Process for the production of formaldehyde polymers

Abstract

The present invention relates to a method for producing a formaldehyde polymer. The object of the present invention is to provide a method for producing a formaldehyde polymer capable of continuously and stably obtaining a formaldehyde polymer with a polymerizer. A method for producing a formaldehyde polymer, which is a method for continuously producing a formaldehyde polymer, characterized by comprising: an introduction step of introducing a raw material substance and a liquid containing a catalyst into a polymerizer using a double pipe composed of an inner pipe and an outer pipe; and a reaction step of generating a formaldehyde polymer by reacting the raw material substance and the catalyst in the polymerizer, wherein, in the introduction step, the raw material substance passes between the inner pipe and the outer pipe of the double pipe, the liquid containing the catalyst passes inside the inner pipe of the double pipe, and a front end portion of the inner pipe is in a shape that is tapered toward the front end in appearance.

Description

Technical Field

[0001] This invention relates to a method for manufacturing formaldehyde polymers. Background Technology

[0002] Formaldehyde polymers possess excellent processability and productivity, enabling the efficient production of products and components of desired shapes through molding methods such as melt injection molding and melt extrusion molding. Leveraging these advantages, formaldehyde polymers are widely used in electrical and electronic materials, the automotive industry, various other industrial materials, food packaging, and component manufacturing. The production of products for these applications requires a formaldehyde polymer manufacturing method that includes a continuous and stable polymerization process for mixing raw materials and polymerization catalysts.

[0003] In methods for obtaining formaldehyde polymers, various approaches have been proposed to date, such as mixing raw materials with a polymerization catalyst and then feeding them into a polymerizer.

[0004] For example, there are methods such as: a method that can operate continuously without causing pipe blockage caused by polymer or poor supply to the polymerizer caused by narrowing by changing the feeding angle of the polymerization catalyst solution pipe introduced into the mixed raw material pipe of monomer and comonomer (see, for example, Patent Document 1); and a method that, in the process of pre-mixing the comonomer and the polymerization catalyst and then mixing them with the monomer, makes the supply direction of the comonomer and the supply direction of the polymerization catalyst the same while contacting and mixing the two (see, for example, Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] [Patent Document 1] Japanese Patent No. 4092545

[0008] [Patent Document 2] Japanese Patent No. 3208377 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In the aforementioned Patent Document 1, a polymerization reaction is carried out by mixing raw materials and catalyst, and the time from the mixing contact section to the polymerizer is specified. However, due to changes in the supply of raw materials and catalyst liquid, and changes in the pressure inside the polymerizer, the residence time in the contact section becomes longer. It is possible that the polymerization will stop due to the polymer adhering to the front end of the pipe and thus causing blockage of the supply section.

[0011] In the aforementioned Patent Document 2, the catalyst liquid and comonomer are pre-mixed to form a mixture, and the linear velocity and mixing time of the mixture flow when mixed with trioxymethylene as a raw material are specified. However, the possibility of polymer solids adhering and clogging the supply pipe when the catalyst liquid, comonomer and trioxymethylene are mixed cannot be ruled out.

[0012] Therefore, the object of the present invention is to provide a method for manufacturing formaldehyde polymers that can continuously and stably obtain formaldehyde polymers using a polymerizer.

[0013] means for solving problems

[0014] In order to solve the problems of the prior art described above, the inventors conducted in-depth research and discovered that polymerization is hindered by the adhesion of polymerized solids to the pipes in which the raw material and the catalyst-containing liquid (hereinafter also referred to as "catalyst liquid") are supplied. Furthermore, the inventors discovered that by using a double-layered pipe with a specific structure to supply the raw material and catalyst liquid to the polymerizer, the above-mentioned problems can be solved, thus completing the present invention.

[0015] That is, this implementation method is as follows. [1]

[0017] A method for manufacturing a formaldehyde polymer, which is a continuous method for manufacturing a formaldehyde polymer, characterized in that the method for manufacturing the formaldehyde polymer includes the following steps:

[0018] The introduction process involves using a double-layered tube consisting of an inner and outer tube to introduce the raw materials and a liquid containing the catalyst into the polymerizer; and

[0019] The reaction process involves reacting the raw materials and the catalyst within the polymerizer to generate a formaldehyde polymer.

