JPS63210152A - High-rigidity and high-melt viscoelasticity propylene homopolymer composition - Google Patents

Abstract

PURPOSE:To make it possible to form a propylene homopolymer composition which yields a sheet remarkably excellent in secondary processability, rigidity and heat-resistant rigidity, by mixing a specified propylene homopolymer with a phosphate compound. CONSTITUTION:100pts.wt. polymer (X) is mixed with 0.01-1pt.wt. phosphate compound of formula II (wherein R1 is a 1-4 C alkylidene or the like, R2 and R3 are each H or a 1-8 C alkyl, M is a mono- to tri-valent metal and n is an integer of 1-3). Polymer (X) is a crystalline propylene homopolymer obtained by polymerizing propylene in multiple stages so that 35-65wt.% of the total polymer by the formed in each of the first and second or latter stages, and satisfying formula I (wherein [eta]H is the intrinsic viscosity of the polymer portion of a higher MW and [eta]L) is the intrinsic viscosity of the polymer portion of a lower MW and the relationship of 1.00>=0.015log MFR+0.955, wherein P is the isotactic pentad fraction of the total polymer and MFR is its melt flow rate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a high stiffness, high melt viscoelastic propylene homopolymer composition. More specifically, the present invention relates to a high-rigidity, high-melt viscoelastic propylene homopolymer composition that is extremely superior in rigidity and heat-resistant rigidity.

[Conventional technology]

In general, propylene polymers have excellent processability, chemical resistance,
Because it has electrical and mechanical properties, it is processed into injection molded products, blow molded products, films, sheets, fibers, etc. and used for various purposes. However, sheets manufactured by processing propylene polymers tend to sag quickly during heat forming for secondary processing, have a narrow range of processing conditions, and have poor forming efficiency; There are various problems such as a large sagging, a tendency for the thickness of the secondary processed product to become uneven, and a tendency for overlapping wrinkles to occur. For this reason, the current situation is that only small molded products can be manufactured. Further, when a propylene polymer is used for blow molding, there are the following problems.

Specifically, (1) the parison sags significantly during molding, resulting in uneven wall thickness of the molded product; For this reason, the blow molding method cannot be applied to small products. ■If a high-molecular-weight propylene polymer is used to prevent the above-mentioned sagging, it will result in poor fluidity, a large load during molding, large energy loss, the risk of mechanical troubles, and rough skin of the molded product, resulting in severe commercial value. There are problems such as loss of information.

On the other hand, depending on the various specific uses of the propylene polymer, the properties of the propylene polymer may not be said to be sufficient, and there is a problem in that the expansion of its specific uses is limited. In terms of stiffness, such as wrinkle stiffness and heat-resistant stiffness, it is inferior to polystyrene, ABS resin, polyester, etc., and this has become a serious bottleneck in expanding the use of propylene-based polymers. Therefore, if it is possible to improve the rigidity, the molded product can be made thinner to that extent, which not only contributes to resource conservation, but also increases the cooling rate of the molded product obtained during molding, so the unit The molding speed in time 1) can be increased, contributing to improved productivity.

For this reason, for the purpose of improving the secondary processability, blow moldability, and rigidity of the above-mentioned sheets related to dipropylene polymers, Japanese Patent Laid-Open No. 58-219207 filed by the same applicant as the present application has been published. discloses propylene homopolymers having a specific molecular weight distribution and a specific isotactic pentad fraction. Furthermore, in the above publication, an organic nucleating agent consisting of aluminum pt-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol is added to the propylene homopolymer for the purpose of further improving the rigidity. Disclosed.

[Problem that the invention seeks to solve]

However, the secondary processability and blow moldability of the propylene homopolymer sheet having a specific molecular weight distribution and a specific isotactic pentad fraction disclosed in JP-A-58-219207 are sufficient for practical use. Although this is satisfactory, the rigidity is still not fully satisfactory, although it has been slightly improved. Further, the propylene homopolymer having the above-mentioned specific molecular weight distribution and specific isotactic pentad fraction is blended with aluminum pt-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol. Although propylene homopolymer compositions have shown some improvement in stiffness, they are still not fully satisfactory when used in applications requiring high stiffness and heat-resistant stiffness.

