CN109923170A - Concentrate composition and polypropylene resin composite comprising the concentrate composition - Google Patents

Concentrate composition and polypropylene resin composite comprising the concentrate composition Download PDF

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Publication number
CN109923170A
CN109923170A CN201780069625.5A CN201780069625A CN109923170A CN 109923170 A CN109923170 A CN 109923170A CN 201780069625 A CN201780069625 A CN 201780069625A CN 109923170 A CN109923170 A CN 109923170A
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composition
weight
concentrate composition
ingredient
compound
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CN109923170B (en
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梶冈宽
安元一寿
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SunAllomer Ltd
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SunAllomer Ltd
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    • 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

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  • 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 kind of concentrate composition, it is to make concentrate composition obtained from propylene and vinyl polymerization using catalyst, and above-mentioned catalyst includes: (A) contains magnesium, titanium, halogen and solid catalyst of the electron donor compound as neccessary composition in succinate based compound；(B) organo-aluminum compound；And (C) external electron donor compound, above-mentioned concentrate composition includes: the Noblen as ingredient (1) and the propylene-ethylene copolymers as ingredient (2), the propylene-ethylene copolymers include the ethylene-derived units of 55 weight of weight %~80 %, ingredient (1): the weight ratio of (2) is 85~60:15~40, and above-mentioned concentrate composition meets condition below: 1) Mw/Mn of the dimethylbenzene indissolvable component of the composition measured using GPC is 6~20；2) inherent viscosity of the xylene soluble components of the composition is 1dl/g~3dl/g；3) melt flow rate (MFR) (230 DEG C, load 21.18N) of the composition is 1g/10 minutes~50g/10 minutes.The composition has high elastic modulus, the high impact under low temperature and low linear expansion coefficient.

Description

Concentrate composition and polypropylene resin composite comprising the concentrate composition
Technical field
The present invention relates to concentrate composition and include the polypropylene resin composite of the concentrate composition.
Background technique
Polypropylene is at low cost and has excellent physical characteristic, therefore has a wide range of applications in terms of mobile applications.But It is, it is known that polypropylene has amorphous component, thus linear expansion coefficient is big.Therefore, in automobile component, have in acrylic resin The problems such as gap can be generated with the joint portion of other materials.In addition, having attempted a large amount of addition talcums to reduce linear expansion coefficient Equal inorganic fillers, but since weight increases, the angle improved from the light-weighted oil consumption based on automobile, this is not ideal 's.
In order to eliminate the problem, a kind of polyolefin composition is proposed in patent document 1, by (A's) 40%~60% The ingredient B of ingredient A and (B) 40%~60% is constituted, and mentioned component A is polydispersity index and 80g/10 point with 5~15 The wide molecular weight distribution acrylic polymers of clock~200g/10 minutes melting flow (according to ASTM-D1238, condition L), room temperature Under in dimethylbenzene be soluble polyolefin composition part inherent viscosity (IVs) with the inherent viscosity of ingredient (A) (IVA) between IVs/IVAThan being 2~2.5；Ingredient B be including at least 65 weight % ethylene, part dimethylbenzene it is insoluble Olefin polymer rubber.The composition has low linear expansion coefficient.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2002-528621 bulletin
Summary of the invention
Problems to be solved by the invention
For automotive part, it is desirable that high impact and low linear expansion coefficient under high elastic modulus, low temperature, usually These characteristics are in shifting relationship, it is difficult to balancedly meet all these characteristics.The composition recorded in patent document 1 Impact strength at low temperature is high and has low linear expansion coefficient, but elasticity modulus is not up to adequately horizontal.In view of the situation, The issue of the present invention is to provide a kind of high impact having under high elastic modulus, low temperature and the groups of low linear expansion coefficient Close object.
Means for solving the problems
The above subject is addressed by the present invention below.
[1] a kind of concentrate composition, to make concentrate composition obtained from propylene and vinyl polymerization, institute using catalyst Stating catalyst includes:
(A) contain magnesium, titanium, halogen and electron donor compound in succinate based compound as it is necessary at The solid catalyst divided；
(B) organo-aluminum compound；And
(C) external electron donor compound,
The concentrate composition includes:
As ingredient (1) Noblen and
As the propylene-ethylene copolymers of ingredient (2), which includes 55 weight of weight %~80 % Ethylene-derived units,
Ingredient (1): the weight ratio of (2) is 85~60:15~40,
The concentrate composition meets condition below:
1) the dimethylbenzene indissolvable component of the composition is 6~20 using the Mw/Mn that GPC is measured；
2) inherent viscosity of the xylene soluble components of the composition is 1dl/g~3dl/g；
3) melt flow rate (MFR) (230 DEG C, load 21.18N) of the composition is 1g/10 minutes~50g/10 minutes.
[2] concentrate composition as described in [1], wherein the ethylene of the propylene-ethylene copolymers in mentioned component (2) spreads out Raw unit is 60 weight of weight %~75 %.
[3] concentrate composition as described in [1] or [2], wherein mentioned component (1): the weight ratio of (2) is 75~60:25 ~40.
[4] concentrate composition as described in any one of [1]~[3], wherein above-mentioned melt flow rate (MFR) is 10g/10 points Clock~35g/10 minutes.
[5] concentrate composition as described in any one of [1]~[4], wherein relative to 100 parts by weight of above-mentioned composition, Include 0.01 parts by weight~5 parts by weight crystallization nucleating agent.
[6] a kind of polypropylene resin composite passes through the concentrate composition described in any one of above-mentioned [1]~[5] The middle mixing elastomer different from ingredient (2) of above-mentioned concentrate composition or the polypropylene-based tree different with above-mentioned concentrate composition At least one of rouge forms.
[7] a kind of polypropylene resin composite comprises more than 5 weight % and 40 in the composition described in above-mentioned [6] Weight % filler below.
[8] a kind of injection-molded article, by the way that polypropylene resin composite described in above-mentioned [6] or [7] to be injection moulded It forms.
The effect of invention
The combination of a kind of high impact having under high elastic modulus, low temperature and low linear expansion coefficient can be provided Object.
Specific embodiment
It as neccessary composition and as needed will include well known additive comprising ingredient (1) and (2) in the present invention Composition is known as " concentrate composition ".The concentrate composition can be used in mixed way with other resins, also can be used alone.It will Include at least one of " concentrate composition ", the elastomer different from the concentrate composition or polypropylene-based resin, Yi Jigen Resin combination according to the filler of needs is known as " polypropylene resin composite ".Hereinafter, the present invention is described in detail.This In invention, " X~Y " includes the X and Y as its end value." X or Y " refers to any one or both sides in X, Y.
1. concentrate composition
Concentrate composition of the invention includes ingredient below.
Ingredient (1): Noblen
Ingredient (2): the propylene-ethylene copolymers of the ethylene-derived units comprising 55 weight of weight %~80 %
(1) ingredient (1): Noblen
It is equal using propylene due to meeting the rigidity and heat resistance of final products requirement as ingredient (1) of the invention Polymers (homo-polypropylene).In Noblen of the invention, due to the presence or transition of the recycle monomer in manufacturing process Product is mixed into, and can include 2.0 weight % or less, preferably 1.0 weight % below few with the degree of lossless inventive concept The ethylene of amount or more than one C4~C10- α-olefin derived unit.
(2) ingredient (2): propylene-ethylene copolymers
Propylene-ethylene copolymers used in the present invention include the ethylene-derived units of 55 weight of weight %~80 %.If The content of ethylene-derived units is less than lower limit value, then linear expansion coefficient increases.In addition, if being more than upper limit value, linear expansion coefficient Increase, impact strength also reduces.And then during manufacturing, the case where especially content of ethylene-derived units is 55 weight % or so Under, if making 25 parts by weight of ratio of ingredient (2) or more, aggregated particles are easy bonding each other, can cause the blocking of pipeline.From This aspect is set out, and the content of ethylene-derived units is preferably 60 weight of weight %~75 %.
(3) ratio of components
The weight ratio of ingredient (1) and (2) is (1): (2)=85~60:15~40.If the amount of ingredient (2) is more than the upper limit, Then rigid reduction becomes significantly, if being less than lower limit, the reduction of impact resistance becomes significant.From this aspect, above-mentioned ratio Example is preferably 75~60:25~40.
