KR20190071316A - Polyamideimide-based block copolymers and polyamideimide-based article comprising the same - Google Patents

Abstract

The present invention relates to a polyamideimide-based block copolymer and a polyamideimide-based molded article comprising the same. The polyamideimide block copolymer according to the present invention is excellent in heat resistance and mechanical properties and exhibits excellent fluidity at high temperature, thereby being able to be easily manufactured into a molded article.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyamide-imide-based block copolymer and a polyamide-

The present invention relates to a polyamideimide-based block copolymer and a polyamideimide-based molded article comprising the same.

The aromatic polyimide resin is a polymer having mostly an amorphous structure and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to its rigid chain structure. Such polyimide resins are widely used as materials for electric / electronic, aerospace, aviation and automobile.

However, the wholly aromatic polyimide resin is generally insoluble and insoluble in spite of excellent heat resistance, so that molding and processability are lowered, and there is a problem that it is difficult to use a usual processing equipment for resin processing.

Therefore, various attempts have been made to improve the melt formability of the polyimide resin while minimizing deterioration of the mechanical properties at high temperatures and excellent heat resistance. For example, in order to increase the flexibility of the chain in the polyimide resin, -O-, -S- group, etc., a method of introducing a meta substituent or a pin molecular structure, and the like have been proposed. However, the polyimide resin according to the proposals has a problem that it is difficult to exhibit sufficient heat resistance by a bending structure or an aliphatic cyclic compound.

In addition, it has been difficult to realize sufficient heat resistance and processability at a high level at an appropriate processing temperature applied to a product. Therefore, there is still a need for research into polyimide resins that have excellent melt moldability in the manufacturing process while minimizing the deterioration of mechanical properties at an appropriate processing temperature.

The present invention is to provide a polyamideimide block copolymer exhibiting excellent fluidity (melt moldability) at a high temperature while being excellent in heat resistance and mechanical properties.

The present invention also provides a polyamide-imide-based molded article comprising the polyamide-imide block copolymer.

The present invention also provides a process for producing a polyamide-imide-based molded article comprising the polyamide-imide-based block copolymer.

According to the present invention, imidic repeating units derived from a diamine-based monomer containing a dianhydride monomer containing at least one ether (-O-) bond and an aliphatic diamine monomer having from 3 to 10 carbon atoms; And

An amide-based repeating unit derived from an aromatic diamine-based monomer and a diacyl-based monomer,

The aliphatic diamine monomer having 3 to 10 carbon atoms is contained in an amount of 15 to 30 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit,

A glass transition temperature (Tg) of 200 DEG C or less,

And a thermal decomposition initiation temperature (Td _1% ) of not less than 410 캜.

According to the present invention, there is also provided a polyamide-imide-based molded article comprising the polyamide-imide-based block copolymer.

According to the present invention, there is also provided a process for producing a polyamideimide-based molded article comprising the polyamideimide-based block copolymer.

Hereinafter, a polyamideimide-based block copolymer according to embodiments of the present invention, a polyamideimide-based molded article containing the same, and a method for producing the same will be described in detail.

Prior to that, unless explicitly stated to the contrary, the terminology is used merely to refer to a specific embodiment and is not intended to limit the invention.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components and / And the like.

In the present specification, terms including ordinals such as 'first' and 'second' are used for distinguishing one element from another, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may also be referred to as a second component, and similarly, a second component may be named as a first component.

Ⅰ. The polyamide-imide block copolymer

According to one embodiment of the present invention, there is provided an amide-based resin composition comprising an imide-based repeating unit and an amide-based repeating unit, wherein the aliphatic diamine monomer is contained in an amount of 15 mol% to 30 mol %, A glass transition temperature (Tg) of 200 占 폚 or less, and a thermal decomposition initiation temperature (Td _1% ) of 410 占 폚 or more.

As a result of continuous research by the inventors of the present invention, it has been found that an aromatic dianhydride monomer and an aliphatic diamine monomer containing at least one ether (-O-) bond in a molecule are copolymerized and the content of the aliphatic diamine monomer is limited to a specific range, It has been confirmed that the amide imide block copolymer can simultaneously realize excellent flowability (melt moldability) at a high temperature within a range not affecting thermal stability and mechanical stability.

