JP3849329B2 - Method for producing polypropylene resin composition - Google Patents

Description

【０１４７】
【表２】

【０１４８】
【表３】

【０１４９】
【表４】

【０１５０】
【表５】

【０１５１】
【表６】

【０１５２】
【表７】

【０１５３】
表５〜表７の注
＊１ ＭＦＲ１：溶融混練前のメルトフローレート、ＡＳＴＭ Ｄ−１２３８、２３０℃、２．１６ｋｇ荷重
＊２ 極限粘度〔η〕：１３５℃デカリン中で測定
＊３ ジェルの個数：（株）プラスチック工学研究所製の２５ｍｍφのＴダイ製膜機で作成した厚さ３０μｍのフィルムのジェルの個数を、ジェルカウンターとして（株）ヒューテック製のフィッシュアイカウンター（商標）を用いて測定した。測定数を、フィルム単位面積（４５０ｃｍ²）あたりのジェル個数として示した。
フィルム作成条件は次の通りである。

【０１５４】
＊４ 溶融張力：下記条件で測定
装置；東洋精機社製キャピログラフ１Ｃ（商標）
温度；２３０℃
オリフィス；Ｌ＝８．００、Ｄ＝２．０９５ｍｍ
押出速度；１５ｍｍ／ｍｉｎ
引取速度；１０ｍ／ｍｉｎ
＊５ 限界剪断速度：下記条件でメルトフラクチャーの発生する剪断速度を測定
装置；東洋精機社製キャピログラフ１Ｃ（商標）
温度；２３０℃
オリフィス；Ｌ＝１０．９、Ｄ＝１．００ｍｍ
＊６ 曲げ弾性率：得られたポリプロピレン樹脂組成物のペレットを用いて射出成形を行い、得られた射出成形品についてＡＳＴＭ Ｄ７９０に準拠した条件で測定した。
【０１５５】
＊７ ＭＦＲ２：溶融混練後のメルトフローレート、ＡＳＴＭ Ｄ−１２３８、２３０℃、２．１６ｋｇ荷重
＊８Ｍｗ／Ｍｎ、Ｍｚ／Ｍｗ：高温高速ゲルパーミエーションクロマトグラフィーで測定した。具体的には、ＧＰＣ装置としてＷａｔｅｒｓ社製の１５０−ＣＶを用い、カラムとして昭和電工（株）製のＳｈｏｄｅｘ ＡＤ−８０Ｍ／Ｓを２本連結し、１３５℃のオルトジクロロベンゼンを移動層として測定した。キャリブレーションは標準ポリスチレンを用い、Ｑファクターとして４１．４を採用した。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a polypropylene resin composition comprising a relatively high molecular weight polypropylene and a relatively low molecular weight polypropylene.ofIt relates to a manufacturing method.
[0002]
[Prior art]
Polypropylene molded products are widely used because they have good mechanical properties, are inexpensive and have relatively good heat resistance. Usually, propylene is polymerized to obtain powdery polypropylene. However, powdery polypropylene is poor in handleability, so it is distributed in pelletized form and improved in handleability, and is used for manufacturing molded products. ing.
[0003]
Usually, the polypropylene used in the molded product is one type having an intrinsic viscosity of less than 3 dl / g. In order to improve its physical properties, other resins such as polyethylene, rubber components, fillers and other components are blended. However, a resin composition that is satisfactory in terms of moldability and other physical properties such as the formation of flow marks and gels has not been obtained.
[0004]
In order to improve such points, it has been proposed to blend relatively high molecular weight polypropylene and relatively low molecular weight polypropylene. For example, Japanese Patent Laid-Open No. 59-149907 describes a polypropylene resin composition that contains high molecular weight polypropylene and low molecular weight polypropylene and is excellent in melt tension, rigidity, and moldability, and Japanese Patent Laid-Open No. 59-172507. Describes a polypropylene resin composition excellent in rigidity, workability, heat resistance and the like, including high molecular weight polypropylene and low molecular weight polypropylene, and JP-A-58-7439 discloses high molecular weight polypropylene and low molecular weight. Polypropylene resin compositions that are excellent in moldability and do not produce fish eyes are described.
[0005]
These polypropylene resin compositions are those in which high-molecular-weight polypropylene and low-molecular-weight polypropylene are uniformly mixed to compensate for each other's weaknesses to produce resin compositions with excellent physical properties. It is said that the viscosity is adjusted to improve moldability, workability, and handleability.
Examples of a method for obtaining the polypropylene resin composition as described above include batch multistage polymerization, continuous multistage polymerization, and blending.
[0006]
Among them, batch multistage polymerization is performed by charging a reaction tank with a catalyst and raw materials to produce a high molecular weight polypropylene, and then further charging the raw materials to produce a low molecular weight polypropylene. In this method, since the catalyst and the raw material are in contact with each other over the residence time necessary for the polymerization of the high molecular weight polypropylene, the high molecular weight polypropylene is formed in the form of fine particles around the catalyst, and the low molecular weight polypropylene is formed around the catalyst. The molecular weight polypropylene and the low molecular weight polypropylene are dispersed in a nearly uniform state. For this reason, even if the powder obtained is melt-kneaded to produce pellets, the melt flow rate (MFR) does not change greatly, and adjustment of the melt flow rate of the pellets is easy.
[0007]
However, batch multistage polymerization has low productivity and cannot efficiently produce a polypropylene resin composition. Therefore, if an attempt is made to produce a resin composition containing high molecular weight polypropylene and low molecular weight polypropylene by continuous multi-stage polymerization or blending method, the melt flow rate value before and after the melt kneading for pelletization changes, so It is difficult to adjust the flow rate.
[0008]
[Problems to be solved by the invention]
  An object of the present invention is to include a relatively high molecular weight polypropylene and a relatively low molecular weight polypropylene, and has a novel property that the melt flow rate decreases at a specific rate by melt kneading, and the melt flow rate of pellets Polypropylene resin composition that can be easily adjusted and can be manufactured with high productivityThingsIt is to propose a method for producing a polypropylene resin composition that can be stably mass-produced at low cost on an industrial scale.
[0009]
[Means for Solving the Problems]
  This invention is the manufacturing method of the following polypropylene resin composition.
(1) First stageWhile supplying catalyst and raw material to the polymerizerA relatively high molecular weight polypropylene having an intrinsic viscosity [η] of 3 to 13 dl / g in the absence of hydrogen so that the content in the composition is 5 to 30% by weight.Polymerized continuously,
  The polymer in the first stage polymerization vessel is continuously transferred to the polymerization vessel in the second and subsequent stages part by part,
  In the second and subsequent stages, a relatively low molecular weight polypropylene having an intrinsic viscosity [η] of 0.1 to 5 dl / g is set so that the content in the composition is 95 to 70% by weight.ContinuouslyBy continuous multistage polymerization to polymerize,
  Melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load, hereinafter referred to as MFR1) before melt kneading is 0.01 to 200 g / 10 min, and melt flow after melt kneading in the absence of a crosslinking agent The rate (ASTM D-1238, 230 ° C., 2.16 kg load, hereinafter referred to as MFR2) is 0.005 to 100 g / 10 min, and MFR1> MFR2, and the absolute value of the difference is 0.005 to 100 Producing a polypropylene resin composition before melt kneading,
  Thereafter, the polypropylene resin composition before melt kneading is melt kneaded in the absence of a crosslinking agent.
(2) Production of polypropylene resin composition according to (1) above, wherein the difference in intrinsic viscosity [η] between relatively high molecular weight polypropylene and relatively low molecular weight polypropylene is 0.5 to 12.9 dl / g. Method.
(3) The method for producing a polypropylene resin composition according to the above (1) or (2), wherein the polypropylene resin composition before melt kneading has an average particle size of 50 to 3000 μm.
[0010]
The polypropylene resin composition of the present invention containing the above relatively high molecular weight polypropylene and the above relatively low molecular weight polypropylene in the above-mentioned specific ratio, and the melt flow rate before and after melt kneading is in the above relationship, By controlling the melt flow rate before melt-kneading to a specific value, the melt flow rate after melt-kneading can be predicted, so that it is easy to adjust the melt flow rate when pelletized.
[0011]
Conventionally, granulation from powder to pellets is generally performed by melting and kneading powdery polypropylene with a granulator or an extruder and then cooling. In this case, when a polypropylene having an intrinsic viscosity [η] of about 3 dl / g is used, the pellet-like polypropylene (ie, the polypropylene after melt kneading) is heated or sheared in the granulator or the extruder. The melt flow rate (MFR2) is generally higher than the melt flow rate (MFR1) of powdery polypropylene (that is, the polypropylene before melt kneading), and generally MFR1 <MFR2.
When granulating, various stabilizers including an antioxidant are also added to polypropylene, and in this case, MFR1 <MFR2.
[0012]
On the other hand, a specific amount of a relatively high molecular weight polypropylene having an intrinsic viscosity [η] of 3 to 13 dl / g and a relatively low molecular weight polypropylene having an intrinsic viscosity [η] of 0.1 to 5 dl / g It was found that the polypropylene resin composition of the present invention contained in MFR1> MFR2 and a correlation was established between MFR1 and MFR2. Therefore, if the relational expression is obtained, the MFR2 of the pellet (after melt kneading) can be predicted from the MFR1 of the powder (before melt kneading).
[0013]
  The present inventionManufactured withThe polypropylene resin composition is a polypropylene resin composition containing a relatively high molecular weight polypropylene and a relatively low molecular weight polypropylene, but may be composed of only the above-mentioned two kinds of polypropylene or three or more kinds. It may be made of polypropylene and contains a small amount of other resins than polypropylene.TheAlso good.
[0014]
  The present inventionManufactured withThe intrinsic viscosity [η] (the intrinsic viscosity measured in 135 ° C. decalin, hereinafter the same) of the relatively high molecular weight polypropylene contained in the polypropylene resin composition is 3 to 13 dl / g, preferably 5 to 12 dl / g. More preferably, it is 6-11 dl / g, The content is 5-5.30% by weight, preferably 8 to30% by weight, more preferably 10-30% By weight. The present inventionManufactured withThe intrinsic viscosity [η] of the polypropylene having a relatively low molecular weight contained in the polypropylene resin composition is 0.1 to 5 dl / g, preferably 0.2 to 4 dl / g, more preferably 0.3 to 3 dl / g. g, and its content is 95 to70% By weight, preferably 92-70% By weight, more preferably 90-70% By weight. The difference in intrinsic viscosity [η] between relatively high molecular weight polypropylene and relatively low molecular weight polypropylene is 0.5 to 12.9 dl / g, preferably 0.7 to 11 dl / g, more preferably 1 to 10 dl. / G.
[0015]
  Of the present inventionBefore melt kneadingThe polypropylene resin composition has a characteristic that the melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load, the same applies hereinafter) is reduced by melt-kneading in the absence of a crosslinking agent. MFR1 before melt-kneading the polypropylene resin composition is 0.01 to 200 g / 10 min, preferably 0.1 to 140 g / 10 min, more preferably 0.2 to 100 g / 10 min, and in the absence of a crosslinking agent. The MFR2 after melt-kneading is 0.005 to 100 g / 10 min, preferably 0.1 to 70 g / 10 min, more preferably 0.3 to 50 g / 10 min. The absolute value of the difference between MFR1 and MFR2 is usually 0. 0.005 to 100, preferably 0.01 to 70, and more preferably 0.02 to 50.
[0016]
  The polypropylene resin composition before melt kneading in which MFR1 is measured is the one before the melt kneading treatment is performed for the purpose of granulation or the like. This polypropylene resin composition is the one immediately after polymerization by continuous multistage polymerization described later., ThatThe average particle size is usually 50 to 3000 μm, preferably 70 to 2000 μm.
[0017]
The polypropylene resin composition for which MFR2 is measured is the one after the polypropylene resin composition before being melt-kneaded is melt-kneaded under granulation conditions in the absence of a crosslinking agent. The melt-kneading conditions are the usual granulation conditions usually employed for pelletizing known polypropylene, for example, a single-screw or twin-screw extruder having an L / D of 10 to 30 in the absence of a crosslinking agent. Can be performed at a temperature of 170 to 300 ° C. The polypropylene resin composition after melt-kneading is usually a pellet-shaped polypropylene resin composition.
[0018]
The crosslinking agent can crosslink polypropylene such as divinylbenzene or a nucleus-substituted derivative thereof, or an ester of (meth) acrylic acid having 1 to 12 carbon atoms and 2 to 3 valent polyvalent alcohol. Specific examples of the ester that are compounds include ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate. When melt kneading using these crosslinking agents, the melt flow rate decreases due to crosslinking, but the polypropylene resin composition of the present invention decreases the melt flow rate after melt kneading without using such a crosslinking agent.
[0019]
When the intrinsic viscosity [η] and the content of relatively high molecular weight polypropylene and relatively low molecular weight polypropylene are in the above range, the melt flow rate of the polypropylene resin composition after melt-kneading is New properties are obtained that are lower than the melt flow rate (MFR1> MFR2).
