JPH07258334A - Manufacture of modified propylene random copolymer and molded product - Google Patents

Abstract

PURPOSE:To obtain a modified properlene random copolymer high in melt strength and excellent in moldability by addn. of a specific amt. of an org. peroxide to a propylene random copolymer having a specific compsn. and subsequent heat treatment thereof. CONSTITUTION:100 pts.wt. propylene random copolymer having a propylene unit content of 99.0 to 70mol%, a polyne unit content of 0.1 to 10mol%, and a 2-12C olefin (other than propylene) unit content of 0 to 20mol% is mixed with 0.001-1 pt.wt. org. peroxide (e.g. benzoyl peroxide) and the resultant mixture is heat-treated at 80 to 350 deg.C. According to the foregoing procedure, a modified propylene random copolymer is obtd., which has the relationship of the formula between the melt strength(MS) thereof at 230 deg.C and the intrinsic viscosity [eta]thereof as measured in tetralin at 135 deg.C, and a boiling xylene extraction residue of at most 1wt.%. A molded product of this copolymer can be recycled for reuse by melting the molded product again after use thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a modified propylene random copolymer and a molded article. More specifically, the method for producing a modified propylene-based random copolymer which has a high melt tension and is excellent in moldability, and can be reused by remelting after being used as a molded article and the method. The present invention relates to a molded article using the modified polypropylene random copolymer obtained.

[0002]

2. Description of the Related Art Polypropylene is widely used in various molding fields because it is excellent in mechanical properties, chemical resistance and the like and is extremely useful in balance with economic efficiency. However, since the melt tension is low, it is inferior in moldability such as hollow molding, foam molding, and extrusion molding.

As a method for increasing the melt tension and crystallization temperature of polypropylene, a method of reacting polypropylene with an organic peroxide and a crosslinking aid in a molten state (Japanese Patent Laid-Open Nos. 59-93711 and 61). -152754
However, there is a problem that an odor remains in the modified polypropylene obtained by using the crosslinking aid. In addition, the improvement of the melt tension is insufficient, and if the addition amount of the organic peroxide and the crosslinking aid is increased to increase the melt tension, the gel will be generated and the moldability will deteriorate. It was also impossible to do.

JP-A-5-194659 discloses that a random copolymer of propylene and 1,9-decadiene exhibits a high melt tension, and further JP-A-5-222.
121 and JP-A-5-222122 disclose polypropylene having a high melt tension by polymerizing propylene using a catalyst which has been prepolymerized by random copolymerization of propylene or ethylene with 1,9-decadiene. Is disclosed. However, when the present inventors made additional tests based on these disclosed techniques using 1,9-decadiene, although the obtained polypropylene had a certain degree of improvement in melt tension at the powder stage, it did In the state, the melt tension was insufficiently improved.

Further, although there is no mention of melt tension in JP-B-44-29742, propylene, ethylene and 1,7-octadiene ternary random copolymer or the ternary random copolymer are used as block segment. A method for modifying a propylene copolymer for melting and kneading one block copolymer and an organic peroxide to improve impact resistance at low temperature is disclosed. According to the results of studies by the present inventors, the improvement of the melt tension was extremely insufficient with the diene content and the amount of organic peroxide in the copolymer shown in the examples of the publication.

On the other hand, in JP-A-57-98534 and JP-A-57-98534, 1,4-dienes and random copolymers of 7-methyl-1,6-octadiene and propylene are referred to as organic compounds. Although a technique for obtaining a crosslinked product having a high gel fraction by using a peroxide or an electron beam is disclosed, the polypropylene obtained by the disclosed technique has a high gel fraction although the melt tension is improved. It was impossible to re-melt and recycle after using as a molded product.

[0007]

As described above, the polypropylene obtained by the method of the prior art is not sufficient in improving the melt tension, but also has an odor or a gel so that it is molded. After being used as a product, there was a problem that it was impossible to remelt and recycle.

