KR101630453B1 - Novel amide compound and crystalline polymer resin composition comprising the same - Google Patents

Abstract

The present invention relates to a novel amide compound, a crystalline polymer resin composition containing the same, and a product made from a crystalline polymer resin containing such a? -Form crystal. The novel amide compound of the present invention can increase the content of the? -Form crystal when used as a nucleating agent and improve the processability.

Amide compounds, nucleating agents, crystalline polymers, polypropylene, beta crystal structure

Description

TECHNICAL FIELD [0001] The present invention relates to a novel amide compound, and a crystalline polymer resin composition containing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel amide compound and a crystalline polymer resin composition containing the same. More specifically, the present invention relates to a novel amide compound which can be used as a nucleant which can improve the processability by increasing the rate of crystallization by including an aromatic terminal group at both ends of the main chain and a crystalline polymer resin composition containing the same .

The crystalline polymer resin such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and polyamide has a low molding cycle performance due to delayed crystallization after melt molding, There is a problem that shrinkage or large crystals are generated by the progress of crystallization and the strength is lowered. In order to solve such a problem, a method of increasing the crystallization temperature of the polymer resin by adding a crystal nucleating agent or the like to promote the generation of fine crystals has been used.

For example, polypropylene has relatively good strength and excellent mechanical properties due to the molecular structure and crystallinity of the polymer chains. Particularly, crystalline polypropylene has been used for various purposes because of its excellent hardness, rigidity, heat resistance and surface gloss. Specifically, crystalline polypropylene is used in various industrial products such as automobile interior and exterior materials requiring high rigidity.

It is known that crystalline polypropylene can be present in the α, β, γ and δ crystalline forms and the smectic crystalline forms formed upon quenching the molten polypropylene. The β-form crystal (hereinafter referred to as "β-form") has a low melting point and a low density as compared with the α-form, and crystal states and debris states thereof are different. Polypropylene containing a high content of beta form can be prepared by melting a polypropylene and then adding a suitable nucleating agent to induce the formation of beta form when cooled.

Examples of such nucleating agents are gamma-quinacridone, diacid and calcium stearate (U.S. Patent No. 5,231,126), diamide (U.S. Patent No. 6,235,823), and the like. The gamma -quinacridone nucleating agent is colored after the preparation of the resin composition, and the beta nucleating agent and the diamide nucleating agent using the diacid and the calcium stearate vary in their ability to form? Crystals depending on the type of resin, .

It is an object of the present invention to provide a novel amide compound which can improve the crystallization rate, reactivity and yield when it is used as a nucleating agent.

Another object of the present invention is to provide a crystalline polymer resin composition containing the novel amide compound of the present invention as a? -Coupling agent.

One aspect of the present invention for achieving the above object is to an amide compound having a structure represented by the following general formula (1).

Wherein X is a straight chain or branched alkyl group having 1 to 20 carbon atoms or 1 group selected from the following formula (2), A ₁ and A ₂ are the same or different and are selected from the group consisting of an aromatic group Device.

Wherein, D represents a single bond or, O, S, CO, SO, SO _2, NH _2, CONH, alkylene group, substituted C 1 -C 20 linear or branched alkyl group, a substituted or unsubstituted C2 to 20 of Or an unsubstituted alkoxysilyl group having 2 to 20 carbon atoms, and each R ₁ is independently a proton, a C 1 to C 5 alkyl group or a halogen group).

Another aspect of the present invention relates to a crystalline polymer resin composition comprising a crystalline polymer resin and a β-nucleating agent, wherein the β-nucleating agent is an amide compound of the above formula (1).

Another aspect of the present invention relates to a product comprising the crystalline polymer composition.

When the novel amide compound of the present invention is used as a nucleating agent, the size of the crystal is small and the melting point is low as compared with the conventional nucleating agent, so that a β-form crystal of 50% or more can be formed even if a small amount is added to the propylene homopolymer. In addition, it can be pelletized with an extruder at a low temperature, thereby improving workability.

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

Unless otherwise specified herein, " substituted " refers to a substituent selected from the group consisting of a halogen atom, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C6 to C30 aryl group, and a C6 to C30 aryloxy group It means to be struck by.

