CN109923170B - Master batch composition and polypropylene resin composition containing the same - Google Patents
Master batch composition and polypropylene resin composition containing the same Download PDFInfo
- Publication number
- CN109923170B CN109923170B CN201780069625.5A CN201780069625A CN109923170B CN 109923170 B CN109923170 B CN 109923170B CN 201780069625 A CN201780069625 A CN 201780069625A CN 109923170 B CN109923170 B CN 109923170B
- Authority
- CN
- China
- Prior art keywords
- composition
- component
- weight
- master batch
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A master batch composition obtained by polymerizing propylene and ethylene using a catalyst, the catalyst comprising: (A) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound selected from succinate compounds as essential components; (B) an organoaluminum compound; and (C) an external electron donor compound, the masterbatch composition comprising: a propylene homopolymer as a component (1) and a propylene-ethylene copolymer as a component (2), the propylene-ethylene copolymer containing 55 to 80% by weight of an ethylene-derived unit, the component (1): (2) the weight ratio of (A) to (B) is 85-60: 15-40, wherein the master batch composition meets the following conditions: 1) the Mw/Mn of the xylene insoluble component of the composition measured by GPC is 6-20; 2) the intrinsic viscosity of the xylene soluble component of the composition is between 1dl/g and 3 dl/g; 3) the melt flow rate (230 ℃ C., load 21.18N) of the composition is 1g/10 min to 50g/10 min. The composition has a high modulus of elasticity, high impact strength at low temperatures and a low coefficient of linear expansion.
Description
Technical Field
The present invention relates to a master batch composition and a polypropylene resin composition comprising the same.
Background
Polypropylene is low in cost and has excellent physical properties, and thus has wide applications in automotive applications. However, polypropylene is known to have an amorphous component and thus a large linear expansion coefficient. Therefore, in the automobile parts, there is a problem that a gap or the like is generated in a joint portion between the polypropylene resin and another material. In addition, in order to reduce the linear expansion coefficient, it has been attempted to add a large amount of an inorganic filler such as talc, but this is not preferable from the viewpoint of improvement in fuel efficiency due to weight reduction of an automobile because of increase in weight.
In order to solve this problem, patent document 1 proposes a polyolefin composition comprising (a)40 to 60% of a component a which is a broad molecular weight distribution propylene polymer having a polydispersity index of 5 to 15 and a melt flow rate (according to ASTM-D1238, condition L) of 80g/10 min to 200g/10 min and (B)40 to 60% of a component B, the Intrinsic Viscosity (IV) of a portion of the polyolefin composition soluble in xylene at room temperatures) Intrinsic Viscosity (IV) with component (A)A) IV in betweens/IVAThe ratio is 2-2.5; component B is a partially xylene-insoluble olefin polymer rubber containing at least 65% by weight of ethylene. The composition has a low coefficient of linear expansion.
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication 2002-528621
Disclosure of Invention
Problems to be solved by the invention
In the automotive parts, a high elastic modulus, a high impact strength at low temperatures, and a low linear expansion coefficient are required, and these properties are generally in a trade-off relationship, and it is difficult to satisfy all of these properties in a well-balanced manner. The composition described in patent document 1 has high impact strength at low temperature and a low linear expansion coefficient, but the elastic modulus is not at a sufficient level. In view of the above circumstances, an object of the present invention is to provide a composition having a high elastic modulus, high impact strength at low temperatures, and a low linear expansion coefficient.
Means for solving the problems
The above problems are solved by the present invention described below.
[1] A masterbatch composition obtained by polymerizing propylene and ethylene using a catalyst comprising:
(A) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound selected from succinate compounds as essential components;
(B) an organoaluminum compound; and
(C) an external electron donor compound, which is a compound having a high electron-withdrawing group,
the masterbatch composition comprises:
a propylene homopolymer as the component (1), and
a propylene-ethylene copolymer as the component (2), which contains 55 to 80% by weight of an ethylene-derived unit,
component (1): (2) the weight ratio of (A) to (B) is 85-60: 15 to 40 of the total amount of the organic compounds,
the masterbatch composition satisfies the following conditions:
1) the xylene insoluble component of the composition has Mw/Mn, as measured by GPC, of 6 to 20;
2) the intrinsic viscosity of the xylene soluble component of the composition is between 1dl/g and 3 dl/g;
3) the melt flow rate (230 ℃ C., load 21.18N) of the composition is 1g/10 min to 50g/10 min.
[2] The masterbatch composition according to [1], wherein the propylene-ethylene copolymer in the component (2) has an ethylene-derived unit content of 60 to 75% by weight.
[3] The master batch composition according to [1] or [2], wherein the above-mentioned component (1): (2) the weight ratio of (A) to (B) is 75-60: 25-40.
[4] The masterbatch composition according to any one of [1] to [3], wherein the melt flow rate is 10g/10 min to 35g/10 min.
[5] The master batch composition according to any one of [1] to [4], wherein the crystal nucleating agent is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the composition.
[6] A polypropylene resin composition obtained by mixing at least one of an elastomer different from the component (2) of the master batch composition and a polypropylene resin different from the master batch composition into the master batch composition according to any one of the above [1] to [5 ].
[7] A polypropylene resin composition, which comprises more than 5% by weight and 40% by weight or less of a filler in the composition according to [6 ].
[8] An injection-molded article obtained by injection-molding the polypropylene resin composition according to [6] or [7 ].
ADVANTAGEOUS EFFECTS OF INVENTION
A composition having a high elastic modulus, a high impact strength at low temperatures and a low linear expansion coefficient can be provided.
Detailed Description
In the present invention, a composition containing the components (1) and (2) as essential components and, if necessary, a known additive is referred to as a "masterbatch composition". The masterbatch composition may be used in admixture with other resins or may be used alone. A resin composition containing a "masterbatch composition", at least one of an elastomer and a polypropylene resin different from the masterbatch composition, and a filler as needed is referred to as a "polypropylene resin composition". The present invention will be described in detail below. In the present invention, "X to Y" includes X and Y as the end values thereof. "X or Y" refers to either or both of X, Y.
1. Masterbatch composition
The masterbatch composition of the present invention comprises the following ingredients.
Component (1): propylene homopolymer
Component (2): propylene-ethylene copolymers comprising from 55 to 80% by weight of ethylene derived units
(1) Component (1): propylene homopolymer
As the component (1) of the present invention, a propylene homopolymer (homopolypropylene) is used because it satisfies rigidity and heat resistance required for a final product. The propylene homopolymer of the present invention may contain a small amount of ethylene or one or more units derived from C4-C10-alpha-olefin of 2.0 wt% or less, preferably 1.0 wt% or less, due to the presence of a recycled monomer or the presence of a transition product during the production process, or the like, to the extent that the gist of the present invention is not impaired.
(2) Component (2): propylene-ethylene copolymer
The propylene-ethylene copolymer used in the present invention comprises from 55 to 80% by weight of ethylene-derived units. If the content of ethylene-derived units is less than the lower limit value, the linear expansion coefficient increases. When the amount exceeds the upper limit, the linear expansion coefficient increases, and the impact strength also decreases. Further, in the case where the content of the ethylene-derived unit is about 55% by weight in the production, when the proportion of the component (2) is 25 parts by weight or more, the polymer particles are liable to adhere to each other, and clogging of the line is caused. From this point of view, the content of the ethylene-derived unit is preferably 60 to 75% by weight.
(3) Composition ratio
The weight ratio of the components (1) to (2) is (1): (2) 85-60: 15 to 40. If the amount of the component (2) exceeds the upper limit, the decrease in rigidity becomes remarkable, and if the amount is less than the lower limit, the decrease in impact resistance becomes remarkable. From this aspect, the ratio is preferably 75 to 60: 25-40.
