JP5541481B2 - Method for producing radical polymer - Google Patents

Description

  The present invention relates to a method for producing a radical polymer. More specifically, the present invention relates to a method for efficiently and smoothly producing a radical polymer using a microreactor in a short time.

A copolymer of a radical polymerizable monomer obtained by polymerizing a radical polymerizable monomer in the presence of a radical polymerization initiator is used in various industrial fields, and its industrial value is remarkable. is there. Due to its excellent physical properties, it is used in a wide range of fields such as printing materials, paints, adhesives, and various coating materials.
Furthermore, a copolymer of a radical polymerizable monomer is used as a medical pressure-sensitive adhesive or as a coating material for photographic materials or optical materials. Radical polymers for such applications are used for the purpose of minimizing changes in adhesive properties over time, irritation and effects on the human body, and in order to minimize the effects on film properties and optical properties. The amount of radical polymerization initiator for decomposition is required to be as low as possible.
Various methods have been adopted as methods for reducing the amount of residual monomer and the amount of undecomposed radical polymerization initiator as much as possible, but generally a method of repeatedly adding a polymerization initiator in the latter half of the polymerization reaction is adopted. However, there is a problem that it takes a long time to decompose the amount of radical polymerization initiator added additionally. Furthermore, it is disclosed as a method for producing a radical polymer in which the reaction temperature is set to a temperature equal to or higher than the boiling point of the polymerization solution in a sealed state at least in the latter half of the polymerization reaction (see, for example, Patent Document 1).
However, these techniques require a pressure vessel to raise the reaction temperature above the boiling point of the solvent, necessitating the introduction of a large apparatus, or a copolymer of radical polymerizable monomers to raise the reaction temperature. There was a problem of coloring.
In addition, a method for continuously treating under pressure is disclosed by increasing the temperature in the method for producing (meth) acrylate syrup (see, for example, Patent Document 2 and Patent Document 3).
However, these techniques are originally methods for producing syrup, and the polymerization rate of radically polymerizable monomers is low.
In recent years, a drastic review of the manufacturing method of chemical products has been urged due to soaring petroleum energy. In this context, interest in microreactors has increased. A microreactor is a device that performs a reaction in a narrow space, and it is not necessary to introduce a large-scale device, and it is expected to reduce investment costs and manufacturing costs. In addition, since the microreactor performs the reaction in a narrow space, the specific surface area per unit volume is large, and thus the reaction temperature can be easily controlled. Several studies on the use of microreactors taking advantage of this feature have also been made for radical polymerization, and disclosed as a method for producing a radical polymer having a narrow molecular weight distribution (see, for example, Patent Document 4 and Patent Document 5).
However, these techniques did not describe any method for reducing the amount of residual monomer or the amount of undecomposed radical polymerization initiator.

JP 09-124467 A Japanese Patent Publication No.59-21325 Japanese Patent Publication No. 01-49295 International Publication No. 2005/010055 JP 2006-199767 A

  The object of the present invention is to provide a radical monomer having excellent characteristics such as a residual monomer amount that can be obtained only slowly over a mild reaction condition in a conventional batch reactor, and a small amount of undecomposed radical polymerization initiator. An object of the present invention is to provide a method for producing a radical polymer in which a coalescence is produced with high production efficiency with a short residence time using a microreactor.

As a result of intensive studies to solve the above problems, the present inventor conducted radical polymerization in the presence of a radical polymerization initiator in the microtubular channel of the heat transfer reaction vessel in which the microtubular channel was formed. obtained by polymerizing a sex monomer, a fluid containing a polymerization solution containing the residual monomers and undecomposed radical polymerization initiator, under pressure to the flow passage, a liquid-tight state, and, continuously by flowing not particularly colored by supplying while controlling the temperature of the flow path as the radical decomposition rate constant we are in the range of computationally 100h ^-1 ~10000h ^-1, the amount of residual monomer, and undecomposed The present inventors have found that it is possible to produce a radical polymer having excellent characteristics with a small amount of the radical polymerization initiator, and have completed the present invention.

That is, the present invention includes, in the fine tubular flow channel is fine small tubular passage of the heat-conducting reaction vessel which is formed, obtained by polymerizing a radical polymerizable monomer in the presence of a radical polymerization initiator, By allowing a fluid containing a polymerization solution containing residual monomer and undecomposed radical polymerization initiator to flow continuously in a liquid-tight state while pressurizing the flow path, the radical decomposition rate constant is calculated. to provide a method of manufacturing a radical polymer and supplying while controlling the temperature of the flow channel to be in the range of 100h ^-1 ~10000h ^-1.

Further, the present invention is obtained by polymerizing a radical polymerizable monomer in the presence of a radical polymerization initiator, fluid radical degradation rate containing a solution obtained by adding a mixture a radical polymerization initiator to the polymerization solution containing the residual monomers as constant is in the range of computationally 100h ^-1 ~10000h ^-1, while controlling the temperature of the fine small tubular passage of the heat-conducting reaction vessel fine tubular flow channel formed therein, supplied to the flow channel A method for producing a radical polymer is also provided.

  According to the method for producing a radical polymer according to the present invention, the amount of residual monomer that can be obtained only slowly over a mild reaction condition in a conventional batch reaction kettle, and the amount of undecomposed radical polymerization initiator is small. A radical polymer having excellent characteristics can be produced with high production efficiency in a short residence time.

It is a perspective view which shows the schematic diagram whole structure including the coupling | bond part of the chemical reaction device used for the manufacturing method of this invention. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of the chemical reaction device used for the manufacturing method of the present invention. FIG. 3 is an exploded perspective view showing two types of plate structures in FIG. 2. It is a schematic block diagram which shows typically the manufacturing apparatus used by the Example and the comparative example. It is a schematic block diagram which shows typically the micromixer used in the Example. It is a schematic block diagram which shows typically the micromixer used in the Example.

