JP2010077362A - Process for producing acrylic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing acrylic resins by which the reaction efficiency is increased and the reaction uniformity is markedly improved by controlling the fluctuation in the amount of extrusion for an extruder having a pressure control mechanism. <P>SOLUTION: A 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 for reaction and/or deaeration, 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. The reaction extruder achieves a desired reaction rate by regulating the various reaction parameters to satisfy formula (1). The scheme is particularly effective for producing imide resins by the reaction of acrylic resins with an imidization agent. In the formula, the pressure is P PMa; reaction reagent concentration is a C part: maximum temperature of the extruder is Q°C; reaction time is t min. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for producing an acrylic resin by a reactive extruder.

  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 an acrylic resin can be manufactured.

  However, the conventional production method in which a thermoplastic resin is melted and reacted cannot control the reaction efficiency and the reaction uniformity, and there is room for improvement.

  Up to now, as a method for improving reaction efficiency and reaction uniformity, there is a method for improving reaction efficiency by using carbon dioxide as a reaction medium for a method for producing a modified thermoplastic resin using an extruder (for example, Patent Document 1). Since such a method uses a reaction medium, the facilities are complicated and expensive, and the manufacturing cost is high.

Further, in a method of adding an imidizing agent to an acrylic resin in an extruder and causing an imidization reaction, there is a method of obtaining desired resin physical properties by setting an extruder barrel temperature to 150 ° C. or higher and lower than 200 ° C. (for example, Patent Document 2). reference). However, in such a method, since the barrel temperature is limited, a control range for obtaining desired resin physical properties is limited, and there is room for improvement in productivity.
JP2002-256042 JP-A-2005-23273

  The present invention has been made in view of such problems of the conventional technology. In the reactive extruder, the acrylic is capable of improving the reaction efficiency and obtaining a desired reaction rate in the reactive extruder. It aims at providing the manufacturing method of a resin.

  According to the present invention, a solid resin raw material is plasticized, a reaction agent for the first stage reaction is supplied to perform the reaction, and the molten resin supplied from the first extruder is subjected to the second stage. A second extruder for supplying an auxiliary raw material for the eye reaction and performing reaction and / or devolatilization, a component connecting the resin discharge port of the first extruder and the second extruder raw material supply port, and the pressure in the first extruder In a reaction extruder having a control mechanism, a desired reaction rate can be obtained by adjusting various reaction parameters so as to satisfy the formula (1).

That is, the present invention relates to the following (i) to (v).
(I) In a method for producing an acrylic resin with an extruder having a pressure control mechanism, when the pressure inside the system is PMPa, the reaction reagent concentration is C parts, the maximum temperature of the extruder is Q ° C., and the reaction time is t minutes. The manufacturing method of the acrylic resin characterized by satisfy | filling following Numerical formula (1).

  (Ii) The production method according to (i), wherein the reaction reagent is an imidizing agent.

(Iii)
The main raw material is a thermoplastic resin having a unit represented by the following general formula (2) or a unit represented by the following general formula (2) and a unit represented by the following general formula (3). The method for producing an acrylic resin according to (i) or (ii).

（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, R4 and R5 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R6 represents hydrogen, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or A substituent containing an aromatic ring having 5 to 15 carbon atoms is shown.)

（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。）
（ｉｖ）

(However, R7 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and R8 represents an aryl group having 6 to 10 carbon atoms.)
(Iv)

  The manufacturing method according to any one of (i) to (iii), wherein the following mathematical formula (3) is satisfied.

  (V) An imide resin in which the acrylic resin has a unit represented by the following general formula (1), a unit represented by the general formula (2) and / or a unit represented by the general formula (3) The method for producing an acrylic resin according to any one of (i) to (iv), 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, R1 and R2 each independently represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and R3 represents hydrogen, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or A substituent containing an aromatic ring having 5 to 15 carbon atoms is shown.)

  According to the present invention, in the method of producing an acrylic resin with an extruder having a pressure control mechanism, the reaction rate is determined by using the system pressure, the reaction reagent concentration, the maximum temperature of the extruder, and the reaction time as reaction operating factors. Provided is a method for producing a thermoplastic resin that can be controlled.

