CN111527141B - Soft polyolefin composition - Google Patents

Soft polyolefin composition Download PDF

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Publication number
CN111527141B
CN111527141B CN201780097476.3A CN201780097476A CN111527141B CN 111527141 B CN111527141 B CN 111527141B CN 201780097476 A CN201780097476 A CN 201780097476A CN 111527141 B CN111527141 B CN 111527141B
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polyolefin composition
ethylene
10min
propylene random
random copolymer
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CN111527141A (en
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陈世平
周信
黄荣才
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Borouge Compounding Shanghai Co ltd
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Borouge Compounding Shanghai Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Abstract

The present invention provides a polyolefin composition comprising a propylene random copolymer and an ethylene/a-olefin multiblock copolymer, an article comprising said polyolefin composition and the use of said polyolefin composition in the preparation of an article, preferably an injection molded article.

Description

Soft polyolefin composition
Technical Field
The present invention relates to a soft polyolefin composition having a high melt flow rate and balanced mechanical properties, to an article comprising said polyolefin composition and to the use of said polyolefin composition in the preparation of an article.
Background
Polypropylene is now the polymer of choice in many applications because polypropylene can be tailored to meet a variety of different uses. One major area of polypropylene application is the automotive industry, where various automotive parts (e.g., bumpers, door panels, dashboards or door coverings) are made of polypropylene.
In particular, thermoplastic polyolefin compounds made from propylene homopolymers or propylene block copolymers and polyolefin elastomers are very attractive materials in the field because they are capable of providing a highly desirable combination of mechanical stiffness and good impact properties. However, these thermoplastic polyolefin compounds have poor flowability due to poor compatibility between the polypropylene component and the polyolefin elastomer component.
However, high flowability and dimensional stability are required for specific applications in the automotive industry (e.g., spoilers).
To obtain higher flowability, the amount of polyolefin elastomer or propylene block copolymer can be reduced. However, this results in a thermoplastic polyolefin compound having poorer elasticity and impact properties. And these compounds have poor dimensional stability at high temperature and high humidity (i.e., dimensional stability against temperature-humidity cycles). Therefore, these thermoplastic polyolefin compounds are not suitable for producing soft spoilers.
Thus, there is a need for polyolefin compositions suitable for soft spoiler applications having high flowability, good dimensional stability at high temperatures and high humidity, and balanced mechanical properties.
Disclosure of Invention
The present invention relates to a polyolefin composition comprising:
(A) 15.0 to 45.0wt% of a propylene random copolymer having propylene monomer units and one or more comonomer units selected from ethylene and/or an alpha-olefin having 4 to 12 carbon atoms, the comonomer units being present in an amount of 1.0 to 6.0wt% based on the total amount of monomer units; and
(B) 55.0 to 85wt% of an ethylene/α -olefin multiblock copolymer having an ethylene monomer unit and one or more comonomer units selected from α -olefins having 4 to 12 carbon atoms, the ethylene/α -olefin multiblock copolymer having a melting temperature Tm of 90 to 130 ℃;
Wherein the melt flow rate MFR of the polyolefin composition 2 (230 ℃ C., 2.16 kg) is 16g/10min to 50g/10min, preferably 20g/10min to 40g/10min, most preferably 25g/10min to 35g/10min.
In another aspect, the present invention relates to an article comprising a polyolefin composition as described above or below, and the use of a polyolefin composition as described above or below in the preparation of an article.
Surprisingly, it has been found that the polyolefin compositions of the invention exhibit an improved balance of properties between high flowability, good dimensional stability at high temperatures and high humidity and balanced mechanical properties (in terms of flexural modulus and Charpy impact strength).
Definition of the definition
A polyolefin composition is a composition in which a majority of its weight is occupied by more than one polyolefin component. The polyolefin component preferably comprises at least 60wt% of the polyolefin composition, more preferably comprises from 75wt% to 100wt% of the polyolefin composition, and still more preferably comprises from 85wt% to 99wt% of the polyolefin composition, most preferably comprises from 90wt% to 98wt% of the polyolefin composition.
Propylene homopolymers are polymers consisting essentially of propylene monomer units. Due to impurities, especially impurities in industrial polymerization processes, the propylene homopolymer may comprise at most 0.1mol% of comonomer units, preferably at most 0.05mol% of comonomer units, most preferably at most 0.01mol% of comonomer units.
The propylene random copolymer is a copolymer of propylene monomer units and comonomer units, the comonomer units preferably being selected from ethylene and C 4 -C 12 Alpha-olefins in which comonomer units are randomly distributed on the polymeric chain. The propylene random copolymer may comprise comonomer units derived from more than one comonomer having different amounts of carbon atoms.
An ethylene/α -olefin multiblock copolymer is a copolymer comprising ethylene and one or more comonomer units selected from α -olefins having 4 to 12 carbon atoms, characterized in that the chemical or physical properties of the multiple blocks or segments of two or more polymerized monomer units are different. The term "ethylene/a-olefin multiblock copolymer" includes block copolymers having two blocks (diblock) and more than two blocks (multiblock).
The term "multimodal" or "bimodal" as used herein refers to the shape of the peak form (modifiability) of a polymer, i.e., its molecular weight distribution curve (which is a plot of molecular weight fraction as a function of its molecular weight).
Hereinafter, the amounts are given as weight% (wt%) unless otherwise indicated.
Detailed Description
Propylene random copolymer (A)
The propylene random copolymer (A) is a copolymer having propylene monomer units and one or more comonomer units selected from ethylene and C 4 -C 12 Alpha-olefins, the comonomer units being randomly distributed on the polymeric chain.
The comonomer units may be selected from two or three, preferably two, of the above-mentioned comonomer units.
Preferably, the comonomer unit is selected from one of the comonomer units described above.
Preferably, the comonomer units are selected from ethylene, 1-butene, 1-hexene and 1-octene, more preferably from ethylene, 1-butene and 1-hexene, most preferably from ethylene.
The propylene random copolymer (A) is preferably a propylene ethylene random copolymer.
The content of the comonomer units of the propylene random copolymer (A) is 1.0 to 6.0wt%, preferably 1.5 to 5.0wt%, most preferably 2.0 to 4.0wt%, based on the total amount of monomer units.
Preferably, the propylene random copolymer (A) has a density of 0.880g/cm 3 To 0.920g/cm 3 More preferably 0.890g/cm 3 To 0.915g/cm 3 Most preferably 0.895g/cm 3 To 0.912g/cm 3 。
Furthermore, the melt flow rate MFR of the propylene random copolymer (A) 2 (230 ℃ C., 2.16 kg) is preferably 1.0 to 80g/10min, more preferably 5.0 to 60g/10min, still more preferably 10 to 50g/10min, most preferably 20 to 40g/10min.
The flexural modulus of the propylene random copolymer (A) is preferably at least 900MPa, more preferably at least 1000MPa, and most preferably at least 1100MPa. The upper limit of the flexural modulus is generally not higher than 2000MPa, preferably not higher than 1750MPa, most preferably not higher than 1500MPa.
Furthermore, the random propylene copolymer (A) preferably has a Charpy notched impact strength at 23℃of at least 4.0kJ/m 2 More preferably at least 4.5kJ/m 2 Most preferably at least 5.0kJ/m 2 . The upper limit of the Charpy notched impact strength is usually not higher than 15kJ/m 2 Preferably not higher than 13kJ/m 2 Most preferably not higher than 10kJ/m 2 。
In a preferred embodiment, the propylene random copolymer (A) is alpha-nucleated. Alpha-nucleation is generally obtained by crystallizing the propylene random copolymer (A) in the presence of an alpha-nucleating agent. Alpha nucleating agents are well known in the art.