(4) Other ingredients
Further, conventional additives generally used for olefin polymers, such as antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, antifogging agents, crystal nucleating agents, flame retardants, dispersants, copper inhibitors, neutralizing agents, plasticizers, antifoaming agents, crosslinking agents, peroxides, oil fillers, and other organic and inorganic pigments, may be added to the masterbatch composition. The additive amount of each additive may be a known amount.
The masterbatch composition of the present invention particularly preferably contains a crystallization nucleating agent. As the crystal nucleating agent, those known in the art can be used. Examples of the crystal nucleating agent include inorganic fillers having a crystal nucleating effect such as talc, and organic crystal nucleating agents such as phosphate esters, carboxylic acid metal salts, benzylidene sorbitol, triaminobenzene derivatives, and the like. The amount of the crystal nucleus agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the composition.
(5) Characteristics of
1) Mw/Mn of XI
The xylene-insoluble fraction (XI) of the composition has an Mw/Mn, as measured by GPC, of 6 to 20. The xylene insoluble component is the crystalline component of the composition. In the present invention, Mw/Mn as an index of molecular weight distribution is in a wide range. That is, a high molecular weight component exists in a large amount, and this component promotes the orientation of polymer chains during molding. Therefore, a low linear expansion coefficient can be achieved. Further, the impact resistance, particularly at low temperatures, is improved by the high molecular weight component. From this viewpoint, Mw/Mn is preferably 7 to 20. The Mw/Mn of XI is determined by obtaining a component insoluble in xylene at 25 ℃ and measuring the component by GPC (gel permeation chromatography).
2)XSIV
The intrinsic viscosity (XSIV) of the xylene soluble fraction (XS) of the composition is also an indicator of the molecular weight of the fraction of the composition which does not have crystallinity. XSIV is determined by obtaining a component soluble in xylene at 25 ℃ and measuring the intrinsic viscosity of the component using conventional methods. In the invention, the XSIV is lower and is 1 dl/g-3 dl/g. When XSIV is low, the component (2) is easily stretched in the injection-molded article, and it is advantageous to achieve a low linear expansion coefficient, but when XSIV is too low, impact resistance is deteriorated. Therefore, it is considered that when XSIV is in this range, both low linear expansion coefficient and high impact resistance can be achieved. From this viewpoint, the intrinsic viscosity is preferably 1.5dl/g to 2.5 dl/g.
3) Melt flow rate
The melt flow rate (hereinafter also referred to as "MFR") of the masterbatch composition at 230 ℃ under a load of 21.18N is 1g/10 min to 50g/10 min. When the MFR is within this range, excellent moldability can be achieved. If the MFR exceeds the upper limit, the MFR of the component (1) becomes very high (molecular weight decreases), and as a result, impact resistance decreases and production becomes difficult. When the MFR value is less than the lower limit value, the MFR of the polypropylene resin composition using the master batch composition is lowered, and molding such as injection molding becomes difficult. From this point of view, the melt flow rate is preferably 5g/10 min to 35g/10 min.
4) Modulus of elasticity
The flexural modulus of the master batch composition of the present invention is preferably 1000MPa to 1500MPa, more preferably 1100MPa to 1300 MPa.
5) Coefficient of linear expansion
The preferable linear expansion coefficient of the master batch composition in the MD direction at-30-80 ℃ is 60-80 multiplied by 10-6Preferably 65 to 78X 10 in terms of/K-6and/K. The linear expansion coefficient can be measured by annealing the molded article and then performing thermomechanical analysis (TMA).
6) Impact strength
The masterbatch composition of the invention preferably has a Charpy impact strength at room temperature of 20kJ/m2～50kJ/m2Preferably, the Charpy impact strength at low temperature (-30 ℃ C.) is 3kJ/m2～6kJ/m2。
(6) Manufacturing method
The masterbatch composition of the present invention is produced by a method comprising the steps of: polymerizing a raw material monomer of the component (1) and a raw material monomer of the component (2) using a catalyst comprising (a) a solid catalyst containing magnesium, titanium, halogen and a succinate-based compound as an internal electron donor; (B) an organoaluminum compound; and (C) an external electron donor compound.
The polymer polymerized by using the catalyst containing the succinate compound as the internal electron donor has a wide molecular weight distribution, and the high molecular weight component and the low molecular weight component are uniformly dispersed. The molecular weight distribution is a physical quantity and can be determined by measurement. However, the measured value cannot indicate the degree of dispersion of the high molecular weight component and the low molecular weight component. For example, by blending a high molecular weight component and a low molecular weight component by powder blending or pellet blending, or by further increasing the number of stages in multistage polymerization, a polymer having the same molecular weight distribution (measured value) as that of the present invention can be obtained at first glance. However, the polymer thus obtained has a different degree of dispersion between the high-molecular weight component and the low-molecular weight component from the polymer of the present invention, and a uniform degree of dispersion is achieved in the present invention. This difference is significant in properties such as a low linear expansion coefficient and high impact resistance.
1) Solid catalyst (component A)
The component (A) can be produced by a known method, for example, by bringing a magnesium compound, a titanium compound and an electron donor compound into contact with each other.
As the titanium compound used in the production of the component (a), preferred is a compound represented by the general formula: ti (OR)gX4-gThe represented 4-valent titanium compound. Wherein R is alkyl, X is halogen, and g is not less than 0 and not more than 4. More specifically, the titanium compound includes TiCl4、TiBr4、TiI4Titanium tetrahalides; ti (OCH)3)Cl3、Ti(OC2H5)Cl3、Ti(On-C4H9)Cl3、Ti(OC2H5)Br3、Ti(OisoC4H9)Br3Titanium trihalides; ti (OCH)3)2Cl2、Ti(OC2H5)2Cl2、Ti(On-C4H9)2Cl2、Ti(OC2H5)2Br2Titanium alkoxides dihalides, etc.; ti (OCH)3)3Cl、Ti(OC2H5)3Cl、Ti(On-C4H9)3Cl、Ti(OC2H5)3Trialkoxytitanium monohalides such as Br; ti (OCH)3)4、Ti(OC2H5)4、Ti(On-C4H9)4And tetraalkoxytitanium, and the like. Among these, preferred are halogen-containing titanium compounds, particularly titanium tetrahalides, and more particularly preferred is titanium tetrachloride.
Examples of the magnesium compound used for the preparation of the component (a) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, pentylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, and butylmagnesium hydride. These magnesium compounds may be used in the form of a complex with an organoaluminum or the like, and may be in a liquid state or a solid state. Further preferable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; aryloxy magnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride, and the like; magnesium alkoxides such as magnesium ethoxide, magnesium isopropoxide, magnesium butoxide, magnesium n-octoxide and magnesium 2-ethylhexoxide; aryloxymagnesium such as phenoxymagnesium, dimethylphenoxymagnesium; magnesium laurate, and magnesium carboxylates such as magnesium stearate.
The electron donor compound used in the preparation of component (A) is generally referred to as "internal electron donor". In the present invention, internal electron donors providing a broad molecular weight distribution are preferably used. Generally, it is known that the molecular weight distribution can be increased by performing polymerization in multiple stages, but it is difficult to increase the molecular weight distribution when the molecular weight of XI is low. However, by using a specific internal electron donor, the molecular weight distribution can be increased even when the molecular weight of XI is low. The composition obtained by polymerization using this catalyst exhibits excellent flowability and large die swell (swell) as compared with a composition having the same molecular weight distribution obtained by blending a polymer obtained by polymerization using another catalyst in the form of pellets or powder, and a composition having the same molecular weight distribution obtained by multistage polymerization. This is considered to be because the high molecular weight component and the low molecular weight component are integrated in a state close to the molecular level in the composition produced using the catalyst, but the latter resin composition is not mixed together in a state close to the molecular level, and shows only the same molecular weight distribution in appearance. Hereinafter, preferred internal electron donors will be described.
