JPH0711075A - Syndiotactic polypropylene composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in transparency, mechanical physical properties, tensile strength, etc., and useful for molding materials such as films or sheets by blending a syndiotactic polypropylene with a specific cyclic organophosphoric acid ester compound. CONSTITUTION:The objective composition is obtained by blending (A) 100 pts.wt. of a syndiotactic polypropylene, preferably having >=80% syndiotactic degree with (B) 0.01-5 pts.wt. of at least one cyclic organophosphoric acid ester of formula I [R1 is H or a 1-4C alkyl; R2 and R3 are H, a 1-12C alkyl, cycloalkyl, aryl or aralkyl; M is H or a metal atom of group III or group IV of Periodic Table; X is hydroxyl group when M is metal atom of group III; X does not exist when M is H; X is O or (OH)2 when M is the metal atom of group IV of Periodic Table; (n) is 1 when M is H and (n) is 2 when M is not H].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a syndiotactic polypropylene composition, and more specifically to a syndiotactic polypropylene composition containing a cyclic organic phosphate compound, which has improved transparency and mechanical properties. A tic polypropylene composition.

[0002]

2. Description of the Related Art Due to the stereoregularity of polypropylene, isotactic polypropylene (hereinafter referred to as i-PP), atactic polypropylene, syndiotactic polypropylene (hereinafter referred to as s-P)
It is known that there are three types (referred to as P). Of these, atactic polypropylene, which has poor stereoregularity, cannot be used as a molded product or the like because it has a low crystallinity and a low heat distortion temperature, and s-PP has an extremely slow polymerization rate and is difficult to produce. In addition, most of the polypropylene currently produced is i-PP, because only polypropylene containing a large amount of isotactic portion could be produced. Since this i-PP has a large stereoregularity and a large degree of crystallinity, it has the advantages of high tensile strength, elongation and bending rigidity, and is widely used as fibers, films, various molded products, etc. ,On the other hand,
It has a drawback that it is inferior in impact strength and transparency, and its use is limited.

In recent years, with the progress of polymerization catalysts used in the production of polypropylene, s-P having a large stereoregularity is obtained by using a homogeneous catalyst called a metallocene catalyst.
Now that P can be manufactured, its application is being studied. This s-PP has a ratio of the weight average molecular weight to the number average molecular weight of about 2, and it is possible to produce a polymer having a narrow molecular weight distribution, and has a large impact strength as compared with i-PP, and , But also has the advantage of good transparency, but in particular, it has the disadvantages of poor tensile strength and bending rigidity. Moreover, the crystallization speed is extremely slow, which not only deteriorates the molding cycle property, but also causes the molded product to shrink after molding. However, from the viewpoint of practical application of s-PP, it was necessary to eliminate these drawbacks.

[0004]

[Means for Solving the Problems] In view of the present situation, the present inventors have made various studies and as a result, have found that the tensile strength of the resin can be improved by adding a specific cyclic organic phosphate compound to s-PP. And, they have found that the bending rigidity can be significantly improved, and have reached the present invention.

That is, in the present invention, 0.01 to 5 parts by weight of at least one cyclic organophosphate compound represented by the following general formula (1) is mixed with 100 parts by weight of s-PP. An s-PP composition is provided.

[0006]

[Chemical 2]

The s-PP composition of the present invention will be described in detail below.

The s-PP used in the present invention has a syndiotactic degree (racemic pentad fraction) of 80%.
As described above, preferably 90% or more is used, and usually a propylene homopolymer is used, but other olefin compounds such as ethylene, butene-1, and pentene- are used as long as the syndiotactic degree is not reduced.
It may be a copolymer of 1,3-methylpentene-1 or the like in a small amount of 10 mol% or less with respect to propylene.

S-P with a syndiotactic degree of 80% or more
P not only exhibits the above-mentioned specific physical properties of s-PP, but in particular, s-P having a syndiotactic degree of 90% or more.
P has a melting point of about 145 ° C. or higher, and can be used in applications requiring a higher high heat distortion temperature. On the other hand, s-PP having a syndiotactic degree of 80% or less is
Not only may the desirable properties of -PP not be obtained, but it is difficult to use in applications requiring high heat distortion temperature.