(4) other compositions
In turn, antioxidant, chlorine absorbent, heat-resisting stabilizing agent, light stabilizer, ultraviolet can be added in concentrate composition Light absorbers, exterior lubricant, antiblocking agent, antistatic agent, antifoggant, crystallization nucleating agent, fire retardant, are divided internal lubricant Powder, copper deactivator, neutralizer, plasticizer, gas-tight infusion, crosslinking agent, peroxide, oil-filled dose and other organic and inorganic face Material etc. is commonly used in the usual additive of olefin polymer.The additive amount of each additive can be well known amount.
Concentrate composition of the invention particularly preferably includes crystallization nucleating agent.As crystallization nucleating agent, the neck can be used Well known substance in domain.As crystallization nucleating agent, for example, there is talcum etc. the inorganic system of Nucleation to fill The organic systems crystallization nucleating agent such as agent, phosphate, carboxylic metallic salt, benzylidene sorbitol, triaminobenzene derivatives.Crystallization nucleation The amount of agent is preferably 0.01 parts by weight~5 parts by weight relative to 100 parts by weight of composition.
(5) characteristic
1) Mw/Mn of XI
The dimethylbenzene indissolvable component (XI) of the composition is 6~20 using the Mw/Mn that GPC is measured.Dimethylbenzene indissolvable component For the crystallinity ingredient in the composition.In the present invention, the Mw/Mn as molecular weight distribution index is in wide scope.That is, high score Son amount ingredient largely exists, which can promote the orientation of polymer chain at the time of molding.Therefore, it can be realized low linear expansion system Number.Further, since high molecular weight components, and improve the impact resistance under impact resistance, particularly low temperature.Go out from this aspect Hair, Mw/Mn is preferably 7~20.The Mw/Mn of XI utilizes GPC (gel by obtaining the ingredient insoluble in 25 DEG C of dimethylbenzene Permeation chromatography) method is measured the ingredient and finds out.
2)XSIV
The inherent viscosity (XSIV) of the xylene soluble components (XS) of the composition is also tied for not having in the composition The index of the molecular weight of the ingredient of crystalline substance.XSIV utilizes conventional method by obtaining the ingredient for the dimethylbenzene for dissolving in 25 DEG C The inherent viscosity of the ingredient is measured and is found out.In the present invention, XSIV is relatively low, is 1dl/g~3dl/g.When XSIV is low, Ingredient (2) is easy to be stretched in injection-molded article, is advantageously implemented low linear expansion coefficient, but impact resistance becomes if too low Difference.Result, it is believed that by making XSIV in the range, taking into account for low linear expansion coefficient and high-impact can be realized.From the party Face is set out, and above-mentioned inherent viscosity is preferably 1.5dl/g~2.5dl/g.
3) melt flow rate (MFR)
Melt flow rate (MFR) (hereinafter also referred to as " MFR ") of the concentrate composition at 230 DEG C, load 21.18N is 1g/ 10 minutes~50g/10 minutes.By making MFR in the range, excellent mouldability can be realized.If MFR is more than upper limit value, The MFR of ingredient (1) becomes very high (molecular weight reduction), and as a result impact resistance reduces, and manufactures and also become difficult.In addition, If MFR value be less than lower limit value, used the MFR of the polypropylene resin composite of concentrate composition to reduce, be injection moulded etc. at Type becomes difficult.From this aspect, melt flow rate (MFR) is preferably 5g/10 minutes~35g/10 minutes.
4) elasticity modulus
The bending modulus of concentrate composition of the invention be preferably 1000MPa~1500MPa, more preferably 1100MPa~ 1300MPa。
5) linear expansion coefficient
The linear expansion coefficient in the direction MD at preferably -30 DEG C~80 DEG C of concentrate composition of the invention is 60~80 × 10-6/ K, preferably 65~78 × 10-6/K.Linear expansion coefficient can be surveyed by carrying out thermo-mechanical analysis (TMA) after molded product is annealed It is fixed.
6) impact strength
The charpy impact intensity of concentrate composition of the invention preferably at room temperature is 20kJ/m2~50kJ/m2, preferred low temperature Charpy impact intensity under (- 30 DEG C) is 3kJ/m2~6kJ/m2。
(6) manufacturing method
Concentrate composition of the invention is manufactured using the method for including following processes: using catalyst by ingredient (1) Starting monomer and the starting monomer of ingredient (2) polymerize, which, which includes (A), contains magnesium, titanium, halogen and as interior The solid catalyst of the succinate based compound of portion's electron donor；(B) organo-aluminum compound；And (C) external electron donor Compound.
Use and contains succinate based compound as point of polymer made of the polymerization catalyst of internal electron donor Son amount distribution is wide, and high molecular weight components and low molecular weight compositions are uniformly dispersed.Molecular weight distribution is physical quantity, Ke Yitong Measurement is crossed to determine.But the measured value can not indicate the degree of scatter of high molecular weight components and low molecular weight compositions.For example, Be blended by admixture of powder or particle and high molecular weight components and low molecular weight compositions be blended, or in multi-stage polymeric into One step increases series, at first sight can also obtain the polymer with molecular weight distribution same as the present invention (measured value).But It is that high molecular weight components and the degree of scatter of low molecular weight compositions be not in the obtained polymer and polymer of the invention Together, uniform degree of scatter is realized in the present invention.The difference is for example in the performances side such as low linear expansion coefficient or high-impact Face is significant.
1) solid catalyst (ingredient A)
Ingredient (A) can be by well known method, for example keep magnesium compound, titanium compound and electron donor compound mutual It contacts and prepares.
Titanium compound used in preparation as ingredient (A), preferred formula: Ti (OR)gX4-g4 represented valence titanizings Close object.In formula, R is alkyl, and X is halogen, 0≤g≤4.As titanium compound, more specifically, TiCl can be enumerated4、TiBr4、 TiI4Equal titanium tetrahalides；Ti(OCH3)Cl3、Ti(OC2H5)Cl3、Ti(On-C4H9)Cl3、Ti(OC2H5)Br3、Ti(OisoC4H9) Br3Deng three halogenated alkoxy titaniums；Ti(OCH3)2Cl2、Ti(OC2H5)2Cl2、Ti(On-C4H9)2Cl2、Ti(OC2H5)2Br2Equal dihalo-s Change alkoxytitanium；Ti(OCH3)3Cl、Ti(OC2H5)3Cl、Ti(On-C4H9)3Cl、Ti(OC2H5)3The list halogenation tri-alkoxy such as Br Titanium；Ti(OCH3)4、Ti(OC2H5)4、Ti(On-C4H9)4Etc. tetraalkoxy titaniums etc..It is preferably that halogen-containing titanizing is closed among these Object, particularly titanium tetrahalide, particularly preferably titanium tetrachloride.
Magnesium compound used in preparation as ingredient (A) can be enumerated with magnesium-carbon key or magnesium-hydrogen bond magnesium Close object, such as dimethyl magnesium, magnesium ethide, dipropyl magnesium, dibutylmagnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl Magnesium chloride, propyl magnesium chloride, butylmagnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl magnesium ethylate, ethyl-butyl magnesium, fourth Base magnesium hydride etc..These magnesium compounds can also for example use in the form of with the complex compound of organo-aluminium etc., and can be liquid State or solid-state.And then be used as preferred magnesium compound, can enumerate magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride it The magnesium halide of class；Methoxy magnesium chloride, ethyoxyl magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octyloxy magnesium chloride Etc Alkoxymagnesium halides；The aryloxymagnesium halides magnesium of phenoxy group magnesium chloride, methylphenoxy magnesium chloride etc；Magnesium ethylate, The alkoxyl magnesium of isopropoxy magnesium, butoxy magnesium, n-octyloxy magnesium, 2- ethyl hexyl oxy magnesium etc；Phenoxy group magnesium, dimethyl benzene The aryloxy group magnesium of oxygroup magnesium etc；The carboxylate etc. of the magnesium of Magnesium dilaurate, magnesium stearate etc.