The α -nucleating propylene random copolymer (a) is not particularly limited, and the α -nucleating agent may be selected from among benzoates, phosphorus-based compounds, sorbitol derivatives, nonitol-based compounds, amide-based compounds, and vinyl-based compounds. .
Thus, the alpha nucleating agent is preferably selected from the group consisting of:
(i) Salts of monocarboxylic and polycarboxylic acids, e.g. sodium benzoate or aluminum tert-butylbenzoate, and
(ii) Dibenzylidene sorbitol (e.g., 1,3:2,4 dibenzylidene sorbitol) and C 1 -C 8 Alkyl-substituted dibenzylidene sorbitol derivatives, such as methyldibenzylidene sorbitol, ethyldibenzylidene sorbitol or dimethyldibenzylidene sorbitol (e.g., 1,3:2,4 bis (methylbenzylidene) sorbitol), or substituted noninitol derivatives, such as 1,2, 3-trideoxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene]Nonitol, and
(iii) Salts of phosphoric acid diesters, for example sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate or aluminum hydroxy-bis [2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ] and
(iv) Vinyl cycloalkane polymer and vinyl alkane polymer (described in detail below), and
(v) Mixtures thereof.
Such additives are generally commercially available and are described, for example, in Hans Zweifel, "Plastic Additives Handbook" (2001, 5 th edition) pages 871 to 873.
Preferably, the propylene random copolymer (a) comprises up to 5.0wt% of an alpha-nucleating agent. In a preferred embodiment, the propylene random copolymer (a) comprises no more than 5000ppm, more preferably from 1 to 5000ppm, more preferably from 5 to 3000ppm, of an α -nucleating agent, in particular selected from dibenzylidene sorbitol (e.g. 1,3:2,4 dibenzylidene sorbitol), dibenzylidene sorbitol derivatives (preferably dimethylbenzylidene sorbitol (e.g. 1,3:2,4 di (methylbenzylidene) sorbitol)) or substituted nonitol derivatives (e.g. 1,2, 3-trideoxy-4, 6:5, 7-bis-O- [ (4-propylphenyl) methylene ] -noniol), vinyl cycloalkane polymers, vinyl alkane polymers and mixtures thereof.
The propylene random copolymer (a) may be unimodal (i.e. have only one distinct peak in the molecular weight distribution curve) or may be multimodal (e.g. bimodal).
The propylene random copolymer is preferably multimodal, more preferably bimodal.
The propylene random copolymer (a) is preferably produced in a polymerization process using at least one polymerization reactor.
In one embodiment, the propylene random copolymer (a) is polymerized in a single polymerization reactor. In this embodiment, the propylene random copolymer (A) is unimodal.
In another embodiment, the propylene random copolymer (a) is polymerized in a multistage process (multistage process) known in the art, wherein different propylene random copolymer (a) fractions (fractions) are polymerized in different polymerization reactors connected in series.
The multistage process may be carried out in two, three, four or more polymerization reactors connected in series. Thus, preferably, the multistage process is carried out in two polymerization reactors, optionally with a prepolymerization reactor preceding the two polymerization reactors.
The polymerization reactor is typically selected from slurry reactors (slurry reactors) and gas phase reactors such as fluidized bed reactors.
First reactor (1) st R') is preferably a Slurry Reactor (SR) and may be any continuous or simply stirred batch tank reactor or loop reactor operating in bulk or slurry. Bulk means polymerized in a reaction medium comprising at least 60% (w/w) monomer. According to the invention, the Slurry Reactor (SR) is preferably a Loop Reactor (LR).
Second reactor (2) nd R'), a third reactor (3) rd R') and a fourth reactor (4) th R') is preferably a Gas Phase Reactor (GPR). Such a Gas Phase Reactor (GPR) may be any mechanically mixed or fluidized bed reactor. Preferably, the Gas Phase Reactor (GPR) comprises a mechanically stirred fluidized bed reactor with a gas velocity of at least 0.2 m/s. Thus, preferably, the gas phase reactor is a fluidized bed type reactor, preferably with a mechanical stirrer.
Thus, in a preferred embodiment, the first reactor (1 st R') is a Slurry Reactor (SR), such as a Loop Reactor (LR), while the second reactor (2 nd R') and optionally a third reactor (3) rd R') and a fourth reactor (4) th R') is a Gas Phase Reactor (GPR). Thus, for the process of the present invention, at least two polymerization reactors (i.e. Slurry Reactor (SR) (e.g. Loop Reactor (LR)), a first gas phase reactor (GPR-1) and optionally a second gas phase reactor (GPR-2) and a third gas phase reactor (GPR-3)) are used, preferably a Slurry Reactor (SR) (e.g. Loop Reactor (LR)) and only one first gas phase reactor (GPR-1) are used, which are connected in series. If necessary, in a slurry reactor (S R) a prepolymerization reactor was placed before.
Preferred multistage processes are, for example, "loop-gas phase" processes developed by the Danish Borealis A/S (known asTechnology) is described, for example, in patent documents EP 0 887 379, WO92/12182, WO2004/000899, WO2004/111095, WO99/24478, WO99/24479 or WO 00/68315.
Another suitable slurry-gas phase process is BasellAnd (3) processing.
Preferably, in the process for producing a propylene random copolymer (A) of the present invention, as described above, it is used in the first reactor (1 st R') (i.e., slurry Reactor (SR), such as Loop Reactor (LR)) may be as follows:
-a temperature of 40 ℃ to 110 ℃, preferably 60 ℃ to 100 ℃, e.g. 68 ℃ to 95 ℃;
the pressure is 20 bar to 80 bar, preferably 40 bar to 70 bar;
-adding a comonomer to control comonomer content in a manner known in the art;
the addition of hydrogen can be carried out in a manner known per se to control the molar mass.
Subsequently, the reaction mixture from the first reactor (1 st The reaction mixture of R') is transferred to a second reactor (2) nd R') (i.e. gas phase reactor (GPR-1)), wherein the conditions are preferably as follows:
-a temperature of 50 ℃ to 130 ℃, preferably 60 ℃ to 100 ℃;
the pressure is 5 bar to 50 bar, preferably 15 bar to 35 bar;
-adding a comonomer to control comonomer content in a manner known in the art;
the addition of hydrogen can be carried out in a manner known per se to control the molar mass.
Optionally and not preferably a third reactor (3 rd R') and a fourth reactor (4) th R')(For example, the conditions in the second gas-phase reactor (GPR-2) and the third gas-phase reactor (GPR-3)) are similar to those of the second reactor (2) nd R')。
The residence times in the different reactors are adjusted, as known in the art, to obtain the desired weight ratio of the propylene random copolymer portion of the propylene random copolymer (a).
Optionally, a catalyst may be introduced into the first reactor (1 st R') (i.e. Slurry Reactor (SR), such as Loop Reactor (LR)) polymerization is carried out in known manner under supercritical conditions and/or polymerization is carried out in condensed mode in Gas Phase Reactor (GPR).
Preferably, the process further comprises a prepolymerization with a catalyst system comprising a Ziegler-Natta procatalyst, an external donor and optionally a cocatalyst.
In a preferred embodiment, the prepolymerization is carried out as a bulk slurry polymerization in liquid propylene, i.e. the liquid phase comprises mainly propylene, in which small amounts of other reactants and optionally inert components are dissolved.
The prepolymerization is usually carried out at a temperature of from 0℃to 50 ℃ (preferably from 10℃to 45 ℃, more preferably from 15℃to 40 ℃).
The pressure in the prepolymerization reactor is not critical, but must be high enough to keep the reaction mixture in the liquid phase. Thus, the pressure may be 20 to 100 bar, for example 30 to 70 bar.