Unless otherwise specified in the present specification, the terms "alkyl group", "alkylene group" and "alkoxysilyl group" mean a C1 to C20 alkyl group, a C2 to C20 alkylene group, and a C2 to C20 alkoxylene group, respectively.

At least one CH present in the aromatic ring may be substituted with a heteroatom selected from the group consisting of N, O, S and P, unless otherwise specified herein.

The novel amide compound of the present invention is an amide compound having a bulky structure at both ends of the molecule. Since the nucleation rate of the amide compound is faster than that of the aliphatic group, The size is smaller. Further, the novel amide compound of the present invention has a melting point as low as 100 DEG C as compared with the conventional amide nucleating agent due to its structural specificity. This feature can be the most important parameter of nucleating agent. It is dissolved in crystalline polymer resin at a low temperature so that β-form crystals can be formed in a small amount. In addition, it has an improved mixing property with the crystalline polymer resin and a wide molding and processing temperature range in molding and processing.

The novel amide compound of one embodiment of the present invention can be represented by the following general formula (1).

[Chemical Formula 1]

Wherein X is a straight chain or branched alkyl group having 1 to 20 carbon atoms or 1 group selected from the following formula (2), A ₁ and A ₂ are the same or different and are selected from the group consisting of an aromatic group Device.

(2)

Wherein, D represents a single bond or, O, S, CO, SO, SO _2, NH _2, CONH, alkylene group, substituted C 1 -C 20 linear or branched alkyl group, a substituted or unsubstituted C2 to 20 of Or an unsubstituted alkoxysilyl group having 2 to 20 carbon atoms, and each R1 is independently a proton, a C1-C5 alkyl group or a halogen group.

(3)

In the compound of Formula 1, X may be a linking group selected from the group of Chemical Scheme 4 below.

In the above formula, R ₁ is each independently a proton, a C1 to C5 alkyl group or a halogen group.

Examples of the compound of formula (1) include, but are not limited to, compounds having the structures of the following formulas (5) to (7).

상기 식에서, R₁은 각각 독립적으로 C1~C5의 알킬기 또는 할로겐기이고, R₂는 단일결합이거나, O, S, CO, SO, SO₂, NH₂, CONH, 탄소수 1 내지 20의 직쇄 또는 분지상 알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 알킬렌기, 치환 또는 비치환된 탄소수 2 내지 20의 알콕실렌기임.

Wherein R ₁ is independently a C1 to C5 alkyl group or a halogen group and R ₂ is a single bond or a straight chain or branched chain having 1 to 20 carbon atoms such as O, S, CO, SO, SO ₂ , NH ₂ , A substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkoxysilylene group having 2 to 20 carbon atoms.

delete

The novel amide compound of the present invention can be prepared basically by a conventional amidation reaction. The usual amidation reaction can be carried out by an amidation reaction using a carboxylic acid conversion reaction product (acid chloride, acid anhydride, esterified product) using a aminolysis reaction in addition to reacting an amine with a carboxylic acid, Either one may be a representative example. Since the reaction consists of a solid-solid reaction and a solid-liquid reaction, the reaction can be carried out in an inert solvent.

(i) reacting the dicarboxylic acid in an inert solvent with the monoamine at about 60 to about 200 DEG C for about 2 to about 8 hours; Monoamines are generally used in about 2 to 10 equivalents per equivalent of dicarboxylic acid. In this process it is preferred to use an activator to promote the reaction. Active agents that can be used here include phosphorus pentoxide, polyphosphoric acid, phosphorus pentoxide - methanesulfonic acid, phosphorous ester (eg triphenylphosphite) -pyridine, phosphorus ester metal salt (eg lithium chloride), triphenylphosphine- Ethane and the like. Usually about 1 mole of active agent per mole of dicarboxylic acid is used.

