JP6697848B2 - Method for producing (meth)acrylic polymer - Google Patents

Description

  The present invention relates to a method for producing a (meth)acrylic polymer having an acid anhydride structure.

  A (meth)acrylic polymer is excellent in transparency and weather resistance, is useful as a molding material, an adhesive, and the like, and is used in electronic members, optical members, industrial materials, daily necessities, and the like. Among these, the (meth)acrylic block copolymer having a methacrylic acid ester-based polymer block and an acrylic acid ester-based polymer block is further useful as a polymer surfactant, a thermoplastic elastomer, and the like ( Patent Document 1).

  Furthermore, it is known that a (meth)acrylic polymer having an acid anhydride structure has excellent heat resistance and reactivity. Examples of the method for producing a (meth)acrylic polymer having an acid anhydride structure include a method of copolymerizing methyl methacrylate, styrene, and maleic anhydride (Patent Document 2), and a method of producing methyl methacrylate and (meth)acrylic acid. A method of heat-treating a copolymer (Patent Document 3), a method of heat-treating a copolymer of methyl methacrylate and t-butyl (meth)acrylate, and the like are known (Patent Document 4).

  In the method of copolymerizing methyl methacrylate, styrene and maleic anhydride, a monomer unit (styrene unit etc.) other than the (meth)acrylic monomer unit is introduced, so that the (meth)acrylic polymer The transparency, weather resistance, etc., which are the characteristics of, tend to be impaired. Moreover, the method of heat-treating the above-mentioned copolymer of methyl methacrylate and (meth)acrylic acid or the copolymer of methyl methacrylate and t-butyl (meth)acrylic acid makes the copolymer as a raw material available. It is extremely scarce and the manufacturing process becomes complicated.

JP, 11-335432, A JP 2001-270905 A JP, 9-003125, A JP, 2007-039562, A

  An object of the present invention is to provide a production method capable of obtaining a (meth)acrylic polymer having an acid anhydride structure excellent in transparency and weather resistance from easily available raw materials with a small number of production steps.

The present invention, as a means for solving the above object,
[1] A mixing step of mixing a (meth)acrylic polymer containing a methyl (meth)acrylate unit (hereinafter referred to as “(meth)acrylic polymer (X0)”) and a secondary amine is included. A method for producing a (meth)acrylic polymer having an acid anhydride structure (hereinafter referred to as "(meth)acrylic polymer (X)");
[2] The (meth)acrylic polymer block (a) in which the (meth)acrylic polymer (X0) contains more than 50 mol% of methyl (meth)acrylate units (hereinafter referred to as "(meth)acrylic polymer block"). (A)) and a (meth)acrylic polymer block (b) containing more than 50 mol% of a (meth)acrylic acid alkyl ester unit having an alkyl group having 2 or more carbon atoms (hereinafter referred to as “(meth)acrylic”). (Meth)acrylic block copolymer (hereinafter referred to as "(meth)acrylic block polymer (Z0)"), which comprises a polymer block (b)"). ;
[3] The secondary amine has the acid anhydride structure of the above [1] or [2], which is a compound represented by the following general formula (1) (hereinafter referred to as "secondary amine (1)"). A method for producing a (meth)acrylic polymer;
[4] The production method according to any one of the above [1] to [3], wherein the mixing step is performed in the presence of an organic solvent; and [5] The above [1] to [3], wherein the mixing step is performed in the absence of an organic solvent. ] The manufacturing method in any one of these.

（一般式（１）中、Ｒ¹およびＲ²はそれぞれ独立して炭化水素基を表し、かつ少なくともいずれかは２級アルキル基、３級アルキル基、脂環式飽和炭化水素基、アリール基、２級アラルキル基、および３級アラルキル基からなる群より選ばれる炭化水素基を表す）

(In the general formula (1), R ¹ and R ² each independently represent a hydrocarbon group, and at least one of them is a secondary alkyl group, a tertiary alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, Represents a hydrocarbon group selected from the group consisting of a secondary aralkyl group and a tertiary aralkyl group)

  According to the present invention, easily available raw materials (typically polymethyl methacrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-n-butyl acrylate copolymer) (Meth)acrylic polymer having an acid anhydride structure excellent in transparency and weather resistance can be easily produced from a polymer or the like in a small number of production steps.

