KR101443173B1 - Polyamide resin having an excellent melt processibility - Google Patents

Abstract

The present invention provides a polyamide resin formed by condensation polymerization of two different dicarboxylic acid monomers and aliphatic diamine monomers. Wherein the two kinds of dicarboxylic acid monomers are cyclic carboxylic acid monomers (B) and aromatic dicarboxylic acid monomers (A) having 8 to 10 carbon atoms which share a similar structure, and the aliphatic diamine monomer (C) 10 to 12, and is polycondensed with the dicarboxylic acid monomer to provide a polyamide resin having excellent melt processability and heat resistance and low absorbency.

Description

[0001] The present invention relates to a polyamide resin having excellent processability,

The present invention relates to a polyamide resin, and more particularly, to a polyamide resin having excellent melt processability and heat resistance and low hygroscopicity.

In general, nylon 66 and nylon 6 are best known as polyamide resins. Aliphatic polyamides of this kind are widely used in automobile parts, electric appliances, electronic products, machine parts and the like. However, aliphatic polyamides do not have sufficient thermal stability to be applied in fields requiring high heat resistance properties.

Aromatic polyamides have higher melting temperatures and higher heat resistance than aliphatic polyamides, but due to such high melting temperatures, processability has been limited.

U.S. Patent No. 2009-0054620 discloses a process for producing a meta-type polyamide resin by reacting meta-type m-phenylenediamine with isophthalic chloride to improve the melt processability rather than the para-type polyamide. However, So that the processability can not be sufficiently improved.

U.S. Patent No. 5102935 has attempted to improve melt processability by copolymerizing a polyamide and an oligomer ester. However, the copolymer has a disadvantage in that the main chain of the polymer is easily decomposed by the hydrolysis of the oligomeric ester group, resulting in poor thermal stability.

U.S. Patent No. 2008-0249238 shows that although a plasticizer is added to a polyamide resin to improve the melt processability, it has a disadvantage that both thermal and mechanical properties are deteriorated.

Japanese Patent No. 2002-293926 discloses a polyamide copolymer prepared by using an aromatic or aliphatic diamine and a dicarboxylic acid having various carbon lengths, but a practical example of a polyamide copolymer prepared by mixing diamines is not disclosed, And the advantages of the polyamide copolymer prepared by applying the diamine monomer to the polyamide copolymer are not mentioned.

U.S. Patent No. 1998-5773558 shows that cyclohexane dicarboxylic acid is produced by reacting an aliphatic diamine with a molding compound having high hardness, solvent resistance and high heat resistance.

An object of the present invention is to provide a polyamide resin excellent in melt processability and heat resistance.

Another object of the present invention is to provide a polyamide resin excellent in low hygroscopicity.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to solve the above-described technical problem, the present invention provides a poly (arylene ether) copolymer comprising a dicarboxylic acid monomer (A) having at least one aromatic ring, a cyclic dicarboxylic acid monomer (B), and an aliphatic diamine monomer Amide resin.

In one embodiment of the present invention, the cyclic carboxylic acid monomer (B) is contained in an amount of 0.1 to 20 mol% based on the total number of moles of the dicarboxylic acid component contained in the polyamide resin of the present invention.

In another embodiment of the present invention, the aromatic dicarboxylic acid monomer (A) and the cyclic dicarboxylic acid monomer (B) are contained in an amount of 30 to 70 mol% based on 100 mol% of the polyamide resin.

In another embodiment of the present invention, the ratio ((C)) of the total molar number of the aromatic dicarboxylic acid and the cyclic dicarboxylic acid monomer mixture (A + B) to the total molar number of the dicarboxylic acid monomer (C) / (A + B)) is 0.90 to 1.30.

According to another aspect of the present invention, there is provided a molded article made from the thermoplastic resin according to the present invention.

The polyamide resin of the present invention is excellent in melt processability and heat resistance and has low hygroscopicity.

Hereinafter, the present invention will be described in more detail.

(A) an aromatic dicarboxylic acid monomer

The aromatic dicarboxylic acid monomer (A) of the present invention is characterized by containing at least one aromatic group. More specifically, examples of the aromatic dicarboxylic acid monomer (A) include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, Dicarboxylic acid, diphenic acid, 4 ', 4'-oxybis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, Diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-diphenylcarboxylic acid. These components may be used alone or in combination.

(B) a cyclic dicarboxylic acid monomer having 8 to 10 carbon atoms

The cyclic dicarboxylic acid monomer (B) of the present invention is a compound having a cyclic structure and is characterized by having a carbon number of 8 or more and 10 or less. Examples of the cyclic dicarboxylic acid monomer (B) include 2-cyclohexene, 1,4-dicarboxylic acid, cyclohexane-1,1-dicarboxylic acid, trans 1,2-cyclohexanedicarboxylic acid Cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethylcyclohexane 1,4-dicarboxylate, and the like, and these components may be used alone Or may be used in combination.