[0020]
The polypropylene constituting the polypropylene resin composition of the present invention is usually preferably composed of only structural units derived from propylene, but a structure derived from other monomers in a small amount, for example, 10 mol% or less, preferably 5 mol% or less. It may contain units. Examples of other monomers include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1 Α-olefins other than propylene such as decene and 1-dodecene; vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; Conjugated dienes; Non-conjugated polyenes such as dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene. In these, ethylene, a C4-C10 alpha olefin, etc. are preferable. Two or more of these may be copolymerized.
[0021]
The polypropylene resin composition of the present invention contains branched olefins such as 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylnorbornane, allylnorbornane, styrene, dimethylstyrene, allylbenzene, allyltoluene, allylnaphthalene , 0.1% by weight or less using a homopolymer or copolymer such as vinyl naphthalene as a prepolymer, Mashiku may contain 0.05 wt% or less. Of these, 3-methyl-1-butene is particularly preferable.
[0022]
The polypropylene constituting the polypropylene resin composition of the present invention may be a propylene block copolymer. In this case, it is preferable because it is excellent in rigidity and impact resistance, and the rubber part (ethylene / propylene copolymer) is preferable. A propylene block copolymer having an intrinsic viscosity [η] of 0.5 to 10 dl / g is particularly preferable.
[0023]
As a preferred method for producing the polypropylene resin composition of the present invention, for example, in the presence of a catalyst for producing a highly stereoregular polypropylene described later, propylene alone or propylene and another monomer is used in the following two or more stages. A method of producing a relatively high molecular weight polypropylene and a relatively low molecular weight polypropylene by continuous multi-stage polymerization can be mentioned.
[0024]
  That is, a relatively high molecular weight polypropylene having an intrinsic viscosity [η] of 3 to 13 dl / g, a content of 5 to 50% by weight, and an intrinsic viscosity [η] of 0.1 to 5 dl / g The content of the low molecular weight polypropylene in the composition is 95 to3Propylene alone or propylene and other monomers are polymerized by continuous multi-stage polymerization so as to be 0% by weight, and MFR1 is 0.01 to 200 g / 10 min.Before melt kneadingProduce a polypropylene resin composition, thenBefore melt kneadingA polypropylene resin composition is melt-kneaded in the absence of a crosslinking agent.Thus, the polypropylene resin composition of the present invention is produced.In this case, a large load is not applied to the granulator or the extruder during melt kneading.
[0025]
  Specific examples of the continuous multistage polymerization method for producing the polypropylene resin composition of the present invention include the following methods.
  Namely, solid titanium catalyst component (a) containing magnesium, titanium, halogen and electron donor, organometallic compound catalyst component (b), cyclopentyl group, cyclopentenyl group, cyclopentadienyl group and derivatives thereof In the presence of a polymerization catalyst formed from an organosilicon compound catalyst component (c) having at least one group selected from the group consisting of: Relatively high molecular weight polypropylene having an intrinsic viscosity [η] measured in decalin at 135 ° C. of 3 to 13 dl / g, preferably 5 to 12 dl / g, more preferably 6 to 11 dl / g. 5 to 5 of the entire polypropylene resin composition finally obtained30% by weight, preferably 8 to30% by weight, more preferably 10-30In the second and subsequent polymerizations, relatively low molecular weight polypropylene is produced. Finally, the average particle size of the obtained polypropylene resin composition is 50 to 3000 μm, preferably 70 to 2000 μm.
[0026]
  The intrinsic viscosity [η] of the relatively low molecular weight polypropylene produced in the second and subsequent polymerizations is 0.1 to 5 dl / g, preferably 0.2 to 4 dl / g, more preferably 0.3 to 3 dl. / G (This intrinsic viscosity [η] is the intrinsic viscosity [η] of the polypropylene produced in that stage alone, not the intrinsic viscosity [η] of the entire polypropylene resin composition containing polypropylene up to the preceding stage) )). The method for adjusting the intrinsic viscosity [η] of the polypropylene produced in the second and subsequent stages is not particularly limited, but a method using hydrogen as a molecular weight regulator is preferred. Relatively low molecular weight polypropylene is 95 to 95% of the total polypropylene resin composition finally obtained.70% by weight, preferably 92-70% by weight, more preferably 90-70Manufactured to a weight percent.
[0027]
As a production order, after relatively high molecular weight polypropylene is polymerized substantially in the absence of hydrogen in the first stage, relatively low molecular weight polypropylene is produced in the second and subsequent stages..Reverse manufacturing orderWhenIn order to polymerize relatively high molecular weight polypropylene in the second and subsequent stages after polymerizing relatively low molecular weight polypropylene in the first stage, it is included in the reaction product in the first stage. Since it is necessary to remove a molecular weight modifier such as hydrogen as much as possible before the start of polymerization in the second and subsequent stages, the polymerization apparatus becomes complicated, and the intrinsic viscosity [η] in the second and subsequent stages is difficult to increase. The polymerization in each case can be performed by a known method such as slurry polymerization or bulk polymerization.
[0028]
When a polypropylene resin composition is produced by a continuous multistage polymerization method, gel is likely to be generated. In order to reduce the generation of gel as much as possible, the production of relatively low molecular weight polypropylene in the second and subsequent stages is preferably carried out using two or more, preferably three or more polymerizers. It is preferable to carry out the polymerization continuously and to transfer the reaction product between the polymerization vessels continuously. Thus, a polypropylene resin composition with little generation | occurrence | production of a gel can be obtained by manufacturing continuously the polypropylene of the 2nd step | paragraph or more using a some polymerizer.
[0030]
  When the monomer is polymerized by continuous multi-stage polymerization so as to contain a relatively high molecular weight polypropylene having a specific intrinsic viscosity and a relatively low molecular weight polypropylene in the specific amount by the above production method., MA polypropylene resin composition having a property of FR1 in the range of 0.01 to 200 g / 10 min, MFR1> MFR2, and an absolute value of the difference of 0.005 to 100 is obtained.
[0031]
At this time, when the MFR2 of the polypropylene resin composition used in injection molding, extrusion molding, or the like is in the range of 0.50 to 50 g / 10 min, the correlation equation between MFR1 and MFR2 is expressed by the following equation.
MFR2 = 0.4407 × MFR1 + 0.2305
The correlation coefficient R2 in the above equation is 0.9927.
[0032]
When such a polypropylene resin composition is melt-kneaded, the melt flow rate is lowered by 0.005 to 100 g / 10 min without any special operation. The value of MFR1 and the degree of decrease in melt flow rate due to melt-kneading select the intrinsic viscosity [η], content and continuous multistage polymerization conditions of relatively high molecular weight polypropylene and relatively low molecular weight polypropylene. Can be adjusted. Therefore, for example, by selecting the conditions for continuous multistage polymerization, MFR2 can be predicted by adjusting MFR1, and pellets of polypropylene resin composition having the desired melt flow rate (ie, MFR2) are produced on an industrial scale. Can be stably mass-produced at low cost.
[0033]
The reason why the polypropylene resin composition of MFR1> MFR2 is obtained is not clear, but is estimated as follows. That is, in continuous multistage polymerization, a polymerization reaction is carried out while supplying a catalyst and raw materials to produce a high molecular weight polypropylene, and the polymer is partially transferred and transferred to the next step. At this time, the residence time of the transferred catalyst is uniform. Instead, a catalyst with a different residence time is transferred, and a high-molecular-weight polypropylene is produced in a catalyst that stays for a long time, but a high-molecular-weight polypropylene is produced in a small amount in a catalyst that stays for a short time. is there. When such a catalyst having a different production amount of high molecular weight polypropylene shifts to the next stage, a catalyst having a small amount of high molecular weight polypropylene has higher activity, and thus a large amount of low molecular weight polypropylene is produced. As a result, high-molecular-weight polypropylene-rich particles and low-molecular-weight polypropylene-rich particles coexist, resulting in a dispersion state of high-molecular weight components and low-molecular weight components different from those in batch multistage polymerization, which is the melt flow rate. Presumed to cause a decrease.
[0035]
As the catalyst for producing a highly stereoregular polypropylene used for producing the polypropylene resin composition of the present invention, various known catalysts can be used. For example,
(A) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor;
(B) an organometallic compound catalyst component;
(C) an organosilicon compound catalyst component having at least one group selected from the group consisting of a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and derivatives thereof;
A catalyst consisting of can be used.
[0036]
The solid titanium catalyst component (a) can be prepared by contacting a magnesium compound (a-1), a titanium compound (a-2) and an electron donor (a-3).
Examples of the magnesium compound (a-1) include a magnesium compound having a reducing ability such as a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, and a magnesium halide, an alkoxy magnesium halide, an allyloxy magnesium halide, an alkoxy magnesium, Examples include magnesium compounds having no reducing ability, such as allyloxymagnesium and magnesium carboxylates.
[0037]
In preparing the solid titanium catalyst component (a), for example, a tetravalent titanium compound represented by the following formula (1) is preferably used as the titanium compound (a-2).
Ti (OR)_gX_4-g        ... (1)
(In the formula (1), R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.)
[0038]
Specifically, TiCl_Four, TiBr_Four, TiI_FourTetrahalogenated titanium such as Ti (OCH_Three) Cl_Three, Ti (OC₂H_Five) Cl_ThreeTi (On-C_FourH₉) Cl_Three, Ti (OC₂H_Five) Br_Three, Ti (O-iso-C_FourH₉) Br_ThreeTrihalogenated alkoxy titaniums such as;
Ti (OCH_Three)₂Cl₂, Ti (OC₂H_Five)₂Cl₂Ti (On-C_FourH₉)₂Cl₂, Ti (OC₂H_Five)₂Br₂Dihalogenated dialkoxytitanium such as;
Ti (OCH_Three)_ThreeCl, Ti (OC₂H_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl, Ti (OC₂H_Five)_ThreeMonohalogenated trialkoxytitanium such as Br;
Ti (OCH_Three)_Four, Ti (OC₂H_Five)_FourTi (On-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_FourTi (O-2-ethylhexyl)_FourAnd tetraalkoxytitanium.
[0039]
Examples of the electron donor (a-3) used in the preparation of the solid titanium catalyst component (a) include alcohols, phenols, ketones, aldehydes, esters of organic acids or inorganic acids, organic acid halides, ethers, acids. Examples include amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds.
[0040]
When contacting the magnesium compound (a-1), titanium compound (a-2) and electron donor (a-3) as described above, other reaction reagents such as silicon, phosphorus, and aluminum are allowed to coexist. In addition, a carrier-supporting solid titanium catalyst component (a) can be prepared using a carrier.
[0041]
The solid titanium catalyst component (a) can be prepared by adopting any method including known methods, but a few examples will be briefly described below.
(1) A hydrocarbon solution of a magnesium compound (a-1) containing an electron donor (liquefaction agent) (a-3) is contacted with an organometallic compound to precipitate a solid, or while depositing A method of causing a contact reaction with the titanium compound (a-2).
(2) A method in which a complex composed of a magnesium compound (a-1) and an electron donor (a-3) is contacted and reacted with an organometallic compound, and then a titanium compound (a-2) is contacted.