[0020] In the introduction process,

[0021] The raw material passes between the inner and outer tubes of the double-layered pipe.

[0022] The catalyst-containing liquid passes through the interior of the inner tube of the double-walled tube, and

[0023] The front end of the inner tube is tapered towards the front. [2]

[0025] The method for manufacturing formaldehyde polymer as described in [1], wherein the contact between the raw material and the liquid containing the catalyst and the introduction into the polymerizer are carried out simultaneously. [3]

[0027] The method for manufacturing formaldehyde polymer as described in [1] or [2], wherein the raw material is trioxymethylene. [4]

[0029] The method for manufacturing formaldehyde polymer as described in any one of [1] to [3], wherein the catalyst is a cationic polymerization catalyst. [5]

[0031] A method for manufacturing formaldehyde polymer as described in any one of [1] to [4], wherein, in at least a portion of the front end of the double-layer tube, the ratio of the linear velocity of the raw material to the linear velocity of the liquid containing the catalyst is in the range of 0.4 to 8.9. [6]

[0033] The method for manufacturing formaldehyde polymer as described in any one of [1] to [5], wherein, in the cross section of the inner tube, the angle of the cone formed by the line constituting the inner surface of the inner tube and the straight line connecting the point where the thickness of the wall of the inner tube begins to gradually decrease and the point where the thickness of the wall of the inner tube reaches its minimum is in the range of 10° to 70°. [7]

[0035] The method for manufacturing formaldehyde polymer as described in [6], wherein the angle of the cone is in the range of 10° to 30°.

[0036] Invention Effects

[0037] The method for manufacturing formaldehyde polymer according to the present invention enables the continuous and stable production of formaldehyde polymer. Attached Figure Description

[0038] Figure 1 This is a cross-sectional view of the double-layered tube used in this embodiment when cut along its axis. Detailed Implementation

[0039] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. This embodiment is merely an example for illustrating the present invention and is not intended to limit the invention to its contents. The present invention can be implemented with various modifications within the scope of its spirit.

[0040] (Manufacturing method of formaldehyde polymer)

[0041] The method for manufacturing formaldehyde polymer according to this embodiment is characterized by comprising the following steps: an introduction step, wherein a raw material and a liquid containing a catalyst are introduced into a polymerizer using a double-walled tube; and a reaction step, wherein a formaldehyde polymer is generated by reacting the raw material with the catalyst within the polymerizer. In the introduction step, the raw material flows through the outer liquid section of the double-walled tube (between the inner and outer tubes), the catalyst liquid flows through the inner liquid section of the double-walled tube (inside the inner tube), and the inner tube has a shape that tapers towards the front end. It should be noted that the front end does not strictly refer only to the tip of the tube, such as... Figure 1 As shown, it also includes a reasonable range for the shape of the tube.

[0042] [Introduction Process]

[0043] The method for manufacturing formaldehyde polymer according to this embodiment includes an introduction step, in which raw materials and a liquid containing a catalyst (catalyst liquid) are supplied to the polymerizer through a double-layered tube consisting of an inner tube and an outer tube. In the introduction step, optional components such as molecular weight regulators (described later) can be supplied to the polymerizer together with the raw materials and catalyst liquid using the double-layered tube.

[0044] Furthermore, in this process, it is preferable that the contact between the raw material and the catalyst liquid and its introduction into the polymerizer are carried out simultaneously. Here, "the contact between the raw material and the catalyst liquid and its introduction into the polymerizer are carried out simultaneously" means that the time difference between the time point when at least a portion of the raw material contacts at least a portion of the catalyst liquid and the time point when it is introduced into the polymerizer is less than 0.1 seconds. Additionally, "the time point when it is introduced into the polymerizer" refers to the time point when the mixture formed by the contact between the raw material and the catalyst liquid is located closer to the inner side of the polymerizer than the opening of the polymerizer (which may be the front end of a double-layered tube).

[0045] Double-layer pipe

[0046] exist Figure 1 The cross-sectional view of the double-layered tube as it is cut along its axis shows the double-layered tube used in this embodiment.

