JPH02279746A - Crystalline propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having high transparency and high rigidity and being free from the problem of bleeding and the formation of granu lar structures during molding by mixing PP with a specified branched alpha-olefin polymer and a specified organic phosphate salt. CONSTITUTION:The title composition is obtained by mixing a crystalline PP of a melt flow rate of 0.1 to 200g/10min with PP of a 3-methyl-1-butene content of 0.001 to 10wt.% and a melt flow rate of 0.1 to 200g/10min and an organic phosphate salt of the formula (wherein R<1> is a direct bond, sulfur or a 1 to 4C alkylidene; R<2> to R<5> are each H, a 1 to 8C alkyl; M is a monovalent to trivalent metal atom; and (n) is an integer of 1 to 3) in such a amounts that the 3-methyl-1-butene content is 0.0001 to 1wt.%, and the salt content is 0.005 to 0.5wt.%. In this way, the subject composition having especially high transpar ency and high rigidity and being free from the problem of bleeding during molding can be obtained.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to improving the properties of crystalline propylene polymers, and in particular to improving the properties of crystalline propylene polymers, and in particular to improving the properties of crystalline propylene polymers, and in particular, improving the properties of crystalline propylene polymers. The present invention relates to a combined composition.

[Conventional technology 1] Crystalline propylene polymer is a general-purpose resin that has excellent moldability, heat resistance, mechanical properties, and chemical stability. Extruded products such as , blow bottles, etc. are used as various packaging materials.

However, since the propylene polymer has a large difference in refractive index between the crystalline portion and the amorphous portion, the transparency may be poor depending on the two fields of application, resulting in loss of commercial value.

Until now, no method has been proposed to improve the transparency of this crystalline propylene polymer. It is known that when these nucleating agents are added, they become crystal nucleating agents, reducing the size of spherulites and improving transparency.However, these nucleating agents They have low compatibility with propylene polymers, and if the amount added is large, there will be problems in terms of cost and bleeding, and there is a limit to improving the transparency of crystalline polyolefins only by adding these nucleating agents. was there.

It is also known that the transparency of propylene polymers can be improved by randomly copolymerizing propylene with comonomers such as ethylene and butene, but this method reduces the rigidity, which is a characteristic of propylene polymers. There are restrictions on the amount of comonomer to be copolymerized.

Recently, an attempt to improve transparency by incorporating a small amount of vinylcycloalkane polymer into propylene polymer has been proposed (Japanese Patent Application Laid-open No. 139731/1983), but this method avoids the problem of bleeding. However, the effect of improving transparency is not necessarily sufficient.

[Problems to be Solved by the Invention] As mentioned above, in order to obtain sufficient transparency in conventional nucleating agents, there is a problem of bleeding during molding.
Additives that did not bleed had insufficient effects on improving transparency. The purpose of the present invention is to have excellent transparency and rigidity,
Another object of the present invention is to develop a crystalline propylene polymer that does not cause bleeding problems during molding.

[Means for Solving the Problem] From this point of view, the present inventors have conducted intensive studies on improving the transparency and rigidity of extruded products of crystalline propylene polymers, and as a result, the present inventors have found that propylene polymers have a specific branched α - By blending an olefin polymer and an organic phosphate with a special structure, a highly crystalline propylene that is extremely transparent and rigid, and does not cause bleeding problems during molding. The present invention was completed by discovering that a polymer composition can be obtained.

That is, the present invention provides a composition comprising the following A, B, and C, in which the 3-methyl-1-butene content is 0.0001-1% by weight, and the C component content is o, oo
This is a crystalline propylene polymer composition with excellent transparency and rigidity, characterized by a content of s to 0.5% by weight.

A, crystalline propylene polymer with a melt flow rate of 0.1-200 g710 minutes B, 3-methyl-1-butene content of 0.001-10% by weight and a melt flow rate of 0.1-200 g710
Propylene polymer C1 Organophosphate represented by the following general formula (in the formula, R'
is a straight chain bond of sulfur or an alkylidene group having 1 to 4 carbon atoms, R2-R5 are hydrogen or the same or different alkyl groups having 1 to 8 carbon atoms, M is a monovalent to trivalent metal atom, and , represents an integer from 1 to 3. ) +11 Crystalline propylene polymer (component A) The crystalline propylene polymer of component A used in the present invention is a propylene homopolymer, propylene and other α
-Random or block copolymers with olefins. Ethylene, butene, pentene, hexene, etc. can be used as the α-olefin.