In one embodiment of the present invention, the cyclic carboxylic acid monomer (B) is preferably contained in an amount of 0.1 to 20 mol% based on the total number of moles of the dicarboxylic acid component contained in the polyamide resin of the present invention.

In another embodiment of the present invention, the aromatic dicarboxylic acid monomer (A) and the cyclic dicarboxylic acid monomer (B) are preferably contained in an amount of 30 to 70 mol% based on 100 mol% of the polyamide resin.

(C) an aliphatic diamine monomer having 10 to 12 carbon atoms

In the present invention, the diamine monomer which is condensed with the aromatic dicarboxylic acid monomer (A) and the cyclic dicarboxylic acid monomer (B) is an aliphatic diamine monomer (C). Specific examples of the aliphatic diamine monomer (C) include 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 5-methyl- Diamino-4,7-dioxo-undecane, 1,10-diamino-4,7-dioxo-5 methyldecane, and the like. These components may be used singly or in combination.

In one embodiment of the present invention, the ratio of the total number of moles of the aromatic dicarboxylic acid and the cyclic dicarboxylic acid monomer mixture (A + B) to the total number of moles of the aliphatic diamine monomer (C) ((C) / + B) is preferably from 0.90 to 1.30. If the molar ratio is out of the range, a sufficient degree of polymerization is not obtained and the molecular weight is low, and heat resistance, molding processability and the like can not be expressed.

(D) an endcapping agent

In order to control the viscosity of the copolymerized polyamide resin in the production of the polyamide resin of the present invention, an end encapsulant (D) may be further included. The viscosity of the synthesized polyamide resin can be controlled by controlling the content of the end encapsulant. The polyamide resin of the present invention can be adjusted to have an intrinsic viscosity [?] Of 0.3 dL / g to 4.0 dL / g, Is preferably controlled.

As the end-capping agent used in the present invention, an aliphatic carboxylic acid or an aromatic carboxylic acid can be used. Examples of the aliphatic carboxylic acid endblocking agent include aliphatic carboxylic acid endblocking agents such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, And the aromatic carboxylic acid end-capping agent may include benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and the like. .

Manufacturing method

The polyamide resin having excellent heat resistance and chemical resistance according to the present invention can be produced by condensation polymerization of diamine monomers (A, B) and dicarboxylic acid (C). The specific manufacturing method is as follows.

The aliphatic diamine is initially introduced into the mixture of the aromatic dicarboxylic acid monomer (A) and the cyclic dicarboxylic acid monomer (B) (A + B), the terminal endblocking agent (D) A certain amount of water or the like is charged into the reactor and stirred at 80 to 120 ° C for 1 hour. The temperature is maintained at 2-4 hours while increasing the temperature to 200-280 ° C., the pressure is kept constant at 25 kgf / cm 2, the pressure is reduced to 15 kgf / cm 2, and the reaction is performed for 1 to 3 hours. The polyamide thus obtained is subjected to solid phase polymerization at a temperature between its glass transition temperature (Tg) and its melting temperature (Tm) in a vacuum for 10 to 30 hours to obtain a final reactant.

In preparing the polyamide resin of the present invention, a phosphorous-based catalyst may be used. Phosphoric acid, phosphorous acid, hypophosphorous acid or a salt or derivative thereof, and more specific examples include phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite, sodium hypophosphite Etc. may be used.

The phosphorus-based catalyst used in the production of the polyamide resin of the present invention may be used in an amount of 0 to 3.0% by weight, preferably 0 to 1.0% by weight, more preferably 0 to 0.5% by weight, .

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

0.572 mole (95 g) of terephthalic acid, 0.03 mole (5.18 g) of 1,4-cyclohexane dicarboxylic acid, 0.614 mole (105.8 g) of 1,10-decanediamine, 0.024 mole (2.94 g) 0.1% by weight (0.204 g) and 140 mL of distilled water were placed in a 1-liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.21 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.03 dL / g.

Example 2

0.572 moles (95 g) of terephthalic acid, 0.03 mole (5.18 g) of 1,4-cyclohexane dicarboxylic acid, 0.614 mole (123.0 g) of 1,12-dodecanediamine, 0.024 mole (2.94 g) 0.1 wt% (0.221 g) of nate and 151 mL of distilled water were placed in a 1-liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.11 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.91 dL / g.