[0047] In this embodiment, the double-walled pipe is used to supply the raw material and catalyst liquid into the polymerizer, and is located at the foremost and upper part of the polymerizer. The double-walled pipe is a structure that allows the raw material to flow between its inner and outer pipes, and allows the catalyst liquid to flow inside the inner pipe. Here, the space inside the inner pipe forms the inner flow section of the double-walled pipe, and the space between the inner and outer pipes forms the outer flow section of the double-walled pipe (see reference). Figure 1The cross-sectional area of ​​the inner flow section of the double-walled tube can be constant over the entire specified extension length of the front end of the inner tube. Furthermore, the cross-sectional area of ​​the outer flow section of the double-walled tube can be constant over the entire specified extension length of the front end of the inner tube (see reference). Figure 1 ).

[0048] Specifically, in the case of homopolymers, the raw material, such as trioxymethylene, and an optional molecular weight regulator are premixed; in the case of copolymers, for example, trioxymethylene as a raw material and cyclic ethers and / or cyclic formaldehyde as comonomers, along with an optional molecular weight regulator, are premixed and passed through the outer liquid flow section of the double-walled tube. The catalyst solution obtained by premixing the catalyst and its diluent is then passed through the inner liquid flow section.

[0049] The ratio (the ratio of the linear velocity of the raw material to the linear velocity of the catalyst liquid) of at least a portion of the front end of the double-walled tube, such as the portion where the raw material flows at a constant linear velocity just before contacting the catalyst liquid (the portion where both the cross-sectional areas of the inner and outer flow portions of the double-walled tube are constant), ranges from 0.4 to 8.9, more preferably from 0.9 to 8.4. Here, m / s is used as the unit of linear velocity.

[0050] In addition, such as Figure 1 As shown, the front end of the inner tube of the double-walled tube has a tapered shape that tapers towards the front. Here, the cross-sectional area of ​​the liquid flow section inside the double-walled tube at the front end can be the same as the cross-sectional area of ​​the liquid flow section inside the double-walled tube outside the front end. That is, in the inner tube of the double-walled tube, the wall thickness gradually decreases towards the front end at the front end. In the cross-section of the inner tube (refer to...) Figure 1 In the diagram, the line forming the inner surface of the inner tube intersects the line connecting the point where the thickness of the inner tube wall begins to gradually decrease and the point where the thickness of the inner tube wall reaches its minimum. In the cross-section of the inner tube, the end of the line forming the inner surface of the inner tube is located closer to the axial outer side of the double-layer tube than the end of the line forming the outer surface of the inner tube.

[0051] The aforementioned cone angle is preferably 10° to 70°, more preferably 10° to 30°, and even more preferably 10° to 20°. It should be noted that the aforementioned cone angle can be set to the smaller of the angles formed by the line constituting the inner surface of the inner tube and the straight line connecting the point where the thickness of the inner tube wall begins to gradually decrease and the point where the thickness of the inner tube wall reaches its minimum.

[0052] In this embodiment, since the range of the ratio obtained by dividing the linear velocity of the raw material by the linear velocity of the catalyst liquid and the front end angle of the inner tube are within the above range, continuous polymerization can be stably carried out without the mixture of raw material and catalyst liquid remaining at the front end of the double-layer tube.

[0053] <Raw Materials>

[0054] In this embodiment, the raw material used may be, for example, trioxymethylene.

[0055] Trioxymethylene can be produced by reacting formaldehyde in the presence of an acidic catalyst.

[0056] The raw materials typically contain water and formic acid as impurities. These impurities act as chain transfer agents, potentially causing the polymer terminal groups of the formaldehyde polymer obtained through polymerization to become thermally unstable, making it difficult to obtain a formaldehyde polymer with high thermal stability. Therefore, it is preferable to purify and remove these impurities to a certain concentration before polymerization begins. Based on the mass of the raw materials, the total content of these impurities in the raw materials is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, and even more preferably 30 ppm by mass or less.

[0057] <Raw materials of copolymer>

[0058] In this embodiment, when manufacturing a copolymer of formaldehyde polymers, cyclic ethers and / or cyclic formaldehydes can be used as comonomer components added to the raw material. Specifically, examples of cyclic ethers and / or cyclic formaldehydes include: ethylene oxide, propylene oxide, epibutylene oxide, epichlorohydrin, epibromopropane, phenylethylene oxide, oxetane, 1,3-dioxacyclopentane, ethylene glycol formaldehyde, propylene glycol formaldehyde, diethylene glycol formaldehyde, triethylene glycol formaldehyde, 1,4-butanediol formaldehyde, 1,5-pentanediol formaldehyde, 1,6-hexanediol formaldehyde, etc. These substances can be used individually or in combination of two or more.