The inventors of the present invention have earnestly studied to solve the problems of the prior art and to invent a method for producing polypropylene suitable for blow molding, foam molding, extrusion molding and the like. As a result, a modified propylene-based random copolymer was obtained by heat-treating a propylene and a polyene, and optionally a random copolymer of an olefin other than propylene and an organic peroxide under specific conditions. It has been found that the use of a high quality propylene random copolymer as a molded product solves the problems of the above-mentioned prior art, and has reached the present invention.

As is clear from the above description, the object of the present invention is a modification having extremely high melt tension and excellent moldability, and further, after being used as a molded product, it can be remelted and recycled. Another object of the present invention is to provide a method for producing a propylene-based random copolymer, and a molded article using the modified propylene-based random copolymer.

[0010]

The present invention has the following respective configurations (1) and (2). (1) Propylene system having a propylene content of 99.9 to 70 mol%, a polyene content of 0.1 to 10 mol%, and an olefin content of 2 to 12 carbon atoms other than propylene of 0 to 20 mol% Random copolymer 100
0.001 to 1 part by weight of an organic peroxide is added to and mixed with parts by weight, and the resulting mixture is heat treated at 80 to 350 ° C. (A) Melt tension at 230 ° C. (MS ) And the intrinsic viscosity [η] measured in tetralin at 135 ° C. are log (MS)> 4.24 ×
log [η] −0.915, and (B) boiling xylene extraction residual rate is 1% by weight or less,
A method for producing a modified propylene-based random copolymer.

(2) Propylene content is 99.9 to 7
0 mol%, polyene content of 0.1 to 10 mol%, and propylene-based random copolymer having 0 to 20 mol% of olefin other than propylene having 2 to 12 carbon atoms, 100 parts by weight, Organic peroxide 0.001
1 part by weight was added and mixed, and the resulting mixture was heat treated at 80 to 350 ° C.,
(A) Melt tension (MS) at 230 ° C. and intrinsic viscosity [η] measured at 135 ° C. in tetralin are log
(MS)> 4.24 × log [η] −0.915, and (B) a modified propylene random copolymer having a boiling xylene extraction residual rate of 1% by weight or less. Molded product used.

The structure and effect of the present invention will be described in detail below. The modified propylene random copolymer obtained by the method of the present invention has the following two essential requirements. That is, (A) the melt tension (MS) at 230 ° C. and the intrinsic viscosity [η] measured at 135 ° C. in tetralin were:
g (MS)> 4.24log [η] −0.915, and (B) boiling xylene extraction residual rate is 1% by weight or less.

The melt tension of the modified propylene random copolymer required to achieve the object of the present invention is, as described above, the melt tension (MS) at 230 ° C. and the intrinsic tension measured at 135 ° C. in tetralin. Viscosity [η] is log
(MS)> 4.24log [η] −0.915, more preferably log (MS)> 4.24lo.
It is necessary that the relationship represented by g [η] -0.740, and most preferably the relationship represented by log (MS)> 4.24 log [η] -0.615.

Here, the melt tension (M
S) is a melt tension tester type 2 manufactured by Toyo Seiki Seisakusho Co., Ltd., which is used to heat the polymer to 230 ° C. in the apparatus, and melt the polymer from a nozzle having a diameter of 2.095 mm at a speed of 20 mm / min. At 23 ° C. into the atmosphere to form a strand, and the tension of the filamentous polymer when the strand was taken at a speed of 3.14 m / min was measured to determine the melt tension (M
S).

The modified propylene random copolymer obtained by the method of the present invention also has a boiling xylene extraction residual rate of 1% by weight or less, more preferably 0.7% by weight, as a measure of the gel content, as described above. Hereafter, it is necessary that the content is most preferably 0.5% by weight or less. When the molded propylene random copolymer obtained by using the modified propylene random copolymer obtained with a high extraction residual ratio is deteriorated in moldability, after the modified propylene random copolymer is used as a molded product However, it becomes extremely difficult to remelt and recycle.