Electron donor compound used in the preparation of ingredient (A) is commonly known as " internal electron donor ".In the present invention, It is preferable to use provide the inside electron donor of wide molecular weight distribution.It is known that, conventionally, being capable of increasing and being polymerize with multistage Molecular weight distribution, but be difficult to increase molecular weight distribution in the case where the molecular weight of XI is low.But by using specific inside Electron donor, even if can also increase molecular weight distribution in the case where the molecular weight of XI is low.About using the polymerization catalyst to obtain The composition arrived carries out obtained from particle or admixture of powder with to the polymer for using other polymerization catalysts to obtain with phase It with the composition of molecular weight distribution and then carries out multi-stage polymeric and there is the composition of identical molecular weight distribution to compare, show Excellent mobility and big extrusion swelling (swell).It is thought that because, it is high in the composition manufactured using the catalyst Molecular weight constituent and low molecular weight compositions are integrally formed in the state of close to molecular level, but the resin combination of the latter does not exist It is mixed in together close in the state of molecular level, only apparently show identical molecular weight distribution.Hereinafter, to preferred Inside electron donor be illustrated.
In the present invention, use succinate based compound as internal electron donor.In the present invention, succinate system chemical combination Object refers to the diester of succinic acid or replaces the diester of succinic acid.Hereinafter, succinate based compound is described in detail.This hair In bright it is preferable to use succinate based compound by formula below (I) represented by.
[changing 1]
In formula, group R1And R2It is same to each other or different, according to circumstances to include heteroatomic C1~C20Threadiness or branch Alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl；Group R3~R6It is same to each other or different, be hydrogen or according to Situation includes heteroatomic C1~C20Threadiness or branch alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkylaryl, The group R being bonded on same carbon atom or different carbon atoms3~R6Ring can be bonded together to form together.
R1And R2Preferably C1~C8Alkyl, naphthenic base, aryl, aralkyl and alkylaryl.R1And R2Particularly preferably Compound in primary alkyl, particularly branched primary alkyl moiety.Preferred R1And R2The example of base is C1~C8Alkyl, such as For methyl, ethyl, n-propyl, normal-butyl, isobutyl group, neopentyl, 2- ethylhexyl.Particularly preferred ethyl, isobutyl group and new Amyl.
By preferred group of the compound represented by formula (I) first is that: R3~R5For hydrogen, R6For with 3~10 carbon atoms Branched alkyl, naphthenic base, aryl, aralkyl and alkylaryl compound.This monosubstituted succinate compound it is excellent Selecting concrete example is sec-butyl diethyl succinate, hexyl diethyl succinate, cyclopropyl diethyl succinate, norborny amber Diethyl phthalate, perhydro diethyl succinate, trimethyl silyl diethyl succinate, methoxyl group diethyl succinate, to first Phenyl diethyl succinate, rubigan diethyl succinate, phenylsuccinic acid diethylester, cyclohexyl succinic acid diethyl Ester, benzyl diethyl succinate, cyclohexyl methyl diethyl succinate, tert-butyl diethyl succinate, isobutyl group succinic acid two Ethyl ester, isopropyl diethyl succinate, neopentyl diethyl succinate, isopentyl diethyl succinate, (1- trifluoromethyl second Base) diethyl succinate, fluorenyl diethyl succinate, phenylsuccinic acid 1- ethyoxyl carbon diisobutyl ester, sec-butyl succinic acid two Isobutyl ester, hexyl di-iso-octyl succinate, cyclopropyl di-iso-octyl succinate, norborny di-iso-octyl succinate, perhydro amber Amber acid diisobutyl ester, trimethyl silyl di-iso-octyl succinate, methoxyl group di-iso-octyl succinate, p-methoxyphenyl amber Amber acid diisobutyl ester, rubigan di-iso-octyl succinate, cyclohexyl di-iso-octyl succinate, benzyl di-iso-octyl succinate, Cyclohexyl methyl di-iso-octyl succinate, tert-butyl di-iso-octyl succinate, isobutyl group di-iso-octyl succinate, isopropyl amber Sour diisobutyl ester, neopentyl di-iso-octyl succinate, isopentyl di-iso-octyl succinate, (1- trifluoromethyl ethyl) succinic acid two Isobutyl ester, fluorenyl di-iso-octyl succinate, two peopentyl ester of sec-butyl succinic acid, two peopentyl ester of hexyl succinic acid, cyclopropyl amber Sour two peopentyl esters, two peopentyl ester of norborny succinic acid, two peopentyl ester of perhydro succinic acid, trimethyl silyl succinic acid two are new Pentyl ester, two peopentyl ester of methoxyl group succinic acid, two peopentyl ester of p-methoxyphenyl succinic acid, two peopentyl ester of rubigan succinic acid, Two peopentyl ester of phenylsuccinic acid, two peopentyl ester of cyclohexyl succinic acid, two peopentyl ester of benzyl succinic acid, cyclohexyl methyl succinic acid two Peopentyl ester, two peopentyl ester of tert-butyl succinic acid, two peopentyl ester of isobutyl group succinic acid, two peopentyl ester of isopropyl succinic acid, neopentyl Two peopentyl ester of succinic acid, two peopentyl ester of isopentyl succinic acid, two peopentyl ester of (1- trifluoromethyl ethyl) succinic acid, fluorenyl succinic acid Two peopentyl esters.
Other preferred groups of compound in the range of formula (I) are: coming from R3~R6At least two group it is different from hydrogen, choosing From according to circumstances comprising heteroatomic C1~C20Threadiness or branch alkyl, alkenyl, naphthenic base, aryl, aralkyl or alkyl The compound of aryl.2 particularly preferably different from hydrogen group bondings are in the compound on same carbon atom.Specifically R3And R4 For the group different from hydrogen, R5And R6For the compound of hydrogen atom.This two replace the preferred concrete example of succinate to be 2,2- bis- Methyl succinic diethyl phthalate, 2- Ethyl-2-Methyl diethyl succinate, 2- benzyl -2- isopropyl diethyl succinate, 2- hexamethylene Ylmethyl -2- isobutyl group diethyl succinate, 2- cyclopenta -2- normal-butyl diethyl succinate, 2,2- diisobutyl succinic acid Diethylester, 2- cyclohexyl -2- ethylsuccinic acid diethylester, 2- isopropyl -2- methyl succinic diethyl phthalate, 2- myristyl -2- Ethylsuccinic acid diethylester, 2- isobutyl group -2- ethylsuccinic acid diethylester, 2- (1- trifluoromethyl ethyl) -2- methylsuccinic acid Diethylester, 2- isopentyl -2- isobutyl group diethyl succinate, 2- phenyl -2- normal-butyl diethyl succinate, 2,2- dimethyl amber Amber acid diisobutyl ester, 2- Ethyl-2-Methyl di-iso-octyl succinate, 2- benzyl -2- isopropyl di-iso-octyl succinate, 2- hexamethylene Ylmethyl -2- isobutyl group di-iso-octyl succinate, 2- cyclopenta -2- normal-butyl di-iso-octyl succinate, 2,2- diisobutyl amber Amber acid diisobutyl ester, 2- cyclohexyl -2- ethylsuccinic acid diisobutyl ester, 2- isopropyl -2- methylsuccinic acid diisobutyl ester, 2- ten Tetraalkyl -2- ethylsuccinic acid diisobutyl ester, 2- isobutyl group -2- ethylsuccinic acid diisobutyl ester, 2- (1- trifluoromethyl ethyl) - 2- methylsuccinic acid diisobutyl ester, 2- isopentyl -2- isobutyl group di-iso-octyl succinate, 2- phenyl -2- normal-butyl succinic acid two Isobutyl ester, two peopentyl ester of 2,2- dimethyl succinate, two peopentyl ester of 2- Ethyl-2-Methyl succinic acid, 2- benzyl -2- isopropyl amber Two peopentyl esters of amber acid, two peopentyl ester of 2- cyclohexyl methyl -2- isobutyl group succinic acid, 2- cyclopenta -2- normal-butyl succinic acid two are new Pentyl ester, two peopentyl ester of 2,2- diisobutyl succinic acid, two peopentyl ester of 2- cyclohexyl -2- ethylsuccinic acid, 2- isopropyl -2- methyl Two peopentyl ester of succinic acid, two peopentyl ester of 2- myristyl -2- ethylsuccinic acid, two peopentyl ester of 2- isobutyl group -2- ethylsuccinic acid, Two peopentyl ester of 2- (1- trifluoromethyl ethyl) -2- methylsuccinic acid, two peopentyl ester of 2- isopentyl -2- isobutyl group succinic acid, 2- benzene Two peopentyl ester of base -2- normal-butyl succinic acid.
