JPH01104638A - High-rigidity and high-melt viscoelastic propylene homopolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having high processability and heat- resistant rigidity, by blending a multi-stage polymer of propylene having a specific relation of a difference in intrinsic viscosity and stereoregular polymer fraction between high-mol.wt. and low-mol.wt. parts to melt index. CONSTITUTION:The aimed composition obtained by polymerizing propylene in an amount of 35-65wt.% based on the weight of the total polymer in the first stage and similarly polymerizing 65-35wt.% in the second stage or thereafter to provide crystalline propylene homopolymer having an intrinsic viscosity [eta]H of a high-mol.wt. polymer part and intrinsic viscosity [eta]L of a low-mol.wt. polymer part in the formed respective polymer parts satisfying formula I and isotatic pentad fraction (P) and melt flow rate (MFR; the amount of a molten resin discharged for 10min when a load of 2.16kg is applied at 230 deg.C) of the total polymer satisfying the relation expressed by formula II and then blending 100pts.wt. resultant polymer with 0.01-1pt.wt. phosphate based compound expressed by formula III (R is H, 1-18C alkyl, phenyl, etc.).

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, we will introduce a high-rigidity, high-melt viscoelastic rubber that can yield molded products with outstanding rigidity and heat-resistant rigidity.
This invention relates to a pyrene homopolymer acid product.

[Prior art] Generally, 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, and the processing conditions range is narrow, resulting in poor forming efficiency, and wide sheets suffer from the aforementioned sagging. In addition, there are problems in that the thickness of the secondary processed product tends to be uneven, and overlapping wrinkles are likely to occur. For this reason, only small molded products can be manufactured. Further, when a propylene polymer is used for blow molding, there are the following problems. That is, (1) the parison sags significantly during molding, resulting in uneven wall thickness of the molded product;

Therefore, it can only be applied to the manufacture of small products.

■If a high molecular weight propylene polymer is used to prevent the above-mentioned sagging, there is a risk of poor fluidity, load holes during molding, large energy loss, and mechanical troubles, and the molded product may become rough. value is lost, etc.

On the other hand, depending on the various specific uses of the propylene polymer, the properties of the propylene polymer may not be sufficient, and there is a problem in that the expansion of its specific uses is limited. In particular, in terms of rigidity such as rigidity and heat resistance, it is inferior to polystyrene, ABS resin, polyester, etc., and this has become a serious bottleneck in expanding the use of propylene polymers. Therefore, if it is possible to improve the rigidity (rigidity and heat resistance rigidity), it will be possible to make the molded product thinner, which will not only contribute to resource conservation, but also increase the cooling rate during molding. Therefore, the molding speed per unit time 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 propylene polymers, Japanese Patent Application Laid-Open No. 58-219207 filed by the same applicant as the present application has been published. Crystalline propylene homopolymers having a specific molecular weight distribution and a specific isotactic pentad fraction are disclosed. Also,
The above publication discloses that an organic nucleating agent such as ρ-t-butylaluminum benzoate or l-3,2-todibenzylidene sorbitol is added to the crystalline propylene homopolymer for the purpose of further improving the rigidity. ing.

[Problems to be Solved by the Invention] However, using the crystalline propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction disclosed in JP-A-58-219207, The resulting sheet has satisfactory secondary processability and blow moldability, and although the rigidity has been considerably improved, it is still not fully satisfactory. Also,
The crystalline propylene homopolymer having the specific molecular weight distribution and specific isotactic pentad fraction is
Sheets using propylene homopolymer compositions containing organic nucleating agents such as t-butylaluminum benzoate or l-3,2-dibenzylidene sorbitol have a considerable improvement in stiffness, but are not highly effective. It is still not fully satisfactory when used in applications that require high rigidity and heat-resistant rigidity.