  Next, details necessary for carrying out the present invention will be described in detail.

The radical polymer obtained by the production method of the first invention of the present invention contains a radical polymerization initiator and a radical polymerizable monomer in the microtubular channel of a heat transfer reaction vessel in which a microtubular channel is formed. By allowing a fluid containing a polymerization solution obtained by polymerizing a polymer to continuously flow while pressurizing the flow path in a liquid-tight state, the radical decomposition rate constant is calculated to be 100 h ⁻ It is produced by carrying out a polymerization reaction while controlling the temperature of the flow path so as to be in the range of ^{1 to} 10000 h ⁻¹ .

The radical polymer obtained by the production method of the second invention of the present invention is obtained by further adding a radical polymerization initiator to a polymerization solution obtained by polymerizing a radical polymerization initiator and radical polymerizable monomers. solution fluid containing, in fine small tubular passage of the heat-conducting reaction vessel fine tubular flow channel formed therein, ranges radical decomposition rate constant of the radical polymerization solution is 100h ^-1 ~10000h ^-1 The radical polymer production method is characterized in that the temperature is supplied while controlling the temperature of the flow path.

  The polymerization solution used in the case of the second invention is not particularly limited, and those prepared by various methods can be used. For example, a polymerization solution in which raw materials such as a radical polymerization initiator, a radical polymerizable monomer, and a solvent are charged in a reaction vessel, and the reaction proceeds by stirring and heating, and the raw materials are continuously polymerized, for example, static A polymerization solution obtained by advancing the reaction using a tubular reactor having a mixing structure, a polymerization obtained by reacting the raw materials through a heat transfer reaction vessel in which a microtubular channel is formed. Examples include solutions.

  The radical polymerization initiator used in the present invention is not particularly limited, and various radical polymerization initiators conventionally used in radical polymerization can be used depending on the type of raw material radical polymerizable monomer and polymerization solvent. It can be selected and used accordingly. Examples of such radical polymerization initiators include organic peroxides, azo compounds, disulfide compounds, redox initiators, persulfates, and the like. In general, when the polymerization solvent is an aqueous medium, water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates, and the like are preferably used, and the polymerization solvent is an organic solvent. For this, oil-soluble organic peroxides and oil-soluble azo compounds are preferably used.

  Examples of the water-soluble organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1 , 3,3-tetramethyl hydroperoxide and the like. Examples of water-soluble azo compounds include 2,2′-diamidinyl-2,2′-azopropane monohydrochloride, 2,2′-diamidinyl-2,2′-azobutane monohydrochloride, 2,2 Examples include '-diamidinyl-2,2'-azopentane monohydrochloride and 2,2'-azobis (2-methyl-4-diethylamino) butyronitrile hydrochloride.

  Examples of redox initiators include a combination of hydrogen peroxide and a reducing agent. In this case, as the reducing agent, divalent iron ions, copper ions, zinc ions, cobalt ions, vanadium ions and other metal ions, ascorbic acid, reducing sugars and the like are used. Examples of the persulfate include ammonium persulfate and potassium persulfate.

  On the other hand, examples of oil-soluble organic peroxides include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, t -Butylperoxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl Peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobutylene T-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t-butyl Peroxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, t-butylcumyl peroxide , T-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, pinane hydroperoxide, 2,5-dimethylhexane-2,5-di Mud peroxide, such as cumene peroxide. Examples of oil-soluble azo compounds include 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis-4-methoxy-2,4. -Dimethylvaleronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, dimethyl-2,2'-azobis (2-methylpropionate), 1,1'-azobis (1-acetoxy-1- Phenylethane), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and the like. These oil-soluble radical polymerization initiators may be used alone or in combination of two or more.

The radical polymerizable monomer used in the production method of the present invention is not particularly limited as long as it is a compound having a radical polymerizable unsaturated group. For example, methyl (meth) acrylate, ethyl (meta ) Acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylic unsaturated monomers of C1-C30 alkyl (meth) acrylates such as acrylates;
Carboxylic acid group-containing unsaturated compounds such as (meth) acrylic acid, itaconic acid or its monoester, maleic acid or its monoester, fumaric acid or its monoester, itaconic acid or its monoester, crotonic acid, p-vinylbenzoic acid Monomers and salts thereof; 2- (meth) acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfonic acid group-containing unsaturated monomers such as α-methylstyrene sulfonic acid and salts thereof;
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, vinylpyrrolidone, N-methylvinylpyridium chloride, (meth) allyltriethylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, etc. A tertiary or quaternary amino group-containing unsaturated monomer; a hydroxyl-containing unsaturated monomer such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol mono (meth) acrylate; ) Amide-containing unsaturated monomers such as acrylamide, N-hydroxyalkyl (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, vinyl lactams
Unsaturated dibasic acid diesters such as maleic acid, fumaric acid, itaconic acid, aromatic unsaturated monomers such as styrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, chloromethylstyrene, vinyltoluene Nitrile unsaturated monomers such as acrylonitrile and methacrylonitrile; conjugated diolefin unsaturated monomers such as butadiene and isoprene; divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, methacrylic acid Polyfunctional unsaturated monomers such as allyl, diallyl phthalate, trimethylolpropane triacrylate, glyceryl diallyl ether, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate; ethylene, propylene Vinyl ester unsaturated monomers such as vinyl acetate, vinyl propionate, octyl vinyl ester, Veova 9, Veova 10, Veova 11 [Beova: Shell Chemical Company, Ltd.], etc. Body; vinyl ether unsaturated monomers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; allyl ether unsaturated monomers such as ethyl allyl ether; vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, chloro Halogen-containing unsaturated units such as trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoro (propyl vinyl ether), perfluoroalkyl acrylate, and fluoromethacrylate Body and the like;
Epoxy group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate; vinyl silanes such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ-methacryloxypropyltrimethoxysilane Unsaturated monomers containing carbonyl groups such as acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl butyl ketone, diacetone acrylate, acetonitrile acrylate, acetoacetoxyethyl (meth) acrylate, vinyl acetophenone, vinyl benzophenone Examples include the body.

