JP4449375B2 - Aromatic amide block copolymer and process for producing the same - Google Patents

Description

  The present invention has properties as a thermoplastic elastomer and has excellent heat resistance, hydrolysis resistance, and mechanical properties, such as an aromatic amide block copolymer, particularly various fibers, films, seat boots, gears, tubes, packings, etc. The present invention relates to an aromatic amide block copolymer suitable for a molding material.

  In recent years, from the viewpoint of recyclability and energy saving, replacement of crosslinked rubber with a thermoplastic elastomer has been advanced. Thermoplastic elastomers are composed of a soft segment rich in rubber elasticity and a hard segment serving as a molecular chain constrained phase, and various thermoplastic elastomers having different hard segment types have been developed and marketed. Among these, polyamide-based and polyester-based thermoplastic elastomers are widely used as automotive elastomers, electrical / electronic parts, industrial parts and the like as thermoplastic elastomers having excellent heat resistance and oil resistance. The polyamide-based and polyester-based elastomers are composed of a polymer compound having a high melting point such as 6-nylon, 6,6-nylon, or poly (butylene terephthalate) in the hard segment. However, these are insufficient in terms of heat resistance, and since a high molecular compound is used as a hard segment, only a relatively high hardness can be obtained, and heat having low heat resistance and excellent rubber elasticity is obtained. It has been difficult to produce a plastic elastomer.

  On the other hand, a new type of thermoplastic elastomer having an aromatic oligomer having a high crystallinity and a high melting point as a hard segment has been reported. For example, a thermoplastic elastomer having a low hardness and excellent heat resistance is disclosed in which 4,4′-dihydroxy-p-quarterphenyl is a hard segment and an aliphatic polyester chain is a soft segment (see, for example, Patent Document 1). ).

  Further, an aromatic ester amide compound and a polyorganosiloxane polyol (for example, see Patent Document 2), or a polyolefin polyol such as an aromatic ester amide compound and a terminal hydroxylated ethylene / butylene copolymer (for example, see Patent Document 3). A method for producing an elastomer by melt polycondensation with is proposed.

Japanese Patent Laid-Open No. 02-276817

JP-A-08-134210 Japanese Patent Application Laid-Open No. 08-253569

  However, since the method proposed in Patent Document 1 has a very high reaction temperature, it tends to cause thermal decomposition and depolymerization of aliphatic polyester, which is a soft segment, and as a result, it is difficult to produce a high molecular weight product. In addition, since the chain length of the soft segment is not uniform, there is a risk of deteriorating mechanical properties.

  Furthermore, the thermoplastic elastomers proposed in Patent Documents 2 and 3 are expected to be excellent in long-term heat resistance and hydrolysis resistance. However, since the compatibility between the aromatic ester amide compound and the polyol is poor, a homogeneous copolymer can be obtained. It is difficult to obtain coalescence.

  An object of the present invention is to solve the above-mentioned problems and provide a thermoplastic elastomer excellent in heat resistance, hydrolysis resistance and mechanical properties in a wide hardness range.

  As a result of intensive studies to achieve the above object, the present inventors have found that the hard segment has an aromatic amide unit, the soft segment has an aliphatic poly (oxyalkylene) unit, a polyorganosiloxane unit, an aliphatic hydrocarbon unit, an oil. An aromatic amide block copolymer excellent in heat resistance, hydrolysis resistance and mechanical properties using a cyclic hydrocarbon unit, an aliphatic polyester unit, and an aliphatic polycarbonate unit has been found, and the present invention has been completed.

  That is, the present invention provides an aromatic amide compound unit represented by the following general formula (1):

（ここで、Ｒ^１およびＲ^２は、それぞれ独立して炭素数１〜２０の炭化水素基を示す。）
一般式（２）で示される単位、

(Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.)
A unit represented by the general formula (2),

（ここで、Ｒ^３は、脂肪族ポリ（オキシアルキレン）、ポリオルガノシロキサン、脂肪族炭化水素基、脂環式炭化水素基、脂肪族ポリエステル、脂肪族ポリカーボネートより選ばれる一種以上の二価の有機基を示す。）
および下記一般式（３）〜（５）に示される群から選ばれる少なくとも１種類以上の鎖延長剤成分単位からなることを特徴とする芳香族アミドブロック共重合体及びその製造方法に関するものである。

(Here, R ³ is one or more divalent organic compounds selected from aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate. Group.)
And an aromatic amide block copolymer comprising at least one chain extender component unit selected from the group represented by the following general formulas (3) to (5), and a method for producing the same. .

（ここで、Ｒ^４は炭素数１〜２０の二価の有機基を示す。）

(Here, R ⁴ represents a divalent organic group having 1 to 20 carbon atoms.)

