JP5261109B2 - Method for producing thermoplastic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing thermoplastic resins which reduces unreacted components and byproducts in a tandem-type reaction extruder. <P>SOLUTION: A tandem-type reaction extruder includes the first extruder in which a sold resin material is plasticized, auxiliary raw materials for the first step reaction are supplied for reaction, the second extruder in which auxiliary raw materials for the second step reaction are fed into the molten resin supplied from the first extruder and reaction and/or deaeration is conducted, a part connecting the outlet for the resin of the first extruder with the raw material inlet of the second extruder, and a pressure control mechanism for the inside of the first reactor. A control mechanism for the pressure inside of the part connecting the outlet for the resin of the first extruder with the raw material inlet of the second extruder is additionally arranged at the raw material inlet of the second extruder of the tandem-type reaction extruder. The pressure difference &Delta;P between the pressure on the side of the first extruder and the pressure on the side of the second extruder is controlled at &ge;2 MPa and &le;10 MPa. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a thermoplastic resin by a tandem reaction extruder and a thermoplastic resin.

  The reaction extrusion method, in which the resin is heated and melted using an extruder and the molten resin and the reactant are reacted continuously, is superior in productivity to the batch method performed in a reaction vessel, etc., and is low cost and efficient. It has the characteristic that a thermoplastic resin can be manufactured.

  However, the conventional production method in which a thermoplastic resin is melted and reacted has a problem that unreacted components and by-products remain because the reaction efficiency and reaction uniformity are low.

  From this, as a method for improving the reaction efficiency and reaction uniformity and reducing the unreacted components, the reaction efficiency is improved by using carbon dioxide as a reaction medium with respect to the method for producing a modified thermoplastic resin using an extruder. There exists a method (for example, refer patent document 1). Since such a method uses a reaction medium, the facilities are complicated and expensive, and the manufacturing cost is high.

In addition, the polymerization kettle, the devolatilization extrusion device, the coupling portion for coupling the polymerization kettle and the devolatilization extrusion device, and the mechanical back pressure valve at the coupling portion are pressurized with the mechanical back pressure valve to reduce the pressure difference. There is a method for producing an acrylic polymer having a small content of volatile components by generating it (see, for example, Patent Document 2). Since such a method uses a polymerization kettle, it becomes a batch-type production method, resulting in poor productivity, complicated facilities, and high cost, and a high production cost.
JP2002-256042 JP2005-112870

  The present invention has been made in view of such problems of the conventional technology, and is a thermoplastic resin capable of greatly reducing unreacted components and by-products in a tandem type reaction extruder. It aims at providing the manufacturing method of.

  The present invention relates to a first extruder, a second extruder, a component connecting a resin discharge port of the first extruder and a raw material supply port of the second extruder, and an outlet of the first extruder and a raw material supply port of the second extruder. It has been found that the above problem can be solved by using a tandem type extruder having an in-part pressure control mechanism for connecting the two.

That is, the present invention
(I) The first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the resin discharge port of the first extruder and the second extruder Using the tandem type extruder having a component internal pressure control mechanism for connecting the raw material supply port, the first stage reaction for treating the main raw material and the auxiliary raw material in the first extruder is performed, and in the second extruder, A method for producing a thermoplastic resin for performing a second-stage reaction in which a reaction product in a first extruder is further treated with other auxiliary raw materials, and includes a “first extruder side pressure of a pressure control mechanism” and a “second pressure”. The production method characterized in that the pressure difference ΔP of the “extruder side pressure” is 2 MPa or more and 10 MPa or less.

  (Ii) The method for producing a thermoplastic resin according to (i), wherein in the tandem reaction extruder, each of the first extruder and the second extruder is a twin screw extruder.

  (Iii) A second stage reaction in which the acrylic resin and the imidizing agent are treated in the first extruder, and the reaction product in the first extruder is further treated with the esterifying agent in the second extruder. The method for producing a thermoplastic resin according to any one of (i) to (ii), wherein a stage reaction is performed.

  (Iv) An imide resin in which the thermoplastic resin has a unit represented by the following general formula (1), a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3) The method for producing a thermoplastic resin according to any one of (i) to (iii), wherein

（但し、Ｒ¹及びＲ²は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ³は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ⁴及びＲ⁵は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ⁶は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ⁷は、水素又は炭素数１〜８のアルキル基を示し、Ｒ⁸は、炭素数６〜１０のアリール基を示す。）

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)

  According to the present invention, the first extruder, the second extruder, the parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and the outlet of the first extruder and the second extruder Using a tandem type extruder having an in-part pressure control mechanism for connecting the raw material supply port, the pressure difference ΔP between the first extruder side pressure and the second extruder side pressure of the pressure adjusting mechanism is 2 MPa or more and 10 MPa or less. As a result, it is possible to significantly reduce unreacted components and by-products, and to provide a production method capable of producing a thermoplastic resin easily and efficiently at low cost.