  It is also possible to use a fluorinated alkyl group-containing ethylenically unsaturated monomer as the radical polymerization monomer.

  The fluorinated alkyl group-containing ethylenically unsaturated monomer can be used without limitation as long as it is a compound having a fluorinated alkyl group and an ethylenically unsaturated group.

In the polymerizable monomer containing a fluorinated alkyl group used in the present invention, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group). , Is a generic name for those in which some hydrogen atoms in the alkyl group are substituted with fluorine atoms (for example, — (CF ₂ ) ₆ H and the like), and may be linear or branched. Further, those containing an oxygen atom in the fluorinated alkyl group (for example, —OCF ₂ CF ₂ (OCF (CF ₃ ) CF ₂ ) ₂ CF ₂ CF ₃ , — (OCF ₂ CF ₂ ) ₈ — etc.)) are also defined in this definition. Shall be included.

The R _f, for _{example, -C 4 F 9, -C 7} F 15, -C 8 F 17, - (CF 2) 4 H, - (CF 2) 6 CF (CF 3) 2, - (OCF 2 _{CF 2) 4 OCF 2 CF 3} , - (OCF 2 CF (CF 3)) 3 C 3 F 7 and the like.

Specific examples of the fluorinated alkyl group-containing ethylenically unsaturated monomer include the following.
_{a-1: CH 2 = CHCOOCH} 2 CH 2 C 8 F 17
_{a-2: CH 2 = C} (CH 3) COOCH 2 CH 2 C 8 F 17
_{a-3: CH 2 = CHCOOCH} 2 CH 2 C 12 F 25
_{a-4: CH 2 = CHCOOCH} 2 CH 2 C 6 F 13
_{a-5: CH 2 = CHCOOCH} 2 CH 2 C 4 F 9
_{a-6: CH 2 = CFCOOCH} 2 CH 2 C 6 F 13
_{a-7: CH 2 = CHCOOCH} 2 CF 3
_{a-8: CH 2 = C} (CH 3) COOCH 2 CF (CF 3) 2
_{a-9: CH 2 = C} (CH 3) COOCH 2 CFHCF 3
_{a-10: CH 2 = CHCOOCH} 2 (CF 2) 6 H
_{a-11: CH 2 = CHCOOCH} 2 CH (OH) CH 2 C 8 F 17
_{a-12: CH 2 = CHCOOCH} 2 CH 2 N (C 3 H 7) SO 2 C 8 F 17
_{a-13: CH 2 = CHCOOCH} 2 CH 2 N (C 2 H 5) COC 7 F 15
_{a-14: CH 2 = CHCOOC} 2 H 4 (CF (CF 3) OCF 2) 3 C 2 F 5
_{a-15: CH 2 = CHCOOCH} 2 (CF (CF 3) OCF 2) 2 C 2 F 5
_{a-16: CH 2 = CHCOOCH} 2 CH 2 NHSO 2 C 4 F 9
_{a-17: CH 2 = CHCOOCH} 2 CH 2 N (CH 3) SO 2 C 4 F 9
_{a-18: CH 2 = CHCOOCH} 2 CH 2 N (C 2 H 5) SO 2 C 4 F 9
_{a-19: CH 2 = CHCOOCH} 2 CH 2 N (C 3 H 7) SO 2 C 4 F 9
_{a-20: CH 2 = C} (CH 3) COOCH 2 CH 2 N (CH 3) SO 2 C 4 F 9

  In the present invention, a polymerization solvent can be used as necessary. This polymerization solvent is appropriately selected according to the type of radical polymerizable monomer to be used. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; methyl chloride, odor Halogenated solvents such as methyl iodide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene; ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate Ester or ester ether solvents such as; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol Examples thereof include amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, heterocyclic compound solvents such as N-methylpyrrolidone, and mixed solvents of two or more of these.

  These radical polymerization initiators, radical polymerizable monomers, and polymerization solvents can be preferably used in both the first and second inventions.

In the first production method of the present invention, the molecular weight of the radical polymer intended for the radical polymerization initiator described above is provided in the microtubular channel of the heat transfer reaction vessel in which the microtubular channel is formed. Depending on the above, it is usually necessary to use 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight of radically polymerizable monomer. If necessary, a fluid containing a polymerization solution obtained by polymerization in the presence of an organic solvent and a chain transfer agent may be continuously circulated in a liquid-tight state while pressurizing the flow path. by, it can be produced by supplying while controlling the temperature of the flow path as the radical decomposition rate constant is in the range of computationally 100h ^-1 ~10000h ^-1.

In the second production method of the present invention, a solution obtained by further mixing a radical polymerization initiator with a polymerization solution obtained by polymerizing a radical polymerization initiator and a radical polymerizable monomer by various methods. a fluid containing, while pressurizing the flow passage, a liquid-tight state, and, by continuously flowing, flow as radical degradation rate constant is in the range of computationally 100h ^-1 ~10000h ^-1 It can be manufactured by supplying while controlling the temperature of the passage.
At this time, the radical polymerization initiator is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight based on 100 parts by weight of the radical polymerizable monomer, depending on the molecular weight of the radical polymer. It is preferable to add parts by weight. Moreover, you may make it superpose | polymerize in presence of a chain transfer agent, if necessary, adding a radically polymerizable monomer, adding an organic solvent, and also if necessary.