(3) A method in which a titanium compound (a-2) and an electron donor (a-3) are contact-reacted with a contact product between an inorganic carrier and an organomagnesium compound (a-1). At this time, the contact product may be previously contacted with the halogen-containing compound and / or the organometallic compound.
(4) A carrier on which a magnesium compound (a-1) is supported from a mixture of a magnesium compound (a-1) solution containing a liquefying agent and optionally a hydrocarbon solvent, an electron donor (a-3) and a carrier Then, the titanium compound (a-2) is then contacted.
(5) A method of contacting a carrier with a solution containing a magnesium compound (a-1), a titanium compound (a-2), an electron donor (a-3), and optionally a hydrocarbon solvent.
[0042]
(6) A method of bringing the liquid organomagnesium compound (a-1) into contact with the halogen-containing titanium compound (a-2). At this time, the electron donor (a-3) is used at least once.
(7) A method in which the liquid organomagnesium compound (a-1) and the halogen-containing compound are contacted, and then the titanium compound (a-2) is contacted. In this process, the electron donor (a-3) is used at least once.
(8) A method of bringing the alkoxy group-containing magnesium compound (a-1) into contact with the halogen-containing titanium compound (a-2). At this time, the electron donor (a-3) is used at least once.
(9) A method of contacting a complex comprising an alkoxy group-containing magnesium compound (a-1) and an electron donor (a-3) with a titanium compound (a-2).
(10) A method in which a complex comprising an alkoxy group-containing magnesium compound (a-1) and an electron donor (a-3) is contacted with an organometallic compound and then contacted with a titanium compound (a-2).
[0043]
(11) A method in which a magnesium compound (a-1), an electron donor (a-3), and a titanium compound (a-2) are contacted and reacted in an arbitrary order. Prior to this reaction, each component may be pretreated with a reaction aid such as an electron donor (a-3), an organometallic compound, or a halogen-containing silicon compound.
(12) A solid magnesium obtained by reacting a liquid magnesium compound (a-1) having no reducing ability with a liquid titanium compound (a-2) in the presence of an electron donor (a-3) -A method of depositing a titanium composite.
(13) A method in which the reaction product obtained in (12) above is further reacted with a titanium compound (a-2).
(14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor (a-3) and a titanium compound (a-2).
(15) A solid material obtained by pulverizing a magnesium compound (a-1), a titanium compound (a-2), and an electron donor (a-3) is converted into a halogen, a halogen compound, or an aromatic carbonization. A method of treatment with any of hydrogen. In this method, only the magnesium compound (a-1), a complex compound composed of the magnesium compound (a-1) and the electron donor (a-3), or the magnesium compound (a-1) and titanium are used. You may include the process of grind | pulverizing a compound (a-2). Further, after the pulverization, it may be pretreated with a reaction aid and then treated with halogen or the like. As the reaction aid, an organometallic compound or a halogen-containing silicon compound is used.
[0044]
(16) A method of contacting the titanium compound (a-2) after pulverizing the magnesium compound (a-1). When the magnesium compound (a-1) is pulverized and / or contacted, the electron donor (a-3) is used together with a reaction aid as necessary.
(17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon.
(18) A method in which a contact reaction product of a metal oxide, organomagnesium (a-1) and a halogen-containing compound is brought into contact with an electron donor (a-3) and preferably a titanium compound (a-2).
(19) Magnesium compounds (a-1) such as magnesium salts of organic acids, alkoxymagnesium and aryloxymagnesium, titanium compounds (a-2), electron donors (a-3), and optionally halogen-containing carbonization Method of contacting with hydrogen.
(20) A method of contacting a hydrocarbon solution containing a magnesium compound (a-1) and an alkoxytitanium with an electron donor (a-3) and, if necessary, a titanium compound (a-2). In this case, it is preferable that a halogen-containing compound such as a halogen-containing silicon compound coexists.
(21) A liquid magnesium compound (a-1) having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, and then an electron donor (a- 3) A method of reacting the titanium compound (a-2).
[0045]
The organometallic compound catalyst component (b) preferably contains a metal selected from Group I to Group III of the Periodic Table, specifically, an organoaluminum compound, a Group I metal as shown below, Examples thereof include complex alkyl compounds with aluminum and organometallic compounds of Group II metals.
[0046]
Formula R¹ _mAl (OR²)_nH_pX_q
(Wherein R¹And R²Is a hydrocarbon group usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same as or different from each other. X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound (b-1) shown by this.
[0047]
Formula M¹AlR¹ _Four
(Where M¹Is Li, Na or K and R¹Is the same as above. A complex alkylated product of a Group I metal and aluminum represented by (b-2).
[0048]
Formula R¹R²M²
(Wherein R¹And R²Is the same as above, and M²Is Mg, Zn or Cd. A dialkyl compound of group II or group III (b-3).
[0049]
Examples of the organoaluminum compound (b-1) include
R¹ _mAl (OR²)_3-m
(R¹And R²Is the same as above, and m is preferably a number of 1.5 ≦ m ≦ 3. ), A compound represented by
R¹ _mAlX_3-m
(R¹Is the same as above, X is a halogen, and m is preferably 0 <m <3. ), A compound represented by
R¹ _mAlH_3-m
(R¹Is the same as above, and m is preferably 2 ≦ m <3. ), A compound represented by
R¹ _mAl (OR²)_nX_q
(R¹And R²Is the same as above, X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3. ) And the like.
[0050]
Specific examples of the organosilicon compound catalyst component (c) include an organosilicon compound represented by the following formula (2).
SiR¹R² _n(OR^Three)_3-n      ... (2)
(In the formula (2), n is 0, 1 or 2, R¹Is a group selected from the group consisting of cyclopentyl, cyclopentenyl, cyclopentadienyl and derivatives thereof, R²And R^ThreeRepresents a hydrocarbon group. )
[0051]
In formula (2), R¹Specific examples of these include cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2-ethylcyclopentyl, 3-propylcyclopentyl, 3-isopropylcyclopentyl, 3-butylcyclopentyl, 3-tert -Butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,2,5-trimethylcyclopentyl group, 2,3,4,5-tetramethylcyclopentyl Groups, 2,2,5,5-tetramethylcyclopentyl group, 1-cyclopentylpropyl group, 1-methyl-1-cyclopentylethyl group and other cyclopentyl groups or derivatives thereof; cyclopentenyl group, 2-cyclopentenyl group, 3- A cyclopentenyl group, -Methyl-1-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 2-ethyl-3-cyclopentenyl group, 2,2-dimethyl-3-cyclopentenyl group Cyclopentenyl such as 2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl-3-cyclopentenyl, 2,2,5,5-tetramethyl-3-cyclopentenyl Group or a derivative thereof; 1,3-cyclopentadienyl group, 2,4-cyclopentadienyl group, 1,4-cyclopentadienyl group, 2-methyl-1,3-cyclopentadienyl group, 2 -Methyl-2,4-cyclopentadienyl group, 3-methyl-2,4-cyclopentadienyl group, 2-ethyl-2,4-cyclopentadienyl group, 2,2-dimethyl- , 4-cyclopentadienyl group, 2,3-dimethyl-2,4-cyclopentadienyl group, 2,5-dimethyl-2,4-cyclopentadienyl group, 2,3,4,5-tetra A cyclopentadienyl group such as a methyl-2,4-cyclopentadienyl group or a derivative thereof; a derivative of a cyclopentyl group, a cyclopentenyl group or a cyclopentadienyl group; an indenyl group, a 2-methylindenyl group, 2- Ethyl indenyl group, 2-indenyl group, 1-methyl-2-indenyl group, 1,3-dimethyl-2-indenyl group, indanyl group, 2-methylindanyl group, 2-indanyl group, 1,3-dimethyl 2-indanyl group, 4,5,6,7-tetrahydroindenyl group, 4,5,6,7-tetrahydro-2-indenyl group, 4,5,6,7-te Examples include a trahydro-1-methyl-2-indenyl group, 4,5,6,7-tetrahydro-1,3-dimethyl-2-indenyl group, a fluorenyl group, and the like.
[0052]
In the formula (2), R²And R^ThreeSpecific examples of the hydrocarbon group include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. R²Or R^ThreeIf there are two or more, R²Each other or R^ThreeMay be the same or different, and R²And R^ThreeMay be the same or different. In the formula (2), R¹And R²And may be cross-linked with an alkylene group or the like.
[0053]
Among the organosilicon compounds represented by the formula (2), R¹Is a cyclopentyl group and R²Is an alkyl group or a cyclopentyl group, and R^ThreeAn organosilicon compound in which is an alkyl group, particularly a methyl group or an ethyl group is preferred.
[0054]
Specific examples of the organosilicon compound represented by the formula (2) include cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and 2,5-dimethylcyclopentyltrimethoxy. Trialkoxysilanes such as silane, cyclopentyltriethoxysilane, cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane, 2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane, fluorenyltrimethoxysilane Dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (3-tert-butylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) Methoxysilane, bis (2,5-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, dicyclopentenyldimethoxysilane, di (3-cyclopentenyl) dimethoxysilane, bis (2,5-dimethyl-3-cyclopentenyl) Dimethoxysilane, di-2,4-cyclopentadienyldimethoxysilane, bis (2,5-dimethyl-2,4-cyclopentadienyl) dimethoxysilane, bis (1-methyl-1-cyclopentylethyl) dimethoxysilane, Cyclopentylcyclopentenyldimethoxysilane, cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane, bis (1,3-dimethyl-2-indenyl) dimethoxysilane, cyclopentadienylindenyldimethoxysilane Dialkoxy silanes such as difluorenyl dimethoxy silane, cyclopentyl fluorenyl dimethoxy silane, indenyl fluorenyl dimethoxy silane; tricyclopentyl methoxy silane, tricyclopentenyl methoxy silane, tricyclopentadienyl methoxy silane, tricyclopentyl Ethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, bis (2,5-dimethylcyclopentyl) cyclopentylmethoxysilane, di Cyclopentylcyclopentenylmethoxysilane, dicyclopentylcyclopentadiene Examples thereof include monoalkoxysilanes such as nylmethoxysilane and diindenylcyclopentylmethoxysilane; ethylenebiscyclopentyldimethoxysilane and the like.
[0055]
When performing polymerization of propylene using a catalyst comprising the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and the organosilicon compound catalyst component (c) as described above, preliminary polymerization is performed in advance. You can also. In the prepolymerization, the olefin is polymerized in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and, if necessary, the organosilicon compound catalyst component (c).
[0056]
Examples of the prepolymerized olefin include linear olefins such as ethylene, propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicocene; 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. Olefin having a branched structure can be used. These may be copolymerized.
[0057]
The prepolymerization is desirably performed so that a polymer of about 0.1 to 1000 g, preferably about 0.3 to 500 g, is produced per 1 g of the solid titanium catalyst component (a). If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease. In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization.
[0058]
When propylene is continuously multistage polymerized using the catalyst as described above, propylene and the other monomers are copolymerized in any stage or in all stages as long as the object of the present invention is not impaired. You may let them.
[0059]
In the case of continuous multistage polymerization, propylene is homopolymerized in each stage, or polypropylene is produced by copolymerizing propylene and other monomers. In each stage, 90 mol% of structural units derived from propylene are produced. It is desirable to produce polypropylene in an amount exceeding 90, preferably 95 to 100 mole percent. The molecular weight of each stage of polypropylene can be adjusted, for example, by changing the amount of hydrogen supplied to the polymerization system. However, in the first stage polymerization, when obtaining a high molecular weight polypropylene, it is preferable to polymerize in a hydrogen-free state.
[0060]
When propylene is continuously multistage polymerized, in addition to the polypropylene component polymerization step by such continuous multistage polymerization, a propylene / ethylene copolymer rubber component is formed by further providing a copolymerization step of propylene and ethylene. Block copolymers can also be produced.
[0061]
In the main polymerization, the solid titanium catalyst component (a) (or the prepolymerized catalyst) is converted to titanium atoms per liter of polymerization volume of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol. It is desirable to use in an amount of. The organometallic compound catalyst component (b) is desirably used in an amount of about 1 to 2000 moles, preferably about 2 to 500 moles, based on 1 mole of titanium atoms in the polymerization system. The organosilicon compound catalyst component (c) is desirably used in an amount of about 0.001 to 50 moles, preferably about 0.01 to 20 moles per mole of metal atoms of the organometallic compound catalyst component (b).