  The present invention relates to a first extruder, a second extruder, a component connecting a resin discharge port of the first extruder and a raw material supply port of the second extruder, and a first extruder outlet and a raw material supply of the second extruder. A differential pressure between the first extruder side pressure and the second extruder side pressure of the pressure adjustment mechanism is controlled by using a tandem type extruder having an in-part pressure control mechanism that connects the ports.

  The tandem type extruder of the present invention is, for example, two parts, a first extruder and a second extruder, which are components that connect the resin discharge port of the first extruder and the raw material supply port of the second extruder (hereinafter referred to as “the second extruder”). In some cases, they are simply connected as connecting parts). If necessary, the third extruder may be connected with a connecting component. If there are at least two or more, the number of connected devices can be set as appropriate. The tandem type extruder can be expected to reduce the resin-derived foreign matter because the resin deterioration is suppressed because an excessive heat history is not applied. In addition, by carrying out the reaction continuously with two or more extruders, it is possible to suppress contamination from foreign substances.

  Further, the tandem type extruder is a “first control mechanism for pressure inside the component that connects the resin discharge port of the first extruder and the raw material supply port of the second extruder (which may be simply abbreviated as“ pressure control mechanism ”). The pressure difference ΔP between the “extruder side pressure” and the “second extruder side pressure” is 2 MPa or more and 10 MPa or less. The differential pressure ΔP is a difference between pressure gauges attached before and after the pressure control mechanism, for example, a pressure gauge is installed at each of the resin discharge port of the first extruder and the raw material supply port of the second extruder. Is the difference in pressure.

  Setting the differential pressure ΔP to 2 MPa or more and 10 MPa or less is preferable because unreacted components and by-products are reduced. More preferably, it is 3 MPa or more and 8 MPa or less.

  When the differential pressure ΔP is less than 2 MPa, the devolatilization property is deteriorated, which is not preferable.

  On the other hand, when the differential pressure is higher than 10 MPa, the pressure difference at the outlet of the pressure control mechanism is large, so that vent-up occurs at the rear vent and devolatilization deteriorates, which is not preferable.

  Furthermore, if ΔP is 2 MPa or more and 10 MPa or less, the pressure on the first extruder side and the second extruder side is not particularly limited, but the first extruder side pressure is 2 MPa or more and 10 MPa or less, the second extruder side The pressure is preferably 0.01 MPa or more and 1 MPa or less. More preferably, the lower limit value of the first extruder side pressure is 2.5 MPa or more, particularly preferably 3 MPa or more, and the second extruder side pressure is 0.02 MPa or more, particularly preferably 0.03 MPa or more. As the upper limit value, the first extruder side pressure is more preferably 8 MPa or less, particularly preferably 6 MPa or less, and the second extruder side pressure is 0.8 MPa or less, particularly preferably 0.6 MPa or less.

  The differential pressure ΔP can be adjusted by controlling with a pressure control mechanism.

  FIG. 1 shows an example of a tandem reaction extruder according to the present invention, but the present invention is not limited to this. As shown in the figure, the first extruder (1) and the second extruder (2) are arranged in a tandem type. The tandem type may be either a parallel arrangement as shown in FIG. 1 or an orthogonal arrangement in which the first extruder (1) and the second extruder (2) are arranged at right angles. The discharge port (6) of the first extruder (1) is connected to the raw material supply port (7) of the second extruder (2) via the connection component (3).

  Examples of the connecting parts include those in which the resin flow path shape is a circular pipe or an L-shaped pipe. The connection component according to the present invention preferably has a gentle volume change of the resin flow path. Particularly preferred is a connecting part having a resin flow path with no volume change. In a connecting part having a resin flow path whose volume has changed rapidly, the resin and the reaction by-product are foamed and separated, the extrusion is fluctuated, and the reaction becomes non-uniform, which is not preferable.

  The tandem type extruder of the present invention can suppress fluctuations in extrusion by providing the connecting part with the pressure control mechanism (4), and the resin of the first extruder (1) -first extruder. The internal pressure of the component (3) connecting the discharge port and the second extruder raw material supply port can be controlled. The pressure control mechanism is a device that can control the pressure loss by changing the resin flow path volume. A preferable pressure control mechanism according to the present invention can be exemplified by a constant flow pressure valve, a gear pump, an orifice, and the like. If the volume of the resin flow path in the pressure control mechanism is suddenly changed, the resin and reaction by-products may foam or separate, and as a result, the extrusion may fluctuate, resulting in a non-uniform reaction. Therefore, a constant flow pressure valve, an orifice and the like are particularly preferable.