The present inventors have solved the above-mentioned problems regarding propylene polymer compositions containing the various nucleating agents described above, namely, the secondary processability and blow moldability of the sheet when it is made into a sheet.
We conducted extensive research to solve the problems of rigidity and heat resistance. As a result, a phosphate compound represented by the following formula [I] (hereinafter referred to as compound A) was blended into a crystalline propylene homopolymer having a specific molecular weight distribution and a specific isotactic pentad fraction. It has been discovered that a composition consisting of the following can solve the problems of the above-mentioned propylene-based polymer compositions, and based on this knowledge, the present invention has been completed.

(However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) As is clear from the above description, the purpose of the present invention is to It is an object of the present invention to provide a propylene homopolymer composition from which a molded article having extremely excellent secondary processability, blow moldability, rigidity, and heat-resistant rigidity of the sheet can be obtained.

cMeans for solving problems] The present invention has the following configuration.

When polymerizing propylene in multiple stages, 35 to 65% by weight of the total polymer amount is polymerized in the first stage,
The same <65 to 35% by weight is polymerized between the second and subsequent stages, and among the polymer parts produced between the first stage and the second stage, the intrinsic viscosity of the polymer part with a high molecular weight is determined. [η1H% When the intrinsic viscosity of the polymer portion with low molecular weight is [η]L, 3.0≦ [η ko8− [η ]
, ≦ 6.5 (1), and the isotactic pentad fraction (P) and melt flow rate (MFR; Load 2.l6kg at 230℃
1.00≧P≧0.015 Q ogM F R10
．． 955, 0.01 to 1 part by weight of a phosphate compound (hereinafter referred to as compound) represented by the following general formula [I]
A high-rigidity, high-melt viscoelastic propylene homopolymer composition consisting of parts by weight.

(However, in the formula, R represents hydrogen, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, an engineering group, or a phenoxy group. ) The crystalline propylene single polymer used in the present invention is used in the multi-stage polymerization of propylene, in which 35 to 35% of the total polymer amount is used in the first stage.
65% by weight is polymerized, and the same <65 to 35% by weight is polymerized between the second and subsequent stages, and among each one of the combined parts produced between the first stage and the second stage, the polymer with a high molecular weight is When the intrinsic viscosity of the polymer part is [418% and the intrinsic viscosity of the polymer part with low molecular weight is [η], 3.0≦[
η1.4-C? ]c≦6,5 ・・・・・・(1
), and the relationship between the isotactic pentad fraction (P) and melt flow rate (MFR) of the total 1 polymer is 1.00≧P≧0.0
It is a crystalline propylene homopolymer with a 15 Q ogM F R+ of 0.955. Such a crystalline propylene homopolymer is produced by the production method described in Japanese Patent Application Laid-Open No. 58-219207, filed by the same applicant as the present application. That is, organoaluminum compound (i) (for example, triethylaluminum, diethylaluminum monochloride, etc.) or organoaluminum compound (1) and an electron donor (for example, diisoamyl ether, ethylene glycol monomethyl ether, etc.)
The solid product (ii) obtained by reacting the reaction product (v) with titanium tetrachloride is further added with an electron donor and an electron acceptor (for example, anhydrous aluminum chloride, titanium tetrachloride,
A solid produced by reacting vanadium tetrachloride, etc.)? ! Combining I(iii) with an organoaluminum compound (1) and an aromatic carboxylic acid ester (iv) (e.g. ethyl benzoate, methyl p-toluate, ethyl p-toluate, 1-2-ethylhexyl p-tolyl, etc.) , the molar ratio of the aromatic carboxylic acid ester (1v) and the solid product (iii) iv/1ii==0.1 to 1
It can be obtained by polymerizing propylene in multiple stages in the presence of a catalyst with a concentration of 0.0. A stage in this case means one section of continuous or temporary feeding of these monomers. In the present invention, the amount of the polymer part (Sl) in the first stage and the part (Sl) in the second stage are close to the same. Desirably, specifically (S 1) and (
The total amount of (S1) + (S2) is within the range of 35 to 65% by weight, preferably 40 to 60% by weight, based on the total amount of (S1) + (S2). 1
00% by weight. If the crystalline propylene homopolymer has a different ratio of (Sl) to (Sl) beyond the above range, sufficient melt fluidity will not be obtained, and the kneading effect during granulation will be insufficient, resulting in Not only is it difficult to obtain a homogeneous molded product, but also the degree of improvement in melt viscoelasticity is small.In addition, the crystalline propylene homopolymer used in the present invention has a molecular weight difference between both types of combined parts as shown in the following formula (1). Must be within a certain range. Therefore, the polymerization conditions are adjusted by adjusting the gas phase hydrogen concentration. Now, if the intrinsic viscosity of the high molecular weight part (135°C, tetralin solution) is [η], and the intrinsic viscosity of the low molecular weight part is [η], then both of them are: 3.0≦[η], -[η]L≦6.5...
...(1) must be satisfied. This relationship substantially corresponds to equation (2) below.