In the present invention, a succinate compound is used as an internal electron donor. In the present invention, the succinate-based compound means a diester of succinic acid or a diester of substituted succinic acid. Hereinafter, the succinate compound will be described in detail. The succinate compound preferably used in the present invention is represented by the following formula (I).
[ solution 1]
In the formula, the group R1And R2Identical or different from each other, as the case may be, C containing a heteroatom1～C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl, or alkylaryl groups; radical R3～R6Identical or different from each other, is hydrogen or C optionally containing heteroatoms1～C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl, or alkylaryl groups, the radicals R being bonded to the same carbon atom or to different carbon atoms3～R6May be bonded together to form a ring.
R1And R2Preferably C1～C8Alkyl, cycloalkyl, aryl, aralkyl, and alkylaryl groups. R1And R2Particular preference is given to compounds selected from primary alkyl groups, in particular branched primary alkyl groups. Preferred R1And R2Examples of radicals are C1～C8Examples of alkyl groups of (a) are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl and neopentyl are particularly preferred.
One of the preferred groups of compounds represented by formula (I) is: r3～R5Is hydrogen, R6Is a compound of branched alkyl, cycloalkyl, aryl, aralkyl and alkylaryl groups having 3 to 10 carbon atoms. Preferred examples of such monosubstituted succinate compounds are diethyl sec-butylsuccinate, diethyl hexylsuccinate, diethyl cyclopropylsuccinate, diethyl norbornylsuccinate, diethyl perhydrosuccinate, diethyl trimethylsilylsuccinate, diethyl methoxysuccinate, p-methoxyphenylDiethyl succinate, diethyl p-chlorophenylsuccinate, diethyl phenylsuccinate, diethyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl cyclohexylmethylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenylsuccinate, 1-ethoxydiisobutyl phenylsuccinate, diisobutyl sec-butylsuccinate, diisobutyl hexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl norbornylsuccinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenylsuccinate, diisobutyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl fluorenylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, diethyl ester of isopropylsuccinate, diisobutyl norbornylsuccinate, diisobutyl ester of perhydrosuccinate, diisobutyl ester of trimethylsilylsuccinate, diisobutyl ester of methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenylsuccinate, diisobutyl ester of, Diisobutyl cyclohexylsuccinate, diisobutyl benzylsuccinate, diisobutyl cyclohexylmethylsuccinate, diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenylsuccinate, dipentyl sec-butylsuccinate, dipentyl hexylsuccinate, dipentyl cyclopropylsuccinate, dineopentyl norbornyl succinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, dineopentyl p-methoxyphenylsuccinate, dineopentyl p-chlorophenylsuccinate, dineopentyl phenylsuccinate, dineopentyl cyclohexylsuccinate, dineopentyl benzylsuccinate, dineopentyl cyclohexylmethylsuccinate, Di-neopentyl tert-butylsuccinate, di-neopentyl isobutylsuccinate, di-neopentyl isopropylsuccinate, di-neopentyl neopentylsuccinate, di-neopentyl isopentylsuccinate, (di-neopentyl 1-trifluoromethylethyl) succinate, di-neopentyl fluorenylsuccinate.
Other preferred groups of compounds within the scope of formula (I) are: from R3～R6At least 2 radicals, different from hydrogen, selected from C optionally containing heteroatoms1～C20Linear or branched alkyl, alkenylA cycloalkyl, aryl, aralkyl, or alkylaryl group. Particularly preferred are compounds in which 2 groups different from hydrogen are bonded to the same carbon atom. In particular R3And R4Is a radical other than hydrogen, R5And R6A compound which is a hydrogen atom. Preferred examples of such di-substituted succinic acid esters are diethyl 2, 2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2, 2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl-2-ethylsuccinate, diethyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diethyl 2-ethylsuccinate, diethyl 2-ethyl-2-ethylsuccinate, diethyl 2-cyclohexylsuccinate, diethyl 2-isopropylsuccinate, diethyl 2-ethylsuccinate, diethyl-ethylsuccinate, diethylsuccinate, and the like, Diethyl 2-isopentyl-2-isobutylsuccinate, diethyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, diisobutyl 2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-butylsuccinate, diisobutyl 2, 2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2-cyclohexylsuccinate, diisobutyl 2-isopropylsuccinate, diisobutyl 2-isobutylsuccinate, diisobutyl 2-cyclohexylsuccinate, diisobutyl-butylsuccinate, diisobutyl 2-dimethylsuccinate, and mixtures thereof, Diisobutyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-phenyl-2-n-butylsuccinate, dipentyl 2, 2-dimethylsuccinate, dipentyl 2-ethyl-2-methylsuccinate, dipentyl 2-benzyl-2-isopropylsuccinate, dipentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dipentyl 2-cyclopentyl-2-n-butylsuccinate, dipentyl 2, 2-diisobutylsuccinate, dipentyl 2-cyclohexyl-2-ethylsuccinate, dipentyl 2-isopropyl-2-methylsuccinate, dipentyl 2-isopropylsuccinate, dipentyl 2-methylsuccinate, and mixtures thereof, 2-tetradecyl-2-ethylsuccinate dipentyl ester, 2-isobutyl-2-ethylsuccinate dipentyl ester, 2- (1-trifluoromethylethyl) -2-methylsuccinate dipentyl ester, 2-isopentyl-2-isobutylsuccinate dipentyl ester, 2-phenyl-2-n-butylsuccinate dipentyl ester.
Furthermore, compounds in which at least 2 groups other than hydrogen are bonded to different carbon atoms are also particularly preferred. In particular R3And R5A compound that is a group other than hydrogen. In this case, R4And R6It may be a hydrogen atom or a group different from hydrogen, but it is preferable that either one is a hydrogen atom (tri-substituted succinate). Preferred specific examples of such compounds are diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2, 2-sec-butyl-3-methylsuccinate, diethyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropylsuccinate, diethyl 2, 3-diisopropyl-2-methylsuccinate, diethyl 2, 3-dicyclohexyl-2-methylsuccinate, diethyl 2, 3-dibenzylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-di-tert-butylsuccinate, Diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, diethyl 2,3- (1-trifluoromethylethyl) succinate, diethyl 2, 3-tetradecylsuccinate, diethyl 2, 3-fluorenylsuccinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diethyl 2, diisobutyl 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropyl-2-methylsuccinate, diisobutyl 2, 3-dicyclohexyl-2-methylsuccinate, diisobutyl 2, 3-dibenzylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-bis (cyclohexylmethyl) succinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisopentylsuccinate, diisobutyl 2,3- (1-trifluoromethylethyl) succinate, diisobutyl 2, 3-tetradecylsuccinate, diisobutyl 2, 3-fluorenylsuccinate, 2-isopropyl-3-isobutyldiisobutyl succinate, 2-tert-butyl-3-isopropyldiisobutyl succinate, 2-isopropyl succinateDiisobutyl 3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, dipentyl 2, 3-bis (trimethylsilyl) succinate, dipentyl 2, 2-sec-butyl-3-methylsuccinate, dipentyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, dipentyl 2, 3-bis (2-ethylbutyl) succinate, dipentyl 2, 3-diethyl-2-isopropylsuccinate, dipentyl 2, 3-diisopropyl-2-methylsuccinate, dipentyl 2, 3-diisopropylsuccinate, Dipentyl 2, 3-dicyclohexyl-2-methylsuccinate, dipentyl 2, 3-dibenzylsuccinate, dipentyl 2, 3-diisopropylsuccinate, dipentyl 2, 3-bis (cyclohexylmethyl) succinate, dipentyl 2, 3-di-tert-butylsuccinate, dipentyl 2, 3-diisobutylsuccinate, dipentyl 2, 3-dineopentylsuccinate, dipentyl 2, 3-diisopentylsuccinate, dipentyl 2, 3-trifluoroethyl-succinate, dipentyl 2,3- (1-trifluoromethylethyl) succinate, dipentyl 2, 3-tetradecylsuccinate, dipentyl 2, 3-fluorenylsuccinate, dipentyl 2-isopropyl-3-isobutylsuccinate, dipentyl 2-tert-butyl-3-isopropylsuccinate, 2-isopropyl-3-cyclohexylsuccinic acid dineopentyl ester, 2-isopentyl-3-cyclohexylsuccinic acid dineopentyl ester, 2-tetradecyl-3-cyclohexylmethylsuccinic acid dineopentyl ester, 2-cyclohexyl-3-cyclopentylsuccinic acid dineopentyl ester.
