KR101469264B1 - Polyamide resin, a method for preparing the same, and an article comprising the same - Google Patents

Abstract

The present invention relates to a polyamide resin, a process for producing the same, and a product containing the same. The present invention provides a polyamide resin having high heat resistance, excellent moldability and melt processability, a method for producing the same, and a product containing the same.

Description

TECHNICAL FIELD The present invention relates to a polyamide resin, a method for producing the same, and a product containing the same.

The present invention relates to a polyamide resin, a method for producing the same, and articles containing the same. The present invention provides a polyamide resin having high heat resistance, excellent moldability and melt processability, a method for producing the same, and articles containing the same.

Nylon 66 and nylon 6 are best known as polyamide resins. These aliphatic polyamide resins are widely used for automobile parts, electric appliances, electronic products, and machine parts. However, aliphatic polyamide resins do not have sufficient thermal stability to be applied in fields requiring high heat resistance characteristics.

Aromatic polyamide resins have a higher melting temperature and higher heat resistance than aliphatic polyamide resins, but their processability has been limited due to such high melting temperatures.

Generally, in the case of high heat-resistant nylon, it has a semi-crystalline structure and can be used in various fields requiring a high heat resistance characteristic because the heat-resistant temperature is considerably higher than that of general nylon. However, in the case of conventional products, the glass transition temperature is 90-120 占 폚 and has a low glass transition temperature. Therefore, it is necessary to develop a polyamide resin having a high glass transition temperature while improving melt processability.

An object of the present invention is to provide a polyamide resin having high heat resistance, excellent moldability and melt processability.

Another object of the present invention is to provide a process for producing the polyamide resin.

It is still another object of the present invention to provide an article molded from the polyamide resin or the polyamide resin produced by the method.

The polyamide resin which is one aspect of the present invention is formed by the polymerization of (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine, and (C) an aliphatic cyclic diamine, wherein the aliphatic cyclic diamine (C) + (C) of 100 mol%, and the glass transition temperature of the polyamide resin may be 140 DEG C or higher.

Another aspect of the present invention is a method for producing a polyamide resin, which comprises polymerizing (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine, and (C) an aliphatic cyclic diamine, The diamine may be included in 15-35 mol% of 100 mol% of (B) + (C).

The molded article which is another aspect of the present invention may comprise the polyamide resin or the polyamide resin produced by the above-mentioned production method.

The present invention provides a polyamide resin having high heat resistance, excellent moldability and melt processability.

A polyamide resin which is one aspect of the present invention may be formed by polymerization of (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine, and (C) an aliphatic cyclic diamine.

In the above polymerization, the aliphatic cyclic diamine (C) may be contained in an amount of 15 to 35 mol% of 100 mol% of (B) + (C). If it is contained in an amount of less than 15 mol%, a Tg of 150 ° C or higher can not be obtained, or the melting temperature is excessively high. If it is contained in an amount exceeding 35 mol%, there may be a problem that the crystallization temperature is excessively high or does not have crystallinity. , Preferably 15-30 mol%, more preferably 15-25 mol%.

(B) The aliphatic linear diamines may be selected from one or more of aliphatic linear diamines having from 4 to 10 carbon atoms. For example, the aliphatic linear diamines may be 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10- However, it is not limited thereto. Preferably, it can be 1,6-hexanediamine or a mixture comprising it.

(B) The aliphatic linear diamine may be included in 65-85 mol% of 100 mol% of (B) + (C). Within this range, it is possible to have an effect of exhibiting a Tg characteristic of 150 ° C or higher. Preferably, it can be contained in an amount of 70-85 mol%.

The aliphatic cyclic diamine (C) may be a compound represented by the following formula (1), but is not limited thereto.

≪ Formula 1 >

(Wherein R 1 to R 22 are hydrogen, an alkyl group having 1-5 carbon atoms, an aryl group having 6-10 carbon atoms, or an amino group (-NH 2), n is an integer of 1 to 5, and at least one of R 1 to R 11 and R 12 Lt; RTI ID = 0.0 > R22 < / RTI >

Preferably, the aliphatic cyclic diamine (C) can be bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane or mixtures thereof.