Q ogHM FR-0,922Q ogM FR
≧1.44 (2) Here, HMFR (high melt flow rate) is the amount of molten resin discharged in 10 minutes when a load of 10.80 kg is applied at a temperature of 230°C. [η]H - [η] When L<3.0, QogH
MFR<0.922logMFR+1.44, and when this crystalline propylene homopolymer is used, the melt flow characteristics during melting are insufficient, and the degree of improvement in melt viscoelasticity is also insufficient. In the sheet obtained using 0, sagging during secondary processing cannot be prevented.On the other hand, [η]H-[η]L>6.5
In this case, the molecular weight difference between the aforementioned (Sl) and (Sl) fractions becomes too large, and as a result, the non-uniformity of the molecular weight between the resulting crystalline propylene homopolymer particles becomes large. The melt flow rate (MF
R) 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, requiring a lot of power for the granulator or molding machine, which is not economical, and the surface of the obtained molded product will be rough. 2.0 will significantly lose its commercial value.
If it exceeds this value, the produced sheet will sag significantly during secondary processing, making the secondary processing difficult. By the way, the above formula (
1) The viscoelasticity that makes it possible to prevent the molding material from sagging during thermoforming of a sheet using a crystalline propylene homopolymer or during blow molding using a crystalline propylene homopolymer. It shows how to design the polymers necessary for imparting coalescence.

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) has the fluidity of the crystalline propylene homopolymer of formula (2). Satisfy the conditions. Here, isotactic pentad fraction (P) is Macromolecules, Volume 6, No. 6,
November-December, pages 925-926 (1973)
[Macro+molecules, Vol. 6.
, Na 6゜Novegber-Dece+gber
, 925-926 (1973), that is, the isotactic fraction in pentad units in a propylene polymer molecular chain measured using C-NMR. In other words, the fraction means the fraction of brobylene motumer units in which five propylene monomer units are consecutively bonded isotacticly. Macromolecules, 8
Volume, No. 5, September-October, pp. 687-689 (1975
) [Macros+ole-cules, Vo
l, 8. Na5. September-October
ber. The limit was increased to 0.001 in terms of isotactic pentad fraction.The requirements for the above relational expression between isotactic pentad fraction (P) and melt flow rate (MFR) are generally based on MFH. Since the fraction P of a low propylene homopolymer decreases, it is a constituent requirement to limit the lower limit of P corresponding to the MFH of the propylene homopolymer to be used. Since P is a fraction, the upper limit is 1.00.The intrinsic viscosity in the two-step polymerization described above is 13
Measure at 5°C. However, the limiting viscosity of the second stage [η]
2 is determined by the following formula. That is, the intrinsic viscosity of the first stage [η] is 1, the total intrinsic viscosity of the polymer produced through the first and second stages [η] is 7, and the ultimate viscosity of the polymer produced in the first and second stages is [η]7. The polymerization ratios a and b of the polymer portion are measured, and [η]r=a[η]++ b[η]2=a[:η]++
(1-a) Obtained from [η]2. The MFR mentioned above is JIS
K? 210, temperature 230℃, load! 2.16
kg, and HMFR is measured in accordance with JIS 7210 at a temperature of 230°C and a load fi of 10.80 kg.

