueous medium, and a dispersion aid is charged into the reaction vessel 110. Next, polymerization is started. Thereafter, the polymerization is stopped. In this way, a polymer is produced. Any surfactant can be used as the dispersion aid.

[0031] In this embodiment, the main body 112 of the reaction vessel 110 includes, for example, a cylindrical body portion and a bottom plate connected to the body portion. The main body 112 may further include a top plate connected to the body portion. The bottom plate and the top plate may be referred to as end plates. In this embodiment, the top plate is connected to one end of the body portion, and the bottom plate is connected to the other end of the body portion. The reaction vessel 110 is installed, for example, such that the extension direction of the body portion (z direction in the figure) is vertical. In this case, the top plate is disposed above the bottom plate.

[0032] Examples of the shape of a cross section (sometimes called a transverse section) of the body section cut along a plane perpendicular to the extension direction of the body section (the xy plane in the drawing) include a circle, an ellipse, a polygon, etc. The shape of the transverse section of the reaction vessel 110 may be a shape that can be substantially regarded as a circle, an ellipse, or a polygon. Examples of polygons include a rectangle, a hexagon, an octagon, etc.

[0033] The internal volume of the main body 112 (sometimes referred to as the capacity of the reaction vessel 110) is not particularly limited, but the internal volume of the main body 112 is preferably 0.01 m 3 or more, and from the viewpoint of reproducibility, 0.01 to 600 m 3 It is preferable that:

[0034] The capacity of the main body 112 is, for example, 1 to 300 ml 3 The lower limit of the capacity of the main body 112 is 40 ml 3 It may be 80m 3 may be 100m 3 It may be 120m 3 It may be 130m 3 It may be 150m 3 It may be 200m 3 It may be 250m 3 The upper limit of the capacity of the main body 112 may be 300 ml. 3 The upper limit of the capacity of the main body 112 is 350 ml. 3 It may be 400m 3 may be also possible.

[0035] The internal capacity of main body 112 is defined as the capacity when main body 112 stores liquid up to a predetermined upper limit position of main body 112. The internal capacity of main body 112 is the internal volume of main body 112 when, for example, no internal structure such as a stirring shaft, blades, baffles, coils, etc. is disposed inside main body 112.

[0036] As described above, in this embodiment, the scale prevention layer 116 is formed on at least a part of the inner surface 114 of the main body 112. The inner surface 114 is a surface that comes into contact with a liquid when the liquid is stored inside the reaction vessel 110. The scale prevention layer 116 is formed, for example, on at least a region of the inner surface 114 of the main body 112 that is submerged in a liquid phase when the polymerization apparatus 100 is used to produce a polymer.

[0037] In this embodiment, the scale prevention layer 116 is formed using a composition including a condensate of an aromatic compound and a carbonyl compound, and a thiol compound. The composition may further include at least one of a solvent, a surfactant, and a pH adjuster.

[0038] For example, a coating solution prepared using the above composition is applied to at least a portion of the inner surface 114 of the body 112 to form the scale prevention layer 116. The coating solution may contain the above composition and at least one of a solvent, a surfactant, and a pH adjuster.

[0039] The scale prevention layer 116 may include a condensate derived from the above composition. The above condensate may be an addition condensate. In one embodiment, the scale prevention layer 116 may include particles mainly composed of a condensate of an aromatic compound and a carbonyl compound. In another embodiment, the scale prevention layer 116 may include a film of a condensate of an aromatic compound and a carbonyl compound. The above composition and coating liquid will be described in detail later. Also, the procedure for forming the scale prevention layer 116 will be described in detail later.

[0040] In this embodiment, the agitator 120 agitates the liquid stored inside the reaction vessel 110. In this embodiment, the agitator shaft 122 holds the agitator blade 124 and rotates the agitator blade 124. In this embodiment, the agitator blade 124 is attached to the agitator shaft 122 and agitates the liquid stored inside the reaction vessel 110.

[0041] The shape of the agitating blade 124 is not particularly limited, but examples of the shape of the agitating blade 124 include Pfaudle blades, blue margin blades, paddle blades, inclined paddle blades, turbine blades, propeller blades, and combinations thereof. As a result, when the agitating shaft 122 rotates, a discharge flow is generated that radially moves from the agitating shaft 122 toward the outer periphery. The number of blades that the agitating blade 124 has is not particularly limited, but examples of the number of blades are 2 to 6. The installation position and the installation number of the agitating blades 124 are not particularly limited, but it is preferable that the agitating blades 124 are installed in multiple stages. Examples of the number of stages of the agitating blades 124 are 2 to 6 stages.

[0042] In this embodiment, the power mechanism 126 rotates the agitation shaft 122. The power mechanism 126 includes, for example, a power unit (not shown) that generates power, and a power transmission unit (not shown) that transmits the power generated by the power unit to the agitation shaft 122. An example of the power unit is an electric motor. An example of the power transmission unit is a reducer.

[0043] The rotation speed of the stirring shaft 122, and the shape, size, number of blades, installation position, installation quantity, and installation interval Pi of the stirring blades 124 are appropriately determined according to the application of the polymerization apparatus 100. The rotation speed of the stirring shaft 122, and the shape, size, number of blades, installation position, installation quantity, and installation interval of the stirring blades 124 are determined in consideration of, for example, the capacity of the reaction vessel 110, the shape of the reaction vessel 110, the internal structure disposed inside the reaction vessel 110, the configuration of the heat removal means, the heat removal capacity, and the composition of the raw materials charged for polymerization.

[0044] For example, when the polymerization apparatus 100 is used for suspension polymerization, the rotation speed of the agitator shaft 122 is determined so that the agitation energy applied to the contents (e.g., an aqueous suspension mixture) is 80 to 200 kgf m / s m3. Here, the "agitation energy" applied to the contents is defined as the net energy required for agitation per unit amount of the contents (sometimes referred to as unit content amount), which is calculated by subtracting various energy losses B such as motor efficiency, conduction loss, mechanical loss, etc. from energy A loaded on the agitator drive motor arranged in the power mechanism 126 during operation of the polymerization apparatus 100. Examples of the unit amount include unit mass and unit volume.

[0045] In this embodiment, the baffle 130 improves the mixing performance of the polymerization apparatus 100. For example, the baffle 130 improves the mixing performance in the vertical direction inside the reaction vessel 110. The installation position of the baffle 130 is not particularly limited, but for example, the baffle 130 is disposed near the inner wall of the reaction vessel 110. The baffle 130 may be supported by the side wall of the reaction vessel 110. In another embodiment, the baffle 130 is supported by the top plate or bottom plate of the reaction vessel 110 and disposed near the stirring blade 124. When the polymerization apparatus 100 is used for the production of a polymer, the baffle 130 may be disposed so that the upper end of the baffle 130 is submerged in the liquid phase, or may be disposed so that the upper end of the baffle 130 is not submerged in the liquid phase.

[0046] The number of baffles 130 is preferably about 1 to 12, more preferably about 2 to 8, more preferably about 3 to 6, and even more preferably about 4 to 6. An even number of baffles 130 are preferably arranged approximately symmetrically around the extension axis (sometimes referred to as the central axis) of the reaction vessel 110. This further improves the mixing performance of the polymerization apparatus 100 and suppresses liquid retention. As a result, the generation of scale can be suppressed.

[0047] In this embodiment, the main body 132 of the baffle 130 improves the mixing performance of the polymerization apparatus 100. The shape of the main body 132 is not particularly limited, but the main body 132 has, for example, a plate-like or cylindrical shape extending approximately parallel to the extension direction of the reaction vessel 110. When the main body 132 has a cylindrical shape, the diameter of the main body 132 may be 40 to 500 mm.

[0048] The length of the body 132 in the extension direction (z direction in the figure) (sometimes referred to as the height of the body 132) is not particularly limited. The length of the body 132 in the direction approximately perpendicular to the extension direction (x or y direction in the figure) (sometimes referred to as the width of the body 132) is not particularly limited. The ratio of the width of the body 132 to the inner diameter of the reaction vessel 110 may be 1 to 10%, may be 2.5 to 7.5%, or may be 3 to 7%.

[0049] When the main body 132 has a cylindrical shape, the ratio of the total value of the cross-sectional area of ​​one or more main bodies 132 each having a cylindrical shape to the cross-sectional area of ​​the straight body part of the reaction vessel 110 may be 0.4 to 3%. When the above ratio is less than 0.4%, the function as a baffle is insufficient, and vertical mixing inside the reaction vessel 110 may be insufficient. For example, when the polymerization apparatus 100 has a single baffle 130, the above ratio may be less than 0.4%. For example, in the suspension polymerization of vinyl chloride monomers, when vertical mixing inside the reaction vessel 110 becomes insufficient, the particle size distribution of the produced polymer may become broad. As a result, when the produced polymer is molded into a sheet, for example, fish eyes may increase, and the quality of the molded product may be reduced.

[0050] On the other hand, if the above ratio exceeds 3%, the power required for the agitator 120 increases excessively. Also, the fluidity of the liquid between the baffle 130 and the inner surface 114 of the reaction vessel 110 may decrease. As a result, scale may easily adhere to the reaction vessel 110 or the internal structure of the reaction vessel 110. For example, if the polymerization apparatus 100 includes more than eight baffles 130, the above ratio may exceed 3% depending on the design of the polymerization apparatus 100.

[0051] The body 132 of at least one baffle 130 may have a flow path for circulating the heat transfer medium. The flow path may be formed inside the body 132, or may be disposed outside the body 132. The flow path may be a single pipe or may have a double pipe structure.

[0052] The heat medium may be a known refrigerant. Examples of the refrigerant include water, brine, freon, and other liquefied gases. When a liquefied gas is used as the refrigerant, the liquefied gas may function as the refrigerant by evaporating inside the cooling pipe 140. The linear velocity of the refrigerant may be about 0.1 to 6.0 m / s.

[0053] The main body 132 is connected to the reaction vessel 110, for example, via a support 134. The distance between the main body 132 and the inner wall surface of the polymerization apparatus 100 is preferably 40 mm or more. If the distance is less than 40 mm, polymer scale may easily adhere between the inner surface 114 of the reaction vessel 110 and the baffle 130 near the gas-liquid interface inside the reaction vessel 110.

[0054] In this embodiment, the support 134 holds the main body 132. For example, one end of the support 134 contacts the inner surface 114 of the reaction vessel 110, and the other end of the support 134 contacts the main body 132. As described above, the support 134 may hold the main body 132 such that the distance between the main body 132 and the inner surface 114 of the reaction vessel 110 is 40 mm or more.

[0055] In this embodiment, the cooling pipe 140 has a flow path therein for circulating a heat medium. The heat medium may be a known refrigerant. Examples of the refrigerant include water, brine, freon, and other liquefied gases. When a liquefied gas is used as the refrigerant, the liquefied gas may function as the refrigerant by evaporating inside the cooling pipe 140. The linear velocity of the refrigerant may be about 0.1 to 6.0 m / s.

[0056] There is no particular limitation on the shape and arrangement of the cooling pipe 140. Examples of the cooling pipe 140 include a ring pipe having a structure in which a plurality of ring-shaped pipes are connected to each other, a spiral pipe that extends in a spiral shape, and a serpentine pipe that extends while meandering.

[0057] In this embodiment, the jacket 170 heats or cools the reaction vessel 110 from outside the reaction vessel 110. As described above, the jacket 170 has the flow path 172 configured to allow a heat medium to flow. The jacket 170 adjusts the amount of heat to be applied to and the amount of heat to be removed from the reaction vessel 110 by controlling at least one of the temperature and the flow rate of the heat medium flowing through the flow path 172.

[0058] The heat medium may be a known refrigerant. Examples of the refrigerant include water, brine, Freon, and various liquefied gases. It is preferable to use a liquid refrigerant as the refrigerant. When a liquefied gas is used as the refrigerant, the liquefied gas may function as the refrigerant by evaporating inside the cooling pipe 140. The linear velocity of the refrigerant may be about 0.1 to 6.0 m / s.

[0059] In this embodiment, the reflux condenser 180 is used to remove heat from the reaction vessel 110. The reflux condenser 180 is attached to the outside of the reaction vessel 110. The reflux condenser 180 condenses a portion of the monomer that evaporates from the solution stored in the reaction vessel 110 during the polymerization reaction of the monomer.

[0060] For example, the reflux condenser 180 is supplied with steam from the reaction vessel 110. The reflux condenser 180 cools and liquefies the steam. The reflux condenser 180 returns the liquid generated by the cooling to the reaction vessel 110. As described above, the reflux condenser 180 has a flow path 182 configured to allow a heat medium to flow. The reflux condenser 180 cools the steam from the reaction vessel 110 by heat exchange between the heat medium flowing through the flow path 182 and the steam from the reaction vessel 110. The amount of heat removed from the reaction vessel 110 can be adjusted by controlling at least one of the temperature and flow rate of the heat medium flowing through the flow path 182.

[0061] In this embodiment, the coating device 190 introduces the above-mentioned coating liquid into the inside of the reaction vessel 110. As a result, the above-mentioned coating liquid is coated on at least a part of the inner surface 114 of the main body 112, and the scale prevention layer 116 is formed. Details of the coating device 190 will be described later.

[0062] I. Overview of Compositions Used to Form Scale Prevention Layer 116 In this embodiment, the composition includes, for example, (i) an addition condensation product of an aromatic compound and a carbonyl compound, and (ii) a thiol compound. The composition may include (i) an addition condensation product of an aromatic compound and a carbonyl compound, (ii) a thiol compound, and (iii) at least one of a solvent, a surfactant, and a pH adjuster.

[0063] By containing a thiol compound in the composition, aggregation and / or precipitation of the above-mentioned addition condensation product during the composition production process is suppressed. As a result, the degree of freedom in adjusting the composition and / or the coating liquid is improved. In addition, for example, even when the composition and / or the coating liquid is heated by steam, the decomposition of the addition condensation product contained in the composition and / or the coating liquid can be suppressed.

[0064] The composition may comprise a mixture of isomers of an addition condensation product of an aromatic compound and a carbonyl compound, for example, a linear condensation product of an aromatic compound and a carbonyl compound, and a cyclic condensation product of an aromatic compound and a carbonyl compound.

[0065] In the above composition, the aromatic compound is, for example, naphthols. The aromatic compound may be at least one selected from the group consisting of 1-naphthol, 2-naphthol, and derivatives thereof. The aromatic compound may be 1-naphthol, 2-naphthol, or derivatives thereof.