The propylene polymer used in the present invention has a melt flow rate (hereinafter abbreviated as VFR) of 0.1 to 2.
00g710min, preferably 0.3-100g/10
boiling n-hebutane extraction residue (isotactic index, hereinafter abbreviated as II).
is 85% or more, preferably 90% or more, or a crystalline propylene homopolymer with II of 60% or more, preferably 85% or more, with an ethylene content of 6% by weight or less, or other α- A propylene copolymer with an olefin content of 15% by weight or less.

Or a mixture thereof is suitable.

If the VFR is below the above range, the molding speed will decrease,
Anything higher than that is unsuitable because it lacks melt tension and tends to sag during secondary processing such as thermoforming, and has low impact resistance.Among these, 0.3 to 3
0g710min, especially 5-l.

g/lo is preferred.

These propylene polymers are made of a titanium-containing solid catalyst such as a catalyst in which a titanium compound is supported on titanium trichloride or magnesium halide, and triethylaluminum or triisobutylaluminum.

By the use of catalyst systems consisting of organoaluminum compounds such as diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, etc.
It is suitably produced by conventional known polymerization methods, such as slurry polymerization in a hydrocarbon solvent such as hexane, hebukun, or benzene, bulk polymerization in liquefied propylene, or gas phase polymerization in propylene gas. Further, in order to improve II of the polymer during polymerization, an electron donor such as a carboxylic acid ester or an organosilicon compound may be added.

(2) 3-methyl-1-butene-containing propylene polymer (
The propylene polymer containing 3-methyl-1-butene used as component B is produced by converting the 3-methyl-1-butene polymer into propylene polymer using the same catalyst as in the production of the propylene non-polymer described above. There are two methods: a method in which 3-methyl-1-butene is prepolymerized using a propylene polymerization catalyst, and then propylene is polymerized. However, the latter method is preferably adopted.

Propylene polymerization catalysts used in the polymerization of 3-methyl-1-butene include magnesium halides and titanium halides, especially when propylene is subsequently polymerized to obtain a propylene/3-methyl-1-butene copolymer. A method using a catalyst formed from a solid titanium catalyst component containing an electron-donating compound as an essential component and an organoaluminum compound is preferred.

The halogen-containing magnesium used in the solid titanium catalyst component used in the production of the propylene/3-methyl-1-butene copolymer as component B is preferably dihalides, such as magnesium chloride, magnesium bromide, and iodide. Magnesium can be used. Particularly preferred is magnesium chloride,5 and preferably substantially anhydrous.

In addition, this halogen-containing magnesium can be used as an electron-donating compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, and organomagnesium compounds. , herosilane, alkoxysilane, silanol, an aluminum compound, a halogenated titanium compound, a titanium tetraalkoxide, or the like.

Typical examples of halogen-containing titanium include trivalent and tetravalent titanium halogen compounds. Preferred titanium halogen compounds are those represented by the following formula (where R is a C1-C1° hydrocarbon residue and X is a halogen), where n=0, l or 2. It is a tetravalent halogenated titanium compound. Specifically, Ti
Cj, , Ti (OBultJ3, Ti (OBul
acla and the like, particularly preferred are titanium tetrahalides and titanium monoalkoxytrihalides compounds such as TiCL and Tx(OBu)C10.

The electron-donating compound is normally used as a modifier for Ziegler type catalysts, and in the present invention, any compound can be selected and used according to the purpose.

Preferred electron-donating compounds to be used as the so-called "internal donor" in the present invention include esters of polyfunctional compounds selected from the group consisting of polycarboxylic acids, polyhydric alcohols, and hydroxy-substituted carboxylic acids, and organosilicon compounds. It is.

Suitable esters of polyfunctional compounds are, for example, aliphatic and aromatic polycarboxylic acid esters, and particularly preferred are those in which at least one of the ester groups has 2 carbon atoms.
It is a diester of the dicarboxylic acid having the above alkyl group. Specific examples of preferred dicarboxylic acid esters include esters of phthalic acid, maleic acid, substituted malonic acid, etc., and alcohols having 2 or more carbon atoms, and particularly preferred are esters of phthalic acid and alcohols having 4 or more carbon atoms. It is a diester.