The catalyst components are preferably all introduced into the prepolymerization step. However, in the case where the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, only a part of the cocatalyst may be introduced into the prepolymerization stage, and the remaining part may be introduced into the subsequent polymerization stage. Also in this case, it is necessary to introduce a large amount of cocatalyst into the prepolymerization stage, so that a sufficient polymerization reaction is obtained in this stage.
Other components may also be added during the prepolymerization stage. Thus, as known in the art, hydrogen may be added to the pre-polymerization stage to control the molecular weight of the prepolymer. In addition, antistatic additives may be used to prevent particles from adhering to each other or to the reactor wall.
Precise control of the prepolymerization conditions and reaction parameters is well known in the art.
The propylene random copolymer (a) is preferably obtained by a multistage polymerization process as described above in the presence of a catalyst system comprising as component (i) a ziegler-natta procatalyst comprising the transesterification product of a lower alcohol and a phthalate.
The procatalyst used in the preparation of the propylene random copolymer (A) of the present invention is prepared as follows:
a) Make MgCl 2 And C 1 -C 2 Spray-crystallised or emulsion-cured adducts of alcohols with TiCl 4 Reacting;
b) At said C 1 -C 2 Transesterification between an alcohol and said dialkyl phthalate of formula (I) under conditions to form an internal donor, reacting the product of step a) with the dialkyl phthalate of formula (I);
wherein R is 1' And R is 2' Independently at least C 5 An alkyl group;
c) Washing the product of step b); or alternatively
d) Optionally reacting the product of step c) with additional TiCl 4 And (3) reacting.
The procatalyst is produced, for example, as described in patent applications WO87/07620, WO92/19653, WO92/19658 and EP 0491566. The contents of these documents are incorporated herein by reference.
First of all, mgCl is formed 2 * MgCl of nROH 2 And C 1 -C 2 Adducts of alcohols, wherein R is methyl or ethyl and n is 1 to 6. Ethanol is preferably used as the alcohol.
The adducts (first melted and then spray crystallized or emulsion cured) are used as catalyst supports.
In a next step, the spray-crystallized or emulsion-solidified compound is of the formula MgCl 2 *nROAdducts of H (wherein R is methyl or ethyl, preferably ethyl; n is 1 to 6) with TiCl 4 Contacting to form a titanium carrier, and then carrying out the following steps:
Adding the following components to the titanated support:
(i) Dialkyl phthalate of formula (I) wherein R 1' And R is 2' Independently at least C 5 Alkyl radicals, e.g. at least C 8 -an alkyl group, which is a group,
or preferably
(ii) Dialkyl phthalate of formula (I) wherein R 1' And R is 2' Identical and at least C 5 Alkyl radicals, e.g. at least C 8 -an alkyl group, which is a group,
or more preferably
(iii) A dialkyl phthalate of formula (I) selected from: propylhexyl phthalate (PrHP), dioctyl phthalate (DOP), di-isodecyl phthalate (DIDP), and di-tridecyl phthalate (DTDP); even more preferably, the dialkyl phthalate of formula (I) is dioctyl phthalate (DOP), such as di-isooctyl phthalate or diethylhexyl phthalate, in particular diethylhexyl phthalate,
forming a first product;
subjecting the first product to suitable transesterification conditions, i.e. to a temperature above 100 ℃ (preferably 100 to 150 ℃, more preferably 130 to 150 ℃) to transesterify the methanol or ethanol with the ester groups of the dialkyl phthalate of formula (I) to form preferably at least 80mol% (more preferably at least 90mol%, most preferably at least 95 mol%) of the dialkyl phthalate of formula (II):
Wherein R is 1 And R is 2 Is a methyl or ethyl group, preferably an ethyl group,
dialkyl phthalate of formula (II) is an internal donor; and
recovering the transesterification product as a procatalyst composition (component (i)).
In a preferred embodiment, the formula MgCl 2 * The adduct of nROH (where R is methyl or ethyl and n is 1 to 6) is melted and then the melt is injected into a cooled solvent or cooled gas, preferably by a gas, thereby crystallizing the adduct into a morphologically advantageous form, for example as described in WO 87/07620.
The crystalline adducts are preferably used as catalyst supports and are reacted with procatalysts which can be used in the present invention, as described in WO92/19658 and WO 92/19653.
When the catalyst residues are removed by extraction, an adduct of the titanium support and the internal donor is obtained in which the groups derived from the ester alcohol have been modified.
If enough titanium remains on the support, it will act as the active element of the procatalyst.
Otherwise, the titanation is repeated after the above-mentioned treatment to ensure a sufficient titanium concentration and thus activity.
Preferably, the procatalyst used in the present invention contains up to 2.5wt% titanium, preferably up to 2.2wt% titanium, and more preferably up to 2.0wt% titanium. The donor content thereof is preferably 4 to 12wt%, more preferably 6 to 10wt%.
More preferably, the procatalyst used in the present invention is prepared by: using ethanol as the alcohol and dioctyl phthalate (DOP) as the dialkyl phthalate of formula (I) yields diethyl phthalate (DEP) as the internal donor compound.
Even more preferably, the catalyst used in the present invention is a catalyst as described in the examples section; in particular dioctyl phthalate is used as dialkyl phthalate of formula (I).
For the production of the propylene random copolymer (A), the catalyst system used preferably comprises, in addition to the particular Ziegler-Natta procatalyst, an organometallic cocatalyst as component (ii).
Thus, the cocatalyst is preferably selected from trialkylaluminums (e.g., triethylaluminum (TEA)), dialkylaluminum chlorides (e.g., diethylaluminum chloride (DEAC)), and alkylaluminum sesquichlorides.
Component (iii) of the catalyst system used is an external donor represented by formula (IIIa) or formula (IIIb). Formula (IIIa) is defined as:
Si(OCH 3 ) 2 R 2 5 (IIIa)
wherein R is 5 Represents a branched alkyl group having 3 to 12 carbon atoms (preferably a branched alkyl group having 3 to 6 carbon atoms), or a cycloalkyl group having 4 to 12 carbon atoms (preferably a cycloalkyl group having 5 to 8 carbon atoms).
Particularly preferably, R 5 Selected from: isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
Formula (IIIb) is defined as:
Si(OCH 2 CH 3 ) 3 (NR x R y ) (IIIb)
wherein R is x And R is y Which may be the same or different, represent hydrocarbyl groups having 1 to 12 carbon atoms.
R x And R is y Independently selected from: a linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched aliphatic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferably, R x And R is y Independently selected from: methyl, ethyl, n-propyl, n-butyl, octyl, decyl, isopropyl, isobutyl, isopentyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
More preferably, R x And R is y Are all the same; even more preferably, R x And R is y All are ethyl groups.
More preferably, the external donor is of formula (IIIa), for example dicyclopentyl dimethoxy silane [ Si (OCH 3) 2 (cyclopentyl) 2 ]Or diisopropyl dimethoxy silane [ Si (OCH) 3 ) 2 (CH(CH 3 ) 2 ) 2 ]。
Most preferably, the external donor of formula (IIIb) is diethylaminotriethoxysilane.
In another embodiment, the ziegler-natta procatalyst may be modified by polymerizing a vinyl compound in the presence of a catalyst system comprising the specific ziegler-natta procatalyst (component (i)), an external donor (component (ii)) and optionally a cocatalyst (component (iii)), wherein the vinyl compound has the formula:
CH 2 ＝CH-CHR 3 R 4
Wherein R is 3 And R is 4 Together forming a 5-or 6-membered saturated, unsaturated or aromatic ring, or independently representing an alkyl group containing from 1 to 4 carbon atoms, the modified catalyst is used to prepare the random propylene copolymers of the present invention. The polymerized vinyl compound may be used as an alpha nucleating agent.