(C) The aliphatic cyclic diamine may be contained in an amount of 15 to 35 mol% of 100 mol% of (B) + (C). , Preferably 15-30 mol%, more preferably 15-25 mol%.

(A) The aromatic dicarboxylic acid may be selected from one or more aromatic dicarboxylic acids having 8 to 20 carbon atoms. For example, the aromatic dicarboxylic acid may be terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, Phenylenic acid, 1,3-phenylene dioxydiacetic acid, diphenic acid, 4'4'-oxybis (benzoic acid), diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone- 4,4'-diphenylcarboxylic acid, or a mixture thereof. Preferably, it may be terephthalic acid, isophthalic acid or a mixture thereof. More preferably, it may be terephthalic acid, or a mixture of terephthalic acid and isophthalic acid.

(A2) isophthalic acid may be contained in a mixture of (A1) terephthalic acid and (A2) isophthalic acid in an amount of 0-30 mol% in 100 mol% of (A1) + (A2). Within the above range, the produced polyamide resin can secure crystallinity. Preferably from more than 0 to less than 30 mol%, more preferably from 1 to 30 mol%, and most preferably from 10 to 30 mol%.

(A1) terephthalic acid may be contained in 70 to 100 mol% of 100 mol% of (A1) + (A2) in the mixture of (A1) terephthalic acid and (A2) isophthalic acid. Within the above range, the produced polyamide resin can secure crystallinity. , Preferably 70 to less than 100 mol%, more preferably 70 to 99 mol%, and most preferably 70 to 90 mol%.

The sum of (A2) isophthalic acid and (C) aliphatic cyclic diamine can be included in 7.5-32.5 mol% of 100 mol% of (A1) + (A2) + (B) + (C). Within the above range, the produced polyamide resin can secure a high crystallinity and a high glass transition temperature. And preferably 15-30 mol%.

In the polyamide resin, aliphatic dicarboxylic acid (D) other than (A) an aromatic dicarboxylic acid may be further polymerized.

(D) The aliphatic dicarboxylic acid may be an aliphatic dicarboxylic acid having 4 to 15 carbon atoms. Specific examples thereof include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, undecanedioic acid, dodecanedioic acid, glutamic acid, traumatic acid, muconic acid and the like, But is not limited thereto.

(D) The aliphatic dicarboxylic acid may be contained in an amount of 1-20 mol% of 100 mol% of (A) + (D). Within the above range, the polyimide resin can secure high heat resistance and excellent moldability. Preferably, it may be contained in an amount of 5-20 mol%.

In one embodiment, the polyamide resin is a mixture of (A) 65-85 mol% of (B) an aliphatic linear diamine and (C) 15-35 mol% of an aliphatic cyclic diamine in 100 mol% of aromatic dicarboxylic acid, 100 mol% of (B) Can be formed by polymerization.

In another embodiment, the polyamide resin is a polyamide resin which comprises (A1) terephthalic acid in an amount of 70 to 100 mol% and (A2) isophthalic acid in an amount of more than 0 and less than 30 mol%, (B) + (C) in 100 mol% of (A1) + (B) 65-85 mol% of an aliphatic linear diamine and (C) 15-35 mol% of an aliphatic cyclic diamine.

In another embodiment, the polyamide resin is a copolymer of (A1) terephthalic acid in an amount of 70 to 90 mol%, (A2) 10 to 30 mol% of isophthalic acid and 100 mol% of (B) + (C) in 100 mol% of (A1) + B) from 65 to 85 mol% of an aliphatic linear diamine and (C) from 15 to 35 mol% of an aliphatic cyclic diamine.

In another embodiment, the polyamide resin comprises 80 mol% or less of (A) aromatic dicarboxylic acid and less than 100 mol% of (D) 100 mol% of (D) an aliphatic dicarboxylic acid; (B) 65-85 mol% of (B) an aliphatic linear diamine and (C) 15-35 mol% of an aliphatic cyclic diamine in 100 mol% of (B) + (C).

In another embodiment, the polyamide resin comprises 80-99 mol% of (A) aromatic dicarboxylic acid and (D) 1-20 mol% of aliphatic dicarboxylic acid, (B) + 100 mol% of (D) 100 mol% of (A) + (B) 65-85 mol% of an aliphatic linear diamine and (C) 15-35 mol% of an aliphatic cyclic diamine.