In the compounds of the formula (I), preference may also be given to using the radicals R3～R6Several of which are bonded together to form a ring. Examples of such compounds include those listed in Japanese patent application laid-open No. 2002-542347, such as 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2-methylcyclohexane, and 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane. In addition to these compounds, cyclic succinate compounds such as diisobutyl 3, 6-dimethylcyclohexane-1, 2-dicarboxylate and diisobutyl cyclohexane-1, 2-dicarboxylate disclosed in International publication No. 2009/069483 can be preferably used. As examples of other cyclic succinate compounds, International publication No. 2 is also preferred009/057747, the compound disclosed in any one of the above patent documents.
In the compounds of formula (I), the radical R3～R6In the case of containing a hetero atom, the hetero atom is preferably a group 15 atom including a nitrogen atom and a phosphorus atom or a group 16 atom including an oxygen atom and a sulfur atom. As the radical R3～R6As the compound containing a group 15 atom, compounds disclosed in Japanese patent laid-open No. 2005-306910 can be mentioned. On the other hand, as the group R3～R6Examples of the compound containing a group 16 atom include compounds disclosed in Japanese patent laid-open No. 2004-131537.
In addition, an internal electron donor which provides a molecular weight distribution equivalent to that of the succinate compound may be used in combination. Examples of such internal electron donors include diphenyldicarboxylate described in Japanese patent laid-open publication No. 2013-28704, cyclohexenedicarboxylate described in Japanese patent laid-open publication No. 2014-201602, bicycloalkyldicarboxylate described in Japanese patent laid-open publication No. 2013-28705, dibenzoate described in Japanese patent laid-open publication No. 4959920, and 1, 2-phenylene dibenzoate described in International publication No. 2010/078494.
2) Organoaluminum Compound (component B)
Examples of the organoaluminum compound of the component (B) include the following compounds.
Trialkylaluminums such as triethylaluminum and tributylaluminum;
trienyl aluminum such as triisopentenyl aluminum;
dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide;
dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride;
partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxide, butylaluminum butoxychloride, ethylaluminum ethoxide and the like.
3) Electron donor compound (component C)
The electron-donor compound of component (C) is generally referred to as "external electron donor". As such an electron donor compound, an organosilicon compound is preferable. Preferred examples of the organosilicon compound include the following compounds.
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-pentylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, or a vinyltrimethoxysilane, or a, N-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, hexyltrimethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, gamma-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltrialkoxysilane, phenyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butylsilicate, trimethylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, or the like, Vinyltris (. beta. -methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane.
Among them, preferred are ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutylmethyldimethoxysilane, isobutylsec-butyldimethoxysilane, ethyl (perhydroisoquinolin-2-yl) dimethoxysilane, bis (decahydroisoquinol-2-yl) dimethoxysilane, tris (isopropenoxy) phenylsilane, hexyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltributoxysilane, butyltrimethoxysilane, butyldimethoxysilane, butyltrimethoxysilane, or a butyltrimethoxysilane, or a butyltrimethoxysilane, or a portion of, Diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, cyclopentyl-t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, di-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, di-n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, di-n-butyldimethoxysilane, di-ethyldimethoxysilane, 2-ethyldimethoxysilane, di-n-ethyldimethoxysilane, di-ethyldimethoxysilane, 2-norbornanetriethyldimethoxysilane, di-2-ethyldimethoxysilane, di-n-methyl-ethyldimethoxysilane, di-tert-n-tert-butyldimethoxysilane, 2-butyldimethoxysilane, p-butyldimethoxysilane, 2-butyldimethoxysilane, p-butyldimethoxysilane, 2-vinyldimethoxysilane, 2-butyldimethoxysilane, 2-vinyldimethoxysilane, p-vinyldimethoxysilane, 2-vinyldimethoxysilane, p-vinyldimethoxysilane, 2-vinyldimethoxysilane, p-vinylsilane, p-vinyldimethoxysilane, p-vinylsilane, Diphenyldiethoxysilane, methyl (3,3, 3-trifluoropropyl) dimethoxysilane, ethyl silicate, and the like.
4) Polymerisation
The raw material monomers are brought into contact with the catalyst prepared as described above to carry out polymerization. In this case, it is preferable to carry out prepolymerization using the above-mentioned catalyst. The preliminary polymerization is a step of forming a polymer chain which becomes the beginning of the main polymerization of the raw material monomer after the preliminary polymerization on the solid catalyst component. The prepolymerization can be carried out by a known method. The prepolymerization is usually carried out at 40 ℃ or lower, preferably 30 ℃ or lower, more preferably 20 ℃ or lower.
Subsequently, the prepolymerized catalyst is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer. In the main polymerization, it is preferable to polymerize the raw material monomer of the component (1) and the raw material monomer of the component (2) using 2 or more reactors. The polymerization can be carried out in the liquid phase, in the gas phase or in the liquid-gas phase. The polymerization temperature is preferably from room temperature to 150 ℃ and more preferably from 40 ℃ to 100 ℃. The polymerization pressure is preferably in the range of 3.3 to 6.0MPa when the polymerization is carried out in a liquid phase, and in the range of 0.5 to 3.0MPa when the polymerization is carried out in a gas phase. Chain transfer agents (e.g., hydrogen or ZnEt) may also be used2) And the like, known in the art.
In addition, a polymerizer having a gradient in monomer concentration or polymerization conditions may also be used. In such a polymerizer, for example, a polymerizer in which at least 2 polymerization zones are connected may be used to polymerize a monomer by gas-phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied to a polymerization zone including a riser to perform polymerization, and a monomer is supplied to a downcomer connected to the riser to perform polymerization, and a polymer product is recovered while circulating the riser and the downcomer. The process is provided with a unit for totally or partially preventing the gas mixture present in the riser from entering the downcomer. In addition, a gas and/or liquid mixture having a different composition from the gas mixture present in the riser is introduced into the downcomer. As the above polymerization method, for example, the method described in JP-A-2002-520426 can be applied.
2. Polypropylene resin composition
The polypropylene resin composition of the present invention is obtained by mixing at least one of an elastomer different from the component (2) of the master batch composition and a polypropylene resin different from the master batch composition into the master batch composition. The total amount of the elastomer and the polypropylene resin different from the master batch composition is preferably 5 to 40% by weight, more preferably 5 to 30% by weight, in the polypropylene resin composition.