  In the present invention, in the method of producing an acrylic resin with an extruder having a pressure control mechanism, the pressure in the system is PMPa, the reaction reagent concentration is C parts, the maximum temperature of the extruder is Q ° C., and the reaction time is t minutes. The present invention relates to a method for producing an acrylic resin characterized by satisfying the following mathematical formula (1).

  First, an extruder having a pressure control mechanism will be described. An extruder having a pressure control mechanism is a device that can control the pressure loss by changing the resin flow path volume. A preferable pressure control mechanism can be exemplified by a valve, such as a constant flow pressure valve, and other gear pumps, orifices, etc., but may be incorporated in the extruder itself.

  The position for attaching the pressure control mechanism is not particularly limited as long as it is a position on the downstream side from the reaction reagent supply port. However, it is preferable to install the pressure control mechanism near the extruder resin discharge port because the reaction part pressure can be increased. Further, in a tandem type extruder having a second extruder, etc., depending on the type of the pressure control mechanism, 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 portion where the pressure difference occurs as an entity may be referred to as the position of the pressure control mechanism.

  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. A tandem type extruder may be used. A tandem type extruder is, for example, a part that connects a resin discharge port of a first extruder and a raw material supply port of a second extruder (hereinafter simply referred to as a connection part) of a first extruder and a second extruder. May be abbreviated as ")". 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 first extruder and the second extruder are used by using a tandem type extruder having a first extruder, a second extruder, and a part connecting a resin discharge port of the first extruder and a raw material supply port of the second extruder. It is also possible to carry out different reactions on the machine. Although an example of a tandem type reaction extruder is shown in FIG. 1, this 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).

  The main raw material of the acrylic resin obtained in the present invention is an acid anhydride such as maleic anhydride or a half ester of them with a linear or branched alcohol having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid , Maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid and other α, β-ethylenically unsaturated carboxylic acids, (meth) acrylic esters and other acrylic monomers and at least one of them The polymer (acrylic resin) etc. which superposed | polymerized can be mentioned. Among them, (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): A polymer or a (meth) acrylic acid ester polymer such as a methyl methacrylate polymer composed of a repeating unit represented by the general formula (2) is preferred.

（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. In the formula (3), R ⁷ is preferably hydrogen, and R ⁸ is preferably a phenyl group.

  In the present invention, a (meth) acrylic acid ester-aromatic vinyl copolymer such as methyl methacrylate-styrene copolymer or a (meth) acrylic acid ester polymer such as methyl methacrylate polymer is polymerized, and this is imide. When the resin is formed, the (meth) acrylic acid ester-aromatic vinyl copolymer and (meth) acrylic acid ester polymer that can be used in the present invention are linear (linear) if imidization reaction is possible. The polymer 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.

  Examples of the acrylic resin obtained by this production method include those obtained by further polymerizing, modifying, or reacting a polymer obtained by polymerizing an acrylic monomer and at least one of them. Methyl acid resin, polystyrene resin, cellulose resin, vinyl chloride resin, polysulfone resin, polyethersulfone resin, maleimide / olefin resin, glutarimide resin, lactone ring-containing polymer, glutaric anhydride Examples thereof include resins such as containing resins, and resin compositions obtained by mixing these resins. A glutarimide resin is preferable.

  For example, when the resulting acrylic resin is an N-methylmaleimide / isobutene copolymer, the first extruder uses a maleic anhydride / isobutene copolymer (Kuraray Co., Ltd., product name Isoban 6) as the production method. It can be treated with an amine to synthesize an N-methylmaleimide / isobutene copolymer, and the second extruder can carry out a devolatilization step that removes volatile matter (for example, as described in WO01 / 037007) It can be applied to the present invention.

  The reaction reagent in the present invention is not particularly limited as long as it reacts with the main raw material to give an acrylic resin.

  Next, the following formula (1) in the present invention will be described.