Hereinafter, the present invention will be described in detail.
According to the production method of the present invention, a (meth)acrylic polymer (X) can be obtained from a (meth)acrylic polymer (X0), and an acid anhydride can be obtained from a (meth)acrylic block copolymer (Z0). A (meth)acrylic block copolymer having a structure (hereinafter referred to as "(meth)acrylic block copolymer (Z)") can be obtained. In addition, in this specification, "(meth)acrylic" is a general term for "methacrylic" and "acrylic."

  The (meth)acrylic polymer (X0) is a polymer containing a methyl (meth)acrylate unit, and is a copolymer of methyl poly(meth)acrylate or methyl methacrylate and another (meth)acrylate ester. Coalescence, copolymer of methyl acrylate and other (meth)acrylic acid ester, copolymer of methyl (meth)acrylate and aromatic vinyl compound, copolymerization of methyl (meth)acrylate and conjugated diene Examples include coalescing.

  Examples of the (meth)acrylic acid ester other than methyl (meth)acrylate capable of forming the (meth)acrylic polymer (X0) include ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic. Acid n-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid n-octyl, (meth)acrylic acid lauryl, (meth ) Tridecyl acrylate, stearyl (meth)acrylate, and the like, (meth)acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms; (meth)acrylic acid cyclohexyl, (meth)acrylic acid isobornyl, and other (meth)acrylic acid Alicyclic ester; aryl ester of (meth)acrylic acid such as phenyl (meth)acrylate, naphthyl (meth)acrylate; aralkyl ester of (meth)acrylic acid such as benzyl (meth)acrylate; (meth)acrylic acid 2 -(Meth)acrylic acid alkoxyalkyl esters such as methoxyethyl, ethoxyethyl (meth)acrylate; 2-aminoethyl (meth)acrylic acid, N,N-dimethylaminoethyl (meth)acrylic acid, (meth)acrylic acid (Meth)acrylic acid aminoalkyl ester such as N,N-diethylaminoethyl; 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, trimethoxy (meth)acrylate Examples thereof include silylpropyl, 2-(trimethylsilyloxy)ethyl (meth)acrylate, and 3-(trimethylsilyloxy)propyl (meth)acrylate.

Examples of the aromatic vinyl compound capable of forming the (meth)acrylic polymer (X0) include styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene.
Examples of the conjugated diene capable of forming the (meth)acrylic polymer (X0) include butadiene and isoprene.

  From the viewpoints of transparency, weather resistance, etc. of the obtained (meth)acrylic polymer (X), specific examples of the (meth)acrylic polymer (X0) include methyl poly(meth)acrylate and methyl methacrylate. Copolymers of other (meth)acrylic acid esters and copolymers of methyl acrylate and other (meth)acrylic acid esters are preferable, and poly(meth)acrylic acid methyl, methacrylic acid are preferable from the viewpoint of availability. More preferred are a copolymer of methyl and methyl acrylate, a copolymer of methyl methacrylate and ethyl acrylate, and a copolymer of methyl methacrylate and n-butyl acrylate.

  The content of the (meth)acrylic acid ester unit in the monomer units constituting the (meth)acrylic polymer (X0) is preferably in the range of 50 to 100% by mass, and 70 to 100% by mass. The range is more preferable, and the range of 90 to 100% by mass is further preferable.

  The content of the methyl (meth)acrylate unit in the monomer units constituting the (meth)acrylic polymer (X0) is preferably in the range of 5 to 100% by mass, and 10 to 99% by mass. The range is more preferable, and the range of 15 to 98% by mass is further preferable.

  The number average molecular weight (Mn) of the (meth)acrylic polymer (X0) is not particularly limited, but is preferably in the range of 4,000 to 3,000,000 from the viewpoint of handleability, fluidity, mechanical properties, and the like. The range of 7,000 to 2,000,000 is more preferable.