[0062]
The polymerization may be performed by any of a gas phase polymerization method, a liquid polymerization method such as a solution polymerization method and a suspension polymerization method, and each stage may be performed by a separate method. Moreover, you may carry out by any system of a continuous type and a semi-continuous type, and you may divide each stage into several polymerizers, for example, 2-10 polymerizers. Industrially, it is most preferable to polymerize by a continuous method. In this case, it is preferable to carry out the polymerization in the second and subsequent stages separately into two or more polymerization vessels, thereby suppressing the generation of gel. .
[0063]
As the polymerization medium, inert hydrocarbons may be used, and liquid propylene may be used as the polymerization medium. The polymerization conditions in each stage are such that the polymerization temperature is in the range of about −50 to + 200 ° C., preferably about 20 to 100 ° C., and the polymerization pressure is normal pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa. It is appropriately selected within the range of (gauge pressure).
[0064]
If necessary, the polypropylene resin composition of the present invention may contain other polymers and / or additives as long as the object of the present invention is not impaired. Examples of the other polymers include polypropylenes that are not included in the polypropylene resin composition of the present invention, such as propylene homopolymers and propylene / α-olefin copolymers. Other examples include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polyolefin, rubber components, engineering plastics, and the like. For example, in order to improve impact strength, rubber components such as ethylene / α-olefin copolymer rubber or conjugated diene rubber can be blended in an appropriate amount in the polypropylene resin composition of the present invention.
[0065]
Specific examples of such rubber components include ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-octene copolymer rubber, and propylene / ethylene copolymer rubber. Amorphous or low crystalline α-olefin copolymer containing no diene component; ethylene / propylene / dicyclopentadiene copolymer rubber; ethylene / propylene / 1,4-hexadiene copolymer rubber, ethylene / propylene / Ethylene / propylene / non-conjugated diene copolymer rubber such as cyclooctadiene copolymer rubber, ethylene / propylene / methylene norbornene copolymer rubber, ethylene / propylene / ethylidene norbornene copolymer rubber; ethylene / butadiene copolymer rubber Etc.
[0066]
Examples of the additives include nucleating agents, antioxidants, hydrochloric acid absorbents, heat stabilizers, weathering stabilizers, light stabilizers, ultraviolet absorbers, slip agents, antiblocking agents, antifogging agents, lubricants, antistatic agents, Flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizers, foaming agents, plasticizers, anti-bubble agents, crosslinkers, peroxides and other flowability improvers, weld strength improvers, natural oils, Examples thereof include inorganic fillers such as synthetic oils, waxes, and talc.
[0067]
In the polypropylene resin composition of the present invention, the above-mentioned prepolymer may be contained as a nucleating agent, and various other nucleating agents may be blended, and the prepolymer is included. Other nucleating agents may be blended. By containing or blending the nucleating agent, the crystal particles are refined and the crystallization speed is improved, thereby enabling high-speed molding. For example, when the polypropylene resin composition of the present invention contains a nucleating agent, the crystal particles can be made finer, the crystallization speed can be improved, and high-speed molding becomes possible. As the nucleating agent other than the prepolymer, various conventionally known nucleating agents such as phosphate nucleating agents, sorbitol nucleating agents, metal salts of aromatic or aliphatic carboxylic acids, inorganic compounds, etc. are particularly limited. Used without.
[0068]
The polypropylene resin composition of the present invention is used as a raw material resin for injection molded products, blow molded products, vacuum molded products, compressed air molded products, calendar molded products, stretched films, inflation films, extruded molded products, foams and the like. Although suitable, it can also be used as a raw resin for other molded articles and molding methods.
[0069]
In order to produce an injection molded product from the polypropylene resin composition of the present invention, a known injection molding apparatus can be used. Also, known conditions can be adopted as the molding conditions. Specifically, injection molding can be performed at various resin shapes by injection molding at a resin temperature of 170 to 300 ° C, preferably 190 to 270 ° C.
[0070]
Injection molded products include automotive parts, household electrical appliance parts, daily necessities, miscellaneous goods, and other molded articles used in various fields. Specifically, armrests, indicator panel lowers, indicator panel cores, indicator panel uppers, cars Automotive interior parts such as cooler housing, console box, club outdoor, glove box, trim, door trim, door pocket, speaker grille, high mount, relay fuse box, lamp housing, meter case, meter hood, pillar, center pillar; bumper, Automotive exterior parts such as front grille side, license plate, louver garnish, side molding, bumper corner, bumper side, side mudguard; air cleaner case, junk Other car parts such as storage box, sirocco fan, corrugated tube, connector, fan shroud, protector, lamp housing, reserve tank (cap), air purifier, battery case; cleaner pipe, dishwasher part, washing machine part, housing, Home appliances such as hot plates and rice cooker bodies; other syringes, caps, connectors, daily necessities, containers, and medical devices.
[0071]
In order to produce a blow molded article from the polypropylene resin composition of the present invention, a known blow molding apparatus can be used. Also, known conditions can be adopted as the molding conditions.
[0072]
In the case of extrusion blow molding, for example, at a resin temperature of 170 to 300 ° C., preferably 170 to 270 ° C., the polypropylene resin composition of the present invention is extruded from a die in a molten state to form a tubular parison, and then a shape to be applied After holding the parison in the mold, air is blown, and the mold is mounted at a resin temperature of 130 to 300 ° C., preferably 200 to 270 ° C., to obtain a blow molded product. The draw ratio is preferably 1.5 to 5 times in the transverse direction.
[0073]
In the case of injection blow molding, for example, the polypropylene resin composition of the present invention is injected into a mold at a resin temperature of 170 to 300 ° C., preferably 170 to 270 ° C. to form a parison, and then in a mold having a shape to be applied. After holding the parison, air is blown into the mold, and the mold is mounted at a resin temperature of 120 to 300 ° C., preferably 140 to 270 ° C. to obtain a blow molded product. The draw ratio is preferably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.
[0074]
In the case of stretch blow molding, for example, the polypropylene resin composition of the present invention is injected into a mold at a resin temperature of 170 to 300 ° C., preferably 170 to 280 ° C. to form a parison, and this is pre-blown under predetermined conditions. Thereafter, stretch blow is performed at a resin temperature of 80 to 200 ° C., preferably 100 to 180 ° C., to obtain a blow molded product. The draw ratio is preferably 1.2 to 4.5 times in the longitudinal direction and 1.2 to 8 times in the transverse direction.
[0075]
Specific blow molded products include automotive bumpers, automotive spoilers, side moldings, front grill guards, bumper guards and other automotive exterior materials; sun visors, radiator tanks, washer tanks, ducts, distributors and evaporator cases. Automotive interior materials such as console boxes, indicator panels, door trims; kerosene tanks, food containers, shampoo containers, cosmetic containers, detergent containers, chemical containers, toner containers, etc .; other toys, containers, etc. It is done. Among these, large-sized blow molded products having a parison weight of 5 kg or more, particularly automobile exterior materials such as automobile bumpers and automobile spoilers are preferable.
[0076]
In order to produce a vacuum or compressed air molded product from the polypropylene resin composition of the present invention, a known vacuum forming apparatus or compressed air forming apparatus can be used. Also, known conditions can be adopted as the molding conditions. For example, a sheet-like molded article comprising the polypropylene resin composition of the present invention is held on a mold having a shape to be applied at a temperature of 180 to 300 ° C, preferably 180 to 270 ° C, more preferably 180 to 250 ° C, A vacuum or compressed air molded product can be obtained by evacuating the inside of the mold or injecting compressed gas into the mold.
[0077]
Specific examples of vacuum or pneumatic molded products include automotive interior materials such as automotive roof liners, refrigerator interior materials, washing machine interior and exterior materials, jelly containers, disposable lunch boxes, trays, food trays, food foam trays, tofu Packs, cups, bags, microwave oven heat-resistant containers, machine protective cases, product packaging cases, and the like can be mentioned.
[0078]
In order to produce a calendar molded article from the polypropylene resin composition of the present invention, a known calendar apparatus can be used. Also, known conditions can be adopted as the molding conditions. For example, using a calender molding apparatus such as an in-line type, an L type, an inverted L type, or a Z type, the resin temperature is 180 to 300 ° C, preferably 180 to 270 ° C, and the heating roll temperature is 170 to 300 ° C, preferably 170 to 270. Calendar molding can be performed under molding conditions of ° C. Further, when molding, paper or cloth can be sent to a roll to produce artificial leather, waterproof cloth or various laminated products.
Specific examples of the calendar molded product include various card stocks and Sunday sundries.
[0079]
In order to produce an extruded product from the polypropylene resin composition of the present invention, a known extrusion apparatus can be used. For example, as the extruded sheet, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder, or the like is used. An annular die or a T die may be attached to the extruder. Moreover, although well-known conditions can be employ | adopted for shaping | molding conditions, It is preferable to manufacture on the following conditions. For example, using an extruder equipped with a T die, the sheet is extruded at a resin temperature of 180 to 300 ° C., preferably 180 to 270 ° C., and at a T die temperature of 180 to 300 ° C., preferably 180 to 290 ° C. preferable. Water is used for cooling the molded product, and an air knife or a cooling roll can be used. Further, when molding, paper, cloth or the like can be sent onto the roll to produce artificial leather, waterproof cloth or various laminated products.
[0080]
Specific examples of extruded products include gutters, curtain rails, window frames, shelves, doors, other building materials, wiring ducts, roller den shutters, shutters, etc .; other tubes, pipes, electric wires (coating) , Film, sheet, plate, fiber, tape and the like.
[0081]
In order to produce a stretched film from the polypropylene resin composition of the present invention, a known stretching apparatus can be used. Examples thereof include a tenter (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching apparatus or a uniaxial stretching apparatus. Also, known conditions can be adopted as the molding conditions. For example, the polypropylene resin composition of the present invention is melt-extruded at 200 to 280 ° C., preferably 240 to 270 ° C., and stretched 2 to 10 times, preferably 2 to 6 times in the longitudinal direction to produce a uniaxially stretched film. can do. As yet another method, the polypropylene resin composition of the present invention is melt-extruded at 200 to 280 ° C., preferably 240 to 270 ° C., and in the atmosphere of 120 to 200 ° C., preferably 130 to 180 ° C. A biaxially stretched film can be produced by stretching 10 times and 3 to 10 times in the transverse direction.
[0082]
Specific examples of stretched films include food packaging films such as confectionery and vegetable packaging; shrink films such as cup noodles; fiber packaging films such as Y-shirts, T-shirts, and pantyhose; clear files, clear sheets, etc. Stationery films; other condenser films, cigarette packaging films, light packaging films, decorative tapes, packaging tapes, and the like.
[0083]