The s-PP used in the present invention is not particularly limited except that it has a syndiotactic degree of 80% or more. For example, a s-PP having a molecular weight of about 50,000 to 1,000,000 is used for its purpose and purpose. It can be used accordingly. Also, s
It is also possible to use a blend of -PP and another thermoplastic polymer material, for example, polyethylene, i-P.
P, polybutene-1, ethylene-propylene random or block copolymers may be mixed with other polyolefins, or may be blended with an elastomer such as an ethylene-propylene copolymer elastomer or an ethylene-propylene-norbornadiene copolymer elastomer, So-called olefinic thermoplastic elastomer (T
It can also be used as PO).

Further, in the cyclic organic phosphate compound represented by the general formula (1) used in the present invention, R ₁
Examples of the alkyl group having 1 to 4 carbon atoms represented by are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl and tert-butyl groups, and R
Examples of the alkyl group having 1 to 12 carbon atoms represented by ₂ and R ₃ include methyl, ethyl, propyl, isopropyl,
Butyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tertiary dodecyl group, etc. can give.

Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups, and examples of the aryl group include phenyl, o-tolyl, m-tolyl and xylyl groups, and the aralkyl group. Examples thereof include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and phenylethyl groups.

The metal atom of Group 3 or 4 of the periodic table represented by M is aluminum, gallium,
Examples thereof include germanium, tin, titanium and zirconium, and a compound in which M is aluminum is particularly preferable.

Therefore, examples of the compound represented by the general formula (1) used in the present invention include the following compounds.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

These cyclic organic phosphoric acid ester compounds are obtained, for example, by reacting an alkali metal salt of an acidic cyclic organic phosphoric acid ester with a polyvalent metal halide or an oxidized polyvalent metal halide, and then hydrolyzing it as necessary. Can be easily produced by a method of reacting an acidic cyclic organic phosphoric acid ester with a polyvalent metal alkoxide, and then hydrolyzing as required.

Further, the particle size of the cyclic organic phosphate ester basic polyvalent metal salt is not particularly limited,
For example, an average particle size of 0.01 to 50 μm can be used.

The amount of the cyclic organic phosphate compound added is 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of s-PP. If the addition amount is less than 0.01 parts by weight, the desired effect cannot be obtained,
Further, even if it is added in an amount exceeding 5 parts by weight, the effect corresponding to the added amount is not recognized and it is not only wasteful, but also other various properties may be adversely affected.

In the present invention, the method of adding each component is not particularly limited, and is a commonly used method, for example, a method of dry blending s-PP powder or pellets with an additive powder, and a high concentration of each component. It is possible to use a method in which a masterbatch containing the same is prepared and added to s-PP. In addition, the s-PP composition of the present invention can be molded into various molded products by well-known processing methods such as extrusion molding, injection molding, vacuum molding, blow molding, and cross-linking foam molding.
It can be used as a fiber, a biaxially stretched film, a sheet or the like.

The composition of the present invention is used for various post-treatments, for example, sterilization by radiation such as medical supplies such as syringes and infusion bags, or food packaging products such as films, sheets or various molded products. In order to improve the surface characteristics such as application or surface properties such as paintability, it can be used for applications such as low temperature plasma treatment after molding.

In the s-PP composition of the present invention, if necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as organic phosphite or phosphonite, a thioether antioxidant, and an ultraviolet absorber. Alternatively, a photostabilizer such as a hindered amine compound can be added to further improve the oxidation stability and photostability thereof. In particular, a heat treatment can be performed by using a phenol-based antioxidant and / or an organic phosphorus-based antioxidant together. It is possible to prevent coloring and deterioration of mechanical properties at the time.

Examples of phenolic antioxidants that can be used in the present invention include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol and stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate],
4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6- Tert-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 1,1,3-
Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] Terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-) Hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-
3- (3,5-Ditert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) Phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl] -2,
4,8,10-Tetraoxaspiro [5.5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5]
-Butylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, particularly 3- (3,5-dialkyl-4-hydroxy). Phenyl) propionic acid ester compound and 1,
A 3,5-tris (alkylated hydroxybenzyl) isocyanurate compound is preferable because of its large effect.

The amount of these phenolic antioxidants added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of s-PP.

Examples of the organophosphorus antioxidant that can be used in the present invention include, for example, trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, tris (2,4-ditert-butylphenyl) phosphite. , Di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4- Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4 ′ -N-butylidene bis (2-tert-butyl -5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2'-methylenebis (4,6) -Di-tert-butylphenyl) octylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) fluoro Phosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
Examples include oxides.