The molecular weight distribution of the (meth)acrylic polymer (X0), that is, the weight average molecular weight/number average molecular weight (Mw/Mn) is preferably in the range of 1.02 to 2.00, and is preferably in the range of 1.05 to 1.80. A more preferred range is 1.10 to 1.50.
In addition, in this specification, Mn and Mw/Mn mean the standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

  A preferable example of the (meth)acrylic polymer (X0) is a (meth)acrylic block copolymer (Z0). The (meth)acrylic block copolymer (Z0) contains the (meth)acrylic polymer block (a) and the (meth)acrylic polymer block (b).

  The (meth)acrylic polymer block (a) contains more than 50 mol% of methyl (meth)acrylate units. The content of methyl (meth)acrylate units in the (meth)acrylic polymer block (a) is preferably in the range of 70 mol% or more, more preferably in the range of 90 mol% or more, and 100 mol. It may be %.

  From the viewpoint of availability of the (meth)acrylic block copolymer (Z0), the methyl (meth)acrylate capable of forming the methyl (meth)acrylate unit in the (meth)acrylic polymer block (a) is Most preferred is methyl methacrylate.

  The (meth)acrylic polymer block (a) may contain a monomer unit other than the methyl (meth)acrylate unit. Examples of the monomer capable of forming such a monomer unit include (meth)acrylic acid esters other than the above-mentioned methyl (meth)acrylate, aromatic vinyl compounds, conjugated dienes and the like. The content of these other monomer units in the (meth)acrylic polymer block (a) is preferably in the range of 30 mol% or less, more preferably 10 mol% or less.

  The (meth)acrylic polymer block (b) contains more than 50 mol% of a (meth)acrylic acid alkyl ester unit having an alkyl group having 2 or more carbon atoms. The content of the (meth)acrylic acid ester unit having an alkyl group having 2 or more carbon atoms in the (meth)acrylic polymer block (b) is preferably 70 mol% or more, and 90 mol% or more. Is more preferable, and may be 100 mol %.

  The Mn per (meth)acrylic polymer block (a) is not particularly limited, but is 500 from the viewpoint of handling property, fluidity, mechanical properties and the like of the (meth)acrylic block copolymer (Z0). The range of 1,000,000 to 1,000,000 is preferable, and the range of 1,000 to 300,000 is more preferable.

  As a (meth)acrylic acid alkyl ester having a C2 or more alkyl group capable of forming the above-mentioned (meth)acrylic acid alkyl ester unit having a C2 or more alkyl group in the (meth)acrylic polymer block (b) Is 4 or more carbon atoms such as n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc., from the viewpoint of the flexibility of the obtained (meth)acrylic block copolymer (Z). Acrylic acid alkyl ester having an alkyl group of: Methacrylic acid alkyl ester having an alkyl group having 6 or more carbon atoms such as 2-ethylhexyl methacrylate and dodecyl methacrylate is preferable, and a (meth)acrylic block copolymer (Z0) From the viewpoint of availability, n-butyl acrylate is most preferable.

  The (meth)acrylic polymer block (b) may contain a monomer unit other than the (meth)acrylic acid alkyl ester unit having an alkyl group having 2 or more carbon atoms. Examples of the monomer capable of forming such a monomer unit include (meth)acrylic acid esters other than the above-mentioned (meth)acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms, aromatic vinyl compounds, conjugated dienes and the like. Can be mentioned. The content of these other monomer units in the (meth)acrylic polymer block (b) is preferably 30 mol% or less, more preferably 10 mol% or less.

  The Mn per one (meth)acrylic polymer block (b) is not particularly limited, but from the viewpoint of handleability, fluidity, mechanical properties and the like of the obtained (meth)acrylic block copolymer (Z0), The range of 3,000 to 2,000,000 is preferable, and the range of 5,000 to 1,000,000 is more preferable.

  The (meth)acrylic block copolymer (Z0) is a block copolymer having at least one (meth)acrylic polymer block (a) and at least one (meth)acrylic polymer block (b). The number of each polymer block and the bonding order are not particularly limited, but it is preferably a linear polymer from the viewpoint of availability of the (meth)acrylic polymer (Z0). More preferably, it is a triblock copolymer in which one (meth)acrylic polymer block (a) is bonded to each end of each (meth)acrylic polymer block (b).