（ここで、Ｒ^５は炭素数２〜２０の二価の炭化水素基を示す。）

(Here, R ⁵ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

（ここで、Ｒ^６はカルボニル基または炭素数１〜２０の二価の有機基を示す。）
上記一般式（１）で示される芳香族アミド化合物単位を構成するＲ^１およびＲ^２は、それぞれ独立して炭素数１〜２０の炭化水素基であり、該炭化水素基としては直鎖状又は分岐状であってもよく、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、２，２−ジメチルトリメチレン基、ヘキサメチレン基、２−メチルヘプタメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、１，４−シクロヘキシレン基、２−ベンジル基、３−ベンジル基、４−ベンジル基、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基等を挙げることができ、その中でも特に耐熱性、耐加水分解性、機械特性に優れた芳香族アミドブロック共重合体となることから、メチレン基、エチレン基、テトラメチレン基が好ましく、特に、エチレン基が好ましい。

(Here, R ⁶ represents a carbonyl group or a divalent organic group having 1 to 20 carbon atoms.)
R ¹ and R ² constituting the aromatic amide compound unit represented by the general formula (1) are each independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is linear or It may be branched, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group, heptamethylene group , Octamethylene group, nonamethylene group, decamethylene group, 1,4-cyclohexylene group, 2-benzyl group, 3-benzyl group, 4-benzyl group, 1,2-phenylene group, 1,3-phenylene group, 1, 4-phenylene group and the like can be mentioned, and among them, it becomes an aromatic amide block copolymer excellent in heat resistance, hydrolysis resistance and mechanical properties. Methylene group, ethylene group, tetramethylene group is preferable, particularly, an ethylene group is preferred.

R ³ constituting the general formula (2) is selected from the group consisting of aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate. One or more divalent organic groups. In addition, since the resulting aromatic amide block copolymer is excellent in heat resistance and molding processability, the number average molecular weight of R ³ is preferably in the range of 300 to 10,000, particularly 500 to 5000. A range is preferable. The aromatic amide block copolymer of the present invention is a group consisting of aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate as R ^3. By being composed of one or more divalent organic groups selected from the above, it is excellent in heat resistance and mechanical properties.

Examples of the aliphatic poly (oxyalkylene) constituting R ³ include poly (ethylene oxide), poly (propylene oxide), poly (tetramethylene oxide), poly (hexamethylene oxide), a copolymer of ethylene oxide and propylene oxide, Examples thereof include a copolymer of ethylene oxide and tetrahydrofuran, and an ethylene oxide addition polymer of poly (propylene oxide).

As the polyorganosiloxane constituting R ^3, for example, the following general formula (8) include those represented by (9).

（式中、Ｒ^１０〜Ｒ^１５はそれぞれ置換又は非置換の炭素数１〜２０の１価の炭化水素基を示す。Ｒ^１６、Ｒ^１７はそれぞれ置換又は非置換の炭素数１〜２０の二価の炭化水素基を示し、ｍは４〜１５０の整数を示す。）
ここで、Ｒ^１０〜Ｒ^１５はそれぞれ置換又は非置換の炭素数１〜２０の１価の炭化水素基で、同一でも異なっていてもよい。該炭化水素基としては、例えばメチル基、エチル基、プロピル基、３，３，３−トリフルオロプロピル基、クロロプロピル基等の置換又は非置換のアルキル基；シクロペンチル基、シクロヘキシル基等の置換又は非置換のシクロアルキル基；ビニル基、プロペニル基、ブテニル基、ヘキセニル基、デセニル基等の置換又は非置換のアルケニル基が挙げられる。

(In the formula, R ^{10 to} R ¹⁵ each represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁶ and R ¹⁷ are each a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. A valent hydrocarbon group, m represents an integer of 4 to 150.)
Here, R ^{10 to} R ¹⁵ are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of the hydrocarbon group include substituted or unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, a 3,3,3-trifluoropropyl group, and a chloropropyl group; a substituted or unsubstituted group such as a cyclopentyl group and a cyclohexyl group; An unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, and a decenyl group.

R ¹⁶ and R ¹⁷ are each a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and the hydrocarbon group may be linear or branched. Examples of the hydrocarbon group include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group, heptamethylene group, octane group. A methylene group, nonamethylene group, decamethylene group, 1,4-cyclohexylene group and the like can be mentioned.

（式中、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１はそれぞれ置換又は非置換の炭素数１〜２０の１価の炭化水素基を示し、ｎは４〜１５０の整数を示す。）
ここで、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１はそれぞれ置換又は非置換の炭素数１〜２０の１価の炭化水素基で、同一でも異なっていてもよい。該炭化水素基としては、例えばメチル基、エチル基、プロピル基、３，３，３−トリフルオロプロピル基、クロロプロピル基等の置換又は非置換のアルキル基；シクロペンチル基、シクロヘキシル基等の置換又は非置換のシクロアルキル基；ビニル基、プロペニル基、ブテニル基、ヘキセニル基、デセニル基等の置換又は非置換のアルケニル基が挙げられる。

(In the formula, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 4 to 150.)
Here, R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of the hydrocarbon group include substituted or unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, a 3,3,3-trifluoropropyl group, and a chloropropyl group; a substituted or unsubstituted group such as a cyclopentyl group and a cyclohexyl group; An unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, and a decenyl group.

The molecular structure of the polyorganosiloxane is usually linear. However, when the novel aromatic amide block copolymer of the present invention is composed of polyorganosiloxane, the aromatic amide block copolymer is a crosslinked product. A small amount of a triorganosiloxane unit or a siloxane unit represented by the formula: SiO ₂ may be contained in a part of the main chain as long as it does not fall.

Examples of the aliphatic hydrocarbon group constituting R ³ include hydroxylation of both ends of homopolymers, random copolymers, alternating copolymers, and block copolymers of olefins such as ethylene, propylene, and isobutylene. A poly (diene) residue derived from a hydroxyl-terminated poly (diene) obtained by hydroxylating both ends of a conjugated diene hydrocarbon such as butadiene or isoprene; Examples thereof include a hydrogenated poly (diene) residue derived from a both-end hydroxyhydrogenated poly (diene) obtained by hydrogenating a (diene) double bond.