[0066] The derivative of 1-naphthol or 2-naphthol may be a compound in which at least one of the hydrogen atoms bonded to the aromatic ring of 1-naphthol or 2-naphthol is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group, and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group). 1-naphthol, 2-naphthol, and the above derivatives have similar reactivity with carbonyl compounds. Therefore, the decomposition behavior in steam of the addition condensation product of 1-naphthol, 2-naphthol, or the above derivatives and the carbonyl compound may also be similar.

[0067] In the above composition, the carbonyl compound is, for example, an aldehyde compound or a ketone compound. The carbonyl compound may be an aldehyde compound or a ketone compound having 1 to 20 carbon atoms. The carbonyl compound may be formaldehyde, acetaldehyde, terephthalaldehyde, benzaldehyde, or a derivative thereof (sometimes referred to as a derivative of a specific aldehyde compound). The ketone compound may be acetone, methyl ethyl ketone, acetylacetone, or a derivative thereof (sometimes referred to as a derivative of a specific ketone compound).

[0068] The derivative of the specific aldehyde compound may be a compound in which at least one hydrogen atom contained in the specific aldehyde compound is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group, and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group).

[0069] The derivative of the specific ketone compound may be a compound in which at least one of the hydrogen atoms contained in the specific ketone compound is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group, and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group). The specific aldehyde compound, the specific ketone compound, and their derivatives have similar reactivity with aromatic compounds. Therefore, the decomposition behavior in steam of the addition condensation product of the specific aldehyde compound, the specific ketone compound, or the above derivative and an aromatic compound may also be similar.

[0070] In the above composition, the thiol compound has, for example, a thiol group and at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. The thiol compound may be at least one selected from the group consisting of thioglycerol, thioglycol, and derivatives thereof. The thiol compound may be 1-thioglycerol or thioglycol.

[0071] The derivative of 1-thioglycerol or thioglycol may be a compound in which at least one hydrogen atom contained in 1-thioglycerol or thioglycol is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, and / or an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group). The above derivative is expected to inhibit the decomposition of the above addition condensate to the same extent as 1-thioglycerol or thioglycol.

[0072] In one embodiment, the composition contains, for example, 0.01 parts by mass or more and 100 parts by mass or less of a thiol compound per 100 parts by mass of an aromatic compound. This can sufficiently suppress the aggregation and / or precipitation of the addition condensate in the production process of the composition. As a result, the degree of freedom in adjusting the composition and / or the coating liquid is further improved. In addition, even when the composition and / or the coating liquid is heated by steam, the decomposition of the addition condensate contained in the composition and / or the coating liquid can be further suppressed.

[0073] In another embodiment, the composition includes, for example, a first type of addition condensate (sometimes referred to as a first condensate) and a second type of addition condensate (sometimes referred to as a second condensate). In this embodiment, the first condensate has a first average molecular weight. The second condensate has a second average molecular weight. In this embodiment, each of the first condensate and the second condensate is an addition condensate of an aromatic compound and a carbonyl compound. In addition, the first average molecular weight and the second average molecular weight are different. The second average molecular weight may be larger than the first average molecular weight.

[0074] For example, when the second average molecular weight is larger than the first average molecular weight, in the above composition, the ratio of the mass of the second condensate to the mass of the first condensate (sometimes referred to as the mass ratio or content ratio of the second condensate to the first condensate) may be 2.3 to 1000. The above content ratio is preferably 2.3 to 100, more preferably 2.3 to 10. The above content ratio may be 2.7 to 1000, 2.7 to 100, or 2.7 to 10. As described above, the above content ratio is obtained, for example, by dividing the mass of the second condensate contained in the above composition by the mass of the first condensate contained in the composition.

[0075] When the content ratio in the composition is 2.3 or more, the content ratio in the coating film obtained by applying the composition by a steam coating method is relatively large. Specifically, the content ratio in the coating film can be maintained at, for example, 0.75 or more (preferably, for example, 0.8 or more). When the content ratio in the coating film is large, the strength of the coating film is improved. As a result, for example, when a polymer is produced using a reactor or polymerization vessel having the coating film, the anti-scaling performance can be maintained until the end of polymerization.

[0076] When the content ratio in the composition is 1000 or less, the strength of the coating film obtained by applying the composition by the steam coating method can be appropriately adjusted. If the strength of the coating film is too high, when a polymer is produced using a reactor or polymerization vessel having the coating film, a relatively large amount of the coating film remains on the inner surface of the reactor or polymerization vessel at the stage when the polymerization in each batch is completed. Therefore, the amount or thickness of the coating film accumulated on the inner surface of the reactor or polymerization vessel increases as the number of batches increases. As a result, the heat removal efficiency of the reactor or polymerization vessel decreases.

[0077] If the strength of the coating film is not properly adjusted, for example, even if the number of repeated polymerization treatments is less than 100 batches, the heat removal efficiency of the reactor or polymerization vessel is significantly reduced. On the other hand, if the content ratio in the composition is 1000 or less, the strength of the coating film is properly adjusted, and the reduction in the heat removal efficiency of the reactor or polymerization vessel is suppressed. As a result, if the content ratio is 1000 or less, for example, continuous operation of 100 batches or more is possible. If the content ratio is 100 or less, for example, continuous operation of 500 batches or more is possible. If the content ratio is 10 or less, for example, continuous operation of 1000 batches or more is possible.

[0078] For example, the first addition condensate is a cyclic condensate of an aromatic compound and a carbonyl compound, and the second addition condensate is a linear condensate of an aromatic compound and a carbonyl compound. In this case, the second average molecular weight may be larger than the first average molecular weight. When the composition contains a linear condensate having a relatively large average molecular weight and a cyclic condensate having a relatively small average molecular weight, for example, when the composition is used as a scale adhesion inhibitor, the strength of the coating film (sometimes referred to as a scale adhesion prevention layer) derived from the composition is improved. As a result, for example, when a polymer is produced using a reactor or polymerization vessel having the above coating film, the scale adhesion prevention performance can be maintained until the end of polymerization.

[0079] The ratio of the mass of the second condensate to the mass of the first condensate in the composition or coating film is calculated, for example, from the area ratio of two peaks among a plurality of peaks obtained by analyzing the composition by liquid chromatography analysis (sometimes called LC method). As the LC method, high performance liquid chromatography analysis (sometimes called HPLC method) may be used.

[0080] When the composition contains two or more components with different average molecular weights, multiple peaks including a peak corresponding to a relatively low molecular weight component (sometimes referred to as a low molecular weight component) and a peak corresponding to a relatively high molecular weight component (sometimes referred to as a high molecular weight component) are observed when the composition is analyzed by LC. The area of ​​each peak is proportional to the content (e.g., mass %) of the component corresponding to each peak in the composition.

[0081] In the LC method, the position of each peak can be identified, for example, by the retention factor of the component corresponding to each peak. The retention factor k of a particular component is determined by the hold-up time t O and the retention time t of the particular component. R Using these, it is derived by the following Equation 1. (Formula 1) k=(t R -t O ) / t O

[0082] When comparing the retention times of two compounds with different molecular weights, the retention factors of the two compounds are often different. Similarly, the retention factor of a compound with a higher molecular weight is often greater than that of a compound with a lower molecular weight.

[0083] The composition may contain three or more kinds of addition condensates having different average molecular weights. Each of the three or more kinds of addition condensates may be an addition condensate of an aromatic compound and a carbonyl compound.

[0084] According to this embodiment, for example, by adjusting the amount of at least one of the thiol compound, the surfactant, and the pH adjuster, a composition having various properties can be prepared. This allows the decomposition of the addition condensate contained in the composition and / or the coating liquid to be sufficiently suppressed even when the composition and / or the coating liquid is heated by steam.

[0085] (Details of the LC analysis procedure) The above-mentioned analysis by the LC method is carried out, for example, according to the following procedure. First, a chromatograph is prepared. The details of the chromatograph are not particularly limited, and the specific configuration of the chromatograph is appropriately selected according to the addition condensation product to be analyzed.

[0086] As the chromatograph, for example, Nexera / Prominence, a general-purpose HPLC manufactured by Shimadzu Corporation, is used. As the system controller of the above chromatograph, for example, SCL-40 (manufactured by Shimadzu Corporation) is used. As the liquid delivery unit of the above chromatograph, for example, two LC-40D (manufactured by Shimadzu Corporation) are used. As the online degassing device of the above chromatograph, for example, DGU-403 (manufactured by Shimadzu Corporation) is used. As the autosampler of the above chromatograph, for example, SIL-20ACHT (manufactured by Shimadzu Corporation) is used. As the column oven of the above chromatograph, for example, CTO-20A (manufactured by Shimadzu Corporation) is used. As the UV-VIS detector of the above chromatograph, for example, SPD-20A (manufactured by Shimadzu Corporation) is used.

[0087] Next, a guard column and an analytical column are prepared. The details of the guard column and the analytical column are not particularly limited, and the specific configurations of the guard column and the analytical column are appropriately selected depending on the addition condensation product to be analyzed.

[0088] As the guard column, for example, Waters Puresil® C18 guard column (100 Å, 5 μm, 3.9 mm×20 mm×1 column) is used. As the analytical column, for example, Waters μ-Bondasphere / DeltaPak® C18 column (100 Å, 5 μm, 3.9 mm×150 mm×1 column) is used.

[0089] Next, an eluent is prepared. In this embodiment, two types of eluent are prepared. Specifically, for example, a solution in which 2 mL of acetic acid is added per 1 L of distilled water (sometimes referred to as eluent A) and a solution in which 1 mL of acetic acid is added per 1 L of acetonitrile (sometimes referred to as eluent B) are prepared.

[0090] (Hold-up time t O Measurement of Next, the hold-up time t, which indicates the time it takes for the unretained material to pass through the column, is calculated according to the following procedure: O is measured. First, an aqueous uracil solution is prepared as a sample for measuring the hold-up time. Specifically, 10 g of distilled water is mixed with 1 mg of uracil. Next, the mixed solution is filtered using a polytetrafluoroethylene filter with a pore size of 0.45 μm. This gives an aqueous uracil solution.

[0091] Next, the uracil aqueous solution after the filtration process is placed in the above-mentioned chromatograph, and measurement of the hold-up time is started. At this time, the temperature of the column oven is set to, for example, 40° C. The detection wavelength of the UV-VIS detector is set to, for example, 288 nm. The injection amount of the uracil aqueous solution to be analyzed is set to, for example, 20 μL. The total flow rate of the eluent A and the eluent B is set to, for example, 1.0 mL / min.

[0092] As for the gradient conditions of the eluent, first, the ratio of eluent B to the total volume of the eluent is set to 40% by volume. Next, the ratio of eluent B to the total volume of the eluent is changed linearly from 40% by volume to 100% by volume over 30 minutes. After that, the state where the ratio of eluent B to the total volume of the eluent is 100% by volume is maintained for 10 minutes.

[0093] After the hold-up time measurement is started, the time until the first peak is observed is measured. The retention time of the first observed peak is the hold-up time t O Represents.

[0094] (Preparation of Samples Containing Addition Condensation Products) Next, a sample containing an addition condensate of an aromatic compound and a carbonyl compound is prepared. In one embodiment, the above composition is used as the sample. The above composition may be prepared or may be purchased. In this way, the sample containing the addition condensate is prepared. In another embodiment, the sample is prepared using a coating film formed by the above composition. In this way, the sample containing the addition condensate is prepared. The coating film may be a coating film formed by steam coating.

[0095] The procedure for preparing the above sample using the coating film is not particularly limited, but for example, the above sample is prepared using the coating film attached to the inner surface 114 of the reaction vessel 110 by the following procedure. First, a sample of the coating film is obtained from the area inside the reaction vessel 110 where the coating film is attached. Specifically, a swab impregnated with N-methyl-2-pyrrolidone (sometimes referred to as NMP) is rubbed on a 10 cm x 10 cm square area included in the above area. Since the addition condensation product contained in the coating film dissolves in NMP, the NMP solution containing the addition condensation product is retained on the swab. In this way, a sample of the coating film is obtained.

[0096] Next, 10.0 mL of NMP and 20 μL of 0.5 N hydrochloric acid are mixed. This prepares a solvent for recovering the NMP solution containing the addition condensation product from the swab. Next, the above solvent is dropped onto the swab in 10 portions of 100 μL each. Also, the washings from the swab are recovered. This gives a sample containing the addition condensation product.

[0097] (The retention time t R Measurement of First, the sample containing the above-mentioned addition condensate is filtered using a polytetrafluoroethylene filter having a pore size of 0.45 μm. Next, the sample after the filtration process (i.e., the filtrate obtained by the filtration process) is set in the above-mentioned chromatograph, and the measurement of the retention time is started.

[0098] retention time t R The measurement conditions are the hold-up time t O The measurement conditions may be the same as those of . Specifically, the temperature of the column oven is set to, for example, 40°C. The detection wavelength of the UV-VIS detector is set to, for example, 288 nm. The injection amount of the sample to be analyzed is set to, for example, 20 μL. The total flow rate of the above-mentioned eluent A and eluent B is set to, for example, 1.0 mL / min.

[0099] As for the gradient conditions of the eluent, first, the ratio of eluent B to the total volume of the eluent is set to 40% by volume. Next, the ratio of eluent B to the total volume of the eluent is changed linearly from 40% by volume to 100% by volume over 30 minutes. After that, the state where the ratio of eluent B to the total volume of the eluent is 100% by volume is maintained for 10 minutes.

[0100] (Derivation of the content ratio of the second condensate to the first condensate) As described above, the composition may include two or more kinds of addition condensates, each of which is an addition condensate of an aromatic compound and a carbonyl compound and has a different average molecular weight.

[0101] The content ratio (sometimes referred to as the content) of each addition condensate in the composition can be derived, for example, based on the area of ​​one or more peaks (sometimes referred to as the peak area) appearing in the measurement results (sometimes referred to as the chromatogram) of the LC method. The content ratio is, for example, mass %. As described above, in the LC method, the position of each peak is specified by the retention coefficient of the component corresponding to each peak.

[0102] For example, when the composition contains at least a first condensate having a first average molecular weight and a second condensate having a second average molecular weight, the content ratio of the first condensate in the composition is proportional to the total area of ​​one or more peaks appearing between the first retention index k1 and the second retention index k2 in the chromatogram. The total value may be derived as the content ratio of the first condensate.

[0103] Similarly, the content ratio of the second condensate in the composition is proportional to the total area of ​​one or more peaks appearing between the third retention index k3 and the fourth retention index k4 in the chromatogram. The total value may be derived as the content ratio of the second condensate.

[0104] The first retention factor k1 may be smaller than the second retention factor k2. The second retention factor k2 may be smaller than the third retention factor k3. The third retention factor k3 may be smaller than the fourth retention factor k4. The first retention factor k1 may be 0 or more. The fourth retention factor k4 may be greater than 0 and equal to or less than 25.

