JPH05310665A - New amide-based compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a beta-crystal nucleating agent for a crystalline polypropylene-based resin. CONSTITUTION:The compound of the formula R<1>-NHCO-X-CONH-R<2> (R<1> and R<2> are 5-12C cycloalkyl; X is formula I or II), e.g. N,N'-dicyclopentyl-2,6- naphthalenedicarboxyamide. This compound is obtained by reacting naphthalenedicarboxylic acid or biphenyldicarboxylic acid with a monoamine in an equiv. amount of 2-10 times based thereon, preferably in the presence of an activator (e.g. phosphorus pentoxide) in an inert solvent (e.g. N- methylpyrrolidone) at 60-200 deg.C for 2-8hr. A composition containing the amine- based compound of the formula has a lower melting point than that of alpha-crystal polypropylene and requires a small force to deform under heated conditions and is useful for improving, etc., the fabricability. Thereby, a molding such as a container, a sheet or a film good in hue can be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amide compound suitable as a β crystal nucleating agent for a crystalline polypropylene resin.

[0002]

2. Description of the Related Art For crystalline polypropylene, α, β,
There are γ and δ transformations and smectic transformation that occurs when molten polypropylene is rapidly cooled. Of these, the β-modification (hereinafter referred to as “β-crystal”) has a lower melting point and a lower density than the α-modification (hereinafter referred to as “α-crystal”) found in conventional general-purpose natural pellets. It is known to have properties that are interesting for application, such as different crystal states and fracture states of polymer (Polymer Chemistry, 30 , 694-698, (1
978)).

As a method for producing β crystal, there are a method of crystallizing molten polypropylene under a temperature gradient and a method of adding and mixing a small amount of a nucleating agent (hereinafter referred to as “β crystal nucleating agent”), but the former is long. The latter method is more practical because it takes time and only a small amount of sample can be obtained.

As such β crystal nucleating agent, γ-quinacridone has been known so far (POLYMERLETTERS, 6 , 539-546,
(1968)). However, when the nucleating agent is applied, the resulting product has a drawback that it is colored red and requires special equipment and operation for mixing with the polymer.

An object of the present invention is to solve the drawbacks of quinacridone compounds and to propose a novel and useful β crystal nucleating agent which can efficiently obtain a β crystal polypropylene product excellent in hue.

[0006]

Means for Solving the Problems As a result of earnest studies to propose a β-crystal nucleating agent capable of achieving the above-mentioned problems, the present inventors have found that
An amide compound having a specific structure was a compound not described in the literature, and it was found that such a compound functions as a β crystal nucleating agent, and the present invention has been completed based on such findings.

That is, a novel amide compound suitable as a β crystal nucleating agent for the crystalline polypropylene resin according to the present invention is
It is characterized by being represented by the general formula (1).

[Chemical 4] [Wherein X is

[Chemical 5] Or

[Chemical 6] Represents. R ¹ and R ² are the same or different and have 5 to 1 carbon atoms.
2 represents a cycloalkyl group. ]

The novel amide compound according to the present invention can be produced, for example, by the following method. (1) Naphthalenedicarboxylic acid or biphenyldicarboxylic acid (hereinafter collectively referred to as "the present dicarboxylic acid") and its part 2
10 equivalents of the corresponding monoamine in an inert solvent,
The reaction is performed at 60 to 200 ° C for 2 to 8 hours.

In the present production method, it is more preferable to use an activator in order to shorten the reaction time.

Examples of the activator include phosphorus pentoxide, polyphosphoric acid, phosphorus pentoxide-methanesulfonic acid, phosphite (triphenylphosphite, etc.)-Pyridine, phosphite-metal salt (lithium chloride). Etc.), triphenylphosphine-hexachloroethane, etc., and they are usually used in about equimolar amounts to the present dicarboxylic acid.

(2) The dichloride of the present dicarboxylic acid and 2 to 3 equivalents of the corresponding monoamine in an inert solvent,
React at 0-100 ° C for 1-5 hours.