In the production method of the present invention, the microtubular channel of the heat transfer reaction vessel in which the microtubular channel is formed is preferably used as the channel that is continuously flowed in a liquid-tight state while being pressurized. The channel is preferably a microtubule because heating can be quickly controlled. As the microtubular channel, it is easy to adjust the time required for the channel having a void size of 0.1 to 4.0 mm ² to reach the polymerization reaction temperature within 20 seconds. from preferably, also, it is preferable from the viewpoint of facilitated the radical decomposition rate constants of polymerization initiator to control the temperature of the flow channel to be in the range of 100h ^-1 ~10000h ^-1. In the present invention, “cross section” means a cross section perpendicular to the flow direction in the flow path, and “cross section” means the cross section.

  The cross-sectional shape of the channel is a square, a rectangle including a rectangle, a polygon including a trapezoid, a parallelogram, a triangle, a pentagon, etc. (a shape with rounded corners, a high aspect ratio, ie including a slit shape) It may be a star shape, a semicircle, a circle including an ellipse, or the like. The cross-sectional shape of the channel need not be constant.

  The method of forming the reaction channel is not particularly limited, but generally, the member (X) having a groove on the surface thereof is laminated, bonded, or the like on the surface having the groove. It is fixed and formed as a space between the member (X) and the member (Y).

  The channel may further be provided with a heat exchange function. In that case, for example, a groove for flowing the temperature adjusting fluid is provided on the surface of the member (X), and another member is bonded or laminated on the surface provided with the groove for flowing the temperature adjusting fluid. What is necessary is just to fix. In general, a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member. A flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.

  At this time, the groove formed on the member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. The method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.

  The layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.

  The flow path is, for example, a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, a liquid storage tank, a membrane separation mechanism, a connection port to the inside or outside of the device, a tangential line, a development path for chromatography or electrophoresis Further, it may be connected to a part of the valve structure (portion surrounding part), a pressurizing mechanism, a depressurizing mechanism, or the like.

  The outer shape of the member need not be particularly limited, and can take a shape according to the purpose of use. The shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant. The material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, or semiconductor.

In the production method of the present invention, in the microtubular channel of the heat transfer reaction vessel in which the microtubular channel is formed, depending on the molecular weight of the radical polymer intended for the radical polymerization initiator described above. Usually, 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight is used for 100 parts by weight of the radically polymerizable monomer, and the radically polymerizable monomer is organic if necessary. By continuously circulating a fluid containing a polymerization solution obtained by polymerization in the presence of a solvent and, if necessary, a chain transfer agent, in a liquid-tight state while pressurizing the flow path. it can be produced by supplying while controlling the temperature of the flow path as the radical decomposition rate constant is in the range of computationally ^{100h -1 ~10000h} -1.

Here, the radical decomposition rate constant of the polymerization initiator is a calculated value obtained by the following formula.
k = A × EXP (−E / RT)
k: radical decomposition rate constant of radical polymerization initiator (h ⁻¹ ), A: frequency factor (h ⁻¹ ),
E: activation energy (J / mol), R: gas constant (= 8.314 J / mol · K)
T: Absolute temperature (K)

When the radical decomposition rate constant of the radical polymerization initiator to be used is smaller than 100 h ⁻¹ , the decomposition takes time, and the treatment of the remaining monomer and the decomposition of the radical polymerization initiator cannot be completed in the flow path. Further, when the radical decomposition rate constant of the polymerization initiator used is larger than 10,000 h ^−1, it is not preferable because the decomposition of the radical polymerization initiator is completed before the reaction of the residual monomer is completed.

From heat-conducting reaction vessel flow path is formed for carrying out the polymerization reaction while the radical decomposition rate constant of the polymerization initiator to control the temperature of the flow channel to be in the range of 100h ^-1 ~10000h ^-1 used As the reaction apparatus, a reaction apparatus having a structure in which a heat conductive plate-like structure having a plurality of grooves formed on the surface is laminated can be used.
Examples of such a reaction apparatus include an apparatus in which the channel (hereinafter, simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.

  Hereinafter, a schematic configuration example of a chemical reaction device 1 provided with a flow channel in a preferable form used in the present invention is shown in FIG.

  In the chemical reaction device 1, a plurality of first plates (2 in FIG. 1) and second plates (3 in FIG. 1) having the same rectangular plate shape in FIG. Configured. Each one first plate is provided with a flow path (hereinafter referred to as a reaction flow path) (hereinafter, a plate provided with the reaction flow path is referred to as a process plate). The second plate is provided with a flow channel for temperature control fluid (hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate). Then, as shown in FIG. 2, the supply ports and the discharge ports are distributed and arranged in each region of the end surface 1b, 1c, side surface 1d, 1e of the chemical reaction device 1, and in these regions, a radical polymerization initiator is disposed. , A radically polymerizable monomer, an organic solvent, and, if necessary, a fluid containing a chain transfer agent, etc., and a joint portion 32 composed of a connector 30 and a joint portion 31 for flowing a temperature control fluid are connected to each other. Yes.

  Via these joint portions, a radical polymerization initiator, a radical polymerizable monomer, an organic solvent, and if necessary, a fluid containing a chain transfer agent or the like is supplied from the end face 1b and discharged to the end face 1c. Temperature control fluid is supplied from the side surface 1e and discharged to the side surface 1d.

  The shape in plan view of the device for chemical reaction 1 is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape in which the distance between the side surfaces 1d and 1e is longer than between the end surfaces 1b and 1c. Therefore, in accordance with the illustrated shape, the direction from the end surface 1b to the end surface 1c is referred to as the longitudinal direction of the process plate and temperature control plate of the chemical reaction device 1, and the direction from the side surface 1d to the side surface 1e is referred to as the chemical reaction device. This is referred to as the short direction of the process plate 1 and the temperature control plate.