For modification of the catalyst, reference is made to International applications WO99/24478, WO99/24479, in particular WO00/68315, which are incorporated herein by reference for the reaction conditions for modification of the catalyst and for the polymerization reaction.
Ethylene/alpha-olefin multiblock copolymer (B)
The ethylene/α -olefin multiblock copolymer (B) is a copolymer comprising ethylene and one or more comonomer units selected from α -olefins having 4 to 12 carbon atoms, characterized in that a plurality of blocks or segments of two or more polymerized monomer units are chemically or physically different. The ethylene/α -olefin multiblock copolymer (B) includes a block copolymer having two blocks (diblock) and two or more blocks (multiblock).
In some embodiments, the ethylene/α -olefin multiblock copolymer may be represented by the formula:
(AB)n
where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or higher, "a" represents a block or segment and "B" represents a different block or segment. Preferably, a and B are linked or covalently bonded in a substantially linear manner or in a linear manner, as opposed to a substantially branched or substantially star-shaped manner. In other embodiments, the a blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymer generally does not have the following structure:
AAA-AA-BBB-BB
In still other embodiments, the block copolymer generally does not have a third block comprising a different comonomer.
Preferably, ethylene comprises a majority mole fraction of the entire block copolymer, i.e., ethylene comprises at least 50 mole% of the total polymer. More preferably, ethylene comprises at least 60mol%, at least 70mol% or at least 80mol%; the remainder of the overall polymer comprises substantially at least one other comonomer, preferably an alpha-olefin having 3 or more carbon atoms or 4 or more carbon atoms. In some embodiments, the ethylene/a-olefin multiblock copolymer may comprise 50 to 98mol% ethylene, or 60 to 95mol% ethylene, or 75 to 90mol% ethylene. For many ethylene/1-octene multi-block copolymers, the composition comprises an ethylene content of greater than 80 mole% of the total polymer and a 1-octene content of 10 mole% to 20 mole% of the total polymer.
Ethylene/α -olefin multiblock copolymers are polymers comprising two or more chemically distinct regions or segments (referred to as "blocks") that are preferably linked (or covalently bonded) in a linear fashion, i.e., polymers comprising chemically distinct units (chemically differentiated units) that are linked end-to-end (end-to-end) rather than pendant (dependent) or grafted with respect to the polymerized ethylene functionality (ethylenic functionality). In one embodiment, the blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, crystallite size caused by the polymer of such compositions, and the like.
Suitable monomers for use in preparing the ethylene/α -olefin multiblock copolymer (B) of the present invention include ethylene and one or more other polymerizable monomers other than ethylene. Examples of suitable comonomers include: linear or branched alpha-olefins having 3 to 30 or 3 to 20 or 4 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cycloolefins having 3 to 30 or 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene (norbornene), 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1, 4,5, 8-dimethylbridge-1, 2,3, 4a,5,8 a-octahydronaphthalene; dienes and polyolefins such as butadiene, isoprene, 4-methyl-1, 3-pentadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 3-octadiene, 1, 4-octadiene, 1, 5-octadiene, 1, 6-octadiene, 1, 7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1, 6-octadiene, 4-ethylene-8-methyl-1, 7-nonadiene and 5, 9-dimethyl-1, 4, 8-decatriene; 3-phenylpropene, 4-phenylpropene, 1, 2-difluoroethylene, tetrafluoroethylene and 3, 3-trifluoro-1-propene.
In one embodiment, the comonomer is selected from the group consisting of 1-butene, 1-hexene and 1-octene, preferably 1-octene.
The ethylene/α -olefin multiblock copolymer (B) may be produced by a chain shuttling process (chain shuttling process), for example as described in U.S. Pat. No. 7,858,706, which is incorporated herein by reference. In particular, suitable chain shuttling agents and related information are listed in column 16, line 39 through column 19, line 44. Suitable catalysts are described in column 19, line 45 to column 46, line 19, and suitable promoters are described in column 46, line 20 to column 51, line 28. This method is described throughout the document, particularly column 51, line 29 to column 54, line 56. This method is also described, for example, in US patent 7,608,668, US 7,893,166 and US 7,947,793.
Melt flow Rate MFR of ethylene/alpha-olefin multiblock copolymer (B) 2 (190 ℃ C., 2.16 kg) is preferably 0.1g/10min to 40g/10min, more preferably 1.0g/10min to 35g/10min, still more preferably 5.0g/10min to 30g/10min, most preferably 10g/10min to 25g/10min.
Further, the melting temperature (Tm) of the ethylene/α -olefin multiblock copolymer (B) is 90 ℃ to 130 ℃, preferably 95 ℃ to 125 ℃, more preferably 110 ℃ to 120 ℃, most preferably 115 ℃ to 118 ℃.
Further, the ethylene/α -olefin multiblock copolymer (B) preferably has a density of 0.850g/cm 3 To 0.890g/cm 3 More preferably 0.855g/cm 3 To 0.880g/cm 3 Most preferably 0.860g/cm 3 To 0.875g/cm 3 。
Furthermore, the content of the α -olefin comonomer units of the ethylene/α -olefin multiblock copolymer (B) is preferably 25 to 55wt%, preferably 30 to 50wt%, most preferably 35 to 45wt%, based on the total amount of monomer units.
In one embodiment, the ethylene/α -olefin multiblock copolymer (B) is an ethylene/1-octene multiblock copolymer and has one, some, any combination or all of the following properties (i) to (ix):
(i) The melting temperature (Tm) is from 90 ℃ to 130 ℃, preferably from 95 ℃ to 125 ℃, more preferably from 110 ℃ to 120 ℃, most preferably from 115 ℃ to 118 ℃;
(ii) The density is 850g/cm 3 To 0.890g/cm 3 Preferably 0.855g/cm 3 To 0.880g/cm 3 Most preferably 0.860g/cm 3 To 0.875g/cm 3 ；
(iii) Melt flow Rate MFR 2 (190 ℃ C., 2.16 kg) of 0.1g/10min to 40g/10min, preferably 1.0g/10min to 35g/10min, more preferably 5.0g/10min to 30g/10min, most preferably 10g/10min to 25g/10min.
Suitable examples of ethylene/α -olefin multiblock copolymers (B) for use in the present invention are: under the trade name INFUSE TM Ethylene/octene multi-block copolymer sold and available from the dow chemical company of midland, michigan, usa. In a particularly preferred embodiment, the ethylene/octene multi-block copolymer is INFUSE TM 9807。
Polyolefin composition
The polyolefin composition of the invention comprises the propylene random copolymer (A) and the ethylene/α -olefin multiblock copolymer (B) as described above or as described below.
The propylene random copolymer (a) is present in the polyolefin composition in an amount of from 15.0 to 45.0wt%, preferably from 20.0 to 40.0wt%, most preferably from 20.0 to 30.0wt%, based on the total amount of the polyolefin composition.
The ethylene/α -olefin multiblock copolymer (B) is present in the polyolefin composition in an amount of 55.0wt% to 85.0wt%, preferably 60.0wt% to 80.0wt%, and most preferably 70.0wt% to 80.0wt%, based on the total amount of the polyolefin composition.
The polyolefin composition may also comprise other components, such as additives, fillers, pigments or other polymeric components.
These other components are preferably present in an amount of 0wt% to 10wt% (more preferably 0.1wt% to 7wt%, still more preferably 0.5wt% to 6 wt%) based on the total amount of the polyolefin composition.