[0059] During polymerization, the amount of cyclic ether and / or cyclic formaldehyde added relative to 1 mole of starting material is preferably in the range of 0.01 mol to 0.2 mol, more preferably in the range of 0.01 mol to 0.15 mol, even more preferably in the range of 0.01 mol to 0.1 mol, and particularly preferably in the range of 0.01 mol to 0.05 mol. If the amount of cyclic ether and / or cyclic formaldehyde added is within the above range, the polymerization rate tends to be accelerated to some extent, the polymerization yield is sufficiently increased, and formaldehyde polymers can be stably produced.

[0060] <Catalyst>

[0061] The catalyst used in the manufacturing method of this embodiment is not particularly limited as long as it can stably produce formaldehyde polymers, but a cationic polymerization catalyst is preferred. Examples of cationic polymerization catalysts include Lewis acids, protic acids, and their esters or anhydrides. Examples of Lewis acids include halides of boron, tin, titanium, phosphorus, arsenic, and antimony; boron trifluoride, boron trifluoride hydrate, and coordination complexes of boron trifluoride with organic compounds containing oxygen or sulfur atoms are particularly preferred. Examples of protic acids and their esters or anhydrides include perchloric acid, trifluoromethanesulfonic acid, tert-butyl perchlorate, acetyl perchlorate, and trimethylolpropionic acid. Hexafluorophosphates, heteropoly acids, isopoly acids, acid salts of heteropoly acids, and acid salts of isopoly acids are preferred, with heteropoly acids being particularly preferred. These substances may be used alone or in combination of two or more.

[0062] From the viewpoint of stable continuous polymerization, the preferred addition amount of polymerization catalyst relative to 1 mole of starting material is 1 × 10⁻⁶. -9 mole ~ 1×10 -2 Within the range of moles, more preferably within 2 × 10 -9 mole ~ 1×10 -2 Within the range of moles, a further preferred value is 5 × 10⁻⁶. -9 mole ~ 1×10 -3 Within the range of moles.

[0063] <Catalyst Liquid>

[0064] The catalyst liquid used in the manufacturing method of this embodiment is prepared by diluting the above-mentioned polymerization catalyst with an inert diluent that has no adverse effect on the polymerization reaction.

[0065] The preferred diluent for diluting the polymerization catalyst is a hydrocarbon compound without hydroxyl groups. Specific examples of hydrocarbon compounds include: aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, and cyclohexane; and ether compounds such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, and 1,4-dioxane. The appropriate choice can be made based on the solubility of the cationic polymerization catalyst to be used. One or more of the aforementioned hydrocarbon compounds without hydroxyl groups can be used alone or in combination. By using such hydrocarbon compounds without hydroxyl groups as diluents, the molecular weight of the formaldehyde polymer can be easily controlled.

[0066] During polymerization, the amount of diluent added relative to 1 mole of the starting material is preferably 0.1 × 10⁻⁶. -3 The range is from 0.2 moles to 0.2 moles, more preferably 0.2 × 10⁻⁶ moles. -3 Within the range of 0.1 moles, further preferably within 0.5 × 10⁻⁶ moles.-3 The amount of diluent added is in the range of 0.05 mol to 0.05 mol. If the amount of diluent added is within the above range, it will not hinder the polymerization reaction, and formaldehyde polymer can be obtained in a higher yield, which is preferred from these considerations.

[0067] <Molecular weight regulator>

[0068] In this embodiment, a low molecular weight acetal compound can be used as a molecular weight regulator. The low molecular weight acetal compound is an acetal compound that acts as a chain transfer agent during the polymerization of the starting material with cyclic ethers and / or cyclic formaldehydes, and has a molecular weight of 200 or less, preferably 60 to 170. Specifically, suitable examples of molecular weight regulators include: methyl acetal, methoxymethyl acetal, dimethoxymethyl acetal, and trimethoxymethyl acetal. These substances can be used alone or in combination of two or more. Furthermore, from the viewpoint of controlling the molecular weight of the formaldehyde polymer within a suitable range, the amount of low molecular weight acetal compound added during polymerization is preferably 0.1 × 10⁻⁶ per mole of the starting material. -4 moles ~ 0.6 × 10 -2 Within the range of moles.