As shown in FIG. 3, the process plate extends on one surface 2 a by passing through a channel 4 having a concave groove shape in the longitudinal direction of the process plate, and a plurality of process plates are arranged at a predetermined interval p ₀ in the short direction. Is. Let L be the length of the flow path 4. The cross-sectional shape is a width w ₀ and a depth d ₀ .

The cross-sectional shape of the flow path 4 is appropriately determined according to the type of fluid including a radical polymerization initiator, a radical polymerizable monomer, an organic solvent, and, if necessary, a chain transfer agent, the flow rate, and the flow path length L. The width w ₀ and the depth d ₀ are 0.1 to 500 [mm] and 0.1 to 5 [mm], respectively, in order to ensure the uniformity of the temperature distribution in the cross section. The range is set. In addition, description of a width | variety and a depth is a case where a drawing is referred, Comprising: This value can be interpreted suitably so that it may become a wide value with respect to a heat transfer surface. Although it does not specifically limit, For example, 1-1000 pieces per plate, Preferably it is 10-100 pieces.

  The radical polymerization initiator, the radical polymerizable monomer, the organic solvent, and, if necessary, a fluid containing a chain transfer agent or the like are caused to flow into each flow path 4, and as shown by arrows in FIGS. , Supplied from one end face 2b side and discharged to the other end face 2c side.

As shown in FIG. 1, the temperature control plate is provided with a temperature control flow path 6 having a concave groove shape on one surface 3 a at a predetermined interval. The cross-sectional area of the temperature control channel 6 is not particularly limited as long as heat can be transferred to the reaction channel, but is approximately in the range of 1 × 10 ^{−2 to} 2.5 × 10 ² (mm ² ). is there. More preferably, it is 0.32-4.0 (mm < ² >). The number of the temperature control flow paths 6 can adopt an appropriate number in consideration of heat exchange efficiency, and is not particularly limited, but is, for example, 1 to 1000, preferably 10 to 100 per plate. It is.

  As shown in FIGS. 1 and 3, the temperature control channel 6 flows in a plurality of main channels 6a arranged in the longitudinal direction of the temperature control plate and upstream and downstream ends of the main channel 6a. You may provide the supply side flow path 6b and the discharge side flow path 6c which are arrange | positioned substantially orthogonally to the path | route 4, and are connected to each main flow path 6a. In FIGS. 1 and 3, the supply-side flow path 6b and the discharge-side flow path 6c are bent at right angles twice and open to the outside from the side surfaces 3d and 3e of the temperature control plate. As for the number of each temperature control channel 6, only the main channel 6 a portion of the temperature control channel 6 is arranged, and the supply side channel 6 b and the discharge side channel 6 c are each composed of one. .

  In addition, each main flow path 6a of the temperature control flow path 6 is provided in a range in which the range in which the flow paths 4 are distributed overlaps the stack direction in the short direction of the temperature control plate with respect to the flow path 4.

  Preferably, the main flow paths 6a are arranged in the stacking direction so as to be positioned between two adjacent flow paths 4, 4. More preferably, each main flow path 6a overlaps each flow path 4 in the stacking direction. Arrange as follows.

  The plurality of process plates and temperature control plates are stacked by alternately stacking process plates and temperature control plates in the same direction, and are fixed to each other and stacked.

  Therefore, in the form of the chemical reaction device 1, each flow path 4 and the temperature control flow path 6 are covered with a lower surface of a plate on which a groove is opened and a tunnel shape having a rectangular cross section with both ends open. It is said.

  Each process plate and temperature control plate can be made of an appropriate metal material. For example, a flow path 4 and a temperature control path 6 are formed by etching a stainless steel plate, and the flow path surface is changed. It can be manufactured by electrolytic polishing finish.

    As an apparatus having a chemical reaction device provided with a flow path used in the manufacturing method of the present invention, for example, a manufacturing apparatus shown in FIG. 4 can be exemplified. Specifically, for example, a production apparatus having the following chemical reaction device can be exemplified.

<Chemical reaction device>
The chemical reaction device has a structure shown in FIG. 1, and as a structure, process plates and temperature control plates are alternately stacked. A flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.

    The chemical reaction device 40 used in the manufacturing apparatus shown in FIG. 4 has 21 temperature control channels 6 formed by etching as well as 20 process plates having 21 reaction channels 4 formed by dry etching. 21 temperature control plates are alternately stacked. The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.

  The chemical reaction device 50 used in the manufacturing apparatus shown in FIG. 4 has five temperature control channels 6 formed by etching as well as two process plates having five reaction channels 4 formed by dry etching. Three temperature control plates are alternately stacked. The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.

  The chemical reaction device 60 used in the manufacturing apparatus shown in FIG. 4 has five temperature control channels 6 formed by etching as well as four process plates having five reaction channels 4 formed by dry etching. Five temperature control plates are alternately stacked. The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.

  In FIG. 4, the outlet of the tank 62 (first tank) into which the fluid (61) containing a radical polymerizable monomer, an organic solvent, and, if necessary, a chain transfer agent, and the like and the flow of the plunger pump 65 are placed. The inlet is connected via a pipe through which a fluid containing a radical polymerizable monomer, an organic solvent, and, if necessary, a chain transfer agent, passes, and a radical polymerization initiator, and if necessary The outlet of the tank 64 (first tank) for containing the organic solvent and the inlet of the plunger pump 66 are connected via a piping through which the radical polymerization initiator and, if necessary, the organic solvent (63) pass. Yes. From the outlet of the plunger pump 65 and the outlet of the plunger pump 66, a radically polymerizable monomer, an organic solvent, and, if necessary, a chain transfer agent are passed through the plunger pump 65 or the plunger pump 66, respectively. The pipe | tube through which the fluid or dical polymerization initiator containing and an organic solvent pass as needed is extended, and these pipe | tubes are connected to the inflow port of the mixer 67. FIG.