The present inventors have conducted extensive research in order to solve the above-mentioned problems regarding propylene-based polymer compositions containing the various nucleating agents described above. As a result, a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) is blended with a propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction. It was discovered that the composition could solve the problems of the above-mentioned propylene-based polymer compositions, and the present invention was completed based on this knowledge.

(However, in the formula, R8 is absent or represents sulfur or an alkylidene group having 1 to 4 carbon atoms, R3 and R3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, and M is a monovalent to trivalent alkyl group. n is an integer of 1 to 3.) As is clear from the above description, the purpose of the present invention is to improve the secondary processability, blow moldability, rigidity and heat resistance of the sheet when it is made into a sheet. An object of the present invention is to provide a propylene homopolymer composition having extremely excellent rigidity.

[Means for solving problems]

The present invention has the following configuration.

Propylene is polymerized in multiple stages, and in the first step, 35 to 65 weight percent of the total polymer is polymerized, and in the second and subsequent stages, 65 to 35 weight percent is polymerized, and the first
Among the polymer parts produced in the second and subsequent stages, the intrinsic viscosity of the polymer part with a high molecular weight is [η] H1 The intrinsic viscosity of the polymer part with a low molecular weight is [η] L 3
．． 0≦[η]5-[η]L≦6.5 ・・・・・・
...-(1), and the isotactic pentad fraction (P) of the total polymer
The relationship between this and the melt flow rate (MFR; the amount of molten resin discharged in 10 minutes when a load of 2.16 kl at 230°C is applied) is 1.00≧P≧0゜01510gMF
Crystalline propylene homopolymer 10 with R+0.955
0.0 parts by weight of the phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A)
A highly rigid and highly melting viscoelastic propylene homopolymer composition containing 1 to 1 part by weight.

(However, in the formula, R1 is absent or represents sulfur or an alkylidene group having 1 to 4 carbon atoms, R2 and R8 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, and M
represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3.

) The crystalline propylene homopolymer used in the present invention is obtained by polymerizing propylene in multiple stages, and in the first stage, the total polymer amount is 35 to 65% by weight, and in the second and subsequent stages, the same amount is 65 to 35% by weight. Among the polymer parts produced in the first and second stages, the intrinsic viscosity of the polymer part with higher molecular weight is [η]□, and the ultimate viscosity of the polymer part with lower molecular weight is When the viscosity is [η]L, 3.0≦
[η]□−[η]L≦6.5 ・・・・・・・・・
(1) The intrinsic viscosity of each polymer portion is as follows, and the relationship between the isotactic pentad fraction (t) and melt flow rate (MFR) of the entire polymer is 1.00≧P≧0
．． It is a crystalline propylene homopolymer with an MFR+ of 0.0151 og MFR+ of 0.955. Such a propylene homopolymer is disclosed in Japanese Unexamined Patent Application Publication No. 1983-1995 filed by the same applicant as the present application.
It is manufactured by the manufacturing method described in Japanese Patent No. 219207. That is, an organoaluminum compound (I), such as triethylaluminum, diethylaluminum monochloride, etc., or a reaction product of the organoaluminum compound (I) and an electron donor, such as diisoamyl ether, is reacted with titanium tetrachloride (Q). The solid product (n) obtained by reacting with the electron donor (8) and the electron acceptor, such as titanium tetrachloride, is further added to the solid product (III) obtained by reacting the solid product (III) with an organoaluminum compound, such as triethyl. aluminum, diethyl 7) v miniram monochloride etc. and an aromatic carboxylic acid ester (V) e.g. /I
It can be obtained by polymerizing propylene in multiple stages in the presence of a catalyst having a ratio of 0.1 to 10.0. A stage in this case means one section of continuous or temporary feeding of these monomers. The following amounts are also easy 2
Stepwise polymerization will be explained.