In the present invention, the 'block copolymer' refers to a polymer composed of a plurality of blocks connected in a line, and according to one embodiment of the present invention, the imide repeating unit and the amide repeating unit each represent one block .

(I) an imide repeating unit

In the present invention, the imide-based repeating unit is derived from a diamine-based monomer containing a dianhydride-based monomer containing at least one ether (-O-) bond and an aliphatic diamine monomer having 3 to 10 carbon atoms. The imide-based repeating unit forms a block copolymer with an amide-based repeating unit described later and can satisfy a glass transition temperature (Tg) of 200 ° C or less and a thermal decomposition initiation temperature (Td _1% ) of 410 ° C or more.

In the present invention, 'derived' means that the above-mentioned monomers (a dianhydride monomer containing at least one ether (-O-) bond and an aliphatic diamine monomer having 3 to 10 carbon atoms) To form a repeating unit.

In the present invention, the imide repeating unit can improve the flexibility of a molecule by introducing a structure of an ether (-O-) bond and a structure of an aliphatic organic group having 3 to 10 carbon atoms in the molecule by using the above-mentioned monomer. Particularly, when the aliphatic diamine monomer having 3 to 10 carbon atoms is contained in an amount of 15 to 30 mol% based on the total amount of monomers used in the imide repeating unit and the amide repeating unit, the thermal stability and the mechanical properties (Melt moldability) at high temperatures without the use of a conventional method.

In the present invention, when the content of the aliphatic diamine monomer having 3 to 10 carbon atoms is less than 15 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit, the meltability is lowered, There is a difficult problem. If it is contained in an amount exceeding 30 mol%, the moldability is excellent but the heat resistance may be deteriorated.

In an embodiment of the present invention, the aliphatic diamine monomer having 3 to 10 carbon atoms used for forming the imide repeating unit may be contained in an amount of preferably from 17 mol% to 25 mol% In this case, the desired effect of the present invention can be maximized without the above-mentioned problems.

In one embodiment of the present invention, the diamine monomer used in the imide repeating unit may further include an aromatic diamine monomer in addition to the aliphatic diamine monomer having 3 to 10 carbon atoms. In this case, in addition to the repeating unit derived from an aliphatic diamine monomer having 3 to 10 carbon atoms, it may further include a repeating unit derived from an aromatic diamine monomer.

Preferably, the aromatic diamine-based monomer may include at least one trifluoromethyl group (-CF ₃ ). In this case, transparency and the like of the resin may be improved to reduce the occurrence of yellowing in a high-temperature molding process .

In one embodiment of the present invention, the imide repeating unit may include a first repeating unit represented by the following formula (1). Here, the first repeating unit is a repeating unit derived from an aliphatic diamine monomer having 3 to 10 carbon atoms.

[Chemical Formula 1]

In the first repeating unit represented by Formula 1,

R ¹ is the same or different from each other in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms including at least one ether (-O-) linkage; The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) can be connected by NH-.

Here, the single bond means a case of chemically bonding to simply connect the groups R ¹ of the next amount in the formula (1).

R ² is the same or different from each other in each repeating unit and each independently represents -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO _{2, -CN, -COCH 3, -CO} 2 C 2 H 5, a silyl group, having 1 to 10 carbon atoms in an aliphatic organic group, or an aromatic organic date can having 6 to 20 carbon atoms having 1 to 10 carbon atoms in the three aliphatic organic have.

n1 and m1 each independently may be an integer of 0 to 3;

Y ¹ may be the same or different from each other in each repeating unit, and each independently may be an aliphatic organic group having 3 to 10 carbon atoms.

E ¹ each independently may be a single bond or -NH-. Here, the single bond means a chemical bond when the simply connected group of side E ¹ is the amount in the formula (1).

Preferably, the first repeating unit may include a repeating unit represented by the following formula (1-1):

[Formula 1-1]

In Formula 1-1,

R ² , n 1 and m 1 are as defined in formula (1).

R ³ is the same or different from each other in each repeating unit and is independently a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, or -C (= O) NH-, preferably -C (CH ₃ ) ₂ -.

P1 may be an integer of 3 to 10.

In one embodiment of the present invention, the imide repeating unit may further include a third repeating unit represented by the following formula (3) in addition to the first repeating unit. Here, the third repeating unit is a repeating unit derived from an aromatic diamine monomer.