Preferably, the additive is selected from: acid scavengers, antioxidants, colorants, light stabilizers, ultraviolet stabilizers, slip agents, scratch resistant agents, dispersants, carriers, and colorants. In order to improve the dispersibility of the at least one additive in the polyolefin composition, the at least one additive is preferably added by using polypropylene powder as a carrier. Preferably, the amount of the at least one additive and carrier in the polyolefin composition of the invention should not exceed 10.0 wt.%, preferably not exceed 9.0 wt.%, most preferably not exceed 5.0 wt.%, based on the total weight of the polyolefin composition.
The pigment may be added in the form of a pigment masterbatch, wherein the pigment is one or more pigments mixed with the carrier polymer in concentrated amounts. Such pigment concentrates are commercially available, for example CMB 992-Black 9545 from Polyone. The pigment masterbatch is generally present in the polyolefin composition in an amount of from 0 to 5.0wt%, preferably from 1.0 to 4.5wt%, based on the total amount of the polyolefin composition.
Preferably, the polyolefin composition comprises, more preferably consists of:
(A) 15.0 to 45.0wt%, preferably 20.0 to 40.0wt%, most preferably 20.0 to 30.0wt% of the propylene random copolymer (A);
(B) 55.0 to 85.0wt%, preferably 60.0 to 80.0wt%, most preferably 70.0 to 80.0wt% of the ethylene/α -olefin multiblock copolymer (B);
(C) From 0wt% to 10.0wt%, preferably from 0.1 to 7.0wt%, most preferably from 0.5 to 5.0wt% of one or more additives, optionally comprising a carrier; and
(D) From 0% to 5.0% by weight, preferably from 1.0% to 4.5% by weight, of pigment comprising a masterbatch.
Melt flow Rate MFR of polyolefin composition 2 (230 ℃ C., 2.16 kg) is 16g/10min to 50g/10min, preferably 20g/10min to 40g/10min, most preferably 25g/10min to 35g/10min.
Further, the polyolefin composition preferably has a density of 0.860g/cm 3 To 0.915g/cm 3 Preferably 0.870g/cm 3 To 0.905g/cm 3 Most preferably 0.880g/cm 3 To 0.900g/cm 3 。
Also preferably, the polyolefin composition has a flexural modulus of 50MPa to 250MPa, preferably 75MPa to 200MPa, most preferably 100MPa to 150MPa.
The polyolefin composition may be prepared as follows: the propylene random copolymer (a) is blended (blending) with the ethylene/a-olefin multiblock copolymer (B) and optionally other components (e.g., additives and pigments) in an extruder, and the obtained blend of the propylene random copolymer (a) with the ethylene/a-olefin multiblock copolymer (B) and optionally other components is extruded in the extruder. The term "blending" according to the present invention refers to the act of providing blending of at least two different pre-existing materials, namely the propylene random copolymer (A) with the ethylene/alpha-olefin multiblock copolymer (B) and optionally other components.
For blending the individual components of the composition of the present invention, i.e. the propylene random copolymer (A) with the ethylene/a-olefin multiblock copolymer (B) and optionally other components, conventional compounding or blending equipment may be used, such as Banbury mixers, twin roll rubber mills, buss co-kneaders or twin screw extruders. The polymeric material recovered from the extruder is typically in the form of pellets. These particles are then preferably further processed, for example, by injection molding, to produce articles and products of the compositions of the present invention.
Article of manufacture
The polyolefin compositions of the invention are suitable for a wide range of applications. In particular, it is understood that the polyolefin compositions of the invention maintain highly desirable mechanical properties (e.g., excellent stiffness and impact strength) while also exhibiting improved flowability. Thus, the polyolefin composition of the invention is suitable for injection molding processes requiring short cycle times.
In view of the very good results obtained with the polyolefin composition according to the invention, said polyolefin composition is particularly suitable for the preparation of molded articles. Accordingly, another aspect of the present invention relates to an article comprising a polyolefin composition as described above or as described below.
For example, the article comprises the polyolefin composition in an amount of at least 60.0wt%, more preferably at least 80.0wt%, and most preferably at least 95.0wt%, based on the total weight of the article. In one embodiment of the invention, the article consists of the polyolefin composition of the invention.
Preferably, the article is a molded article, preferably an injection molded article. A preferred example of such injection molded articles are large parts for applications in the automotive industry. For example, the present invention relates to automotive articles, and in particular to automotive exterior trim (e.g., spoilers).
The invention thus relates in particular to automotive articles, in particular automotive exterior trim (e.g. spoilers), comprising, even more preferably consisting of, at least 60.0 wt. -%, more preferably at least 80.0 wt. -%, still more preferably at least 95.0 wt. -% of the polyolefin composition according to the invention.
Thus, another aspect of the present invention relates to the use of a polyolefin composition as described above or as described below in the preparation of a molded article. Preferably, the polyolefin composition as described above or as described below is used for the preparation of injection molded articles.
Examples
1. The measuring method comprises the following steps:
a) Melt flow Rate
Melt flow rate is the amount of polymer extruded in grams at a load for 10 minutes at a temperature in accordance with the test equipment standardized by ISO 1133.
Melt flow Rate MFR of propylene Polymer 2 The measurement is carried out according to ISO 1133 at 230℃under a load of 2.16kg (MFR 230 ℃/2.16).
Melt flow Rate MFR of ethylene Polymer 2 The measurement is carried out according to ISO 1133 at 190℃under a load of 2.16kg (MFR 190 ℃/2.16).
b) Density of
The density was measured according to ISO 1183D. Sample preparation was performed by compression molding according to ISO 1872-2:2007.
c) Comonomer content
Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.
Comonomer content quantification of poly (propylene-co-ethylene) copolymers
For the purpose of 1 H and 13 c, quantification in solution was recorded using Bruker Advance III NMR spectrometers operating at 400.15MHz and 100.62MHz, respectively 13 C{ 1 H } NMR spectra. At 125℃under nitrogen for all atmospheres 13 C optimized 10mm extension temperature probe, record all spectra. About 200mg of the material was mixed with chromium (III) acetylacetonate (Cr (acetylacetonate) 3 ) Together dissolved in 3mL of 1, 2-tetrachloroethane-d 2 (TCE-d 2 ) In the solvent, a 65mM relaxation agent solution {8} was obtained. To ensure homogeneity of the solution, after preparing the initial sample in the hot zone, the NMR tube was further heated in a rotary oven for at least 1 hour. After inserting the magnet, the tube was rotated at 10 Hz. This setting is chosen mainly for high resolution and for the quantitative requirements needed for accurate ethylene content quantification. In the absence of NOE, the optimal tip angle, 1s recycling delay, and dual level WALTZ16 decoupling system were employed to use standard single pulse excitation {3,4}. A total of 6144 (6 k) transients were obtained for each spectrum.
To quantitative determination 13 C{ 1 The H } NMR spectrum is processed, integrated, and the quantitative nature of the correlation is determined from the integration using a proprietary computer program. Using chemical shifts of the solvent, all chemical shifts are indirectly referenced to the central methylene of the ethylene block (EEE) at 30.00 ppm. Even if such structural units are not present, the method makes it comparable to a reference. A characteristic signal {7} corresponding to ethylene incorporation is observed.
The method of Wang et al {6} was used, by integration 13 C{ 1 Multiple signals throughout the spectral region in the H } spectrum to quantify the comonomer fraction. This method is chosen for its robustness and optionally its computational power for the presence of region defects. The integration zone is slightly adjusted to improve applicability to the comonomer content encountered over the entire range.
For systems where only isolated ethylene in the PPEPP sequence is observed, the method of Wang et al is altered to reduce the effect of non-zero integration of sites that are not known to be present. This method reduces overestimation of the ethylene content of such systems and is achieved by reducing the number of sites used to determine the absolute ethylene content:
E＝0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))
by using this set of sites, the corresponding integral equation becomes:
E＝0.5(I H +I G +0.5(I C +I D ))
the same symbols as used in Wang et al, article {6}, are used. The equation for absolute propylene content is not modified.