11- In the present invention, it is desirable that the polymer part (Sl) in the first stage and the part (S2) in the second stage be in nearly equal amounts, and specifically, (Sl) and ( S2) are both (s
l) 35 to 65 respectively for the total amount of +(S2)
Weight factor, preferably within the range of 4-0 to 60 weight factor (S
The total amount of L)+(82) is 100 parts by weight. (Sl.
) and (S2) in a crystalline propylene homopolymer with a different amount ratio beyond the above range, sufficient melt fluidity may not be obtained, and the crosstalk effect during granulation may be insufficient, resulting in poor final performance. Not only is it difficult to obtain a homogeneous molded product, but the degree of improvement in melt viscoelasticity is also small. Further, in the crystalline propylene homopolymer used in the present invention, the molecular weight difference between both types of combined portions must also be within a certain range as shown in formula (1) below. Therefore, the polymerization conditions are controlled by adjusting the gas phase hydrogen concentration. Now, the intrinsic viscosity of the high molecular weight part (135°C, tetralin solution) is [η]■,
If the intrinsic viscosity of the low molecular weight part is [η]L, both of them are 3
．． 0≦[η]H−[η]L≦6.5 ・・・−・・
...(1) must be satisfied. This relationship is
This substantially corresponds to the formula (2) below.

log HMFR-0,9221,og MF R≧1
．． 44-・-・・(2) Here, HMFR is the temperature of 230℃
This is the amount of molten resin discharged for 10 minutes when a load of 10.80 Yu was applied. That is, [η]H−[η)L
<3.0 logHMF R<0.922 log
MFR+ is 1.44, and when the crystalline propylene homopolymer is used, the melt flow characteristics during melting are insufficient, and the degree of improvement in melt viscoelasticity is also insufficient. The sheets obtained using this method cannot prevent sagging during secondary processing. On the contrary, [η
]H-[η) When L>6.5, the above (Sl), (S2)
If the molecular weight difference in the image area is too large, the non-uniformity of the molecular weight between the obtained propylene homopolymer particles becomes large, and as a result, the surface roughness of molded products made from such propylene homopolymer becomes noticeable. . The melt flow rate (MFR) of the crystalline propylene homopolymer of the present invention obtained as described above is preferably 0.03 to 2.0 g/10 minutes.

If it is less than 0.03, the fluidity of the melt during granulation or molding will be poor and the granulator or molding machine will require a lot of power, which is not economical, and the surface roughness of the resulting molded product will be poor. , roughness causes a significant loss of commercial value. Moreover, if it exceeds 2.0, the manufactured sheet will sag during secondary processing and the secondary processing will become difficult. In short, the above-mentioned formula (1) can prevent the molding material from sagging during thermoforming of sheets using crystalline propylene homopolymer or during blow molding using crystalline propylene homopolymer. This paper shows a method for designing a polymer necessary for imparting viscoelasticity to the crystalline propylene homopolymer. Similarly, the above formula (
2) indicates the fluidity of the crystalline propylene homopolymer, and the crystalline propylene homopolymer of the present invention having the structure of the polymer of formula (1) satisfies the condition of formula (2).

By the way, isotactic pentad fraction is Macromolecules, Volume 6, Issue 6, November-December, 925
-926 pages (1973) (Macrom.

Iecules, Vol. 6, 46. November
-December.

925-926 (1973)), that is, the isotactic fraction in pentad units in a propylene polymer molecular chain measured using 13C-NMR. In other words, the fraction means the fraction of one propylene monomer unit in which five propylene monomer units are isotacticly bonded consecutively. 1 mentioned above
The method for determining the attribution of spectral peaks in measurements using 3C-NMR is described in Macromolecules, Vol. 8, No. 5, September-October, pp. 687-689 (1975) (
Macrom.

1ecules, 'Vo1.8. A5. Sept
ember-October, 687-689 (1
975) ). By the way, FT-NMR's 270
Using a MHz device, 27. The signal detection limit was improved to 0.001 in terms of isotactic pentad fraction through OO0 integrated measurements. The requirements for the above relational expression between the isotactic pentad fraction (P) and melt flow rate (MFR) are that propylene homopolymers with low MFH generally have a lower fraction P, so the propylene homopolymer to be used is As a combination, a constituent requirement is to limit the lower limit value of P corresponding to the MFH. Since P is a fraction, the upper limit is 1.00. The intrinsic viscosity in the two-stage polymerization described above is measured in a tetralin solution at 135°C. However, the second stage intrinsic viscosity [η]2 was determined by the following formula. That is, the first
Intrinsic viscosity of the stage [η] 1, that is, the first stage and the second stage
Intrinsic viscosity [η]T of the polymer produced through the steps, 1st
Polymerization ratio a of the polymer portion produced in the step and the second step
and b, [η)T=a[η]1+b[η)2
=a[η)t+(1-a)[η]2. The MFR mentioned above is based on JIS K 7210 at 230°C and a load of 2.16 kg, and the HMFR is based on JIS K 721.
0, and is measured at 230°C and a load of 10.80.