  Here, the system pressure PMPa is the maximum pressure in the reaction section of the extruder. Specifically, it is the highest pressure in a pressure measuring device installed in an extruder or a pressure control mechanism, a pressure measuring device installed in a reaction reagent press-fitting part or line, or any other measuring device that can analyze the pressure in the extruder. The P value is preferably 2 MPa or more and 50 MPa or less. More preferably, it is 2 MPa or more and 20 MPa or less, More preferably, it is 2 MPa or more and 15 MPa or less. When the P value is less than 2 MPa, the reaction efficiency in the extruder is lowered, and the reaction by-product is foamed and separated in the reaction part, the fluctuation of extrusion becomes large, and the reaction becomes non-uniform, which is not preferable. .

  Further, when the pressure inside the extruder is higher than 50 MPa, particularly when the pressure resistance specification of the extruder speed reducer is exceeded, the extruder may be damaged, which is not preferable.

  The reaction reagent concentration C part is the reaction reagent supply part by weight when the supply resin amount is 100 parts by weight. What is necessary is just to determine the addition amount of a reaction reagent suitably according to a required physical property. Preferably, it is 5 to 30 parts by weight with respect to 100 parts by weight of the main raw material. More preferably, it is 5-25 weight part, More preferably, it is 8-20 weight part. If the amount is less than 1 part by weight, the reaction rate decreases, and if it exceeds 50 parts by weight, the production cost increases, which is not preferable.

  Extruder maximum temperature part temperature Q ° C. is the temperature of the highest temperature part of the extruder in the reaction part from the extruder reaction reagent press-fitting part to the pressure control mechanism. The temperature at the highest temperature point is the highest among the devices that can measure the reaction part temperature in the extruder, such as the barrel temperature, the temperature analyzed from the indication value of the resin thermometer installed in the extruder, and the measured value of the resin temperature. Refers to temperature. The Q value is preferably 220 ° C. or higher and 320 ° C. or lower. More preferably, it is 240 degreeC or more and 310 degrees C or less, More preferably, it is 250 degreeC or more and 300 degrees C or less. When the temperature is lower than 220 ° C., the reaction efficiency is lowered and the productivity is lowered. A temperature higher than 320 ° C. is not preferable because the resin is thermally deteriorated.

  The reaction time t minutes is the time from when the resin and the reaction reagent are supplied into the extruder having a pressure control mechanism until the resin and the reaction reagent are separated. The reaction time is preferably from 0.2 minutes to 60 minutes. More preferably, it is 0.35 minutes or more and 30 minutes or less, More preferably, it is 0.5 minutes or more and 15 minutes or less. If it is 0.2 minutes or less, the reaction rate is low, and if it exceeds 60 minutes, the resin is thermally deteriorated, which is not preferable.

  In the present invention, the following mathematical formula (2);

で表される数式（２）の値が０．２０以上、０．９９以下であることが好ましい。数式（２）の下限値としては、０．３０以上であることがさらに好ましく、０．３５以上であることが特に好ましい。上限値としては、０.９０以下であることが好ましく０．８５以下であることが特に好ましい。０．２５未満または０．９９よりも大きいと反応が十分に進行せず好ましくない。

Is preferably 0.20 or more and 0.99 or less. As a lower limit of numerical formula (2), it is more preferable that it is 0.30 or more, and it is especially preferable that it is 0.35 or more. The upper limit is preferably 0.90 or less, and particularly preferably 0.85 or less. If it is less than 0.25 or larger than 0.99, the reaction does not proceed sufficiently, which is not preferable.

  Here, a method for producing a glutarimide resin (hereinafter sometimes referred to as an imide resin) as the acrylic resin will be described as an example. Specifically, a reaction in which an acrylic resin and an imidizing agent are treated in a first extruder using a tandem reaction extruder having a pressure control mechanism will be described.

  An example of the reaction agent 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.

  In the glutarimide resin, the imidization rate is preferably 20% or more and 95% or less, more preferably 40% or more and 90% or less, and particularly preferably 50% or more and 80% or less. When not satisfy | filling above-mentioned numerical formula (1), the imide resin which has the imidation ratio of the said range cannot be obtained.