As the organosilicon compound, an organosilicon compound represented by the following formula is used.

R'R'3-+5Si(OR")n where R7 is a branched hydrocarbon residue, Ha and R9 are branched or linear hydrocarbon residues, respectively, and n is 2≦n≦3
is the number of

R7 is preferably branched from the carbon atom adjacent to the silicon atom. In that case, the branching group is an alkyl group,
Preferably it is a cycloalkyl group or an aryl group (for example a phenyl group or a methyl-substituted phenyl group). More preferred R9 is one in which the carbon atom adjacent to the silicon atom, that is, the carbon atom at positions 0 to 1, is a secondary or tertiary carbon atom.

Particularly preferred is one having a structure in which three alkyl groups emerge from a carbon atom bonded to a silicon atom, R? The number of carbon atoms is usually 3 to 20, preferably 4 to 10.

R8 is usually a branched or linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 10. R9 is an aliphatic hydrocarbon group, preferably an aliphatic group having 1 to 4 carbon atoms. In the present invention, where a hydrocarbon group is usually used, either one of the above-mentioned ester of a polyfunctional compound and an organosilicon compound, or a combination of both can be used as the "internal donor."

Moreover, the above-mentioned organosilicon compounds can be used as an external donor if necessary.

The aluminum compound used in the production of the propylene copolymer, which is the daily ingredient used in the present invention, is
'nX3-. (Here, R' is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen or alkoxy group, and 0<n≦3) is preferable.

Such organoaluminum compounds are specifically, for example, triethylaluminum, trilopropylaluminum, trilobylaluminum, triisobutylaluminum, triisohexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminum hydrite, diisobutyl These include aluminum hydride, diethylaluminium monochlorite, ethylaluminum sesquichloride, diethylaluminum monoethoxide, and the like. Of course,
It is also possible to use two or more of these organoaluminum compounds in combination.

Generally, a suitable method for polymerizing the propylene copolymer as component B is a method in which 3-methyl-1-butene is polymerized in advance in the presence of the above-mentioned catalyst, and propylene is subsequently polymerized.

The 3-methyl-1-butene-containing propylene polymer as component B has a 3-methyl-1 to butene content of 0 and 0.
1 to 10% by weight and MFR of 0.1 to 200g7
10 minutes is used in the present invention.

3-methyl-! -If the butene content is too low, the effect of the present invention will not be achieved, if it is too high, the dispersibility in component A will deteriorate, which is undesirable, and if the VFR is too high, the catalyst activity will decrease during polymerization, which is uneconomical. If it is too low, the dispersibility in component A will deteriorate, which is not preferable.

The blending ratio of the above daily ingredients is 3-methyl-
- The butene content may be determined to be 0.0001-1% by weight, preferably 0.001-0.1% by weight,
If the amount of 3-methyl-1-butene is below this range, the effects of improving transparency and rigidity, which are the objectives of the present invention, will be insufficient, while if it exceeds this range, no further improvement effects can be expected. or economically disadvantageous.

(3) Organic phosphate compound (component C) The organic phosphate compound as component C used in the present invention is a compound represented by the following general formula.

In the formula, R1 is a linear bond or an alkylidene group having 1 to 4 carbon atoms, and 11 to R'' are each hydrogen or an alkylidene group having 1 to 4 carbon atoms.
The same or different alkyl groups 1M in 8 are monovalent to trivalent metal atoms, and n represents an integer of 1 to 3.