[0105] For example, when the combination of the aromatic compound and the carbonyl compound constituting the first condensate is the same as the combination of the aromatic compound and the carbonyl compound constituting the second condensate, the first retention factor k1 may be a retention factor corresponding to the first peak of the aromatic compound dimer produced by the reaction of the aromatic compound and the carbonyl compound in a molar ratio of 2:1. The second retention factor k2 may be a retention factor corresponding to the last peak of the aromatic compound cyclic tetramer produced by the reaction of the aromatic compound and the carbonyl compound in a molar ratio of 4:4. The third retention factor k3 may be a retention factor corresponding to the peak appearing next to the peak corresponding to the second retention factor k2. The fourth retention factor k4 may be 25.

[0106] For example, when the aromatic compound is α-naphthol and the carbonyl compound is formaldehyde, the first retention factor k1 may be 7 or more, and the second retention factor k1 may be less than 16. The third retention factor k3 may be 16 or more, and the fourth retention factor k4 may be 25 or less.

[0107] In this case, the content ratio of the first condensate in the composition is proportional to the total area of ​​one or more peaks appearing in a retention index between 7 and less than 16. Similarly, the content ratio of the second condensate in the composition is proportional to the total area of ​​one or more peaks appearing in a retention index between 16 and 25.

[0108] As described above, in the above composition, the content ratio of the second condensate to the first condensate is obtained by dividing the mass of the second condensate contained in the composition by the mass of the first condensate contained in the composition. The above content ratio can be derived as the ratio of the content ratio of the second condensate in the composition to the content ratio of the first condensate in the composition. The above content ratio in the coating film can be derived according to the same procedure as the above content ratio in the composition.

[0109] According to the composition of this embodiment, since the content ratio falls within the above-mentioned numerical range, the coating film produced using the composition contains a large amount of addition condensation products having a relatively large molecular weight. This prevents the coating film from being scraped off by the polymerization slurry during the period when the polymerization reaction is proceeding inside the reaction vessel. As a result, for example, the anti-scaling performance can be maintained until the end of the polymerization.

[0110] (Effect of steam exposure on content ratio) As described above, depending on the composition of the scale adhesion inhibitor, when the scale adhesion inhibitor is introduced into the inside of a reaction vessel using steam, the active ingredient of the scale adhesion inhibitor may be thermally decomposed, which may result in difficulty in use as a scale adhesion inhibitor. In contrast, since the composition according to the present embodiment contains a thiol compound, even when the composition is exposed to steam under certain conditions, for example, thermal decomposition of the second condensate having a relatively large average molecular weight may be suppressed. As a result, the decrease in the content ratio of the second condensate to the first condensate described above may be suppressed.

[0111] According to this embodiment, the decrease in the content ratio is suppressed, so that, for example, even if the coating film is produced by a steam coating method, the coating film contains a large amount of addition condensation products having a relatively large molecular weight. This suppresses the coating film from being scraped off by the polymerization slurry during the period in which the polymerization reaction proceeds inside the reaction vessel. As a result, the anti-scaling performance can be maintained until the end of the polymerization.

[0112] According to this embodiment, the content ratio of the second condensate to the first condensate in the composition exposed to steam under specific conditions is, for example, 0.75 to 1000. The above content ratio may be 0.75 to 100, or 0.75 to 10. The above content ratio may be 0.8 to 1000, or 0.8 to 100, or 0.8 to 10.

[0113] In one embodiment, the specific condition may be exposure to steam at 0.717 MPaG (171.4°C) for 120 seconds. In another embodiment, the specific condition may be exposure to steam at an internal volume of 2 m 3 The above composition may be flowed into a cylindrical reactor having a flow rate of 10.8 kg / h for 120 seconds using 240 kg / h of steam at 0.717 MPaG (171.4° C.) as a carrier.

[0114] II. Composition of the Composition (A. Addition Condensation Product) As described above, the composition includes an addition condensate of an aromatic compound and a carbonyl compound. The composition may include (i) a linear condensate of an aromatic compound and a carbonyl compound, (ii) a cyclic condensate of an aromatic compound and a carbonyl compound, or (iii) a mixture of the linear condensate and the cyclic condensate. The addition condensate may be present as a salt in the composition. As described above, in this embodiment, the term addition condensate means the addition condensate and / or the salt of the addition condensate.

[0115] The above-mentioned addition condensate may be an aromatic compound multimer in which two or more aromatic compound-derived structural units are bonded via one carbonyl compound-derived structural unit, respectively. Specifically, the aromatic compound has a portion constituting the aromatic compound-derived structural unit (A) in the addition condensate. The carbonyl compound has a portion constituting the carbonyl compound-derived structural unit (B) in the addition condensate. The aromatic compound dimer is, for example, a compound having an ABA structure. The aromatic compound multimer is, for example, a compound having an ABA-...-BA structure in which "A" and "B" are arranged alternately.

[0116] The addition condensate can be obtained, for example, by reacting an aromatic compound and a carbonyl compound in the presence of a catalyst and a surfactant. The addition condensate can be obtained, for example, by (i) preparing a mixture of a reaction solvent, an aromatic compound, a carbonyl compound, and a thiol compound, and (ii) reacting the aromatic compound and the carbonyl compound in the mixture in the presence of a catalyst and a surfactant.

[0117] (aromatic compounds) Examples of the aromatic compound include benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, and non-benzene aromatic compounds. The aromatic compound may be a compound selected from the group consisting of benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, and non-benzene aromatic compounds, and may be a compound containing 3 to 20 conjugated π bonds. A single type of aromatic compound may be used, or two or more types of aromatic compounds may be used in combination.

[0118] Examples of benzene derivatives include (i) phenols and their derivatives, (ii) aromatic amines and their derivatives, (iii) nitro and nitroso derivatives, (iv) aromatic aldehydes, (v) benzene derivatives having one more substituent besides the aldehyde group, (vi) benzene derivatives having one more substituent besides the acyl group, (vii) benzene or toluene derivatives having three or more different substituents, (viii) aralkyl compounds, and (ix) at least one compound selected from the group consisting of diazo compounds and azo compounds. Examples of phenols and their derivatives include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, and 3,5-dimethylphenol. Examples of aromatic amines and their derivatives include pyridine, quinoline, carbazole, o-phenanthroline, p-phenanthroline, 3,6-diaminoacridine, 3-aminophenothiazine, 2-aminophenazine, phenothiazine, and 2-hydroxy-4-methylquinoline. Examples of nitro and nitroso derivatives include nitrobenzene, phenazine, phenazine oxide, 1-phenylazo-2-naphthol, trifluorodioxazine, and 4-nitroxanthone. Examples of aromatic aldehydes include benzaldehyde and benzoflavin. Examples of benzene derivatives having one more substituent besides the aldehyde group include 1-hydroxy-2,4-methylfluorone, 3-phenylcoumarone, coumarin-3-carboxylic acid ethyl ester, 3-acetylcoumarin, 5-chloro-3-(4-hydroxyphenyl)anthranyl, and 3-nitroacridone. Examples of benzene derivatives having one more substituent besides the acyl group include xanthone, 2-benzoylxanthone, xanthene, and fluorene. Examples of benzene or toluene derivatives having three or more different substituents include 7-acetoxy-8-methoxy-3-(2-nitrophenyl)carbosteryl. Examples of aralkyl compounds include 9-benzylacridine. Examples of diazo compounds and azo compounds include 1,1'-azonaphthalene and azoxyphenol.

[0119] Examples of naphthalene derivatives include at least one compound selected from the group consisting of (i) alkyl, alkenyl and phenylnaphthalenes, (ii) dinaphthyls, (iii) naphthylarylmethanes, (iv) naphthylarylethanes, (v) hydronaphthalenes, (vi) nitronaphthalene and its derivatives, (vii) halogenated naphthalenes, (viii) naphthylhydroxylamines, naphthylpyrazines and naphthylureas, (ix) naphthalene-based aralkyl compounds, (x) naphthaldehydes and their derivatives, (xi) acetonaphthene and benzoylnaphthalenes, and (xii) naphthols. Examples of alkyl, alkenyl and phenylnaphthalenes include 2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1,2-dimethylnaphthalene, etc. Examples of dinaphthyls include 1,1'-dinaphthyl, 1,2'-dinaphthyl, and 2,2'-dinaphthyl. Examples of naphthylarylmethanes include 1-benzylnaphthalene, 2-benzylnaphthalene, 1-(α,α-dichlorobenzyl)naphthalene, diphenyl-α-naphthylmethane, diphenyl-β-naphthylmethane, and di-α-naphthylmethane. Examples of naphthylarylethanes include 1,2-di-α-naphthylmethane and 1,2-di-β-naphthylmethane. Examples of hydronaphthalenes include 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, and 1,2,3,4-tetrahydronaphthalene. Examples of nitronaphthalene and its derivatives include nitromethylnaphthalene, nitroalkylnaphthalene, nitrophenylnaphthalene, halonitronaphthalene, halodinitronaphthalene, nitrosonaphthalene, diaminonaphthalene, triaminonaphthalene, tetraaminonaphthalene, etc. Examples of halogenated naphthalenes include 1-fluoronaphthalene, 1-chloronaphthalene, 1-chloro-3,4-dihydronaphthalene, etc. Examples of naphthylhydroxylamine, naphthylpyrazine, and naphthylureas include α-naphthylhydroxylamine, β-naphthylthiohydroxylamine, N-nitroso-α-naphthylhydroxylamine, α-naphthylhydrazine, 1,2-dibenzocarbazole, etc.Examples of naphthalene-based aralkyl compounds include dibenzanthracene, acenaphthene, diphenylnaphthyl chloromethane, and nitromethylnaphthalene. Examples of naphthaldehydes and their derivatives include α-naphthaldehyde and 2-(2,4-dinitrophenyl)-1-(α-naphthyl)ethylene. Examples of acetonaphthene and benzoylnaphthalenes include (1,2 or 5,6-)dibenzanathracene, 2'-methyl-2,1'-dinaphthyl ketone, 2-methyl-1,1'-dinaphthyl ketone, and styryl-2-naphthyl ketone. Examples of naphthols include 1-naphthol (sometimes referred to as α-naphthol), 2-naphthol (sometimes referred to as β-naphthol), 1,3-dihydroxy-naphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 6-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 1-hydroxy-8-naphthoic acid.

[0120] Examples of polynuclear aromatic compounds include at least one compound selected from the group consisting of (i) anthracenes and their derivatives, (ii) phenanthrenes and their derivatives, and (iii) other polynuclear aromatic compounds and their derivatives. Examples of anthracenes and their derivatives include anthracene, 1,2-dihydroanthracene, 1-chloroanthracene, 1,4-dichloroanthracene, 1-nitroanthracene, 9,10-dinitroanthracene, 1-aminoanthracene, 2-dimethylaminoanthracene, 2-anilinoanthracene, 9-methylaminoanthracene, and 1,4-diaminoanthracene. Examples of phenanthrene and its derivatives include phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenanthrene, and 1-chlorophenanthrene. Other examples of polynuclear aromatic compounds and their derivatives include pentacene, hexacene, benzophenanthrene, benzo[a]anthracene, pyrene, and coronene.

[0121] Examples of non-benzene aromatic compounds include azulene, cyclodecapentane, cyclotetradecaheptane, cyclooctadecanonaene, cyclotetracosadodecane, heptalene, fulvalene, sesquifulvalene, heptafulvalene, perinaphthene, etc. The non-benzene aromatic compound may be a derivative of the above compounds.

[0122] As the aromatic compound, naphthols may be used. This allows the addition condensation product to be produced under mild conditions. As a result, the production cost of the addition condensation product can be reduced. As the aromatic compound, a compound represented by the following general formula (1) may be used.

[0123] (General formula 1) [ka]

[0124] In the general formula (1), R 1 , R 2 , R 3 are each a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an n-octyl group.

[0125] In the general formula (1), R 1 , R 2 , R 3 are each a hydrogen atom or a hydrocarbon group, and each of the hydrocarbon groups is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or an n-octyl group, has a similar reactivity with a carbonyl compound. Therefore, the decomposition behavior in steam of the addition condensation product of the aromatic compound represented by the general formula (1) and the carbonyl compound may also be similar.

[0126] As the aromatic compound, 1-naphthol, 2-naphthol or a derivative thereof is preferably used. The derivative of 1-naphthol or 2-naphthol may be a compound in which at least one hydrogen atom bonded to the aromatic ring of 1-naphthol or 2-naphthol is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group). The aromatic compound may be 1-naphthol.

[0127] (Carbonyl compounds) The carbonyl compound may be an organic compound having a carbonyl group, and the details thereof are not particularly limited. A single type of carbonyl compound may be used, or two or more types of carbonyl compounds may be used in combination. Examples of the carbonyl compound include aldehydes (sometimes called aldehyde compounds), ketones (sometimes called ketone compounds), and derivatives thereof. The carbonyl compound may be an aldehyde compound or a ketone compound having 1 to 20 carbon atoms.

[0128] Examples of aldehydes include formaldehyde, acetaldehyde, terephthalaldehyde, and derivatives thereof. The derivatives of the aldehyde compounds may be compounds in which at least one hydrogen atom contained in the aldehyde compound is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group, and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group). The carbon number of the substituent may be adjusted so that the aldehyde compound has 1 to 20 carbon atoms.

[0129] Examples of ketones include acetone, methyl ethyl ketone, acetylacetone, and derivatives thereof. The derivatives of the ketone compounds may be compounds in which at least one of the hydrogen atoms contained in the ketone compounds is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group), an amino group, and / or a thiol group. The thiol group may be a thiol group having 1 to 20 carbon atoms (for example, an alkanethiol group). The carbon number of the substituent may be adjusted so that the carbon number of the aldehyde compound is 1 to 20.

[0130] The carbonyl compound may be an aldehyde compound represented by the following general formula (2), which can reduce the production cost of the addition condensation product.

[0131] (General formula 2) R 1 -CHO In the above general formula (2), R 1 is a hydrogen atom or a hydrocarbon group. The carbon number of the above hydrocarbon group may be 1 to 20. The carbon number of the above hydrocarbon group may be 1 to 19. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an n-octyl group.

[0132] In the general formula (2), R 1 A compound in which is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 19 carbon atoms has a similar reactivity with an aromatic compound. Therefore, the decomposition behavior in steam of an addition condensation product of an aromatic compound and an aldehyde compound represented by general formula (2) may also be similar.

[0133] As the carbonyl compound, formaldehyde and / or acetaldehyde may be used. The carbonyl compound may be formaldehyde.