In this case, the [l] may be [η] or [η
]H, and the same applies to [η]2.

In addition, the crystalline propylene homopolymer used in the present invention may be a normal crystalline propylene-based polymer, that is, a crystalline propylene homopolymer, or propylene containing 70% by weight or more of a propylene component, to the extent that the effects of the present invention are not impaired. Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as ethylene, butene-1, pentene-1,4, methyl-pentene-1, hexene-1, octene-1, etc. Polymer, copolymer of propylene and vinyl acetate or acrylic ester, or saponified product of the copolymer, copolymer of propylene and unsaturated silane compound, copolymer of propylene and unsaturated carboxylic acid or its anhydride. Copolymers, reaction products of copolymers and metal ion compounds, modified propylene polymers obtained by modifying crystalline propylene polymers with unsaturated carboxylic acids or derivatives thereof, crystalline propylene polymers, etc. It can also be used as a mixture of silane-modified propylene polymers modified with unsaturated silane compounds, and various synthetic rubbers (e.g. ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber) can also be used. , polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, acrylonitrile-
butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or Thermoplastic synthetic resins (e.g. ultra-low density polyethylene, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-high molecular weight polyethylene, polybutene, propylene-based polymers such as poly-4-methylpentene-1) Polyolefin, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-excluding coalescence
(butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.) can also be used as a mixture.

Compound A used in the present invention includes aluminum hydroxy-di-phenyl phosphate, aluminum hydroxy bis(ρ-methylphenyl) phosphate, aluminum hydroxy-bis(p-ethylphenyl) phosphate, aluminum hydroxy −
Bis(p-n-pro-ruphenyl) phosphate, aluminum hydroxy-bis(p-i-propylphenyl) phosphate, aluminum hydroxy-bis(p-n-butylphenyl) phosphate, aluminum hydroxy-bis(p-n-butylphenyl) phosphate (p-i-butylphenyl)
phosphate, aluminum hydroxy-bis(p
-s-butylphenyl) phosphate, aluminum hydroxy-bis(p-t-butylphenyl) phosphate, aluminum hydroxy-bis(p-n-
aluminum hydroxy-bis(p-s-amylphenyl) phosphate, aluminum hydroxy-bis(p-s-amylphenyl) phosphate, aluminum hydroxy-bis(p-s-amylphenyl) phosphate, aluminum hydroxy-bis(p-s-amylphenyl) phosphate, ) phosphate, aluminum hydroxy-bis(p-hexylphenyl) phosphate, aluminum hydroxy-bis(
p-n-octylphenyl) phosphate, aluminum hydroxy-bis(p-2-ethylhexylphenyl) phosphate, aluminum hydroxy-bis(p-t-octylphenyl) phosphate, aluminum hydroxy-bis( p-nonylphenyl) phosphate, aluminum hydroxy-bis(p-
dodecylphenyl) phosphate, aluminum hydroxy-bis(ρ-tridecylphenyl) phosphate, aluminum hydroxy-bis(ρ-hexadecylphenyl) phosphate, aluminum hydroxy-bis(p-octadecylphenyl) phosphate, Aluminum hydroxy-bis(ρ-methoxyphenyl) phosphate, aluminum hydroxy-
Bis(p-ethoxyphenyl) phosphate, aluminum hydroxy-bis(p-propoxyphenyl)
phosphate, aluminum hydroxy-bis(ρ
-butoxyphenyl) phosphate, aluminum hydroxy-bis(ρ-octoxyphenyl) phosphate, aluminum hydroxy-bis(ρ-cyclohexylphenyl) phosphate, aluminum hydroxy-bis(p-biphenylyl) phosphate and aluminum hydroxy-bis(ρ-phenoxyphenyl) phosphate, particularly aluminum hydroxy-bis(p-t-butylphenyl).
Phosphates are preferred. These phosphate compounds may of course be used alone, or two or more phosphate compounds may be used in combination. The blending ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the above-mentioned crystalline propylene homopolymer.
0.5 parts by weight. With a blend of 0.01 fft without grooves, the effect of improving rigidity and heat resistance rigidity is not sufficiently exhibited.
Although it is possible to exceed 1 part by weight, it is not only impractical, but also uneconomical, as no further improvement in the above-mentioned effects can be expected.