The polyamide resin may be encapsulated with an end capping agent whose terminal group is selected from aliphatic carboxylic acids or aromatic carboxylic acids.

The endblocking agent may be 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, pivalic acid, ? -naphthalenecarboxylic acid,? -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and the like can be used, but are not limited thereto.

The terminal endblock can be contained in an amount of 0 to 5 mol%, preferably 0.01 to 3 mol% based on 100 mol% of (A) + (B) + (C) or (A1) + have.

The glass transition temperature (Tg) of the polyamide resin may be 140 ° C or higher. Within the above range, it is possible to provide high heat resistance and fire resistance. Preferably, the glass transition temperature may be 150 ° C or higher, more preferably 150 to 170 ° C.

The polyamide resin may be a resin in a semi-crystalline form.

The ratio of the melting temperature to the glass transition temperature of the polyamide resin can be from 1.9 to 2.3. Within this range, the effect of having a Tg characteristic at a high temperature while having a semi-crystalline structure can be obtained.

The melting temperature of the polyamide resin may be 300-330 占 폚. Within this range, the polyamide resin may have good processability.

The polyamide resin may have an intrinsic viscosity [?] Of 0.7-4.0 dL / g, preferably 0.7-1.0 dL / g, measured by a Ubbelodhde viscometer at 25 ° C and 97% sulfuric acid solution.

Another aspect of the present invention is a method for producing a polyamide resin, which comprises polymerizing (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine and (C) an aliphatic cyclic diamine, (B) + (C) of 15 mol% to 35 mol% of 100 mol%.

Details of the aromatic dicarboxylic acid, the aliphatic linear diamine and the aliphatic cyclic diamine are as described above.

The copolymerization may be carried out by a conventional copolymerization method.

The polymerization temperature may be 80-300 ℃, preferably 80-280 ℃, the polymerization pressure may be the 10-40kgf / cm ^2.

In one embodiment, a mixture of (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine and (C) an aliphatic cyclic diamine, a catalyst and water are charged into the reactor and stirred at 80-150 ° C for 0.5-2 hours. The temperature is maintained at 200 to 280 ° C for 2 to 4 hours, the pressure is maintained at 20 to 40 kgf / cm ² , the pressure is reduced to 10 to 20 kgf / cm ^2, and the reaction is performed for 1 to 3 hours. The obtained polyamide is solid-state polymerized at a temperature between the glass transition temperature (Tg) and the melting temperature (Tm), for example, 150-360 ° C for 10-30 hours in a vacuum to obtain a final reaction product have.

A catalyst may be used for the polymerization reaction. Preferably, a phosphorous-based catalyst may be used. Specifically, phosphoric acid, phosphorous acid, hypophosphorous acid or a salt or derivative thereof may be used. As a more specific example, phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphate, sodium hypophosphonate and the like can be used.

The catalyst is preferably used in an amount of 0-3.0 wt%, preferably 0-1.0 wt%, more preferably 0.001-0.5 wt% of the total monomer weight.

In the production of the polyamide resin, an end sealant may be used when the mixture of (A) + (B) + (C) is added. The viscosity of the synthesized polyamide copolymer resin can be controlled by controlling the amount of the end sealant used.

The end-capping agent may be an aliphatic carboxylic acid or an aromatic carboxylic acid. In an embodiment, the end-capping 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, pivalic acid, , Toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid, and methylnaphthalenecarboxylic acid. These may be used alone or in combination of two or more.

The terminal endblock can be contained in an amount of 0 to 5 mol%, preferably 0.01 to 3 mol% based on 100 mol% of (A) + (B) + (C) or (A1) + have.

An article which is another aspect of the present invention can be molded with the polyamide resin, or a polyamide resin produced by the production method. For example, it can be used for automotive UTH applications requiring a high glass transition temperature, but is not limited thereto. The article forming method may be any known method.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example  One

A mixture of 0.70 mol (116.30 g) terephthalic acid, 0.47 mol (54.46 g) 1,6-hexamethylenediamine, 0.25 mol (53.08 g) bis (4- aminocyclohexyl) methane, 0.042 mol 0.1 wt% of nate (0.23 g) and water (76 mL) were charged in a 1-liter autoclave and filled with nitrogen. Stirred at 130 ℃ 60 minutes and reacted for then was warmed for 2 hours at 250 ℃ while maintaining 25kgf / cm ² during the reaction for 3 hours at the same temperature under reduced pressure to 15kgf / cm ² 1 hours polyamide pre-copolymer . The polyamide prepolymer was subjected to solid phase polymerization at 230 DEG C for 8 hours to obtain a polyamide resin.