Examples of the alicyclic hydrocarbon group constituting R ^3, include, for example, those represented by the general formula (10).

（式中、Ｒ^２２、Ｒ^２３はそれぞれアルキレン基、Ｒ^２４、Ｒ^２５はそれぞれアルキル基を示し、Ｒ^２２〜Ｒ^２５の炭素数の総和は２２〜３４である。）
該脂環式炭化水素基の具体例としては、例えばリノール酸、リノレン酸、オレイン酸等の不飽和脂肪酸を二量化し水素添加して得られる水素添加ダイマージオールの残基等が挙げられる。中でもＲ^２２〜Ｒ^２５の炭素数の総和が２８の水素添加ダイマージオールは入手が容易であることから好ましい。

(In the formula, R ²² and R ²³ are each an alkylene group, R ²⁴ and R ²⁵ are each an alkyl group, and the total number of carbon atoms of R ^{22 to} R ²⁵ is ^{22 to} 34.)
Specific examples of the alicyclic hydrocarbon group include residues of hydrogenated dimer diol obtained by dimerizing and hydrogenating unsaturated fatty acids such as linoleic acid, linolenic acid, and oleic acid. Among these, a hydrogenated dimer diol having a total carbon number of R ^{22 to} R ²⁵ of 28 is preferable because it is easily available.

In addition, the aliphatic polyester constituting R ³ is not particularly limited in terms of structure, and residues of both-end hydroxy aliphatic polyester obtained by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, or ring opening of lactone. Mention may be made, for example, of polylactone residues obtained by polymerization. Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, Examples include 1,6-hexanediol and 1,9-nonanediol. Examples of the aliphatic polyester include poly (ethylene adipate), poly (tetramethylene adipate), and poly (hexamethylene adipate). Examples of the polylactone include poly (propiolactone), poly (butyrolactone), poly (valerolactone), poly (caprolactone), poly (methylvalerolactone), poly (enanthrolactone), and poly (caprolactone). ) And the like.

In addition, the aliphatic polycarbonate constituting R ³ is not particularly limited with respect to the structure, and examples thereof include residues of the both-end hydroxy aliphatic polycarbonate obtained by reacting the above-mentioned aliphatic diol with carbonate ester or phosgene. For example, poly (propylene carbonate), poly (tetramethylene carbonate), poly (hexamethylene carbonate) and the like can be mentioned.

The chain extender component unit represented by the general formula (3) represents a chain extender component unit composed of a divalent carbonyl organic compound group, and R ⁴ is a divalent organic group having 1 to 20 carbon atoms. , Arylene group, substituted arylene group, alkylene group, substituted alkylene group and the like, and the substituent may contain a hetero atom. Specific examples of the organic group include, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group, heptamethylene. Group, alkylene group such as octamethylene group, nonamethylene group and decamethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group , 2,7-naphthylene group, arylene group such as biphenylene group, and the like. Among them, since it becomes an aromatic amide block copolymer excellent in heat resistance, 1,3-phenylene group, 1,4- A phenylene group is preferred.

  Specific examples of the chain extender component unit represented by the general formula (3) include, for example, aliphatic groups such as malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, and sebacoyl group. Dicarboxylic acid residue: phthaloyl group, isophthaloyl group, terephthaloyl group, 2,6-naphthalenedicarbonyl group, 1,5-naphthalenedicarbonyl group, 2,7-naphthalenedicarbonyl group, 4,4′-biphenylenedicarbonyl group Arylene dicarboxylic acid residues such as pyromellitic dianhydride residue, 1,4,5,8-naphthalene tetracarboxylic dianhydride residue, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid di Carboxylic acid dianhydride residues such as anhydride residues and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride residues It can, since the aromatic amide block copolymer, particularly excellent heat resistance. Among them, isophthaloyl group, is terephthaloyl group are preferable.

The chain extender component unit represented by the general formula (4) is a chain extender component unit composed of a divalent amide organic compound group, and R ⁵ in the general formula (4) is 2 to 20 carbon atoms. Valent hydrocarbon group, and examples of the hydrocarbon group include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group , Alkylene groups such as heptamethylene group, octamethylene group, nonamethylene group, decamethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,5 -Arylene groups such as naphthylene group, 2,7-naphthylene group and biphenylene group; alkyl substituted products such as xylylene group; methylene groups such as 4,4'-diphenylmethane group In addition, a substituent in which an alkylene group and an arylene group are bonded to each other can be mentioned. Among them, an aromatic amide block copolymer having particularly excellent heat resistance is obtained, so that a 4,4′-diphenylmethane group, A -phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a xylylene group, a hexamethylene group, and a methyl-substituted product thereof are preferable.