The boiling xylene extraction residual ratio was obtained by placing 1 g of the polymer in a 200 mesh wire net using a Soxhlet extractor, extracting with p-xylene 200 ml with boiling xylene for 6 hours, and then measuring the extraction residue by dry weighing. , (Extraction residue weight / pre-extraction weight) × 100%.

Next, a method for producing the modified propylene random copolymer of the present invention having the above-mentioned characteristic requirements will be described. The propylene-based random copolymer used in the method for producing a modified propylene-based random copolymer of the present invention is a random copolymer of propylene and polyene, or propylene, polydiene, and an olefin having 2 to 12 carbon atoms other than propylene. It is a random copolymer with an olefin containing OH and has an intrinsic viscosity [η] measured in tetralin at 135 ° C. of 0.5 to 6 dl / g is preferably used, and particularly preferably 0.7 to 5 d.
It is preferably 1 / g from the viewpoint of moldability.

The polyene used in the production of the propylene-based random copolymer according to the present invention is a compound having two or more carbon-carbon double bonds in the molecule, and specifically, the following polyenes are used. Is mentioned. 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene,
1,8-nonadiene, 1,9-decadiene, 1,5,9
Straight chain aliphatic polyenes such as decatriene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,5-octadiene, 6-methyl-1,6-octadiene, 5,6-dimethyl-1,
6-octadiene, 7-methyl-1,6-octadiene, 7-methyl-1,6-decadiene, 7-ethyl-
Branched aliphatic polyenes such as 1,6-decadiene, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 1,3-divinylcyclopentane, 1,3-divinylcyclohexane, 1,4
-Divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-divinylcyclohexane,
Alicyclic polyenes such as 1,4-diallylcyclohexane, 1,5-diallylcyclooctane, 1,3,4-trivinylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, divinylbenzene, vinylisopropenylbenzene, etc. Such as aromatic polyene.

These polyenes can be used alone or in combination of two or more. Further, among these polyenes, polyenes having 7 or more carbon atoms are more preferably used.

Specifically, 1,6-heptadiene, 1,
6-octadiene, 1,7-octadiene, 1,9-decadiene, 1,5,9-decatriene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl- 1,6-octadiene, 1,3-
Divinylcyclopentane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-
4-divinylcyclohexane, 1,4-diallylcyclohexane, 1,3,4-trivinylcyclohexane and divinylbenzene.

Of these, more preferred is a carbon number of 8.
Of the above polyenes, polyenes having 9 or more carbon atoms are particularly preferable, and specific examples thereof include 1,9-decadiene and 7-methyl-1,6-octadiene.

The carbon number other than propylene used in the production of the propylene-based random copolymer according to the present invention is 2 to 1
Examples of the olefin of 2 include the following olefins. Ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,
4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1
-Hexene, 4-ethyl-1-hexene, styrene and the like. These olefins can be used alone or in combination of two or more.

Regarding the content of each component in the propylene random copolymer used in the present invention, the propylene content is 99.9 to 70 mol%, the polyene content is 0.1 to 10 mol%, and propylene. Other than 2 to 1 carbon
A olefin content of 2 in the range 0 to 20 mol% is suitable. Preferably, the propylene content is 99.5 to 8
5 mol%, the polyene content is 0.5 to 5 mol%, and the olefin content other than propylene having 2 to 12 carbon atoms is 0 to 10 mol%. Most preferably, the propylene content is in the range of 99.5 to 95 mol% and the polyene content is in the range of 0.5 to 5 mol%.

If the polyene content is less than 0.1 mol%, the improvement of the melt tension of the modified propylene random copolymer obtained is insufficient and the object of the present invention is not achieved. Also,
When the polyene content exceeds 10 mol%, the productivity of the propylene-based random copolymer itself is poor, and the propylene-based random copolymer and the modified propylene-based random copolymer have tackiness, heat resistance and It is not preferable because the rigidity is lowered and gel is likely to be generated in the modified propylene random copolymer.