Example 3

0.541 mole of terephthalic acid (90.0 g), 0.03 mole (5.2 g) of 1,4-cyclohexane dicarboxylic acid, 0.525 mole (95.5 g) of 1,10- decanediamine, 0.058 mole ), 0.024 mol (2.79 g) of benzoic acid, 0.1 wt% (0.194 g) of sodium hyphaphosphonate and 133 mL of distilled water were charged in a 1 liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.16 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.95 dL / g.

Example 4

0.511 mole (85.0 g) of terephthalic acid, 0.053 mole (15.5 g) of 1,4-cyclohexane dicarboxylic acid, 0.522 mole (99.5 g) of 1,10- decanediamine, 0.03 mole ), 0.012 mol (1.47 g) of benzoic acid, 0.1 wt% (0.192 g) of sodium hyphaphosphinate and 139 mL of distilled water were charged in a 1 liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.17 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.97 dL / g.

Example 5

0.539 mole (95 g) of terephthalic acid, 0.03 mole (5.2 g) of 1,4-cyclohexane dicarboxylic acid, 0.522 mole (89.9 g) of 1,10- decanediamine, 0.092 mole (18.5 g) , 0.024 mol (2.94 g) of benzoic acid, 0.1 wt% (0.21 g) of sodium hyphaphosphonate and 141 mL of distilled water were placed in a 1 liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.13 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was subjected to solid state polymerization at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.93 dL / g.

Example 6

0.572 moles (95 g) of terephthalic acid, 0.03 mole (5.18 g) of 1,2-cyclohexane dicarboxylic acid, 0.614 mole (105.8 g) of 1,10-decanediamine, 0.024 mole (2.94 g) 0.1% by weight (0.204 g) and 140 mL of distilled water were placed in a 1-liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.22 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was subjected to solid state polymerization at 230 DEG C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.2 dL / g.

Comparative Example 1

(1-liter autoclave) of 0.602 mol (100 g) of terephthalic acid, 0.614 mol (105.8 g) of 1,10-decanediamine, 0.024 mol ) And filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.41 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.28 dL / g.

Comparative Example 2

0.511 moles (85.0 g) of terephthalic acid, 0.522 moles (99.5 g) of 1,10-decanediamine, 0.03 moles (6.1 g) of 1,12-dodecanediamine, 0.012 moles (1.47 g) % (0.192 g) and distilled water (139 mL) were charged in a 1-liter autoclave and filled with nitrogen.

The mixture was stirred at 100 DEG C for 60 minutes, heated at 250 DEG C for 2 hours, maintained at 25 kgf / cm < 2 > at that temperature for 3 hours, reduced in pressure to 15 kgf / cm < A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.12 dL / g.

Comparative Example 3

0.421 mole (60 g) of terephthalic acid, 0.18 mole (41.1 g) of 1,4-cyclohexane dicarboxylic acid, 0.614 mole (105.8 g) of 1,10-decanediamine, 0.024 mole (2.94 g) 0.1% by weight (0.179 g) of high-phosphonate and 140 mL of distilled water were placed in a 1-liter autoclave and filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.09 dL / A prepolymer was prepared.

Comparative Example 4

(1-liter autoclave) was charged with 0.602 mol (100 g) of terephthalic acid, 1404 g of 1,14-tetradecanediamine, 1404 g of benzoic acid, 0.024 mol autoclave) and filled with nitrogen. The mixture was stirred at 100 DEG C for 60 minutes, heated at 250 DEG C for 2 hours, maintained at 25 kgf / cm < 2 > at that temperature for 3 hours, reduced in pressure to 15 kgf / cm < A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was subjected to solid state polymerization at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 1.31 dL / g.

Comparative Example 5 (Addition)

A 1 liter autoclave was charged with 0.602 mols (100 g) of terephthalic acid, 0.813 mols (140.10 g) of 1,10-decanediamine, 0.421 mols (69.94 g) of benzoic acid, 0.1 weight% ) And filled with nitrogen. The mixture was stirred at 100 ° C. for 60 minutes, heated at 250 ° C. for 2 hours, maintained at 25 kgf / cm 2 for 3 hours at that temperature, reduced in pressure to 15 kgf / cm 2 and reacted for 1 hour to obtain 0.08 dL / A prepolymer was prepared.

The polyamide prepolymer obtained by the above method was solid-state polymerized at 230 ° C for 24 hours to finally obtain a polyamide resin having an intrinsic viscosity of 0.15 dL / g.

Property evaluation

The thermal properties and intrinsic viscosity of the polyamide resin prepared in the above Examples and Comparative Examples were measured before and after the solid phase polymerization. Thermal properties were measured by different scanning calorimeter (DSC) and thermogravimetric analyzer (TGA). The intrinsic viscosity was determined by dissolving the polyamide in concentrated sulfuric acid solution (98%) and then measuring the intrinsic viscosity using a Ubbelodhde viscometer at 25 ° C. The flowability test was carried out using Sumitomo Injector SG75H-MIV. The cylinder temperature and the mold temperature were set at 320 DEG C, and the injection pressure was set at 15 MPa.