(ii) The dicarboxylic acid is usually converted to the acid chloride of the dicarboxylic acid by treatment with thionyl-chloride. These reactions take place in the nucleophilic acylation reaction pathway, where the dicarboxylic acid reacts first with a highly reactive chlorosulfite intermediate. The acid chloride of the dicarboxylic acid in an inert solvent is reacted with the monoamine at about 20 to 150 DEG C for about 1 to 10 hours. Acid chlorides of dicarboxylic acids react rapidly with ammonia and amines to produce amides with good yields. The monoamine is usually used in an amount of 1 to 4 equivalents per equivalent of the dicarboxylic acid acid chloride.

(iii) The ester reacts with ammonia or an amine to form an amide. The diester of the dicarboxylic acid, in particular the di (C1-3) alkyl ester, in an inert solvent is reacted with the monoamine in the presence of a catalyst at about 0 to 150 DEG C for about 3 to 10 hours. Monoamines are usually used in about 1 to 10 equivalents per equivalent of dicarboxylic acid diester. The catalyst may be an acidic or basic catalyst that is compatible with the ester-amide interchange reaction, and preferred is a basic catalyst. However, the above reaction is not often used because it has a lower yield than the direct reaction between dicarboxylic acid and amine and the reaction with acid chloride of dicarboxylic acid.

(iv) The most common method for preparing acid anhydrides of dicarboxylic acids is the nucleophilic acylation reaction of acid chlorides and carboxy anions. The amide reaction using the acid anhydride of the dicarboxylic acid is the same as the reaction of the acid chloride of the dicarboxylic acid. Although the acid anhydride reacts more slowly than the acid chloride, the reaction forms of the two functional groups proceed in the same way.

Inert solvents which can be used in the above method include benzene, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, acetonitrile, and N-methylpyrrolidone. N, N-dimethylformamide, N, N-dimethylacetamide and the like are preferable.

The dicarboxylic acid used in the above process may be an aliphatic, alicyclic or aromatic dicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid include C3-20, preferably C3-14 saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, glutaric acid , 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18- And discrete.

The alicyclic dicarboxylic acids include C6-30, preferably C8-12 saturated or unsaturated dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , 1,4-cyclohexane diacetic acid, and the like.

Examples of the aromatic dicarboxylic acids include C8-30, preferably C8-22 aromatic dicarboxylic acids such as p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-t-butylphthalic acid, isophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenic acid, 3 , 3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 3 , 3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 3,3'- - thiodibenzoic acid, 4,4 '- (p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyldibenzoic acid, 4,4'- Dodecylbenzoic acid, dithiosalicylic acid, and the like.

The monoamines used in the above methods (i), (ii), (iii) and (iv) are R ¹ -NH ₂ Naphthyl, anthracene and heteroaromatic cyclic compounds corresponding to < RTI ID = 0.0 > For example, 1-naphthylamine, 2-naphthylamine, 1-anthraceneamine, 2-anthraceneamine, 5-anthraceneamine, adenine, histamine, pyrrole, imidazole, indole, benzimidazole, benzotriazole, quinoline, quinoline Pyridine, thiophene-2-methylamine, thiazine, oxazine, Namine A and the like. Particularly preferred is 1-naphthylamine or 2-naphthylamine.

The novel amide compounds prepared by the above methods can be isolated and purified by conventional methods such as chromatography, reprecipitation, recrystallization, fractional crystallization and the like.

In the process, the diamine is an alicyclic, heterocyclic or aromatic diamine. Therefore, it is preferable that X is a residue formed by removing two amino groups of any one of the following alicyclic, heterocyclic, and aromatic diamines.

Examples of the alicyclic diamine include C4-28, preferably C6-15 alicyclic diamines such as 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexyl, 4 , 4'-diamino-3,3'-dimethyldicyclohexyl, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and additionally isophoronediamine, mentenediamine and the like.

Examples of the heterocyclic diamines include 5- or 6-membered cyclic diamines having 4 to 14 carbon atoms containing 1 or 2 nitrogen atoms or sulfur atoms in the ring structure such as 2,3-diaminopyridine, 2,6-diaminopyridine, 3 , 4-diaminopyridine, o-tolylidine sulfone, and the like.