  In the first extruder of the tandem type 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 referred to as an imidizing agent). It is possible to obtain a resin (hereinafter, sometimes referred to as 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 temperature is in the range of 150 to 320 ° 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.

  Further, the esterifying agent contained in the imide resin intermediate 2 may be removed by devolatilization under reduced pressure or the like.

  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 320 ° 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 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.

  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 the imide resin obtained as described above, for example, various types can be produced by appropriately setting the type and amount of the main raw material and the auxiliary raw material by the above-described method. What has the unit represented by (1), the unit represented by the said General formula (2), and / or the unit represented by the said General formula (3) is mention | raise | lifted.

（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 glutarimide 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 has 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 Field, optical communication field such as optical fiber, optical switch, optical connector, etc., automotive field such as automobile headlight, tail lamp lens, inner lens, instrument cover, sunroof, eyeglasses, contact lens, lens for internal vision, need for sterilization treatment Medical supplies Appliances field, road translucent board, pair glass lens, lighting window and carport, lighting lens and cover, building material sizing, etc., microwave cooking container (tableware), home appliance housing, toy , 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. In addition, each measuring method of the physical property measured in the following Examples and Comparative Examples is as follows.

(1) Measurement of imidation ratio 1 g of product pellets were dissolved in 5 cc of dichloromethane, and an IR spectrum was measured at room temperature using an IR meter 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.

(2) Measurement of ratio of acid component remaining in resin 0.3 g of product pellets were dissolved in 37.5 ml of dichloromethane, and 37.5 ml of methanol was added. To this solution, 2 drops of 1 wt% phenolphthalein ethanol solution was added, 5 ml of 0.1N sodium hydroxide aqueous solution was added, and the mixture was stirred for 1 hour. 0.1N hydrochloric acid was added dropwise to this solution, and the amount of 0.1N hydrochloric acid added (Aml) until the reddish purple color of the solution disappeared was measured.

  Next, 2 drops of 1 wt% phenolphthalein ethanol solution was added to a mixed solution of 37.5 ml of dichloromethane and 37.5 ml of methanol. To this, 5 ml of 0.1N sodium hydroxide aqueous solution was added and stirred for 1 hour. 0.1N hydrochloric acid was added dropwise to this solution, and the amount of 0.1N hydrochloric acid added (Bml) until the reddish purple color of the solution disappeared was measured.

  The ratio of the acid component (mono derived from a carboxyl group and an acid anhydride group) remaining in the resin was defined as Cmmol / g, and the following formula was used.

    C = 0.1 × ((5-AB) /0.3)

(3) Variation In this example and comparative example, pellets were collected every 1 minute from 1 hour after the start of production, and the imidization rate and the ratio of acid components were measured by the above methods. The difference between the maximum value and the minimum value of the measured values obtained was regarded as the variation in the imidization rate and the variation in the acid component, respectively.

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 constant weight 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. The positions of the vents in the first extruder and the second extruder were also the same as those shown in FIG. 1, and the degree of vacuum of each vent was -0.095 MPa. Further, the first extruder and the second extruder are connected by a pipe having a diameter of 38 mm and a length of 2 m (connection 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 internal pressure control mechanism (4). The resin (strand) discharged from the second extruder was cooled by a cooling conveyor and then cut by a pelletizer to form pellets. 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, the maximum temperature of the extruder was 280 ° 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. Moreover, the constant flow pressure valve was installed just before the 2nd extruder raw material supply port, and the 1st extruder monomethylamine press-fit part pressure was adjusted so that it might be set to 8 Mpa.

  Regarding the second extruder, after devolatilizing the imidization reaction reagent and by-products remaining in the rear vent and vacuum vent, a mixed solution of dimethyl carbonate and triethylamine is added as an esterifying agent to produce an imide resin intermediate 2 did. At this time, each barrel temperature of the extruder was 260 ° C., the screw rotation speed was 55 rpm, the addition amount of dimethyl carbonate was 2.4 parts with respect to 100 parts of the raw material resin, and the addition amount of triethylamine was 0.2 parts with respect to 100 parts of the raw material resin. 6 parts. Furthermore, the esterifying agent was removed with a vent to obtain an imide resin.