Specific examples of such compounds include sodium-2,
2'-methylene-bis-(4,6-di-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis-(4,6-di-butylphenyl) phosphate, lithium-2,2' -methylene-bis-(4,
6-di-L-butylphenyl) phosphate, lithium-2,2°-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-2,2°-
Ethylidene-bis-(4-1-propyl-6-t-butylphenyl)phosphate, lithium-2,2°-methylene-bis-(4-methyl-6(-butylphenyl)phosphate, lithium-2,2° -methylene-bis-(
4-ethyl-6-4-butylphenyl) phosphate,
Calcium-bis-[2,2'-thiobis-(4-methyl-6-t-butylphenyl)phosphate 1, Calcium-bis-[2,2°-thiobis-(4-ethyl-6
-t-butylphenyl) phosphate], calcium-
Bis-[2゜2'-thiobis-(4,6-di-t-butylphenyl)phosphate], magnesium-bis-[
2,2'-thiobis-(4,6-di-t-butylphenyl)phosphate], magnesium-bis-12,2-
Thiobis-(4t-octylphenyl)phosphate]
, sodium-2,2°-butylidene-bis-(4°6
-di-methylphenyl)phosphate, sodium-2
, 2-butylidene-bis(4,6-di-t-butylphenyl)phosphate, sodium-2,2-di-butylmethylene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-2, Calcium-bis-12,2-methylene-bis-+4,6-di-t-butylphenyl)phosphate, Magnesium-bis -[2,2°-methylene-
Bis-(4,6-di-butylphenyl)phosphate1. barium-bis-[2,2°-methylene-bis-
(4,6-di-butylphenyl)phosphate],
Sodium-2,2'-methylene-bis-(4-methyl-6-t-butylphenyl)phosphate, Sodium-2,2'-methylene-bis-(4-ethyl-6-t-
butylphenyl) phosphate, sodium (4,4-
Dimethyl-6,6'-di-t-butyl-22'-biphenyl)phosphate, calcium-bis-[(4,4-
Dimethyl-6,6°-di-t-butyl-2,2°-biphenyl)phosphate1. Sodium-2,2-ethylidene-bis-(4-8-butyl-6-1,-butylphenyl) phosphate, Sodium-2,2°-methylene-bis-(4,6-di-methylphenyl) phosphate, Sodium-2,2-methylene-bis(4,6-cy-nitylphenyl)phosphate, potassium-2,2-
Ethylidene-bis-(4,6-di-t-butylphenyl)phosphate, Calcium-bis-[2゜2'-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate], Magnesium-bis-[ 2,2-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate], barium-bis-[2,2-ethylidene-
Bis-(4,6-di-t-butylphenyl) phosphate, aluminum tris-[2,2°-methylene-bis-(4,6-di-t-butylphenyl) phosphate 1, aluminum tris-[2, 2°-ethylidene-
bis-(4,6-di-L-butylphenyl) phosphate] or a mixture of two or more thereof. In particular, sodium-2,2'-methy1non-bis-(4,6
-dibutylphenyl) phosphate is preferred.

The organophosphate compound is usually present in the composition of the present invention in an amount of 0.0
0.05 to 0.5% by weight, preferably 0.05 to 0.5% by weight. O1 to o, i are contained in an amount of % by weight. If the content is less than the above range, the effect of improving transparency and rigidity will be insufficient, while if the content exceeds the above range, it will be economically disadvantageous.In the composition of the present invention, additional components may be added in addition to the above essential components. , may be further added within a range that does not significantly impair the effects of the present invention. These additional components include antioxidants, neutralizers, ultraviolet absorbers, antifoaming agents, dispersants, antistatic agents, lubricants, molecular weight regulators (peroxides), etc. used for ordinary polyolefins. Examples include various auxiliary agents such as nucleating agents, rubber components, and coloring agents.

The method of blending the composition of the present invention is not particularly related to the order of addition or the equipment used, but commonly used Henschel mixers, super mixers, blenders, tumbler mixers, ribbon blenders, Banbury mixers, kneader blenders, or extruders may be used. It is preferable to mix the mixture for a predetermined time using a mixer or mixer, and then form it into a pellet using an ordinary extruder.

The composition of the present invention is processed into various molded products through extrusion molding, blow molding, film molding, injection molding, compression molding, and the like.

[Example J In the following examples, the following 3-methyl-1-butene-containing propylene polymer was used as the B component.

(Production of 3-methyl-!-butene-containing propylene polymer) After purging a 500 m1 glass three-meter flask equipped with a thermometer and a stirring bar with nitrogen, 75++1 purified hebutane was added. , 751 titanium tetrabutoxide and 10 g
of anhydrous magnesium chloride. The flask was heated to 90°C and magnesium chloride was completely dissolved over 2 hours.Next, the flask was cooled to 40°C and 15ml of methylhydrodiene polysiloxane was added to dissolve the magnesium chloride/titanium tetrabutoxide complex. Let it precipitate.