As the inert solvent for the above methods (1) and (2), benzene, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, tetrahydrofuran, dioxane, acetonitrile, N, N-dimethylformamide, N, Examples include N-dimethylacetamide and N-methylpyrrolidone.

Examples of the above-mentioned monoamines include cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, and other cycloalkyl (C5-12) amines.

The resin composition containing the novel amide compound according to the present invention has features such as a lower melting point and a smaller force required for deformation under heating as compared with α-crystal polypropylene, and secondary processability. It is very useful for improvement of, by molding under the desired mixing method and molding processing conditions,
It is possible to easily obtain a molded product containing β crystals at a high degree (concentration of 98% by weight has been confirmed at present), which is unprecedented, and has a good hue. This polypropylene molded product can be applied to a wide range of fields such as containers, sheets and films.

In the resin composition containing the novel amide compound according to the present invention, the content ratio of the α-type crystal structure and the β-type crystal structure can be controlled by selecting molding conditions such as cooling conditions. This property is particularly effective for roughening the surface of the biaxially stretched film. The obtained surface-roughened film is excellent in blocking resistance, printability, adhesiveness and the like, and is very useful in the fields of packaging films, printing paper, tracing paper, oil-immersed plastic capacitors and the like.

[0016]

EXAMPLES The present invention will be described in detail below with reference to examples. The β crystal content was determined by the following measuring method.

[Measurement of β crystal content] D:
Set it in the SC sample holder and run it in a nitrogen atmosphere at 230
After melting at 0 ° C for 5 minutes, the temperature is lowered to near room temperature at 20 ° C / minute. Then, the temperature is raised at 20 ° C./min, and the β crystal content (area%) is determined from the peak areas of α crystal and β crystal of the DSC thermogram obtained at this time.