In addition, also at least two group bondings particularly preferably different from hydrogen is in the compound on different carbon atoms.Specifically It is R3And R5For the compound of the group different from hydrogen.In this case, R4And R6It can be hydrogen atom, or not with hydrogen Same group, but preferably any one is hydrogen atom (three replace succinate).The preferred concrete example of this compound is 2, Bis- (trimethyl silyl) diethyl succinates of 3-, 2,2- sec-butyl -3- methyl succinic diethyl phthalate, 2- (3,3,3- trifluoro Propyl) -3- methyl succinic diethyl phthalate, bis- (2- ethyl-butyl) diethyl succinates of 2,3-, 2,3- diethyl -2- isopropyl amber Amber diethyl phthalate, 2,3- diisopropyl -2- methyl succinic diethyl phthalate, 2,3- dicyclohexyl -2- methyl succinic diethyl phthalate, 2, Bis- (cyclohexyl methyl) diethyl succinates of 3- dibenzyl diethyl succinate, 2,3- diisopropyl diethyl succinate, 2,3-, 2,3- di-t-butyl diethyl succinate, 2,3- diisobutyl diethyl succinate, 2,3- di neo-pentyl diethyl succinate, 2, 3- diisoamyl diethyl succinate, 2,3- (1- trifluoromethyl ethyl) diethyl succinate, 2,3- myristyl succinic acid two Ethyl ester, 2,3- fluorenyl diethyl succinate, 2- isopropyl -3- isobutyl group diethyl succinate, 2- tert-butyl -3- isopropyl amber Diethyl phthalate, 2- isopropyl -3- cyclohexyl diethyl succinate, 2- isopentyl -3- cyclohexyl diethyl succinate, the 2- tetradecane Base -3- cyclohexyl methyl diethyl succinate, 2- cyclohexyl -3- cyclopenta diethyl succinate, 2,3- diethyl -2- isopropyl Di-iso-octyl succinate, 2,3- diisopropyl -2- methylsuccinic acid diisobutyl ester, 2,3- dicyclohexyl -2- methylsuccinic acid two Isobutyl ester, 2,3- dibenzyl di-iso-octyl succinate, 2,3- diisopropyl di-iso-octyl succinate, 2,3- bis- (cyclohexyl methyls) Di-iso-octyl succinate, 2,3- di-t-butyl di-iso-octyl succinate, 2,3- diisobutyl di-iso-octyl succinate, 2,3- bis- are new Amyl di-iso-octyl succinate, 2,3- diisoamyl di-iso-octyl succinate, 2,3- (1- trifluoromethyl ethyl) succinic acid two are different Butyl ester, 2,3- myristyl di-iso-octyl succinate, 2,3- fluorenyl di-iso-octyl succinate, 2- isopropyl -3- isobutyl group amber Sour diisobutyl ester, 2- tert-butyl -3- isopropyl di-iso-octyl succinate, 2- isopropyl -3- cyclohexyl di-iso-octyl succinate, 2- Isopentyl -3- cyclohexyl di-iso-octyl succinate, 2- myristyl -3- cyclohexyl methyl di-iso-octyl succinate, 2- cyclohexyl - Bis- two peopentyl esters of (trimethyl silyl) succinic acid of 3- cyclopenta di-iso-octyl succinate, 2,3-, 2,2- sec-butyl -3- methyl Two peopentyl ester of succinic acid, two peopentyl ester of 2- (3,3,3- trifluoro propyl) -3- methylsuccinic acid, bis- (2- ethyl-butyl) ambers of 2,3- Sour two peopentyl esters, two peopentyl ester of 2,3- diethyl -2- isopropyl succinic acid, 2,3- diisopropyl -2- methylsuccinic acid two new penta Ester, two peopentyl ester of 2,3- dicyclohexyl -2- methylsuccinic acid, two peopentyl ester of 2,3- dibenzyl succinic acid, 2,3- diisopropyl amber Amber acid two peopentyl esters, bis- two peopentyl esters of (cyclohexyl methyl) succinic acid of 2,3-, two peopentyl ester of 2,3- di-t-butyl succinic acid, 2,3- Two peopentyl ester of diisobutyl succinic acid, two peopentyl ester of 2,3- di neo-pentyl succinic acid, two peopentyl ester of 2,3- diisoamyl succinic acid, Two peopentyl ester of 2,3- (1- trifluoromethyl ethyl) succinic acid, two peopentyl ester of 2,3- myristyl succinic acid, 2,3- fluorenyl succinic acid Two peopentyl esters, two peopentyl ester of 2- isopropyl -3- isobutyl group succinic acid, two peopentyl ester of 2- tert-butyl -3- isopropyl succinic acid, 2- are different Two peopentyl ester of propyl -3- cyclohexyl succinic acid, two peopentyl ester of 2- isopentyl -3- cyclohexyl succinic acid, 2- myristyl -3- hexamethylene Two peopentyl ester of ylmethyl succinic acid, two peopentyl ester of 2- cyclohexyl -3- cyclopenta succinic acid.
It, can also it is preferable to use group R in the compound of formula (I)3~R6In several groups bond together to form the change of ring together Close object.As such compound, the compound enumerated in Japanese Unexamined Patent Application Publication 2002-542347, such as 1- (second can be enumerated Epoxide carbonyl) -1- (Ethoxyacetyl base) -2,6- dimethyl cyclohexane, 1- (ethoxy carbonyl) -1- (Ethoxyacetyl base) - 2,5- dimethylcyclopentane, 1- (ethoxy carbonyl) -1- (Ethoxyacetylmethyl) -2- hexahydrotoluene, 1- (ethyoxyl carbonyl Base) -1- (ethyoxyl (cyclohexyl) acetyl group) hexamethylene.It in addition to this, such as can also it is preferable to use International Publication No. 2009/ 3,6- dimethyl cyclohexane -1,2- dioctyl phthalate diisobutyl ester, hexamethylene -1,2- dioctyl phthalate diisobutyl ester disclosed in 069483 etc. Cyclic annular succinate compound.As the example of other cyclic annular succinate compounds, it is also preferred that International Publication 2009/057747 Compound disclosed in number.
In the compound of formula (I), group R3~R6Comprising in heteroatomic situation, hetero atom preferably comprise nitrogen-atoms and 15th race's atom of phosphorus atoms or the 16th race's atom including oxygen atom and sulphur atom.As group R3~R6Include the 15th race original The compound of son, can enumerate compound disclosed in Japanese Unexamined Patent Publication 2005-306910.On the other hand, as group R3~R6 Compound comprising the 16th race's atom can enumerate compound disclosed in Japanese Unexamined Patent Publication 2004-131537.
In addition to this, it can also share and provide the inside electron of same molecular weight distribution with succinate based compound Body.As such internal electron donor, for example, the diphenyl recorded in Japanese Unexamined Patent Publication 2013-28704 bulletin Cyclohexene dicarboxylic acid ester, the Japanese Unexamined Patent Publication No. 2013-28705 number recorded in dicarboxylic ester, Japanese Unexamined Patent Publication 2014-201602 bulletin It is the bicyclic alkyl dicarboxylic ester recorded in bulletin, the dibenzoic acid diol ester recorded in Japanese Patent No. 4959920, international public Open the 1,2- phenylene dibenzoate recorded in the 2010/078494th.
2) organo-aluminum compound (ingredient B)
As the organo-aluminum compound of ingredient (B), compound below can be enumerated.
The trialkylaluminiums such as triethyl aluminum, tri-butyl aluminum；
The trialkenyl aluminium of three isopentene group aluminium etc；
The dialkyl group aluminum alkoxides such as diethylaluminum ethoxide, dibutyl butoxy aluminium；
The alkyl sesquialter aluminum alkoxides such as ethyl sesquialter aluminum ethoxide, butyl sesquialter butoxy aluminium；
The alkyl dihalides aluminium of ethylaluminum dichloride, propyl al dichloride, butyl aluminum dibromide or the like etc. is partially halogenated Alkyl aluminum；
The dialkyl group aluminum hydride such as diethylaluminum hydride, dibutyl aluminum hydride；
The partially hydrogenated alkyl aluminums such as the alkyl aluminum dihydrides such as ethyl dihydroaluminium, propyl aluminum dihydride；
Parts alkoxylate and the halogen such as ethyl ethyoxyl aluminium chloride, butyl butoxy aluminium chloride, ethyl ethyoxyl aluminium bromide The alkyl aluminum of change.