  Specific examples of the chain extender component unit represented by the general formula (4) include, for example, 1,2-ethanedicarbamoyl group, 1,3-propanedicarbamoyl group, 1,4-butanedicarbamoyl group, 1,5-pentanedicarbamoyl group, 1,6-hexanedicarbamoyl group, 1,7-heptanedicarbamoyl group, 1,8-octanedicarbamoyl group, 1,9-nonanedicarbamoyl group, 1,10-de Alkylenedicarbamoyl groups such as candicarbamoyl group; 1,2-phenyldicarbamoyl group, 1,3-phenyldicarbamoyl group, 1,4-phenyldicarbamoyl group, 2,6-naphthalenedicarbamoyl group, 1,5- Arylene carbamoyl groups such as naphthalene dicarbamoyl group, 2,7-naphthalene dicarbamoyl group; xylylene dicarbamoyl group These alkyl-substituted products include: a methylene group such as diphenylmethane-4,4′-dicarbamoyl group or a substituent in which an alkylene group and an arylene group are bonded, and among them, an aromatic amide particularly excellent in heat resistance Since it becomes a block copolymer, diphenylmethane-4,4′-dicarbamoyl group, 1,2-phenylcarbamoyl group, 1,3-phenylcarbamoyl group, 1,4-phenyldicarbamoyl group, xylylenedicarbamoyl group, A 1,6-hexanedicarbamoyl group or a methyl-substituted product thereof is preferable.

The chain extender component unit represented by the general formula (5) is a chain extender component unit composed of a carbonyl group or a divalent organic group, and R ⁶ in the general formula (5) is a carbonyl group or a carbon number of 1 -20 divalent organic groups are shown. Examples of the divalent organic group include an arylene group, a substituted arylene group, an alkylene group, and a substituted alkylene group, and the substituent may contain a hetero atom. Specific examples of the organic group include, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group, heptamethylene. Group, alkylene group such as octamethylene group, nonamethylene group and decamethylene group; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,5-naphthylene group Arylene groups such as 2,7-naphthylene group and biphenylene group; diglycidyl ester compound residues of dicarboxylic acid such as diglycidyl ester residue of terephthalic acid; diglycidyl ether compound residues such as p-phenylene diglycidyl ether Can be mentioned.

  As a method for producing the aromatic amide block copolymer of the present invention, any method may be used as long as the aromatic amide block copolymer can be produced. For example, the aromatic amide block copolymer may be represented by the following general formula (6). The dihydroxy aromatic amide compound can be produced by reacting at least one of one or more dihydroxy compounds represented by the following general formula (7) and a chain extender.

（ここで、Ｒ^７およびＲ^８は、それぞれ独立して炭素数１〜２０の炭化水素基を示す。）

(Here, R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms.)

（ここで、Ｒ^９は、脂肪族ポリ（オキシアルキレン）、ポリオルガノシロキサン、脂肪族炭化水素基、脂環式炭化水素基、脂肪族ポリエステル、脂肪族ポリカーボネートより選ばれる一種以上の二価の有機基を示す。）。
上記一般式（６）で示されるジヒドロキシ芳香族アミド化合物を構成するＲ^７およびＲ^８は、それぞれ独立して炭素数１〜２０の炭化水素基であり、該炭化水素基としては直鎖状又は分岐状であってもよく、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、２，２−ジメチルトリメチレン基、ヘキサメチレン基、２−メチルヘプタメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、１，４−シクロヘキシレン基、２−ベンジル基、３−ベンジル基、４−ベンジル基、１，２−フェニレン基、１，３−フェニレン基、１，４−フェニレン基等を挙げることができ、その中でも得られる芳香族アミドブロック共重合体が熱可塑性エラストマーとしての特性に優れることから、メチレン基、エチレン基、テトラメチレン基が好ましく、特に、エチレン基が好ましい。該ジヒドロキシ芳香族アミド化合物としては、例えば、Ｎ，Ｎ’−ビス（４−（ヒドロキシメチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（２−ヒドロキシエチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（３−ヒドロキシプロピルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（４−ヒドロキシブチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（５−ヒドロキシペンチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（６−ヒドロキシヘキシルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（ヒドロキシメチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（２−ヒドロキシエチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（３−ヒドロキシプロピルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（４−ヒドロキシブチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（５−ヒドロキシペンチルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（３−（６−ヒドロキシヘキシルカルバモイル）フェニル）テレフタルアミド、Ｎ，Ｎ’−ビス（４−（ヒドロキシメチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（２−ヒドロキシエチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（３−ヒドロキシプロピルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（４−ヒドロキシブチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（５−ヒドロキシペンチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（６−ヒドロキシヘキシルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（ヒドロキシメチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（２−ヒドロキシエチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（３−ヒドロキシプロピルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（４−ヒドロキシブチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（５−ヒドロキシペンチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（３−（６−ヒドロキシヘキシルカルバモイル）フェニル）イソフタルアミド等を挙げることができる。その中でも得られる芳香族アミドブロック共重合体が熱可塑性エラストマーとしての特性に優れることから、Ｎ，Ｎ’−ビス（４−（２−ヒドロキシエチルカルバモイル）フェニル）イソフタルアミド、Ｎ，Ｎ’−ビス（４−（２−ヒドロキシエチルカルバモイル）フェニル）テレフタルアミドが好ましい。該ジヒドロキシ芳香族アミド化合物は、例えば、特願２００３−０８５７７３公報に記載の製造方法により製造することも可能である。