Example  2

In Example 1, 0.53 mol (87.2 g) of terephthalic acid, 0.18 mol (29.07 g) of isophthalic acid, 0.61 mol (70.53 g) of 1,6-hexamethylenediamine and 0.11 mol ), 0.028 mol (1.68 g) of acetic acid, 0.1 wt% (0.21 g) of sodium hyphaphosphinate, and 70 mL of water were used.

Example  3

(87.22 g) of terephthalic acid, 0.18 mol (29.07 g) of isophthalic acid, 0.54 mol (62.84 g) of 1,6-hexamethylenediamine, 0.18 g of bis (4-amino-3-methylcyclohexyl) except that 0.042 mol (2.52 g) of acetic acid, 0.1 wt% (0.22 g) of sodium hyphaphosphinate, and 71 mL of water were used in place of the polyimide resin (42.97 g).

Example  4

(98.85 g) of terephthalic acid, 0.11 mol (15.35 g) of adipic acid, 0.54 mol (62.84 g) of 1,6-hexamethylenediamine and 0.18 mol (37.92 g), 0.042 mol (2.52 g) of acetic acid, 0.1 wt% (0.22 g) of sodium hyphaphosphonate and 77 mL of water.

Example  5

In Example 1, 0.63 mol (104.67 g) of terephthalic acid, 0.07 mol (10.23 g) of adipic acid, 0.49 mol (57.51 g) of 1,6-hexamethylenediamine, 0.21 mol g), 0.014 mol (0.84 g) of acetic acid, 0.1 wt% (0.22 g) of sodium hyphaphosphonate and 73 mL of water.

Comparative Example  One

0.70 mol (116.30 g) of terephthalic acid, 0.65 mol (75.41 g) of 1,6-hexamethylenediamine, 0.072 mol (1.517 g) of bis (4-aminocyclohexyl) methane, 0.042 mol 0.1 wt% of nate (0.21 g) and water (70 mL) were charged in a 1 liter autoclave and filled with nitrogen. The mixture was stirred at 130 ° 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 a polyamide prepolymer . The polyamide prepolymer was subjected to solid phase polymerization at 230 DEG C for 8 hours to obtain a polyamide resin.

Comparative Example  2

In Comparative Example 1, 0.7 mol (116.30 g) of terephthalic acid, 0.32 mol (37.70 g) of 1,6-hexamethylenediamine, 0.40 mol (83.41 g) of bis (4-aminocyclohexyl) ), 0.1 wt% (0.24 g) of sodium hyphaphosphonate, and 80 mL of water were used as the polyamide resin.

Experimental Example

The properties of the polyamide resins prepared in the above Examples and Comparative Examples were evaluated in the following Table 1, and the results are shown in Table 1.

Property evaluation method

(1) Melting temperature, crystallization temperature and glass transition temperature: The polyamide resin obtained after the solid phase polymerization in Examples and Comparative Examples was measured using a different scanning calorimeter (DSC). The DSC was measured under the conditions of a nitrogen atmosphere, a temperature range of 30 ° C to 400 ° C, a temperature raising rate of 10 ° C / min, and a cooling rate of 10 ° C / min. At this time, the crystallization temperature was the maximum point of the exothermic peak during cooling, and the melting temperature was determined as the maximum point of the endothermic peak at the second temperature rise. The glass transition temperature was determined as the temperature measured at the second temperature rise.