(3)

In Formula 3,

R ⁶ is the same or different from each other in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one -O- linking group; The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) can be connected by NH-.

R ⁷ is the same or different from each other in each repeating unit and each independently represents -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO _{2, -CN, -COCH 3, -CO} 2 C 2 H 5, a silyl group, having 1 to 10 carbon atoms in an aliphatic organic group, or an aromatic organic date can having 6 to 20 carbon atoms having 1 to 10 carbon atoms in the three aliphatic organic have.

n3 and m3 each independently may be an integer of 0 to 3;

Y ⁴ is the same or different from each other in each repeating unit, and is independently a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one trifluoromethyl group (-CF ₃ ), and the aromatic organic group is present singly do or; Two or more aromatic organic groups may be bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) can be connected by NH-.

E ⁵ may be a single bond or -NH-, each independently.

Preferably, the third repeating unit may include a repeating unit represented by the following formula (3-1).

[Formula 3-1]

In Formula 3-1,

R ⁷ , n 3 and m 3 are as defined in formula (3)

R ⁶ is the same or different from each other in each repeating unit and each independently represents a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C _{(CH 3) 2 -, -C} (CF 3) 2 - can be, or -C (= O) NH-.

(Ii) amide-based repeating units

In the present invention, the amide-based repeating unit is derived from an aromatic diamine-based monomer and a diacyl-based monomer. The amide-based repeating unit forms a block copolymer with the above-mentioned imide-based repeating unit and can satisfy a glass transition temperature (Tg) of 200 ° C or less and a thermal decomposition initiation temperature (Td _1% ) of 410 ° C or more.

In the present invention, the diacyl-based monomer is a compound containing two acyl groups in the molecule, and includes, for example, at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid and dicarboxylate have.

Accordingly, the amide-based repeating unit includes a divalent linking group of -C (= O) -AC (= O) - form derived from a diacyl monomer, wherein A is a divalent aromatic organic group having 6 to 20 carbon atoms , A divalent heteroaromatic organic group having 4 to 20 carbon atoms, or a divalent alicyclic group-containing organic group having 6 to 20 carbon atoms, and two -C (= O) - may be located at para positions relative to each other.

In the present invention, the aromatic diamine-based monomer may include at least one trifluoromethyl group (-CF ₃ ). In this case, transparency and the like of the resin can be improved to reduce yellowing, etc. in a high- .

According to an embodiment of the present invention, the imide repeating unit may include a second repeating unit represented by the following formula (2).

(2)

In Formula 2,

Y ² is the same or different from each other in each repeating unit, and each independently is a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one trifluoromethyl group (-CF ₃ ); The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) can be connected by NH-.

E ² , E ³ and E ⁴ each independently may be a single bond or -NH-. Here, the single bond means a case where E ² , E ^3, and E ⁴ in the formula (1) are chemical bonds that simply connect the groups on both sides.

Y ³ is the same or different from each other in each repeating unit and is -C (= O) -AC (= O) derived from at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid and dicarboxylate, O) -form divalent linking group.

In Y ³ , A is a divalent aromatic organic group having 6 to 20 carbon atoms, a divalent heteroaromatic organic group having 4 to 20 carbon atoms, or a divalent alicyclic group having 6 to 20 carbon atoms, - can be located at para positions relative to A.

Preferably, the second repeating unit may include a repeating unit represented by the following formula (2-1).

[Formula 2-1]

In Formula 2-1,

R ⁴ is the same or different from each other in each repeating unit and each independently represents a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, or -C (= O) NH-, preferably a single bond. Here, the single bond means a case where E ⁴ , E ⁵ or E ⁶ is a chemical bond that simply connects groups or repeating units on both sides.

In addition, R ⁵ are each independently -H, -F, -Cl, -Br, -I, -CF 3, -CCl 3, -CBr 3, -CI 3, -NO 2, -CN, -COCH 3, -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms, .

n2 and m2 may each independently be an integer of 0 to 5;

E ² , E ³ and E ⁴ each independently may be a single bond or -NH-.