  In this mixer 67, a radically polymerizable monomer, an organic solvent, and if necessary, a fluid (61) containing a chain transfer agent and the like, a radical polymerization initiator, and an organic solvent (63) as necessary are mixed. Then, a fluid containing a radical polymerization initiator, a radical polymerizable monomer, an organic solvent, and, if necessary, a chain transfer agent is formed. This fluid moves through the piping connected to the outlet of the mixer 67 to the chemical reaction device 40, 50, or 60 to the inlet 1b. A temperature control device 68 is connected to the chemical reaction device 40, 50, or 60. Then, the radical polymerizable monomer undergoes a polymerization reaction by moving through the minute flow path in the chemical reaction device 40, 50, or 60. It moves through the microchannel in the chemical reaction device 40, 50, or 60 and reaches the outlet 1c of the chemical reaction device 40, 50, or 60. Then, it moves to the inflow port of the cooling heat exchanger 69 through the pipe connected to the outflow port.

  The fluid containing the polymerization reaction product that has moved to the inlet of the cooling heat exchanger 69 is cooled while moving in the cooling heat exchanger 69 and reaches the outlet of the cooling heat exchanger 69. The fluid β is discharged from the cooling heat exchanger 69 through the pipe connected to the outlet, and is discharged to the receiving container 72 through the exhaust pressure valve 71.

Fluid temperature in the production method of the present invention may be any fluid temperature as the radical decomposition rate constant of the polymerization initiator used is in the range of ^{100h -1 ~10000h -1, 100 ℃ ~220} ℃, more preferably The temperature range is 120 ° C to 200 ° C, more preferably 140 ° C to 180 ° C. By controlling the fluid temperature within this temperature range, it is possible to achieve both the treatment of the residual monomer and the decomposition treatment of the undecomposed radical polymerization initiator.

In the flow path for producing a radical polymer in the present invention, a fluid containing a solution in which a radical polymerization initiator is added to a polymerization solution obtained by polymerizing a radical polymerization initiator and a radical polymerizable monomer is radicalized. degradation rate constant is possible to further enhance the efficiency of the residual monomer process by supplying while controlling the temperature of the flow channel to be in the range of computationally 100h ^-1 ~10000h ^-1.

  The method of additionally mixing the radical polymerization initiator can be performed by using a micromixer provided with an inlet for additionally mixing the radical polymerization initiator.

  As the micromixer for this purpose, a commercially available micromixer can be used. For example, a microreactor having an interdigital channel structure, a single mixer manufactured by Institute, Futur, Microtechnique Mainz (IMM), and Caterpillar mixer; Microglass reactor manufactured by Microglass; Cytos manufactured by CPC Systems; YM-1 and YM-2 mixer manufactured by Yamatake Corporation; Mixing tee and tee (T-shaped connector) manufactured by Shimadzu GLC; Examples include IMT chip reactor; Toray Engineering Development Micro-High Mixer, etc., any of which can be used in the present invention.

Further, as a preferred form of the micromixer system, a process plate having a flow path through which a radical polymer passes and a process plate having a flow path through which a polymerization initiator pass are stacked one above the other, and the two fluids are united at the flow path outlet. It is preferable to combine a mixer and a micromixer having a flow path through which the fluid after joining passes.
The reaction channel described in the above formation method is a combination of at least two members and the space formed between the members is used as the reaction channel. It may be used as a reaction channel.

  As the radical polymerization initiator to be additionally mixed, either the same radical polymerization initiator as the initial polymerization reaction or a different radical polymerization initiator can be used. Examples of such radical polymerization initiators include the organic peroxides, azo compounds, disulfide compounds, redox initiators, persulfates and the like described above. In general, when the polymerization solvent is an aqueous medium, water-soluble organic peroxides, water-soluble azo compounds, redox initiators, persulfates, and the like are preferably used, and the polymerization solvent is an organic solvent. For this, oil-soluble organic peroxides and oil-soluble azo compounds are preferably used.

Hereinafter, the present invention will be described in more detail by way of examples. In the examples,% and weight are based on weight unless otherwise specified.
<Chemical reaction device used in Examples and Comparative Examples>
In this example, a chemical reaction device having the structure shown in FIG. 1 was used. As a structure, the process plate 2 and the temperature control plate 3 were laminated | stacked alternately. A flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.
The chemical reaction device is formed by alternately stacking seven temperature control plates having 21 temperature control channels 6 formed by etching as well as six process plates having 21 reaction channels 4 formed by dry etching. . The material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm. The cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm × depth 0.5 mm.

<Micromixer used in this example>
In this embodiment, the mixing process plates 7 and 8 having the structure shown in FIGS. 5 and 6 were used. As a structure of the micromixer, a micromixer in which the temperature control plates 2 used in FIG. 1 are stacked on top and bottom of the mixing plate 7 in which the flow paths 9 and 10 are formed by dry etching, and a flow path by dry etching. A structure was used in which micromixers in which the temperature control plates 2 were stacked on the upper and lower sides of the mixing process plate 8 formed with 11 were connected in series. Specifically, in this embodiment, the fluid that has undergone the polymerization reaction in the radical polymer production method is introduced into the flow path 9 of the plate 7, the additional polymerization initiator is introduced into the flow path 10, and the flow path outlet The two fluids were combined at E and F. Thereafter, the polymerization reaction product and the additional polymerization initiator were further mixed by passing through the flow path 11 of the plate 8. The material of the process plates 7 and 8 is SUS304, and the plate thickness is 1 mm.