The mole percent of comonomer incorporated was calculated from the mole fraction:
E[mol％]＝100*fE
the weight percent of incorporated comonomer was calculated from the mole fraction:
E[wt％]＝100*(fE*28.06)/((fE*28.06)+((1-fE)*42.08))
reference is made to:
1)Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443.
2)Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,A.L.,Macromolecules 30(1997)6251.
3)Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225.
4)Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128.
5)Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253.
6)Wang,W-J.,Zhu,S.,Macromolecules 33(2000),1157.
7)Cheng,H.N.,Macromolecules 17(1984),1950.
8)Singh,G.,Kothari,A.,Gupta,V.,Polymer Testing 28 5(2009),475.
9)Kakugo,M.,Naito,Y.,Mizunuma,K.,Miyatake,T.Macromolecules 15(1982)1150.
10)Randall,J.Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C 2 9,201.
11)Resconi,L.,Cavallo,L.,Fait,A.,Piemontesi,F.,Chem.Rev.2000,100,1253.
comonomer content quantification of poly (ethylene-co-1-octene) copolymer
For the purpose of 1 H and 13 c, quantification was recorded in the molten state using Bruker Advance III NMR spectrometers operating at 500.13MHz and 125.76MHz, respectively 13 C{ 1 H } NMR spectra. At 150℃nitrogen was used for all atmospheres, using 13 C optimized 7mm Magic Angle Spinning (MAS) probe, all spectra were recorded. About 200mg of material was charged into a zirconia MAS rotor of 7mm outer diameter and rotated at 4 kHz. The arrangement is chosen primarily for the high sensitivity and accurate quantification required for rapid identification [1],[2],[3],[4] . Transient NOE with 3s short recirculation delay [5],[1] And RS-HEPT decoupling scheme [6],[7] Standard single pulse excitation was used. Each spectrum obtains a total of 1024 (1 k) transients. This setting was chosen because of its high sensitivity to low comonomer content.
To quantitative determination 13 C{ 1 H } NMR spectra are processed, integrated, and fixed usingThe quantitative nature was determined by a spectroscopic analysis automated procedure. All chemical shifts are internally referenced to the overall methylene signal (delta) at 30.00ppm + ) [8] 。
Characteristic signals corresponding to 1-octene binding were observed [8],[9],[10],[11],[12] And all comonomer contents are calculated relative to all other monomers present in the polymer.
Characteristic signals resulting from isolated 1-octene binding (i.e., EEOEE comonomer sequences) were observed. Isolated 1-octene binding was quantified using integration of the signal at 38.32 ppm. The integral is assigned to the unresolved signals corresponding to the isolated (EEOEE) 1-octene sequence and the isolated double discontinuous (EEOEE) 1-octene sequence at positions B6 and βb6b6, respectively. To compensate for the effects of two βb6b6b6 sites, the integral of βb6b6 site at 24.7ppm was used:
O＝I *B6+*βB6B6 -2*I ββB6B6
characteristic signals resulting from continuous 1-octene binding (i.e., EEOOEE comonomer sequences) were also observed. Such continuous 1-octene binding was quantified using the signal integral at 40.48ppm assigned to the ααb6b6sites to account for the number of reporting sites per comonomer:
OO＝2*I ααB6B6
Characteristic signals resulting from isolated discontinuous 1-octene binding (i.e., eeoeoeoee comonomer sequences) were also observed. The number of reporting sites per comonomer was calculated using signal integration at 24.7ppm assigned to the ββb6b6site, to quantify such isolated discontinuous 1-octene binding:
OEO＝2*I ββB6B6
characteristic signals resulting from isolated tri-continuous 1-octene binding (i.e., EEOOOEE comonomer sequences) were also observed. Such isolated tri-consecutive 1-octene binding was quantified using the signal integral at 41.2ppm assigned to the ααγb6b6b6b66 sites accounting for the number of reporting sites per comonomer:
OOO＝3/2*I ααγB6B6B6
in the case where no other signal indicative of other comonomer sequences was observed, the total 1-octene comonomer content was calculated based only on the amounts of isolated (EEOEE), isolated bicontinuous (EEOOEE), isolated discontinuous (EEOEE), and isolated tri-continuous (EEOOOEE) 1-octene comonomer sequences:
O total (S) ＝O+OO+OEO+OOO
Characteristic signals generated by saturated end groups (end-groups) were observed. Such saturated end groups were quantified using the average integral of the two resolved signals at 22.84 and 32.23 ppm. The 22.84ppm integral was assigned to the unresolved signal at the 2B6 and 2S sites corresponding to the 1-octene and saturated chain ends, respectively. The 32.23ppm integral was assigned to the unresolved signal at the 3B6 and 3S sites corresponding to the 1-octene and saturated chain ends, respectively. To compensate for the effects of the 2B6 and 3B6 1-octene sites, the total 1-octene content is used:
S＝(1/2)*(I 2S+2B6 +I 3S+3B6 -2*O Total (S) )
The ethylene comonomer content was quantified by integration using the overall methylene (overall) signal at 30.00 ppm. This integration includes the gamma and 4B6 charges from 1-octene + A site. Based on the integral and compensating for the observed 1-octene sequence and end groups, the total ethylene comonomer content was calculated:
E total (S) ＝(1/2)*[I Integral body +2*O+1*OO+3*OEO+0*OOO+3*S]
It should be noted that since the number of insufficient and excess ethylene units is equal, there is no need to compensate for the integral for the presence of an isolated triple-bound (EEOOOEE) 1-octene sequence.
The total mole fraction of 1-octene in the polymer is then calculated:
fO＝(O total (S) /(E Total (S) +O Total (S) )
The total amount of comonomer incorporation of 1-octene in weight percent is calculated from the mole fraction in a standard manner:
O[wt％]＝100*(fO*112.21)/((fO*112.21)+((1-fO)*28.05))
[1]Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.
[2]Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.
[3]Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer 50(2009)2373.
[4]NMR Spectroscopy of Polymers:Innovative Strategies for Complex Macromolecules,Chapter 24,401(2011).
[5]Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.
[6]Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239.
[7]Griffin,J.M.,Tripon,C.,Samoson,A.,Filip,C.,and Brown,S.P.,Mag.Res.in Chem.2007 45,S1,S198.
[8]J.Randall,Macromol.Sci.,Rev.Macromol.Chem.Phys.1989,C29,201.
[9]Liu,W.,Rinaldi,P.,McIntosh,L.,Quirk,P.,Macromolecules 2001,34,4757.
[10]Qiu,X.,Redwine,D.,Gobbi,G.,Nuamthanom,A.,Rinaldi,P.,Macromolecules 2007,40,6879.
[11]Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128.
[12]Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.,Winniford,B.,J.Mag.Reson.187(2007)225.
d) DSC analysis, melting temperature (Tm) and crystallization temperature (Tc):
5mg to 7mg samples were measured using a TA Instrument Q2000 Differential Scanning Calorimeter (DSC). DSC was run at a heating/cooling/heating cycle at a scan rate of 10 ℃/min over a temperature range of-30 ℃ to +225 ℃ in accordance with ISO 11357/part 3/method C2.
The crystallization temperature and heat of crystallization (Hc) are determined by the cooling step, while the melting temperature and heat of fusion (Hf) are determined by the second heating step.
e) Flexural modulus
According to ISO 178, an injection mould according to EN ISO 1873-2 at a test speed of 2mm/min and a force of 100NPlastic with a size of 80x10x4mm 3 The flexural modulus of the polyolefin composition was determined on test samples (length x width x thickness), wherein the length of the span between the supports was 64mm.