  In the present invention, the position where the pressure control mechanism is attached is not particularly limited as long as it is within the part connecting the second extruder raw material supply port and the first extruder discharge port, but “the second extruder raw material supply port and the pressure control”. The “distance to the mechanism” is preferably shorter than the “distance between the first extruder discharge port and the pressure control mechanism”. The shorter the “distance between the second extruder raw material supply port and the pressure control mechanism” is, the shorter is preferable, and the case where the distance is directly connected to the second extruder raw material supply port is most preferable. When the “distance between the second extruder raw material supply port and the pressure control mechanism” is equal to the “distance between the first extruder discharge port and the pressure control mechanism”, or “the second extruder raw material supply port and the pressure control mechanism When the “distance between the first extruder discharge port and the pressure control mechanism” is shorter than the “distance”, or when the first extruder discharge port and the pressure control mechanism are directly connected, the resin in the connecting part after the pressure control mechanism The reaction by-product is foamed or separated and the extrusion is fluctuated, resulting in a non-uniform reaction. Also, depending on the type of pressure control mechanism, when the pressure control mechanism and the connecting part or the second extruder raw material supply port (position where kneading is started in the second extruder) are integrated, The resulting pressure difference is referred to as ΔP.

  In the present invention, the raw material can be a solid-state resin, which is supplied from the raw material supply port (5) of the first extruder (1) by a feeder device or the like, and is heated and melted in the extruder. Examples of the feeder device include a constant weight feeder and a constant volume feeder. From the auxiliary raw material supply port (8) of the first stage reaction provided in the part after the resin is melted in the extruder, the auxiliary raw material in a solid, liquid or gaseous state is supplied using a supply device such as a pump. The first stage reaction of the resin and the auxiliary material is performed.

  The first-stage reaction product in the first extruder is guided to the second extruder raw material supply port via a connecting part connected to the resin discharge port without being isolated from the resin discharge port. It is thrown into.

  Next, the first stage reaction in the reaction product in the first extruder supplied from the first extruder at the vent port (9) provided after the second extruder (2) raw material supply port (7). Unreacted by-products, reaction by-products and decomposition products are removed. Examples of the pressure at the vent port include atmospheric pressure, vacuum, and the like, and preferably vacuum. A plurality of vent openings may be provided as necessary.

  The secondary raw material in the second stage reaction to the second extruder (2) is supplied from the secondary raw material supply port (10) of the second stage reaction using a pump or the like. Then, the second stage reaction is performed with the reaction product and the auxiliary material in the first extruder.

  Next, a vent port (11) is provided downstream from the by-material feed port (10) of the second extruder (2), and unreacted by-products, reaction by-products, decomposition in the second stage reaction product Remove things. What is necessary is just to set the distance to a vent port suitably from the reaction rate etc. of the reaction to implement. Examples of the pressure at the vent port include atmospheric pressure, vacuum, and the like, and preferably vacuum. A plurality of vent openings may be provided as necessary.

  Further, in the second extruder (2), the second-stage reaction of the first-stage reaction product and the second-stage auxiliary material is not performed, and the first-stage is made with a plurality of vents as necessary. It is also possible to carry out only the devolatilization of unreacted by-products, reaction by-products and decomposition products of the eye reaction.

  Various additives such as catalysts, antioxidants, heat stabilizers, plasticizers, lubricants, UV absorbers, antistatic agents, colorants, shrinkage inhibitors, etc. are fed from the first extruder (1) raw material supply port (5). Can be supplied with resin. Moreover, various additives can also be supplied from the additive supply port (12) of the second extruder (2) as required. Examples of a method for supplying various additives from the additive supply port (12) include a side feed method, an individual feed method for adding from the upper part of the extruder, and the like.

  As the extruder in the present invention, a single screw extruder, a co-directional meshing type twin screw extruder, a co-directional non-meshing type twin screw extruder, a different direction meshing type twin screw extruder, a different direction non-meshing type twin screw Various extruders such as an extruder and a multi-screw extruder can be applied. Among them, in particular, various twin screw extruders are preferably applied from the viewpoint of high kneading / dispersing ability, and the same direction meshing twin screw extruder is more preferred because of high kneading / dispersing ability and productivity.

  In the present invention, different reactions can be carried out between the first extruder and the second extruder using the tandem extruder.

  Specifically, the first stage reaction in which the main raw material and the auxiliary raw material are processed in the first extruder is performed, and the reaction product in the first extruder is further processed with another auxiliary raw material in the second extruder. A second stage reaction can be performed.

  The thermoplastic resin obtained by this production method is not particularly limited as long as it is a thermoplastic resin that can be produced by the above production method. For example, imide resin, polymethyl methacrylate resin, polycarbonate resin, polystyrene Resin, cycloolefin resin, cellulose resin, vinyl chloride resin, polysulfone resin, polyethersulfone resin, maleimide / olefin resin, glutarimide resin, lactone ring-containing polymer, glutaric anhydride-containing resin And a resin composition formed by mixing these resins. Preferably it is an imide resin.