[0134] (Specific examples of combinations of aromatic compounds and carbonyl compounds) In one embodiment, the aromatic compound may be a compound represented by the above general formula (1), and the carbonyl compound may be an aldehyde compound represented by the above general formula (2). In another embodiment, the aromatic compound may be 1-naphthol, and the carbonyl compound may be formaldehyde.

[0135] (B. Thiol Compounds) As described above, the composition includes a thiol compound. A single type of thiol compound may be used, or two or more types of thiol compounds may be used in combination.

[0136] The thiol compound may be an organic compound having a thiol group, and the details thereof are not particularly limited. The thiol compound has, for example, a thiol group and at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. The thiol compound preferably has at least one hydroxyl group.

[0137] This can provide the thiol compound with water solubility and surface activity. The thiol compound may be present as a salt in the composition. As described above, in this embodiment, the term thiol compound refers to the thiol compound and / or the salt of the thiol compound.

[0138] Examples of thiol compounds include alkyl mercaptans, aromatic mercaptans, thiocarboxylic acids, thiocarboxylic acid alkyl esters, nitrogen-containing thiols, polythiols, and mixtures thereof. Examples of alkyl mercaptans include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan. Examples of aromatic mercaptans include benzyl mercaptan, dodecyl benzyl mercaptan, and p-chlorobenzyl mercaptan. Examples of thiocarboxylic acids include thioacetic acid, thiopropionic acid, thiobutyric acid, thiovaleric acid, thiolactic acid, 3-mercaptopropionic acid, thiosuccinic acid, and thiobenzoic acid. Examples of alkyl thiocarboxylates include glycerol monothiolactate, ammonium thiolactate, MEA-thiolactate, glycerol 3-mercaptopropionate, ethylene glycol 3-mercaptopropionate, n-butyl mercaptopropionate, n-butyl thioglycolate, ethyl thioglycolate, isooctyl thioglycolate, dodecyl mercaptopropionate, octadecyl mercaptopropionate, and tridecyl thioglycolate.

[0139] Examples of nitrogen-containing thiols include cysteamine, N-acetylcysteamine, N-propionylcysteamine, cysteine, N-acetylcysteine, N-alkanoylcysteine, cysteine ​​alkyl esters, homocysteine, thioglycolic acid, ethanolamine thioglycolate, glyceryl thioglycolate, thiomalic acid, glutathione, α-thioglycerol (sometimes referred to as 1-thioglycerol, 3-mercapto-1,2-propanediol, etc.), thioglycol (sometimes referred to as β-mercaptoethanol, 2-mercaptoethanol, etc.), thiodiglycol, dithiothreitol, thioxanthine, thiosalicylic acid, thiopropionic acid, lipoic acid, monoethanolamine thioglycolate, 2-dimethylamineethanethiol hydrochloride, 2-dimethylaminoethanethiol hydrochloride, diaminopropanethiol hydrochloride, and 2-mercaptoamine hydrochloride. Examples of polythiols include 2,2'-dimercaptodiethyl ether, dithiol terephthalic acid, glycol dimercaptoacetate, pentaerythritol tetrathioglycolate, trimethylolethane trithioglycolate, and trimethylolpropane trithioglycolate.

[0140] As described above, the thiol compound may be at least one selected from the group consisting of thioglycerol, thioglycol, thiodiglycol, and derivatives thereof. The thiol compound may be at least one selected from the group consisting of thioglycerol, thioglycol, and derivatives thereof. The derivative of thioglycerol, thioglycol, or thiodiglycol may be a compound in which at least one hydrogen contained in thioglycerol, thioglycol, or thiodiglycol is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, and / or an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group).

[0141] The thiol compound may be 3-mercapto-1,2-propanediol, 2-mercaptoethanol, or a derivative thereof. The above derivative may be a compound in which at least one hydrogen atom contained in 3-mercapto-1,2-propanediol or 2-mercaptoethanol is substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, and / or an aminoalkyl group having 1 to 20 carbon atoms (sometimes referred to as an alkylamino group). The thiol compound may be 3-mercapto-1,2-propanediol and / or 2-mercaptoethanol.

[0142] The composition contains, for example, 0.01 parts by mass or more and 100 parts by mass or less of a thiol compound relative to 100 parts by mass of an aromatic compound. The composition may contain 0.1 parts by mass or more and 20 parts by mass or less of a thiol compound relative to 100 parts by mass of an aromatic compound, may contain 0.1 parts by mass or more and 10 parts by mass or less of a thiol compound relative to 100 parts by mass of an aromatic compound, may contain 0.5 parts by mass or more and 10 parts by mass or less of a thiol compound relative to 100 parts by mass of an aromatic compound, or may contain 1 part by mass or more and 5 parts by mass or less of a thiol compound relative to 100 parts by mass of an aromatic compound.

[0143] The content ratio of the aromatic compound in the composition is identified, for example, by using a mass spectrometer (sometimes referred to as MS) as a detector in the above-mentioned LC method (sometimes referred to as LC / MS method).Similarly, the content of the thiol compound in the composition is identified, for example, by the above-mentioned LC / MS method. (C. Solvent) As described above, the composition may contain a solvent (sometimes referred to as a reaction solvent). The solvent may be a compound that is liquid under the reaction conditions for producing the above-mentioned addition condensation product, and the details thereof are not particularly limited. Examples of the reaction conditions include reaction temperature and reaction pressure. A single type of solvent may be used, or two or more types of solvents may be used in combination.

[0144] Examples of the reaction solvent include water or an organic solvent. Examples of the organic solvent include alcohols, ketones, esters, and amides. Examples of the alcohols include methanol, ethanol, and propanol. Examples of the ketones include acetone and methyl ethyl ketone. Examples of the esters include methyl acetate and ethyl acetate. Examples of the amides include dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0145] The content of the solvent in the composition is, for example, 95% by mass or less. This allows the components of the composition other than the solvent to be applied efficiently. The content of the solvent in the composition may be 50% by mass or more and 95% by mass or less.

[0146] (D. Surfactants) As described above, the composition may contain a surfactant. The surfactant is, for example, a compound containing a hydrophilic group and a hydrophobic group (sometimes referred to as a surface active compound). A single type of surfactant may be used, or two or more types of surfactants may be used in combination. Examples of the surfactant include known compounds used in the production of the above-mentioned addition condensation products, and known compounds added to scale adhesion inhibitors (for example, scale adhesion inhibitors used in the polymerization of polyvinyl chloride).

[0147] The composition contains, for example, 0.01 equivalent or more of a surfactant relative to the aromatic compound. The composition may contain 0.1 equivalent or more and 5.0 equivalent or less of a surfactant relative to the aromatic compound, or may contain 0.5 equivalent or more and 2.0 equivalent or less of a surfactant. This improves the stability of an aqueous solution of the composition when the composition is used as a scale adhesion inhibitor.

[0148] The content of the surfactant in the composition is, for example, 0.01 equivalent or more relative to the structural unit derived from the aromatic compound contained in the addition condensate. The content of the surfactant in the composition may be 0.1 equivalent or more and 5.0 equivalent or less, or 0.5 equivalent or more and 2.0 equivalent or less, relative to the structural unit derived from the aromatic compound contained in the addition condensate.

[0149] The surfactant is added to the reaction system together with a catalyst for the condensation reaction, for example, in the process of producing an addition condensation product. The surfactant is added to the reaction system, for example, in an amount of 0.01 equivalent or more relative to the aromatic compound. The surfactant may be added to the reaction system, for example, in an amount of 0.1 equivalent or more and 5.0 equivalents or less relative to the aromatic compound. The surfactant may be added to the reaction system, for example, in an amount of 0.5 equivalent or more and 2.0 equivalents or less relative to the aromatic compound.

[0150] In the present embodiment, the surfactant may be an anionic surfactant. The surfactant may include a pyrrolidone-based surfactant. The pyrrolidone-based surfactant includes, for example, pyrrolidones or derivatives thereof.

[0151] The surfactant may be a non-polymeric compound. The non-polymeric compound may be a compound having a weight average molecular weight (in terms of polystyrene) of less than 10,000. The weight average molecular weight is measured, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF). The non-polymeric compound may be a polymer or condensate having a value (sometimes referred to as average molecular weight) obtained by multiplying a value represented by a degree of polymerization or a degree of condensation by the molecular weight of a monomer unit of less than 10,000.

[0152] Examples of surfactants include polyvinyl alcohol, cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodium dodecyl sulfate, sodium dodecane sulfonate, ammonium lauryl sulfate, sodium cetyl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, sodium phenylphenol, sucrose, maltose, glucose, fructose, sorbitol, mannitol, xylitol, sodium benzoate, linear sodium dodecylbenzenesulfonate, branched sodium dodecylbenzenesulfonate, and dodecane. Examples of surfactants include sodium hexadecanesulfonate, sodium octanoate, sodium butylnaphthalenesulfonate, sodium 1-naphthalenesulfonate, sodium hexadecanesulfonate, sodium octanesulfonate, ethanol, ethoxyethanol, t-butanol, propanol, methoxyethanol, glycerin, acetic acid, malic acid, salicylic acid, propionic acid, glutamic acid, aspartic acid, citric acid, ascorbic acid, ethylenediaminetetraacetic acid, histidine, ethanolamine, dextrin, lauryl betaine, niacinamide, triisopropanolamine, quaternium-22, quaternium-45, etc. The surfactant may be at least one compound selected from the group consisting of sodium dodecyl sulfate, sodium hexadecanesulfonate, sodium dodecanoate, sodium butylnaphthalenesulfonate, sodium octanesulfonate, sodium 1-naphthalenesulfonate, propanol, ethanol, and 1-methoxyethanol.

[0153] (E. Catalyst) Examples of the catalyst include Bronsted acids, Lewis acids, and bases. Examples of the Bronsted acids include hydrochloric acid, sulfuric acid, phosphoric acid, and citric acid. Examples of the Lewis acids include aluminum chloride, monoborane, diborane, boron trifluoride, and alumina. Examples of the bases include ammonia, triethylamine, and alkali metal hydroxides. Examples of the alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. It is preferable to use an alkali metal hydroxide as the catalyst.

[0154] (F. Auxiliaries) The composition containing the addition condensate may contain various auxiliary agents. Examples of the auxiliary agent include a reducing agent, a water-soluble polymer, a pH adjuster, and / or other compounds. Examples of the other compounds include an inorganic colloid, an alkali metal silicate, and an antioxidant. The auxiliary agent is added as necessary within a range that does not impair the purpose and effect of the composition. The content of the auxiliary agent in the composition is adjusted to, for example, 0% by mass or more and 50% by mass or less. The auxiliary agent may be added to the composition at any timing in the production process of the composition.

[0155] (reducing agent) Examples of reducing agents include sulfites, phosphites, nitrites, reducing sugars, and thiourea dioxide. A single type of reducing agent may be used, or two or more types of reducing agents may be used in combination. As the reducing agent, sulfites and / or thiourea dioxide may be used.

[0156] Examples of sulfites include ammonium sulfite, potassium sulfite, sodium sulfite, ammonium hydrogen sulfite, sodium hydrogen sulfite, sodium dithionite (Na2S2O4), Rongalite, and the like.

[0157] Examples of phosphites include ammonium phosphite, sodium phosphite, potassium phosphite, calcium phosphite, uranyl phosphite, cobalt phosphite, ferrous phosphite, ferric phosphite, copper phosphite, barium phosphite, hydrazinium phosphite, ammonium hydrogen phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, potassium hydrogen phosphite, calcium hydrogen phosphite, cobalt hydrogen phosphite, cuprous hydrogen phosphite, cupric hydrogen phosphite, ferrous hydrogen phosphite, ferric hydrogen phosphite, lead hydrogen phosphite, barium hydrogen phosphite, magnesium hydrogen phosphite, manganese hydrogen phosphite, and hydrazinium hydrogen phosphite.

[0158] Examples of nitrites include ammonium nitrite, sodium nitrite, potassium nitrite, calcium nitrite, zinc nitrite, silver nitrite, potassium cobalt nitrite, sodium cobalt nitrite, strontium nitrite, cesium nitrite, cerium nitrite, cupric nitrite, nickel nitrite, barium nitrite, magnesium nitrite, lithium nitrite, and rubidium nitrite.

[0159] Reducing sugars are sugars that have a free aldehyde group or carbonyl group and exhibit reducing properties. Examples of reducing sugars include maltose, lactose, and glucose.

[0160] The content of the reducing agent in the composition may be 0.01 to 10 parts by mass relative to 100 parts by mass of the addition condensate. The content of the reducing agent in the composition is preferably about 0.1 to 3 parts by mass relative to 100 parts by mass of the addition condensate.

[0161] Adding a reducing agent to the composition improves the uniform stability of the composition including the condensation reaction product obtained by the condensation reaction. Also, adding a reducing agent to the composition suppresses the formation of gelled matter in the composition. This extends the shelf life of the composition. Also, the incorporation of gelled matter into polymer products can be prevented. Furthermore, adding a reducing agent to the composition can improve the anti-scaling effect of the scale prevention layer 116 (sometimes simply referred to as a coating of the composition) formed using the composition.

[0162] (Water-soluble polymer) Examples of the water-soluble polymer include anionic polymer compounds, amphoteric polymer compounds, cationic polymer compounds, nonionic polymer compounds, and hydroxyl group-containing polymers. The water-soluble polymer may be a compound of a different type from the above-mentioned surface active compounds.

[0163] The water-soluble polymer may be a compound having a weight-average molecular weight (in terms of polystyrene) of 10,000 or more. The weight-average molecular weight is measured, for example, by gel permeation chromatography (GPC) using tetrahydrofuran (THF). Compounds having a weight-average molecular weight of less than 10,000 may not be considered to be water-soluble polymers.

[0164] The K value of the water-soluble polymer can be adjusted so as to sufficiently improve the hydrophilicity of the coating film of the composition and to sufficiently increase the solubility in the solvent contained in the composition. The K value is, for example, the K value based on the Fikentscher formula at 25° C. Specifically, the K value of the water-soluble polymer is preferably 10 or more and 200 or less, more preferably 80 or more and 150 or less.

[0165] The content of the water-soluble polymer in the composition is adjusted, for example, taking into consideration the viscosity of the composition. The content of the water-soluble polymer in the composition is adjusted, for example, so that the composition is not difficult to handle. Specifically, the content of the water-soluble polymer is preferably 0.001% by mass or more and 50% by mass or less, more preferably 0.01% by mass or more and 30% by mass or less.

[0166] The addition of a water-soluble polymer to the composition improves the hydrophilicity of the coating film of the composition, thereby improving the anti-scale adhesion performance of the coating film.