  Ratio of mass of (meth)acrylic polymer block (a) and mass of (meth)acrylic polymer block (b) constituting the (meth)acrylic block copolymer (Z0) [(meth)acrylic The polymer block (a):(meth)acrylic polymer block (b)] is not particularly limited, but is preferably 85:15 to 5:95, and 80:20 to 7:93. Is more preferable, and it is further preferable that it is 75:25 to 10:90.

  The (meth)acrylic block copolymer (Z0) contains the (meth)acrylic polymer block (a) and the (meth)acrylic polymer block (b). The acid anhydride structure of the obtained (meth)acrylic block copolymer (Z) is selective to the polymer block derived from the (meth)acrylic polymer block (a) due to the difference in the constitutional units of the polymer blocks. Will be introduced to.

The method for producing the (meth)acrylic polymer (X0) used in the present invention is not particularly limited, but it is a (meth)acrylic polymer usually obtained by an anionic polymerization method or a radical polymerization method, and a commercially available commercially available product can be used. Can be used.
In the mixing step according to the production method of the present invention, the (meth)acrylic polymer (X0) and the secondary amine are mixed.

  Examples of the secondary amine include N-methylcyclohexylamine, N-methylbutylamine, dimethylamine, diisopropylamine, piperidine, piperazine, morpholine, α-pyrrolidone, pyrrolidine, and 2-(isopropylamino)ethanol. Amine (1) is preferred. The structure of the secondary amine (1) is represented by the following general formula (1).

（一般式（１）中、Ｒ¹およびＲ²はそれぞれ独立して炭化水素基を表し、かつ少なくともいずれかは２級アルキル基、３級アルキル基、脂環式飽和炭化水素基、アリール基、２級アラルキル基、および３級アラルキル基からなる群より選ばれる炭化水素基を表す）；
上記Ｒ¹およびＲ²が表す炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、イソブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基等の１級アルキル基；
イソプロピル基、ｓｅｃ−ブチル基、１−メチルブチル基等の２級アルキル基；
ｔ−ブチル基、１，１−ジメチルプロピル基等の３級アルキル基；
シクロプロピル基、シクロブチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基等の脂環式飽和炭化水素基；
フェニル基、トリル基、ナフチル基等のアリール基；
１−メチルベンジル基等の２級アラルキル基；
１，１−ジメチルベンジル基等の３級アラルキル基；などが挙げられる。
かかる２級アミン（１）の具体例としては、ジイソプロピルアミン、Ｎ−メチルシクロヘキシルアミンなどが挙げられる。

(In the general formula (1), R ¹ and R ² each independently represent a hydrocarbon group, and at least one of them is a secondary alkyl group, a tertiary alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, Represents a hydrocarbon group selected from the group consisting of a secondary aralkyl group and a tertiary aralkyl group);
Examples of the hydrocarbon group represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, and n. -Primary alkyl groups such as heptyl group and n-octyl group;
Secondary alkyl groups such as isopropyl group, sec-butyl group, 1-methylbutyl group;
tertiary alkyl groups such as t-butyl group and 1,1-dimethylpropyl group;
Alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclohexyl group, norbornyl group and adamantyl group;
Aryl groups such as phenyl group, tolyl group, naphthyl group;
A secondary aralkyl group such as a 1-methylbenzyl group;
A tertiary aralkyl group such as a 1,1-dimethylbenzyl group; and the like.
Specific examples of the secondary amine (1) include diisopropylamine and N-methylcyclohexylamine.

  The amount of the secondary amine used is preferably in the range of 0.1 to 300 mol, based on 100 mol of the (meth)acrylic acid ester unit in the (meth)acrylic polymer (X0), and 0.2 Is more preferably in the range of 150 to 150 moles, and further preferably in the range of 0.3 to 60 moles.