In order to produce an inflation film from the polypropylene resin composition of the present invention, a known inflation device can be used. Also, known conditions can be adopted as the molding conditions. For example, the resin temperature is 180 ° C. to 240 ° C., the cooling air is one or two stages, the temperature is 10 to 40 ° C., the take-up speed is 5 to 200 m / min, and the expansion ratio is 1.1 to 5 times. be able to. Such an inflation film has a thickness in the range of about 10 μm to 1 mm, preferably about 15 μm to 0.5 mm.
[0084]
Specific examples of the inflation film include food packaging films such as confectionery and vegetable packaging; textile packaging films such as Y-shirts, T-shirts, and pantyhose; stationery films such as clear files and clear sheets; cleaning bags, Examples include fashion bag films, agricultural films, and cups.
[0085]
When the foam is produced, the foaming method is not particularly limited, and a known foaming method such as an atmospheric foaming method, an extrusion foaming method, a pressure foaming method, an injection foaming method, or a bead foaming method can be employed. A foam is produced by heating a foam molding composition comprising the polypropylene resin composition of the present invention, a foaming agent, and, if necessary, a foam nucleating agent, an organic peroxide and a crosslinking aid. can do.
[0086]
The shape of the foam may be any shape, and examples include a block shape, a sheet shape, and a monofilament shape. In order to produce the foam from the polypropylene resin composition of the present invention, a known foam molding apparatus can be used. Also, known conditions can be adopted as the molding conditions.
[0087]
For example, the polypropylene resin composition of the present invention, a foaming agent that is liquid or solid at room temperature and generates a gas upon heating, an organic peroxide, a crosslinking aid and, if necessary, a heat stabilizer, are added to a Henschel mixer, V- Mixing with a blender, ribbon blender or tumbler blender, etc., and using an extruder, preferably a vented extruder, while absorbing unnecessary volatile substances from the vent installed after the high temperature heating part, A cross-linked modified foamable sheet containing a substantially undegraded foaming agent that is kneaded in a temperature range in which the organic peroxide decomposes but the foaming agent does not decompose and is attached to an extruder. Get. Thereafter, known foaming methods, such as a press foaming method in which the foaming agent is pressure-decomposed under pressure, a molten salt bath heating foaming method in which the foaming agent is thermally decomposed under normal pressure, a hot air oven method heating foaming method, radiant heat ray heating foaming The foam can be produced by foaming by a method, a high-frequency heating foaming method, or a method combining two or more of these methods.
[0088]
Further, as another method for producing a foam, the polypropylene resin composition of the present invention, a foaming agent that is liquid or solid at room temperature and generates a gas by heating, and a heat-resistant stabilizer, if necessary, are added to a Henschel mixer, V- Mix with a blender, ribbon blender, tumbler blender, etc., and knead the resulting composition at a temperature range where the foaming agent decomposes using an extruder and substantially through a T die or an annular die attached to the extruder. A foamed sheet can be produced.
[0089]
Further, as another method for producing a foam, the polypropylene resin composition of the present invention, a foam nucleating agent, and, if necessary, a heat stabilizer may be mixed with a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender. The resulting composition is kneaded while continuously supplying gaseous gases or low-boiling volatile blowing agents (low-boiling organic solvents) at normal temperature and pressure from a blowing agent injection nozzle provided in the middle of the extruder cylinder. It is also possible to produce a substantially foamed sheet through a T die or an annular die attached to an extruder.
[0090]
Further, as another method for producing a foam, the composition obtained by mixing the polypropylene resin composition of the present invention and, if necessary, a heat stabilizer in a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender. The product is kneaded using an extruder to obtain pellets. Next, this pellet and the low boiling point volatile foaming agent (low boiling point organic solvent) are treated in a high temperature and high pressure tank to obtain impregnated beads. The obtained impregnated beads are heated with water vapor, preliminarily foamed to adjust the particle diameter of the foamed cells, and further transferred to an aging step for returning the internal pressure of the beads to normal pressure, and sufficiently brought into contact with air. Further, the aged beads can be heated with steam or the like in a mold to produce a foam.
[0091]
Specific examples of foams include stationery supplies such as file cases, automobile interior materials such as automobile roof liners, trays, food trays, noodle containers, lunch boxes, fast food containers, retort containers, frozen food containers, prepared dishes. Containers, microwave heat-resistant containers, cups, synthetic wood, various foam materials, various cushioning materials, various heat insulating materials, various soundproofing materials, various vibration-proofing materials, and the like.
[0092]
When molding a molded product, for example, an injection molded product, a blow molded product, a vacuum or compressed air molded product, a calendar molded product, an extruded product, a stretched film, an inflation film, a foam, etc. using the polypropylene resin composition of the present invention, The polypropylene resin composition as a raw material preferably contains at least one or more of a phenol stabilizer, an organic phosphite stabilizer, a thioether stabilizer, a hindered amine stabilizer, or a higher fatty acid metal salt. Such an additive is desirably used in an amount of 0.005 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight, with respect to 100 parts by weight of the polypropylene resin composition of the present invention.
[0093]
The polypropylene resin composition of the present invention is a novel polypropylene resin composition in which the melt flow rate of the pellet is lower than the melt flow rate of the powder before granulation without causing a chemical reaction such as crosslinking. It has different properties from polypropylene.
[0094]
【The invention's effect】
  The present inventionMelt kneading manufactured inThe previous polypropylene resin composition includes a relatively high molecular weight polypropylene and a relatively low molecular weight polypropylene, and is a polypropylene resin composition having a novel property that the melt flow rate decreases at a specific rate by melt kneading. is there. thisAfter melt kneading obtained from a polypropylene resin composition before melt kneadingThe polypropylene resin composition is easy to adjust the melt flow rate of the pellets and can be manufactured with high productivity.
[0095]
  The method for producing a polypropylene resin composition of the present invention comprises a continuous multistage process of propylene so as to include a specific amount of a relatively high molecular weight polypropylene having a specific viscosity [η] in a specific range and a relatively low molecular weight polypropylene. Polymerized by polymerization and has a specific melt flow rateBefore melt kneadingManufactured polypropylene resin compositionAndAfter melt kneadingDoSoIt is easy to adjust the melt flow rate of the pellets, and the melt flow rate after the melt kneading is adjusted.Polypropylene resin composition on an industrial scaleEasy andIt can be stably mass-produced at low cost.
[0096]
DETAILED DESCRIPTION OF THE INVENTION
In order to describe the present invention in more detail, examples are shown below, but the present invention is not limited thereto.
[0097]
<Manufacture of solid titanium catalyst component>
Production Example 1
A vibration mill equipped with four grinding pots with an internal volume of 4 liters containing 9 kg of steel balls with a diameter of 12 mm was prepared. To each pot, 300 g of anhydrous magnesium chloride, 115 ml of diisobutyl phthalate, and 60 ml of titanium tetrachloride were added in a nitrogen atmosphere and ground for 40 hours. 5 g of this co-ground product was placed in a 200 ml flask, 100 ml of toluene was added, and the mixture was stirred at 114 ° C. for 30 minutes. Subsequently, after leaving still, the supernatant liquid was removed. Subsequently, the solid content was washed with 100 ml of n-heptane at 20 ° C. Washing was performed 3 times. Next, the solid content was dispersed in 100 ml of n-heptane to obtain a slurry of solid titanium catalyst component-1. The obtained solid titanium catalyst component-1 contained 2.0% by weight of titanium and 18% by weight of diisobutyl phthalate.
[0098]
Production Example 2
An autoclave with an internal volume of 200 liters was charged with 250 g of the solid titanium catalyst component-1 obtained in Production Example 1, 32.1 g of triethylaluminum (hereinafter sometimes abbreviated as TEA), and 125 liters of heptane. did. Next, 1250 g of propylene was charged while maintaining the internal temperature at 10 ° C., stirred for 30 minutes, and then charged with 18 g of titanium tetrachloride to obtain a slurry of prepolymerized catalyst component-2.
[0099]
Example 1
Polymerizer-1 having an internal volume of 500 liters contains 87 liter / hour of heptane, 9.6 g / hour of prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 18.2 g / hour of triethylaluminum, Cyclopentyldimethoxysilane (hereinafter sometimes abbreviated as DCPMS) was continuously fed at a rate of 37.2 g / hour, and the internal pressure of the polymerizer-1 was maintained at a temperature of 60 ° C. and substantially free of hydrogen. Was continuously charged so as to maintain the pressure at 0.69 MPa (gauge pressure) (first stage polymerization). The slurry of Polymerizer-1 was sampled and the intrinsic viscosity [η] of polypropylene was measured and found to be 9.1 dl / g.
[0100]
The obtained slurry was continuously fed to the polymerization vessel-2 having an internal volume of 500 liter and further polymerized. The polymerization vessel-2 is charged with heptane at a rate of 32 liter / hour, the internal pressure of the polymerization vessel-2 is kept at 0.69 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase is kept at 6 vol%. Propylene and hydrogen were continuously fed to (second stage polymerization).
[0101]
After removing unreacted monomers from the slurry exiting the polymerizer-2, the heptane was centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 80 kg / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 0.56 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 30% by weight.
[0102]
The intrinsic viscosity [η] of the polypropylene produced by the second stage polymerization was determined as follows. That is, the intrinsic viscosity [η] of the finally obtained powdery polypropylene resin composition is linear in proportion to the intrinsic viscosity [η] of the polypropylene produced by the first and second stage polymerizations. Assuming that, the intrinsic viscosity [η] of the polypropylene produced by the second stage polymerization was determined from the following equation. As a result, it was 1.91 dl / g.
Second stage intrinsic viscosity [η] = (Intrinsic viscosity [η] of finally obtained polypropylene resin composition−Intrinsic viscosity [η] of first stage polypropylene × Ratio of first stage polypropylene) ) / Proportion of second stage polypropylene
[0103]
100 parts by weight of the above powdery polypropylene resin composition, 0.2 parts by weight of a phosphorus-based antioxidant, 0.4 parts by weight of a phenolic antioxidant, 0.1 parts by weight of calcium stearate as a neutralizing agent, 20 liters of Henschel Mix for 2 minutes with a mixer. Thereafter, this mixture was subjected to a die temperature of 250 ° C. and a cylinder temperature of 220 to 240 ° C. (C1: 220 ° C., C2: 230 ° C., C3: 240 ° C., C4: 240) using a single screw extruder with L / D = 28. ° C), screw rotation speed 700 rpm, screen mesh 60 #, extrusion amount 25 kg / hr, melt-kneaded under nitrogen atmosphere, extruded, granulated, and pelletized. The pellets had a melt flow rate (MFR2) of 0.42 g / 10 min, Mw / Mn = 10.5, and Mz / Mw = 4.3. The reaction conditions are shown in Table 1, and the results are shown in Table 5.
[0104]
Example 2
The prepolymerization catalyst component-2 charged to the polymerization vessel-1 was changed to a rate of 7.4 g / hour, triethylaluminum was changed to 13.5 g / hour, and DCPMS was changed to 28.7 g / hour. The powdered polypropylene resin composition was polymerized in the same manner as in Example 1 except that heptane to be added was changed to 40 liter / hour, the internal pressure was changed to 0.59 MPa (gauge pressure), and the hydrogen concentration in the gas phase was changed to 23 vol%. Got. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 4.2 g / 10 min. The proportion of the polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 26% by weight.