Examples of the aromatic diamine include aromatic diamines having 6 to 28, preferably 6 to 15 carbon atoms, such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4- Diaminotoluene, 3,4-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5- Dimethyl-o-phenylenediamine, 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,7- , 10-diaminophenthrene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy- '-Diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-methylenedio- Toluene, 4,4'-methylene di-2,6-xylidine, 4,4'-methylene di-2,6-diethylaniline, 4,4'-diamino-2,2 -Dimethylbibenzyl, 4,4'-diaminostilbene, 3,4'-diamino-2,2-diphenylpropane, 4,4'-diamino-2,2-diphenylpropane, '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 3,3'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, 2,7 Aminophenyl aniline, 1,3-bis (4-aminophenylpropyl) benzene, 1,4-bis (4-aminophenyl) (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone and 9,9-bis (4-aminophenyl) fluorene.

The novel amide compound of the present invention can be added to the crystalline polymer resin at any stage during the production of the crystalline polymer resin as a? -Nucleating agent, that is, during the polymerization reaction or after the production of the polymer.

Another aspect of the present invention relates to a crystalline high molecular weight resin composition comprising the amide compound as a nucleating agent.

The crystalline polymer resin composition of the present invention is a crystalline polymer resin composition comprising a crystalline polymer resin and a β-nucleating agent, wherein the β-nucleating agent comprises an amide compound represented by the following formula (1).

[Chemical Formula 1]

Wherein X is a straight chain or branched alkyl group having 1 to 20 carbon atoms or 1 group selected from the following formula (2), A ₁ and A ₂ are the same or different and are selected from the group consisting of an aromatic group Device.

(2)

Wherein A ¹ is a single bond or a straight or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, -O-, -S-, -CO-, -SO ₂ -, -NH ₂ -, -CONH- A substituted or unsubstituted alkoxysilyl group having 2 to 20 carbon atoms, and each R ₁ is independently a proton, a C 1 to C 5 alkyl group, or a halogen group.

(3)

As the crystalline polymer resin in the present invention, there may be mentioned, for example, low-density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polybutene-1, poly-3-methylbutyl, Olefin polymers; Thermoplastic linear polyesters such as polyethylene terephthalate polybutylene terephthalate and polyhexamethylene terephthalate; Polyphenylene sulfide, and straight chain polyamides such as polycaprolactone and polyhexamethylene adipamide. In particular, the present invention relates to crystalline < RTI ID = 0.0 > a-olefin < / RTI > Ethylene / propylene copolymers, and mixtures of these propylene polymers with other? -Olefin polymers.

The term " polypropylene resin " as used herein means a polymer composed mainly of propylene as well as a polypropylene homopolymer, especially a polymer consisting of at least 50 wt%, preferably at least 80 wt% propylene. Examples of the latter polymer include a propylene-ethylene random copolymer, a propylene-ethylene block copolymer, a polymer such as a polypropylene resin and a small amount of a thermoplastic resin such as high density polyethylene, polybutene-1 and poly- ≪ / RTI >

The amount of the β-nucleating agent added is not particularly limited as long as a desired effect can be obtained. It is generally used in an amount effective to increase the content of the? -Form crystal. In particular, about 0.0001 to 5 parts by weight, preferably about 0.001 to 1 part by weight of? -Nucleating agent based on 100 parts by weight of a crystalline polymer resin, especially a polypropylene resin, can be used. When the amount of the? -nucleating agent used is less than 0.0001 part by weight, formation of the? -form crystal can not be sufficient. On the other hand, if the amount of the? -nucleating agent is more than 5 parts by weight, no corresponding effect can be obtained.

The β-nucleating agent of the present invention enables the crystalline polypropylene resin to be transferred into β-crystal form even with a very small amount of addition, and a molded product having β-type crystal content as described above can be obtained under suitable molding conditions. According to the crystalline polymer resin composition of the present invention, a molded article having a β-form content of about 5 to 98%, specifically about 20 to 90%, can be obtained under ordinary molding conditions.

In the crystalline polymer resin composition of the present invention, the method of adding each component is not particularly limited, and examples of a commonly used method include a method of dry-blending the crystalline polymer resin powder or pellet with the additive powder, A master batch containing each component at a high concentration is prepared and added to the crystalline polymer resin

Method or the like can be used. The β-nucleating agent of formula (1) may be added to the polypropylene resin at any stage, ie during the polymerization reaction or after the polymer is prepared.