The content of the olefin having 2 to 12 carbon atoms other than propylene, which is optionally used, is preferably 0 to 10 mol%. It is preferably 0 to 5 mol%. Further, from the viewpoint of rigidity and heat resistance of the obtained modified propylene random copolymer, it is preferable that the olefin other than propylene is not contained. When the content of the olefin other than propylene exceeds 10 mol%, the heat resistance and rigidity of the propylene random copolymer and the modified propylene random copolymer are deteriorated, and the original properties of polypropylene are lost, which is not preferable.

The above-mentioned propylene-based random copolymer used in the present invention comprises a transition metal compound catalyst component, an organometallic compound catalyst component containing a metal selected from Groups 1 to 3 of the periodic table, and, if necessary, It is a propylene-based random copolymer obtained by copolymerizing propylene and a polyene, and optionally an olefin other than propylene, using a catalyst obtained by combining an electron donor.

Examples of the transition metal compound catalyst component include compounds containing a transition metal selected from Groups 3 to 8 of the Periodic Table, specifically Ti and Z.
1 selected from r, Hf, Nb, Ta, Cr and V
Examples include compounds containing one or more transition metals.

Examples of such transition metal compound catalyst components include known olefin polymerization catalyst components. Specifically, titanium compounds, magnesium compounds, and, if necessary, oxygen and nitrogen in the molecule. , A supported catalyst component comprising titanium, magnesium, halogen and, if necessary, an electron donor, which is obtained by contacting an electron donor containing at least one of phosphorus, sulfur and titanium tetrachloride. Examples of the titanium trichloride-based catalyst component obtained by contacting the obtained titanium trichloride composition with a tetravalent titanium compound and / or an electron donor. Further, a metallocene compound obtained by contacting a cyclopentadienyl compound and a transition metal compound can also be used. As the metallocene compound, those supported on an inorganic compound such as SiO ₂ , Al ₂ O ₃ or a polymer compound such as polyethylene or polypropylene can also be used.

Specific examples of the organometallic compound catalyst component containing a metal selected from Groups 1 to 3 of the above periodic table include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide and aluminoxane. Organoaluminum compounds are preferably used.

Further, as the electron donor used as necessary, any one of oxygen, nitrogen, phosphorus and sulfur in the molecule can be used.
Examples thereof include compounds containing at least one species, and specifically, organic silicon compounds having a Si—O bond, esters, ethers and the like are preferably used.

Using a catalyst prepared by combining the above transition metal compound catalyst component, an organometallic compound catalyst component containing a metal selected from Groups 1 to 3 of the periodic table, and an electron donor, if necessary. , Slurry polymerization in which the polymerization is carried out in an inert solvent, bulk polymerization using the monomer itself as a solvent, propylene and polyene by a known polymerization method in which gas phase polymerization mainly including a monomer gas or a combination thereof is performed,
Further, a propylene-based random copolymer obtained by further polymerizing an olefin other than propylene is used in the present invention, if necessary.

Since the propylene random copolymer is required to be mixed with an organic peroxide in the form of the propylene random copolymer, it is in a state immediately after the completion of the polymerization step obtained by the various methods described above and before being pelletized. Powder is the preferred form.