In this case, the [η]1 may be [η]L or [η]
]H may be used.

In addition, in the crystalline propylene homopolymer used in the present invention, the homopolymer contains propylene, ethylene, butene.
1. Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as pentene-1,4-methyl-pentene-1, hexene-1, octene-1, propylene Copolymers of and vinyl acetate, acrylic esters, etc. or saponified products of these copolymers, copolymers of propylene and unsaturated carboxylic acids or their anhydrides, and reaction products of these copolymers with metal ion compounds. It is also possible to use a mixture of a propylene polymer and a modified propylene polymer modified with an unsaturated carboxylic acid or its derivative. Ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene flock copolymer , styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resins (e.g.

polyolefins excluding propylene polymers such as polyethylene, polybutene, and poly-4-methylpentene-1;
polystyrene, styrene-acrylonitrile copolymer,
(acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, etc.) can also be used in combination. At this time, the mixture has the above formula (
1) and the above 1.00≧P≧0.015
Any material may be used as long as it satisfies log MFR+0.955.

Compound A used in the present invention is sodium-2,2'
-methylene-bis-(4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis-(4,6-di-t-butylphenyl) phosphate, lithium-2° 2'-methylene-bis-(4,
6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis-(4,6-di-t
-butylphenyl)phosphate, sodium-2,
2'-ethylidene-bis-(4-i-7'pill-6
-t-butylphenyl)phosphate, lithium-2
, 2'-methylene-bis-(4-methyl-6-1-butylphenyl) phosphate, lithium-2,2'-methylene-bis-(4-ethyl-6-t--f tylphenyl) phosphate, Calcium-bis-(2,2'-
Thiobis-(4-methyl-6-t-]f-ruphenyl) phosphate], 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-[2゜2'-thiobis-(4-1-
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'-t-octylmethylene-bis-(46-di-methylphenyl)phosphate, sodium-2,2'-t-octylmethylene-
Bis-(4,6-di-t-butylphenyl)phosphate, Calcium-bis-[2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate], Magnesium-bis-[2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate] -(2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate], barium-bis-(2,2'-methylene-bis-(
4,6-di-t-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, @'-di-t-butyl-2,2'
-biphenyl) phosphate, calcium bis-[
(4,4'-dimethyl-6,6'-di-t-butyl-2
,2'-biphenyl)phosphate], sodium-
2,2'-ethylidene-bis-(4-5-butyl-6-
t-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)phosphny)), barium-bis-(2,2'-ethylidene-bis-(4,6
-di-t-butylphenyl)phosphate], aluminumtris-[2゜2'-methylene-bis=(4,
6-di-t-butylphenyl) phosphate], aluminumtris-(2,2'-ethylidene-bis-(
Examples include 4,6-di-t-butylphenyl) phosphate coma and a mixture of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the above-mentioned crystalline propylene homopolymer. A blend of 0.01 part by weight without grooves will not sufficiently improve the stiffness and heat resistance stiffness, and although it is possible to exceed 1 part by weight, it is not practical as no further improvement can be expected. It is not only economical but also uneconomical.

The composition of the present invention includes various additives that are usually added to propylene polymers, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, antifogging agents, antiblocking agents, anti-drop agents, pigments, heavy metal deactivators (copper damage inhibitors), radical generators such as peroxides, dispersants such as metal soaps, or medium powders, inorganic fillers (e.g. talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, sulfuric acid) barium, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate, metal fiber, etc.) or coupling agents (such as silane, titanate, boron, aluminate, zircoaluminate, etc.) The above-mentioned inorganic fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) that have been surface-treated with a surface treatment agent such as those described above can be used in combination without impairing the purpose of the present invention. In particular, when an inorganic filler is used in combination, the rigidity and heat-resistant rigidity are further improved, so it is preferable to use the inorganic filler in combination.