[0105]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 2.2 g / 10 min, Mw / Mn = 18.0, and Mz / Mw = 5.5. The reaction conditions are shown in Table 1, and the results are shown in Table 5.
[0106]
Example 3
The polymerization in the first stage was carried out by a continuous two-stage polymerization method using one polymerization vessel and the polymerization in the second stage using two polymerization vessels. That is, 151 liter / hour of heptane in Polymerizer-1 having an internal volume of 500 liter, 8.9 g / hour of prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 16.9 g / hour of triethylaluminum, And DCPMS are continuously supplied at a rate of 34.5 g / hr, and the internal pressure of the polymerization vessel-1 is maintained at 0.78 MPa (gauge pressure) at a temperature of 55 ° C. under substantially no hydrogen. Was continuously charged with propylene (first stage polymerization). The slurry of Polymerizer-1 was sampled, and the intrinsic viscosity [η] of polypropylene was measured and found to be 9.2 dl / g.
[0107]
The polymerization in the second stage was carried out by a continuous method using two polymerization vessels. That is, the slurry of the polymerizer-1 subjected to the first stage polymerization was first continuously fed to the polymerizer-2 having an internal volume of 500 liter, and further polymerized. Polymerizer-2 was charged with heptane at a rate of 14.7 liter / hour, the internal pressure of polymerizer-2 was 0.78 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was 6 vol%. Propylene and hydrogen were fed continuously to maintain. Next, the slurry of the polymerization vessel-2 was continuously fed to the polymerization vessel-3 having an internal volume of 300 liter, and further polymerized. Polymerizer-3 was charged with heptane at a rate of 16.4 liters / hour, the internal pressure of polymerizer-3 was 0.74 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was 6 vol%. Propylene and hydrogen were fed continuously to maintain.
[0108]
After removing the unreacted monomer from the slurry exiting the polymerizer-3, the heptane is centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 80 kg / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 0.60 g / 10 min. The proportion of the polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 33% by weight.
[0109]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 0.45 g / 10 min, Mw / Mn = 14.4, Mz / Mw = 3.8. The reaction conditions are shown in Table 1, and the results are shown in Table 5.
[0110]
Example 4
The polymerization in the first stage was carried out by a continuous two-stage polymerization method using one polymerization vessel and the polymerization in the second stage using 4 polymerization vessels. That is, 53 liter / hour of heptane in Polymerizer-1 having an internal volume of 500 liter, 8.0 g / hour of prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 15.2 g / hour of triethylaluminum, And DCPMS were continuously fed at a rate of 31 g / hour, and propylene was fed so that the internal pressure of the polymerization vessel-1 was kept at 0.76 MPa (gauge pressure) at a temperature of 60 ° C. and substantially free of hydrogen. Charged continuously (first stage polymerization). The slurry of Polymerizer-1 was sampled, and the intrinsic viscosity [η] of polypropylene was measured and found to be 9.5 dl / g.
[0111]
The polymerization in the second stage was carried out by a continuous method using four polymerization vessels. That is, the slurry of the polymerizer-1 subjected to the first stage polymerization was first continuously fed to the polymerizer-2 having an internal volume of 500 liter, and further polymerized. Polymerizer-2 was charged with heptane at a rate of 56 liter / hour, the internal pressure of polymerizer-2 was maintained at 0.21 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was maintained at 6 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerization vessel-2 was continuously fed to the polymerization vessel-3 having an internal volume of 500 liter, and further polymerized.
[0112]
The polymerization vessel-3 was charged with heptane at a rate of 24 liter / hour, the internal pressure of the polymerization vessel-3 was kept at 0.15 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was kept at 6 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerizer-3 was continuously fed to the polymerizer-4 having an internal volume of 500 liter, and further polymerized. Polymerizer-4 was charged with heptane at a rate of 17 liter / hour, the internal pressure of polymerizer-4 was maintained at 0.10 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was maintained at 6 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerizer-4 was continuously fed to the polymerizer-5 having an internal volume of 300 liter, and further polymerized. The polymerization vessel-5 is charged with heptane at a rate of 10 liter / hour, the internal pressure of the polymerization vessel-5 is 0.020 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase is kept at 6 vol%. Propylene and hydrogen were continuously fed to the reactor.
[0113]
After removing unreacted monomers from the slurry exiting the polymerizer-5, the heptane was centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 78 kg / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 0.60 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 32% by weight.
[0114]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 0.54 g / 10 min, Mw / Mn = 9.8, and Mz / Mw = 4.0. The reaction conditions are shown in Table 2, and the results are shown in Table 5.
[0115]
Example 5
The prepolymerization catalyst component-2 charged to the polymerization vessel-1 was changed to a rate of 5.4 g / hour, triethylaluminum was changed to 10.3 g / hour, and DCPMS was changed to a rate of 20.9 g / hour. Heptane to be used is 70 liter / hour, internal pressure is 0.61 MPa (), hydrogen concentration in the gas phase is 30 vol%, heptane charged to the polymerizer-3 is 10 liter / hour, and internal pressure is 0.47 MPa (gauge pressure) The heptane charged into the polymerizer-4 is 15 liter / hour, the internal pressure is 0.52 MPa (gauge pressure), the hydrogen concentration in the gas phase is 30 vol%, and the internal pressure of the polymerizer-5 is 0.32 MPa (gauge pressure). Polymerization was carried out in the same manner as in Example 4 except that the hydrogen concentration in the gas phase was changed to 30 vol% to obtain a powdery polypropylene resin composition. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 6.3 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 25% by weight.
[0116]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 3.2 g / 10 min, Mw / Mn = 18.9, and Mz / Mw = 4.8. The reaction conditions are shown in Table 2, and the results are shown in Table 6.
[0117]
Example 6
The polymerization in the first stage was carried out by a continuous two-stage polymerization method using one polymerization vessel and the polymerization in the second stage using two polymerization vessels. That is, 151 liter / hour of heptane in Polymerizer-1 having an internal volume of 500 liter, 9.1 g / hour of prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 17.0 g / hour of triethylaluminum, And DCPMS are continuously fed at a rate of 34.5 g / hour, and the internal pressure of the polymerization vessel-1 is maintained at 0.80 MPa (gauge pressure) at a temperature of 55 ° C. under substantially no hydrogen. Was continuously charged with propylene (first stage polymerization). The slurry of Polymerizer-1 was sampled and the intrinsic viscosity [η] of polypropylene was measured and found to be 9.8 dl / g.
[0118]
The polymerization in the second stage was carried out by a continuous method using two polymerization vessels. That is, the slurry of the polymerizer-1 subjected to the first stage polymerization was first continuously fed to the polymerizer-2 having an internal volume of 500 liter, and further polymerized. The polymerization vessel-2 was charged with heptane at a rate of 14.3 liter / hour, the internal pressure of the polymerization vessel-2 was 0.85 MPa (gauge pressure) at a temperature of 75 ° C., and the hydrogen concentration in the gas phase was 45 vol%. Propylene and hydrogen were fed continuously to maintain. Next, the slurry of the polymerization vessel-2 was continuously fed to the polymerization vessel-3 having an internal volume of 300 liter, and further polymerized. Polymerizer-3 was charged with heptane at a rate of 16.9 liter / hour, the internal pressure of polymerizer-3 was 0.78 MPa (gauge pressure) at a temperature of 74 ° C., and the hydrogen concentration in the gas phase was 45 vol%. Propylene and hydrogen were fed continuously to maintain.
[0119]
After removing the unreacted monomer from the slurry exiting the polymerizer-3, the heptane is centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 71 kg / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 15 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 20% by weight.
[0120]
100 parts by weight of the above powdery polypropylene resin composition, 0.2 parts by weight of a phosphorus antioxidant, 0.1 parts by weight of a phenolic antioxidant, 0.05 parts by weight of calcium stearate as a neutralizing agent, and NA as a nucleating agent -11UY (Asahi Denka Kogyo Co., Ltd., trademark) was mixed with a 20 liter Henschel mixer for 2 minutes. Thereafter, this mixture was subjected to a die temperature of 220 ° C. and a cylinder temperature of 190 to 220 ° C. (C1: 190 ° C., C2: 2200 ° C., C3: 210 ° C., C4: 220 using a single screw extruder with L / D = 28. ° C), screw rotation speed 900 rpm, screen mesh 60 #, extrusion rate 30 kg / hr, melt-kneaded under nitrogen atmosphere, extruded, granulated and pelletized. The melt flow rate (MFR2) of the pellets was 8.5 g / 10 min, Mw / Mn = 23.1, and Mz / Mw = 6.1. The reaction conditions are shown in Table 1, and the results are shown in Table 6.
[0121]
Example 7
The polymerization in the first stage was carried out by a continuous two-stage polymerization method using one polymerization vessel and the polymerization in the second stage using two polymerization vessels. That is, 157 liter / hour of heptane in the polymerization vessel-1 having an internal volume of 500 liter, 9.8 g / hour of the prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 17.0 g / hour of triethylaluminum, And DCPMS are continuously fed at a rate of 34.5 g / hour, and the internal pressure of the polymerization vessel-1 is maintained at 0.76 MPa (gauge pressure) at a temperature of 52 ° C. and substantially in the absence of hydrogen. Was continuously charged with propylene (first stage polymerization). The slurry of Polymerizer-1 was sampled, and the intrinsic viscosity [η] of polypropylene was measured and found to be 6.8 dl / g.
[0122]
The polymerization in the second stage was carried out by a continuous method using two polymerization vessels. That is, the slurry of the polymerizer-1 subjected to the first stage polymerization was first continuously fed to the polymerizer-2 having an internal volume of 500 liter, and further polymerized. The polymerization vessel-2 was charged with heptane at a rate of 14.0 liter / hour, the internal pressure of the polymerization vessel-2 was 0.96 MPa (gauge pressure) at a temperature of 77 ° C., and the hydrogen concentration in the gas phase was 48 vol%. Propylene and hydrogen were fed continuously to maintain. Next, the slurry of the polymerization vessel-2 was continuously fed to the polymerization vessel-3 having an internal volume of 300 liter, and further polymerized. The polymerization vessel-3 was charged with heptane at a rate of 16.8 liter / hour, the internal pressure of the polymerization vessel-3 was 0.81 MPa (gauge pressure) at a temperature of 77 ° C., and the hydrogen concentration in the gas phase was 48 vol%. Propylene and hydrogen were fed continuously to maintain.
[0123]
After removing the unreacted monomer from the slurry exiting the polymerizer-3, the heptane is centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 73 g / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 34 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 25% by weight.
[0124]
The powdery polypropylene resin composition was granulated in the same manner as in Example 6. The melt flow rate (MFR2) of the pellets obtained at this time was 15 g / 10 min, Mw / Mn = 17.3, and Mz / Mw = 7.4. The reaction conditions are shown in Table 1, and the results are shown in Table 6.
[0125]
Example 8
The polymerization in the first stage was carried out by a continuous two-stage polymerization method using one polymerization vessel and the polymerization in the second stage using 4 polymerization vessels. That is, 44 liter / hour of heptane in Polymerizer-1 having an internal volume of 500 liter, 8.0 g / hour of prepolymerized catalyst component-2 obtained in Production Example 2 as a catalyst, 15.2 g / hour of triethylaluminum, And DCPMS are continuously fed at a rate of 31.0 g / hr, and the internal pressure of the polymerization vessel-1 is maintained at 0.27 MPa (gauge pressure) under the condition of substantially no hydrogen at a temperature of 60 ° C. Propylene was continuously charged (first stage polymerization). The slurry of Polymerizer-1 was sampled and the intrinsic viscosity [η] of polypropylene was measured and found to be 9.8 dl / g.