[0167] (pH adjuster) When the pH of the composition needs to be adjusted, various acids and / or alkali compounds are used as pH adjusters. The pH of the composition is appropriately adjusted depending on the type of compound constituting the composition and / or the type of raw material of the composition. When the pH of the composition is adjusted, the pH of the composition is preferably adjusted to 6 to 14, more preferably adjusted to 8 to 13, and even more preferably adjusted to 9 to 12.

[0168] Examples of acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, diphosphoric acid, myo-inositol-1,2,3,4,5,6-hexaphosphoric acid, etc. Examples of alkali compounds include alkali metal compounds and amine compounds, etc. Examples of alkali metal compounds include LiOH, NaOH, KOH, Na2CO3, Na2HPO4, etc. Examples of amine compounds include NH3, methylamine, ethylamine, ethylenediamine, etc.

[0169] The above-mentioned compounds used as catalysts may be used as pH adjusters. For example, the above-mentioned bases such as alkali metal hydroxides are used as pH adjusters. Similarly, the above-mentioned thiol compounds may be used as pH adjusters. By increasing the amount of thiol compounds added, the amount of other pH adjusters added may be reduced.

[0170] (III. Method for producing the composition) The composition containing the addition condensation product of an aromatic compound and a carbonyl compound, and a thiol compound is produced, for example, by the following procedure. First, a mixture (sometimes referred to as a raw material solution) of a solvent, an aromatic compound, a carbonyl compound, and a thiol compound is prepared. As described above, the raw material solution may contain, for example, a surfactant and / or a pH adjuster. Next, the aromatic compound and the carbonyl compound contained in the mixture are reacted in the presence of a catalyst and a surfactant. This produces an addition condensation product of an aromatic compound and a carbonyl compound. As a result, a composition containing the addition condensation product of an aromatic compound and a carbonyl compound, and a thiol compound is produced. The details of the method for producing the above composition will be described later.

[0171] (IV. Use of the composition as a scale adhesion inhibitor) As described above, the composition according to the present embodiment is used as a scale inhibitor. In particular, the composition is used as a polymer scale inhibitor when vinyl chloride or a monomer mixture mainly containing vinyl chloride is polymerized to produce a polymer.

[0172] According to one embodiment, the stock solution of the addition condensate is used as a scale adhesion inhibitor. In this case, the content of the addition condensate in the stock solution may be 0.1% by mass or more and 15% by mass or less. According to another embodiment, a solution (sometimes called an adjusted solution) in which an arbitrary solvent (sometimes called an adjustment solvent) is added to the stock solution of the addition condensate is used as a scale adhesion inhibitor. The adjusted solution may be prepared by adding an adjustment solvent and at least one of a pH adjuster, a reducing agent, and a water-soluble polymer to the stock solution of the addition condensate. The content of the addition condensate in the adjusted solution may be 0.1% by mass or more and 15% by mass or less.

[0173] The coating liquid containing the above-mentioned addition condensate is applied, for example, in the process of producing an olefin-based polymer in the polymerization reactor. The above-mentioned coating liquid is particularly preferably used in the process of polymerizing an ethylenically unsaturated group-containing monomer. The above-mentioned coating liquid is preferably used in the process of producing a polymer or copolymer of an ethylenically unsaturated group-containing monomer or a copolymer of the above-mentioned monomer mixture by subjecting a vinyl halide such as vinyl chloride, a vinylidene halide such as vinylidene chloride, or a monomer mixture mainly containing these and other monomers to suspension polymerization or emulsion polymerization in an aqueous medium.

[0174] In suspension polymerization or emulsion polymerization, various additives may be added to the polymerization system as necessary. Examples of additives include suspension stabilizers, anionic emulsifiers, nonionic emulsifiers, stabilizers, chain transfer agents, pH adjusters, and the like. Examples of suspension stabilizers include partially saponified polyvinyl alcohol and methyl cellulose. Examples of anionic emulsifiers include sodium lauryl sulfate. Examples of nonionic emulsifiers include sorbitan monolaurate and polyoxyethylene alkyl ether. Examples of stabilizers include tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, and dioctyltin mercaptide. Examples of chain transfer agents include trichloroethylene and mercaptans. The coating film derived from the coating solution containing the above-mentioned addition condensate can effectively suppress the adhesion of polymer scale even when these additives are present in the polymerization system.

[0175] A coating film formed using a coating solution containing the above-mentioned addition condensate exhibits high durability even when applied to the polymerization of monomers having high dissolving ability for coating films having conventionally known polymer scale adhesion prevention performance, such as α-methylstyrene, acrylic acid esters, methacrylic acid esters, acrylonitrile, vinyl acetate, etc. Therefore, the coating solution containing the above-mentioned addition condensate is also suitably used in the production of polymer beads or latexes such as polystyrene, polymethyl methacrylate, polyacrylonitrile, etc., the production of synthetic rubbers such as styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), isoprene rubber (IR), butyl rubber (IIR), etc. (Note that these synthetic rubbers are usually produced by emulsion polymerization), and the production of ABS resin.

[0176] As described above, the composition according to the present embodiment contains a thiol compound. In addition, various physical properties of the above composition are adjusted in a state in which the thiol compound is included. Similarly, the composition of the coating liquid using the above composition is adjusted in a state in which the thiol compound is included. As a result, when the scale prevention layer 116 is formed on the inner surface 114 of the reaction vessel 110, decomposition of the addition condensation product of the aromatic compound and the carbonyl compound, which are the active ingredients of the scale adhesion inhibitor, is suppressed. As a result, a dense coating film of the addition condensation product is formed as the scale prevention layer 116 derived from the above composition. In addition, the productivity of the polymer is improved by forming the scale prevention layer 116 with excellent scale adhesion prevention performance. In addition, the inclusion of foreign matter in the product is suppressed.

[0177] (V. Procedure for forming scale prevention layer 116) For example, a coating of the above-mentioned addition condensate is formed by applying the composition prepared according to the above procedure to the inner surface 114 of the reaction vessel 110. As a result, the addition condensate adheres to the inner surface 114 of the reaction vessel 110.

[0178] The method of applying the composition is not particularly limited. For example, first, a coating liquid containing the composition is prepared. As described above, examples of the coating liquid include (i) a stock solution obtained by a condensation reaction, and (ii) a prepared solution obtained by adding at least one of a pH adjuster, a reducing agent, a water-soluble polymer, and water to the stock solution. Next, the coating liquid is sprayed from a nozzle, so that the coating liquid is applied to the inside of the reaction vessel 110. For example, the coating liquid is applied to at least a part of the inner surface 114 of the reaction vessel 110. Examples of carriers for spraying the coating liquid from a nozzle include nitrogen, air, and water vapor. The nozzle may be disposed at a spray outlet provided relatively above (sometimes referred to as the upper stage) the reaction vessel 110. The procedure for applying the composition will be described in detail later.

[0179] (VI. Composition and Amount of Adhesion Condensate) The amount of the addition condensate in the composition adhering to the reaction vessel 110 is determined based on the peak area of ​​the measurement result (sometimes referred to as a chromatogram) obtained by, for example, high performance liquid chromatography (HPLC). As described above, the composition may contain a first condensate and a second condensate. The content ratio of the first condensate and / or the second condensate in the composition, and the content ratio of the first condensate to the second condensate may be derived using the above chromatogram. The details of the apparatus (sometimes referred to as a chromatograph) used for high performance liquid chromatography and the measurement conditions may be as described above.

[0180] (VII. Materials of Each Part of Polymerization Apparatus 100) The material of each part of the polymerization apparatus 100 is appropriately determined in consideration of mechanical strength, corrosion resistance, heat transfer, etc. For example, examples of materials used for the stirring shaft 122, the stirring blade 124, the baffle 130, and / or the cooling pipe 140 include stainless steels such as high-chromium high-purity ferritic stainless steel, duplex stainless steel, and austenitic stainless steel. These materials have excellent heat transfer properties and corrosion resistance.

[0181] Examples of the material of the main body 112 of the reaction vessel 110 include carbon steel, stainless steel, nickel alloy, titanium alloy, aluminum alloy, etc. Examples of the material of the inner surface 114 of the reaction vessel 110 include carbon steel, stainless steel, nickel alloy, titanium alloy, aluminum alloy, etc. The material of the inner surface 114 of the reaction vessel 110 may be clad steel including stainless steel. The material of the outer layer of the clad steel is preferably carbon steel, and the material of the inner layer of the clad steel is preferably stainless steel.

[0182] The surfaces of the body 112 and / or the inner surface 114 of the reaction vessel 110 may be polished as necessary. Examples of the polishing include mechanical polishing, electrolytic polishing, etc. The surfaces of the body 112 and / or the inner surface 114 of the reaction vessel 110 may be plated as necessary.

[0183] VIII. Uses of Polymerization Apparatus 100 As described above, the polymerization apparatus 100 is used for producing a polymer. Examples of the polymerization method include suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization. In producing a polymer, various additives such as an emulsifier, a stabilizer, a lubricant, a plasticizer, a pH adjuster, and a chain transfer agent may be used. This can more effectively prevent, for example, the deposition of polymer scale.

[0184] In suspension polymerization, for example, first, water and a dispersant are charged into a reaction vessel 110, and then a polymerization initiator is charged into the reaction vessel 110. The amounts of water, dispersant, and polymerization initiator are, for example, 20 to 500 parts by mass of water, 0.01 to 30 parts by mass of dispersant, and 0.01 to 5 parts by mass of polymerization initiator relative to 100 parts by mass of a monomer described below.

[0185] Next, the inside of the reaction vessel 110 is evacuated. According to one embodiment, the inside of the reaction vessel 110 is depressurized to about 0.001 to 101 kPa·G (about 0.01 to 760 mmHg). According to another embodiment, the inside of the reaction vessel 110 is adjusted to atmospheric pressure. Next, the internal pressure of the reaction vessel 110 is adjusted to, for example, 49 to 2940 kPa·G (0.5 to 0.5 kgf / cm 2The amount of monomer is charged so that the total amount of monomer is equal to the amount of monomer (G).

[0186] Thereafter, the temperature inside the reaction vessel 110 is adjusted to a predetermined reaction temperature. This initiates the polymerization reaction. The reaction temperature is, for example, 30 to 150°C. The reaction temperature during polymerization varies depending on the type of monomer to be polymerized. For example, in the case of polymerization of vinyl chloride, the reaction temperature is 30 to 80°C. For example, in the case of polymerization of styrene, the reaction temperature is 50 to 150°C.

[0187] During the polymerization reaction, one or more of water, a dispersant, and a polymerization initiator are added as necessary. Then, the internal pressure of the reaction vessel 110 is adjusted to 0 to 686 kPa·G (0 to 7 kgf / cm 2 The polymerization reaction is considered to be completed when the temperature drops to 0.5° C. (−G), or when the difference between the inlet temperature and outlet temperature of the cooling water flowing into and out of the flow passage 172 of the jacket 170 becomes smaller than a predetermined value (i.e., when heat generation due to the polymerization reaction ceases).

[0188] In solution polymerization, an organic solvent is used as a polymerization medium instead of water. Examples of organic solvents include toluene, xylene, pyridine, etc. In solution polymerization, a dispersant is used as necessary. Other conditions and procedures may be the same as those of suspension polymerization.

[0189] In bulk polymerization, the inside of the reaction vessel 110 is evacuated in the same manner as in suspension polymerization, and after monomers and a polymerization initiator are charged into the reaction vessel 110, the temperature inside the reaction vessel 110 is adjusted to a predetermined reaction temperature. The reaction temperature is, for example, -10 to 250°C. For example, in the case of polymerization of vinyl chloride, the reaction temperature is 30 to 80°C. For example, in the case of polymerization of styrene, the reaction temperature is 50 to 150°C.

[0190] More specifically, the polymerization apparatus 100 is used for the purpose of producing a polymer by polymerizing various vinyl monomers, for example, olefins such as ethylene and propylene, vinyl halides such as vinyl chloride and vinylidene chloride, vinyl esters such as vinyl acetate, vinyl ethers such as ethyl vinyl ether, (meth)acrylic acid esters such as methyl methacrylate, metal salts or esters of maleic acid or fumaric acid, aromatic vinyls such as styrene, diene monomers such as butadiene, chloroprene, and isoprene, acrylonitrile, etc. The polymerization apparatus 100 is particularly suitable for the purpose of producing a polymer by polymerizing vinyl chloride or a monomer mixture mainly composed of vinyl chloride.

[0191] When a polymer is produced using the polymerization apparatus 100, each raw material is supplied from a supply port (not shown) of the polymerization apparatus, and when the temperature of the reaction compound charged inside the reaction vessel 110 reaches a predetermined temperature, heat removal from the reaction compound is started by circulating a coolant through each of the baffle 130, the cooling pipe 140, and the jacket 170. On the other hand, the timing to start removing heat by the reflux condenser 180 is preferably after the polymerization conversion rate reaches 4%, and more preferably when the polymerization conversion rate is 4 to 20%.

[0192] Even when a polymer is produced using the polymerization apparatus 100, various polymerization conditions may be similar to known polymerization conditions. Examples of the polymerization conditions include the charging ratio of raw materials, the charging method of raw materials, and the polymerization temperature.

[0193] For example, when a vinyl chloride polymer is produced by suspension polymerization using polymerization apparatus 100, the aqueous medium, vinyl chloride monomer, and optionally other comonomers, dispersing aids, polymerization initiators, etc. are charged in the same manner as in known methods for producing vinyl chloride polymers. The polymerization conditions may also be the same as in known methods for producing vinyl chloride polymers.

[0194] As the monomer to be polymerized, vinyl chloride alone or a monomer mixture mainly composed of vinyl chloride (vinyl chloride 50% by mass or more) can be used. Examples of the comonomer to be copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters or methacrylic acid esters such as methyl acrylate and ethyl acrylate; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; vinylidene chloride; and other monomers copolymerizable with vinyl chloride.

[0195] The above dispersion aid is a compound that is usually used when vinyl chloride is polymerized in an aqueous medium. Examples of the above dispersion aid include water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; partially saponified polyvinyl alcohol, acrylic acid polymers; and water-soluble polymers such as gelatin. The above dispersion aids may be used alone or in combination of two or more. The dispersion aid is added, for example, in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the monomer to be charged.