Other additives may be added to the resin composition of the present invention in a concentration range that does not adversely affect the advantageous effects of the present invention. These other additives may be selected from the group consisting of stabilizers, antioxidants, antimicrobials, ultraviolet absorbers, heat stabilizers, light stabilizers, neutralizers, antistatic agents, block inhibitors, heavy metal deactivators, flame retardants, lubricants, peroxides, hydrotalcites, , Processing aids, additional nucleating agents, reinforcing agents, plasticizers, and the like, and mixtures thereof. The crystalline polymer resin composition of the present invention may contain, if necessary, an organic phosphorus-based antioxidant such as a phenolic antioxidant, an organic phosphite or phosphonite, a thioether-based antioxidant, an ultraviolet light- A light stabilizer can be added to further improve the oxidation stability and the light stability. In particular, the phenol-based antioxidant and / or the organic phosphorus-based antioxidant can be used in combination to prevent under-coloration and mechanical properties at the time of heat processing.

When the resin composition of the present invention is used, the ratio of? Type to? Type in the final product can be controlled as desired by suitable solidification conditions. By appropriately selecting the cooling conditions under the above-described molding conditions, the? -Type to? -Type ratio can be controlled.

The crystalline polymer resin composition, particularly the crystalline polypropylene resin composition, according to the present invention can be advantageously used for producing articles of various shapes. For example, the crystalline polymer resin composition of the present invention can be applied to a wide range of applications such as automobile devices (e.g., bumpers, instrument panels, batters, lining, automobile lights, door panels, windows, (Such as showers, bath seats, covers and washbasins), personal hygiene products, optical and industrial films, industrial and household products, Pipes, large-size packaging materials, food packaging materials, and various kinds of household products.

Another aspect of the present invention relates to a product comprising the crystalline polymer resin composition of the present invention, which is preferably produced by injection molding, extrusion molding, compression molding, blow molding, and other molding methods using a conventional molding machine Molded product. The preferred molding conditions can be selected according to the molding method selected, the molding material and the like.

The molded product of the present invention containing much more beta -form crystals than before can be easily obtained by molding the crystalline polymer resin composition of the present invention produced using the above mixing method under the above molding conditions. The molded product of the present invention is excellent in processability and mechanical characteristics and can be manufactured in various forms such as a package, a sheet, and a film.

Hereinafter, the present invention will be described in more detail with reference to examples, but these are for the purpose of illustration only and are not intended to limit the present invention.

[Example]

 The? -Form content of the polypropylene pellets obtained in each of the examples and comparative examples was measured by the following method.

In order to measure the content of β-form using an X-ray diffraction analyzer (XRD), a sample was fixed to a goniometer of XRD (D8 Discover, Bruker AXS) in chip or plate form (about 5 mm × 5 mm) A line is irradiated to obtain the 2D pattern of Fig. The obtained 2D pattern is converted into a 1D pattern to store data in the range of 2 degrees to 5 degrees to 30 degrees. (Fig. 1). The stored data includes peaks of? And? -Type crystals, ) The beta -type content (area%) is calculated from the intensity of peaks corresponding to alpha ₁ (110), beta ₁ (300), alpha ₂ (040) and alpha ₃ (130) using the following equation :

-type content (%) = 100 x I _{beta 1} / [I _{beta 1} + (I alpha ₁ + I alpha ₂ + I alpha ₃ )]

I _{alpha 1} , I _{alpha 2} and I _{alpha 3} are the intensities of the alpha -type peaks (110), (040) and (130), and I _{beta 1} is the intensity of the beta -type peak (300).

 In addition, the content of β-form obtained by X-ray diffractometer (XRD) can be verified and evaluated by differential scanning calorimetry (DSC). A finely cut sample (5 to 10 mg) is fixed in a sample holder of a differential scanning calorimeter (DSC) and measured under a nitrogen gas atmosphere. The temperature is raised from room temperature to 200 占 폚 at a rate of 10 占 폚 / min, held for 5 minutes, and then cooled at the same rate. The α- and β-form crystals thus recorded have melting points at different temperature ranges. (Content% of area) is calculated from the peak area of the? -Form crystal and the? -Form crystal formed on the DSC temperature recorder using the following equation:

beta type content (%) = 100 x A _beta / (A _alpha + A _beta )

In the above formula, A _? Is a peak area of? Type, and A _? Is a peak area of? Type.