Y ³ is the same as or different from each other in each repeating unit and can be selected from the group represented by the following structural formula:

Specifically, Y ³ is preferably selected from the group consisting of terephthaloyl chloride (TPC), terephthalic acid, cyclohexane-1,4-dicarbonyl chloride, cyclohexane- Cyclohexane-1,4-dicarboxylic acid, pyridine-2,5-dicarbonyl chloride, pyridine-2,5-dicarboxylic acid, 2,5-dicarboxylic acid, 5-dicarboxylic acid, pyrimidine-2,5-dicarbonyl chloride, pyrimidine-2,5-dicarboxylic acid, , 4'-biphenyldicarbonyl Chloride (BPC), and 4,4'-biphenyldicarboxylic acid), and the like. May be a divalent linking group.

(Iii) a block copolymer

The polyamideimide block copolymer of the present invention contains the imide repeating unit and the amide repeating unit and has a glass transition temperature (Tg) of 200 DEG C or less, a thermal decomposition initiation temperature (Td _1% ), Satisfies 410 ° C or higher. By satisfying the glass transition temperature (Tg) and the pyrolysis initiation temperature (Td _1% ) within the above range, excellent heat resistance and excellent molding characteristics at high temperature can be secured at the same time.

In the present invention, when the glass transition temperature (Tg) exceeds 200 DEG C, there may arise a problem that the workability is significantly lowered, and the glass transition temperature may preferably be 195 DEG C or lower.

In the present invention, 'thermal decomposition initiation temperature (Td _1% )' means a temperature at which about 1% by weight of the total weight of the copolymer is decomposed. Specifically, the thermogravimetric analysis (TGA) is a measurement of the temperature at the time when the degree of thermal decomposition of the entire resin becomes about 1 wt%, which can be regarded as a value indicative of thermal stability in the present invention.

In the present invention, when the thermal decomposition initiation temperature (Td _1% ) is less than 410 ° C, the heat resistance of the copolymer is low, and deformation (carbonization, etc.) of the polymer may occur during the extrusion molding process. When placed, durability is considerably lowered and yellowing may occur. Preferably, the thermal decomposition initiation temperature (Td _1% ) may be 440 캜 or higher.

The polyamideimide block copolymer of the present invention comprises the aforementioned imide repeating units and amide repeating units, and their molar ratio can be determined by the content of the monomers used in each repeating unit.

In one embodiment of the present invention, the molar ratio of the imide repeating unit to the amide repeating unit may be 3: 1 to 1: 1, preferably 3: 1 to 2.5: 1. When the molar ratio is satisfied, excellent heat resistance and high-temperature fluidity can be realized within a range that does not deteriorate the mechanical properties by satisfying the desired glass transition temperature and thermal decomposition starting temperature.

The imide repeating unit may be a first repeating unit or may further comprise a first repeating unit and a third repeating unit. The amide-based repeating unit may be a second repeating unit.

However, the molar ratio of the repeating units satisfies the content ratio of the aliphatic diamine monomer having 3 to 10 carbon atoms (15 to 30 mol% based on the total amount of monomer used in the imide repeating unit and the amide repeating unit) Range.

In addition, the polyimide block copolymer according to one embodiment of the present invention may have a weight average molecular weight of 30,000 to 300,000 g / mol, preferably 50,000 to 100,000 g / mol. When the weight average molecular weight is in the above range, it is suitable for exhibiting excellent moldability at high temperature.

On the other hand, the polyimide block copolymer may be prepared by mixing a compound forming the imide repeating unit in an appropriate solvent to initiate a reaction; Adding a compound forming the amide-based unit to the reaction mixture in the above step and reacting; And a compound such as acetic anhydride or pyridine is added to the reaction mixture to induce a chemical imidization reaction or a thermal imidization reaction of amic acid is carried out by Azeotropic Distillation And < / RTI >

When the imide-based repeating unit further comprises a third repeating unit in addition to the first repeating unit in the polyamide-imide block copolymer, the compound forming the first repeating unit is dissolved in an appropriate solvent Mixing and initiating the reaction; Adding a compound forming the second repeating unit to the reaction mixture of the above step and reacting; Adding a compound forming the third repeating unit to the reaction mixture of the above step and reacting; And a compound such as acetic anhydride or pyridine is added to the reaction mixture to induce a chemical imidization reaction or a thermal imidization reaction of amic acid is carried out by Azeotropic Distillation And < / RTI >

The polyamideimide block copolymer may be prepared by low-temperature solution polymerization, interfacial polymerization, melt polymerization, solid phase polymerization, or the like.