<Measurement method of residual monomer amount>
Measurement was performed using a GCMS device GCMS-QP5050ACI manufactured by Shimadzu Corporation. The polymerization solution was dissolved in acetone and measured.
<Measurement method of undecomposed azo compound>
This was carried out using a GPC device HLC-8220 GPC manufactured by Tosoh Corporation. The polymerization solution was dissolved in THF and measured.

<Measurement method of undecomposed oil-soluble organic peroxide>
Chloroform 35mL was put into a conical stoppered Erlenmeyer flask with an internal volume of 100 mL, nitrogen was introduced into the flask, and then 5 g of the polymerization solution was accurately measured and charged. Next, 1 mL of a saturated aqueous solution of sodium iodide was added, the contents were mixed well, and left in a dark place for 5 minutes. The solution was titrated with 0.01N sodium thiosulfate solution until colorless, and a blank test was performed under the same conditions to determine undecomposed oil-soluble organic peroxidation.

Example 1
After preparing a reaction mixture liquid consisting of 233 g of methyl isobutyl ketone, 30 g of perfluoro (C6) alkyl ethyl acrylate, 70 g of polypropylene glycol monomethacrylate, and 7.5 g of tert-butyl peroxyoctate, prepared in a syringe pump The reaction mixture liquid was injected, and the reaction mixture was introduced from a syringe pump into a reaction tube made of stainless steel and having an inner diameter of 2.17 mm so as to have a flow rate of 6.0 g / min. The reaction tube was 20 m long and immersed in a thermostatic bath, and the temperature of the thermostatic bath was set to 110 ° C. A radical polymerization liquid was produced by continuously flowing the reaction mixture through a reaction tube, a cooling heat exchanger, and a pressure relief valve, and receiving the discharged polymerization liquid in a receiving vessel. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the heat exchanger for cooling, a polymerization liquid comprising a residual monomer amount of 1,520 ppm and an undecomposed initiator amount of 0.85% was obtained by continuously carrying out a polymerization reaction with a heating medium at 70 ° C. in a temperature controller. The polymerization solution was introduced into the chemical device shown in FIG. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) at a temperature of 160 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant at 160 ° C. of the polymerization initiator tert-butylperoxy-2-ethylhexanoate used was calculated to be 388 h ⁻¹ .

  When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the amount of residual monomer was 100 ppm or less and the amount of undecomposed initiator was 0.10%, which were very low levels.

(Example 2)
The polymerization liquid obtained in Example 1 was introduced into the chemical device shown in FIG. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) at a temperature of 180 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant of the polymerization initiator tert-butylperoxy-2-ethylhexanoate used at 180 ° C. was calculated to be 1737 h ⁻¹ .

  When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the amount of residual monomer was 100 ppm or less, which was a very low level. In addition, the amount of undegraded initiator was not detected.

(Example 3)
The polymerization liquid obtained in Example 1 was introduced into the chemical device shown in FIG. The simultaneous electrochemical device was produced radical polymerization liquid by flowing continuously the temperature 20 0 ° C. of temperature control fluid (oil). The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant of the polymerization initiator tert-butylperoxy-2-ethylhexanoate used at 200 ° C. was calculated to be 6856h ⁻¹ .

  When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the amount of residual monomer was 100 ppm or less, which was a very low level. In addition, the amount of undegraded initiator was not detected.

Example 4
After preparing a reaction mixture liquid consisting of 233 g of methyl isobutyl ketone, 30 g of perfluoro (C6) alkyl ethyl acrylate, 70 g of polypropylene glycol monomethacrylate, and 7.5 g of 2,2′-azobisisobutyronitrile, a syringe The prepared reaction mixture solution was injected into the pump, and the reaction mixture was introduced from the syringe pump into the same operation as in Example 1 so that the flow rate became 6.0 g / min. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) at a temperature of 100 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a 70 ° C. heating medium was continuously passed through a temperature control device to obtain a polymerization liquid having a residual monomer amount of 1,800 ppm and an undecomposed initiator amount of 0.75%. The polymerization solution was introduced into the chemical device shown in FIG. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) at a temperature of 160 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant at 160 ° C. of the polymerization initiator 2,2′-azobisisobutyronitrile used was calculated to be 1562 h ⁻¹ .

  When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the amount of residual monomer was 120 ppm and the amount of undecomposed initiator was 0.05%, which were very low levels.

(Example 5)
After preparing a reaction mixture liquid consisting of 233 g of methyl isobutyl ketone, 30 g of perfluoro (C6) alkyl ethyl acrylate, 70 g of polypropylene glycol monomethacrylate, and 7.5 g of tert-butyl peroxyoctate, prepared in a syringe pump The reaction mixture liquid was injected, and the reaction mixture was introduced from a syringe pump into a reaction tube made of stainless steel and having an inner diameter of 2.17 mm so as to have a flow rate of 6.0 g / min. The reaction tube was 20 m long and immersed in a thermostatic bath, and the temperature of the thermostatic bath was 130 ° C. A radical polymerization liquid was produced by continuously flowing the reaction mixture through a reaction tube, a cooling heat exchanger, and a pressure relief valve, and receiving the discharged polymerization liquid in a receiving vessel. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a polymerization liquid was obtained by continuously carrying out a polymerization reaction with a heating medium at 70 ° C. in a temperature controller, and having a residual monomer amount of 1,280 ppm and an undecomposed initiator not detected.