3) electron donor compound (ingredient C)
The electron donor compound of ingredient (C) is commonly known as " external electron donor ".As such electron donor Close object, preferably organo-silicon compound.As preferred organo-silicon compound, compound below can be enumerated.
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon Alkane, diisopropyl dimethoxy silane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl Methyldiethoxysilane, dimethoxydiphenylsilane, phenyl methyl dimethoxysilane, diphenyl diethoxy silane, Double o-tolyl dimethoxysilanes, it is double between tolyl dimethoxysilane, double p-methylphenyl dimethoxysilanes, double to toluene Base diethoxy silane, double ethylphenyl dimethoxysilanes, dicyclopentyl dimethoxyl silane, dicyclohexyl dimethoxy silicon Alkane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl methyl diethoxy silane, ethyl trimethoxy silane, three ethoxy of ethyl Base silane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyl triethoxysilane, decyl trimethoxy silicon Alkane, ruthenium triethoxysilane, phenyltrimethoxysila,e, γ-r-chloropropyl trimethoxyl silane, methyltriethoxysilane, Ethyl triethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, hexyl trimethoxysilane, positive fourth Ethyl triethoxy silicane alkane, isobutyl triethoxy silane, phenyl triethoxysilane, γ aminopropyltriethoxy silane, chlorine Triethoxysilane, three isopropoxy silane of ethyl, vinyltributoxysilane, cyclohexyl trimethoxy silane, cyclohexyl Triethoxysilane, 2- norbornane trimethoxy silane, 2- norbornane triethoxysilane, 2- norbornane methyl dimethoxy Oxysilane, silester, butyl silicate, trimethyl phenoxysilane, methyl triolefin the npropoxysilane, (β-first of vinyl three Oxygroup Ethoxysilane), vinyltriacetoxy silane, dimethyl tetraethoxy disiloxane.
Wherein preferred ethyl triethoxysilane, n-propyl triethoxysilane, n-propyl trimethoxy silane, tert-butyl Triethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, t-butylethyl dimethoxy It is silane, tert-butyl propyldimethoxy-silane, tert-butyl tert-butoxy dimethoxysilane, tert-butyl trimethoxy silane, different Butyl trimethoxy silane, isobutyl methyl dimethoxysilane, isobutyl group sec-butyidimethoxysilane, (perhydro is different for ethyl Quinoline -2- base) dimethoxysilane, bis- (Decahydroisoquinolinpreparation -2- base) dimethoxysilanes, three (isopropyl alkenyloxy group) phenyl silicon Alkane, hexyl trimethoxysilane, vinyltriethoxysilane, phenyl triethoxysilane, phenyltrimethoxysila,e, ethylene Three butoxy silane of base, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, Isobutyl group isopropyl dimethoxysilane, cyclopenta tert-butoxy dimethoxysilane, dicyclopentyl dimethoxyl silane, hexamethylene Ylmethyl dimethoxysilane, cyclohexyl isobutyl group dimethoxysilane, cyclopenta isobutyl group dimethoxysilane, cyclopenta are different Propyldimethoxy-silane, di-sec-butyl dimethoxysilane, diethylamino triethoxysilane, tetraethoxysilane, four It is methoxy silane, isobutyl triethoxy silane, phenyl methyl dimethoxysilane, phenyl triethoxysilane, double to toluene Base dimethoxysilane, p-methylphenyl methyl dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-ethyl dimethoxy Base silane, 2- norbornane triethoxysilane, 2- norbornane methyl dimethoxysilane, diphenyl diethoxy silane, Methyl (3,3,3- trifluoro propyl) dimethoxysilane, silester etc..
4) it polymerize
Starting monomer is set to contact the catalyst prepared as described above and be polymerize.At this point, being urged first it is preferable to use above-mentioned Agent carries out prepolymerization.Prepolymerization refers to be formed on solid catalyst component after beginning for formally polymerizeing of starting monomer Polymer chain process.Prepolymerization can use well known method and carry out.Prepolymerization is usually at 40 DEG C or less, preferably at 30 DEG C Below, it is more preferably carried out at 20 DEG C or less.
Then, it will be imported in polymerization reaction system through pre-polymerized catalyst, and carry out the formal polymerization of starting monomer.Formally It is preferable to use 2 or more reactors to polymerize the starting monomer of the starting monomer of ingredient (1) and ingredient (2) for polymerization.It is poly- Close to implement in the liquid phase, in gas phase or in liquid-gas phase.Polymerization temperature is preferably room temperature~150 DEG C, more preferably 40 DEG C~ 100℃.About polymerization pressure, in the case where carrying out in the liquid phase, the preferably range of 3.3MPa~6.0MPa, in the gas phase into It is the range of 0.5MPa~3.0MPa in the case where row.Also chain-transferring agent (such as hydrogen or ZnEt can be used2) etc. in the field Known usual molecular weight regulator.
Alternatively, it is also possible to use monomer concentration or polymerizing condition that there is the polymerizer of gradient.In this polymerizer, such as Monomer, is polymerize by the polymerizer that the connection of at least two zone of convergency can be used by gas-phase polymerization.Specifically, urging In the presence of agent, it is polymerize using the zone of convergency supply monomer comprising tedge, utilizes the decline connecting with tedge Pipe supply monomer is polymerize, and is on one side recycled tedge and down-comer, is recycled polymer product on one side.This method has Comprehensively or it is partially prevented from the unit that the admixture of gas being present in tedge enters down-comer.In addition, will have and deposit The gas and/or liquid mixture for being the admixture of gas difference composition in tedge are imported into down-comer.As above-mentioned Polymerization, such as can be using the method recorded in Japanese Unexamined Patent Application Publication 2002-520426 bulletin.
2. polypropylene resin composite
Polypropylene resin composite of the invention in above-mentioned concentrate composition by mixing and above-mentioned concentrate composition At least one of the different elastomer of ingredient (2) or the polypropylene-based resin different from the concentrate composition and obtain.Elasticity The total amount of body and the polypropylene-based resin different from the concentrate composition in polypropylene resin composite be preferably 5 weight %~ 40 weight %, more preferably 5 weight of weight %~30 %.
(1) elastomer
Elastomer is flexible polymer, primarily to improving the impact resistance of composition and adding.As Elastomer used in the present invention can enumerate the copolymer of ethylene and alpha-olefin.As alpha-olefin, carbon atom number can be enumerated For 3~12 alpha-olefin, specifically, it is preferable that propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene etc..Elastomer preferably has There is density more lower than the polymer of ingredient (1) and ingredient (2).Such as the density of elastomer does not limit, preferably 0.850g/ cm3~0.890g/cm3, more preferably 0.860g/cm3~0.880g/cm3.Such elastomer such as can be such as Japanese Unexamined Patent Publication It using homogeneous catalysts such as metallocene or semi-metallocenes prepared by monomer polymerization as being recorded in No. 2015-113363.Bullet Property body MFR preferably 0.1g/10 minutes~50g/10 minutes under 190 DEG C, the load of 21.6N.
(2) polypropylene-based resin different from concentrate composition
The polypropylene-based resin different from concentrate composition is the mobility, rigidity, impact resistance in order to improve composition Property etc. and add.As the polypropylene-based resin different from concentrate composition, Noblen can be enumerated, comprise more than 0 It is weight % and the random copolymer of propylene of 5 weight % ethylene below or more than one C4~C10- alpha-olefin, poly- in propylene In the presence of conjunction object (also referred to as by polyblend obtained from ethylene and more than one C3~C10- alpha-olefin polymerization HECO).Concentrate composition of the invention is also one kind of HECO, and the HECO being added in concentrate composition also can use and mother The identical method of feed composition is manufactured, but the two is different in composition.