[0126]
The polymerization in the second stage was carried out by a continuous method using four polymerization vessels. That is, the slurry of the polymerizer-1 subjected to the first stage polymerization was first continuously fed to the polymerizer-2 having an internal volume of 500 liter, and further polymerized. The polymerization vessel-2 is charged with heptane at a rate of 54 liter / hour, the internal pressure of the polymerization vessel-2 is kept at 0.59 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase is kept at 44 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerization vessel-2 was continuously fed to the polymerization vessel-3 having an internal volume of 500 liter, and further polymerized.
[0127]
The polymerization vessel-3 was charged with heptane at a rate of 31 liter / hour, the internal pressure of the polymerization vessel-3 was kept at 0.67 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was kept at 44 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerizer-3 was continuously fed to the polymerizer-4 having an internal volume of 500 liter, and further polymerized. Polymerizer-4 is charged with heptane at a rate of 22 liter / hour, the internal pressure of polymerizer-4 is kept at 0.42 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase is kept at 44 vol%. Propylene and hydrogen were continuously fed to the reactor. Next, the slurry of the polymerizer-4 was continuously fed to the polymerizer-5 having an internal volume of 500 liter, and further polymerized. The polymerization vessel-5 was charged with heptane at a rate of 10 liter / hour, the internal pressure of the polymerization vessel-5 was maintained at 0.31 MPa (gauge pressure) at a temperature of 70 ° C., and the hydrogen concentration in the gas phase was maintained at 44 vol%. Propylene and hydrogen were continuously fed to the reactor.
[0128]
After removing unreacted monomers from the slurry exiting the polymerizer-5, the heptane was centrifuged by a usual method, and then dried at 80 ° C. and 9300 Pa (gauge pressure) for 10 hours to obtain a powdery polypropylene resin composition Got. This powdery polypropylene resin composition was obtained at a rate of 78 kg / hour. The melt flow rate (MFR1) of this powdery polypropylene resin composition was 29 g / 10 min. The proportion of polypropylene produced by the first stage polymerization in the finally obtained powdery polypropylene resin composition calculated from the mass balance was 22% by weight.
[0129]
The powdery polypropylene resin composition was granulated in the same manner as in Example 6. The melt flow rate (MFR2) of the pellets obtained at this time was 18 g / 10 min, Mw / Mn = 22.8, and Mz / Mw = 7.4. The reaction conditions are shown in Table 2, and the results are shown in Table 6.
[0130]
Example 9
Melt flow rate = 1.5 g / 10 min, intrinsic viscosity [η] = 3.1 dl / g, Mw / Mn = 4.2 single-stage polymerized polypropylene powder (powder average particle size 100 μm) 40 parts by weight, melt flow rate = 240 g / 10 min, intrinsic viscosity [η] = 0.95 dl / g, Mw / Mn = 4.5 single-stage polymerized polypropylene powder (powder average particle size 400 μm) 60 parts by weight Mix with a mixer. It was 48 g / 10min when the melt flow rate of the obtained powdery mixture was measured. Thereafter, this mixture was melt-kneaded in the same manner as in Example 6, and the melt flow rate (MFR2) of the pellets was measured and found to be 21 g / 10 min. A film was formed using this pellet, and the number of gels was measured in the same manner as in Example 1.²Met.
[0131]
Comparative Example 1
Under a nitrogen atmosphere, a polymerization vessel having an internal volume of 3000 liters was charged with 1180 liters of heptane, 125 g of diluted triethylaluminum, 217 g of DCPMS, and 55 g of the solid titanium catalyst component-1 obtained in Production Example 1. After removing nitrogen in the polymerization vessel with a vacuum pump, propylene was charged, and then the temperature was raised. At a temperature of 70 ° C., the pressure in the polymerization vessel was 0.74 MPa (gauge pressure), and propylene and hydrogen were continuously charged so as to keep the hydrogen concentration in the gas phase at 0.3 vol%, and polymerization was performed for 6.0 hours. Continued. After completion of the polymerization, 144.3 ml of methanol was charged to terminate the polymerization, and purified and dried by a usual method to obtain 700 kg of powdery polypropylene. The melt flow rate (MFR1) of this powdery polypropylene was 0.40 g / 10 min.
[0132]
The powdery polypropylene was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 0.53 g / 10 min, Mw / Mn = 5.1, Mz / Mw = 3.2. The reaction conditions are shown in Table 3, and the results are shown in Table 7.
[0133]
Comparative Example 2
In a nitrogen atmosphere, a polymerization vessel having an internal volume of 3000 liters was charged with 1180 liters of heptane, 137 g of diluted triethylaluminum, 279 g of DCPMS, and 72 g of the solid titanium catalyst component-1 obtained in Production Example 1. After removing nitrogen in the polymerization vessel with a vacuum pump, propylene was charged, and then the temperature was raised. Propylene was continuously charged so that the pressure in the polymerization vessel was kept at 0.49 MPa (gauge pressure) at a temperature of 60 ° C., and polymerization was continued for 3.0 hours under the condition that hydrogen was not substantially present ( (End of first stage polymerization). After completion of the first stage polymerization, a part of the slurry in the polymerization vessel was sampled and analyzed. As a result, the intrinsic viscosity [η] of polypropylene was 9.6 dl / g.
[0134]
Next, the temperature was adjusted to 70 ° C., propylene and hydrogen were continuously charged so that the internal pressure was 0.20 MPa (gauge pressure), and the hydrogen concentration in the gas phase was maintained at 25 vol%, and polymerization was continued for 4.0 hours ( (End of second stage polymerization). After completion of the polymerization, 144.3 ml of methanol was charged to terminate the polymerization, and purified and dried by a usual method to obtain 690 kg of a powdery polypropylene resin composition. Thus, the melt flow rate (MFR1) of the whole powdery polypropylene resin composition finally obtained was 0.69 g / 10 min. In addition, the ratio of the polypropylene produced | generated by the superposition | polymerization of the 1st step | paragraph in the powdery polypropylene resin composition finally obtained computed from the mass balance was 42 weight%.
[0135]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 0.79 g / 10 min, Mw / Mn = 19.0, and Mz / Mw = 4.8. The reaction conditions are shown in Table 4, and the results are shown in Table 7.
[0136]
Comparative Example 3
The polymerization time in the first-stage polymerization vessel was changed to 1.5 hours, the internal pressure of the second-stage polymerization vessel was 0.13 MPa (gauge pressure), the hydrogen concentration in the gas phase was 19 vol%, the polymerization time Polymerization was carried out in the same manner as in Comparative Example 2 except that the time was changed to 5.0 hours to obtain a powdery polypropylene resin composition. Thus, the melt flow rate (MFR1) of the whole powdery polypropylene resin composition finally obtained was 3.1 g / 10 min. In addition, the ratio of the polypropylene produced | generated by the superposition | polymerization of the 1st step | paragraph in the powdery polypropylene resin composition finally obtained computed from the mass balance was 18 weight%.
[0137]
The powdery polypropylene resin composition was granulated in the same manner as in Example 1. The melt flow rate (MFR2) of the pellets obtained at this time was 3.8 g / 10 min, Mw / Mn = 17.2, and Mz / Mw = 4.3. The reaction conditions are shown in Table 4, and the results are shown in Table 7.
[0138]
Comparative Example 4
In a nitrogen atmosphere, a polymerization vessel having an internal volume of 3000 liters was charged with 1180 liters of heptane, 360 g of diluted triethylaluminum, 360 g of DCPMS, and 93 g of the solid titanium catalyst component-1 obtained in Production Example 1. After removing nitrogen in the polymerization vessel with a vacuum pump, propylene was charged, and then the temperature was raised. Propylene and hydrogen were continuously charged so that the pressure in the polymerization vessel was kept at 0.28 MPa (gauge pressure) at a temperature of 60 ° C., and polymerization was continued for 2.5 hours (end of first stage polymerization). . After completion of the first stage polymerization, a part of the slurry in the polymerization vessel was sampled and analyzed. As a result, the intrinsic viscosity [η] of polypropylene was 5.7 dl / g.
[0139]
Next, the temperature was adjusted to 70 ° C., propylene and hydrogen were continuously charged so that the internal pressure was 0.44 MPa (gauge pressure), and the hydrogen concentration in the gas phase was maintained at 65 vol%, and polymerization was continued for 5.0 hours ( (End of second stage polymerization). After completion of the polymerization, 144.3 ml of methanol was charged to terminate the polymerization, and purified and dried by a usual method to obtain 650 kg of a powdery polypropylene resin composition. Thus, the melt flow rate (MFR1) of the whole powdery polypropylene resin composition finally obtained was 15 g / 10 min. In addition, the ratio of the polypropylene produced | generated by the superposition | polymerization of the 1st step | paragraph in the powdery polypropylene resin composition finally obtained computed from the mass balance was 29 weight%.
[0140]
The powdery polypropylene resin composition was granulated in the same manner as in Example 6. The melt flow rate (MFR2) of the pellets obtained at this time was 17 g / 10 min, Mw / Mn = 24.7, and Mz / Mw = 6.6. The reaction conditions are shown in Table 4, and the results are shown in Table 7.
[0141]
Comparative Example 5
In a nitrogen atmosphere, a polymerization vessel having an internal volume of 3000 liters was charged with 1180 liters of heptane, 279 g of diluted triethylaluminum, 279 g of DCPMS, and 72 g of the solid titanium catalyst component-1 obtained in Production Example 1. After removing nitrogen in the polymerization vessel with a vacuum pump, propylene was charged, and then the temperature was raised. Propylene was continuously charged so that the pressure in the polymerization vessel was kept at 0.27 MPa (gauge pressure) at a temperature of 60 ° C., and polymerization was continued for 2.5 hours under the condition that substantially no hydrogen was present ( (End of first stage polymerization). After completion of the first stage polymerization, a part of the slurry in the polymerization vessel was sampled and analyzed. As a result, the intrinsic viscosity [η] of polypropylene was 9.8 dl / g.
[0142]
Next, propylene and hydrogen were continuously charged so that the temperature was 70 ° C., the internal pressure was 0.66 MPa (gauge pressure), and the hydrogen concentration in the gas phase was maintained at 60 vol%, and polymerization was continued for 5.0 hours ( (End of second stage polymerization). After completion of the polymerization, 144.3 ml of methanol was charged to terminate the polymerization, and purified and dried by a usual method to obtain 650 kg of a powdery polypropylene resin composition. Thus, the melt flow rate (MFR1) of the whole powdery polypropylene resin composition finally obtained was 31 g / 10 min. In addition, the ratio of the polypropylene produced | generated by the superposition | polymerization of the 1st step | paragraph in the powdery polypropylene resin composition finally obtained computed from the mass balance was 19 weight%.
[0143]
The powdery polypropylene resin composition was granulated in the same manner as in Example 6. The melt flow rate (MFR2) of the pellets obtained at this time was 36 g / 10 min, Mw / Mn = 27.0, and Mz / Mw = 8.4. The reaction conditions are shown in Table 4, and the results are shown in Table 7.
[0144]
Comparative Example 6
A film was formed using the powdery polypropylene resin composition obtained in Example 8 as powder without pelletizing, and the number of gels was measured in the same manner as in Example 1. As a result, the number of gels is 29975/450 cm.²Compared to the case of melt-kneading, the appearance was very deteriorated and the product was at a reject level.
[0145]
Comparative Example 7
A film was formed by using the powdery mixture obtained in Example 9 as powder without pelletizing, and the number of gels was measured in the same manner as in Example 1. As a result, the number of gels is 78600 / 450cm.²Compared to the case of melt-kneading, the appearance was very deteriorated and the product was at a reject level.
[0146]
[Table 1]