The mixing step in the production method of the present invention may be performed in the presence of an organic solvent or in the absence of an organic solvent.
The temperature at which the (meth)acrylic polymer (X0) and the secondary amine are mixed in the mixing step (mixing temperature) is 150 to 150 from the viewpoint of suppressing the formation of an amide structure as a by-product and increasing the reaction rate. It is preferably in the range of 240° C., more preferably in the range of 180 to 230° C., and further preferably in the range of 200 to 220° C. from the viewpoint of suppressing decomposition and coloring of the mixture.

When the mixing step is performed in the presence of an organic solvent, the reaction can proceed uniformly and quickly.
When the (meth)acrylic polymer (X0) and the secondary amine are mixed in the presence of an organic solvent, it is preferably carried out in a pressure resistant container from the viewpoint of suppressing evaporation of the organic solvent.

  Examples of the organic solvent used include saturated hydrocarbons such as cyclohexane; aromatic compounds such as benzene, ethylbenzene, xylene, toluene and phenol; and ethers such as tetrahydrofuran and butyl cellosolve, (meth)acrylic polymer (X0), An organic solvent in which the (meth)acrylic polymer (X) and the secondary amine used are soluble is preferable. These may be used alone or in combination of two or more.

  When the production method of the present invention is carried out in the absence of an organic solvent, a melt kneading method can be adopted. In the melt kneading method, melt kneading can be performed using a known kneader such as a single-screw extruder, a twin-screw extruder, a kneader or a Banbury mixer. Above all, it is preferable to use a twin-screw extruder which has a large shearing force during melt-kneading and can be continuously operated.

  The time for melt-kneading in the melt-kneading method (melt-kneading time) varies depending on the mixing temperature in the mixing step and the content of the acid anhydride structure in the intended (meth)acrylic polymer, but is in the range of 30 seconds to 120 minutes. Is preferred. If the melt-kneading time is shorter than 30 seconds, the introduction rate of the acid anhydride structure tends to be insufficient, and if it exceeds 120 minutes, deterioration or coloring of the mixture tends to be remarkable.

  Further, in the present invention, a resin composition of the (meth)acrylic polymer (X) and another resin can be obtained. Such other resin may be mixed with the (meth)acrylic polymer (X0) in advance before the mixing step, or such other resin may be added and mixed after the mixing step.

  The content of the acid anhydride structure in the (meth)acrylic polymer (X) obtained in the present invention is not particularly limited, but in the range of 0.001 to 5 mmol/g from the viewpoint of heat resistance, reactivity and the like. It is preferably present, and more preferably in the range of 0.005 to 2 mmol/g. Such content can be quantified by potentiometric titration.

  The (meth)acrylic polymer (X) obtained in the present invention may have a carboxyl group. Such a carboxyl group can be introduced by adjusting the amount of secondary amine used in the mixing step, the amount of water in the system, and the like.

  The (meth)acrylic polymer (X) obtained in the present invention may have an amide structure. Such an amide structure can be introduced by adjusting the type of secondary amine and the mixing temperature in the mixing step.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The technical scope of the present invention is not limited to the following examples.
(material)
(Meth)acrylic polymer (X0): methyl methacrylate-methyl acrylate random copolymer (methyl methacrylate/methyl acrylate=97.5/2.5 (mass ratio), MFR2, commercial product)
(Meth)acrylic block copolymer (Z0): methyl methacrylate-n-butyl acrylate block copolymer (Clarity (registered trademark) LA2140, manufactured by Kuraray Co., Ltd., methyl methacrylate unit 24% by mass)
Secondary amine: N-methylcyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Confirmation of acid anhydride structure and amide structure)
The IR spectrum was measured with the resulting (meth) the following conditions an acrylic polymer in Example, absorption derived from an acid anhydride structure (1800 cm ^-1, 1760 cm ^-1) derived from and amide structures absorption (1640 cm ^-1 )).

As a result, the absorption derived from the acid anhydride structure was confirmed in the (meth)acrylic polymers obtained in all the examples.
In addition, absorption derived from the amide structure was confirmed only in the (meth)acrylic polymers obtained in Examples 3 and 10.
Measuring device: Bio-Rad FTS 3000MX
Measurement method: ATR method Temperature: 25°C

(Quantification of carboxyl group content)
A solution was prepared by dissolving 1.0 g of the (meth)acrylic polymer (X) obtained in each example in 49 g of tetrahydrofuran. A 0.1 M potassium hydroxide ethanol solution was added dropwise to this solution at 0.1 mL/20 sec, and the content (c1) of the carboxyl group derived from the (meth)acrylic acid unit was calculated by potentiometric titration.