The addition amount of these organic phosphorus-containing compounds is s
It is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, relative to 100 parts by weight of PP.

Examples of the thioether antioxidant include dilauryl thiodipropionate, dimyristyl,
Examples thereof include dialkylthiodipropionates such as myristyl stearyl and distearyl esters, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the ultraviolet absorber include 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tertiary octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-ditertiary butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; Ethyl-α -Cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
Examples include cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate.

Examples of light stabilizers such as hindered amine compounds include 2,2,6,6-tetramethyl-4.
-Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, tetrakis (2,2,
6,6-Tetramethyl-4-piperidyl) butane tetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butane tetracarboxylate, bis (1,2,2,
6,6-Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6)
-Tetramethyl-4-piperidylamino) hexane /
2,4-Dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-second Trioctylamino-s-triazine polycondensate,
1,5,8,12-Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,
5,8,12-Tetraazadodecane, 1,5,8,12
-Tetrakis [2,4-bis (N-butyl-N- (1,
2,2,6,6-Pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12
-Tetraazadodecane, 1,6,11-tris [2,4
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
Examples thereof include hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

In addition, in the s-PP composition of the present invention, if necessary, a nonionic, cationic or anionic antistatic agent, aluminum-p-tertiary butyl benzoate, dibenzylidene sorbitol, bis (4 -Methylbenzylidene) Add other nucleating agents such as sorbitol, hydrotalcites, aliphatic carboxylates of alkaline earth metals, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids, etc. be able to.

[0036]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1 The following formulation A was mixed in a mixer for 5 minutes and then at a temperature of 230.
Pellets were prepared using an extruder under the conditions of ° C and a rotation speed of 20 rpm. The pellets were molded by an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. to prepare a test piece having a thickness of 1 mm. Using this test piece, ASTM D-
Haze value (%) according to 1003, ASTM D-
638 tensile strength at 23 ° C (kg /
cm ² ), flexural rigidity (kg / cm ² ) at 23 ° C. was measured according to ASTM D-790. The compounds shown below were used as Comparative Compound No. 1 and Comparative Compound No. 2. The results are shown in Table-1.

[0038]

[Chemical 10]

[0039]

[Chemical 11]

<Formulation A> s-PP (syndiotactic pentad fraction 0.915, intrinsic viscosity (η) 1.4)
0) 100 parts by weight, tetrakis [methylene-3- (3,3
5-di-tert-butyl-4-hydroxyphenylpropionate] methane 0.1 part by weight, calcium stearate 0.05 part by weight, sample compound (Table-1) 0.1 part by weight.

[0041]

[Table 1]

Example 2 Using the following formulation B, a test piece was prepared in the same manner as in Example 1, and the same test as in Example 1 was performed. The results are shown in Table-2.

<Compound B> s-PP (syndiotactic pentad fraction 0.947, intrinsic viscosity (η) 1.3)
0) 100 parts by weight, tetrakis [methylene-3- (3,3
5-di-tert-butyl-4-hydroxyphenylpropionate] methane 0.1 part by weight, calcium stearate 0.05 part by weight, sample compound (Table-2) 0.1 part by weight.

[0044]

[Table 2]

As is clear from the results of Examples 1 and 2, the full metal salt or sodium salt of cyclic organic phosphate ester is not effective in improving the physical properties of s-PP, and particularly the tensile strength and bending rigidity are improved. The effect is very small.

On the other hand, the specific cyclic organic phosphoric acid ester compound of the present invention is remarkably effective in improving the tensile strength and flexural rigidity, which are the disadvantages of s-PP, and is also remarkable in improving the transparency. Is played.

[0047]

By adding a specific cyclic organic phosphate compound to s-PP, its disadvantages such as tensile strength and flexural rigidity can be remarkably improved, and it can be used as various molding materials. Sufficient physical properties can be imparted.

Claims (2)

[Claims] 1. A syndiotactic polypropylene 10
0.01 to 5 of at least one cyclic organophosphate compound represented by the following general formula (1) per 0 part by weight.
A syndiotactic polypropylene composition containing 1 part by weight. [Chemical 1] 2. A syndiotactic polypropylene having a syndiotactic degree of 80% or more is used.
Composition.