(2) Intrinsic viscosity (dL / g): The polyamide resin was dissolved in a 97% sulfuric acid solution and then measured using a Ubbelodhde viscometer at 25 ° C.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 (B) (mol%) * 65.3 84.7 75 75 70 90 44.5 (C) (mol%) * 34.7 15.3 25 25 30 10 55.5 Melting temperature
(° C) 328 316 305 324 325 355 - Crystallization temperature
(° C) 285 267 260 285 284 325 - Glass transition temperature
(° C) 162 153 160 150 159 146 175 Intrinsic viscosity
(dL / g) 1.0 0.9 0.88 0.77 0.98 0.6 0.9

(B) or (C) in 100 mol% of (B) + (C)

As shown in Table 1, the polyamide resin according to the present invention has a high glass transition temperature, a high melting temperature, and has heat resistance and excellent moldability. On the other hand, the polyamide resin polymerized with less than 15 mol% or more than 35 mol% of (C) in 100 mol% of (B) + (C) has no crystallinity or a low glass transition temperature and is excellent in heat resistance, The processability can not be secured (see Comparative Example 1-2).

Claims (17)

A polyamide resin formed by polymerization of (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine and (C) an aliphatic cyclic diamine,
(C) the aliphatic cyclic diamine is contained in 15 mol% to 35 mol% of 100 mol% of (B) + (C), and the polyamide resin has a glass transition temperature of 140 ° C or higher. The polyamide resin according to claim 1, wherein the polyamide resin is a resin in a semi-crystalline form. The polyamide resin according to claim 1, wherein the polyamide resin has a glass transition temperature of 150 ° C or higher. The polyamide resin according to claim 1, wherein the ratio of the melting temperature to the glass transition temperature of the polyamide resin is 1.9 to 2.3. The polyamide resin according to claim 1, wherein the aliphatic linear diamine (B) is at least one selected from aliphatic linear diamines having 4 to 10 carbon atoms. The polyamide resin according to claim 1, wherein the aliphatic cyclic diamine (C) is bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane or a mixture thereof. The polyamide resin according to claim 1, wherein the (A) aromatic dicarboxylic acid comprises (A1) a mixture of terephthalic acid and (A2) isophthalic acid. 8. The polyamide resin according to claim 7, wherein the isophthalic acid (A2) in the mixture is contained in an amount of more than 0 and not more than 30 mol% in 100 mol% of (A1) + (A2). The positive resist composition according to claim 7, wherein the sum (A2) + (C) of (A2) and (C) is 7.5-32.5 mol% in 100 mol% of (A1) + By weight. 8. The polyamide resin composition according to claim 7, wherein the polyamide resin comprises (A1) terephthalic acid in an amount of 70 to 100 mol% and (A2) isophthalic acid in an amount of more than 0 and less than 30 mol%, (B) (B) 65-85 mol% of an aliphatic linear diamine and (C) 15-35 mol% of an aliphatic cyclic diamine in 100 mol% of the polyamide resin. The polyamide resin according to claim 1, wherein the polyamide resin is further polymerized with an aliphatic dicarboxylic acid. 2. The polyamide resin according to claim 1, wherein the polyamide resin is encapsulated with a terminal end-capping agent selected from an aliphatic carboxylic acid or an aromatic carboxylic acid. 13. The composition of claim 12, wherein the 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, pivalic acid, Wherein the polyamide resin is at least one selected from the group consisting of an acid, benzoic acid, toluic acid,? -Naphthalenecarboxylic acid,? -Naphthalenecarboxylic acid and methylnaphthalenecarboxylic acid. (A) an aromatic dicarboxylic acid, (B) an aliphatic linear diamine, and (C) an aliphatic cyclic diamine,
Wherein the aliphatic cyclic diamine (C) is contained in 15 mol% to 35 mol% of 100 mol% of (B) + (C) in the polymerization, and the glass transition temperature of the polyamide resin is 140 ° C. or higher . 15. The method according to claim 14, wherein the (A) aromatic dicarboxylic acid comprises (A1) a mixture of terephthalic acid and (A2) isophthalic acid. [15] The polyamide resin composition according to claim 15, wherein the polyamide resin comprises (A1) terephthalic acid in an amount of 70 to 100 mol% and (A2) isophthalic acid in an amount of more than 0 and less than 30 mol%, (B) (B) 65 to 85 mol% of an aliphatic linear diamine and (C) 15 to 35 mol% of an aliphatic cyclic diamine in 100 mol% of the polyamide resin. An article formed from the polyamide resin of any one of claims 1 to 13 or the polyamide resin produced by the method of any one of claims 14 to 16.