In the composition of the present invention, various additives that are usually added to propylene polymers, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, etc. , lubricants, antistatic agents, antifogging agents, antiblocking agents, anti-drop agents, pigments, heavy metal deactivators (copper inhibitors), radical generators such as peroxides, dispersants such as metal soaps, or Neutralizing agents, 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-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.) The above-mentioned inorganic fillers or organic fillers (for example, wood flour, bulbs, waste paper, synthetic fibers, natural fibers, etc.) that have been surface-treated with a surface-treating agent 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 mixing the crystalline propylene homopolymer according to the present invention with predetermined amounts of Compound A and the various additives described above that are normally added to propylene polymers using a conventional mixing device, such as a Hensel device. mixer (product name),
Mix using a super mixer, ribbon blender, Pan Bali mixer, etc., and melt and knead with a normal single screw extruder, twin screw extruder, Brabender or roll, etc. at a melt kneading temperature of 17.
It can be obtained by melt-kneading and 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.

[Function] In the present invention, the phosphate compound represented by compound A is disclosed in Japanese Patent Publication No. 41-16303 and Japanese Unexamined Patent Publication No. 53
It is generally known that it acts as a nucleating agent to improve rigidity and heat-resistant rigidity, similar to the phosphate compound disclosed in Japanese Patent No.-105550. However, the above-mentioned Japanese Patent Publication No. 41-16303 and Japanese Patent Application Laid-Open No. 53-1
Compound A, which is a basic aluminum salt of a phosphate compound (aluminum normal salt) disclosed in Japanese Patent No. 05550, is converted into a crystalline compound having a specific molecular weight distribution and a specific isotactic pentad fraction according to the present invention. It has been found that by blending propylene alone with a single coalescence, a surprising synergistic effect that cannot be predicted from the combination of conventionally known nucleating agents is exhibited, and a composition with extremely excellent rigidity and heat-resistant rigidity can be obtained.

[Effects of the Invention] The composition of the present invention is significantly superior in (1) rigidity and heat-resistant rigidity compared to conventionally known propylene homopolymer compositions containing various nucleating agents.

(2) Not only can the molded product be made thinner, contributing to resource conservation, but also the cooling rate during molding can be increased, increasing the molding speed per unit time and improving productivity. I can contribute. (3) It is now possible to use polypropylene resin in applications where polyesters such as polystyrene, ABS resin, polyethylene terephthalate, and polybutylene terephthalate have traditionally been used, making it possible to expand the applications of polypropylene resin. (4) Since the sheet has excellent secondary processability and blow moldability, it can be suitably used for manufacturing sheets for secondary processing and blow molded products.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, Comparative Examples, and Production Examples, but the present invention is not limited thereby.

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

1) Secondary processability of the sheet (heat vacuum formability): A sheet with a width of 60 aya and a thickness of 0.4 mm was created by extrusion molding using the pellets provided, and the heat vacuum formability of the sheet was evaluated. In order to evaluate it as a model, the sheet was 40cs
Cut it into 11 x 40cs, fix it tightly in a 40cs x 40cm frame, and place it in a constant temperature room at 200°C. The sheet, which has been neatly fixed with 1 force, is 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 drooping just before the sheet starts to return is measured as the maximum amount of drooping (M).

(b) Measure the amount of deformation (m) at which the sheet returns to its original position from the point where it sagged to its maximum, and record (the amount of deformation 7R large droop fi) x 100 as the maximum amount of return (%). .

(C) The time (seconds) from when the sheet returned to its maximum position until it sags again for 10 minutes is measured, and this is defined as the holding 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 return, and long holding time.