(Quantification of content of acid anhydride structure)
The (meth)acrylic polymer (X) obtained in each example was pulverized and immersed in hot water at 80° C. for 72 hours to convert the acid anhydride structure into a carboxyl group. It was confirmed that the physical structure did not remain. After the solid was taken out by filtration and dried, the content (c3) of the acid anhydride structure was calculated from the content (c2) of the carboxyl group calculated in the same manner as the content (c1) of the carboxyl group by the following formula. Were determined.
(C3)=((c2)-(c1))/2 (mol/g)

(appearance)
Using the solution prepared by dissolving the (meth)acrylic polymer (X) obtained in each example in tetrahydrofuran so that the solid content concentration was 10% by mass, a film having a thickness of about 1 mm was cast. It was made. The color and transparency of the obtained film were visually confirmed.

[Example 1] [Production of (meth)acrylic polymer (X1)]
A (meth)acrylic polymer (X0) was fed from a hopper to a twin-screw extruder (manufactured by Parker Corporation) at 0.66 kg/hour, and n-methylcyclohexylamine was added at 0.15 kg/hour ((( It is supplied in an amount of 20 moles per 100 moles of methyl (meth)acrylate unit in the (meth)acrylic polymer (X0), melt-kneaded at a cylinder temperature of 220° C. and a screw rotation speed of 100 rpm, and ) An acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer (X1)") was obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X1) was analyzed. Further, a film was prepared using the (meth)acrylic polymer (X1), and the appearance was confirmed. The results are shown in Table 1.

[Example 2] [Production of (meth)acrylic polymer (X2)]
A (meth)acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer (X2)") was obtained in the same manner as in Example 1 except that the cylinder temperature was 180°C.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X2) was analyzed. In addition, a film was produced using the (meth)acrylic polymer (X2), and the appearance was confirmed. The results are shown in Table 1.

[Example 3] [Production of (meth)acrylic polymer (X3)]
A (meth)acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer (X3)") was obtained in the same manner as in Example 1 except that the cylinder temperature was 260°C.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X3) was analyzed. Further, a film was prepared using the (meth)acrylic polymer (X3), and the appearance was confirmed. The results are shown in Table 1.

[Example 4] [Production of (meth)acrylic polymer (X4)]
Except that n-methylcyclohexylamine was supplied in an amount of 3.7 g/hour (0.5 mol based on 100 mol of methyl (meth)acrylate units in the (meth)acrylic polymer (X0)). A (meth)acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer (X4)") was obtained in the same manner as in Example 1.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X4) was analyzed. In addition, a film was produced using the (meth)acrylic polymer (X4), and the appearance was confirmed. The results are shown in Table 1.

[Example 5] [Production of (meth)acrylic polymer (X5)]
The (meth)acrylic polymer (X0) was supplied at 4.0 kg/hour from the hopper, and n-methylcyclohexylamine was added from the middle of the cylinder to 0.91 kg/hour (((meth)acrylic polymer (X0) in ( (Meth)acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer") was prepared in the same manner as in Example 1 except that the amount was 20 mol per 100 mol of methyl (meth)acrylate unit. (X5)" is obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X5) was analyzed. Further, a film was prepared using the (meth)acrylic polymer (X5), and the appearance was confirmed. The results are shown in Table 1.

[Example 6] [Production of (meth)acrylic polymer (X6)]
The (meth)acrylic polymer (X0) was fed at 0.17 kg/hour from the hopper, and n-methylcyclohexylamine was added at 39 g/hour from the middle of the cylinder ((meth) in the (meth)acrylic polymer (X0). (Meth)acrylic polymer (X) (hereinafter referred to as "(meth)acrylic polymer (X6) in the same manner as in Example 1 except that the amount was 20 mol per 100 mol of methyl acrylate units). )”).