(1) Elastic body
Elastomers are polymers having elasticity and are added mainly for the purpose of improving the impact resistance of the composition. The elastomer used in the present invention may be a copolymer of ethylene and an α -olefin. The α -olefin includes α -olefins having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and the like are preferable. The elastomer preferably has a lower density than the polymers of component (1) and component (2). For example, the density of the elastomer is not limited, but is preferably 0.850g/cm3～0.890g/cm3More preferably 0.860g/cm3～0.880g/cm3. Such an elastomer can be produced by polymerizing a monomer using a homogeneous catalyst such as a metallocene or a half-metallocene as described in Japanese patent laid-open publication No. 2015-113363. The MFR of the elastomer is preferably 0.1g/10 min to 50g/10 min at 190 ℃ under a load of 21.6N.
(2) Polypropylene resin different from the master batch composition
The polypropylene resin different from the master batch composition is added for the purpose of improving the flowability, rigidity, impact resistance, etc. of the composition. Examples of the polypropylene resin different from the master batch composition include a propylene homopolymer, a propylene random copolymer containing more than 0% by weight and not more than 5% by weight of ethylene or one or more C4 to C10- α -olefins, and a polymerization mixture (also referred to as HECO) obtained by polymerizing ethylene and one or more C3 to C10- α -olefins in the presence of a propylene polymer. The masterbatch composition of the present invention is also one type of HECO, and HECO added to the masterbatch composition can also be manufactured by the same method as the masterbatch composition, but the two are different in composition.
(3) Filler
The polypropylene resin composition of the present invention may contain a filler. The filler is added mainly to increase the rigidity of the material. Examples of the filler include inorganic fillers such as talc, clay, calcium carbonate, magnesium hydroxide, and glass fiber, and organic fillers such as carbon fiber and cellulose fiber. In order to improve the dispersibility of these fillers, surface treatment of the filler or preparation of a master batch of the filler and the resin may be carried out as necessary. Talc is preferable because it can be easily mixed with a propylene (co) polymer and a copolymer of ethylene and an α -olefin, and the rigidity of a molded article can be easily increased. The amount of the filler in the polypropylene resin composition is preferably more than 5% by weight and 40% by weight or less, and more preferably 10% by weight to 35% by weight.
(4) Other ingredients
To the polypropylene resin composition of the present invention, conventional additives generally used for olefin polymers, such as antioxidants, chlorine absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, antifogging agents, crystallization nucleating agents, flame retardants, dispersants, copper inhibitors, neutralizers, plasticizers, antifoaming agents, crosslinking agents, peroxides, oil fillers, and other organic and inorganic pigments, may be added. The additive amount of each additive may be a known amount.
(5) Manufacturing method
The polypropylene resin composition of the present invention can be produced by melt-kneading the above components. The kneading method is not limited, and a method using a kneader such as an extruder is preferred. The kneading conditions are not particularly limited, but the cylinder temperature is preferably 180 to 250 ℃. The polypropylene resin composition thus obtained is preferably in the form of pellets. Alternatively, a dry blend of the above components is measured in an injection molding machine and kneaded in a melt-kneading section (cylinder), whereby a polypropylene resin composition is produced as a molded article. Thus, the polypropylene resin composition of the present invention is obtained by mixing the master batch composition with other ingredients. The phase structure of the polypropylene resin composition is considered to be a structure in which a propylene-ethylene copolymer component derived from the master batch composition and an elastomer (a copolymer of ethylene and an α -olefin derived from HECO different from the master batch composition, depending on the case) are dispersed in a matrix mainly composed of a propylene homopolymer derived from the master batch composition, and the effect of the present invention can be exhibited by forming the phase structure.
(6) Injection molding
The master batch composition and the polypropylene resin composition of the present invention are suitable for injection molding. The polypropylene resin composition of the present invention has high rigidity, high impact resistance and low linear expansion coefficient, and is therefore suitable for automobile parts. The usual injection conditions are a cylinder temperature of 200 to 230 ℃, a mold temperature of 20 to 50 ℃ and an injection speed of 30 to 50 mm/sec.
Examples
1. Masterbatch composition
[ example 1]
A master batch composition was produced containing 65.5 wt% of a polypropylene homopolymer as component (1) and 34.5 wt% of a propylene-ethylene copolymer having 65.7 wt% of ethylene-derived units as component (2).
The solid catalyst component was prepared according to the preparation method described in the example of Japanese patent application laid-open No. 2011-500907. Specifically, the preparation was performed as follows.
250mL of TiCl were introduced into a 500mL four-necked round-bottomed flask purged with nitrogen at 0 deg.C4. While stirring, 10.0g of finely spherical MgCl was added2·1.8C2H5OH (made according to the method described in example 2 of U.S. patent 4,399,054, but run at 3000rpm instead of 10000 rpm) and 9.1 mmol of diethyl 2,3- (diisopropyl) succinate. The temperature was raised to 100 ℃ and maintained for 120 minutes. Next, the stirring was stopped, the solid product was allowed to settle, and the supernatant liquid was aspirated. Then, the following operations were repeated 2 times: 250mL of fresh TiCl were added4The mixture was allowed to react at 120 ℃ for 60 minutes, and the supernatant liquid was aspirated. The solid was washed 6 times with anhydrous hexane (6X 100mL) at 60 ℃.
The above solid catalyst, Triethylaluminum (TEAL) and Dicyclopentyldimethoxysilane (DCPMS) were contacted at room temperature for 5 minutes in an amount such that the weight ratio of TEAL to the solid catalyst was 18 and the weight ratio of TEAL/DCPMS was 10. The resulting catalyst system was kept in suspension in liquid propylene at 20 ℃ for 5 minutes, thereby carrying out prepolymerization.
The obtained prepolymer was introduced into a first-stage liquid phase polymerization reactor to obtain a propylene homopolymer, and the obtained polymer was introduced into a second-stage gas phase polymerization reactor to polymerize a copolymer (propylene-ethylene copolymer). In the polymerization, the temperature and pressure are adjusted and hydrogen is used as molecular weight regulator. As for the polymerization temperature and the ratio of the reactants, the polymerization temperature and the hydrogen concentration in the reactor in the first stage were 70 ℃ and 0.31 mol%, respectively, and the polymerization temperature, H2/C2, C2/(C2+ C3) in the reactor in the second stage were 80 ℃, 0.16 mol ratio and 0.69 mol ratio, respectively. Further, the residence time distribution in the first stage and the second stage was adjusted so that the amount of the copolymer component was 34.5 parts by weight based on 100 parts by weight of the polymer.
To 100 parts by weight of the obtained polypropylene polymer, 2250.2 parts by weight of B2250.2 from BASF corporation as an antioxidant and 0.05 part by weight of calcium stearate produced by southern chemical Co., Ltd as a neutralizing agent were blended and stirred in a Henschel mixer for 1 minute, and then melt-kneaded at a cylinder temperature of 200 ℃ by a twin-screw extruder (model KZW15TW-30MG produced by Technovel, Ltd.) having a screw diameter of 15mm and extruded. And cooling the strands in water, and cutting by using a granulator to obtain granules. Subsequently, the pellets were injection-molded into various test pieces by an injection molding machine (model number Roboshot S-2000i 100B, manufactured by FANUC). The molding conditions were a cylinder temperature of 200 ℃, a mold temperature of 40 ℃ and an injection speed of 200 mm/sec. Various physical properties were evaluated using test pieces. The evaluation method is as described below.