  The imide resin was produced for about 7 days under the above conditions, and the resulting imide resin had an imidation ratio of 73%, a variation of 1%, and an acid component remaining in the resin (mono derived from carboxyl group and acid anhydride group) The variation was 0.01 mmol / g with respect to 0.20 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the central portion of the first extruder and the second extruder connecting pipe was 1.0 MPa. The results are shown in Table 1.

(Example 2)
An imide resin was produced in the same manner as in Example 1, except that the internal pressure was 5 MPa, the addition amount of monomethylamine was 14 parts with respect to 100 parts of the raw material resin, and the esterification agent addition amount was 4.3 parts by weight. .

  As a result, the obtained imide resin had a variation of 1% with respect to an imidation rate of 53%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.20 mmol / g. The variation in the pressure of the first extruder monomethylamine press-fit portion was 1.0 MPa.

(Example 3)
As the raw material resin, commercially available polymethyl methacrylate (Sumitex MG manufactured by Sumitomo Chemical Co., Ltd.) is used, and the addition amount of dimethyl carbonate is 4 parts and the addition amount of triethylamine is 1 part (each 100 parts of raw material resin). An imide resin was produced in the same manner as in Example 1 except that.

  As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 75%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the central portion of the first extruder and the second extruder connecting pipe was 1.0 MPa.

Example 4
An imide resin was produced in the same manner as in Example 1 except that the raw material resin supply rate was 200 kg / h. As a result, the obtained imide resin had a variation of 1% with respect to the imidization rate of 63%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the central portion of the first extruder and the second extruder connecting pipe was 1.0 MPa.

(Comparative Example 1)
An imide resin was produced in the same manner as in Example 1 except that the internal pressure was 5 MPa, the reaction reagent was 15 parts by weight, and the extruder maximum temperature was 200 ° C. As a result, the obtained imide resin had a variation of 1% with respect to an imidization rate of 18%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the central portion of the first extruder and the second extruder connecting pipe was 1.0 MPa.

(Comparative Example 2)
The imide was prepared in the same manner as in Example 1 except that the raw material resin supply rate was 300 kg / h, the first extruder screw rotation speed was 120 rpm, the internal pressure was 5 MPa, the reaction reagent was 5 parts by weight, and the maximum temperature of the extruder was 330 ° C. A resin was produced. As a result, the obtained imide resin had a variation of 1% with respect to an imidation rate of 10%, and a variation of 0.01 mmol / g with respect to the ratio of the acid component remaining in the resin of 0.10 mmol / g. The variation in the pressure at the outlet of the first extruder and the pressure at the central portion of the first extruder and the second extruder connecting pipe was 1.0 MPa.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st extruder 2 2nd extruder 3 Connection component 4 Component internal pressure control mechanism 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 Secondary raw material supply port for second stage reaction 11 Second extruder vent port 12 Various additions Agent Supply Port 13 Second Extruder Vent Port

Claims (5)

In the method of producing an acrylic resin with an extruder having a pressure control mechanism, when the system pressure is PMPa, the reaction agent concentration is C parts, the extruder maximum temperature is Q ° C, and the reaction time is t minutes, The manufacturing method of acrylic resin characterized by satisfying (1).

  The production method according to claim 1, wherein the reaction reagent is an imidizing agent. The main raw material is a thermoplastic resin having a unit represented by the following general formula (2) or a unit represented by the following general formula (2) and a unit represented by the following general formula (3). The method for producing an acrylic resin according to claim 1 or 2.

(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.) The manufacturing method according to claim 1, wherein the following mathematical formula (3) is satisfied.

The acrylic resin is an imide resin having a unit 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). The manufacturing method of the acrylic resin of any one of Claims 1-4 characterized by these.

(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.)

Images