(Here, R ⁹ is one or more divalent organic compounds selected from aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate. Group.)
R ⁷ and R ⁸ constituting the dihydroxy aromatic amide compound represented by the general formula (6) are each independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is linear or It may be branched, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-methylheptamethylene group, heptamethylene group , Octamethylene group, nonamethylene group, decamethylene group, 1,4-cyclohexylene group, 2-benzyl group, 3-benzyl group, 4-benzyl group, 1,2-phenylene group, 1,3-phenylene group, 1, 4-phenylene group and the like, and among them, the obtained aromatic amide block copolymer has excellent properties as a thermoplastic elastomer. Since, methylene group, ethylene group, tetramethylene group is preferable, particularly, an ethylene group is preferred. Examples of the dihydroxy aromatic amide compound include N, N′-bis (4- (hydroxymethylcarbamoyl) phenyl) terephthalamide and N, N′-bis (4- (2-hydroxyethylcarbamoyl) phenyl) terephthalamide. N, N′-bis (4- (3-hydroxypropylcarbamoyl) phenyl) terephthalamide, N, N′-bis (4- (4-hydroxybutylcarbamoyl) phenyl) terephthalamide, N, N′-bis ( 4- (5-hydroxypentylcarbamoyl) phenyl) terephthalamide, N, N′-bis (4- (6-hydroxyhexylcarbamoyl) phenyl) terephthalamide, N, N′-bis (3- (hydroxymethylcarbamoyl) phenyl ) Terephthalamide, N, N′-bis (3- (2-hydroxyethyl) Carbamoyl) phenyl) terephthalamide, N, N′-bis (3- (3-hydroxypropylcarbamoyl) phenyl) terephthalamide, N, N′-bis (3- (4-hydroxybutylcarbamoyl) phenyl) terephthalamide, N , N′-bis (3- (5-hydroxypentylcarbamoyl) phenyl) terephthalamide, N, N′-bis (3- (6-hydroxyhexylcarbamoyl) phenyl) terephthalamide, N, N′-bis (4- (Hydroxymethylcarbamoyl) phenyl) isophthalamide, N, N′-bis (4- (2-hydroxyethylcarbamoyl) phenyl) isophthalamide, N, N′-bis (4- (3-hydroxypropylcarbamoyl) phenyl) isophthal Amide, N, N′-bis (4- (4-hydroxybutyl Rubamoyl) phenyl) isophthalamide, N, N′-bis (4- (5-hydroxypentylcarbamoyl) phenyl) isophthalamide, N, N′-bis (4- (6-hydroxyhexylcarbamoyl) phenyl) isophthalamide, N , N′-bis (3- (hydroxymethylcarbamoyl) phenyl) isophthalamide, N, N′-bis (3- (2-hydroxyethylcarbamoyl) phenyl) isophthalamide, N, N′-bis (3- (3 -Hydroxypropylcarbamoyl) phenyl) isophthalamide, N, N'-bis (3- (4-hydroxybutylcarbamoyl) phenyl) isophthalamide, N, N'-bis (3- (5-hydroxypentylcarbamoyl) phenyl) isophthal Amide, N, N′-bis (3- (6-hydroxyhexyl) And carbamoyl) phenyl) isophthalamide. Among them, since the obtained aromatic amide block copolymer has excellent properties as a thermoplastic elastomer, N, N′-bis (4- (2-hydroxyethylcarbamoyl) phenyl) isophthalamide, N, N′-bis (4- (2-Hydroxyethylcarbamoyl) phenyl) terephthalamide is preferred. The dihydroxy aromatic amide compound can also be produced, for example, by the production method described in Japanese Patent Application No. 2003-085773.

The dihydroxy compound represented by the general formula (7) is a compound having a hydroxyl group at both ends, and R ⁹ may be the same as R ³ described above. Specific examples of the dihydroxy compound include poly (oxyethylene) glycol, poly (oxypropylene) glycol, poly (oxytetramethylene) glycol, poly (oxyhexamethylene) glycol, ethylene oxide and propylene having hydroxyl groups at both ends. Copolymers of oxides, copolymers of ethylene oxide and tetrahydrofuran having hydroxyl groups at both ends, aliphatic poly (oxyalkylene) glycols such as poly (propylene oxide) ethylene oxide addition polymers; dihydroxy poly (dimethylsiloxane), dihydroxy poly Poly (organosiloxane) having hydroxyl groups at both ends, such as (diethylsiloxane); homopolymers of olefins such as ethylene, propylene, isobutylene, random copolymers, alternating copolymers, Dihydroxy polyolefin with hydroxylated at both ends of the lock copolymer; dihydroxypoly (diene) with hydroxylated at both ends of conjugated diene hydrocarbon such as butadiene and isoprene, and the double bond of the poly (diene) was hydrogenated Dihydroxy hydrogenated poly (diene), etc .; hydrogenated dimer diol obtained by dimerizing and hydrogenating unsaturated fatty acids such as linoleic acid, linolenic acid, oleic acid, etc .; poly (propiolactone), poly (butyrolactone), Poly (valerolactone), poly (caprolactone), poly (methylvalerolactone), poly (enanthrolactone), poly (caprylolactone) and the like dihydroxypolylactone having hydroxyl groups at both ends; poly (ethylene adipate), poly (Tetramethylene adipate), poly (hexamethy Dihydroxy aliphatic polyesters having hydroxyl groups at both ends such as poly (propylene carbonate), poly (tetramethylene carbonate), poly (hexamethylene carbonate), and the like. . These may be used alone or in combination of two or more.

  The molecular weight of the dihydroxy compound is not particularly limited, and any one can be used. However, the number average molecular weight is in the range of 300 to 10,000 because a thermoplastic elastomer that is easy to handle the dihydroxy compound and has low hardness and excellent flexibility can be obtained. It is preferable that it exists, and it is preferable that it is the range of 500-5000 especially.

  The molar ratio of the dihydroxy aromatic amide compound and the dihydroxy compound used in the present invention is not particularly limited, but is preferably a dihydroxy aromatic amide compound: dihydroxy compound = 2: 1 to 1: 2 molar ratio.