[0196] The polymerization initiator is a compound that is generally used in vinyl chloride polymerization.The polymerization initiator may be exemplified by percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, etc.; perester compounds such as α-cumyl peroxyneodecanate, t-butyl peroxyneodecanate, t-butyl peroxyneoheptanoate, hexyl peroxyneodecanate, octyl peroxyneodecanate, etc.; peroxides such as acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, etc.; azo compounds such as azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), etc. Other examples of the polymerization initiator include bis(2-ethylhexyl)peroxydicarbonate, 3,5,5-trimethylhexanoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, t-butyl peroxypivalate, bis(2-ethoxyethyl)peroxydicarbonate, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, α,α'-azobisisobutyronitrile, α,α'-azobis-2,4-dimethylvaleronitrile, di-2-ethylhexyl diperoxyisophthalate, potassium persulfate, and ammonium persulfate.

[0197] The above polymerization initiators may be used alone or in combination of two or more. The polymerization initiator may be added, for example, in an amount of 0.01 to 3 parts by mass per 100 parts by mass of the monomer, and is preferably added in an amount of 0.05 to 3 parts by mass per 100 parts by mass of the monomer.

[0198] Furthermore, if necessary, polymerization regulators, chain transfer agents, pH regulators, buffers, gelation improvers, antistatic agents, antiscaling agents, etc., which are appropriately used in vinyl chloride polymerization, may be added. With regard to the reduced viscosity (K value) of the vinyl chloride polymer obtained by the present invention, a polymer having a reduced viscosity in the desired range can be obtained by using the apparatus of the present invention, and preferably a polymer having a reduced viscosity in the range of 40 to 90 can be obtained.

[0199] Examples of pH adjusters or buffers include citric acid, trisodium citrate, diammonium citrate, triammonium citrate, potassium hydrogen phthalate, sodium nitrate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, disodium phosphate, dipotassium phosphate, tripotassium phosphate, etc. The above pH adjusters or buffers may be used alone or in combination of two or more.

[0200] The polymerization apparatus 100 may be an example of a reaction apparatus. The reaction vessel 110 may be an example of a reactor. The inner surface 114 of the reaction vessel 110 may be an example of an inner wall surface of a reactor. The scale prevention layer 116 may be an example of a condensate layer. The reflux condenser 180 may be an example of a condensation section. The raw solution of the addition condensate may be an example of a composition. The adjusted solution may be an example of a composition.

[0201] The cyclic condensate of an aromatic compound and a carbonyl compound may be an example of the first component. The linear condensate of an aromatic compound and a carbonyl compound may be an example of the second component. The first condensate may be an example of a first type of addition condensate. The second condensate may be an example of a second type of addition condensate.

[0202] (An example of another embodiment) In this embodiment, the polymerization apparatus 100 has been described in detail, taking as an example a case in which the scale prevention layer 116 is formed on the inner surface 114 of the reaction vessel 110. However, the polymerization apparatus 100 is not limited to this embodiment. In other embodiments, in addition to the inner surface 114 of the reaction vessel 110, the scale prevention layer 116 may be formed on at least one surface of the stirrer 120, the baffle 130, and the cooling pipe 140.

[0203] 2 is a schematic diagram of an example of a coating apparatus 190. In this embodiment, the coating apparatus 190 includes, for example, a coating liquid supply unit 212 and a cleaning water supply unit 214.

[0204] In this embodiment, the coating liquid supply unit 212 has, for example, a coating nozzle 220 and a line 222. The coating liquid supply unit 212 has, for example, a first coating liquid storage tank 230, a pump 232, a line 234, and a valve 236. The coating liquid supply unit 212 has, for example, a second coating liquid storage tank 240, a pump 242, a line 244, and a valve 246. The coating liquid supply unit 212 has, for example, a steam supply source 250, a line 254, and a valve 256.

[0205] In this embodiment, the cleaning water supply unit 214 includes, for example, a cleaning nozzle 260. The cleaning water supply unit 214 includes, for example, a cleaning water storage tank 270, a pump 272, a line 274, and a valve 276.

[0206] (Overview of each part of the coating liquid supply unit 212) In this embodiment, the coating nozzle 220 sprays the first coating liquid supplied from the first coating liquid storage tank 230, the second coating liquid supplied from the second coating liquid storage tank 240, and the steam supplied from the steam supply source 250 into the inside of the reaction vessel 110. The coating nozzle 220 is disposed, for example, facing downward. The coating nozzle 220 is disposed, for example, in a region inside the reaction vessel 110 and above a region where the scale preventive layer 116 is formed. The line 222 supplies the first coating liquid supplied from the first coating liquid storage tank 230, the second coating liquid supplied from the second coating liquid storage tank 240, and the steam supplied from the steam supply source 250 to the coating nozzle 220.

[0207] In this embodiment, the first coating liquid storage tank 230 stores the first coating liquid containing the above-mentioned composition. The details of the first coating liquid will be described later. The pump 232 pumps the first coating liquid stored in the first coating liquid storage tank 230. The line 234 connects the outlet of the pump 232 and the line 222. The valve 236 is disposed midway along the line 234 and adjusts the flow rate of the first coating liquid.

[0208] In this embodiment, the second coating liquid storage tank 240 stores the second coating liquid having a different composition from the first coating liquid. The second coating liquid is used, for example, to wash away excess addition condensate applied to the inner surface of the reaction vessel 110 in the process of forming the scale preventive layer 116. The content of the above composition in the second coating liquid may be smaller than the content of the above composition in the first coating liquid. The second coating liquid may not substantially contain the above composition. The details of the second coating liquid will be described later. The pump 242 pumps the second coating liquid stored in the second coating liquid storage tank 240. The line 244 connects the outlet of the pump 242 and the line 222. The valve 246 is disposed in the middle of the line 244 and adjusts the flow rate of the first coating liquid.

[0209] In this embodiment, the steam supply source 250 supplies steam to the line 254. The steam may be saturated steam or superheated steam. The pressure of the steam may be 0.1 to 3.5 MPaG, and may be 0.1 to 2.0 MPaG. The pressure of the steam is preferably 0.28 to 2.0 MPaG, and more preferably 0.5 to 1.0 MPaG. The temperature of the steam may be 120 to 270°C, and preferably 140 to 230°C. The above temperature and pressure may be measured at a position near the valve 256 of the line 254, on the side of the steam supply source 250. The line 254 connects the steam supply source 250 and the line 222. The valve 256 is disposed in the middle of the line 254 to adjust the flow rate of the steam.

[0210] When the composition is applied using steam as a carrier, the application time may be 10 seconds to 1000 seconds, and preferably 30 seconds to 300 seconds. The value obtained by dividing the mass flow rate of the composition by the mass flow rate of steam (sometimes referred to as the mass flow rate ratio) may be 0.01 to 1.00, and preferably 0.02 to 0.2.

[0211] In this embodiment, the cleaning nozzle 260 sprays water supplied from the cleaning water storage tank 270 into the inside of the reaction vessel 110. The cleaning nozzle 260 is disposed, for example, facing downward. The cleaning nozzle 260 is disposed, for example, in a region inside the reaction vessel 110 and above a region where the scale prevention layer 116 is formed.

[0212] In this embodiment, the cleaning water storage tank 270 stores water for cleaning (sometimes referred to as cleaning water). The pump 272 pumps the cleaning water stored in the cleaning water storage tank 270. The line 274 connects the outlet of the pump 272 to the cleaning nozzle 260. The valve 276 is disposed midway along the line 274 and adjusts the flow rate of the cleaning water.

[0213] (An example of another embodiment) In this embodiment, the details of the coating device 190 are described by taking as an example a case where the composition of the first coating liquid is different from the composition of the second coating liquid. However, the coating device 190 is not limited to this embodiment. In another embodiment, the composition of the first coating liquid may be the same as the composition of the second coating liquid. In this case, the coating device 190 may not include the second coating liquid storage tank 240, the pump 242, the line 244, and the valve 246. In still another embodiment, both the first coating liquid and the second coating liquid may contain the above composition. In still another embodiment, the first coating liquid may be substantially free of the above composition, and the second coating liquid may contain the above composition.

[0214] 3 is a schematic diagram of an example of a method for producing a composition. According to this embodiment, first, in step 322 (the step may be simply abbreviated as S), a raw material solution is prepared. As described above, the raw material solution contains a solvent, an aromatic compound, a carbonyl compound, and a thiol compound.

[0215] As described above, the raw material solution may contain a single type of aromatic compound or may contain two or more types of aromatic compounds. Similarly, the raw material solution may contain a single type of carbonyl compound or may contain two or more types of carbonyl compounds.

[0216] The ratio of the aromatic compound and the carbonyl compound is appropriately selected depending on the type of aromatic compound, carbonyl compound, reaction solvent and catalyst used, reaction time, reaction temperature, etc. The raw material solution contains, for example, 0.1 to 10 moles of the carbonyl compound per mole of the aromatic compound. The raw material solution may contain 0.5 to 3.0 moles of the carbonyl compound per mole of the aromatic compound. The raw material solution may contain 0.1 mole or more and less than 1 mole (e.g., 0.999 moles) of the carbonyl compound per mole of the aromatic compound, or may contain 0.5 mole or more and less than 1 mole (e.g., 0.99 moles) of the carbonyl compound per mole of the aromatic compound. This allows the molar ratio of the aromatic compound dimer to the aromatic compound multimer to be adjusted within the above-mentioned numerical range.

[0217] Next, in S324, the raw material solution is mixed with a catalyst and a surfactant. As described above, the catalyst may be an alkali metal hydroxide. Similarly, the surfactant may be a known anionic surfactant. In addition, in S326, an aromatic compound and a carbonyl compound (sometimes referred to as reaction components) are reacted in a reaction solvent in the presence of the catalyst and the surfactant. This causes a condensation reaction of the aromatic compound and the carbonyl compound to produce an addition condensate of the aromatic compound and the carbonyl compound.

[0218] The reaction is carried out so as to satisfy predetermined conditions related to temperature and / or time. In order to initiate, progress and / or stop the reaction, multiple steps with different temperature and / or time conditions may be carried out. After the reaction is initiated, multiple steps with different temperature and time conditions may be carried out.

[0219] The temperature conditions are not particularly limited, but examples of the temperature conditions include room temperature to 200°C, 30 to 150°C, etc. The time conditions are not particularly limited, but examples of the time conditions include 1 to 100 hours, 1 to 30 hours, etc. The temperature and time conditions may be a combination of any temperature condition and any time condition. The temperature and time conditions are, for example, room temperature to 200°C and 1 to 100 hours.

[0220] The reaction temperature and reaction time of the condensation reaction may be room temperature to 200° C. and 1 to 100 hours, and preferably 30 to 150° C. and 2 to 30 hours. The reaction temperature and reaction time of the condensation reaction may be room temperature to 97° C. and 1 to 100 hours, and preferably 30 to 95° C. and 2 to 30 hours. This allows the molar ratio of the aromatic compound dimer to the aromatic compound multimer to be adjusted within the above-mentioned numerical range.

[0221] The maximum temperature reached in the condensation reaction may be 60 to 97° C. The condensation reaction may be controlled so that the reaction temperature and reaction time are 1 to 100 hours at the maximum temperature. The condensation reaction is preferably controlled so that the reaction temperature and reaction time are 2 to 30 hours at the maximum temperature.

[0222] The pH of the medium in which the condensation reaction is carried out may be in the range of 1 to 14. The pH may be 1 to 12. The pH may be 6 to 14, 8 to 13, or 9 to 12. The pH of the medium may be adjusted by any pH adjuster. As the pH adjuster, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, or potassium hydroxide is used. This allows the solubility of the condensate to be well maintained.

[0223] This results in a composition containing an addition condensate (e.g., the specific addition condensate described above). The addition condensate in the composition is an aromatic compound multimer in which two or more (preferably 2 to 50) constituent units derived from an aromatic compound are bonded via one constituent unit derived from a carbonyl compound. The addition condensate includes, for example, aromatic compound dimers as well as aromatic compound trimers (e.g., compounds represented by ABABA) to aromatic compound pentamers (e.g., compounds represented by ABA-...-BA and containing 50 A's).

[0224] According to this embodiment, a composition containing an addition condensation product of an aromatic compound and a carbonyl compound, and a thiol compound is obtained. In addition, a coating liquid prepared using the above composition is applied to at least a part of the inner surface 114 of the main body 112 to form a dense scale prevention layer 116. Therefore, adhesion of scale due to polymerization is suppressed. In addition, the scale prevention layer 116, together with the scale adhered to the scale prevention layer 116, is suppressed from peeling off from the inner surface 114 of the reaction vessel 110.

[0225] In response to this, for example, Patent Document 2 discloses a polymer scale adhesion inhibitor using a first coating liquid containing a quinone compound condensate and a second coating liquid containing polyphosphoric acid. Even when a polymer is synthesized using a reaction vessel having a scale prevention layer formed using the polymer scale adhesion inhibitor described in Patent Document 2, adhesion of scale during polymerization is suppressed. However, the scale prevention layer formed using the polymer scale adhesion inhibitor described in Patent Document 2 is likely to peel off from the inner surface of the reaction vessel together with the scale adhered to the scale prevention layer. A mixture of the scale prevention layer and scale peeled off from the inner surface of the reaction vessel may be mixed into the product as a foreign matter, and may cause, for example, fish eyes.

[0226] (An example of another embodiment) In this embodiment, an example of the method for producing the composition described above is described by taking the case where the thiol compound is added to the raw material solution before the raw material solution is mixed with the catalyst and the surfactant. However, the method for producing the composition described above is not limited to this embodiment. The timing of adding the thiol compound to the raw material solution is not particularly limited as long as it is before the condensation reaction is completed.

[0227] In addition, when the condensation reaction of the aromatic compound and the carbonyl compound is started without adding the thiol compound, the addition condensation product of the aromatic compound and the carbonyl compound may aggregate depending on the preparation condition of the raw material solution. Therefore, in order to improve the degree of freedom in preparation of the raw material solution, it is preferable that the thiol compound is added to the raw material solution before the condensation reaction of the aromatic compound and the carbonyl compound is started.

[0228] 4 shows an example of a method for producing a polymer. According to this embodiment, first, in S422, a polymerization apparatus 100 is prepared. For example, a scale prevention layer 116 is formed on the inner surface 114 of a reaction vessel 110. The scale prevention layer 116 is formed, for example, according to the following procedure.

[0229] First, the inner surface 114 of the reaction vessel 110 is preheated by flowing a heating medium such as hot water or steam into the flow path 172 of the jacket 170. For example, the preheating treatment of the inner surface 114 is performed so that the inner surface 114 is at least 20°C, preferably at 30 to 95°C.

[0230] Also, a first coating liquid containing the above-mentioned composition is prepared. In one embodiment, the above-mentioned composition containing an addition condensation product of an aromatic compound and a carbonyl compound and a thiol compound is used as the first coating liquid without being diluted with a solvent. In another embodiment, the above-mentioned composition is diluted with any solvent to prepare the first coating liquid. The above-mentioned solvent may be deionized water.