The composition of the present invention is prepared by adding predetermined amounts of the compound A and the various additives usually added to propylene polymers to the crystalline propylene homopolymer according to the present invention using a conventional mixing apparatus. Ba Hensel mixer (product name),
Mix using a Suhar mixer, ribbon blender, Pan Bali mixer, etc., and use a normal single-screw extruder, twin-screw extruder, Brabender, or roll to reach a melt mixing temperature of 17.
Much better results can be obtained by melt-mixing pelletizing at 0°C to 300°C, preferably 200°C to 250°C. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding. In particular, when the composition of the present invention is used for producing sheets for secondary processing and blow-molded products, the effects of the present invention are particularly preferable.

[For production]

In the present invention, the phosphate compound represented by Compound A is generally known to act as a nucleating agent to improve rigidity and heat-resistant rigidity, as disclosed in JP-A-58-1736.

However, by blending the compound into the propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction according to the present invention, it is possible to obtain An unexpected and surprising synergistic effect is exerted, resulting in a composition with outstanding stiffness and heat-resistant stiffness.

〔effect〕

The composition of the present invention has the advantage that (
1) Excellent rigidity and heat resistance. (2) It is possible to make the molded product thinner, which contributes to resource saving, and the cooling rate during molding is also faster, so the molding speed per unit time can be increased, which improves productivity. can also contribute. (3) It is now possible to use polypropylene resin in applications for which polystyrene, ABS resin, polyester, etc. have traditionally been used, and the applications of polypropylene resin can be expanded.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited by the present invention.

The evaluation method used in Examples and Comparative Examples was as follows.

■) Secondary processability of the sheet (heat vacuum formability): A sheet with a width of 60 ns and a thickness of 0.4B was made by extrusion molding using the obtained pellets, and the heat vacuum formability of the sheet was evaluated as a model. In order to evaluate the sheet, 40crrL×
Cut into 40cIrL, fix in a 40α x 40cm frame in a taut state, and place in a constant temperature room at 200°C. Eventually, the sheet fixed to the frame gets heated and the center of the frame begins to sag, and at a certain point it begins to return to its original position due to heat contraction. After that, it starts to droop again. At this time, (a) the amount of sagging immediately before the sheet starts to be returned is measured as the maximum amount of sagging (□nm).

(b) Measure the amount of deformation (ti) at which the sheet returned to its original position from the point where it sagged to the maximum, and set the amount of deformation returned to the maximum/maximum amount of droop x 100 as the maximum amount of return (ti). Record. (C) 10 minutes from the point where the sheet returns to maximum
The time until it starts to sag again (mm) is measured and defined as the retention time.

A material with good secondary processability (vacuum formability) of a sheet according to the above evaluation method refers to a material with minimum droop, maximum retraction, and long holding time.

■) Stiffness: Medium 60crIL1 using the obtained pellets
A sheet with a thickness of 0.4 urn was made by extrusion molding, and a specified test piece was prepared using the sheet, and Young's modulus (according to ASTM D e82) and tensile yield strength (according to ASTM D e82) were measured. The stiffness was evaluated by performing the following: A highly rigid material is one that has a high Young's modulus and a high tensile yield strength.

In addition, in the Examples and Comparative Examples, Young's modulus and tensile yield strength were measured using two types of test pieces: MD (vertical; extrusion direction) and TD (horizontal; direction perpendicular to the extrusion direction) of the sheet.
The average value is shown.

m) Heat resistance rigidity: length 130m using the obtained pellets
A test piece with a width of 13 g and a thickness of 6.5 strips was made by injection molding, and the heat distortion temperature was measured using the test piece (JIS
The heat resistance rigidity was evaluated based on K 7207; 4.6 kgfA-Il load). A material with high heat resistance and rigidity is one that has a high heat deformation temperature.