  The chain extender used in the present invention has a functional group capable of reacting with a hydroxyl group present at both ends of a dihydroxy aromatic amide compound and a dihydroxy compound, and the aromatic amide block copolymer of the present invention can be produced. As the compound, for example, a bifunctional acid halide compound, a bifunctional isocyanate compound, a bifunctional carbonate compound, a bifunctional ester compound, a bifunctional acyllactam compound, a bifunctional compound can be used. Examples include epoxy compounds and bifunctional aromatic tetracarboxylic acid anhydrides. These chain extenders may be used alone or in combination of two or more, and are particularly excellent in reactivity and efficient. Since a coalescence is obtained, a bifunctional acid halide compound, a bifunctional isocyanate compound, a bifunctional carbonate compound, a bifunctional It is preferably a ester compound.

  Examples of the bifunctional acid halide compound include oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, and dodecanoic acid. Bifunctional acid chlorides such as dichloride, terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride; oxalic acid dibromide, malonic acid dibromide, succinic acid dibromide, glutaric acid dibromide, adipic acid dibromide, pimelic acid dibromide , Suberic acid dibromide, azelaic acid dibromide, sebacic acid dibromide, dodecanoic acid dibromide, terephthalic acid dibromide, isophthalic acid dibromide, Bifunctional acid bromides such as barrel acid dibromide, and the like. Furthermore, these may be used independently and may use 2 or more types together.

  Examples of the difunctional isocyanate compound include diphenylmethane-4,4′-diisocyanate, toluene diisocyanate, phenylene diisocyanate, xylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 2, Examples include 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, norbornene diisocyanate, but are not limited thereto. . Furthermore, these may be used alone or in combination of two or more. Preferably, diphenylmethane-4,4'-diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are used.

  Examples of the bifunctional carbonate compound include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, etc. Among them, particularly excellent in reactivity and efficiently obtaining an aromatic amide block copolymer. Therefore, dimethyl carbonate and diphenyl carbonate are preferable. Furthermore, these may be used alone or in combination of two or more.

  Examples of the bifunctional ester compound include diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 2,6-naphthalenedicarboxylate, diphenyl 2,7-naphthalenedicarboxylate, diphenyl 4,4-biphenyldicarboxylate, Dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, dimethyl 4,4-biphenyldicarboxylate, diethyl terephthalate, diethyl isophthalate, diethyl phthalate , Diethyl 2,6-naphthalenedicarboxylate, diethyl 2,7-naphthalenedicarboxylate, diethyl 4,4-biphenyldicarboxylate, etc. Among them, particularly excellent in reactivity and efficient aromatic amide block. Since the copolymer is obtained, diphenyl terephthalate, dimethyl terephthalate, diphenyl isophthalate, dimethyl isophthalate preferred. Furthermore, these may be used alone or in combination of two or more.

  Examples of the bifunctional acyllactam compound include terephthaloyl biscaprolactam, isophthaloyl biscaprolactam, adipoyl biscaprolactam, succinyl biscaprolactam, and among others, the amide block is particularly excellent in reactivity and efficient. From the viewpoint of obtaining a copolymer, terephthaloyl biscaprolactam and isophthaloyl biscaprolactam are preferable. Furthermore, these may be used alone or in combination of two or more.

  Examples of the bifunctional epoxy compounds include aromatic diglycidyl esters such as terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and phthalic acid diglycidyl ester; and p-phenylene diglycidyl ether. Ether; Aliphatic dicarboxylic acid diglycidyl ester such as diethylene glycol diglycidyl ester; Aliphatic dicarboxylic acid diglycidyl ether such as diethylene glycol diglycidyl ether and the like, and these may be used alone or in combination of two or more. May be.

  Examples of the bifunctional aromatic tetracarboxylic anhydride include pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone. Examples thereof include tetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and these may be used alone or in combination of two or more.

  The amount of the chain extender to be added is not particularly limited and may be appropriately selected depending on the type and reactivity of the chain extender to be used. For example, an equimolar amount with respect to the sum of the number of moles of the dihydroxy aromatic amide compound and the dihydroxy compound. About 1.5 times the molar amount may be used. When the addition amount is small, the chain extension reaction is insufficient and it is difficult to obtain a desired copolymer.

  The order of addition of the dihydroxy aromatic amide compound, the dihydroxy compound and the chain extender is not particularly limited. After the reaction of the dihydroxy compound and the chain extender, the dihydroxy aromatic amide compound can be added and copolymerized, After the reaction between the dihydroxy aromatic amide compound and the chain extender, the dihydroxy compound can be added and copolymerized. Further, a chain extender may be added and copolymerized in the presence of a dihydroxy aromatic amide compound or a dihydroxy compound.

  There are no particular limitations on the reaction conditions for the chain extension reaction, and the reaction is usually carried out in the range of room temperature to 250 ° C. and 5 minutes to 100 hours. At this time, the reaction can be performed in an inert gas atmosphere such as nitrogen, helium, or argon. It is also possible to carry out in a solvent. The solvent is a dihydroxy aromatic amide compound, a dihydroxy compound, or a compound that does not react with a chain extender, preferably an aromatic hydrocarbon such as toluene or xylene, an aliphatic or alicyclic hydrocarbon such as hexane or cyclohexane, N- Aprotic polar solvents such as methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide can be used, but are not limited thereto. Among them, an aprotic polar solvent rich in solubility of the dihydroxy aromatic amide compound is preferable.