The organic peroxide used in the present invention is
It is possible to use generally known organic peroxides.
Specifically, when the half-life is 1 minute, the decomposition temperature is 80 to 2
An organic peroxide exhibiting about 70 ° C., i-butyl peroxide (1 minute half-life temperature: 89 ° C., the same applies hereinafter),
2,4-dichlorobenzoyl peroxide (111
C), o-chlorobenzoyl peroxide (111
C), o-methylbenzoyl peroxide (113
C.), bis-3,5,5-trimethylhexanoyl peroxide (114.degree. C.), lauroyl peroxide (116.degree. C.), benzoyl peroxide (130.degree.
C), p-chlorobenzoyl peroxide (132
C.) and the like, 2,4,4-trimethylpentyl-2-hydroperoxide (190
° C), di-i-propylbenzene hadoroperoxide (252 ° C), t-butyl hydroperoxide (255 ° C), cumene hydroperoxide (264).
C) etc., hydroperoxide, tris- (t-butylperoxy) triazine (174 ° C.), dicumyl peroxide (179 ° C.), 2,5-dimethyl-2,5-
Di- (t-butylperoxy) -hexane (181
C.), 1,3-bis- (t-butylperoxy-i-propyl) -benzene (183.degree. C.), t-butylcumyl peroxide (183.degree. C.), di-t-butyl peroxide (192.degree. C.), 2,5-dimethyl-2,5-di-
(T-Butylperoxy) -hexyne-3 (193 ° C)
Dialkyl peroxides such as 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane (152 ° C.), 1,1-di-t-butylperoxycyclohexane (156 ° C.), 2, 2-di- (t-butylperoxy) -butane (161 ° C), 2,2-bis-
(4,4-di-t-butylperoxycyclohexyl)
-Peroxyketal such as propane (181 ° C), α-
Cumyl peroxy neodecanoate (86 ℃), 2,
4,4-Trimethylpentylperoxyneodecanoate (91 ° C), 2,4,4-Trimethylpentylperoxyphenoxyacetate (96 ° C), t-butylperoxyneodecanoate (99 ° C), t- Butylperoxy neohexipivalate (112 ° C), 2,4,4-trimethylpentylperoxy-2-ethylhexanoate (124 ° C), t-amylperoxy-2-ethylhexanoate (127 ° C) , T-butylperoxy-2
-Ethyl hexanoate (133 ° C), t-butylperoxy-i-butyrate (133 ° C), di-t-butylperoxyhexahydroterephthalate (142 ° C),
Di-t-butyl peroxyazelate (157 ° C.), t
-Alkylperesters such as -butylperoxy-3,5,5-trimethylhexoate (159 ° C), t-butylperoxyacetate (163 ° C), t-butylperoxytrimethyladipate (169 ° C), di- 3-
Methoxybutyl peroxydicarbonate (85 ° C),
Bis (4di-t-butylcyclohexyl) peroxydicarbonate (92 ° C), di-i-propylperoxydicarbonate (93 ° C), t-butylperoxy-i
-Percarbonates such as propyl carbonate (156 ° C).

Of these organic peroxides, when the heat treatment described below is carried out at a temperature at which the propylene random copolymer maintains the particle shape, that is, at a temperature lower than the melting point of the copolymer, Half-life temperature of 1 minute is 80-150
The organic peroxide having a temperature of 0 ° C is preferable, and the organic peroxide having a temperature of 80 to 120 ° C is particularly preferable. It is also an aspect of the present invention that the same heat treatment is carried out at a temperature at which the copolymer is in a molten state. In this case, the one-minute half-life temperature is 150 to 270 ° C. Organic peroxides are preferred, especially 1
Organic peroxides at 50-250 ° C are preferred.

In the method of the present invention, first, an organic peroxide is added to and mixed with the propylene random copolymer described above. Proportion of propylene-based random copolymer 1
0.001 to 1 part by weight of an organic peroxide relative to 00 parts by weight, more preferably a propylene random copolymer 1
0.005-0.5 parts by weight of organic peroxide to 100 parts by weight, most preferably 10 parts by weight of propylene-based random copolymer
The amount of the organic peroxide is 0.005 to 0.25 part by weight based on 0 part by weight. Further, when the propylene random copolymer is a straight chain aliphatic polyene used as the polyene, gel is likely to occur in the modified propylene random copolymer obtained, and therefore a more preferable mixing ratio of the organic peroxide. Is 0.003 to 0.2 parts by weight of an organic peroxide based on 100 parts by weight of a propylene random copolymer, and most preferably 0.003 to 0. It is 08 parts by weight. If the addition ratio of the organic peroxide is small, the improvement of the melt tension of the modified propylene random copolymer obtained is insufficient, and if the addition ratio of the organic peroxide is too large, the modified propylene random copolymer obtained. Polymers now include gels, both outside the scope of the present invention.