2) Rigidity: Using the obtained pellet, a sheet with a width of 60 cI + and a thickness of 0.4 m was created by extrusion molding, and the sheet was used to measure Young's modulus (according to ASTM 0882) and tensile yield strength ( The stiffness was evaluated by performing the following method (based on ASTM 0882). 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, two types of test pieces were prepared: MD (vertical: extrusion direction) and TD (horizontal: direction perpendicular to the extrusion direction) of the sheet, and the Young's modulus and tensile yield strength were measured using the test pieces. was measured and shown as the average value.

3) Heat resistance rigidity: length 130m using the obtained pellets
A test piece with a width of 13 m and a thickness of 6.5 m was created by injection molding, and the heat distortion temperature was measured using the test piece (JI
5 and 7207; 4.8 kgf/cm2 load), the heat resistance rigidity was evaluated. 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 Homopolymers Used in Examples and Comparative Examples) (1) Preparation of Catalyst 600 mol of n-hexane, 0.50 mol of diethylaluminium monochloride (DEAC), 1.20 mol of diisoamyl ether 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). 4.0 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product liquid (V) was added dropwise over a period of 180 minutes, kept at the same temperature for 30 minutes, and heated to 75°C. The temperature was raised to ℃ and allowed to react for another 1 hour, cooled to room temperature (20℃), the supernatant liquid was removed, 4000 ml of n-hexane was added, and the supernatant liquid was removed by decantation, which was repeated 4 times.
190 g of solid product (ii) were obtained. This solid product (
In a state where the entire amount of 2) was suspended in 300°C of n-hexane, 160g of diisoamyl ether and 350g of titanium tetrachloride were added at 20°C over about 1 minute at room temperature, and the mixture was stirred at 65°C for 1 minute.
Allowed time to react. 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, allowed to stand, and the supernatant liquid removed.The operation was repeated six times. Drying under reduced pressure gave a solid product (iii).

(2) Pre-activated catalyst! J1a! After purging a stainless steel reactor with internal volume 200 with inclined blades with nitrogen gas, 15Q n-hexane, 42g1 diethylaluminum monochloride solid product (i
i) After adding 30g at room temperature, 15NQ of hydrogen was added and reacted for 5 minutes at a propylene partial pressure of 5kg/ca2G, unreacted propylene, hydrogen and n-hexane were removed under reduced pressure, and the preactivated catalyst (vi) I wanted to obtain a solid product (Ni) in the form of granules (82.0 g of propylene per Ig of reaction).

(3) Polymerization of propylene In a polymerization vessel with an internal volume of 50Q that was purged with nitrogen gas, 8 g of dried n-hexane 20Q1 diethylaluminium monochloride, 2 g of the preactivated catalyst (vi), and ρ-
2.28% of methyl toluate was charged, hydrogen was added, and the inside of the vessel was maintained at 70°C. Then, propylene is supplied into the vessel,
The pressure inside the vessel was 10 kg/c 2 Gs, the hydrogen concentration in the gas phase was 11 mol% for Production Example 1, 6 mol% for Production Example 2, and 14 mol% for Production Example 3, and the temperature was 70°C for the first stage. Polymerization was carried out. When the amount of polymer reached 3 kg, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and hydrogen and unreacted propylene were released. Then, a portion of the polymerization slurry was extracted, and the intrinsic viscosity [η] 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 catalyst.