  Examples of the acid scavenger used as necessary in the chain extension reaction include pyridine, trimethylamine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, and the like. The addition amount of is preferably 2 times to 5 times the mole, more preferably 2 times to 3 times the mole of the sum of the number of moles of the dihydroxy aromatic amide compound and the dihydroxy compound.

  Since the molecular weight of the aromatic amide block copolymer of the present invention is excellent in the balance of mechanical properties, melt fluidity and molding processability, the number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography is The range of 10,000 to 500,000 is preferable, and the range of 30,000 to 300,000 is particularly preferable.

  In order to improve the heat resistance of the aromatic amide block copolymer of the present invention, particularly the thermochromic property, a stabilizer may be added during or after the production. Examples of the stabilizer include phosphoric compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite. Hindered phenol compounds; sulfur-containing compounds such as thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; tin compounds such as tin malate and dibutyltin monoxide; These addition amounts are not particularly limited, but are usually 0.01 to 5 parts by weight with respect to 100 parts by weight of the copolymer.

  In addition, the aromatic amide block copolymer of the present invention includes, for the purpose of improving moldability, for example, stearates such as calcium, barium, and aluminum; stearic acid esters; silicon oils; waxes; A lubricant can be added. These addition amounts are not particularly limited, but are usually 0.05 to 5 parts by weight with respect to 100 parts by weight of the copolymer.

  In addition, the aromatic amide block copolymer of the present invention includes known dyes, organic or inorganic pigments, inorganic reinforcing agents, plasticizers, hindered amine light stabilizers, ultraviolet absorbers, foaming agents, epoxy compounds and isocyanate compounds. Additives can be added.

  The aromatic amide block copolymer of the present invention can be molded by an ordinary thermoplastic resin molding method such as injection molding, extrusion molding, transfer molding, inflation molding, blow molding, heat molding, compression molding, vacuum molding, etc. It can be used in a wide range of applications such as various molded products, fibers, films, sheets, plastic modifiers, paints, and adhesives.

  The present invention relates to an aromatic amide unit in a hard segment; an aliphatic poly (oxyalkylene) unit, a polyorganosiloxane unit, an aliphatic hydrocarbon unit, an alicyclic hydrocarbon unit, an aliphatic polyester unit, an aliphatic polycarbonate in a soft segment. An aromatic amide block copolymer comprising a unit selected from units and having an excellent balance of heat resistance, hydrolysis resistance and mechanical properties in a wide hardness range, and a method for producing the same.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited only to these Examples.

  The analytical instruments and methods used for the analysis of the aromatic amide block copolymer of the present invention are as follows.

(1) Molecular weight measurement Under conditions of a column temperature of 40 ° C. and a flow rate of 0.4 ml / min using a GPC device (manufactured by Tosoh, trade name HLC-8020) equipped with a column (trade name TSK-GEL GMHHR-H, manufactured by Tosoh Corporation). The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured with standard polystyrene using N-methyl-2-pyrrolidone (hereinafter simply referred to as NMP) containing 20 mmol / l lithium chloride in the eluent. Calculated by conversion.

(2) Thermal decomposition temperature (Td)
Using a thermogravimetric measuring device (trade name TG-DTA200, manufactured by Seiko Denshi Kogyo Co., Ltd.), the temperature was increased at a rate of 20 ° C./min.

(3) Glass transition temperature (Tg) and melting point (Tm)
A differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC200) was used, and the temperature was measured at a temperature rising rate of 10 ° C./min and in the range of −100 to 300 ° C.

Synthesis Example 1 (Synthesis of dihydroxy aromatic amide compound)
4-Amino-N- (2-hydroxyethyl) benzamide 72.1 g (0.4 mol) and NMP 200 ml were added to a 500 ml four-necked flask equipped with a nitrogen inlet tube, a thermometer and a stirring blade to obtain a homogeneous solution. It was. Separately, 40.6 g (0.2 mol) of isophthalic acid dichloride and 100 ml of NMP were added to a 200 ml dropping funnel equipped with a nitrogen introduction tube, stirred to obtain a homogeneous solution, and this solution was dropped into the previous solution over 1 hour. did. Furthermore, after making it react at 50 degreeC for 2 hours, the obtained slurry was thrown into 2.5 l of acetone, and white solid was collect | recovered by suction filtration. The obtained solid was recrystallized with NMP to obtain 88.8 g (yield 90.5%) of a dihydroxy aromatic amide compound.

  The obtained dihydroxy aromatic amide compound is N, N′-bis (4- (2-hydroxyethylcarbamoyl) phenyl) isophthalamide, and the structural formula thereof is shown in the following general formula (11). Hereinafter, the dihydroxy aromatic amide compound is referred to as compound (a).