When an organic peroxide is added to and mixed with the modified propylene random copolymer, toluene, xylene, isoparaffin, and isoparaffin are added for handling and for uniform mixing.
It is also possible to use one diluted with a hydrocarbon solvent such as octane or decane or an inert medium represented by an inorganic substance such as calcium carbonate. The concentration of organic peroxide in the medium is 1
It is used in an amount of about 0 wt% or more.

The addition and mixing of the organic peroxide to the propylene random copolymer is usually carried out by a known method. For example, it can be carried out using a stirring and mixing device such as a Henschel mixer (trade name) or a super mixer. The temperature during the addition and mixing is preferably 40 ° C. or lower and 0 ° C. or higher.

In the present invention, subsequently, a mixture of the propylene random copolymer and the organic peroxide is added in an amount of 80 to 3
Heat treatment at 50 ° C. The heat treatment in the present invention can be carried out in various modes and is not particularly limited, but the following modes are more preferable. The first is heat treatment under a temperature condition in which the propylene-based random copolymer maintains the particle shape,
The second is heat treatment under a temperature condition in which the propylene-based random copolymer is in a molten state. It is also one of the preferable embodiments of the present invention to combine the second embodiment after the first embodiment. The second aspect is particularly preferable.

The heat treatment carried out under the temperature condition for keeping the particle shape of the propylene random copolymer, which is the first aspect, is 80 ° C. or higher and not higher than the melting point of the propylene random copolymer, More preferably 80 to 15
It is carried out at 0 ° C., particularly preferably at 80 to 140 ° C.
The heat treatment time is 5 minutes to 5 hours, preferably 10 minutes to 3 hours. Further, the heat treatment is preferably carried out in an inert gas atmosphere.

The heat treatment carried out under the temperature condition in which the propylene-based random copolymer according to the present invention is in the molten state, which is the second aspect, is the melting point of the propylene-based random copolymer or more and 350 ° C. or less. Temperature, more preferably 190 to 300 ° C., particularly preferably 200 to 280
Conduct at ℃. A method of using a melt kneader is simple for the heat treatment, and a known ordinary melt kneader is used as the melt kneader. For example, single screw extruder, twin screw extruder,
An extruder, a Brabender, a Banbury mixer, etc., in which these are combined with a gear pump. The melt-kneading time varies depending on the melt-kneader and is not specified, but usually 20 seconds to 30 minutes is sufficient. Usually, after melt-kneading, it is subsequently cut into granules and pelletized.

In the melt-kneading, if necessary, before heating and melting, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an anti-blocking agent, a colorant, an inorganic or organic substance. Various additives such as the above-mentioned filler can be blended.

The modified propylene-based random copolymer obtained by the production method of the present invention is obtained by the above-mentioned method. In order to achieve the object of the present invention, the modified propylene-based random copolymer is one of the above-mentioned two types. Must have characteristic requirements. That is, it cannot be said that the obtained modified propylene random copolymer has two characteristic requirements even within the range of the above-mentioned production method, and therefore the propylene random copolymer to be used is used. It is necessary to select an appropriate combination of the amount of the organic peroxide and the heat treatment condition according to the combination of the type of the organic peroxide and the type of the organic peroxide from the production conditions of the present invention described above.

Thus, the modified propylene random copolymer obtained by the method of the present invention has an extremely high melt tension and excellent moldability, and can be reused by remelting after being used as a molded product. Therefore, it is particularly suitable for hollow molding, foam molding, extrusion molding, but is not limited to the molding field, and various containers such as hollow containers by injection molding, T-die molding, thermoforming, films, sheets, It can be used for various molded products such as pipes and fibers.