For example, as a method for producing an imide resin, a first-stage reaction in which an acrylic resin and an imidizing agent are treated in a first extruder, and a reaction product in the first extruder is further esterified in a second extruder. The reaction which performs the 2nd step | paragraph reaction processed with an agent can be mention | raise | lifted.
As another method for producing a thermoplastic resin, as a method for producing a lactone ring-containing polymer, in the first extruder, a polymer having a hydroxyl group and an ester group in a molecular chain is subjected to a lactone cyclocondensation reaction to produce a lactone ring-containing polymer. And a first step of reaction with an esterifying agent that modifies the acid component produced as a by-product by polymerization into an ester group. In the machine, a reaction for performing a devolatilization process excluding volatile matter can be given. Further, as a method for producing an N-methylmaleimide / isobutene copolymer, in the first extruder, a maleic anhydride / isobutene copolymer (manufactured by Kuraray Co., Ltd., product name Isoban 6) is treated with methylamine, and N- A reaction in which a methylmaleimide / isobutene copolymer is synthesized and a devolatilization step for removing volatile matter is performed in the second extruder can be mentioned.

  Here, the 1st stage reaction which processes acrylic resin and an imidizing agent with a 1st extruder is performed, and the reaction product in the 1st extruder is further processed with an esterifying agent with a 2nd extruder. A production method for obtaining the imide resin by performing the second stage reaction will be specifically described. In the first extruder of the tandem reaction extruder, first, an acrylic resin is used as a raw material resin (main raw material), and this is used as a secondary raw material for the first-stage reaction such as ammonia or substituted amine (hereinafter, imidization). It is possible to obtain a resin (hereinafter sometimes referred to as an imide resin intermediate 1) that has been treated.

  This imide resin intermediate 1 is treated with a secondary raw material of the second stage reaction (hereinafter sometimes referred to as an esterifying agent) in the second extruder of the tandem type reaction extruder, and heated if necessary. By performing the treatment or the like, the ratio of the acid component (mono derived from the carboxyl group and the acid anhydride group) remaining in the resin can be controlled (hereinafter sometimes referred to as “imide resin intermediate 2”). At this time, it is possible to perform only heat treatment or the like without treatment with an esterifying agent. In the second extruder, when only heat treatment (mixing / dispersion of molten resin in the extruder) is performed, dehydration reaction between carboxyl groups in the imide resin intermediate 1 and / or desorption of carboxyl groups and alkyl ester groups. Some or all of the carboxyl groups can be converted into acid anhydride groups by alcohol reaction or the like. The heat treatment is carried out at a reaction temperature in the range of 150 to 400 ° C. in order to suppress decomposition, coloring, etc. of the resin due to excessive heat history. 180-320 degreeC is preferable and 200-280 degreeC is more preferable.

  Furthermore, the imide resin intermediate 2 can be removed by removing the esterifying agent contained in the resin by devolatilization under reduced pressure or the like, thereby obtaining the imide resin of the present invention.

  In order to obtain the imide resin intermediate 1 and the imide resin intermediate 2 of the present invention, the reaction temperature is increased in order to proceed with imidization or acid component control and to suppress decomposition, coloring, etc. of the resin due to excessive thermal history. Is performed in the range of 150 to 400 ° C. 180-320 degreeC is preferable and 200-280 degreeC is more preferable.

  In addition to the production method as described above, the production method is not particularly limited as long as the imide resin can be obtained by the tandem reaction extruder of the present invention.

  In this case, the acrylic resin as the main raw material is not particularly limited, but acid anhydrides such as maleic anhydride or half esters of them with a linear or branched alcohol having 1 to 20 carbon atoms; acrylic acid, methacrylic acid Examples thereof include α, β-ethylenically unsaturated carboxylic acids such as acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid. Moreover, (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer comprising a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3): Or a (meth) acrylic acid ester polymer such as a methyl methacrylate polymer composed of a repeating unit represented by the general formula (2).

（但し、Ｒ⁴及びＲ⁵は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ⁶は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

（但し、Ｒ⁷は、水素又は炭素数１〜８のアルキル基を示し、Ｒ⁸は、炭素数６〜１０のアリール基を示す。）

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)

In the formula (2), R ⁴ is preferably a hydrogen atom, and R ⁵ is preferably a methyl group. R ⁶ is preferably a methyl group. R ⁷ is preferably hydrogen, and R ⁸ is preferably a phenyl group.

  When producing the imide resin of the present invention, first, a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester weight such as methyl methacrylate polymer is used. When a polymer is polymerized and converted into an imide resin, the (meth) acrylate-aromatic vinyl copolymer and (meth) acrylate polymer that can be used in the present invention can undergo an imidization reaction. As long as it is a linear polymer, it may be a block polymer, a core-shell polymer, a branched polymer, a ladder polymer, or a crosslinked polymer. The block polymer may be an A-B type, an A-B-C type, an A-B-A type, or any other type of block polymer. The core-shell polymer may be composed of only one core and only one shell, or each may be a multilayer.