Synthetic example  One

 (0.03 mol) of 2,6-naphthalenedicarboxylic acid was added to a 4-neck reactor (2 L) equipped with a stirrer, a thermometer, a condenser and a gas inlet, and 1-naphthyl N, N'-dimethylformamide (N, N'-dimethylformamide), 9.45 g (0.066 mol) of 1-naphthylamine, 20.48 g (0.066 mol) of triphenyl phosphate, 23.7 g N'-dimethylformamide) was charged, and the reaction was carried out under nitrogen gas atmosphere at 110 DEG C for 3 hours with stirring. After completion of the reaction, the mixture is cooled to 1 캜 / min and crystallization is carried out until the temperature reaches 30 캜. When the crystallization is complete, the mixture is recovered by filtration using a 0.8 mu m membrane filter. In the recovery process, the filtrate is reused for further reaction. The amount of filtrate is about 84 parts by weight based on 100 parts by weight of the total reactants. After filtration, the recovered reaction mixture is poured into 200 ml of isopropyl alcohol / water = 1: 1, reprecipitated and washed. After the mixture is stirred for 2 hours or more, the pH of the precipitate is measured. When the pH is in the range of 6 to 7, stirring is completed. When the washing process is completed, the mixture is recovered by filtration using a 0.8 mu m membrane filter. In the recovery process, the filtrate is reused for subsequent washing reactions. The filtrate contains unreacted amine (1-naphthylamine), activator (triphenylphosphite, pyridine) and organic solvents such as N, N'-dimethylformamide and isopropyl alcohol. The material contained in the supernatant is recovered using a thin film evaporator or a distillation column. The recovered solvent is recovered in an amount of 98 parts by weight or more based on 100 parts by weight of the initial charge. After the washing reaction, the recovered reaction mixture was dried under reduced pressure at 110 ° C to obtain 12.04 g of N, N'-dinaphthyl-2,6-naphthalenedicarboxamide (Yield: 86%). This compound was a gray powder having a melting point of 285.4 DEG C and a molecular weight of 466.53 g / mol.

(FIG. 3), IR (FIG. 4), DSC (FIG. 5), Melting Point Meter (FIGS. 6A to 6C), TGA Mass spectrometry (MALDI-ToF MS) (FIG. 8). The results are shown in FIGS. 3 to 8. FIG.

      The conditions for NMR measurement are as follows:

5 mg of the sample was dissolved in 0.5 ml of TFA, diluted with CDCl ₃ ,

Using an ECX 400 model, ¹ H-NMR was performed under the condition of a scan number of 100

     Analyze.

     The conditions for IR measurement are as follows:

     Bruker IFS 88 is used to analyze the sample itself by ATR (Attenuated Total Reflection) method.

     The conditions for DSC measurement are as follows:

     Sample: 2.2 mg

     Starting temperature: 40.0 캜, Stopping temperature: 400.0 캜

     Heatign rate: 10.0 DEG C / min.

     The conditions of the Melt Point Meter are as follows:

     Sample: 2 mg

     Starting temperature: 230.0 캜, Stopping temperature: 350.0 캜

     Heatign rate: 5.0 占 폚 / min.

     Onset point threshold: 70% Single point threshold: 50%

     Clear point threshold: 10%

     The conditions for TGA measurement are as follows:

     Sample: 0.4 mg

     Starting temperature: 40.0 캜, Stopping temperature: 850.0 캜

     Heatign rate: 20.0 DEG C / min.

     The conditions for measuring MALDI-ToF are as follows:

     4 mg of the sample was dissolved in 2 ml of DMF, and Dithranol and the sample were mixed in a ratio of 1: 1

     1 μl of sample solution is dispensed on the sample plate. The number of laser shots is 100,

     The analysis range is set to 10 ~ 850m / z.