Ⅱ. Polyamideimide-based molded articles

According to another embodiment of the present invention, there is provided a polyamideimide-based molded article comprising the above-described polyamideimide-based block copolymer.

As a result of continuous research by the inventors of the present invention, it has been found that an aromatic dianhydride monomer and an aliphatic diamine monomer containing at least one ether (-O-) bond in a molecule are copolymerized and the content of the aliphatic diamine monomer is limited to a specific range, It has been confirmed that the amide imide block copolymer can simultaneously realize excellent flowability (melt moldability) at a high temperature within a range not affecting thermal stability and mechanical stability.

As a result, the polyamide-imide-based molded article comprising the polyamide-imide block copolymer can be applied to various products which are excellent in moldability at high temperature and at the same time have high mechanical properties and heat resistance. Particularly, the molded article of the present invention is an extrusion molded article requiring a high-temperature extrusion process, and is highly heat-resistant engineering plastic, and is suitable for automobile and industrial machinery parts.

The molded article according to one embodiment of the present invention may contain four additional additives within the range not deviating from the intended effect of the present invention in order to further improve the physical properties and improve the processability. Examples of the additional additives include at least one colorant selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, lubricants, flame retardants, light stabilizers, heat stabilizers, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments, .

Ⅲ. A method for producing a polyamide-imide-based molded article.

According to another embodiment of the present invention, there is provided a process for producing a polyamideimide-based molded article comprising the above-described polyamideimide-based block copolymer.

The method for producing a molded article of the present invention includes a step of extruding a polyamideimide-based block copolymer prepared according to the above-described method at a temperature of 300 ° C to 380 ° C, preferably at a temperature of 300 ° C to 350 ° C . The polyamideimide-based block copolymer according to the present invention has excellent heat resistance and melt moldability, so that even if the extrusion is performed at a high temperature as described above, molding is easy without deforming the polymer.

If the temperature for the extrusion step is less than 300 ° C, the meltability is lowered and the production of the molded article is somewhat difficult. When the temperature exceeds 380 ° C, deformation (carbonization, etc.) of the polymer may occur.

The method for producing a molded article according to an embodiment of the present invention can be applied without particular limitation to the method used in the art, for example, a polyamideimide block copolymer (when the additive is included, ) Can be extruded under the above-mentioned temperature condition by using an extruder to obtain a molded article.

The polyamideimide block copolymer according to the present invention is excellent in heat resistance and moldability at high temperature without deteriorating the mechanical properties, and is easily molded into a molded product through an extrusion step.

FIG. 1 shows the thermogravimetric analysis (TGA) analysis results of Example 1 and Comparative Example 1. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Example  And Comparative Example  : Preparation of polyamideimide block copolymer

Example  1: Preparation of A-1

In a 1000 mL round flask equipped with a dean-stark apparatus and a condenser, 6.265 g (1.505 eq., 0.01956 mol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) 20.231 g (2.99 eq., 0.03887 mol) of bisphenol dianhydride (BPADA) and 200 ml of N-methylpyrrolidone (NMP) were added and stirred. Then, 2.273 g (1.505 eq., 0.01956 mol) of hexamethylenediamine (HMDA) was dissolved in N-methylpyrrolidone (NMP) (20 mL) and then added by slow dropping. After the addition of hexamethylene diamine (HMDA) was completed, the reaction was carried out at room temperature under nitrogen atmosphere for 4 hours.

After the reaction, imide block polyamic acid was formed. Then, 4.121 g (0.99 eq., 0.01287 mol) of 2,2'-bis (trifluoromethyl) benzidine and 2.666 g (1.01 eq ., 0.01313 mol) and additional N-methyl pyrrolidone (NMP) (250 ml) were added and stirred at 40 占 폚 for 4 hours to proceed amide block synthesis.

After completion of the reaction, 200 ml of chlorobenzene was added, and the temperature was raised to 190 ° C. The imidization reaction of amic acid was carried out by azotropic distillation with stirring for about 15 hours. After completion of the reaction, the mixture was precipitated in isopropyl alcohol and dried at 120 ° C to obtain a final polyamideimide block copolymer.