Production Examples 1 to 3 (Production Examples of Crystalline Propylene Homopolymer Used in Examples and Comparative Examples) (1) Preparation of Catalyst 7600 yd of n-hexa, 0.50 mol of diethylaluminium monochloride (DBAC), diisoamyl ether 1.20 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (V[(molar ratio of diisoamyl ether/DEAC 2.4). Reactor purged with nitrogen. 4.0 mol of titanium tetrachloride was added to the solution, heated to 35°C, and the entire amount of the reaction product solution (9) was added dropwise to this over 180 minutes, kept at the same temperature for 30 minutes, and then heated to 75°C. The reaction was continued for another 1 hour, cooled to room temperature (20°C), the supernatant liquid was removed, n-hexane (4000 mA!) was added, and the supernatant liquid was removed by decantation, which was repeated 4 times to obtain a solid product. (I[) 190 # was obtained. The entire amount of this solid product (II) was suspended in 3000 TrL of n-hexane and diisoamyl ether 160 # was obtained at 20°C.
I and titanium tetrachloride 350. F was added at room temperature for about 1 minute, and the mixture was reacted at 65° C. for 1 hour.

After the reaction was completed, the mixture was cooled to room temperature, the supernatant liquid was removed by decantation, 4000-N-hexane was added, stirred for 10 minutes, left to stand, and the supernatant liquid removed. The process was repeated 5 times. Afterwards, it was dried under reduced pressure to obtain a solid product (DI).

(2) Preparation of preactivated catalyst After purging a stainless steel reactor with inclined vanes with an internal volume of 2 (l) with nitrogen gas, n-hexane 1511 di-tyl aluminum monochloride 4211 solid product (IIl) 3
After adding 0g of hydrogen at room temperature, 15N of hydrogen was added and the reaction was carried out for 5 minutes at a propylene partial pressure of 5kg/~G. Unreacted propylene, hydrogen and n-hexane were removed under reduced pressure, and the preactivated catalyst (4) was It is possible to obtain powder or granular material (solid product (I[[)
1, g per dipropylene 82. ON reaction).

(3) Polymerization of propylene 2011 n-hexane dried in a 5010 volume polymerization vessel purged with nitrogen gas 811 diethylaluminium monochloride (4) 2I and p-)methyl ruylate 2.2I! Prepare and add hydrogen to bring the inside of the vessel to 7.
It was kept at 0°C. Next, propylene was supplied into the vessel, the pressure inside the vessel was 10kllF/cdG, the hydrogen concentration in the gas phase was 11% as in Production Example 1, 5% in Production Example 2 and 14% in Production Example 3, and the temperature was set to 70%. The first stage polymerization was carried out at a temperature of .degree. The amount of polymer is 3kl! When this temperature is reached, the supply of propylene is stopped, the temperature inside the vessel is cooled to room temperature, and
Hydrogen and unreacted propylene were released. Then, a portion of the polymerization slurry was extracted, and measurement of [η]1 and analysis of the titanium content in the polymer were performed by fluorescent X-ray method to determine the polymer yield per unit weight of catalyst.

Then, the temperature inside the polymerization vessel was raised to 70℃ again, and the polymerization pressure was 10kg.
/c//LG1 Gas phase hydrogen concentration is 0.0 as Production Example 1.
4%, 0.07% in Production Example 2, and 0.08% in Production Example 3, the second stage of polymerization was carried out.

When the amount of polymer in the second stage reached 3 kli, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and propylene that had not reacted with hydrogen was discharged. Next, a part of the polymerization slurry was extracted, and [η]T was measured and the titanium content in the polymer was analyzed using a fluorescent X-ray method to determine the polymer yield per unit weight of the catalyst, and the above-mentioned first step was carried out. Using this yield value, calculate the ratio of the amount of polymer in the first stage and the second stage, and calculate the intrinsic viscosity [η] of the polymer obtained only in the second stage polymerization.
] Calculate 2. After the extraction, 51 methanol was added to the polymer slurry, and the mixture was stirred at 90°C for 30 minutes, followed by addition of 20 parts by weight of an aqueous sodium hydroxide solution (40), and further stirred for 20 minutes. Next, the slurry was cooled to room temperature, added with 5 g of water, washed with water and separated three times, and the resulting slurry was filtered, and the filtrate was dried to obtain a white polymer powder. The analysis results of the polymer are shown in Table 1. Therefore, [η], = [
η]1, [η]H=[η]2.