[0231] The first coating liquid is adjusted, for example, so that the ratio of the mass of the aromatic compound used in preparing the above-mentioned addition condensate to the mass of the first coating liquid is 0.2% by mass to 20% by mass. The above ratio is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. The above ratio may be about 5% by mass (for example, 4% by mass to 6% by mass). The first coating liquid adjusted according to the above procedure is stored in the first coating liquid storage tank 230.

[0232] Similarly, the second coating liquid described above is prepared. The second coating liquid is stored in the second coating liquid storage tank 240. In this embodiment, the second coating liquid includes at least one auxiliary agent. As described above, the second coating liquid may be substantially free of the above composition.

[0233] The second coating liquid contains, for example, a water-soluble polymer. The water-soluble polymer may be poly-N-vinylpyrrolidone. This makes it possible to remove excess addition condensation products that have been applied to the inner surface of the reaction vessel 110 in the process of forming the scale prevention layer 116.

[0234] Furthermore, since the second coating liquid contains a water-soluble polymer, the coating film formed on the inner surface of the reaction vessel 110 becomes soft, and a part of the coating film peels off during the batch polymerization process. As a result, the amount of the coating film remaining on the inner surface of the reaction vessel 110 after polymerization may decrease. Since the thickness of the coating film is about 10 nm, even if the coating film peels off during the batch polymerization process, the effect of the peeled coating film on the quality of the polymer is relatively small.

[0235] In contrast, if the next patch polymerization process is repeatedly started with a relatively large amount of coating remaining on the inner surface of the reaction vessel 110, an accumulation layer is formed on the inner surface of the reaction vessel 110, in which the coating, unreacted monomer, polymerization aid, etc. are accumulated in a composite manner. Since the thickness of the accumulation layer is relatively large, if the accumulation layer peels off during the batch polymerization process, foreign matter having a size on the order of microns or larger may be mixed into the polymer. According to the present embodiment, the mixing of such large foreign matter into the polymer is suppressed, and therefore a polymer of good quality is obtained.

[0236] The second coating liquid contains, for example, a pH adjuster. The pH adjuster may contain a phosphoric acid compound. The phosphoric acid compound may be myo-inositol-1,2,3,4,5,6-hexaphosphoric acid. The phosphoric acid compound acts on the material of the inner surface of the reaction vessel 110 (for example, stainless steel), thereby dissolving excess iron on the inner surface of the reaction vessel 110. This improves the corrosion resistance of the inner surface of the reaction vessel 110. As a result, adhesion of scale to the inner surface of the reaction vessel 110 is suppressed.

[0237] The second coating liquid contains, for example, a base. The base may be ethylenediamine. The pH of the second coating liquid may be alkaline. This suppresses precipitation of a solid or gel when the first coating liquid and the second coating liquid are mixed. As a result, clogging of the line 222 is suppressed.

[0238] (First coating step) Next, the first coating liquid is supplied into the reaction vessel 110. Specifically, first, the opening of the valve 256 is adjusted, and steam is supplied to the coating nozzle 220. Next, the pump 232 is started, and the opening of the valve 236 is adjusted, thereby supplying the first coating liquid to the line 222. As a result, the first coating liquid is transported into the reaction vessel 110 by the steam. The mixture ratio (L / G) of the steam (G) and the coating liquid (L) may be 0.01 to 1.0, and preferably 0.02 to 0.3, in terms of a flow rate ratio based on mass.

[0239] The application time of the first coating liquid is adjusted so that a coating film of an amount effective for preventing adhesion of scale is formed. The application time of the first coating liquid may be from 1 second to 600 seconds, and preferably from 10 seconds to 300 seconds. This allows a coating film of an amount effective for preventing adhesion of scale to be formed at an economically reasonable cost.

[0240] As a result, a layer derived from the first coating liquid (sometimes referred to as a first coating layer) is formed on the inner surface 114 of the reaction vessel 110. As described above, the first coating layer may also be formed on the surfaces of the stirring shaft 122, the stirring blades 124, the baffle 130, and / or the cooling pipe 140. Thereafter, the valve 236 is closed, and the pump 232 is stopped.

[0241] (2nd coat) Next, the second coating liquid is supplied into the reaction vessel 110. Specifically, while steam is being supplied to the coating nozzle 220, the pump 242 is started and the opening of the valve 246 is adjusted, thereby supplying the second coating liquid to the line 222. As a result, the second coating liquid is transported into the reaction vessel 110 by the steam. The mixture ratio (L / G) of the steam (G) and the coating liquid (L) may be 0.01 to 1.0, and preferably 0.02 to 0.3, in terms of a flow rate ratio based on mass.

[0242] The coating time of the second coating liquid is appropriately adjusted within an economically reasonable range. The coating time of the second coating liquid may be from 1 to 600 seconds, and preferably from 10 to 300 seconds.

[0243] As a result, a layer derived from the second coating liquid (sometimes referred to as a second coating layer) is formed on the first coating layer. After that, valve 246 is closed and pump 242 is stopped. Also, valve 256 is closed and the supply of steam is stopped.

[0244] (washing with water) Next, the inside of the reaction vessel 110 is washed with the washing water. Specifically, first, the pump 272 is started, and the opening of the valve 276 is adjusted to supply the washing water to the washing nozzle 260. As a result, the washing water is transported into the inside of the reaction vessel 110, and the scale prevention layer 116 is washed.

[0245] Next, in S424, a mixture containing monomers (sometimes referred to as a raw material mixture) is prepared. In addition, in S426, the raw material mixture is stored inside the reaction vessel 110. This completes the charging process for the polymerization reaction.

[0246] Next, in S432, the polymerization reaction of the monomers is started, and in S434, the polymerization reaction of the monomers is terminated, thereby obtaining a polymer.

[0247] As described above, according to this embodiment, a scale prevention layer 116 derived from the above-described composition is formed on the inner surface 114 of the reaction vessel 110. The scale prevention layer 116 has a dense coating of a condensation product of an aromatic compound and a carbonyl compound. This inhibits the formation and accumulation of polymer scale. As a result, polymer productivity is improved. In addition, the intrusion of foreign matter including an addition condensation product of an aromatic compound and a carbonyl compound is inhibited.

[0248] Specifically, the content of the above-mentioned addition condensation product is 1% by mass or more, and the inclusion of foreign matter having a major axis of 250 μm or more is suppressed. 3The number of the above-mentioned foreign objects contained in each unit is, for example, 4 or less. The number of the above-mentioned foreign objects may be 1 to 4, 1 to 3, 2 to 4, or 2 to 3. The number of the above-mentioned foreign objects is measured according to or in accordance with JIS K6737. EXAMPLES

[0249] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0250] (Synthesis Example 1) A coating solution containing an addition condensate and a thiol compound was prepared according to the following procedure. First, 1384 mL of deionized water was charged into a reactor that had been fully substituted with nitrogen by flowing nitrogen, and the reactor was heated to 35°C while stirring the deionized water, thereby performing a preliminary heating. 5.0 g of 3-mercapto-1,2-propanediol, 12.2 g of thorium hydroxide, and 150.0 g of α-naphthol were added to the deionized water in the reactor, and then the mixture was stirred for 30 minutes. Then, 71.8 g of a 37% by mass aqueous formaldehyde solution was added to the mixture in the container.

[0251] Next, the temperature in the reactor was raised to 60°C, and the mixture in the reactor was reacted for 3 hours. After that, the temperature in the reactor was raised to 80°C, and the mixture in the reactor was reacted for 1 hour. Then, cooling of the reactor was started, and the temperature in the reactor was lowered to 40°C. In addition, when the temperature in the reactor was lowered to 40°C, 219 mL of deionized water was added to the mixture in the reactor. This resulted in a coating solution (sometimes referred to as coating solution No. 1-1).

[0252] (Synthesis Example 2) A coating solution (sometimes referred to as Coating Solution No. 1-2) was prepared in the same manner as in Synthesis Example 1, except that the amount of deionized water added before the preliminary heating was 1339 mL and the amount of 3-mercapto-1,2-propanediol added was 10.0 g.

[0253] (Synthesis Example 3) A coating solution (sometimes referred to as Coating Solution No. 1-3) was prepared in the same manner as in Synthesis Example 1, except that 5.0 g of 2-mercaptoethanol was added instead of 3-mercapto-1,2-propanediol.

[0254] (Synthesis Example 4) A coating solution (sometimes referred to as Coating Solution No. 1-4) was prepared in the same manner as in Synthesis Example 3, except that the amount of deionized water added before the preliminary heating was 1339 mL and the amount of 2-mercaptoethanol added was 10.0 g.

[0255] (Synthesis Example 5) A coating solution (sometimes referred to as Coating Solution No. 1-5) was prepared in the same manner as in Synthesis Example 1, except that 5.0 g of sodium dithionite was added instead of 3-mercapto-1,2-propanediol.

[0256] (Synthesis Example 6) A coating solution (sometimes referred to as Coating Solution No. 1-6) was prepared in the same manner as in Synthesis Example 1, except that 5.0 g of L-ascorbic acid was added instead of 3-mercapto-1,2-propanediol.

[0257] (Synthesis Example 7) A coating solution (sometimes referred to as Coating Solution No. 1-7) was prepared in the same manner as in Synthesis Example 1, except that 5.0 g of N,N-diethylhydroxylamine was added instead of 3-mercapto-1,2-propanediol.

[0258] (Synthesis Example 8) A coating solution substantially free of addition condensation products was prepared according to the following procedure. First, 500 mg of calcium dihydrogen diphosphate was added to 20 mL of deionized water to prepare an aqueous calcium dihydrogen diphosphate solution. Next, 930 mL of deionized water and 50 mL of ethanol were charged into a reactor.

[0259] Next, 10 g of poly N-vinyl-2-pyrrolidone with a weight average molecular weight of 2.8 million was added to the deionized water in the reactor while stirring the deionized water in the reactor. After visually confirming that poly N-vinyl-2-pyrrolidone had dissolved, the previously prepared aqueous calcium dihydrogen diphosphate solution was added to the mixture in the container and stirred for 5 hours. This resulted in a coating solution (sometimes referred to as coating solution No. 2-1).

[0260] Example 1 (Formation of anti-scale adhesion layer) First, a stainless steel polymerization vessel having the same configuration as the above-described polymerization apparatus 100 was prepared. The internal volume of the polymerization vessel was 2 m 3 Next, a scale adhesion preventive layer was formed on the inner wall surface of the polymerization vessel by the following procedure.

[0261] First, hot water was passed through the jacket of the polymerization vessel to heat the inner wall surface of the polymerization vessel to 45°C. Next, steam of 0.717 MPaG (171.4°C) was supplied into the inside of the polymerization vessel. The steam supply flow rate was 240 kg / h, and the steam supply time was 60 seconds. This completed the preheating of the polymerization vessel.

[0262] Next, the coating solution No. 1-1 was fed into the polymerization vessel using the steam as a carrier. The feed flow rate of the coating solution was 120 g / min, and the feed time of the coating solution was 120 seconds.

[0263] Thereafter, the supply of steam and the coating solution was stopped, and the flow of hot water to the jacket was also stopped, resulting in the formation of a scale adhesion preventive layer on the inner wall surface of the polymerization vessel.

[0264] (Preparation of polymer) Using the polymerization vessel in which the scale adhesion prevention layer was formed by the above procedure, a vinyl chloride polymer was produced by the following procedure. First, 200 parts by weight of deionized water, 0.020 parts by weight of partially saponified polyvinyl alcohol, and 0.026 parts by weight of 2-hydroxypropylmethylcellulose (product name: Metolose, manufactured by Shin-Etsu Chemical Co., Ltd.) were charged into the polymerization vessel. The inside of the polymerization vessel was degassed to 50 mmHg, and then 100 parts by weight of vinyl chloride monomer (VCM) was charged into the polymerization vessel.

[0265] For reference, the degree of substitution of methoxyl groups in Metolose manufactured by Shin-Etsu Chemical Co., Ltd. was 1.9, and the degree of substitution of 2-hydroxypropoxyl groups was 0.25. The degree of substitution of methoxyl groups indicates the average number of hydroxyl groups in the glucose ring unit of cellulose that have been replaced with methoxyl groups. The degree of substitution of 2-hydroxypropoxyl groups indicates the number of moles of hydroxyalkoxyl groups added per glucose ring unit of cellulose.

[0266] Next, while stirring the reaction mixture stored inside the polymerization vessel, 0.03 parts by weight of t-butyl peroxyneodecanate was pumped in. After that, while stirring the raw materials stored inside the polymerization vessel, hot water was passed through the jacket to heat the raw materials. When the temperature inside the polymerization vessel reached 52°C, cooling water was passed through the jacket to maintain the temperature inside the polymerization vessel at 52°C, and the polymerization reaction was allowed to proceed. When the pressure inside the polymerization vessel reached 5 kgf / cm 2 The polymerization reaction was terminated when the pressure reached 0.49 MPa·G. After recovering the unreacted monomer, the reaction mixture, which was a slurry, was removed from the polymerization vessel. The reaction mixture was dehydrated and dried to obtain a vinyl chloride polymer.

[0267] Example 2 (Formation of anti-scale adhesion layer) First, a stainless steel polymerization vessel having the same configuration as the above-described polymerization apparatus 100 was prepared. The internal volume of the polymerization vessel was 2 m 3 Next, a scale adhesion preventive layer was formed on the inner wall surface of the polymerization vessel by the following procedure.

[0268] First, hot water was passed through the jacket of the polymerization vessel to heat the inner wall surface of the polymerization vessel to 45°C. Next, steam of 0.717 MPaG (171.4°C) was supplied into the inside of the polymerization vessel. The steam supply flow rate was 240 kg / h, and the steam supply time was 60 seconds. This completed the preheating of the polymerization vessel.

[0269] Next, the coating solution No. 1-1 was supplied into the polymerization vessel using the steam as a carrier. The supply flow rate of the coating solution was 120 g / min, and the supply time of the coating solution was 120 seconds. Thereafter, the supply of the coating solution No. 1-1 was stopped. As a result, the first coating layer described above was formed.

[0270] Next, the coating solution No. 2-1 was supplied into the polymerization vessel using the steam as a carrier. The supply flow rate of the coating solution was 285 g / min, and the supply time of the coating solution was 40 seconds. As a result, the second coating layer described above was formed.

[0271] Thereafter, the supply of steam and the supply of the coating solution No. 2-1 were stopped. Also, the flow of hot water to the jacket was stopped. As a result, a scale adhesion preventive layer was formed on the inner wall surface of the polymerization vessel.