The measurement of the flexural modulus of the propylene random copolymer RG569MO was deviated therefrom, since a test speed of 5mm/min was used.
f) Charpy notched impact strength
80X10X4mm injection molded according to ISO 294-1/1 eA/DIN 53453 was used at 23℃and-30℃prepared according to ISO 294-1:1996 3 Bar-shaped specimens were measured for charpy notched impact strength (charpy NIS).
g) Dimensional stability/resistance to temperature-humidity cycling
Testing was performed according to GMW 14650.3.
Test instrument: a high and low temperature alternating temperature-humidity circulation tank, model "ZTH300L", purchased from Zengda Environment Instrument co., ltd. (Shanghai, china).
Test procedure: spoiler samples made of the PP compounds of the present invention were prepared by injection molding and tested in a test instrument under conditions simulating as close as possible to the actual conditions of use.
Subjecting the complete test assembly to a test cycle comprising the following steps in sequence:
17 hours at 30+ -3deg.C
72 hours at 80+ -3deg.C
24 hours at 40+/-3℃and 93+/-5% RH (relative humidity)
7 hours at 30+ -3deg.C
24 hours at 40.+ -. 3 ℃ and 93.+ -. 5% RH
24 hours at 22+ -3deg.C
Evaluating the test results:
by: the spoiler samples showed no cracking, crazing, noticeable color change, discoloration, cloudiness (cloudiness), blistering, detrimental shrinkage, deformation.
NG: the spoiler samples exhibited one or more defects in cracking, crazing, perceived color change, fading, cloudiness, blistering, detrimental shrinkage, deformation.
h) Visual appearance inspection
Spoiler samples made from the PP compounds of the polyolefin compositions of the invention were prepared by injection molding. The surface quality was checked and assessed with the naked eye.
By: the surface is free from tiger stripes, silvery stripes, flow marks, weld lines, bubbles, weld lines, and the like.
NG: the surface has at least one surface defect selected from tiger stripe, silver stripe, flow mark, welding line, bubble, welding line, etc.
2. Component (A)
The following components were used to prepare the polyolefin compositions of inventive example IE1 and comparative examples CE2-CE 3:
a) Polymerization of propylene random copolymers
Catalyst preparation
A catalyst for polymerizing propylene random copolymer was prepared according to example 8 of WO2004/029112A1, except that diethylaluminum chloride (DEAC) was used as a cocatalyst instead of triethylaluminum.
Bis (cyclopentyl) dimethoxysilane (donor D) was used as external donor.
Table 1: polymerization conditions of propylene random copolymer
The product obtained from the polymerization was compounded with an ethylene multiblock copolymer, remelted and mixed with additives (0.2 wt% DMDBS. Alpha. -nucleating agent, 0.03wt% Irganox1010 antioxidant, 0.06wt% Irgafos168 antioxidant, 0.05wt% zinc stearate) and pelletized.
The properties of the products obtained from the individual reactors are naturally not measured on homogeneous materials but on reactor samples (spotting). In the extrusion mixing process described below, the properties of the final resin are measured on a homogeneous material and the MFR is measured on the pellets made therefrom 2 。
The propylene-ethylene random copolymer had a density of 0.900g/cm 3 To 0.910g/cm 3 Melt flow Rate MFR 2 30g/10min, a flexural modulus of 1150MPa, a Charpy notched impact strength at 23℃of 6kJ/m 2 。
b) Commercial resin:
BJ356AI is a heterophasic propylene copolymer based on the proprietary Borstar Nucleation Technique (BNT), with a density of 0.906g/cm 3 Melt flow Rate MFR 2 (230 ℃ C., 2.16 kg) 100g/10min, a flexural modulus of 1550MPa and a Charpy notched impact strength at 23 ℃ C. Of 4.5kJ/m 2 . BJ356AI is commercially available from Boruge Pte Ltd.
EE050AE is a heterophasic polypropylene copolymer with a density of 0.900kg/m 3 Melt flow Rate MFR 2 (230 ℃ C., 2.16 kg) 11g/10min, a flexural modulus of 0.950MPa, and a Charpy notched impact strength at-20 ℃ C. Of 10.5kJ/m 2 . EE050AE is commercially available from Borouge Pte ltd.
·INFUSE TM 9807 is an ethylene/1-octene multi-block copolymer having a density of 0.860kg/m3, melt flow rate MFR 2 (190 ℃/2.16 kg) 15g/10min, a 1-octene comonomer content of 40wt% and a melting temperature Tm of 118 ℃. INFUSE TM 9807 is commercially available from the dow chemical company (united states).
·ENGAGE TM 7447 is an ethylene/1-butene elastomer having a density of 0.865g/cm 3 Melt flow Rate MFR 2 (190 ℃ C./2.16 kg) was 5g/10min, and the melting peak was 35 ℃. ENGAGE TM 7447 is commercially available from the dow chemical company (united states).
PP-H, GD,225 is a propylene homopolymer in powder form, melting temperature Tm being 160 ℃.
Irgafos 168 (AO 1 for short), tris (2, 4-di-tert-butylphenyl) phosphite, CAS number 31570-04-4, commercially available from BASF SE.
Irganox 1076 (AO 2 for short), octadecyl 3- (3 ',5' -di-tert-butyl-4-hydroxyphenyl) propionate, CAS number 2082-79-3, commercially available from BASF SE.
Irganox 1010, pentaerythritol-tetrakis (3- (3 ',5' -di-tert-butyl-4-hydroxyphenyl) -propionate, CAS number 6683-19-8, commercially available from BASF SE.
DMDBS,1,3:2,4 bis (3, 4-dimethylbenzylidene) sorbitol, CAS number 135861-56-2, commercially available from Milliken under the designation "Millad 3988".
Cyasorb UV3808 (abbreviated as UV), a mixture of n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate (CAS No. 67845-93-6) and a mixture of esters of 2, 6-tetramethyl-4-piperidinol with higher fatty acids (mainly stearic acid) (CAS No. 86403-32-9), commercially available from Cytec.
Calcium stearate (Ca stearate for short), CAS number 1592-23-0, commercially available from Faci.
RIKEMAL AS-105 (AS-105 for short) is a monoglyceride, having a melting temperature Tm of from 63℃to 68℃and being commercially available from Rikevita (Malaysia) SDN BHD.
CMB 992-Black 9545 (CMB for short) is a Black masterbatch commercially available from Ngai Hing Hong Group (Shanghai, china).
3. Preparation of examples
The polyolefin compositions of inventive example IE1 and comparative examples CE2 and CE3 were based on the formulations listed in table 2 below and were prepared by using a counter-rotating twin screw extruder with a main feeder and two side feeders.
The propylene-ethylene random copolymer for IE1 or the mixture of BJ356AI and EE050ae for CE2 and CE3 was fed through the main feeder (feeder 1).
Ethylene INFUSE for IE1 TM 9807 or ENGAGE for CE2 and CE3 TM 7447 is fed by a first side feeder (feeder 2).
PP-H, GD,225 (PP powder) was premixed with all additives as carrier and then fed into the second side feeder (feeder 3).
Compounding conditions in a twin screw extruder are disclosed in table 3 below.
The properties of the compounded compositions of example IE1, comparative examples CE2 and CE3 are shown in table 4 below.