The polyamideimide block copolymer (A-1) thus prepared contains the following repeating units. The aliphatic diamine monomer having 3 to 10 carbon atoms used in the preparation of Example 1 (A-1) was 18.8 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit, 160,000 g / mol.

[First Repeating Unit]

[Second Repeating Unit]

[Third Repeating Unit]

Example  2: Preparation of A-2

(1.73 eq., 0.02249 mol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 1,933 g (1.28 eq., 0.01664 mol) of hexamethylenediamine (HMDA) in the synthesis of imide block polyamic acid (manufactured by Nippon Polyurethane Industry Co., Ltd.), and 20.231 g (2.99 eq., 0.03887 mol) of 4,4'-bisphenol dianhydride (BPADA) A-2).

The aliphatic diamine monomer having 3 to 10 carbon atoms used in the preparation of Example 2 (A-2) was 16 mol% based on the total amount of monomers used in the imide repeating unit and the amide repeating unit, and the weight average molecular weight was about 210,000 g / mol.

Example  3: Preparation of A-3

(0.85 eq., 0.01105 mol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB), 3.263 g of hexamethylenediamine (HMDA) (2.16 eq., 0.02808 (2.99 eq., 0.03387 mol) of 4,4'-bisphenol dianhydride (BPADA) and 20.231 g (2.99 eq., 0.03387 mol) of 4,4'-bisphenol dianhydride A-3).

The aliphatic diamine monomer having 3 to 10 carbon atoms used in the preparation of Example 3 (A-3) was 28.3 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit, 120,000 g / mol.

Comparative Example  1: Preparation of A-4

(2.113 eq., 0.02113 mol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB), 1.042 g (0.897 eq., 0.00897 mol) of hexamethylenediamine (HMDA) in the synthesis of imide block polyamic acid (2.99 eq., 0.0299 mol) of 4,4'-bisphenol dianhydride (BPADA) (manufactured by Nippon Polyurethane Industry Co., Ltd.) A-4).

The aliphatic diamine monomer having 3 to 10 carbon atoms used in the production of the comparative example 1 (A-4) was 10.4 mol% based on the total amount of monomers used in the imide repeating unit and amide repeating unit, and the weight average molecular weight was about 130,000 g / mol.

Comparative Example  2: Preparation of A-5

4.819 g (3.01 eq., 0.01515 mol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB), 4,4'-biphenyltetracarboxylic dianhydride (A-5) was obtained in the same manner as in Example 1, except that 7.781 g (2.99 eq., 0.01495 mol) of 4'-bisphenol dianhydride (BPADA) .

The aliphatic diamine monomer having 3 to 10 carbon atoms used in the preparation of Comparative Example 1 (A-5) was 0 mol%, and the weight average molecular weight was about 200,000 g / mol.

Comparative Example  3: A-6

A polyimide polymer containing the following repeating units was used.

Manufactured by Solvay Co., Ltd., Torlon, weight average molecular weight of about 139,000 g / mol

Comparative Example  3: Preparation of A-7

(3.01eq., 0.03913mol) of hexamethylenediamine (HMDA), 4.447g (3.09eq.) Of tetrabutylammonium bromide were used in the synthesis of imidoblock polyamic acid without using 2,2'-bis (trifluoromethyl) benzidine (A-7) was prepared in the same manner as in Example 1, except that 20.231 g (2.99 eq., 0.03887 mol) of bisphenol dianhydride (BPADA) Respectively.

The aliphatic diamine monomer having 3 to 10 carbon atoms used in the production of the comparative example 3 (A-7) was 37.6 mol% based on the total amount of monomers used in the imide repeating unit and amide repeating unit, and the weight average molecular weight was about 70,000 g / mol.

Test Example

The polyamideimide block copolymers prepared in Examples and Comparative Examples were tested according to the following methods. The results are shown in Table 1.

1) Glass transition temperature ( Tg , ℃) Evaluation

The loss modulus of the polyamideimide-based block copolymer was measured under the conditions of 0.1% ± 0.005% strain, 0.05 ± 0.0005 force, and 1 ± 0.01 Hz frequency at room temperature (about 25 ° C. to 350 ° C.) Respectively. The glass transition temperature was measured from the temperature of the peak value of the measured loss elastic modulus, and the results are shown in Table 1.