Then, the temperature inside the polymerization vessel was raised to 70°C again, and the polymerization pressure was increased to 10ky.
, /cva2G, gas phase hydrogen concentration is 0.4 mol% for Production Example 1, 0.07 mol% for Production Example 2, and 0.0 for Production Example 3.
The second stage of polymerization was carried out while maintaining the concentration at 8 mol%. When the amount of polymer in the second stage reached 3 kg, the supply of propylene was stopped, the temperature inside the vessel was cooled to room temperature, and unreacted propylene with hydrogen was discharged. Next, a part of the polymerization slurry was extracted, and the intrinsic viscosity [η] was measured and the titanium content in the polymer was analyzed by fluorescent X-ray method to determine the polymer yield per unit weight of catalyst. Using the yield value, the ratio of the amount of polymer in the first stage and the second stage was determined, and the intrinsic viscosity [η]2 of the polymer obtained only in the second stage polymerization was determined by calculation. . 5Q of methanol was added to the polymerization slurry after the extraction, and after stirring at 90°C for 30 minutes, a 20% by weight aqueous sodium hydroxide solution was added.
mQ was added and stirred for an additional 20 minutes. Next, the mixture was cooled to room temperature, 5Q of water was added thereto, water washing and water separation were performed 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. here[
η]L=[η]I, [η]H=[η]2.

Examples 1 to 3, Comparative Examples 1 to 9 Each intrinsic viscosity ([η]), each melt flow rate (MFR), each high melt flow rate ( HMFR) and powdered crystalline propylene homopolymer toO having each isotactic pentad fraction (P), aluminum hydroxy-bis(p-t-butylphenyl) phosphate and other A predetermined amount of each additive was placed in a Hensel mixer (trade name) at the mixing ratio listed in Table 2 below, and after stirring and mixing for 3 minutes,
The mixture was melt-mixed at 200°C in a single-screw extruder and pelletized. In addition, as Comparative Examples 1 to 9, 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 100 parts by weight of a crystalline propylene homopolymer was blended with predetermined amounts of each of the additives listed in Table 2 below, and subjected to melt mixing treatment according to Examples 1 to 3 to obtain pellets.

The sheets used for sheet secondary processability and rigidity tests are:
The resulting pellet was prepared by extrusion molding at a resin temperature of 250°C. Moreover, the test piece used for the heat resistance 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 by the test method described above. These results are shown in Table 2.

Examples 4 to 6, Comparative Examples 10 to 18 Each intrinsic viscosity ([η), each melt flow rate (MFR), each high melt flow rate ( HMFR) and 100 parts by weight of a powdered crystalline propylene homopolymer having each isotactic pentad fraction (P), aluminum hydroxy-bis(p-t-butylphenyl) phosphate as compound A, and an inorganic filler. As an agent, the average particle size is 2 to 3.
The predetermined amounts of microparticulate talc μ and other additives were mixed using a Hensel mixer at the mixing ratios listed in Table 3 below.
After stirring and mixing for 3 minutes, melt i! at 200℃ using a single screw extruder with a diameter of 40 mm. The mixture was kneaded and pelletized. In addition, as Comparative Examples 10-18, 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 the mixture was melt-kneaded in accordance with Examples 4 to 6 to obtain pellets.

The sheets used for sheet secondary processability and rigidity tests are:
The resulting pellet was prepared by extrusion molding at a resin temperature of 250°C. Moreover, the test piece used for the heat resistance 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 by the test method described above. These results are shown in Table 3.

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

Compound A Nialuminum hydroxy-bis(pt-
butylphenyl)phosphate nucleating agent 1: p-t-butylaluminum benzoate nucleating agent 2: 1-3.2,4-dibenzylidene sorbitol nucleating agent 3: sodium-bis(p-t-butylphenyl) Phosphate [manufactured by Adeka Argus Chemical; MARK
NA-10UFI Nucleating agent 4 Nialuminum-bis(pt-butylphenyl) phosphate Nucleating agent 5 Nialuminum-2,2'-methylene-bis(
4,6-di-t-butylphenyl) phosphate nucleating agent 6: aluminum hydroxy-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate phenolic antioxidant 1: 2 , 6-di-t-butyl-p-cresol phenolic antioxidant 2: Tetrakis[methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phosphorus antioxidant 1: Tetrakis(2,4-di-t-butylphenyl) -4,4'- Biphenylene-di-phosphonite Phosphorus antioxidant 2: Bis(2,4-di-t-butylphenyl)-pentaerythritol-siphosphite Ca-5t lucium stearate Inorganic filler: Talc (average particle size 2~3μ)-・
The Examples and Comparative Examples listed in Table 1 and Table 2 are crystalline propylene alone 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 a polymer is used. 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, Examples 1 to 3 and Comparative Examples 1 to 3 (no S-containing nucleating agent added to a crystalline propylene homopolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention) A comparison shows that Examples 1 to 3 and Comparative Examples 1 to 3 have the same degree of secondary processability, but Comparative Examples 1 to 3 still have insufficient effects of improving rigidity and heat-resistant rigidity. Furthermore, in order to improve the rigidity and heat-resistant rigidity of Comparative Examples 1 to 3, a compound other than Compound A was added to a crystalline propylene alone having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Comparing Comparative Examples 4 to 9 containing an organic nucleating agent and Examples 1 to 3, Comparative Example 4
Although the improvement effect of rigidity and heat-resistant rigidity is considerably recognized in ~9, it is still not sufficient, Examples 1-3 are extremely excellent in rigidity and heat-resistant rigidity, and a remarkable synergistic effect is recognized by blending compound A. I understand that.