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X6) was analyzed. In addition, a film was produced using the (meth)acrylic polymer (X6), and the appearance was confirmed. The results are shown in Table 1.

[Example 7] [Production of (meth)acrylic polymer (X7)]
15 g of (meth)acrylic polymer (X0), 17.5 g of toluene, 17.5 g of phenol, and 3.4 g of n-methylcyclohexylamine (methyl (meth)acrylate in (meth)acrylic polymer (X0) 20 mol per 100 mol of the unit) was introduced into an autoclave equipped with a stirring blade, and the inside was replaced with nitrogen.

  The temperature in the autoclave was maintained at 220° C., and the mixture was stirred for 5 hours, then the solvent was removed at 1.3 Pa and 100° C. to remove the (meth)acrylic polymer (X) (hereinafter “(meth)acrylic polymer ( X7)").

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic polymer (X7) was analyzed. In addition, a film was produced using the (meth)acrylic polymer (X7), and the appearance was confirmed. The results are shown in Table 1.

[Example 8] [Production of (meth)acrylic block copolymer (Z1)]
A (meth)acrylic block copolymer (Z0) was supplied from a hopper to a twin-screw extruder (manufactured by Parker Corporation) at 0.66 kg/hour, and n-methylcyclohexylamine was added at 72 g/hour ((( (Meth)acrylic block copolymer (Z0) in an amount of 40 moles per 100 moles of methyl methacrylate units), and melt-kneaded at a cylinder temperature of 220° C. and a screw rotation speed of 100 rpm to obtain (meth). An acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block copolymer (Z1)") was obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z1) was analyzed. In addition, a film was produced using the (meth)acrylic block copolymer (Z1), and the appearance was confirmed. The results are shown in Table 2.

[Example 9] [Production of (meth)acrylic block copolymer (Z2)]
A (meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block copolymer (Z2)") was obtained in the same manner as in Example 8 except that the cylinder temperature was 180°C. .

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z2) was analyzed. Further, a film was produced using the (meth)acrylic block copolymer (Z2), and the appearance was confirmed. The results are shown in Table 2.

[Example 10] [Production of (meth)acrylic block copolymer (Z3)]
A (meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block copolymer (Z3)") was obtained in the same manner as in Example 8 except that the cylinder temperature was 260°C. ..

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z3) was analyzed. In addition, a film was produced using the (meth)acrylic block copolymer (Z3), and the appearance was confirmed. The results are shown in Table 2.

[Example 11] [Production of (meth)acrylic block copolymer (Z4)]
Example 8 except that n-methylcyclohexylamine was supplied in an amount of 1.8 g/hour (1 mol based on 100 mol of methyl methacrylate units in the (meth)acrylic block copolymer (Z0)). A (meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block copolymer (Z4)") was obtained by the same method.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z4) was analyzed. Further, a film was prepared using the (meth)acrylic block copolymer (Z4), and the appearance was confirmed. The results are shown in Table 2.

[Example 12] [Production of (meth)acrylic block copolymer (Z5)]
Example 8 except that n-methylcyclohexylamine was supplied at 0.18 kg/hr (100 mol per 100 mol of methyl methacrylate units in the (meth)acrylic block copolymer (Z0)). A (meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block copolymer (Z5)") was obtained by the same method.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z5) was analyzed. In addition, a film was produced using the (meth)acrylic block copolymer (Z5), and the appearance was confirmed. The results are shown in Table 2.

[Example 13] [Production of (meth)acrylic block copolymer (Z6)]
The (meth)acrylic block copolymer (Z0) was fed from the hopper at 4.0 kg/hr, and n-methylcyclohexylamine was added 0.43 kg/hr ((meth)acrylic block copolymer (Z0) from the middle of the cylinder. (Amount of 40 moles relative to 100 moles of methyl methacrylate unit in) in the same manner as in Example 8 except that the (meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic"). A system block copolymer (Z6)" was obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z6) was analyzed. Further, a film was produced using the (meth)acrylic block copolymer (Z6), and the appearance was confirmed. The results are shown in Table 2.