Examples 1 to 3, Comparative Examples 1 to 6 Each intrinsic viscosity, each melt flow rate (MFR), each high melt flow rate (HMFR), and each manufactured in Production Examples 1 to 3 shown in Table 2 below. Sodium-2 as compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having an isotactic pentad fraction.
, 2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate and other additives at the mixing ratios listed in Table 2 below. caliber 40 after stirring and mixing for 3 minutes.
The mixture was melt-kneaded and processed at 200°C using a single-screw extruder (M) to form pellets. In addition, as Comparative Examples 1 to 6, powders having each intrinsic viscosity, each melt flow rate, each high melt flow rate, and each isotactic pentad fraction manufactured in Production Examples 1 to 3 shown in Table 2 below Predetermined amounts of each of the additives listed in Table 2 below were blended with 100 parts by weight of a crystalline propylene homopolymer, and pellets were obtained by melt mixing according to Examples 1 to 3.

The sheets used for sheet secondary processability and rigidity tests are:
The obtained pellets were prepared by extrusion molding at a resin temperature of 250°C. Moreover, the test piece used for the heat-resistant rigidity test was prepared by injection molding the obtained pellet at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained sheet and test piece, the sheet's secondary processability, rigidity, and heat-resistant rigidity were evaluated according to the test method described above. These results are shown in Table 2.

Examples 4 to 6, Comparative Examples 7 to 12 Each intrinsic viscosity, each melt flow rate (MFR), each bail melt flow rate (HMFR), and each manufactured in Production Examples 1 to 3 shown in Table 3 below. Sodium-2,2'-methylenebis-(4,6-di-t-butylphenyl)phos was added as compound A to 100 parts by weight of a powdered crystalline propylene homopolymer having an isotactic pentad fraction [F]. Predetermined amounts of phate, fine particle talc with an average particle size of 2 to 3 μm as an inorganic filler, and other additives were placed in a Hensel mixer (trade name) at the mixing ratios listed in Table 3 below, and mixed by stirring for 3 minutes. After that, caliber 4
The mixture was melt mixed at 200° C. and pelletized using a 0 m single-screw extruder. In addition, as Comparative Examples 7 to 12, powders having each intrinsic viscosity, each melt flow rate, each high melt flow rate, and each isotactic pentad fraction manufactured in Production Examples 1 to 3 shown in Table 3 below. Predetermined amounts of each of the additives listed in Table 3 below were blended with 100 parts by weight of a crystalline propylene homopolymer, and pellets were obtained by melt mixing according to Examples 4 to 6.

The sheets used for sheet secondary processability and rigidity tests are:
The obtained pellets were prepared by extrusion molding at a resin temperature of 250°C. Moreover, the test piece used for the heat-resistant rigidity test was prepared by injection molding the obtained pellet at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained sheets and test pieces, the secondary workability, rigidity, and heat machinability of the sheets were evaluated by the test method described above. These results are shown in Table 3.

The compounds and additives according to the present invention shown in Tables 2 and 3 are as follows.

Compound A; Sodium-2,2'-methylene-bis-(
4,6-di-t-butylphenyl) phosphate [manufactured by Adeka Argus Chemical ■; MARK NA-11) Nucleating agent 1; Aluminum p-t-butylbenzoate nucleating agent 2; 1, 3, 2, 4-dibenzylidene sorbitol Nucleating agent 3: Sodium-bis(4-t-butylphenyl)phosphate phenolic antioxidant 1: 2,6-di-t-butyl-
p-cresol phenolic antioxidant 2; Tetrakis [methylene-3
-(3/, s/-di-t-butyl-4'-hydroxyphenyl)propionate comethane phosphorus antioxidant 1; tetrakis(2,4-di-t-butylphenyl) -4,4'- Biphenylene-diphosphonitophosphoric antioxidant 2; bis(2,4-di-t-butylphenyl)-pentaerythritol-siphosphite Ca-8t; calcium stearate inorganic filler; talc (average particle size 2~3μ) 1st
The Examples and Comparative Examples listed in Table 2 are crystalline propylene homopolymers having various intrinsic viscosities, various melt flow rates, various high melt flow rates, and various isotactic pentad fractions as propylene polymers. This is the case when .