Table 2: polyolefin compositions of example IE1, comparative examples CE2 and CE3
IE1 CE2 CE3
Propylene random copolymer [ wt ]] 23.5 - -
BJ356AI[wt％] - 10.5 10.5
EE050AE[wt％] - 23.0 43.0
ENGAGE 7447[wt％] - 60.0 40.0
INFUSE 9807[wt％] 70.0 - -
PP-H,GD,225[wt％] 1.2 1.2 1.2
AO1[wt％] 0.2 0.2 0.2
AO2[wt％] 0.2 0.2 0.2
Calcium stearate [ wt ]] 0.3 0.3 0.3
AS-105[wt％] 0.3 0.3 0.3
UV[wt％] 0.3 0.3 0.3
CMB[wt％] 4.0 4.0 4.0
Table 3: compounding conditions for example IE 1:
process conditions Setting up
Zone of extruder Temperature (. Degree. C.)
Zone 1 100
Zone 2 180
Zone 3 200
Zone 4 210
Zone 5 210
Zone 6 210
Zone 7 210
Zone 8 210
Region 9 210
Region 10 210
Region 11 210
Die head 200
Melting temperature 210
Compounding:
throughput (kg/hour) 50
Screw rotating speed (rpm) 580
Torque (%) 60
Vacuum (MPa) -0.6
Table 4: properties of example IE1, comparative examples CE2 and CE3
IE1 CE2 CE3
MFR 2 [g/10min，230℃/2.16kg] 30 15 15
Density [ g/cm ] 3 ] 0.89 0.89 0.89
Flexural modulus [ MPa ]] 120 300 600
Charpy NIS,23 ℃ [ kJ/m ] 2 ] Unbroken Unbroken Unbroken
Charpy NIS, -30 ℃ [ kJ/m ] 2 ] Unbroken Unbroken Unbroken
Visual appearance inspection By passing through NG By passing through
For temperature-Tolerance to humidity cycling By passing through NG NG
The PP compound of the polyolefin composition of the invention had better flowability and better dimensional stability against temperature and humidity cycles than those of the reference examples CE2 to CE 3.
Furthermore, reference examples CE2 to CE3 use EE050AE and Engage 7447 to improve impact properties, and EE050AE and Engage 7447 each have well known good elasticity and impact properties. However, the examples of the present invention use only ethylene block copolymer elastomer to improve impact and obtain comparable impact properties.

Claims (25)

1. A polyolefin composition comprising:
(A) 20.0 wt% to 40.0 wt% of a propylene random copolymer having propylene monomer units and one or more comonomer units selected from ethylene, 1-butene, 1-hexene and 1-octene, the comonomer units being present in an amount of 1.0 wt% to 6.0 wt% based on the total amount of monomer units; and
(B) 60.0 wt% to 85 wt% of an ethylene/α -olefin multiblock copolymer having ethylene monomer units and one or more comonomer units selected from the group consisting of 1-butene, 1-hexene and 1-octene, the ethylene/α -olefin multiblock copolymer having a melting temperature Tm of 90 ℃ to 130 ℃;
wherein the polyolefin composition has a melt flow rate MFR measured at 230℃under a load of 2.16 kg 2 From 16 g/10min to 50 g/10min, said polyolefin composition having a flexural modulus, determined according to ISO 178, of from 50 MPa to 250 MPa, and
wherein the ethylene/α -olefin multiblock copolymer (B) has an α -olefin comonomer unit content of 30 wt% to 50 wt% based on the total amount of monomer units.
2. The polyolefin composition according to claim 1, wherein the polyolefin composition has a melt flow rate MFR measured at 230 ℃ under a load of 2.16 kg 2 20 g/10min to 40 g/10min.
3. The polyolefin composition according to claim 1, wherein the polyolefin composition has a melt flow rate MFR measured at 230 ℃ under a load of 2.16 kg 2 25 g/10min to 35 g/10min.
4. A polyolefin composition according to any of claims 1 to 3 wherein the comonomer units of the propylene random copolymer (a) are selected from ethylene.
5. The polyolefin composition according to any of claims 1 to 3, wherein the propylene random copolymer (a) is a-nucleated.
6. The polyolefin composition according to any of claims 1 to 3, wherein the propylene random copolymer (a) has a melt flow rate MFR measured at 230 ℃ under a load of 2.16 kg 2 Is 1.0 g/10min to 80 g/10min.
7. A polyolefin composition according to any of claims 1 to 3 wherein the propylene random copolymer (a) has a flexural modulus determined according to ISO 178 of at least 900 MPa.
8. The polyolefin composition according to any of claims 1 to 3, wherein the propylene random copolymer (a) has a charpy notched impact strength at 23 ℃ of at least 4.0 kJ/m 2 。
9. A polyolefin composition according to any of claims 1 to 3 wherein the ethylene/α -olefin multiblock copolymer (B) has an α -olefin comonomer content of 35 wt% to 45 wt% based on the total amount of monomer units.
10. A polyolefin composition according to any of claims 1 to 3 wherein the comonomer units of the ethylene/a-olefin multiblock copolymer (B) are selected from 1-octene.
11. A polyolefin composition according to any of claims 1 to 3 wherein the ethylene/α -olefin multiblock copolymer (B) has a melt flow rate MFR measured at 190 ℃ under a load of 2.16 kg 2 From 0.1 g/10min to 40 g/10min.
12. The polyolefin composition according to any of claims 1 to 3, wherein the polyolefin composition comprises the following components:
Based on 100wt% of the total polyolefin composition,
(A) 20.0 wt% to 40.0 wt% of the propylene random copolymer;
(B) 60.0 wt% to 80.0 wt% of the ethylene/α -olefin multiblock copolymer;
(C) From 0wt% to 10.0 wt% of one or more additives, optionally comprising a carrier; and
(D) 0.0 wt% to 5.0% wt% of pigment comprising a masterbatch.
13. The polyolefin composition according to claim 12, wherein the polyolefin composition consists of:
based on 100wt% of the total polyolefin composition,
(E) 20.0 wt% to 40.0 wt% of the propylene random copolymer;
(F) 60.0 wt% to 80.0 wt% of the ethylene/α -olefin multiblock copolymer;
(G) From 0wt% to 10.0 wt% of one or more additives, optionally comprising a carrier; and
(H) 0.0 wt% to 5.0% wt% of pigment comprising a masterbatch.
14. The polyolefin composition according to claim 12, wherein the polyolefin composition comprises the following components:
based on 100wt% of the total polyolefin composition,
(A) 20.0 wt% to 30.0 wt% of the propylene random copolymer;
(B) 70.0 wt% to 80.0 wt% of the ethylene/α -olefin multiblock copolymer;
(C) 0.1wt% to 7.0 wt% of one or more additives, optionally comprising a carrier; and
(D) 1.0 wt% to 4.5 wt% of a pigment comprising a masterbatch.
15. The polyolefin composition according to any of claims 1 to 3, wherein the polyolefin composition has a density of 0.860 g/cm 3 To 0.915 g/cm 3 。
16. The polyolefin composition of claim 15, wherein the polyolefin composition has a density of 0.870 g/cm 3 To 0.905 g/cm 3 。
17. The polyolefin composition of claim 15, wherein the polyolefin composition has a density of 0.880 g/cm 3 To 0.900 g/cm 3 。
18. The polyolefin composition according to any of claims 1 to 3, wherein the polyolefin composition has a flexural modulus, determined according to ISO 178, of 75 MPa to 200 MPa.
19. The polyolefin composition of claim 18, wherein the polyolefin composition has a flexural modulus of from 100 MPa to 150 MPa as determined according to ISO 178.
20. An article comprising the polyolefin composition of any of claims 1 to 3.
21. The article of claim 20, wherein the article is a molded article.
22. The article of claim 20, wherein the article is an injection molded article.
23. The article of claim 21, wherein the article is an automotive spoiler.
24. Use of the polyolefin composition of any of claims 1 to 3 in the preparation of an article.
25. Use according to claim 24 for the preparation of injection molded articles.
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