  An example of the auxiliary material is an imidizing agent. Examples of imidizing agents include amines containing aliphatic hydrocarbon groups such as methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, n-hexylamine, and aniline. Aromatic hydrocarbon group-containing amines such as benzylamine, toluidine, and trichloroaniline, alicyclic hydrocarbon group-containing amines such as cyclohexylamine, and ammonia. In addition, urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea that generate these amines by heating can also be used. Of these imidizing agents, methylamine, ammonia, and cyclohexylamine are preferable from the viewpoint of cost and physical properties, and methylamine is particularly preferable.

  What is necessary is just to determine suitably the addition amount of an imidation agent by the imidation rate for expressing a required physical property. Preferably, it is 1 to 100 parts by weight with respect to 100 parts by weight of the main raw material.

  Examples of the esterifying agent include dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, dimethyl sulfate, methyl toluene sulfonate, methyl trifluoromethyl sulfonate. , Methyl acetate, methanol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, dimethylcarbodiimide, dimethyl-t-butylsilyl chloride, isopropenyl acetate, dimethylurea, tetramethylammonium hydroxide, dimethyldiethoxysilane, tetra-N-butoxy Silane, dimethyl (trimethylsilane) phosphite, trimethyl phosphite Trimethyl phosphate, tricresyl phosphate, diazomethane, ethylene oxide, propylene oxide, cyclohexene oxide, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether.

  The addition amount of the esterifying agent is determined by the ratio of the acid component in the resin for expressing necessary physical properties. Preferably, it is 1 to 100 parts by weight with respect to 100 parts by weight of the imide resin intermediate 1.

  When the imide resin intermediate 1 is treated with an esterifying agent and / or heat-treated, or for the imide resin intermediate 2, generally used catalysts, antioxidants, heat stabilizers, plasticizers, lubricants, UV absorption An agent, an antistatic agent, a coloring agent, an anti-shrinkage agent and the like may be added as long as the object of the present invention is not impaired.

  As described above, examples of the thermoplastic resin that can be synthesized by effectively applying the present invention include imide resins.

  As the imide resin, for example, various types can be produced by appropriately setting the kind and amount of the main raw material and the auxiliary raw material by the above-described method. Specifically, the imide resin is represented by the following general formula (1). And a unit represented by the general formula (2) and / or a unit represented by the general formula (3).

（但し、Ｒ¹及びＲ²は、それぞれ独立に、水素又は炭素数１〜８のアルキル基を示し、Ｒ³は、水素、炭素数１〜１８のアルキル基、炭素数３〜１２のシクロアルキル基、又は炭素数５〜１５の芳香環を含む置換基を示す。）

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

  The first structural unit constituting the imide resin of the present invention is represented by the general formula (1) and is generally called a glutarimide unit (hereinafter referred to as the general formula (1)). Sometimes abbreviated as glutarimide unit.)

As a preferable glutarimide unit, R ¹ and R ² are hydrogen or a methyl group, and R ³ is hydrogen, a methyl group, a butyl group, or a cyclohexyl group. The case where R ¹ is a methyl group, R ² is hydrogen, and R ³ is a methyl group is particularly preferred.

The glutarimide unit may be a single type or may include a plurality of types in which R ¹ , R ² , and R ³ are different.

  In addition, a glutarimide unit can be formed by imidizing the main raw material demonstrated in the method to manufacture the imide resin mentioned above.

  The second structural unit constituting the imide resin is represented by the general formula (2) and is generally called a (meth) acrylic acid ester unit (here, (meth) Acrylic acid ester refers to acrylic acid ester and methacrylic acid ester.Hereinafter, general formula (2) may be abbreviated as (meth) acrylic acid ester unit).

  When manufacturing an imide resin, when (meth) acrylic acid ester-aromatic vinyl copolymer or (meth) acrylic acid ester polymer is first polymerized and then imidized, it is specifically ( The raw material for giving a meth) acrylic acid ester unit as a residue is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned. Of these, methyl methacrylate is particularly preferred.

These second structural units may be of a single type, or may include a plurality of types in which R ⁴ , R ⁵ and R ⁶ are different. Similarly, a plurality of types of raw materials that give the (meth) acrylic acid ester unit as a residue may be used.

  The third structural unit contained in the imide resin of the present invention as needed is represented by the general formula (3), and is generally called an aromatic vinyl unit (hereinafter referred to as general vinyl). (Formula (3) may be abbreviated as an aromatic vinyl unit.)

Preferred aromatic vinyl structural units include styrene in which R ⁷ is hydrogen and R ⁸ is a phenyl group, and α-methylstyrene in which R ⁷ is a methyl group and R ⁸ is a phenyl group. Of these, styrene is particularly preferred.

These third structural units may be of a single type, or may include a plurality of types in which R ⁷ and R ⁸ are different.