(3) filler
Polypropylene resin composite of the invention may include filler.Filler is primarily to improve the rigidity of material And add.As filler, for example, the inorganic fills such as talcum, clay, calcium carbonate, magnesium hydroxide, glass fibre The organic fillers such as agent, carbon fiber, cellulose fibre.In order to improve the dispersibility of these fillers, can carry out as needed The preparation of the masterbatch of the surface treatment of filler or filler and resin.In filler, due to being easy to be mixed into propylene (total) In the copolymer of polymer and ethylene and alpha-olefin, it is easy to improve the rigidity of formed body, thus preferably talc.In acrylic resin In composition, the amount of filler is preferably greater than 5 weight % and is 40 weight % hereinafter, more preferably 10 weights of weight %~35 Measure %.
(4) other compositions
It is steady that antioxidant, chlorine absorbent, heat-resisting stabilizing agent, light can be added in polypropylene resin composite of the invention Determine agent, ultraviolet absorbing agent, internal lubricant, exterior lubricant, antiblocking agent, antistatic agent, antifoggant, crystallization nucleating agent, Fire retardant, dispersing agent, copper deactivator, neutralizer, plasticizer, gas-tight infusion, crosslinking agent, peroxide, oil-filled dose and other have Machine and inorganic pigment etc. are commonly used in the usual additive of olefin polymer.The additive amount of each additive can be well known Amount.
(5) manufacturing method
Polypropylene resin composite of the invention can carry out melting mixing to mentioned component and manufacture.Mixing method does not have Limit the method, it is preferable to use the kneading machines such as extruder.Compounding conditions are not particularly limited, are preferably set as barrel temperature 180 DEG C~250 DEG C.The obtained polypropylene resin composite is preferably granular.Alternatively, being measured in injection (mo(u)lding) machine above-mentioned The dry-blend of ingredient is simultaneously kneaded at melting mixing portion (barrel), and acrylic resin combination is thus produced as molded product Object.In this way, polypropylene resin composite of the invention is obtained and mixing concentrate composition with other compositions.About poly- third The phase structure of olefine resin composition, it is believed that divided in the Noblen matrix as main component from concentrate composition Dissipate have propylene-ethylene copolymers ingredient from concentrate composition and elastomer (depending on the situation, for from masterbatch group Close the ethylene of the different HECO of object and the copolymer of alpha-olefin) structure can be played of the invention by forming the phase structure Effect.
(6) it is injection moulded
Concentrate composition and polypropylene resin composite of the invention is suitable for being injection moulded.Acrylic resin of the invention Composition has high rigidity, high-impact, low linear expansion coefficient, therefore is suitable for automobile component.Common injecting condition is 200 DEG C~230 DEG C of barrel temperature, 20 DEG C~50 DEG C of mold temperature, injection speed 30mm/ seconds~50mm/ seconds.
Embodiment
1. concentrate composition
[embodiment 1]
Following manufacture concentrate composition, the concentrate composition include 65.5 weight of polypropylene homopolymer as ingredient (1) The % and 34.5 weight % of propylene-ethylene copolymers as ingredient (2) is measured, which has 65.7 weight % Ethylene-derived units.
According to the preparation method recorded in Japanese Unexamined Patent Publication 2011-500907 embodiment, solid catalyst component is prepared. Specifically, being prepared as follows.
At 0 DEG C, the TiCl of 250mL is imported in the 500mL four round flask that Xiang Liyong nitrogen is purged4.One Side stirring, is added the fine spherical MgCl of 10.0g on one side2·1.8C2H5OH is (according to the embodiment 2 of United States Patent (USP) 4,399,054 The method of middle record, but replace 10000rpm and manufactured with 3000rpm operating) and 9.1 mMs of 2,3- (two Isopropyl) diethyl succinate.Temperature is risen to 100 DEG C, is kept for 120 minutes.Then, stop stirring, keep solid product heavy Supernatant is sucked out in drop.Then, it is repeated 2 times following operation: addition 250mL new TiCl4, mixture is made to react 60 points at 120 DEG C Supernatant is sucked out in clock.Solid is cleaned 6 times with anhydrous hexane (6 × 100mL) at 60 DEG C.
For above-mentioned solid catalyst, triethyl aluminum (TEAL) and dicyclopentyl dimethoxyl silane (DCPMS), with TEAL The amount that weight ratio relative to solid catalyst is 18, the weight ratio of TEAL/DCPMS is 10 makes it contact 5 points at room temperature Clock.Obtained caltalyst is tied up in liquid propene and is kept for 5 minutes with suspended state in 20 DEG C, prepolymerization is thus carried out.
Obtained prepolymer is imported into the liquid-phase polymerization device of first segment, Noblen is obtained, later will Obtained polymer is imported into the gas-phase polymerization reactor of second segment, carries out the poly- of copolymer (propylene-ethylene copolymers) It closes.In polymerization, temperature and pressure is adjusted, uses hydrogen as molecular weight regulator.About the ratio of polymerization temperature and reactant, In the reactor of first segment, polymerization temperature, hydrogen concentration are respectively 70 DEG C, 0.31 mole of %, in the reactor of second segment, are gathered Close temperature, H2/C2, C2/ (C2+C3) are respectively 80 DEG C, 0.16 molar ratio, 0.69 molar ratio.In addition, according to copolymer composition Measure the residence time destribution that the mode in 100 parts by weight of polymer for 34.5 parts by weight has adjusted first segment and second segment.
BASF AG B225 0.2 weight of the mixture as antioxidant in obtained 100 parts by weight of polyacrylic polymer Measure part, as neutralizer light southern Chemical Co., Ltd. manufacture 0.05 parts by weight of calcium stearate, stirred using Henschel mixer After mixing, mixing 1 minute, double screw extruder (Co., Ltd. Technovel manufacture, model that screw diameter is 15mm are utilized KZW15TW-30MG it) with 200 DEG C of progress melting mixings of barrel temperature and squeezes out.After strands are cooled down in water, pelletizer is utilized It is cut, obtains particle.Then, injection (mo(u)lding) machine (manufacture of FANUC company, model roboshot S-2000i are utilized The particle 100B) is injection molded into various test films.Condition of molding is 200 DEG C of barrel temperature, 40 DEG C of mold temperature, injection speed Degree 200mm/ seconds.Various physical property are evaluated using test film.Evaluation method is as described later.
[embodiment 2]
The hydrogen concentration of the reactor of first segment is set as 0.28 mole of %, by H2/C2, C2/ (C2 of the reactor of second segment + C3) it is set to 0.22 molar ratio, 0.59 molar ratio, it is 32.9 in 100 parts by weight of polymer according to the amount of copolymer composition The mode of parts by weight is adjusted the residence time destribution of first segment and second segment, makes similarly to Example 1 in addition to this Make polyacrylic polymer.Using the polyacrylic polymer, the concentrate composition of this example and progress are manufactured similarly to Example 1 Evaluation.
[embodiment 3]
Talcum is further added in the polyacrylic polymer obtained in example 2, in addition to this similarly to Example 1 Melting mixing prepares particle, and is evaluated.Talcum (manufacture of trade name HTP05L, IMI Fabi company) is relative to polymer The blend amount of 100 parts by weight is 1 parts by weight.
[comparative example 1]
The method recorded in embodiment 5 by No. 728769 bulletins of European Patent No. prepares solid catalyst, the solid Catalyst is in MgCl2Upper load has Ti and the diisobutyl phthalate as internal donor.Then, it is urged using above-mentioned solid Agent, as the triethyl aluminum (TEAL) of organo-aluminum compound and as the bicyclopentyl diformazan of external electron donor compound Oxysilane (DCPMS), according to TEAL relative to the weight ratio of solid catalyst be 20, the weight ratio of TEAL/DCPMS is 10 Amount contacts it 24 minutes.Obtained caltalyst is tied up in liquid propene and is kept with suspended state in 20 DEG C 5 minutes, thus carry out prepolymerization.
Using obtained prepolymer, Noblen is manufactured by multi-stage polymeric using two liquid-phase polymerization devices. The hydrogen concentration of first polymer reactor is set as 0.16 mole of %, the hydrogen concentration of second polymer reactor is set as 1.70 and is rubbed You are %, with 70 DEG C of adjustment polymerization pressures of polymerization temperature, carries out in such a way that respective ratio is 50:50 to residence time destribution Adjustment.