[0044]

EXAMPLES Next, the present invention will be specifically described with reference to examples. Definitions of terms and measurement methods used in Examples and Comparative Examples are as follows. (1) Polyene content: measured using ¹³ C-NMR. (Unit: mol%) (2) Intrinsic viscosity: [η], measured by the method described above.
(Unit: dl / g) (3) Melt tension: (MS), measured by the method described above. (Unit: gf)

Example 1 Magnesium chloride-supporting titanium catalyst component obtained by the method described in Example 1 of JP-A No. 62-104812 and triethylaluminum were added in an amount of 200 mol per 1 mol of titanium in the titanium catalyst component, And a catalyst in which 20 mol of diisopropyldimethoxysilane as the third component is combined with 1 mol of titanium in the titanium catalyst component, in the presence of hydrogen as a molecular weight controlling agent in n-hexane, propylene and 7-methyl. The intrinsic viscosity [η] obtained by slurry-polymerizing -1,6-octadiene is 2.
A propylene-7-methyl-1,6-octadiene random copolymer powder having 94 dl / g, a 7-methyl-1,6-octadiene content of 3.1 mol% and an average particle diameter of 450 μm is used in the present invention. 10 kg of a propylene random copolymer, 12 g of 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane as an organic peroxide, and tetrakis [methylene-] as an additive.
10 g of 3- (3′-5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 10 g of calcium stearate were put into a Henschel mixer (trade name) having an internal volume of 80 l. Then, the mixture was stirred and mixed at 25 ° C. for 2 minutes. Further, the mixture is mixed with a screw diameter of 40 mm.
After melt-kneading at 230 ° C. using the extrusion granulator, the modified propylene random copolymer of the present invention was obtained as pellets.

Examples 2 and 3 and Comparative Examples 1 to 4 In Example 1, the propylene random copolymer used as a raw material contained 7-methyl-1,6-octadiene in content and intrinsic viscosity, and further, organic peroxide. Pellets were obtained in the same manner as in Example 1 except that the addition amount of 2,5-dimethyl-2,5-di- (t-butylperoxy) -hexane was changed as shown in Table 1. It was

The above Examples 1 to 3 and Comparative Examples 1 to 4
The conditions and results are shown in Table 1.

[0048]

[Table 1]

Example 4 In Example 1, a propylene-based resin having an intrinsic viscosity [η] of 1.77 dl / g, containing 0.84 mol% of 1,9-decadiene in place of 7-methyl-1,6-octadiene. Using a random copolymer, 2, as an organic peroxide
5-dimethyl-2,5-di- (t-butylperoxy)
Pellets were obtained in the same manner as in Example 1 except that 1 g of dicumyl peroxide was used instead of hexane, and the melt-kneading temperature was 220 ° C.

Comparative Examples 5 and 6 Pellets were obtained in the same manner as in Example 4 except that the amount of dicumyl peroxide added in Example 4 was changed to the amount shown in Table 2.

Comparative Example 7 A propylene homopolymer was used in place of the propylene random copolymer used as the raw material in Example 4,
Pellets were obtained in the same manner as in Example 4 except that the other conditions were changed as shown in Table 2.

Example 5 In Example 1, the propylene random copolymer used as a raw material had an intrinsic viscosity [η] of 2.73 dl /
g, 7-methyl-1,6-octadiene content of 1.3
Example 1 except that propylene-7-methyl-1,6-octadiene-1-butene random copolymer powder having 5 mol% and 1-butene content of 0.5 mol% was used.
Pellets were obtained in the same manner as in.

Table 2 shows the conditions and results of Examples 4 and 5 and Comparative Examples 5 to 7 described above.

[0054]

[Table 2]

Example 6 With respect to 100 parts by weight of a mixture of a propylene random copolymer obtained by the same method as in Example 1, an organic peroxide and an additive, 0.1 part by weight of talc was further used as a nucleating agent for foaming. Was mixed, and the mixture was supplied to a single-screw extruder set to a screw diameter of 65 mm and an extruder temperature of 230 ° C. Then, 22 parts by weight of 1,1,2,2-tetrafluorodichloroethane was injected as a foaming agent from the middle of the extruder. Extrusion foam molding was carried out at a mold temperature of 155 ° C. using a nozzle-shaped mold having a diameter of 5 mm mounted on an extruder. The surface of the obtained foam was smooth, and abnormal cells were not observed, and the cells had uniform cells.