The content of the glutarimide unit represented by the general formula (1) in the imide resin depends on, for example, the structure of R ³ , but is preferably 20% by weight or more of the imide resin. The preferable content of the glutarimide unit is 20% to 95% by weight, more preferably 40 to 90% by weight, and still more preferably 50 to 80% by weight. When the ratio of the glutarimide unit is smaller than this range, the resulting imide resin may have insufficient heat resistance or the transparency may be impaired. On the other hand, if it exceeds this range, the heat resistance and melt viscosity are unnecessarily increased, the moldability becomes worse, the mechanical strength of the resulting film becomes extremely brittle, and the transparency may be impaired.

  The content of the aromatic vinyl unit represented by the general formula (3) of the imide resin may be set according to the required physical properties, and is not particularly limited, but based on the total repeating unit of the imide resin, 1% by weight or more is preferable. The content of the aromatic vinyl unit is preferably 1 to 40% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 25% by weight. When the aromatic vinyl unit is larger than this range, the resulting imide resin may have insufficient heat resistance. If it is smaller than this range, the mechanical strength of the resulting film may be lowered.

  By adjusting the ratio of the general raw materials, general formulas (2) and (3), and the imidizing agent, which is a secondary raw material, the unit represented by general formula (1) and the general formula (2) Can be obtained, and an imide resin containing the unit represented by the general formula (3) in an arbitrary ratio can be obtained, and the ratios of the general formulas (1), (2), and (3) are adjusted. Therefore, it is possible to adjust to various required physical properties. For example, when the imide resin of the present invention is first formed by polymerizing a (meth) acrylic ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer, for example, a (meth) acrylic ester is used. The ratio of the general formula (3) is determined by adjusting the polymerization ratio of the aromatic vinyl and the aromatic vinyl (the ratio of the general formula (3) can be set to 0), and the addition ratio of the imidizing agent during imidization is further determined. By adjusting, the ratios of the general formulas (1) and (2) can be further adjusted.

  The imide resin may further be copolymerized with a fourth structural unit as necessary. A constitution obtained by copolymerizing nitrile monomers such as acrylonitrile and methacrylonitrile, and maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide as the fourth structural unit Units can be used. These may be directly copolymerized in a thermoplastic resin or may be graft copolymerized. The fourth structural unit is preferably contained in the main raw material.

  In the imide resin obtained in the production method of the present invention, the type containing the general formula (3) is obtained by adjusting the content of each constituent unit and glutarimide unit in the methyl methacrylate-styrene copolymer. It is also possible to impart a feature that does not substantially have orientation birefringence. Moreover, it has positive orientation birefringence by reducing the content of the general formula (3), not including the general formula (3), or increasing the content of the general formula (1). An imide resin can also be produced. Oriented birefringence refers to birefringence that develops when stretched at a predetermined temperature and a predetermined draw ratio. In this specification, unless otherwise specified, it means birefringence that develops when uniaxially stretched at a temperature 5 ° C. higher than the glass transition temperature of the imide resin.

Here, the orientation birefringence is the product of the intrinsic birefringence derived from the polymer structure and the orientation distribution function derived from the molecular orientation state. The refractive index (nx) in the stretching axis direction and the axial refractive index (ny) orthogonal thereto. ) From the following formula: Δn _or = nx−ny
The phase difference Re (nm) measured by a phase meter is divided by the thickness d (μm).

Oriented birefringence Δn _or = Re / d
As described above, the orientation birefringence is the difference between the refractive index (nx) in the stretching axis direction and the refractive index (ny) in the axial direction perpendicular thereto, and therefore, when nx is larger than ny, it shows a positive value and vice versa. When nx is smaller than ny, a negative value is indicated. In the said imide resin, it is possible to adjust the value of orientation birefringence according to the use to be used.

The value of the orientation birefringence of the imide resin having substantially no orientation birefringence is preferably −0.1 × 10 ^{−3 to} 0.1 × 10 ⁻³ , and −0.01 × 10 ^It is more preferable that it is ^{−3 to} 0.01 × 10 ⁻³ .

  In order to obtain an imide resin having substantially no orientation birefringence, the amount of each structural unit in the (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer is adjusted, Further, it is necessary to prepare the degree of imidization, and the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3) are 0.5: 1.0 to 10.0 in weight ratio. Is preferably in the range of 1.0, more preferably in the range of 2.0: 1.0 to 9.0: 1.0, and in the range of 3.0: 1.0 to 7.0: 1.0. Is more preferable, and the range of 4.0: 1.0 to 6.5: 1.0 is particularly preferable.

The imide resin of the present invention preferably has a weight average molecular weight of 1 × 10 ⁴ to 5 × 10 ⁵ . When an excessive thermal history is given to the resin during the production process of the thermoplastic resin, thermal decomposition occurs, and the weight average molecular weight is less than 1 × 10 ⁴ . Furthermore, crosslinking may occur and the weight average molecular weight may exceed 5 × 10 ⁵ . When the method for producing a thermoplastic resin according to the present invention is applied, the heat history for the resin can be reduced in the process of producing the thermoplastic resin, and the range of the weight average molecular weight can be achieved. When the weight average molecular weight is less than 1 × 10 ⁴ , the mechanical strength in the case of a film is insufficient, and when it exceeds 5 × 10 ⁵ , the viscosity at the time of melt extrusion is high and the molding processability is lowered. , Productivity of molded products may decrease.