In particular, it is clear that Comparative Example 7, in which a positive aluminum salt of Compound A (-basic aluminum salt) according to the present invention is blended, does not exhibit the effects of the present invention, and this is confirmed by the aforementioned Japanese Patent Publication No. 41-16303. Publication No. and Japanese Unexamined Patent Publication No. 5
No. 3-105550 does not contain any description. That is, the stiffness and heat-resistant stiffness obtained in the present invention can be seen for the first time when the compound ¥1JA is blended with a crystalline propylene homopolymer having an isotactic pentad fraction within the range limited in the present invention. This can be said to be a unique effect.

Table 3 shows the 10-pyrene polymer used in Table 2,
Furthermore, talc is used as an inorganic filler,
In this case, the same effect as described above was confirmed.

This shows that the composition of the present invention has better sheet fabrication properties, stiffness, and stiffness resistance than conventional compositions made by blending a nucleating agent with a crystalline propylene homopolymer. It was found that the composition of the present invention had a remarkable effect on the composition of the present invention.

that's all

Claims (7)

[Claims] (1) When polymerizing propylene in multiple stages, 35 to 65% by weight of the total polymer is polymerized in the first stage, and 65 to 35% by weight of the total polymer is polymerized in the second and subsequent stages. Among the polymer parts produced in the first stage and the second stage, the intrinsic viscosity of the polymer part with high molecular weight is [η]_H, and the intrinsic viscosity of the polymer part with low molecular weight is [η]_L. When 3.0≦[η]_H−[η
]_L≦6.5...(1), and the isotactic pentad fraction (P) and melt flow rate (MFR) of the entire polymer are ;
10 when applying a load of 2.16 kg at 230°C
Discharge amount of molten resin per minute) is 1.00≧P≧0
．． 015logMFR+0.955, the following general formula [
A high-rigidity, high-melt viscoelastic propylene homopolymer composition containing 0.01 to 1 part by weight of a phosphate compound represented by formula I (hereinafter referred to as compound A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) (2) A high-rigidity, high-melt viscoelastic propylene homopolymer according to claim (1), wherein the crystalline propylene homopolymer has a melt flow rate (MFR) of 0.03 to 2.0 g/10 min. Coalescing composition. (3) The crystalline propylene homopolymer has a high melt flow rate (HMFR; load at 230°C of 10.80
logHMFR-0.922logMFR≧1.44・
...The high-rigidity, high-melt viscoelastic propylene homopolymer composition according to claim (1), which has HMFR and MFR that satisfy (2). (4) The high rigidity and high melt viscosity according to any one of claims (1) to (3), wherein in the general formula [I], R is an alkyl group having 1 to 9 carbon atoms. Elastic propylene homopolymer composition. (5) The polymer according to any one of claims (1) to (3), wherein aluminum hydroxy-bis(p-t-butylphenyl) phosphate is blended as compound A. Rigid high melt viscoelastic propylene homopolymer composition. (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.