[ example 2]
A polypropylene polymer was produced in the same manner as in example 1 except that the hydrogen concentration in the reactor in the first stage was 0.28 mol%, the H2/C2 and C2/(C2+ C3) in the reactor in the second stage were 0.22 mol% and 0.59 mol%, respectively, and the residence time distributions in the first stage and the second stage were adjusted so that the amount of the copolymer component was 32.9 parts by weight based on 100 parts by weight of the polymer. Using this polypropylene polymer, a master batch composition for this example was produced and evaluated in the same manner as in example 1.
[ example 3]
Pellets were prepared and evaluated by melt-kneading in the same manner as in example 1 except that talc was further added to the polypropylene polymer obtained in example 2. The blending amount of talc (trade name HTP05L, manufactured by IMI Fabi Co.) was 1 part by weight based on 100 parts by weight of the polymer.
Comparative example 1
A solid catalyst prepared by the method described in example 5 of European patent publication No. 728769, wherein the solid catalyst is MgCl2Loaded with Ti and diisobutylphthalate as internal donor. Subsequently, the solid catalyst, Triethylaluminum (TEAL) as an organoaluminum compound, and Dicyclopentyldimethoxysilane (DCPMS) as an external electron donor compound were contacted at 12 ℃ for 24 minutes in such an amount that the weight ratio of TEAL to the solid catalyst was 20 and the weight ratio of TEAL/DCPMS was 10. The resulting catalyst system was kept in suspension in liquid propylene at 20 ℃ for 5 minutes, thereby carrying out prepolymerization.
Using the obtained prepolymer, a propylene homopolymer was produced by multistage polymerization using two liquid phase polymerization reactors. The hydrogen concentration in the first polymerization reactor was set to 0.16 mol%, the hydrogen concentration in the second polymerization reactor was set to 1.70 mol%, and the polymerization pressure was adjusted at a polymerization temperature of 70 ℃ in respective proportions of 50: 50, the residence time distribution is adjusted.
Subsequently, the obtained propylene homopolymer was introduced into a gas phase polymerization reactor, and polymerization of a copolymer (propylene-ethylene copolymer) was carried out in the same manner as in example 1. In the polymerization, the temperature and pressure are adjusted and hydrogen is used as molecular weight regulator. In the reactor in the second stage, the polymerization temperature, H2/C2, and C2/(C2+ C3) were 80 ℃, 0.12 molar ratio, and 0.68 molar ratio, respectively. Further, the residence time distribution in the first stage and the second stage was adjusted so that the amount of the copolymer component was 30.0 parts by weight based on 100 parts by weight of the polymer.
Using the polypropylene polymer thus obtained, a master batch composition for comparison was produced and evaluated in the same manner as in example 1.
Comparative example 2
Pellets were prepared and evaluated by melt-kneading in the same manner as in example 1 except that talc was further added to the polypropylene polymer obtained in comparative example 1. The blending amount of talc (trade name HTP05L, manufactured by IMI Fabi Co.) was 1 part by weight based on 100 parts by weight of the polymer.
Comparative example 3
A polypropylene polymer was produced in the same manner as in example 1, except that the hydrogen concentration in the reactor in the first stage was 0.44 mol%, and the hydrogen concentration in the reactor in the second stage, C2/(C2+ C3), were 2.04 mol% and 0.37 mol%, respectively, and the residence time distributions in the first and second stages were adjusted so that the amount of the copolymer component was 35.6 parts by weight based on 100 parts by weight of the polymer. Using the polypropylene polymer thus obtained, a master batch composition for comparison was produced and evaluated in the same manner as in example 1.
Comparative example 4
Using the same prepolymerization catalyst as in example 1, a propylene homopolymer was produced in the first stage reactor with a polymerization temperature and a hydrogen concentration of 70 ℃ and 0.29 mol%, respectively, and after purging the unreacted monomers, ethylene was introduced into the second stage polymerization reactor to produce an ethylene homopolymer. The polymerization temperature in the reactor of the second stage and the H2/C2 were set to 80 ℃ and a molar ratio of 0.16, respectively, and the residence time distributions in the first and second stages were adjusted so that the amount of the ethylene homopolymer was 29.8 parts by weight based on 100 parts by weight of the polymer, thereby obtaining a polypropylene polymer. A comparative masterbatch composition was produced and evaluated in the same manner as in example 1 except that this polymer was used.
Comparative example 5
A polypropylene polymer was produced in the same manner as in example 1, except that the hydrogen concentration in the reactor in the first stage was 0.34 mol%, and the hydrogen concentration in the reactor in the second stage, C2/(C2+ C3), were 4.13 mol% and 0.19 mol%, respectively, and the residence time distributions in the first and second stages were adjusted so that the amount of the copolymer component was 31.5 parts by weight based on 100 parts by weight of the polymer. Using the polypropylene polymer thus obtained, a master batch composition for comparison was produced and evaluated in the same manner as in example 1.
Comparative example 6
Using the prepolymerized catalyst of comparative example 1, the hydrogen concentration in the first liquid phase polymerization reactor was set to 0.73 mol%, the hydrogen concentration in the second liquid phase polymerization reactor was set to 3.46 mol%, and the residence time distributions in the liquid phase reactor and the gas phase reactor were adjusted so that the amount of the copolymer component was 49.0 parts by weight based on 100 parts by weight of the polymer, respectively, to 0.12 mol% and 0.68 mol% in each of H2/C2 and C2/(C2+ C3) in the gas phase polymerization reactor, thereby producing a polypropylene polymer. Using the polypropylene polymer thus obtained, a master batch composition for comparison was produced and evaluated in the same manner as in example 1.
Comparative example 7
A polypropylene polymer was produced in the same manner as in comparative example 6 except that the hydrogen concentration in the liquid phase polymerization reactor in the first stage was set to 1.86 mol%, and the residence time distributions in the liquid phase reactor and the gas phase reactor were adjusted so that the amount of the copolymer component was 37.0 parts by weight based on 100 parts by weight of the polymer. Using the polypropylene polymer thus obtained, a master batch composition for comparison was produced and evaluated in the same manner as in example 1.
The results are shown in table 1.
2. Polypropylene resin composition
[ example 4]
A polypropylene polymer was produced in the same manner as in example 1, except that the hydrogen concentration in the reactor in the first stage was 0.59 mol%, and the residence time distributions in the first and second stages were adjusted so that the amount of the copolymer component was 30.7 parts by weight based on 100 parts by weight of the polymer. Next, a master batch composition was produced using the polypropylene polymer in the same manner as in example 1. This master batch composition, talc (trade name HTP05L, product of IMI Fabi) and an elastomer (trade name Engage8200, product of Dow Chemical) were melt-kneaded in the same manner as in example 1 to prepare pellets. Subsequently, the polypropylene resin composition was evaluated in the same manner as in example 1.
[ example 5]
A polypropylene polymer was produced in the same manner as in example 1 except that the hydrogen concentration in the reactor in the first stage was 0.59 mol%, the H2/C2 and C2/(C2+ C3) in the reactor in the second stage were 0.14 mol% and 0.56 mol%, respectively, and the residence time distributions in the first stage and the second stage were adjusted so that the amount of the copolymer component was 29.5 parts by weight based on 100 parts by weight of the polymer. Then, a polypropylene resin composition was produced and evaluated in the same manner as in example 4 using this polypropylene polymer.
[ example 6]
A polypropylene polymer was produced in the same manner as in example 1 except that the hydrogen concentration in the reactor in the first stage was 0.59 mol%, the H2/C2 and C2/(C2+ C3) in the reactor in the second stage were 0.12 mol% and 0.59 mol%, respectively, and the residence time distributions in the first stage and the second stage were adjusted so that the amount of the copolymer component was 32.3 parts by weight based on 100 parts by weight of the polymer. Next, a polypropylene resin composition was produced and evaluated in the same manner as in example 4, except that the contents of the master batch composition and talc were changed as shown in table 2 using the polypropylene polymer.