  By connecting a micromixer to the obtained polymerization liquid, a final catalyst solution consisting of 25 g of methyl isobutyl ketone and 1.5 g of tert-butyl peroxyoctate was added to a radical polymerization liquid with a flow rate of 5 g / min at 1.5 g / min. Additional mixing at speed. The mixed solution was introduced into the chemical device shown in FIG. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) at a temperature of 180 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant at 180 ° C. of the polymerization initiator tert-butyl peroxyoctoate used was calculated to be 1737 h ⁻¹ .
When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the residual monomer amount was as low as 210 ppm. In addition, the amount of undegraded initiator was not detected.

(Comparative Example 1)
The polymerization liquid obtained in Example 1 was introduced into the chemical device shown in FIG. At the same time, a radical polymerization liquid was produced by continuously flowing a temperature-controlled fluid (oil) having a temperature of 110 ° C. through the chemical device. The internal pressure of the pipe was 2.5 MPa with the exhaust pressure valve. In the cooling heat exchanger, a heating medium at 70 ° C. was continuously flowed by a temperature control device.

The radical decomposition rate constant at 110 ° C. of the polymerization initiator tert-butyl peroxyoctoate used was calculated to be 4.6 h ⁻¹ .

When the amount of residual monomer in the polymerization liquid and the measurement of undecomposed tert-butyl peroxyoctoate were performed, the residual monomer amount was 900 ppm, the undecomposed initiator amount was 0.8%, and both the monomer and the initiator remained. I understood.
(Comparative Example 2)
200 g of the polymerization solution obtained in Example 1 was added to a 500 mL glass reaction vessel equipped with a stirrer, a thermometer, and a condenser, and the temperature was raised to 110 ° C. The internal temperature was kept at 110 ° C. and stirring was performed for 30 minutes. After completion, the internal temperature was cooled to room temperature.

  When the amount of residual monomer in the polymerization solution and undecomposed tert-butyl peroxyoctoate were measured, the amount of residual monomer was as low as 100 ppm or less, but 0.12% of undecomposed initiator was detected. .

α ······································································· of fluid containing radical polymerization initiator and radical polymerizable monomer Fluid containing reactant γ ... Temperature control fluid 1 ... Chemical reaction device 1b ... End face of chemical reaction device 1c ... End face of chemical reaction device 1d ...・ ・ Side side of chemical reaction device 1e ・ ・ ・ Side side of chemical reaction device 2 ・ ・ ・ First plate (process plate)
2a ... the first plate surface 2b ... the first plate end surface 2c ... the first plate end surface 2d ... the first plate side surface 2e ... the first plate side surface 3 ... 2nd plate (temperature control plate)
3a ··· surface of the second plate 3b ··· end surface of the second plate 3c ··· end surface of the second plate 3d ··· side surface of the second plate 3e ··· side surface of the second plate 4... Cross-sectional groove-shaped channel 6... Cross-sectional groove-shaped temperature control channel 6 a... Cross-sectional groove-shaped main channel 6 b. Supply side flow path 6c ··· Discharge side flow path with a concave groove shape p0 ··· Predetermined interval w0 ··· width d0 ··· depth L · ··· length of flow path 7... Mixing plate 8... Mixing plate 9... Mixing plate cross-sectional groove-shaped channel 10... Mixing plate cross-sectional groove-shaped channel 11・ ・ ・ ・ ・ Mixing plate cross-section channel 30 …… Connector 31 …… Joint 32... Joint part 40... Chemical reaction device 50... Chemical reaction device 60... Chemical reaction device 80. (A)
62... First tank 63... Compound (B)
64 ... Second tank 65 ... Plunger pump 66 ... Plunger pump 67 ... Mixer 68 ... Temperature controller 69 ... Heat exchanger for cooling 70 ... Temperature controller 71 ... Exhaust pressure valve 72 ... Receptacle container 80 ... Model of resin production equipment used in Examples and Comparative Examples Schematic configuration diagram

Claims (6)

Fine small tubular flow path of heat-conducting reaction vessel fine tubular flow channel is formed in the interior, the radical polymerization initiator obtained by polymerizing a radical polymerizable monomer in the presence of residual monomers and undegraded By flowing a fluid containing a polymerization solution containing a radical polymerization initiator in a liquid-tight state continuously while pressurizing the flow path, the radical decomposition rate constant of radicals in the polymerization solution is calculated. A method for producing a radical polymer, characterized in that it is supplied while controlling the temperature of the flow path so as to be in the range of 100 h-1 to 10000 h-1. As the radical decomposition rate constant of the polymerization initiator used is in the range of ^{100h -1 ~10000h} -1, the temperature of the flow path to control the temperature of the flow path in the range of 120 ° C. to 220 ° C. While the polymerization reaction The method for producing a radical polymer according to claim 1.   The method for producing a radical polymer according to claim 1 or 2, wherein the polymerization reaction is performed using a reaction apparatus having a flow path installed in a heat transfer reaction vessel.   4. The method for producing a radical polymer according to claim 1, wherein the heat transfer reaction vessel has a structure in which a heat transfer plate-like structure having a plurality of grooves formed on a surface thereof is laminated.   2. The radical weight according to claim 1, wherein the flow path in the reaction apparatus installed in the heat transfer reaction vessel has a void size such that a cross-sectional area of fluid flowing in a liquid-tight state is 0.1 to 4.0 mm 2. Manufacturing method of coalescence. Obtained by polymerizing a radical polymerizable monomer in the presence of a radical polymerization initiator, a fluid containing a solution obtained by adding a mixture a radical polymerization initiator to the polymerization solution containing the residual monomers, the radical decomposition rate constant of the fluid as but the range of computationally 100h ^-1 ~10000h ^-1, while controlling the temperature of the fine small tubular passage of the heat-conducting reaction vessel fine tubular flow channel formed therein, supplied to the flow path A method for producing a radical polymer.

Images