  The glass transition temperature in the imide resin of the present invention is preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. When the glass transition temperature is lower than the above value, the application range is limited in applications where heat resistance is required.

  If necessary, other thermoplastic resins can be added to the imide resin of the present invention. When molding, generally used antioxidants, heat stabilizers, plasticizers, lubricants, ultraviolet absorbers, antistatic agents, colorants, shrinkage inhibitors, etc. are added within the range that does not impair the purpose of the present invention. You may do it.

  When synthesizing an imide resin using the present invention, the resulting imide resin can provide a novel thermoplastic resin having a variation in imidization rate of within 1%.

  Further, an imide resin having an oxidation variation of 0.1 mmol / g or less can be obtained.

  Here, the variation in the imidization rate means the imide per unit time (1 minute) of the resin produced within 30 minutes after the reaction for obtaining the imide resin intermediate 1 is stabilized after the production of the imide resin is started. It is the difference between the maximum value and the minimum value of the conversion rate.

  The variation of the acid component is the unit time of the resin produced within 30 minutes after the reaction for obtaining the imide resin intermediate 1 or the reaction for obtaining the imide resin intermediate 2 is stabilized after the production of the imide resin is started. It is the difference between the maximum value and the minimum value of the acid component per minute).

  Molded articles obtained from the imide resin of the present invention include, for example, imaging fields such as cameras, VTRs, projector lenses, viewfinders, filters, prisms, and Fresnel lenses, optical disc pickups such as CD players, DVD players, and MD players. Information equipment such as lens fields such as lenses, optical recording fields for optical disks such as CD players, DVD players, and MD players, liquid crystal light guide plates, liquid crystal display films such as polarizer protective films and retardation films, and surface protective films Fields, optical communication fields such as optical fiber, optical switch, optical connector, etc., automotive headlights, tail lamp lenses, inner lenses, instrument covers, sunroofs, and other vehicle fields, glasses, contact lenses, internal vision lenses, need for sterilization Medical supplies Appliances field, road translucent plates, pair glass lenses, lighting windows and carports, lighting lenses and covers, building material sizing, etc., microwave cooking containers (tableware), home appliance housings, toys , Sunglasses, stationery, etc.

  The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(1) Quantification method of unreacted components The amount of unreacted components contained in 1 g of the product pellets was determined by heating with a Dionex DX-120 liquid collection-ion chromatographic method at heating conditions of 270 ° C. (90 minutes) and a flow rate of 200 mL. / Min (nitrogen). Here, the unreacted component is a component monomethylamine used as an imidizing agent.

(2) Measurement of imidation ratio 1 g of the pellet of the product was dissolved in 5 cc of dichloromethane, and IR spectrum was measured at room temperature using FT / IR-4100 manufactured by JASCO Corporation. From the obtained spectrum, determined with the absorption intensity (Abs _Ester) attributed to the ester carbonyl group of 1720 cm ^-1, the imidization ratio from the ratio of the absorption intensity assignable to an imide carbonyl group of 1660cm ^-1 (Abs _imide) It was. Here, the imidation rate refers to the proportion of the imide carbonyl group in all carbonyl groups. In this example and comparative example, pellets were collected every 10 minutes from 1 hour after the start of production, and the ratio of the imidization rate was measured by the above method. The difference between the maximum value and the minimum value of the measured values obtained was regarded as variation in the imidization rate.

Example 1
An apparatus equivalent to that shown in FIG. 1 was used. As for the tandem type reactive extruder, the first extruder (1) and the second extruder (2) are both in the same direction meshing type with a diameter of 75 mm and L / D (ratio of the length L to the diameter D of the extruder) of 74. Using a twin screw extruder, the raw material resin was supplied to the raw material supply port of the first extruder using a coil screw type constant volume feeder (manufactured by Kubota Corporation). The supply positions of the first stage reaction auxiliary material (imidizing agent) and the second stage reaction auxiliary material (esterifying agent) were the same as those shown in FIG. In addition, the positions of the vents in the first extruder and the second extruder are also the same as those shown in FIG. 1, and the pressure reduction of the vents (10) and (12) is -0.1 MPa, and the pressure reduction of the vent (9). Was -0.003 MPa. Further, the first extruder and the second extruder are connected by a pipe having a diameter of 38 mm and a length of 1.8 m (connecting part (3)), and the resin discharge port of the first extruder and the second extruder raw material supply port are connected. A constant flow pressure valve was used for the in-part pressure control mechanism (4) to be connected. The resin (strand) discharged from the second extruder was cooled in a water tank and then cut into pellets by a pelletizer. Here, the outlet of the first extruder, the first extruder and the second extruder are used to adjust the pressure in the part connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, or to determine the fluctuation of the extrusion. A resin pressure gauge was provided at the center of the machine connecting part and at the outlet of the second extruder.