[0147]
[Table 2]

[0148]
[Table 3]

[0149]
[Table 4]

[0150]
[Table 5]

[0151]
[Table 6]

[0152]
[Table 7]

[0153]
Notes on Table 5 to Table 7
* 1 MFR1: Melt flow rate before melt kneading, ASTM D-1238, 230 ° C., 2.16 kg load
* 2 Intrinsic viscosity [η]: measured in decalin at 135 ° C
* 3 Number of gels: The number of gels on a 30-μm-thick film made with a 25 mmφ T-die film forming machine manufactured by Plastic Engineering Laboratory Co., Ltd. ). The number of measurements is the film unit area (450 cm²) Per gel number.
The film production conditions are as follows.

[0154]
* 4 Melt tension: measured under the following conditions
Equipment: Capillograph 1C (trademark) manufactured by Toyo Seiki Co., Ltd.
Temperature: 230 ° C
Orifice; L = 8.00, D = 2.095mm
Extrusion speed: 15mm / min
Take-off speed: 10 m / min
* 5 Critical shear rate: Measures the shear rate at which melt fracture occurs under the following conditions.
Equipment: Capillograph 1C (trademark) manufactured by Toyo Seiki Co., Ltd.
Temperature: 230 ° C
Orifice; L = 10.9, D = 1.00mm
* 6 Bending elastic modulus: Injection molding was performed using the obtained pellets of the polypropylene resin composition, and the obtained injection molded product was measured under conditions in accordance with ASTM D790.
[0155]
* 7 MFR2: Melt flow rate after melt-kneading, ASTM D-1238, 230 ° C., 2.16 kg load
* 8 Mw / Mn, Mz / Mw: Measured by high-temperature high-speed gel permeation chromatography. Specifically, 150-CV manufactured by Waters was used as a GPC device, two Shodex AD-80M / S manufactured by Showa Denko Co., Ltd. were connected as a column, and 135 ° C. orthodichlorobenzene was measured as a moving bed. did. Standard polystyrene was used for calibration, and 41.4 was adopted as the Q factor.

Claims (3)

While supplying the catalyst and the raw material to the first stage polymerization vessel, a relatively high molecular weight polypropylene having an intrinsic viscosity [η] of 3 to 13 dl / g, and a content in the composition of 5 to 30 wt% So that it polymerizes continuously in the absence of hydrogen,
The polymer in the first stage polymerization vessel is continuously transferred to the polymerization vessel in the second and subsequent stages part by part,
In the second and subsequent stages, a relatively low molecular weight polypropylene having an intrinsic viscosity [η] of 0.1 to 5 dl / g is continuously polymerized so that the content in the composition is 95 to 70% by weight. By continuous multistage polymerization
Melt flow rate (ASTM D-1238, 230 ° C., 2.16 kg load, hereinafter referred to as MFR1) before melt kneading is 0.01 to 200 g / 10 min, and melt flow after melt kneading in the absence of a crosslinking agent The rate (ASTM D-1238, 230 ° C., 2.16 kg load, hereinafter referred to as MFR2) is 0.005 to 100 g / 10 min, and MFR1> MFR2, and the absolute value of the difference is 0.005 to 100 Producing a polypropylene resin composition before melt kneading,
Thereafter, the polypropylene resin composition before melt kneading is melt kneaded in the absence of a crosslinking agent.   The method for producing a polypropylene resin composition according to claim 1, wherein the difference in intrinsic viscosity [η] between the relatively high molecular weight polypropylene and the relatively low molecular weight polypropylene is 0.5 to 12.9 dl / g.   The method for producing a polypropylene resin composition according to claim 1 or 2, wherein the average particle size of the polypropylene resin composition before melt kneading is 50 to 3000 µm.