Synthetic example  2

 The procedure of Example 1 was repeated, except that 9.45 g (0.066 mol) of 2-naphthylamine was used instead of 1-naphthylamine as the monoamine to obtain N, N'-dinaphthyl- 11.43 g (yield 71%) of 2,6-naphthalenedicarboxamide (N, N'-dinaphthyl-2,6-naphthalenedicarboxamide) was obtained. The melting point of the obtained compound was 276.15 占 폚.

Synthetic example  3

 N, N'-dianthracal-2,6-naphthalenedicarboxylic acid (1-anthraceneamine) was obtained by repeating the steps of Synthesis Example 1 except that 12.75 g (0.066 mol) of 1-anthraceneamine was used as the monoamine. 14.62 g (17.00 g, yield 76%) of N, N'-dianthracyl-2,6-naphthalenedicarboxamide is obtained. The obtained compound had a thermal decomposition temperature of 910.21 占 폚 and a molecular weight of 566.65 g / mol. The NMR results of the obtained novel amide compound are shown in Fig.

Synthetic example  4

 The procedure of Synthesis Example 1 was repeated except that 7.47 g (0.066 moles) of thiophene-2-methylamine was used as the monoamine to obtain N, N'-dithiophene-2-methyl- 10.50 g (12.20 g, 86% yield) of 2,6-naphthalene dicarboxamide (N, N'-dithiophene-2-methyl-2,6-naphthalenedicarboxamide) is obtained. The obtained compound had a thermal decomposition temperature of 705.89 占 폚 and a molecular weight of 406.52 g / mol. The NMR results of the obtained novel amide compounds are shown in Fig.

Synthetic example  5

 N, N'-diadenyl-2,6-naphthalenedicarboxamide (N, N ', N'-diphenylmethacrylate) was repeated by repeating the steps of Synthesis Example 1 except that 8.92 g (0.066 mol) of adenine was used as the monoamine. -diadenyl-2,6-naphthalenedicarboxamide) (13.51 g, yield 80%). The obtained compound had a thermal decomposition temperature of 1211.26 캜 and a molecular weight of 450.41 g / mol. The NMR results of the obtained novel amide compound are shown in Fig.

Synthetic example  6

 The procedure of Synthesis Example 1 was repeated except that 7.34 g (0.066 mol) of histamine was used as the monoamine to prepare N, N'-dihistamyl-2,6-naphthalenedicarboxamide (N, N -dihistamyl-2,6-naphthalenedicarboxamide) (12.07 g, yield 80%). The molecular weight of the obtained compound was 402.45 g / mol. The NMR results of the obtained novel amide compounds are shown in Fig.

Synthetic example  7

 The procedure of Synthesis Example 1 was repeated except that 9.52 g (0.066 moles) of quinolin-5-amine was used as the monoamine to obtain N, N'-di-5-quinolinyl- , 12.08 g (14.06 g, yield 80%) of 6-naphthalenedicarboxamide (N, N'-di-5-quinolinyl-2,6-naphthalenedicarboxamide). The obtained compound had a pyrolysis temperature of 857.15 DEG C and a molecular weight of 468.51 g / mol. The NMR results of the obtained novel amide compounds are shown in Fig.

Example  One

 0.5 part by weight of N, N'-dinaphthyl-2,6-naphthalenedicarboxamide obtained in Synthesis Example 1 was added to 100 parts by weight of the propylene homopolymer powder, and the mixture was pelletized at 260 DEG C by a single screw extruder. The? -Form content of the resulting pellets is 84.2%.

Comparative Example  One

0.5 part by weight of N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide was added to 100 parts by weight of the propylene homopolymer powder, and the mixture was pelletized at 260 DEG C by a single screw extruder. The? -Form content of the resulting pellets is 73.5%.

Example  2

 The procedure of Example 1 was repeated except that the pelletization temperature condition was used at 220 캜 to provide pellets. The? -Form content of this pellet is 79.9%.

Example  3

 0.1 part by weight of N, N'-dinaphthyl-2,6-naphthalenedicarboxamide was added to 100 parts by weight of the propylene homopolymer powder, and the mixture was pelletized at 230 DEG C by a single screw extruder. The? -Form content of the resulting pellets is 75.3%.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. All changes and modifications are to be construed as being included within the scope of protection of the present invention.