[ example 7]
A polypropylene polymer was produced in the same manner as in example 4 except that the hydrogen concentration in the reactor in the first stage was 0.39 mol%, and the residence time distributions in the first and second stages were adjusted so that the amount of the copolymer component was 37.5 parts by weight based on 100 parts by weight of the polymer. Next, a polypropylene resin composition was produced and evaluated in the same manner as in example 4, except that this polypropylene polymer was used and a master batch composition, talc and a propylene homopolymer having an MFR of 1750g/10 min and a xylene-soluble fraction at 25 ℃ of 2.3 wt% were compounded in amounts shown in table 2.
Comparative example 8
Using the prepolymerized catalyst of comparative example 1, the hydrogen concentration in the first liquid phase polymerization reactor was set to 0.68 mol%, the hydrogen concentration in the second liquid phase polymerization reactor was set to 3.46 mol%, and the residence time distributions in the liquid phase reactor and the gas phase reactor were adjusted so that the amount of the copolymer component was 26.8 parts by weight based on 100 parts by weight of the polymer, respectively, to 0.08 mol% and 0.68 mol% in each of H2/C2 and C2/(C2+ C3) in the gas phase polymerization reactor, thereby producing a polypropylene polymer. Then, a polypropylene resin composition for comparison was produced and evaluated in the same manner as in example 4 using the polypropylene polymer.
Comparative example 9
The prepolymerized catalyst of comparative example 1 was used to produce a polypropylene polymer by adjusting the residence time distributions in the liquid phase reactor and the gas phase reactor so that the amount of the copolymer component was 26.4 parts by weight based on 100 parts by weight of the polymer, with the hydrogen concentration in the polymerization reactor of the first stage being 1.44 mol%, and the hydrogen concentration in the polymerization reactor of the second stage, C2/(C2+ C3), being 1.75 mol% and 0.22 mol%, respectively. Then, a polypropylene resin composition for comparison was produced and evaluated in the same manner as in example 4 using the polypropylene polymer.
Comparative example 10
A polypropylene polymer was produced in the same manner as in comparative example 8 except that the hydrogen concentration in the first liquid phase polymerization reactor was 0.42 mol%, and the residence time distributions in the liquid phase reactor and the gas phase reactor were adjusted so that the amount of the copolymer component was 28.0 parts by weight based on 100 parts by weight of the polymer, and the obtained polymer was used. Next, a polypropylene resin composition for comparison was produced and evaluated in the same manner as in example 4, except that the blending amount of the master batch composition and talc was changed to the same amount as in example 6 shown in table 2, using the polypropylene polymer.
The results are shown in table 2.
3. Evaluation method
[MFR]
The measurement was carried out in accordance with JIS K7210 under the conditions of 230 ℃ and 21.18N load.
[ ethylene concentration in copolymer and amount of copolymer in masterbatch composition ]
As the sample dissolved in the mixed solvent of 1,2, 4-trichlorobenzene/deuterated benzene, AVANCEIII HD400 (manufactured by Bruker Co., Ltd.) (89400) was used13C resonant frequency of 100MHz), at a measurement temperature of 120 deg.CThe rotation angle is 45 degrees, the pulse interval is 7 seconds, the rotating speed of the sample is 20Hz, and the integration times are 5000 times13Spectrum of C-NMR.
< Total ethylene amount in masterbatch composition >
The spectrum obtained above was used to determine the total ethylene content (wt%) of the master batch composition according to the method described in Kakugo, Y.Naito, K.Mizunuma and T.Miyatake, Macromolecules, 15, 1150-1152 (1982).
< ethylene concentration in copolymer (component (2) >
The ethylene concentration in the copolymer was determined by the same method as the total ethylene amount except that the integrated intensity obtained by the following formula was used instead of the integrated intensity of T β obtained above.
T’ββ＝0.98×Sαγ×A/(1－0.98×A)
Here, a is S α γ/(S α γ + S α δ).
< amount of copolymer (component 2) in masterbatch composition >
The calculation is performed by the following equation.
The amount (wt%) of the component (2) is the total ethylene amount/(ethylene concentration in the copolymer/100)
[ obtaining of xylene-soluble component ]
2.5g of the polymer was charged into a 250mL flask containing o-xylene (solvent), and after completely dissolving the composition by nitrogen purging at 135 ℃ while stirring for 30 minutes using a heating plate and a reflux apparatus, cooling was performed at 25 ℃ for 1 hour. The resulting solution was filtered using filter paper. 100mL of the filtered filtrate was collected, transferred to an aluminum cup or the like, evaporated to dryness at 140 ℃ while purging with nitrogen, and allowed to stand at room temperature for 30 minutes to obtain a xylene-soluble fraction (XS).
[XSIV]
The Intrinsic Viscosity (IV) of the xylene-soluble fraction was measured in tetrahydronaphthalene at 135 ℃ using an Ubbelohde viscometer (SS-780-H1, manufactured by Chaishan scientific instruments Co., Ltd.).
Among them, since the ethylene homopolymer of the component (2) of the master batch composition of comparative example 4 hardly has a xylene-soluble component, the IV of the component (2) was calculated assuming the additive property of IV by using the ratio of the component (2) estimated from the ethylene content of the master batch composition, the IV of the whole master batch composition, and the value of the IV of the component (1).
[ obtaining of xylene-insoluble fraction ]
When the xylene-soluble fraction was filtered as described above, acetone was added to the residue (mixture of xylene-insoluble fraction and solvent) remaining on the filter paper and filtered, and then the unfiltered fraction was evaporated to dryness in a vacuum drying oven set to 80 ℃ to obtain a xylene-insoluble fraction (XI).
[ Mw and Mw/Mn of xylene-insoluble fraction ]
The xylene-insoluble fraction was used as a sample, and the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were measured as follows.
A column in which 1,2, 4-trichlorobenzene containing an antioxidant was used as a mobile phase and UT-G (1), UT-807 (1), and UT-806M (2) were connected in series, manufactured by SHOWA DENKO K.K., was used as a column, and a differential refractometer was used as a detector, using PL GPC220 manufactured by Polymer Laboratories as an apparatus. Further, as a solvent of the sample solution of the xylene-insoluble fraction, the same solvent as the mobile phase was used, and the sample was dissolved at a sample concentration of 1mg/mL for 2 hours at a temperature of 150 ℃ with shaking to prepare a measurement sample. The thus obtained sample solution (500. mu.L) was injected into a column and measured at a flow rate of 1.0 mL/min, a temperature of 145 ℃ and data acquisition intervals of 1 second. The calibration of the column was carried out by a cubic approximation using a polystyrene STANDARD sample (shodex STANDARD, Showa Denko K.K.) having a molecular weight of 580 to 745 ten thousand. For the coefficient of Mark-Houkins, the polystyrene standard sample used had K of 1.21X 10-4α ═ 0.707, and K ═ 1.37 × 10 was used for the polypropylene polymer-4、α＝0.75。
[ flexural modulus ]
The bending test was carried out at room temperature (23 ℃ C.) according to JIS K6921-2. The measurement was carried out at a crosshead speed of 2 mm/min.
[ Charpy impact Strength ]
To obtainThe polypropylene resin molded article (test piece for evaluating physical properties) was subjected to cutting, and the obtained test piece (80 (length) × 10 (width) × 4 (thickness)) mm was subjected to cutting3) The Charpy impact strength at 23 ℃ and-30 ℃ was determined in accordance with ISO 179-1.