[0069] [Reaction Process]

[0070] The manufacturing method of this embodiment includes a reaction step in which a formaldehyde polymer is generated by reacting a raw material with a catalyst in a polymerizer. The formaldehyde polymer is polymerized by cationic polymerization using a bulk polymerization method. There are no particular limitations on the shape (structure) of the polymerization reactor used; generally, a biaxial paddle or screw-type stirred mixing polymerization reactor capable of allowing a heat medium to pass through a jacket is suitable.

[0071] The polymerization reaction temperature is preferably maintained in the range of 63°C to 135°C. More preferably, the polymerization reaction temperature is in the range of 70°C to 120°C, and even more preferably, in the range of 70°C to 100°C.

[0072] The residence (reaction) time in the polymerization reactor is preferably 0.1 minutes to 30 minutes, more preferably 0.1 minutes to 25 minutes, and even more preferably 0.1 minutes to 20 minutes.

[0073] By adjusting the polymerization reaction temperature and the residence time in the polymerization reactor to the above ranges, the thermal decomposition of formaldehyde polymers can be suppressed more effectively, and more thermally stable formaldehyde polymers can be produced.

[0074] <Post-polymerization cleaning, filtration, and drying process>

[0075] Then, after polymerization, the polymerization catalyst can be removed by washing from the obtained formaldehyde polymer. As a method for removing the polymerization catalyst, conventional methods can be used, such as adding the formaldehyde polymer discharged from the polymerization reactor to water only or to an aqueous solution containing at least one of the following deactivating agents: amines such as ammonia, triethylamine, and tri-n-butylamine; hydroxides of alkali metals or alkaline earth metals; inorganic salts; or organic acid salts. The polymerization catalyst is then washed away while continuously stirred in a slurry state within a temperature range of room temperature to below 100°C for several minutes to several hours. When the formaldehyde polymer is in large lumps, from the viewpoint of improving the efficiency of removing the polymerization catalyst, it is preferable to pulverize or micronize the formaldehyde polymer to facilitate its removal. After removing the polymerization catalyst, the target formaldehyde polymer can be obtained by filtering using a centrifuge or similar device and drying under a nitrogen atmosphere.

[0076] [Example]

[0077] The following describes this embodiment in detail with specific examples and comparative examples, but this embodiment is not limited to the following examples as long as it does not deviate from its spirit.

[0078] It should be noted that the evaluation methods and raw materials used in the examples and comparative examples are as follows.

[0079] [Operational Stability Evaluation Methods]

[0080] When feeding raw materials and catalyst liquid into the polymerizer via a double-layered pipe and continuously polymerizing it, the continuous operating time until the pressure fluctuation rate of the raw material supply section and catalyst liquid supply section caused by blockage at the front end of the double-layered pipe reaches more than 50% of the stable value is evaluated.

[0081] [Example 1]

[0082] A twin-shaft paddle-type continuous polymerization reactor (manufactured by Kurimoto Iron Works Co., Ltd., diameter 2B, L / D = 14.8) rotating in the same direction and set to 80°C was used as the polymerizer. It should be noted that, to prevent oxygen contamination, 60L of nitrogen gas was introduced every hour near the feed inlet of the polymerization reactor. A double-walled tube with a conical tip was used, the angle θ of which is described later. Trioxymethylene was then supplied to the polymerization reactor at a rate of 4000g / hour through the outer flow section of the double-walled tube. Additionally, 0.045 mol (148.0g / hour) of 1,3-dioxane, a cyclic ether and / or cyclic formaldehyde, was fed into the polymerization reactor relative to 1 mol of trioxymethylene. Then, ferric chloride, used as a polymerization catalyst, was diluted with 1,4-dioxane as a diluent in an appropriate proportion, and the resulting polymerization catalyst solution was supplied to the polymerizer through the inner flow section of the double-walled tube, and polymerization was initiated. The time difference between the contact point of the mixture of paraformaldehyde and 1,3-dioxane with the 1,4-dioxane solution of ferric chloride and the time point when their mixture is located closer to the inside than the opening of the polymerization reactor is less than 0.1 seconds.