Then, obtained Noblen is imported into gas-phase polymerization reactor, is total to similarly to Example 1 The polymerization of polymers (propylene-ethylene copolymers).In polymerization, temperature and pressure is adjusted, uses hydrogen as molecular weight regulator.? In the reactor of second segment, polymerization temperature, H2/C2, C2/ (C2+C3) are respectively 80 DEG C, 0.12 molar ratio, 0.68 molar ratio.Separately Outside, by the amount of copolymer composition in 100 parts by weight of polymer in the way of 30.0 parts by weight to first segment and second segment Residence time destribution is adjusted.
Using the obtained polyacrylic polymer, manufacture is compared with concentrate composition and is carried out similarly to Example 1 Evaluation.
[comparative example 2]
Talcum is further added in the polyacrylic polymer obtained in comparative example 1, in addition to this similarly to Example 1 Melting mixing prepares particle, and is evaluated.Talcum (manufacture of trade name HTP05L, IMI Fabi company) is relative to polymer The blend amount of 100 parts by weight is 1 parts by weight.
[comparative example 3]
The hydrogen concentration of the reactor of first segment is set as 0.44 mole of %, by the hydrogen concentration of the reactor of second segment, C2/ (C2+C3) 2.04 moles of %, 0.37 molar ratio are set to, are in 100 parts by weight of polymer according to the amount of copolymer composition The mode of 35.6 parts by weight is adjusted the residence time destribution of first segment and second segment, in addition to this similarly to Example 1 Ground manufactures polyacrylic polymer.Using the obtained polyacrylic polymer, manufacture is compared with masterbatch group similarly to Example 1 It closes object and is evaluated.
[comparative example 4]
Using pre-polymerized catalyst same as Example 1, in the reactor of first segment, by polymerization temperature, hydrogen concentration It is set to 70 DEG C, 0.29 mole of %, manufactures Noblen, after being purged to unreacted monomer class, to the poly- of second segment It closes and imports ethylene in reactor, manufacture Alathon.The polymerization temperature of the reactor of second segment, H2/C2 are set to 80 DEG C, 0.16 molar ratio, adjust pressure, according to the amount of Alathon in 100 parts by weight of polymer be 29.8 parts by weight side Formula is adjusted the residence time destribution of first segment and second segment, obtains polyacrylic polymer.Using the polymer, except this with It manufactures the concentrate composition compared similarly to Example 1 outside and is evaluated.
[comparative example 5]
The hydrogen concentration of the reactor of first segment is set as 0.34 mole of %, by the hydrogen concentration of the reactor of second segment, C2/ (C2+C3) 4.13 moles of %, 0.19 molar ratio are set to, are in 100 parts by weight of polymer according to the amount of copolymer composition The mode of 31.5 parts by weight is adjusted the residence time destribution of first segment and second segment, in addition to this similarly to Example 1 Ground manufactures polyacrylic polymer.Using the obtained polyacrylic polymer, manufacture is compared with masterbatch group similarly to Example 1 It closes object and is evaluated.
[comparative example 6]
Using the pre-polymerized catalyst of comparative example 1, the hydrogen concentration of first liquid-phase polymerization device is set as 0.73 and is rubbed You are %, the hydrogen concentration of second liquid-phase polymerization device is set as 3.46 moles of %, by H2/C2, C2/ of gas-phase polymerization reactor (C2+C3) it is set to 0.12 molar ratio, 0.68 molar ratio, is in 100 parts by weight of polymer according to the amount of copolymer composition The mode of 49.0 parts by weight is adjusted the residence time destribution of Liquid-phase reactor and gas-phase reactor, manufactures polypropylene polymerization Object.Using the obtained polyacrylic polymer, manufacture is compared with concentrate composition and is evaluated similarly to Example 1.
[comparative example 7]
The hydrogen concentration of the liquid-phase polymerization device of first segment is set as 1.86 moles of %, according to the amount of copolymer composition poly- It closes in 100 parts by weight of object and the residence time destribution of Liquid-phase reactor and gas-phase reactor is adjusted for the mode of 37.0 parts by weight It is whole, polyacrylic polymer is manufactured in the same manner as comparative example 6 in addition to this.Using the obtained polyacrylic polymer, with implementation Example 1, which similarly manufactures, to be compared with concentrate composition and is evaluated.
Result above is shown in table 1.
2. polypropylene resin composite
[embodiment 4]
The hydrogen concentration of the reactor of first segment is set as 0.59 mole of %, according to the amount of copolymer composition in polymer 100 The residence time destribution of first segment and second segment is adjusted for the modes of 30.7 parts by weight in parts by weight, in addition to this with reality It applies example 1 and similarly manufactures polyacrylic polymer.Then, using the polyacrylic polymer, masterbatch group is manufactured similarly to Example 1 Close object.For the concentrate composition, talcum (manufacture of trade name HTP05L, IMI Fabi company) and elastomer (trade name Engage8200, the manufacture of Dow Chemical company), melting mixing, prepares particle similarly to Example 1.Then, with implementation Example 1 similarly evaluates the polypropylene resin composite.
[embodiment 5]
The hydrogen concentration of the reactor of first segment is set as 0.59 mole of %, by H2/C2, C2/ (C2 of the reactor of second segment + C3) it is set to 0.14 molar ratio, 0.56 molar ratio, it is 29.5 in 100 parts by weight of polymer according to the amount of copolymer composition The mode of parts by weight is adjusted the residence time destribution of first segment and second segment, makes similarly to Example 1 in addition to this Make polyacrylic polymer.Then, using the polyacrylic polymer, polypropylene resin composite is manufactured simultaneously similarly to Example 4 It is evaluated.
[embodiment 6]
The hydrogen concentration of the reactor of first segment is set as 0.59 mole of %, by H2/C2, C2/ (C2 of the reactor of second segment + C3) it is set to 0.12 mole of %, 0.59 molar ratio, it is 32.3 in 100 parts by weight of polymer according to the amount of copolymer composition The mode of parts by weight is adjusted the residence time destribution of first segment and second segment, makes similarly to Example 1 in addition to this Make polyacrylic polymer.Then, using the polyacrylic polymer, the content of concentrate composition and talcum is changed as shown in table 2, is removed Polypropylene resin composite is manufactured other than this similarly to Example 4 and is evaluated.
[embodiment 7]
The hydrogen concentration of the reactor of first segment is set as 0.39 mole of %, according to the amount of copolymer composition in polymer 100 The residence time destribution of first segment and second segment is adjusted for the modes of 37.5 parts by weight in parts by weight, in addition to this with reality It applies example 4 and similarly manufactures polyacrylic polymer.Then, using the polyacrylic polymer, with the mixed masterbatch composition of amount shown in table 2 Object, talcum and MFR are the Noblen that the xylene soluble components at 1750g/10 minutes, 25 DEG C are 2.3 weight %, remove this It manufactures polypropylene resin composite similarly to Example 4 in addition and is evaluated.
[comparative example 8]
Using the pre-polymerized catalyst of comparative example 1, the hydrogen concentration of first liquid-phase polymerization device is set as 0.68 and is rubbed You are %, the hydrogen concentration of second liquid-phase polymerization device is set as 3.46 moles of %, by H2/C2, C2/ of gas-phase polymerization reactor (C2+C3) it is set to 0.08 molar ratio, 0.68 molar ratio, is in 100 parts by weight of polymer according to the amount of copolymer composition The mode of 26.8 parts by weight is adjusted the residence time destribution of Liquid-phase reactor and gas-phase reactor, manufactures polypropylene polymerization Object.Then, using the polyacrylic polymer, manufacture is compared with polypropylene resin composite and is commented similarly to Example 4 Valence.
[comparative example 9]
Using the pre-polymerized catalyst of comparative example 1, the hydrogen concentration of the polymer reactor of first segment is set as 1.44 moles of %, The hydrogen concentration of the polymer reactor of second segment, C2/ (C2+C3) are set to 1.75 moles of %, 0.22 molar ratio, according to copolymerization Stop of mode of the amount of object ingredient in 100 parts by weight of polymer for 26.4 parts by weight to Liquid-phase reactor and gas-phase reactor Annual distribution is adjusted, and manufactures polyacrylic polymer.Then, it using the polyacrylic polymer, manufactures similarly to Example 4 Compare with polypropylene resin composite and is evaluated.