2) Pyrolysis initiation temperature ( Td _One% , ℃) (heat resistance) evaluation

A thermogravimetric analysis (TGA) was performed on the polyamideimide block copolymer using a thermogravimetric analyzer (TGA Q500) manufactured by TA Instrument, heated to 800 ° C at a rate of 10 ° C / min, The temperature at which the degree of thermal decomposition of the entire resin reached about 1 wt% was measured, and the results are shown in Table 1. Fig. 1 shows the TGA analysis results of Example 1 and Comparative Example 1. Fig.

3) Melt Flow at 350 ° C ( Melting ability ) evaluation

The polyamide-imide block copolymer was measured by using a Rheometer (ARES-G2) from TA Co., and measuring the zero-shear viscosity (poise) according to shear rate at 350 ° C. The meltability was evaluated. The results are shown in Table 1. The zero-shear viscosity according to the shear rate refers to the viscosity value when the shear rate is zero.

<Evaluation Criteria>

○: Less than 10 ⁵ poise

?: 10 ⁵ to 10 ⁷ poise

X: Measurement impossible, almost no change in appearance due to heat

division
HDMA content (mol%) Glass transition temperature
(° C) Td _1%
(° C) Melt Flow at 350 Example 1 18.8 193 441 ○ Example 2 16 200 420 △ Example 3 27 152 410 ○ Comparative Example 1 10.4 207 403 △ Comparative Example 2 0 238 468 X Comparative Example 3 0 261 445 X Comparative Example 4 37.62 127 369 Carbonized

As shown in Table 1, in the case of the polyamideimide-based block copolymer copolymerized with the aliphatic diamine monomer in a specific amount in accordance with the present invention, it is excellent in heat resistance and moldability at high temperature, And it was confirmed that it was easy.

The block copolymer having an aliphatic diamine content exceeding the content limit of the present invention was deteriorated in heat resistance, and it was confirmed that when heated to 350, the polymer was carbonized and the meltability could not be measured.

Further, in the case of the copolymer containing no aliphatic diamine of the present invention, the heat resistance was high, but the moldability was deteriorated. In particular, since the meltability was remarkably lowered at 350, it was confirmed that the molded product was difficult to manufacture.

Claims (11)

An imide-based repeating unit derived from a diamine-based monomer containing a dianhydride-based monomer containing at least one ether (-O-) bond and an aliphatic diamine monomer having from 3 to 10 carbon atoms; And
An amide-based repeating unit derived from an aromatic diamine-based monomer and a diacyl-based monomer,
The aliphatic diamine monomer having 3 to 10 carbon atoms is contained in an amount of 15 to 30 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit,
A glass transition temperature (Tg) of 200 DEG C or less,
And a thermal decomposition initiation temperature (Td _1% ) of 410 캜 or higher.
The method according to claim 1,
Wherein the aliphatic diamine monomer having 3 to 10 carbon atoms is contained in an amount of 17 to 25 mol% based on the total amount of monomers used in the imide-based repeating unit and the amide-based repeating unit.
The method according to claim 1,
The diamine monomer used in the imide repeating unit further comprises an aromatic diamine monomer.
The method according to claim 1,
Wherein the imide repeating unit comprises a first repeating unit represented by the following formula (1)
Wherein the amide-based repeating unit comprises a second repeating unit represented by the following formula (2): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
R ¹ is the same or different from each other in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one ether (-O-) bond; The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) NH-, and are connected by a;
R ² is the same or different from each other in each repeating unit and each independently represents -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO _{2, -CN, -COCH 3, -CO} 2 C 2 H 5, a silyl group, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms having 1 to 10 carbon atoms in the three aliphatic organic and ;
n1 and m1 are each independently an integer of 0 to 3;
Y ¹ is the same or different from each other in each repeating unit, and each independently is an aliphatic organic group having 3 to 10 carbon atoms;
E ¹ is each independently a single bond or -NH-;
(2)