  Regarding the first extruder, a commercially available methyl methacrylate-styrene copolymer (MS-800 manufactured by Nippon Steel Chemical Co., Ltd.) is used as a raw material resin, and an intermediate imide resin using monomethylamine as an imidizing agent. Body 1 was produced. At this time, each barrel temperature of the extruder was 260 ° C., the screw rotation speed was 60 rpm, the raw material resin supply amount was 150 kg / hour, and the addition amount of monomethylamine was 16 parts with respect to 100 parts of the raw material resin. Further, the first extruder side pressure of the pressure adjusting mechanism was adjusted to 5.6 MPa, the second extruder side pressure was adjusted to 0.1 MPa, and the pressure difference was adjusted to be ΔP5.5 MPa.

  Regarding the second extruder, an imide resin intermediate 2 was produced using a mixed solution of dimethyl carbonate and triethylamine as an esterifying agent. At this time, each barrel temperature of the extruder was 260 ° C., the screw rotation speed was 55 rpm, and the addition amount of dimethyl carbonate was 4 parts with respect to 100 parts of the raw resin. Furthermore, the esterifying agent was removed with a vent to obtain an imide resin.

  The production was carried out for about 2 hours under the above conditions, and the variation was 1% and the unreacted component was 0 ppm with respect to the imidization rate of 70% of the obtained imide resin.

(Example 2)
Venting in the second extruder makes it difficult to confirm the devolatilizing effect in the pressure adjusting mechanism. Therefore, the second extruder does not perform esterification, and is performed except that the decompression of the vent in the second extruder is stopped. The variation was 1% and the unreacted component was 8 ppm with respect to the imidation ratio of 70% of the imide resin produced by the same method as in Example 1.

(Comparative Example 1)
Except for not using a pressure control mechanism and no differential pressure, the imide resin produced by the same method as in Example 1 had an imidation rate of 50% and the reaction was insufficient.

(Comparative Example 2)
The same conditions as in Example 2 were followed, except that the first extruder and the second extruder were not connected, and the imidization reaction was performed with the first extruder to form the extruded strand into pellets. However, the reaction extruder actually used was as shown in FIG. 2 and the L / D was 90. The other conditions were the same as in Example 2.

  As a result, the variation was 1% and the unreacted component was 20 ppm with respect to the imidization rate of 70% of the obtained imide resin.

It is a block diagram of the tandem type | mold reaction extruder by this invention. It is a block diagram of the reaction extruder in the comparative example 2 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st extruder 2 2nd extruder 3 Connection component 4 Pressure control mechanism in components which connects the resin discharge port of a 1st extruder, and a 2nd extruder raw material supply port 5 1st extruder raw material supply port 6 1st extrusion Machine discharge port 7 Second extruder raw material supply port 8 Secondary raw material supply port for first stage reaction 9 Second extruder vent port 10 Second extruder vent port 11 Secondary raw material supply port 12 for second stage reaction Extruder vent port 13 Various additive supply ports 14 Extruder 15 Raw material supply port 16 Reaction auxiliary material supply port 17 Vent port

Claims (4)

First extruder,
A second extruder having a vent port ;
Parts connecting the resin discharge port of the first extruder and the raw material supply port of the second extruder, and
Using a tandem type extruder having an in-part pressure control mechanism that connects the resin discharge port of the first extruder and the raw material supply port of the second extruder,
In the first extruder, the first stage reaction between the resin and the auxiliary material I row to obtain a reaction product,
In the second extruder , the second stage reaction and devolatilization of the reaction product and other auxiliary materials in the first extruder, a method for producing a thermoplastic resin ,
The first extruder side pressure force and 10MPa der less differential pressure △ P is more than 2MPa second extruder lateral pressure force of the pressure control mechanism is, the first extruder side pressure of the pressure control mechanism or less 10MPa or more 2MPa, The second extruder side pressure is 0.01 MPa or more and 1 MPa or less,
Parts in the pressure control mechanism, the manufacturing method characterized by constant flow pressure valve or orifice der Rukoto.   2. The method for producing a thermoplastic resin according to claim 1, wherein in the tandem-type reaction extruder, each of the first extruder and the second extruder is a twin-screw extruder. The first stage reaction between the acrylic resin and the imidizing agent is performed in the first extruder, and the second stage reaction between the reaction product and the esterifying agent in the first extruder is performed in the second extruder. The method for producing a thermoplastic resin according to claim 1, characterized in that it is characterized in that The thermoplastic resin is an imide resin having a unit represented by the following general formula (1), a unit represented by the following general formula (2) and / or a unit represented by the following general formula (3). The method for producing a thermoplastic resin according to claim 1, wherein:

(However, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ³ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R ⁴ and R ⁵ each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁶ represents hydrogen, an alkyl group having 1 to 18 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(However, R ⁷ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents an aryl group having 6 to 10 carbon atoms.)

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