After washing this with purified heptane, silicon tetrachloride B, 7
(1) Add 1 and 2.0 g of phthaloyl chloride and hold at 50°C for 2 hours. Thereafter, the purified product was washed with butane, and further 25 mj of titanium tetrachloride was added and kept at 25°C for 2 hours. This was washed with purified butane to obtain a solid catalyst component.

The titanium content in the solid catalyst component was 2.7% by weight.

3-Methyl-1-butene A In a stirred autoclave with an internal volume of 1, 500 gml of purified hebutane, 0.8 g of the solid catalyst component prepared above, 3
2g of 3-methyl-1-butene, 2g of triisobutylaluminum and 0.6g of tert-butylethyldimethoxysilane were introduced and reacted at 50°C for 3 hours! Thereafter, the purified product was washed with butane to remove unreacted components. The amount of polymerized 3-methyl-1-butene is 25g per 1g of solid catalyst.
Met.

After fully purging a stirred autoclave with an internal volume of 3 with propylene, fully dehydrated n-hebutane (1.5 kg) was introduced and kept at 75°C, and then 7 kg/ca + 2 G of propylene was added.
Pressurized to 0 then triethylaluminum 0.38
g, 0.16 g of diphenyldimethoxysilane and 780 mg of the above 3-methyl-1-butene polymerized catalyst component.
(containing 30 mg of solid catalyst) was introduced, and polymerization was carried out at 75°C for 3 hours while adjusting the hydrogen concentration in the gas phase to 0.3% by volume. Afterwards, purge the propylene and remove the butanol 1
(Polymerization is stopped by adding lsj, filtration,
After drying, 356 g of propylene copolymer powder was obtained. This propylene copolymer powder contains 3-methyl-1-
It contained 2100 ppm of butene.

Examples 1 to 4 Ethylene-propylene random copolymer with ethylene content of 2.5% by weight [MFR: 10g 710 minutes (2,16k
g load, 230°C)] 3-methyl-1-butene-containing propylene polymer and sodium-2,2°-methylene-bis-(4°6- D-butylphenyl) phosphate (
NAII) manufactured by Adeka Argus, and further contains 0.1 part by weight of 3.5-di-t-butyl-4-hydroxytoluene and 0.05 parts by weight of calcium stearate as stabilizers.
After adding parts by weight and blending with a Henschel mixer,
The mixture was kneaded at 230°C using a 30-■φ extruder to form pellets.

The obtained pellet was molded into a test piece using an injection molding machine (240° C.), and the flexural modulus (JIS K7203) and haze (JIS 6714, 2@■ thick sheet) were measured. ! ! Table 1 shows the fixed connection tube.

Table 1 are shown in Table 1.

[Effects of the Invention] The crystalline propylene polymer composition of the present invention unexpectedly becomes transparent by blending a small amount of 3-methyl-■-butene polymer and an organic phosphate compound with a specific structure into the propylene polymer. It has improved properties in terms of elasticity and flexural modulus, and does not cause problems such as bleeding or lumps during extrusion molding, which is the case when conventional nucleating agents are blended.

The composition of the present invention has excellent transparency and rigidity, and can be suitably used as a packaging material for cigarettes, fibers, foods, etc., or as a shrink wrapping material, and for applications such as VTR cassette cases.

Comparative examples 1 to 4

Claims (1)

[Claims] (1) A composition containing the following A, B and C, with a 3-methyl-1-butene content of 0.0001
1% by weight, and a C component content of 0.005 to 0.5% by weight. A crystalline propylene polymer composition having excellent transparency and rigidity. A, a crystalline propylene polymer with a melt flow rate of 0.1 to 200 g/10 min B, a 3-methyl-1-butene content of 0.001 to 10 wt% and a melt flow rate of 0.1 to 200 g/10 Propylene polymer C, organophosphate represented by the general formula below ▲ Numerical formulas, chemical formulas, tables, etc. , R^2 to R^5 are hydrogen or the same or different alkyl groups having 1 to 8 carbon atoms, M is a monovalent to trivalent metal atom, and n is an integer of 1 to 3.)