[0083] The results are shown in Table 1.

[0084] [Examples 2-7]

[0085] Except that the linear velocity ratio of the raw material to the catalyst liquid and the inner tube front end angle are set to the conditions shown in Table 1, the procedure is the same as in Example 1.

[0086] The results are shown in Table 1.

[0087] [Table 1]

[0088]

[0089] [Compare Examples 1 and 2]

[0090] Except that the linear velocity ratio of the raw material to the catalyst liquid and the inner tube front end angle are set to the conditions shown in Table 2, the procedure is the same as in Example 1.

[0091] The results are shown in Table 2.

[0092] [Table 2]

[0093] Comparative Example 1 Comparative Example 2 Angle θ (°) 90 90 linear velocity ratio 3.2 6.9 Running time (hours) 3 2

[0094] As shown in Table 1, in Examples 1 to 7, since the front end of the inner tube is narrowed towards the front end, there is no pressure fluctuation in the supply pipe, and it can run continuously for more than 7 hours without problems.

[0095] As shown in Table 2, in Comparative Examples 1 and 2, because the front end of the inner tube did not taper towards the front, the pressure fluctuation in the supply pipe was significant, and the polymerizer stopped operating shortly after polymerization began. After the polymerizer stopped, observation of the front end of the double-layer tube revealed pipe blockage caused by polymer precipitation, indicating a level unsuitable for practical use.

[0096] Industrial practicality

[0097] The method for manufacturing formaldehyde polymer according to the present invention enables the continuous and stable production of formaldehyde polymer.

Claims

1. A method for manufacturing a formaldehyde polymer, characterized in that, The method for manufacturing the formaldehyde polymer includes the following steps: The introduction process involves using a double-layered tube consisting of an inner and outer tube to introduce the raw materials and a liquid containing the catalyst into the polymerizer; and The reaction process involves reacting the raw materials and the catalyst within the polymerizer to generate a formaldehyde polymer. The raw material in the introduction process is trioxymethylene, or a mixture of trioxymethylene with cyclic ethers and / or cyclic formaldehyde. In the introduction process, The raw material passes between the inner and outer tubes of the double-layered pipe. The catalyst-containing liquid passes through the interior of the inner tube of the double-walled tube, and The front end of the inner tube is tapered towards the front. In at least a portion of the front end of the double-layered tube, the ratio of the linear velocity of the raw material to the linear velocity of the catalyst-containing liquid is in the range of 0.6 to 8.

5. In the cross-section of the inner tube, the angle between the line forming the inner surface of the inner tube and the straight line connecting the point where the thickness of the inner tube wall begins to gradually decrease and the point where the thickness of the inner tube wall reaches its minimum is within the range of 10° to 70°.

2. The method for manufacturing formaldehyde polymer as described in claim 1, wherein, The contact between the raw material and the liquid containing the catalyst and its introduction into the polymerizer occur simultaneously.

3. The method for manufacturing the formaldehyde polymer as described in claim 1 or 2, wherein, The raw material is trioxymethylene.

4. The method for manufacturing the formaldehyde polymer as described in claim 1 or 2, wherein, The raw material is trioxymethylene, and cyclic ethers and / or cyclic formaldehyde are added to the raw material as comonomers.

5. The method for manufacturing the formaldehyde polymer as described in claim 4, wherein, The cyclic ether and / or cyclic formaldehyde is selected from one or more of the group consisting of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, bromopropylate, phenyl ethylene oxide, oxacyclobutane, 1,3-dioxacyclopentane, ethylene glycol formaldehyde, propylene glycol formaldehyde, diethylene glycol formaldehyde, triethylene glycol formaldehyde, 1,4-butanediol formaldehyde, 1,5-pentanediol formaldehyde, and 1,6-hexanediol formaldehyde.

6. The method for manufacturing the formaldehyde polymer as described in claim 4, wherein, The amount of cyclic ethers and / or cyclic formaldehyde added relative to 1 mole of trioxymethylene is in the range of 0.01 moles to 0.2 moles.