Comparative Example 8 When extrusion foam molding was carried out in the same manner as in Example 6 except that the organic peroxide was not added, the resulting foam had gas outgassing and had a poor appearance. There was a large nest, which was unsatisfactory and could not be used.

Example 7 A modified propylene random copolymer pellet obtained in the same manner as in Example 1 was subjected to extrusion sheeting at 260 ° C. using an extruder with a T-die and a screw diameter of 65 mm. Then, a sheet having a thickness of 0.5 mm was obtained. Next, in order to evaluate the heating vacuum formability of the sheet as a model,
The sheet was fixed to a 40 cm square frame, placed in a thermostatic chamber at 210 ° C., and the behavior was observed. By heating, the central portion of the sheet started to hang down, and when it hung down by 35 mm, the hang-down stopped, and conversely the lower part rose. The sheet started to hang down again 12 seconds after the drooping stopped, and only hung down thereafter. It was found that the amount of drooping was small and the time until the start of re-drooping was as long as 12 seconds, and the sheet was extremely excellent in the heat vacuum forming property.

Comparative Example 9 The procedure of Example 7 was repeated except that the modified propylene random copolymer pellet obtained by the method of the present invention was replaced by the pellet obtained in the same manner as in Comparative Example 1. Got a sheet. When the heating behavior of the sheet was observed in the same manner as in Example 9, it was found that the sheet stopped hanging at 40 mm, and the time until the start of re-hanging was as short as 5 seconds. It was inferior in heating vacuum formability.

Example 8 The modified propylene random copolymer pellets obtained in the same manner as in Example 1 were heated at a molding temperature of 230 ° C. and a mold temperature of 20 ° C. using a direct blow molding machine having a screw diameter of 65 mm. When a kerosene tank having an internal volume of 100 l was hollow-molded, a homogeneous hollow-molded product was obtained in which the parison did not draw down and the thickness was uniform. Subsequently, the hollow molded article was crushed into a crushed product. A propylene random copolymer composition comprising 10% by weight of the pulverized product of the molded product thus obtained and 90% by weight of the modified propylene random copolymer pellets obtained in the same manner as in Example 1 was obtained. When a kerosene tank having an internal volume of 100 l was hollow-molded in the same manner as above, a homogeneous hollow-molded product was obtained in which the parison was not drawn down and the thickness was uniform.

[0060]

As is apparent from the above-mentioned embodiment,
The modified propylene random copolymer of the present invention has an extremely high melt tension and excellent moldability, and it is possible to expand the fields of application, which have been limited by conventional polypropylene.

Claims (2)

[Claims] 1. A propylene content of 99.9 to 70 mol%, a polyene content of 0.1 to 10 mol%, and an olefin content of 2 to 12 carbon atoms other than propylene of 0 to 20 mol%. To 100 parts by weight of the propylene-based random copolymer, 0.001 to 1 part by weight of organic peroxide was added and mixed, and the resulting mixture was mixed with 80 to 35 parts by weight.
(A) Melt tension (MS) at 230 ° C. and intrinsic viscosity [η] measured at 135 ° C. in tetralin are log,
(MS)> 4.24 × log [η] −0.915, and (B) a boiling xylene extraction residual rate of 1% by weight or less, of a modified propylene-based random copolymer Production method. 2. The propylene content is 99.9 to 70 mol%, the polyene content is 0.1 to 10 mol%, and the olefin content other than propylene having 2 to 12 carbon atoms is 0 to 20 mol%. To 100 parts by weight of the propylene-based random copolymer, 0.001 to 1 part by weight of organic peroxide was added and mixed, and the resulting mixture was mixed with 80 to 35 parts by weight.
The melt tension (MS) at 230 ° C. and the intrinsic viscosity [η] measured at 135 ° C. in tetralin, obtained by the method of heat treatment at 0 ° C., are log
(MS)> 4.24 × log [η] −0.915, and (B) a modified propylene random copolymer having a boiling xylene extraction residual rate of 1% by weight or less. Molded product used.