Example 1 300 equipped with a stirrer, thermometer, cooling pipe and gas inlet
2,6-naphthalenedicarboxylic acid 6.
48 g (0.03 mol), cyclopentylamine 5.61
g (0.066 mol), triphenyl phosphite 20.46
g (0.066 mol), pyridine 25 g and N-methylpyrrolidone 100 g were charged, and the reaction was carried out at 100 ° C. for 3 hours under a nitrogen atmosphere with stirring. After cooling, the reaction solution was mixed with isopropyl alcohol / water (= 1/1) 70
It was poured into 0 ml and reprecipitated and washed. After stirring for 2 hours, the precipitate was filtered off and dried under reduced pressure at 110 ° C to obtain N, N '.
There was obtained 9.03 g (yield 86%) of -dicyclopentyl-2,6-naphthalenedicarboxamide. This compound was a white powder and had a melting point of 375.4 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 2 6.53 g (0.5) of cyclohexylamine as a monoamine
066 mol), and N, N 'in the same manner as in Example 1.
9.64 g (yield 85%) of -dicyclohexyl-2,6-naphthalenedicarboxamide was obtained. This compound was a white powder and had a melting point of 384.2 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 3 8.38 g (0.30 g) of cyclooctylamine as a monoamine
066 mol), and N, N 'in the same manner as in Example 1.
9.63 g (yield 74%) of -dicyclooctyl-2,6-naphthalene dicarboxamide were obtained. This compound was a white powder and had a melting point of 30.8 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 4 12.08 g of cyclododecylamine as a monoamine
In the same manner as in Example 1 except that (0.066 mol) was used,
13.3 g (yield 81%) of N, N'-dicyclododecyl-2,6-naphthalene dicarboxamide was obtained. This compound was a white powder and had a melting point of 321.8 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 5 2,7-naphthalenedicarboxylic acid as the present dicarboxylic acid 6.
N, N'-dicyclohexyl-2,7-naphthalene dicarboxamide 8.39 g (yield 74%) was obtained in the same manner as in Example 2 except that 48 g (0.03 mol) was used. This compound was a white powder and had a melting point of 337.1 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 6 N, N'-dicyclopentyl-4,4 was prepared in the same manner as in Example 1 except that 7.26 g (0.03 mol) of 4,4'-biphenyldicarboxylic acid was used as the present dicarboxylic acid. Thus, 8.12 g (yield 72%) of'-biphenyldicarboxamide was obtained. This compound was a white powder and had a melting point of 355.0 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 7 6.53 g (0.5%) of cyclohexylamine as a monoamine
066 mol) and N, N 'in the same manner as in Example 6.
There was obtained 9.94 g (yield 82%) of -dicyclohexyl-4,4'-biphenyldicarboxamide. This compound was a white powder and had a melting point of 370.8 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 8 8.38 g (0.30 g) of cyclooctylamine as a monoamine
066 mol) and N, N 'in the same manner as in Example 6.
10.8 g (yield 78%) of -dicyclooctyl-4,4'-biphenyldicarboxamide were obtained. This compound was a white powder and had a melting point of 30.2 ° C. (decomposition). The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 9 12.08 g of cyclododecylamine as a monoamine
In the same manner as in Example 6 except that (0.066 mol) was used,
17.16 g (yield 82%) of N, N'-dicyclododecyl-4,4'-biphenyldicarboxamide was obtained. This compound was a white powder and had a melting point of 346.7 ° C. (decomposition).
The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Example 10 8.37 g of 2,2'-biphenyldicarboxylic acid dichloride
(0.03 mol), cyclohexylamine 11.88 g
(0.12 mol) and 120 g of chlorobenzene were charged into a reaction vessel, and the reaction was performed at 80 ° C. for 2.5 hours under a nitrogen atmosphere. After cooling, the reaction solution was poured into 1000 ml of hexane for reprecipitation and washing. Next, the precipitate separated by filtration was washed with 600 ml of 0.5% aqueous sodium hydroxide solution,
Further, it was thoroughly washed with purified water. The precipitate is filtered off, 110
After drying under reduced pressure at ℃, N, N'-dicyclohexyl-2,2'-
Biphenyldicarboxamide 6.08 g (yield 50
%) Was obtained. This compound is a white powder and has a melting point of 229.2.
Was -229.8 ° C. The elemental analysis values and characteristic infrared absorption are shown in Table 1.

Application Example 1 Propylene homopolymer powder (MFR = 14 g / 10
Min) 100 parts by weight of the amide compound obtained in Example 2 was added in an amount of 0.05 parts by weight and mixed with a Henschel mixer.
Pelletized with a 20 mmφ uniaxial extruder. Next, the obtained pellets are compression molded under the condition of 230 ° C. × 10 minutes,
A sheet having a thickness of 0.5 mm was used. The β crystal content of the obtained sample was 97%, and coloring of the sheet was not observed.

Application Comparative Example 1 A sheet was prepared in the same manner as in Application Example 1 except that the amide compound was not added, and the β crystal content of the obtained sample was measured and found to be a trace amount.

Application Example 2 A sheet was prepared in the same manner as in Application Example 1 except that the amide compound obtained in Example 7 was used as the β crystal nucleating agent. The β crystal content of the obtained sample was 59%, and coloring of the sheet was not observed.

[0031]

INDUSTRIAL APPLICABILITY The present invention relates to a novel and useful amide compound, and by applying a crystalline polypropylene resin composition containing the compound as a β-crystal nucleating agent, under industrial conditions, A molded product containing a large amount of β crystal can be efficiently manufactured.

[Table 1]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Hiroshi Kitagawa 13 13 Yakura-cho, Fukumi-ku, Kyoto City, Kyoto Prefecture Shin Nihon Rika Co., Ltd. Rika Co., Ltd.

Claims (1)

[Claims] 1. A novel amide compound represented by the general formula (1). [Chemical 1] [In the formula, X is Or Represents. R ¹ and R ² are the same or different and have 5 to 1 carbon atoms.
2 represents a cycloalkyl group. ]