[0272] (Preparation of polymer) The polymerization vessel on which the scale adhesion preventive layer was formed by the above procedure was used to produce a vinyl chloride polymer. The procedure for producing the vinyl chloride polymer was the same as in Example 1.

[0273] Example 3 Except for using Coating Liquid No. 1-2 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0274] Example 4 Except for using Coating Liquid No. 1-2 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0275] Example 5 Except for using Coating Liquid No. 1-3 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0276] Example 6 Except for using Coating Liquid No. 1-3 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0277] Example 7 Except for using Coating Liquid No. 1-4 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0278] Example 8 Except for using Coating Liquid No. 1-4 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0279] Comparative Example 1 Except for using Coating Liquid No. 1-5 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0280] Comparative Example 2 Except for using Coating Liquid No. 1-5 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0281] Comparative Example 3 Except for using Coating Liquid No. 1-6 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0282] Comparative Example 4 Except for using Coating Liquid No. 1-6 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0283] Comparative Example 5 Except for using Coating Liquid No. 1-7 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 1. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 1 using the above polymerization vessel.

[0284] Comparative Example 6 Except for using Coating Liquid No. 1-7 instead of Coating Liquid No. 1-1, a scale adhesion preventive layer was formed on the inner wall surface of a polymerization vessel in the same manner as in Example 2. Furthermore, a vinyl chloride polymer was produced in the same manner as in Example 2 using the above polymerization vessel.

[0285] (Evaluation of Examples 1 to 8 and Comparative Examples 1 to 6) (Prevents scale buildup) After the polymerization reaction was completed, the amount of scale adhering to the liquid phase portion of the inner wall surface of the polymerization vessel was visually observed for each of Examples 1 to 8 and Comparative Examples 1 to 6. The observation results are shown in Table 1.

[0286] In the column "Scaling prevention effect" in Table 1, ○ indicates that no scaling was observed. △ indicates that scaling was observed to the extent that continuous operation was possible. More specifically, △ indicates that the number of batches that could be continuously operated was 10 batches or more but less than 100 batches. × indicates that scaling was observed to the extent that frequent cleaning was necessary. More specifically, × indicates that the number of batches that could be continuously operated was less than 10 batches.

[0287] (Prevents foreign matter from entering) For each of Example 2 and Comparative Example 2, 200 cm of the product polymer was 3 The number of foreign matter particles having a major axis of 250 μm or more per unit area was measured according to JIS K6737. The content of addition condensation products of aromatic compounds and carbonyl compounds in the foreign matter was 1 mass% or more in all cases. The measurement results for Example 2 and Comparative Example 2 are shown in Table 1. In the "Number of foreign matter" column in Table 1, "-" indicates that the measurement was not performed.

[0288] (Composition of addition condensation product contained in coating liquid) For each of Examples 2, 4, 6, and 8, and Comparative Example 2, the composition of the addition condensate contained in the coating solution used to prepare the scale adhesion preventive layer was determined by high performance liquid chromatography analysis. Specifically, the content ratio of the first condensate to the second condensate described above was (sometimes referred to as the content ratio in the coating solution) was derived. The results of the derivation for each of Examples 2, 4, 6, and 8, and Comparative Example 2 are shown in Table 1. In the column of "content ratio in the coating solution" in Table 1, "-" indicates that the content ratio was not derived. Details of the device and measurement conditions used for high performance liquid chromatography were as follows.

[0289] (Details of chromatogram and measurement conditions) As the chromatograph, Nexera / Prominence, a general-purpose HPLC manufactured by Shimadzu Corporation, was used. As the system controller of the above chromatograph, SCL-40 (manufactured by Shimadzu Corporation) was used. As the liquid delivery unit of the above chromatograph, two LC-40D (manufactured by Shimadzu Corporation) were used. The injection amount of the sample was set to 20 μL.

[0290] DGU-403 (Shimadzu Corporation) was used as the online degasser for the chromatograph. SIL-20ACHT (Shimadzu Corporation) was used as the autosampler for the chromatograph. CTO-20A (Shimadzu Corporation) was used as the column oven for the chromatograph. The temperature of the column oven was set to 40°C. SPD-20A (Shimadzu Corporation) was used as the UV-VIS detector for the chromatograph. The detection wavelength was set to 288 nm.

[0291] The guard column used was a Puresil® C18 guard column (100 Å, 5 μm, 3.9 mm × 20 mm × 1 column) manufactured by Waters, and the analytical column used was a μ-Bondasphere / DeltaPak® C18 column (100 Å, 5 μm, 3.9 mm × 150 mm × 1 column) manufactured by Waters.

[0292] Two types of solutions (referred to as eluent A and eluent B) were used as eluents. As eluent A, a solution was prepared by adding 2 mL of acetic acid per 1 L of distilled water. As eluent B, a solution was prepared by adding 1 mL of acetic acid per 1 L of acetonitrile.

[0293] (An example of detailed measurement procedure) (Hold-up time t O Measurement of According to the procedure described in relation to the analytical procedure by the LC method, first, the hold-up time t O The hold-up time t OIn the measurement, the injection amount of the uracil aqueous solution was set to 20 μL. The total flow rate of eluent A and eluent B was set to 1.0 mL / min. As for the gradient conditions of the eluent, the ratio of eluent B to the total volume of the eluent was first set to 40% by volume. Next, the ratio of eluent B to the total volume of the eluent was changed linearly from 40% by volume to 100% by volume over 30 minutes. Next, the ratio of eluent B to the total volume of the eluent was kept at 100% by volume for 10 minutes.

[0294] (The retention time of each component in the coating solution t R Measurement of First, the coating solution according to each Example and Comparative Example was filtered using a polytetrafluoroethylene filter having a pore size of 0.45 μm to obtain a filtrate. Next, the filtrate was set in the above-mentioned chromatograph, and the retention time t R The measurement of retention time t R The measurement conditions are the hold-up time t O The measurement conditions were the same as those of .

[0295] (Content ratio in coating solution) First, the hold-up time t O and the retention time t of each component contained in the coating solution used to prepare the scale adhesion preventive layer in each Example and Comparative Example. R Based on the above, the retention coefficients of the peaks appearing in the chromatograms of each of the Examples and Comparative Examples were derived. Next, the total area of ​​one or more peaks appearing in the chromatograms with a retention coefficient of 16 or more and 25 or less was divided by the total area of ​​one or more peaks appearing in the chromatograms with a retention coefficient of 7 or more and less than 16 to derive the content ratio in the coating liquid.

[0296] The sum of the areas of one or more peaks appearing in a retention index between 7 and less than 16 corresponds to the content of addition condensates having a relatively small average molecular weight. The sum of the areas of one or more peaks appearing in a retention index between 16 and 25 corresponds to the content of addition condensates having a relatively large average molecular weight.

[0297] (Composition of addition condensation product contained in scale adhesion prevention layer) For each of Examples 2, 4, 6, and 8, and Comparative Example 2, the composition of the addition condensate contained in the scale adhesion preventive layer was determined by high performance liquid chromatography analysis. Specifically, the content ratio of the first condensate to the second condensate described above (sometimes referred to as the content ratio in the coating film) was derived. The derived results for each of Examples 2, 4, 6, and 8, and Comparative Example 2 are shown in Table 1. In the column of "Content ratio in the coating film" in Table 1, "-" indicates that the content ratio has not been derived.

[0298] The apparatus and measurement conditions used for the high performance liquid chromatography were the same as those used for the procedure for deriving the content ratio in the coating liquid. The samples of the scale adhesion preventive layer were collected according to the following procedure. The retention time t R The measurement of was carried out by the following procedure. The content ratio in the coating film was derived by the following procedure.

[0299] (Collecting a sample of the anti-scale layer) In each Example and Comparative Example, the inside of the polymerization vessel was visually inspected to confirm the location where the scale adhesion preventive layer was formed. Next, a swab impregnated with N-methyl-2-pyrrolidone (sometimes referred to as NMP) was rubbed against a 10 cm x 10 cm square area inside the scale adhesion preventive layer to obtain a sample of the scale adhesion preventive layer.

[0300] Next, 10.0 mL of NMP and 20 μL of 0.5 N hydrochloric acid were mixed to prepare a solvent for recovering the NMP solution containing the addition condensate from the swab. Next, the above solvent was dropped onto the swab in 10 portions of 100 μL each, and the washings were recovered. As a result, samples of the scale adhesion prevention layer according to each of the examples and comparative examples were obtained.

[0301] (The retention time t R Measurement of First, the above samples according to each Example and Comparative Example were filtered using a polytetrafluoroethylene filter having a pore size of 0.45 μm to obtain a filtrate. Next, the above filtrate was set in the above-mentioned chromatograph, and the retention time t R The measurement of retention time t R The measurement conditions are the hold-up time t O The measurement conditions were the same as those of . (Content ratio in coating film) First, the hold-up time t O and the retention time t of each component contained in the sample of the scale adhesion preventive layer formed in each Example and Comparative Example. R Based on the above, the retention coefficients of the multiple peaks appearing in the chromatograms of each of the Examples and Comparative Examples were derived. Next, the total area of ​​one or more peaks appearing in the retention coefficient range of 16 to 25 was divided by the total area of ​​one or more peaks appearing in the retention coefficient range of 7 to less than 16 to derive the content ratio in the coating film.

[0302] [Table 1]

[0303] As shown in Table 1, the composition used as the scale adhesion preventive agent contains a thiol compound, so that the scale adhesion preventive layer has an excellent scale adhesion prevention effect even when the scale adhesion preventive layer is formed by a steam coating method. This prevents a decrease in the heat removal efficiency of the polymerization can. In addition, the inclusion of foreign matter in the product is prevented. As a result, the product yield is improved.

[0304] Furthermore, as shown in Table 1, the scale prevention effect of the scale prevention layer is reduced in Comparative Examples 1 to 6, which relate to coating solutions containing antioxidants such as sodium dithionite, L-ascorbic acid, and N,N-diethylhydroxylamine. This shows that thiol compounds are particularly excellent as additives to compositions containing addition condensates of aromatic compounds and carbonyl compounds, compared to antioxidants or among antioxidants.

[0305] Although the present invention has been described above using the embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It is clear to those skilled in the art that various modifications or improvements can be made to the above embodiments. In addition, the matters described for a specific embodiment can be applied to other embodiments to the extent that they are not technically inconsistent. It is clear from the claims that such modified or improved forms can also be included in the technical scope of the present invention.

[0306] It should be noted that the order of execution of each process, such as operations, procedures, steps, and stages, in the devices, systems, programs, and methods shown in the claims, specifications, and drawings is not specifically stated as "before," "prior to," etc., and may be realized in any order unless the output of a previous process is used in a later process. Even if the operational flow in the claims, specifications, and drawings is explained using "first," "next," etc. for convenience, it does not mean that it is essential to perform the process in this order. [Explanation of symbols]

[0307] 100 Polymerization device, 110 Reaction vessel, 112 Main body, 114 Inner surface, 116 Scale prevention layer, 120 Stirrer, 122 Stirring shaft, 124 Stirring blade, 126 Power mechanism, 130 Baffle, 132 Main body, 134 Support, 140 Cooling tube, 170 Jacket, 172 Flow path, 180 Reflux condenser, 182 Flow path, 190 Coating device, 212 Coating liquid supply section, 214 Washing water supply section, 220 Coating nozzle, 222 Line, 230 First coating liquid storage tank, 232 Pump, 234 Line, 236 Valve, 240 Second coating liquid storage tank, 242 Pump, 244 Line, 246 Valve, 250 Steam supply source, 254 Line, 256 Valve, 260 Washing nozzle, 270 Wash water reservoir, 272 pump, 274 line, 276 valve

Claims

1. an addition condensation product of an aromatic compound and a carbonyl compound; A thiol compound, A composition comprising:

2. The composition contains 0.01 parts by mass or more and 100 parts by mass or less of the thiol compound relative to 100 parts by mass of the aromatic compound. The composition of claim 1.

3. The addition condensate is a first type of addition condensate having a first average molecular weight; a second type of addition condensate having a second average molecular weight; and Including, the first average molecular weight and the second average molecular weight are different; The composition of claim 1.

4. a ratio of the mass of the second type of addition condensate to the mass of the first type of addition condensate is 2.3 to 1000; The second average molecular weight is greater than the first average molecular weight. The composition of claim 3.

5. The thiol compound is A thiol group, At least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group; having The composition of claim 1.

6. The thiol compound is thioglycerol, thioglycol, or a derivative thereof. The composition of claim 1.

7. The aromatic compound is a naphthol. The composition of claim 1.

8. The carbonyl compound is an aldehyde compound, a ketone compound, or a derivative thereof. The composition of claim 1.

9. The aromatic compound is 1-naphthol, the carbonyl compound is formaldehyde; The thiol compound is 1-thioglycerol or thioglycol. The composition of claim 1.

10. A scale inhibitor for preventing adhesion of scale containing a polymer, The composition according to any one of claims 1 to 9, Scale prevention agent.

11. providing a mixture of a solvent, an aromatic compound, a carbonyl compound, and a thiol compound; reacting the aromatic compound and the carbonyl compound contained in the mixture in the presence of a catalyst and a surfactant to prepare a composition containing an addition condensation product of the aromatic compound and the carbonyl compound, and the thiol compound; A method for producing a composition comprising:

12. the catalyst is an alkali metal hydroxide; The surfactant is an anionic surfactant. A method for producing the composition of claim 11.

13. 1. A reactor for polymerizing monomers, comprising: A reactor configured to be capable of storing a solution containing a monomer, The reactor has a coating layer disposed on at least a part of an inner wall surface that is a surface that comes into contact with the solution, The coating layer contains an addition condensate of an aromatic compound and a carbonyl compound, The addition condensate is a first type of addition condensate having a first average molecular weight; a second type of addition condensate having a second average molecular weight; and Including, the second average molecular weight is greater than the first average molecular weight; The ratio of the mass of the second type of addition condensate to the mass of the first type of addition condensate is 0.75 to 1000. Reactor.

14. Providing a reactor as claimed in claim 13; charging a solution containing monomers into a reactor of the reactor; initiating a polymerization reaction of the monomers within the reactor; terminating the polymerization reaction of the monomer within the reactor; A method for producing a polymer comprising:

15. A particulate polymer, The polymer 200 cm measured according to JIS K6737 ３ The number of foreign objects having a major axis of 250 μm or more contained in each hit is 2 to 4, The content of the addition condensation product of the aromatic compound and the carbonyl compound in the foreign matter is 1% by mass or more. Polymer.

Images