7. The method for manufacturing the formaldehyde polymer as described in claim 4, wherein, The amount of cyclic ethers and / or cyclic formaldehyde added relative to 1 mole of trioxymethylene is in the range of 0.01 moles to 0.15 moles.

8. The method for manufacturing the formaldehyde polymer as described in claim 4, wherein, The amount of cyclic ethers and / or cyclic formaldehyde added relative to 1 mole of trioxymethylene is in the range of 0.01 moles to 0.1 moles.

9. The method for manufacturing the formaldehyde polymer as described in claim 4, wherein, The amount of cyclic ethers and / or cyclic formaldehyde added relative to 1 mole of trioxymethylene is in the range of 0.01 moles to 0.05 moles.

10. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The catalyst is a cationic polymerization catalyst.

11. The method for manufacturing the formaldehyde polymer as described in claim 10, wherein, The cationic polymerization catalyst is one or more selected from the group consisting of Lewis acids and protic acids and their esters or anhydrides.

12. The method for manufacturing the formaldehyde polymer as described in claim 11, wherein, The Lewis acid is one or more selected from the group consisting of halides of boron, tin, titanium, phosphorus, arsenic and antimony.

13. The method for manufacturing the formaldehyde polymer as described in claim 11 or 12, wherein, The Lewis acid is selected from one or more of the group consisting of boron trifluoride, boron trifluoride hydrate, and coordination complexes of boron trifluoride with an organic compound containing an oxygen atom or a sulfur atom.

14. The method for manufacturing the formaldehyde polymer as described in claim 11, wherein, The protic acid and its ester or anhydride are selected from perchloric acid, trifluoromethanesulfonic acid, tert-butyl perchlorate, acetyl perchlorate, trimethylolpropionic acid, etc. It consists of one or more of the following groups: hexafluorophosphate, heteropolyacid, isopolyacid, acid salts of heteropolyacid, and acid salts of isopolyacid.

15. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The amount of catalyst added relative to 1 mole of the raw material is 1 × 10⁻⁶. -9 mole ~ 1×10 -2 Within the range of moles.

16. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The amount of catalyst added relative to 1 mole of the raw material is 2 × 10⁻⁶. -9 mole ~ 1×10 -2 Within the range of moles.

17. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The amount of catalyst added relative to 1 mole of the raw material is 5 × 10⁻⁶. -9 mole ~ 1×10 -3 Within the range of moles.

18. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The diluent used to dilute the catalyst in the liquid containing the catalyst is one or more selected from the group consisting of benzene, toluene, xylene, n-hexane, n-heptane, cyclohexane, diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, and 1,4-dioxane.

19. The method for manufacturing the formaldehyde polymer as described in claim 18, wherein, The amount of diluent added relative to 1 mole of the raw material is 0.1 × 10⁻⁶. -3 Within the range of 0.2 moles to 0.2 moles.

20. The method for manufacturing the formaldehyde polymer as described in claim 18, wherein, The amount of diluent added relative to 1 mole of the raw material is 0.2 × 10⁻⁶. -3 The range is from 0.1 moles to 0.1 moles.

21. The method for manufacturing the formaldehyde polymer as described in claim 18, wherein, The amount of diluent added relative to 1 mole of the raw material is 0.5 × 10⁻⁶. -3 The range is from 0.05 moles to 0.05 moles.

22. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, In the reaction process, the formaldehyde polymer is polymerized by cationic polymerization using bulk polymerization.

23. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The polymerization reaction temperature is in the range of 63℃ to 135℃.

24. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The polymerization reaction temperature is in the range of 70℃ to 120℃.

25. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The polymerization reaction temperature is in the range of 70℃ to 100℃.

26. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The residence time in the aggregator is 0.1 minutes to 30 minutes.

27. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The residence time in the aggregator is 0.1 minutes to 25 minutes.

28. The method for manufacturing the formaldehyde polymer as described in claim 22, wherein, The residence time in the aggregator is 0.1 minutes to 20 minutes.

29. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The ratio of the linear velocity of the raw material to the linear velocity of the liquid containing the catalyst is in the range of 0.9 to 8.

4.

30. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The angle of the cone is in the range of 10° to 30°.

31. The method for manufacturing the formaldehyde polymer as described in claim 1, wherein, The angle of the cone is in the range of 10° to 20°.

Images