As can be seen from Table 2, Examples 1 to 3 were obtained by blending Compound A with a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Comparing Examples 1 to 3 and Comparative Examples 1 to 3 (crystalline propylene homopolymer having a molecular weight distribution and isotactic pentad fraction within the range of the present invention without using an organic nucleating agent) As a result, although the secondary processability of the sheets in Examples 1 to 3 and Comparative Examples 1 to 3 is comparable, Comparative Examples 1 to 3 still have insufficient effects of improving rigidity and heat resistance rigidity. Furthermore, Comparative Example 1~
In order to improve the rigidity and heat-resistant rigidity of No. 3, an organic nucleating agent consisting of a compound other than compound A is used in a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Comparing Examples 1 to 3 with Comparative Examples 4 to 6, Comparative Examples 4 to 6 showed a slight improvement in stiffness and heat resistance, but it was still not sufficient, and Examples 1 to 3 significantly improved stiffness and heat resistance. It can be seen that a remarkable synergistic effect is observed by using Compound A, which has excellent rigidity.

That is, the stiffness and heat-resistant stiffness obtained in the present invention are based on the characteristic properties observed when Compound A is used in a crystalline propylene homopolymer having an isotactic pentad fraction within the range limited in the present invention. This can be said to be effective.

Table 3 shows the propylene polymer used in Table 2,
Furthermore, talc was also used as an inorganic filler, and the same effects as described above were confirmed with this as well.

This shows that the composition of the present invention has better sheet fabrication properties, stiffness, and heat-resistant stiffness than conventionally known compositions made by simply blending a nucleating agent with a crystalline propylene homopolymer. The remarkable effects of the composition of the present invention were confirmed.

that's all

Claims (1)

[Scope of Claims] (1) Propylene is polymerized in multiple stages, and in the first stage, 35 to 65% by weight of the total polymer is polymerized, and in the second and subsequent stages, 65 to 35% by weight is polymerized. let me,
Among the polymer parts produced in the first stage and the second stage, the intrinsic viscosity of the polymer part with a high molecular weight is [η]_
H, when the intrinsic viscosity of the polymer portion with low molecular weight is [η]_L, 3.0≦[η]_H−[η]_L≦6.5……(1)
The intrinsic viscosity of each polymer portion is as follows, and the isotactic pentad fraction (P) of the entire polymer and the melt flow rate (MFR; load at 230°C: 2.16 kg)
The relationship between the amount of molten resin discharged for 10 minutes when adding
A highly rigid product made by blending 0.01 to 1 part by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) to 100 parts by weight of a crystalline propylene homopolymer. High melt viscoelastic propylene homopolymer composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, in the formula, there is no R_1, sulfur or carbon number 1-4
R_2 and R_3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3. ) (2) The high rigidity high melt viscoelastic propylene alone according to claim (1), wherein the crystalline propylene homopolymer has a melt flow rate (MFR) of 0.03 to 2.0 g/10 min. Polymer composition. (3) High melt flow rate (HMFR; load 10.80k at 230°C of crystalline propylene homopolymer)
The relationship between melt flow rate (MFR) and melt flow rate (discharge amount of molten resin for 10 minutes when adding g) is logHMFR-0.922logMFR≧1.44...
...The high-rigidity, high-melt viscoelastic propylene homopolymer composition according to claim (1), which uses a crystalline propylene homopolymer having (HMFR) and (MFR) that satisfy (2). (4) In the general formula [I], R_1 is a methylene group,
The high-rigidity, high-melt viscoelastic propylene homopolymer composition according to any one of claims (1) to (3), wherein the alkyl groups represented by R_2 and R_3 are t-butyl groups. . (5) Claims (1) to (1) containing sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate as compound A.
3) The high rigidity and high melt viscoelastic propylene homopolymer composition according to any one of items 3). (6) Claim No. 1 containing an inorganic filler
The high rigidity and high melt viscoelastic propylene homopolymer composition according to any one of items ) to item (3). (7) Inorganic fillers such as talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide,
Claim (6) uses one or more selected from zinc sulfide, barium sulfate, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate, and metal fiber. High stiffness, high melt viscoelastic propylene homopolymer composition.