In Formula 2,
Y ² is the same or different from each other in each repeating unit, and each independently is a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one trifluoromethyl group (-CF ₃ ); The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) NH-, and are connected by a;
E ² , E ³ and E ⁴ are each independently a single bond or -NH-;
Y ³ is the same or different from each other in each repeating unit and is -C (= O) -AC (= O) derived from at least one compound selected from the group consisting of diacyl halide, dicarboxylic acid and dicarboxylate, O) -form divalent linking group;
In Y ³ , A is a divalent aromatic organic group having 6 to 20 carbon atoms, a divalent heteroaromatic organic group having 4 to 20 carbon atoms, or a divalent alicyclic group having 6 to 20 carbon atoms, - are located at para positions relative to A.
5. The method of claim 4,
Wherein the imide repeating unit further comprises a third repeating unit represented by the following general formula (3): &lt; EMI ID =
(3)

In Formula 3,
R ⁶ is the same or different from each other in each repeating unit, and each independently includes a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one ether (-O-) linkage; The aromatic organic group is present alone; Two or more aromatic organic groups are bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) NH-, and are connected by a;
R ⁷ is the same or different from each other in each repeating unit and each independently represents -H, -F, -Cl, -Br, -I, -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO _{2, -CN, -COCH 3, -CO} 2 C 2 H 5, a silyl group, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms having 1 to 10 carbon atoms in the three aliphatic organic and ;
n3 and m3 are each independently an integer of 0 to 3;
Y ⁴ is the same or different from each other in each repeating unit, and is independently a divalent aromatic organic group having 6 to 30 carbon atoms and containing at least one trifluoromethyl group (-CF ₃ ), and the aromatic organic group is present singly do or; Two or more aromatic organic groups may be bonded to each other to form a divalent condensed ring; Or two or more aromatic organic group is a single bond, a fluorenyl group, -O-, -S-, -C (= O) -, -CH (OH) -, -S (= O) 2 -, -Si ( _{CH 3) 2 -, - (} CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where _{1≤q≤10), -C (CH 3)} 2 -, -C ( CF _{3) 2} -, or -C (= O) NH-, and are connected by a;
E ⁵ is being single bond or -NH-, each independently.
5. The method of claim 4,
Wherein the first repeating unit comprises a repeating unit represented by the following formula (1-1): &lt; EMI ID =
[Formula 1-1]

In Formula 1-1,
R ² , n 1, m 1 are as defined in formula (1)
R ³ is the same or different from each other in each repeating unit and is independently a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C _{(CH 3) 2 -, -C} (CF 3) 2 -, or -C (= O) NH-, and;
p1 is an integer of 3 to 10;
5. The method of claim 4,
Wherein the second repeating unit comprises a repeating unit represented by the following formula (2-1): &lt; EMI ID =
[Formula 2-1]

In Formula 2-1,
R ⁴ is the same or different from each other in each repeating unit and each independently represents a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C _{(CH 3) 2 -, -C} (CF 3) 2 -, or -C (= O) NH-, and;
R ⁵ are each independently -H, -F, -Cl, -Br, -I, -CF 3, -CCl 3, -CBr 3, -CI 3, -NO 2, -CN, -COCH 3, -CO ₂ C ₂ H ₅ , a silyl group having three aliphatic organic groups having 1 to 10 carbon atoms, an aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms;
n2 and m2 are each independently an integer of 0 to 5;
E ² , E ³ and E ⁴ are each independently a single bond or -NH-;
Y ³ is the same or different from each other in each repeating unit and is selected from the group represented by the following structural formula:

.
6. The method of claim 5,
Wherein the third repeating unit comprises a repeating unit represented by the following formula (3-1): &lt; EMI ID =
[Formula 3-1]

In Formula 3-1,
R ⁷ , n 3 and m 3 are as defined in formula (3)
R ⁶ is the same or different from each other in each repeating unit and each independently represents a single bond, a fluorenylene group, -O-, -S-, -C (= O) -, -CH (OH) _{(= O) 2 -, -Si} (CH 3) 2 -, - (CH 2) p - ( where _{1≤p≤10), - (CF 2)} q - ( where 1≤q≤10), -C _{(CH 3) 2 -, -C} (CF 3) 2 -, or -C (= O) NH- Im.
The method according to claim 1,
And a weight average molecular weight of 30,000 to 300,000 g / mol.
A polyamideimide-based molded article comprising the polyamideimide block copolymer of claim 1.
A process for producing a polyamideimide-based molded article, which comprises extruding the polyamide-imide block copolymer of claim 1 at a temperature of 300 ° C to 380 ° C.

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