Fig. 1 shows the results of X-ray diffraction analysis of the resin composition obtained in Example 1. Fig.

Fig. 2 shows the results after removing the background from the X-ray diffraction analysis results of the resin composition obtained in Example 1. Fig.

3 shows NMR results of the amide compound obtained in Synthesis Example 1. FIG.

4 shows the IR result of the amide compound obtained in Synthesis Example 1. Fig.

5 shows the DSC evaluation result of the amide compound obtained in Synthesis Example 1. Fig.

6A-6C show the results of evaluation using the melting point system of the amide compound obtained in Synthesis Example 1. FIG.

7 shows the result of pyrolysis evaluation of the amide compound obtained in Synthesis Example 1 using TGA.

8 shows the evaluation results of the amide compound obtained in Synthesis Example 1 using MALDI-ToF MS.

9 shows NMR results of the amide compound obtained in Synthesis Example 3. Fig.

10 shows NMR results of the amide compound obtained in Synthesis Example 4. Fig.

11 shows NMR results of the amide compound obtained in Synthesis Example 5.

12 shows NMR results of the amide compound obtained in Synthesis Example 6. Fig.

13 shows NMR results of the amide compound obtained in Synthesis Example 7. Fig.

Claims (10)

1. An amide compound having a structure represented by the following formula (1). [Chemical Formula 1]

Wherein X is a straight chain or branched alkyl group having 1 to 20 carbon atoms or 1 group selected from the following formula (2), A ₁ and A ₂ are the same or different and are selected from the group consisting of an aromatic group Device. (2)

Wherein, D represents a single bond or, O, S, CO, SO, SO _2, NH _2, CONH, alkylene group, substituted C 1 -C 20 linear or branched alkyl group, a substituted or unsubstituted C2 to 20 of Or an unsubstituted alkoxysilyl group having 2 to 20 carbon atoms, and each R ₁ is independently an alkyl group having 1 to 5 carbon atoms or a halogen group. (3)

The novel amide compound according to claim 1, wherein X in the formula (1) is selected from the group of the following formula (4). [Chemical Formula 4]

Wherein each R < ₁ > is independently C1 to C5 alkyl or halogen. The novel amide compound according to claim 1, wherein the compound of formula (1) has the structure of formula (5). [Chemical Formula 5]

Wherein R ₁ is independently a C1 to C5 alkyl group or a halogen group and R ₂ is a single bond or a straight chain or branched chain having 1 to 20 carbon atoms such as O, S, CO, SO, SO ₂ , NH ₂ , A substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkoxysilylene group having 2 to 20 carbon atoms. A crystalline polymer resin composition comprising a crystalline polymer resin and a β-nucleating agent, wherein the β-nucleating agent is an amide compound represented by the following formula (1): [Chemical Formula 1]

Wherein X is a straight chain or branched alkyl group having 1 to 20 carbon atoms or 1 group selected from the following formula (2), A ₁ and A ₂ are the same or different and are selected from the group consisting of an aromatic group Device. (2)

Wherein A ¹ is a single bond or a straight or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, -O-, -S-, -CO-, -SO ₂ -, -NH ₂ -, -CONH- A substituted or unsubstituted C2-C20 alkoxysilyl group, and each of R < ₁ > is independently a C1-C5 alkyl group or a halogen group. (3)

5. The crystalline polymer resin composition according to claim 4, wherein X in the formula (1) is selected from the group of the following formula (4) [Chemical Formula 4]

Wherein each R < ₁ > is independently C1 to C5 alkyl or halogen. The method of claim 4, wherein the crystalline polymer is selected from the group consisting of polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyamide, and polyolefin By weight based on the total weight of the polymeric resin composition. The crystalline polymer resin composition according to claim 6, wherein the crystalline polymer is a crystalline polypropylene resin. 5. The crystalline polymer resin composition according to claim 4, wherein the crystalline polymer resin has a beta -form crystal content of 40 to 98%. A product comprising the crystalline polymer resin composition according to claim 4. 10. The article of claim 9, wherein the article is a molded article.

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