The tensile strength was measured according to ISO 527 (23 ° C, 5 mm / min). The tensile strength before and after the treatment for 24 hours at a temperature of 80 ° C and a humidity of 95% in a thermo-hygrostat was measured.

Moisture absorption rate was 100mm in length, 100mm in width and 3mm in thickness. After the dried weight (W0) is measured, the specimen is treated in a thermo-hygrostat at 50 ° C and 90% RH for 48 hours and the weight (W1) is measured.

Water Absorption Rate (%) = [(W1-W0) / W0] * 100

The following Table 1 shows the content of each component added to the above Examples and Comparative Examples, and Table 2 shows properties of Examples and Comparative Examples.

In view of the physical property evaluation results of the examples and comparative examples, the polyamide resins of Examples 1 to 6 maintain the melting temperature and the crystallization temperature, and the fluidity and the low hygroscopicity are remarkably improved.

In the case of Comparative Example 1 which does not contain the cyclic dicarboxylic acid (B), the fluidity is lowered and the intrinsic viscosity of the resin is thereby increased. Therefore, since fluidity can not be ensured, a problem may arise in resin processing.

Comparative Example 2 In the same manner as in Comparative Example 1, a small amount of 1,12-dodecanediamine was used to improve the fluidity in the case where the cyclic dicarboxylic acid (B) was not contained, but sufficient fluidity could not be secured Able to know.

In Comparative Example 3, the amount of the cyclic dicarboxylic acid monomer (B) relative to the total dicarboxylic acid moles in an amount of 30 mol% was relatively large, which is an element that inhibits the regularity of the nylon as a semi-crystalline polymer Which may cause the lowering of the melting temperature and the crystallization temperature, and it is not suitable as a high heat resistant aromatic polyamide resin.

In Comparative Example 4, the melting temperature and the glass transition temperature were decreased using 1,14-tetradecanediamine (C ') having an aliphatic diamine monomer having more than 12 carbon atoms, and thus heat resistance was not sufficiently secured.

In Comparative Example 5, when the ratio of total moles ((C) / (A + B)) exceeded 1.30, the molecular weight of the final polyamide resin was excessively decreased.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

Aromatic dicarboxylic acid monomer (A);
A cyclic dicarboxylic acid monomer (B) having 8 to 10 carbon atoms; And
And an aliphatic diamine monomer (C) having 10 to 12 carbon atoms,
The content of the cyclic dicarboxylic acid monomer (B) is in the range of 0.1 to 20 mol% based on the total carboxylic acid component (A + B), and
The ratio (A / B) of the total molar number (A + B) of the aromatic dicarboxylic acid monomer (A) and the cyclic dicarboxylic acid monomer (B) to the total molar number of the aliphatic diamine monomer (C) B) is from 0.90 to 1.30.
delete delete The aromatic dicarboxylic acid monomer (A) according to claim 1, wherein the aromatic dicarboxylic acid monomer (A) is at least one member selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, Acid, 1,4-phenylene dioxyphenylenic acid, 1,3-phenylenedioxy-diacetic acid, diphenic acid, 4'4'-oxybis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid , Diphenylsulfone-4,4'-dicarboxylic acid, 4-4'-diphenylcarboxylic acid, and mixtures thereof.
The method according to claim 1, wherein the cyclic compound dicarboxylic acid monomer (B) is at least one selected from the group consisting of 2-cyclohexene, 1,4-dicarboxylic acid, cyclohexane-1,1-dicarboxylic acid, trans 1,2- Hexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, dimethylcyclohexane 1,4-dicarboxylate, and mixtures thereof Characterized by the polyamide resin.
The polyimide of claim 1, wherein the aliphatic diamine monomer (C) is linear or branched and is selected from the group consisting of 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, Diaminodiamine, 1,10-diamino-4,7-dioxo-undecane, 1,10-diamino-4,7-dioxo-5 methyldecane, and mixtures thereof. Polyamide resin.
The polyamide resin according to claim 1, wherein the polyamide resin further comprises a terminal sealing agent (D), and the terminal sealing agent is an aliphatic carboxylic acid or an aromatic carboxylic acid.
The method according to claim 7, wherein the aliphatic carboxylic acid endblocking agent is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, Wherein the aromatic carboxylic acid end-capping agent is selected from the group consisting of benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid And mixtures thereof. ≪ RTI ID = 0.0 > 11. < / RTI >