[comparative example 10]
The hydrogen concentration of first liquid-phase polymerization device is set as 0.42 mole of %, the amount according to copolymer composition is polymerizeing The residence time destribution of Liquid-phase reactor and gas-phase reactor is adjusted for the mode of 28.0 parts by weight in 100 parts by weight of object It is whole, using obtained polymer, polyacrylic polymer is manufactured in the same manner as comparative example 8 in addition to this.Then, using this poly- third The blend amount of concentrate composition and talcum is changed to amount identical with embodiment 6 shown in table 2, in addition to this by alkene polymer Manufacture is compared with polypropylene resin composite and is evaluated similarly to Example 4.
Result above is shown in table 2.
3. evaluation method
[MFR]
According to JIS K 7210, it is measured under conditions of 230 DEG C, load 21.18N.
[amount of the ethylene concentration and copolymer in copolymer in concentrate composition]
About being dissolved in 1, the sample of 2,4- trichloro-benzenes/deuterated benzene in the mixed solvent is manufactured using Bruker company AVANCEIII HD400(13C resonant frequency 100MHz), in 120 DEG C of measuring temperature, 45 degree of flip angle, 7 seconds pulse spacings, sample Revolving speed 20Hz, it obtains under conditions of integral number of times 5000 times13The spectrum of C-NMR.
<total ethylene volume in concentrate composition>
Using spectrum obtained above, according to Kakugo, Y.Naito, K.Mizunuma and T.Miyatake, Macromolecules, 15, the method recorded in the document of 1150-1152 (1982) find out total ethylene volume of concentrate composition (weight %).
<ethylene concentration in copolymer (ingredient (2))>
Instead of the integrated intensity of T β β obtained above using the integrated intensity found out by following formula, utilize in addition to this Method identical with total ethylene volume is calculated, and the ethylene concentration in copolymer is found out.
β=0.98 T ' β × S α γ × A/ (1-0.98 × A)
Herein, A=S α γ/(S α γ+S α δ).
<amount of the copolymer (ingredient 2) in concentrate composition>
It is found out by following formula.
The amount (weight %) of ingredient (2)=total ethylene volume/(ethylene concentration/100 in copolymer)
[acquirements of xylene soluble components]
Polymer 2.5g is added in the flask equipped with ortho-xylene (solvent) 250mL, is filled using heating plate and reflux It sets, in 135 DEG C of progress nitrogen purgings, while stirring 30 minutes, after being completely dissolved composition, carried out at 25 DEG C 1 hour It is cooling.Obtained solution is filtered using filter paper.Filtrate 100mL after acquisition filter, moves in aluminium cup etc., on one side into Row nitrogen purging is evaporated at 140 DEG C on one side, is allowed to stand at room temperature for 30 minutes, is obtained xylene soluble components (XS).
[XSIV]
Using above-mentioned xylene soluble components as sample, Ubbelohde viscometer (SS-780-H1, bavin mountain instruments for scientific research system are used Manufactured by work) in 135 DEG C of naphthanes carry out inherent viscosity (IV) measurement.
Wherein, it there's almost no in the Alathon of the ingredient (2) of the concentrate composition of comparative example 4 and dissolve in dimethylbenzene Ingredient, therefore using the IV of the ratio of ingredient (2), concentrate composition entirety estimated by the ethylene contents of concentrate composition, The value of the IV of ingredient (1), it is assumed that the additivity of IV calculates the IV of ingredient (2).
[acquirement of dimethylbenzene indissolvable component]
When paraxylene soluble constituent as described above is filtered, to the residue remained on filter paper, (dimethylbenzene is insoluble The mixture of ingredient and solvent) acetone is added and is filtered, later by the ingredient not the filtered vacuum for being set as 80 DEG C Drying oven is evaporated, and obtains dimethylbenzene indissolvable component (XI).
[Mw and Mw/Mn of dimethylbenzene indissolvable component]
Using above-mentioned dimethylbenzene indissolvable component as sample, weight average molecular weight (Mw) and molecular weight distribution (Mw/ are carried out as follows Mn measurement).
The PL GPC220 for using Polymer Laboratories company to manufacture will include antioxidant as device 1,2,4- trichloro-benzenes is as mobile phase, the UT-G (1) manufactured using Showa Denko K. K, UT-807 (1), UT- The column that 806M (2) is connected in series is counted as column using differential refraction rate as detector.In addition, as dimethylbenzene insoluble group The solvent of the sample solution divided, using solvent identical with mobile phase, with the sample solution concentration of 1mg/mL one at a temperature of 150 DEG C Side oscillation is dissolved 2 hours on one side, prepares measurement sample.Thus obtained 500 μ L of sample solution is injected in column, with flow velocity 1.0mL/ minutes, 145 DEG C of temperature, be measured within data acquisition interval 1 second.The correction of column is 580~7,450,000 using molecular weight Polystyrene standard samples (shodex STANDARD, Showa Denko K. K's manufacture), are carried out using cubic expression tertiary approximation.It is right In the coefficient of Mark-Houkins, polystyrene standard samples use K=1.21 × 10-4, α=0.707, polypropylene-based polymer Use K=1.37 × 10-4, α=0.75.
[bending modulus]
Bend test is carried out under room temperature (23 DEG C) according to JIS K6921-2.It was surveyed with crosshead speed 2mm/ minutes It is fixed.
[charpy impact intensity]
Machining is carried out to obtained acrylic resin formed body (evaluation of physical property test film), for obtained Test film (80 (length) × 10 (width) × 4 (thickness) mm3), 23 DEG C and -30 DEG C of charpy impact intensity is measured according to ISO179-1.
[linear expansion coefficient]
By the central part (wide 10mm) of obtained acrylic resin formed body (evaluation of physical property test film, thickness 4mm) It is cut into the length of 10mm along the flow direction (MD) of resin, is placed 24 hours in 80 DEG C of baking oven, by obtained object Matter is measured as sample according to JIS K7197.
<experimental rig>Ulvac MTS9000 (manufacture of vacuum science and engineering)
<experimental condition>heating rate: 5 DEG C/min
Load: 5.0g weight
Measuring temperature: -30 DEG C~80 DEG C
Known to: concentrate composition of the invention has low linear expansion coefficient, high rigidity, high-impact.Furthermore known to: making The polypropylene resin composite manufactured with concentrate composition also has low linear expansion coefficient, high rigidity, high-impact.

Claims (8)

1. a kind of concentrate composition, described to urge to make concentrate composition obtained from propylene and vinyl polymerization using catalyst Agent includes:
(A) contain magnesium, titanium, halogen and the electron donor compound in succinate based compound as neccessary composition Solid catalyst；
(B) organo-aluminum compound；And
(C) external electron donor compound,
The concentrate composition includes:
As ingredient (1) Noblen and
As the propylene-ethylene copolymers of ingredient (2), which includes the second of 55 weight of weight %~80 % Alkene derived units,
Ingredient (1): the weight ratio of (2) is 85~60:15~40,
The concentrate composition meets condition below:
1) the dimethylbenzene indissolvable component of the composition is 6~20 using the Mw/Mn that GPC is measured；
2) inherent viscosity of the xylene soluble components of the composition is 1dl/g~3dl/g；
3) 230 DEG C of the composition, the melt flow rate (MFR) under the conditions of load 21.18N be 1g/10 minutes~50g/10 minutes.
2. concentrate composition as described in claim 1, wherein the ethylene of the propylene-ethylene copolymers in the ingredient (2) spreads out Raw unit is 60 weight of weight %~75 %.
3. concentrate composition as claimed in claim 1 or 2, wherein the ingredient (1): the weight ratio of (2) is 75~60:25 ~40.
4. concentrate composition according to any one of claims 1 to 3, wherein the melt flow rate (MFR) is 10g/10 points Clock~35g/10 minutes.
5. concentrate composition as described in any one of claims 1 to 4, wherein relative to 100 parts by weight of composition, Include 0.01 parts by weight~5 parts by weight crystallization nucleating agent.
6. a kind of polypropylene resin composite, by being mixed in concentrate composition according to any one of claims 1 to 5 In the elastomer or the polypropylene-based resin different with the concentrate composition different from ingredient (2) of the concentrate composition At least one is formed.
7. a kind of polypropylene resin composite comprises more than 5 weight % and 40 weights in composition as claimed in claim 6 Measure % filler below.
8. a kind of injection-molded article, by the way that polypropylene resin composite described in claim 6 or 7 to be injection moulded.
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