実施例１
窒素導入管、温度センサー、マグネチック攪拌翼を備えた３００ｍｌの４ツ口フラスコに、窒素雰囲気下、アジピン酸ジクロライド４．５ｇ（０．０２４６モル）、ＮＭＰ１０ｇを加え均一溶液を得た。別途に、窒素導入管を備えた２００ｍｌ滴下ロートに、ジヒドロキシ脂肪族ポリエステル［クラレ製、商品名Ｐ−２０１０；数平均分子量＝２０１８）］２４．７ｇ（０．０１２２モル）、ピリジン１．９ｇ（０．０２４５モル）、ＮＭＰ７０ｇを加え、撹拌し均一溶液とし、この溶液を先の溶液中に３０分かけて滴下した。さらに室温で２時間反応させた後、ピリジン１．９ｇ（０．０２４５モル）、化合物（ａ）６．０ｇ（０．０１２２モル）を加え、さらに５０℃で３時間反応させた後、得られた均一溶液をメタノール１．５ｌに投入し、吸引ろ過により良好なゴム弾性を示す生成物３１．３ｇ（収率：９４％）得た。生成物のＭｎ；３０１００、Ｍｗ；４９４００、Ｔｍ；２７０℃、Ｔｇ；−５４℃、Ｔｄ；３９３℃であった。

Example 1
Under a nitrogen atmosphere, 4.5 g (0.0246 mol) of adipic acid dichloride and 10 g of NMP were added to a 300 ml four-necked flask equipped with a nitrogen inlet tube, a temperature sensor, and a magnetic stirring blade to obtain a uniform solution. Separately, in a 200 ml dropping funnel equipped with a nitrogen introduction tube, 24.7 g (0.0122 mol) of dihydroxy aliphatic polyester [manufactured by Kuraray, trade name P-2010; number average molecular weight = 2018)], 1.9 g of pyridine ( 0.0245 mol) and 70 g of NMP were added, and the mixture was stirred to obtain a homogeneous solution. This solution was added dropwise to the previous solution over 30 minutes. After further reaction at room temperature for 2 hours, 1.9 g (0.0245 mol) of pyridine and 6.0 g (0.0122 mol) of compound (a) were added, and further reacted at 50 ° C. for 3 hours. The obtained homogeneous solution was put into 1.5 l of methanol, and 31.3 g (yield: 94%) of a product showing good rubber elasticity was obtained by suction filtration. Product Mn: 30100, Mw: 49400, Tm: 270 ° C, Tg: -54 ° C, Td: 393 ° C.

Example 2
The same conditions as in Example 1 except that 24.2 g (0.0123 mol) of dihydroxy aliphatic polycarbonate [manufactured by Kuraray, trade name C-2050R; number average molecular weight = 1975]] was used instead of dihydroxy aliphatic polyester. To obtain 31.0 g (yield: 94%) of the product. Product Mn; 34400, Mw; 56400, Tm; 268 ° C, Tg; -34 ° C, Td;

Example 3
The same conditions as in Example 1 except that 24.6 g (0.0122 mol) of dihydroxypolylactone [manufactured by Daicel Chemical Industries, trade name: Plaxel 220; number average molecular weight = 2015)] was used instead of dihydroxy aliphatic polyester. To obtain 31.2 g (yield: 94%) of the product. Product Mn: 30000, Mw: 51000, Tm: 270 ° C., Tg: −60 ° C., Td: 387 ° C.

Example 4
To a 300 ml four-necked flask equipped with a nitrogen introduction tube, a temperature sensor, and a magnetic stirring blade, under a nitrogen atmosphere, 6.1 g (0.0244 mol) of diphenylmethane-4,4′-diisocyanate and 10 g of NMP were added to obtain a homogeneous solution. Obtained. Separately, 24.7 g (0.0122 mol) of dihydroxy aliphatic polyester [manufactured by Kuraray, trade name P-2010; number average molecular weight = 2018)] and 70 g of NMP are added to a 200 ml dropping funnel equipped with a nitrogen introduction tube and stirred. The resulting solution was added dropwise to the previous solution over 30 minutes. After further reacting at 80 ° C. for 2 hours, 6.0 g (0.0122 mol) of compound (a) was added, and further reacted at 80 ° C. for 3 hours, and then the resulting homogeneous solution was added to 1.5 l of methanol. Then, 34.6 g (yield: 94%) of a product showing good rubber elasticity was obtained by suction filtration. Product Mn; 32000, Mw; 51000, Tm; 269 ° C., Tg; −52 ° C., Td;

Claims (3)

An aromatic amide compound unit represented by the following general formula (1):

(Here, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.)
A unit represented by the general formula (2),

(Here, R ³ is one or more divalent organic compounds selected from aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate. Group.)
And a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography, comprising at least one chain extender component unit selected from the group represented by the following general formulas (3) to (5): An aromatic amide block copolymer characterized by being from 10,000 to 500,000.

(Here, R ⁴ represents a divalent organic group having 1 to 20 carbon atoms.)

(Here, R ⁵ represents a divalent hydrocarbon group having 2 to 20 carbon atoms.)

(Here, R ⁶ represents a carbonyl group or a divalent organic group having 1 to 20 carbon atoms.) A dihydroxy aromatic amide compound represented by the following general formula (6):

(Here, R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms.)
A dihydroxy compound represented by the general formula (7),

(Here, R ⁹ is one or more divalent organic compounds selected from aliphatic poly (oxyalkylene), polyorganosiloxane, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aliphatic polyester, and aliphatic polycarbonate. Group.)
And the method of producing an aromatic amide block copolymer according to claim 1, wherein a chain extender is reacted. Chain extender is bifunctional halide compound, difunctional isocyanate compound, bifunctional carbonate compound, bifunctional ester compound, bifunctional acyllactam compound, bifunctional epoxy compound, bifunctional tetracarboxylic anhydride The method for producing an aromatic amide block copolymer according to claim 2, wherein the compound is at least one compound selected from the group consisting of: