JPH03152142A - Crystalline propylene polymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] <Industrial Application Field> The present invention relates to a crystalline polypropylene polymer composition containing a large amount of β-type crystal structure.

<Prior art> Polypropylene produced by conventional methods has an α-type (monoclinic) crystal structure, and most of the polypropylene natural pellets currently on the market belong to this type. ing.

On the other hand, β-type polypropylene, which has a hexagonal crystal structure, has a lower melting point than α-type polypropylene, so this property can be used to make products such as rolling up biaxially stretched polypropylene film into containers. Many attempts have been made to roughen the surface for this purpose (for example, JP-A-49-1781, JP-A-52-35272, JP-A-53-42269; Showa 55-980
6, Japanese Patent Application Laid-Open No. 60-23023, etc.

).

A method for obtaining such β-type crystalline polypropylene is a method in which quinacridone is added to polypropylene obtained by polymerizing by a conventional method (H).

”, Laugering: Makromol, Chet,
109.204-218 (I) ~ (IV987) and ^, T, Jeans et al.: Pot, YMERLET
TER8, 6539-546 (I) ~ (IV968))
is widely known.

<Problems to be Solved by the Invention> However, such a method is impractical because the added quinacridone causes a problem in that the product is colored red.

[Summary of the invention]

Summary> As a result of extensive research to solve the above problems, the present inventors have developed a β-type crystal structure with no interstices between six colors by blending a specific compound at a specific concentration into a crystalline propylene polymer. The present invention was completed based on the finding that a crystalline propylene polymer composition containing a large amount of

That is, the crystalline propylene polymer composition of the present invention is
crystalline propylene polymer and 0.1 to 0.1 to the polymer;
10. The following structural formulas (I) to (IV) at a concentration of OOOppm
) to (TV).

(R and R2 in the above formula each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Effect> The crystalline propylene polymer composition of the present invention contains a propylene polymer having a β-type aggregate structure. Since it is a propylene polymer with a β-type structure that contains a large amount of H and does not cause coloring problems, products that take advantage of the properties of this polymer, such as roughened propylene polymer films, especially two-wheel stretched films, etc. It can be used as

[Detailed description of the invention]

(I) to (IV3) Components (I) to (IV) Crystalline propylene polymer component The crystalline propylene polymer component used in the crystalline propylene polymer composition of the present invention includes a stereoregular catalyst. A crystalline propylene homopolymer or copolymer obtained by polymerization, and generally has a melt flow rate of 0.1 to 100 g/10 min, preferably 0.5 to 50 g/10 min.
g/10 minutes.

The catalyst for producing the crystalline propylene polymer component used in the present invention is a combination of a titanium trichloride composition or a solid catalyst component in which a titanium compound is supported on a magnesium compound carrier and an organoaluminum compound component. However, a solid catalyst component supported on a magnesium compound, which is a highly active catalyst, is preferably used because it has less catalyst residue and is less likely to act as a nucleating agent for forming β-type crystals.

(2) Compound component Compound components contained in the crystalline propylene polymer composition of the present invention include structural formulas (I) to (
These are compounds represented by IV) to (IV).

(R1 and R2 in the above formula each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 28 or more of these compounds can be used in combination.

Among these compounds, those represented by the structural formulas (I[I) and (mV) are particularly preferred.

Among the compounds represented by the above structural formulas (I) to (IV), preferred are phthalimide, 4-methylphthalimide, 4-ethylphthalimide, and the like.

Among the compounds represented by the above structural formula (II), preferable ones include 3-imidazolinone, 5-methyl-3-imidazolinone, and 5-ethyl-3-imidazolinone.

Among the compounds represented by the above structural formula (III), preferred are 4(3H)-quinazolinone, 2-methyl-
4(3H)-quinazolinone, 2-ethyl-4(3H)
- such as quinazolinone.

Among the compounds represented by the above structural formula (IV), preferred are 1,8-naphthosartam, 4-methyl-1,8-
Naphthosultam, 4-ethyl-1°8-naphthosultam, and the like.

(3) Other components (optional components) The crystalline propylene polymer composition of the present invention may optionally contain antioxidant stabilizers, thermal decomposition inhibitors, weather resistance stabilizers, fatty acid salts, other compounding agents, and other resins. , rubber, stone coloring agent, etc. can be incorporated within a range that does not significantly impair the expression of the effect.

([3 Production of Compositions There are various methods for infusing the compound components represented by the above structural formulas (I) to (IV) into the crystalline propylene polymer component. A chemical mixing method in which a crystalline propylene polymer is produced in the presence of a polymerization catalyst during the polymerization of propylene before formation, or during granulation after the formation of a crystalline propylene polymer. Although there are physical mixing methods in which the polymers are mixed when they are melted, chemical mixing methods are preferred in order to improve the dispersion of the above compounds.

The compound components represented by the above structural formulas (I) to (IV) to (IV) are present in the crystalline propylene conjugate component in an amount of 0.1 to 1
0.0.00ppm, preferably 1-1,000ppm
Adjust the blending amount or the amount of polymer produced so that the concentration is as follows. If it is less than this range, a satisfactory amount of β-type crystals cannot be obtained, while if it exceeds this range, the amount of β-type crystals produced will be saturated, which is not preferable, since it will be disadvantageous economically.

(I [I) Crystalline propylene polymer composition The crystalline propylene polymer composition of the present invention obtained as described above has the above structural formulas (I) to (IV) to CTV"
) and a crystalline propylene polymer component, the compound component is 0.1 to 10.
Although it is only contained in a small amount of 000 ppm, it acts as a nucleating agent for β-type crystals when the crystalline propylene polymer crystallizes, and increases the size of the crystal structure of the crystalline propylene polymer in the composition. can be converted into a β-type crystal structure.

Therefore, the crystalline propylene polymer composition of the present invention has β
The proportion of propylene polymer having a type of crystal structure is usually 20 to 90% by weight, in particular 40 to 85% by weight.

Therefore, in the crystalline propylene polymer composition of the present invention, a propylene polymer with a β-type crystal structure and a propylene polymer with an α-type crystal structure are mixed, and propylene polymers with such different crystal structures are mixed. When the crystalline propylene polymer composition of the present invention containing coalescence is formed into a two-wheel stretched film, each solidifies in a different crystal form, so its surface is roughened to form a satin finish. It is possible to show the surface structure.

A film whose surface has been roughened in this manner can have improved slip properties, winding properties, printing properties, and the like.

Further, the β-type polypropylene in the crystalline propylene polymer of the present invention can always stably assume a β-type crystal structure even after repeated melting, cooling, and solidification.

Even if the crystalline propylene polymer composition of the present invention is used after being diluted with ordinary polypropylene, the above structural formulas (I) to (IV
If the concentration range of the compound represented by ) to (IV) is within the above range, a β-type structure can be expressed, so the crystalline propylene polymer composition obtained in the present invention can be used as a masterbatch. You can.

[Experiment example]

The content of the present invention will be explained in more detail below with reference to Examples and Comparative Examples of the present invention, but the embodiments of the present invention are not limited thereto.

In addition, the content of the β-crystal component of β-type polypropylene is DS
It was determined from the peak area ratio of α crystal and β crystal in the C thermogram.

Example 1 Production of solid catalyst component 200 ml of dehydrated and deoxygenated n-hebutane was introduced into a flask which had been thoroughly purged with nitrogen. Then M
gCl20.4 mol and Ti (0-nCH)
0.8 mol was introduced and reacted at 494 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and 48 ml of methylhydrodiene polysiloxane (20 centistoke) was introduced.
Allowed time to react. The solid component produced was washed with n-hebutane.

Next, 50 milliliters of purified n-hebutane was introduced into a flask that had been sufficiently purged with nitrogen, and 0.24 mol of the solid component synthesized above was introduced therein in terms of Mg atoms. Then add 5iC140,4 to 25 ml of n-hebutane.
The moles were mixed, introduced into a flask at 30°C for 60 minutes, and reacted at 90°C for 3 hours.

Further, 0.016 mol of phthaloyl chloride was mixed with 25 ml of n-hebutane, and the mixture was introduced into a flask at 90°C for 30 minutes, and reacted at 90°C for 1 hour.

After the reaction was completed, it was washed with n-hebutane. Then add S to this
Introducing 24 mmol of iC140.3 at 100°C.
Allowed time to react. After the reaction was completed, it was thoroughly washed with n-hebutane.

Furthermore, tert-butylmethyldimethoxysilane 5.0
milliliter was introduced and the mixture was stirred and brought into contact at 30° C. for 2 hours. After the contact was completed, it was thoroughly washed with n-hebutane to obtain a solid catalyst component.

Phthalimide treatment of solid catalyst components Add 3 g of the above solid catalyst component to a 300 ml flask.

0.3 g of phthalimide and 150 ml of n-hebutane were introduced, and the mixture was stirred at 20° C. for 2 hours for treatment.

In an autoclave equipped with a stirring device and having an internal volume of 3 liters of propylene polymerization, 1.5 liters of n-hebutane, 0.75 g of triethylaluminum, and 0.11 g of the mixed contact mixture of the solid catalyst component and phthalimide prepared by the above method were placed. was introduced and the temperature was raised to 75°C.

Furthermore, 300ml of hydrogen was introduced, and 7kg/c of propylene was added.
The pressure was increased to jG to start polymerization.

After 2 hours, the polymerization was stopped by purging the monomer, and the polymer slurry was further filtered and dried to obtain a crystalline propylene polymer powder.

Table 1 shows the measurement results of the physical properties of the obtained crystalline propylene polymer composition.

Examples 2 to 6 The same experiments as in Example 1 were conducted except that the solid catalyst components and the types of nucleating agents were changed to those shown in Table 1.

The measurement results of physical properties are shown in Table 1.

Comparative Example 1 An experiment similar to Example 1 was conducted except that the solid catalyst component was not treated with phthalimide.

Table 1 shows the measurement results of the physical properties of the obtained crystalline propylene polymer composition.

Comparative Example 2 An experiment similar to Example 1 was conducted except that 30 g of phthalimide was introduced during the phthalimide treatment of the solid catalyst component.

As a result, the catalyst activity decreased significantly and the polymer powder was colored yellow due to the influence of the catalyst residual liquid.

Table 1 shows the measurement results of the physical properties of the obtained crystalline propylene polymer composition.

Claims (1)

[Scope of Claims] A crystalline propylene polymer, and a
The following structural formulas (I) to (IV) at a concentration of 10,000 ppm
) A crystalline propylene polymer composition comprising at least one compound represented by: (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. Yes▼ (R^1 and R^2 in the above formula each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)