[Example 14] [Production of (meth)acrylic block copolymer (Z7)]
(Meth)acrylic block copolymer (Z0) was supplied at 0.17 kg/hour from the hopper, and 18 g/hour of n-methylcyclohexylamine was supplied from the middle of the cylinder (in (meth)acrylic block copolymer (Z0)). (Meth)acrylic block copolymer (Z) (hereinafter referred to as "(meth)acrylic block") in the same manner as in Example 8 except that the amount was 40 mol per 100 mol of the methyl methacrylate unit. A copolymer (Z7)" was obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z7) was analyzed. Further, a film was produced using the (meth)acrylic block copolymer (Z7), and the appearance was confirmed. The results are shown in Table 2.

[Example 15] [Production of (meth)acrylic block copolymer (Z8)]
15 g of (meth)acrylic block copolymer (Z0), 17.5 g of toluene, 17.5 g of phenol, and 0.81 g of n-methylcyclohexylamine ((meth)acrylic block copolymer (Z0) The amount was 20 mol with respect to 100 mol of methyl methacrylate unit therein), and the mixture was introduced into an autoclave equipped with a stirring blade, and the inside was replaced with nitrogen.

  The temperature in the autoclave was maintained at 220° C., the mixture was stirred for 5 hours, then the solvent was removed at 1.3 Pa and 100° C., and the (meth)acrylic block copolymer (Z) (hereinafter referred to as “(meth)acrylic A block copolymer (Z8)" was obtained.

  The content of the carboxyl group and the acid anhydride structure in the obtained (meth)acrylic block copolymer (Z8) was analyzed. In addition, a film was produced using the (meth)acrylic block copolymer (Z8), and the appearance was confirmed. The results are shown in Table 2.

Claims (5)

The (meth)acrylic polymer (X0) containing a methyl (meth)acrylate unit and N-methylcyclohexylamine were added to 100 mol of the methyl (meth)acrylate unit in the (meth)acrylic polymer (X0). On the other hand, a (meth)acrylic polymer (X) having an acid anhydride structure and not having a carboxyl group, which includes a mixing step of mixing in an amount of 0.5 to 20 mol in the range of 180 to 260°C. ) Is a manufacturing method of
The (meth)acrylic polymer (X0) is a methyl methacrylate homopolymer, a methyl acrylate homopolymer, a copolymer consisting of methyl methacrylate and methyl acrylate,
Methyl (meth)acrylate,
(Meth)acrylic acid alkyl ester other than methyl (meth)acrylate, (meth)acrylic acid alicyclic ester, (meth)acrylic acid aralkyl ester, (meth)acrylic acid alkoxyalkyl ester, (meth)acrylic acid aminoalkyl Ester, tetrahydrofurfuryl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, 2-(trimethylsilyloxy)ethyl (meth)acrylate , and 3-(trimethylsilyloxy)propyl (meth)acrylate. A copolymer consisting only of at least one monomer,
Or a mixture of these,
Further, the content of the methyl (meth)acrylate unit in the monomer units constituting the (meth)acrylic polymer (X0) is in the range of 5 to 100% by mass, (meth)acrylic polymer Method of manufacturing (X).   The (meth)acrylic polymer block (a) in which the (meth)acrylic polymer (X0) containing a methyl (meth)acrylate unit contains more than 50 mol% of a (meth)acrylic acid unit, and a carbon number of 2 The (meth)acrylic block copolymer comprising the (meth)acrylic polymer block (b) containing more than 50 mol% of a (meth)acrylic acid alkyl ester unit having an alkyl group as described above. The method for producing a (meth)acrylic polymer (X) having the acid anhydride structure of 1.   Content of the methyl (meth)acrylate unit in the monomer unit which comprises the said (meth)acrylic-type polymer (X0) is the range of 15-100 mass %, The Claim 1 or 2 characterized by the above-mentioned. A method for producing a (meth)acrylic polymer (X) having an acid anhydride structure.   The method for producing a (meth)acrylic polymer (X) having an acid anhydride structure according to claim 1, wherein the mixing step is performed in the presence of an organic solvent. The method for producing a (meth)acrylic polymer (X) having an acid anhydride structure according to claim 1, wherein the mixing step is performed in the absence of an organic solvent.