[ coefficient of Linear expansion ]
The center (width: 10mm) of the obtained polypropylene resin molded article (test piece for physical property evaluation, thickness: 4mm) was cut into a length of 10mm along the flow direction (MD) of the resin, and the resulting product was placed in an oven at 80 ℃ for 24 hours, and the obtained product was measured in accordance with JIS K7197.
< test apparatus > Ulvac MTS9000 (manufactured by vacuum processor)
< test conditions > rate of temperature rise: 5 ℃ per minute
Loading: 5.0g weight
Measuring temperature: -30 ℃ to 80 DEG C
Therefore, the following steps are carried out: the master batch composition has low linear expansion coefficient, high rigidity and high impact resistance. Furthermore, it can be seen that: the polypropylene resin composition produced by using the master batch composition also has a low coefficient of linear expansion, high rigidity and high impact resistance.
Claims (7)
1. A masterbatch composition obtained by polymerizing propylene and ethylene using a catalyst comprising:
(A) a solid catalyst containing magnesium, titanium, halogen and an electron donor compound selected from succinate compounds as essential components;
(B) an organoaluminum compound; and
(C) an external electron donor compound, which is a compound having a high electron-withdrawing group,
the masterbatch composition comprises:
a propylene homopolymer as the component (1), and
a propylene-ethylene copolymer as the component (2), which contains 55 to 80% by weight of an ethylene-derived unit,
component (1): (2) the weight ratio of (A) to (B) is 75-60: 25 to 40 of the total amount of the organic compounds,
the masterbatch composition satisfies the following conditions:
1) the xylene insoluble component of the composition has Mw/Mn, as measured by GPC, of 6 to 20;
2) the intrinsic viscosity of the xylene soluble component of the composition is between 1dl/g and 3 dl/g;
3) the melt flow rate of the composition at 230 ℃ under a load of 21.18N is 1g/10 min to 50g/10 min.
2. The masterbatch composition according to claim 1, wherein the propylene-ethylene copolymer in the component (2) has an ethylene-derived unit of 60 to 75% by weight.
3. The masterbatch composition of claim 1 or 2, wherein the melt flow rate is 10g/10 min to 35g/10 min.
4. The master batch composition according to claim 1 or 2, wherein the crystallization nucleating agent is contained in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the composition.
5. A polypropylene resin composition obtained by mixing the master batch composition according to any one of claims 1 to 4 with at least one of an elastomer different from the component (2) of the master batch composition and a polypropylene resin different from the master batch composition.
6. A polypropylene resin composition comprising more than 5% by weight and 40% by weight or less of a filler in the polypropylene resin composition according to claim 5.
7. An injection-molded article obtained by injection-molding the polypropylene resin composition according to claim 5 or 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016222226A JP6831218B2 (en) | 2016-11-15 | 2016-11-15 | Masterbatch composition and polypropylene resin composition containing it |
| JP2016-222226 | 2016-11-15 | ||
| PCT/JP2017/041091 WO2018092805A1 (en) | 2016-11-15 | 2017-11-15 | Master batch composition and polypropylene resin composition containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109923170A CN109923170A (en) | 2019-06-21 |
| CN109923170B true CN109923170B (en) | 2021-10-26 |
Family
ID=62146431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780069625.5A Active CN109923170B (en) | 2016-11-15 | 2017-11-15 | Master batch composition and polypropylene resin composition containing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6831218B2 (en) |
| CN (1) | CN109923170B (en) |
| WO (1) | WO2018092805A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7114361B2 (en) * | 2018-06-19 | 2022-08-08 | サンアロマー株式会社 | Polypropylene composition and molded article |
| JP7249126B2 (en) * | 2018-10-18 | 2023-03-30 | サンアロマー株式会社 | Polypropylene composition and molded article |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821303A (en) * | 2007-10-15 | 2010-09-01 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the preparation of high fluidity propylene polymers |
| CN103154124A (en) * | 2010-10-14 | 2013-06-12 | 巴塞尔聚烯烃意大利有限责任公司 | Automotive interior element |
| JP2013151670A (en) * | 2011-12-28 | 2013-08-08 | Sunallomer Ltd | Polymer composition for battery case |
| JP2014091781A (en) * | 2012-11-02 | 2014-05-19 | Sunallomer Ltd | Polypropylene-based resin composition for compression molding and molded product |
| CN104736627A (en) * | 2012-10-03 | 2015-06-24 | 胜亚诺盟股份有限公司 | Propylene resin composition for retort pouch-packaging film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU760406B2 (en) * | 1998-11-03 | 2003-05-15 | Montech Usa Inc. | Polyolefin composition having a high balance of stiffness and impact strength |
| TW200427763A (en) * | 2003-04-03 | 2004-12-16 | Basell Poliolefine Spa | Impact resistant polyolefin compositions |
| JP2008516025A (en) * | 2004-10-04 | 2008-05-15 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Elastomer polyolefin composition |
| JP4688135B2 (en) * | 2005-01-18 | 2011-05-25 | 東邦チタニウム株式会社 | Solid catalyst components and catalysts for olefin polymerization |
| JP6454131B2 (en) * | 2014-11-04 | 2019-01-16 | サンアロマー株式会社 | Method for producing a film or sheet comprising a polypropylene composition |
-
2016
- 2016-11-15 JP JP2016222226A patent/JP6831218B2/en active Active
-
2017
- 2017-11-15 CN CN201780069625.5A patent/CN109923170B/en active Active
- 2017-11-15 WO PCT/JP2017/041091 patent/WO2018092805A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821303A (en) * | 2007-10-15 | 2010-09-01 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the preparation of high fluidity propylene polymers |
| CN103154124A (en) * | 2010-10-14 | 2013-06-12 | 巴塞尔聚烯烃意大利有限责任公司 | Automotive interior element |
| JP2013151670A (en) * | 2011-12-28 | 2013-08-08 | Sunallomer Ltd | Polymer composition for battery case |
| CN104736627A (en) * | 2012-10-03 | 2015-06-24 | 胜亚诺盟股份有限公司 | Propylene resin composition for retort pouch-packaging film |
| JP2014091781A (en) * | 2012-11-02 | 2014-05-19 | Sunallomer Ltd | Polypropylene-based resin composition for compression molding and molded product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6831218B2 (en) | 2021-02-17 |
| JP2018080231A (en) | 2018-05-24 |
| CN109923170A (en) | 2019-06-21 |
| WO2018092805A1 (en) | 2018-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3559113B1 (en) | Masterbatch composition | |
| CN1639251A (en) | Polyolefin masterbatch for preparing impact-resistant polyolefin articles | |
| EP3784734B1 (en) | Polypropylene composition and molded article | |
| JP6998175B2 (en) | Polypropylene resin composition and injection compression molded product | |
| CN109923170B (en) | Master batch composition and polypropylene resin composition containing the same | |
| JP6884061B2 (en) | Polypropylene resin composition and injection compression molded product | |
| EP3810661B1 (en) | Polypropylene composition and molded article | |
| JP7096682B2 (en) | Polypropylene compositions and moldings | |
| EP3867285B1 (en) | Polypropylene composition and molded article | |
| JP6860326B2 (en) | Polypropylene composition and matte film formed by molding the polypropylene composition | |
| JP6588286B2 (en) | Polypropylene resin composition for inflation film | |
| EP3765566B1 (en) | Polypropylene composition and molded article | |
| BR112021005854B1 (en) | COMPOSITION OF POLYPROPYLENE AND MOLDED ARTICLE | |
| JP2020183457A (en) | Polypropylene-based resin composition for automobile interior part, method for manufacturing the same, and molding for automobile interior part |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |