CN104710691A - Polyolefin compositions having low hardness and low gloss - Google Patents
Polyolefin compositions having low hardness and low gloss Download PDFInfo
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- CN104710691A CN104710691A CN201510056331.1A CN201510056331A CN104710691A CN 104710691 A CN104710691 A CN 104710691A CN 201510056331 A CN201510056331 A CN 201510056331A CN 104710691 A CN104710691 A CN 104710691A
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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
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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Abstract
A polyolefin composition comprising, in percent by weight: A. 10-25% of a propylene homopolymer or copolymer with up to 8% of comonomer (S); B. 75-90% of a copolymer of ethylene and (i) propylene or (ii) CH2=CHR alpha-ole-fins, where R is a 2-8 carbon alkyl radical, or (iii) a combination thereof, optionally with minor amounts of a diene, containing from 54-65% of ethylene; wherein the weight ratio B/XS of the content B of copolymer component (B) to the fraction XS soluble in xylene at room temperature, both referred to the total weight of (A)+(B), is of 1.50 or less.
Description
The application is the divisional application of following application: the applying date: on October 24th, 2007; Application number: 200780044763.4 (PCT/EP2007/061384); Denomination of invention: " there is the polyolefin compositions of soft and low-luster ".
The present invention relates to polyolefin compositions with soft and low-luster and preparation method thereof.
Known people by propylene (optionally comprising a small amount of olefin comonomer), be then the sequential polymerization of ethylene/propene or ethylene/alpha-olefin hydrocarbon mixture, obtain the polyolefin compositions (technology identical with thermoplastic polymer can be used to be translated into finished product) while keeping good thermoplastic behavior with elastic performance.
Catalyzer based on the halogenated titanium compound be carried on magnesium chloride is used for this object.
Known to reasons such as the typical valuable character of polyolefine (such as unreactiveness, mechanical property and nontoxicity), constantly increase the actual interest of the type composition, therefore this area constantly makes great efforts to expand the use of described composition in many different field.
The disclosed patent application 400333 in Europe describes the Elastoplastic polyolefin compositions obtained by sequential polymerization, and described polyolefin compositions comprises:
A) crystalline polymer of the propylene of 10-60 weight part or multipolymer;
B) 10-40 weight part comprise ethene, room temperature under be insoluble to the polymer fractions of dimethylbenzene;
Be dissolved in dimethylbenzene under the room temperature of C) 30-60 weight part and comprise the ethylene/propene copolymer fraction of 40-60% weight percent ethylene.
Described composition is pliable and tough and have valuable elastic performance, this confirmed by the low Flexural Modulus values associated with good set value (lower than 700MPa and usually above 200MPa), but not there is particularly preferred hardness value and optical property, especially in gloss value, on the other hand, for such as extrusion sheet, thermoforming, automobile top layer, blowing, the purposes of film, should preferably gloss value between 10 to 40, described gloss value measures on extrusion sheet, it associates with low hardness (shore) value with the Flexural Modulus values of 200MPa or lower.
On the other hand, in the disclosed patent application 472946 in Europe, show the fraction C by reducing xylene soluble) and therefore reduce the ethylene content of total elastomeric copolymers of ethylene with propylene fraction, the balance between modulus in flexure and hardness may be improved.But gloss value is still too high in this case, this will illustrate in the examples below.
Therefore, pliable and tough (namely there is lower Flexural Modulus values), soft (namely there is comparatively low durometer) and also there is the Elastoplastic polyolefin compositions of low gloss value is needed.
In order to meet this demand, the invention provides a kind of polyolefin compositions, described polyolefin compositions comprises:
A) alfon of 10-25% weight, preferably 15-25% weight or propylene and one or more be selected from ethene and CH
2the multipolymer of the comonomer of=CHR alpha-olefin or the combination of described polymkeric substance, wherein R is the alkyl of 2-8 carbon, and this multipolymer comprises one or more comonomers of 8% weight at the most;
B) ethene of 75-90% weight, preferably 75-85% weight and (i) propylene or (ii) CH
2the multipolymer of=CHR alpha-olefin or (iii) its combination, wherein R is the alkyl of 2-8 carbon, and optional containing a small amount of diene, this multipolymer comprises the ethene of 54 to 65% weight, preferably 55 to 63% weight;
Wherein be dissolved in fraction XS in dimethylbenzene under the content B of copolymer component (B) and room temperature (about 25 DEG C) all based on the total weight of (A)+(B), its weight ratio B/XS is 1.50 or less, preferably 1.40 or less, be in particular 1.50 to 0.9 or 1.40 to 0.9.
The total amount of the ethene of copolymerization is preferably 30% weight to 65% weight, more preferably 30% weight to 60% weight, especially 30% weight to 55% weight.
Other of the present composition are preferably characterized as:
-gloss value is equal to or less than 15%, is more preferably equal to or less than 10%, is especially equal to or less than 7%;
-shore A value is equal to or less than 90, is more preferably equal to or less than 85;
-shore D value is equal to or less than 35, and especially 35 to 15;
-MFR the value that measures according to ASTM-D 1238, condition L (230 DEG C, 2.16kg load) is 0.01 to 10g/10 minute, more preferably 0.05 to 5g/10 minute;
-be equal to or greater than 2g/10 minute according to the MFR value of the component (A) of ASTM-D 1238, condition L mensuration, be more preferably equal to or greater than 3g/10 minute;
-modulus in flexure is equal to or less than 200MPa;
-rupture stress: 2-13MPa;
-elongation at break: be greater than 200% weight;
-substantially do not bleach (turning white) when the plate that bending 1mm is thick;
Being dissolved in the total weight of amount (XS) based on (A)+(B) of the fraction in dimethylbenzene under-room temperature, is 40 to 70% weight, more preferably 45 to 65% weight;
The fraction XS in dimethylbenzene and ethylene total content C is dissolved under-room temperature
2all based on the total weight of (A)+(B), its weight ratio XS/C
2be 1.15 or larger, more preferably 1.20 or larger, especially 1.15 to 1.50 or 1.20 to 1.50;
The limiting viscosity [η] of-XS fraction is less than 3dl/g, especially 2.9 to 1.5dl/g;
The isotactic index (II) of-component (A) is equal to or greater than 90% weight, is more preferably equal to or greater than 95% weight.
For the preparation of the present composition polymerization process can continuously or intermittent mode carry out, according to known technique, under existence or operate in the liquid phase under there is not inert diluent, or to operate in the gas phase, or adopt the liquid-gas technological operation of mixing.
Polymerization time and temperature are not crucial and advantageously respectively in the scope of 0.5 to 5 hour and 50 DEG C to 90 DEG C.
Can at ethene or CH
2=CHR alpha-olefin makes propylene polymerization form component (A) under existing, wherein R is the alkyl of 2-8 carbon, such as 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene and 1-octene or its combination.
Can in diene (conjugation or non-conjugation, such as divinyl, 1,4-hexadiene, 1,5-hexadiene and ethidine-1-norbornylene) existence under there is the copolymerization of ethene and propylene or other one or more alpha-olefins (example provides about in the description of component (A) above) or its combination thus form component (B).
The amount of diene is generally relative to (B) weight 0.5 to 10%.
Specifically, can be used in the sequential polymerization method of carrying out at least two stages and prepare composition, one or more stage, other stages were for the synthesis of component (B) for the synthesis of component (A).Polyreaction in each successive phases (subsequent stages) occurs under resulting polymers and the existence for the catalyzer of last stage.By adopting normally used molecular weight regulator (as hydrogen and ZnEt
2) carry out the adjustment of molecular weight.
Directly can obtain high MFR value in polymerization or by the subsequent degradation (usually being undertaken by chemical viscosity reduction) of polymkeric substance.
The chemical viscosity reduction of polymkeric substance is carried out under the existence of radical initiator (such as superoxide).The example that can be used for the radical initiator of this object has two (the t-butyl peroxy)-hexane of 2,5-dimethyl-2,5-and dicumyl peroxide.
By using the radical initiator of appropriate amount to carry out viscosity reduction process, and preferably carry out in inert atmosphere (such as nitrogen).Methods known in the art, device and operational condition can be used to implement present method.
Before the effect of degradation method is, limiting viscosity [η] value of the XS fraction of the polymer composition of the present invention of definition have dropped.
Particularly preferably be by the polymer composition to the gained that comprises the same composition (A) of same ratio and (B) (component namely mentioned above and ratio) but the precursor composition that the viscosity [η] of XS fraction is 3dl/g or higher carries out degrading, the viscosity [η] of its XS fraction is less than 3dl/g, especially 2.9 to 1.5dl/g.
But the viscosity of XS fraction [η] is 3dl/g or higher, especially 3 to 4dl/g polymer composition also within the scope of the invention.
As already mentioned, polymerization can occur in liquid phase, gas phase or liquid-gas phase.
Such as, can liquid propene be used to prepare component (A) as thinner at polymerization stage and prepare component (B) in the gas phase in copolymerization stage subsequently, except propylene fraction is degassed, there is no the intermediate stage.
Preferably all by implementing polymerization preparation component (A) and (B) in the gas phase.Order prepared by each component is not crucial.
Temperature of reaction for the preparation of one or more polymerization stages of component (A) may be the same or different with the temperature of reaction for the preparation of one or more polymerization stages of component (B), temperature of reaction for the preparation of component (A) is generally 40 DEG C to 90 DEG C, preferably 50 to 80 DEG C, the temperature of reaction for the preparation of component (B) is 40 to 70 DEG C.
If carried out in liquid monomer, the pressure in single stage is the pressure similar with the vapour pressure of the liquid propene under the service temperature used, this pressure passes through the overvoltage correction of one or more monomers and the hydrogen as molecular weight regulator, and can by a small amount of vapour pressure correction for adding the inert diluent in catalyst mixture.
If carried out in the liquid phase, the polymerization pressure of instruction can be 5 to 30 normal atmosphere.
The residence time in two or more stages is depended on ratio required between component (A) and (B) and is generally 15 minutes to 8 hours.
Described polymerization process carries out usually under the existence being carried on the stereoregular Ziegler-Natta catalyst on magnesium dihalide.
The described stereoregular catalyzer for being polymerized comprises the reaction product of following material:
1) solid ingredient being carried on titanium compound on magnesium dihalide (preferred muriate) and electronic donor compound capable (interior electron donor(ED)) is comprised;
2) alkylaluminium cpd (promotor); With optional,
3) electronic donor compound capable (external electronic donor).
Preferred described catalyzer can prepare the homopolymer polypropylene that isotactic index is greater than 90%.
Ingredient of solid catalyst (1) comprises the compound as electron donor(ED), this compound be usually selected from ether, ketone, lactone, containing the compound of N, P and/or S atom and monocarboxylic acid and dicarboxylic ester.
The catalyzer with above-mentioned character is known in the patent literature; Particularly advantageously see and be set forth in United States Patent (USP) 4,399,054 and European patent 45977 in catalyzer.
Specially suitable described electronic donor compound capable is phthalic ester and succinate.
Suitable succinate is represented by formula (I):
Wherein R
1and R
2base is same to each other or different to each other, and for C1-C20 is linear or the alkyl of branching, thiazolinyl, cycloalkyl, aryl, arylalkyl or kiki fang alkyl group, optionally comprises heteroatoms; Radicals R
3-R
6be same to each other or different to each other, the alkyl of or branching linear for hydrogen or C1-C20, thiazolinyl, cycloalkyl, aryl, arylalkyl or kiki fang alkyl group, optionally comprise heteroatoms, be connected to the radicals R in identical carbon atoms
3to R
6ring can be joined together to form.
R
1and R
2be preferably C1-C8 alkyl, cycloalkyl, aryl, arylalkyl and kiki fang alkyl group.Particularly preferred is wherein R
1and R
2be selected from primary alkyl and the compound of the especially primary alkyl of branching.Suitable R
1and R
2the example of group has methyl, ethyl, n-propyl, normal-butyl, isobutyl-, neo-pentyl, 2-ethylhexyl.Particularly preferred is ethyl, isobutyl-and neo-pentyl.
One of preferred group of the compound that formula (I) describes is wherein R
3to R
5for hydrogen and R
6for having the alkyl of the branching of 3 to 10 carbon atoms, cycloalkyl, aryl, arylalkyl and alkylaryl.Another kind of preferred formula (I) compound is wherein R
3to R
6in at least two groups be different from hydrogen and be selected from the alkyl of the linear of C1-C20 or branching, thiazolinyl, cycloalkyl, aryl, arylalkyl or kiki fang alkyl group, optionally comprise heteroatoms.Particularly preferred compound is that wherein two groups are different from hydrogen and are connected to the compound on identical carbon atom.In addition, wherein at least two groups are different from hydrogen and are connected to (i.e. R on different carbon atoms
3and R
5or R
4and R
6) compound be also particularly preferred.
As shown in disclosed European patent application EP-A-361 493 and 728769, other specially suitable electron donor(ED)s have 1,3-diether.
With regard to promotor (2), preferably use trialkyl aluminium compound, such as triethyl aluminum, triisobutyl aluminium and three n-butylaluminum.
Electronic donor compound capable (3) (the adding in alkylaluminium cpd) that can be used as external electronic donor comprises aromatic esters (such as phenylformic acid alkyl ester), heterogeneous ring compound (such as 2,2,6,6-tetramethyl piperidine and 2,6-diisopropylpiperidine), especially comprise the silicon compound of at least one Si-OR key (wherein R is alkyl).1,3-before described diether is also suitable as external electronic donor.When interior electron donor(ED) is one of described 1,3-diether, external electronic donor can be save.
Catalyzer and a small amount of alkene pre-contact (prepolymerization) can be made, keep catalyzer to be suspended in hydrocarbon solvent, and polymerization at room temperature to 60 DEG C, thus prepare the polymkeric substance of 0.5 to 3 times that its amount is catalyst weight.
Operation also can betide in liquid monomer, in this case, prepares the polymkeric substance of 1000 times of its amount up to catalyst weight.
Other catalyzer that can be used in the inventive method are metallocene-type catalyst, as USP5,324,800 and EP-A-0 129 368 described in; Particularly advantageously bridge joint two-indenyl metallocenes, such as, as USP 5,145,819 and EP-A-0 485 823 described in.Another kind of suitable catalyzer is so-calledly limit shape catalyzer, as described in EP-A-0 416 815 (Tao Shi), EP-A-0420 436 (Exxon), EP-A-0 671 404, EP-A-0 643 066 and WO 91/04257.These Metallocenic compounds can be used in particular for preparation component (B).
Composition of the present invention also can comprise the additive, weighting agent and the pigment that are generally used for olefin polymer, such as nucleator, drawing oil (extension oil), mineral filler, organic and mineral dye.
Polyolefin compositions of the present invention be applied to especially extrude, blowing, injection moulding and thermo forming fields for the preparation of various goods as sheet material, film and trolley part.
Enforcement of the present invention and advantage are open below in an example.These embodiments are only illustrative, and are not intended to limit the scope of the invention by any way.
Following analytical procedure is used for characterizing polymeric compositions.
melt flow rate (MFR): ASTM-D 1238, condition L (230 DEG C, 216kg).
[η] limiting viscosity: determine at 135 DEG C in naphthane.
ethylene content: infrared spectra.
glossiness: ASTM D 523 (1mm extrusion sheet) method
shore A and D: ISO 868 (holoplast that 4mm is thick)
modulus in flexure: ISO 178 (holoplast that 4mm is thick)
rupture stress: ISO 527 (extrusion sheet of 1mm)
elongation at break: ISO 527 (extrusion sheet of 1mm)
xylene soluble with insoluble fraction
By 2.5g polymkeric substance and 250cm
3dimethylbenzene is introduced to be furnished with in the glass flask of rerigerator and magnetic stirring apparatus.Temperature rose to the boiling point of solvent in 30 minutes.Then gained clear solution is made to keep backflow and stir 30 minutes again.Then by close flask in ice-water bath, keeps 30 minutes and same in the water bath with thermostatic control of 25 DEG C maintenance 30 minutes.Formed solid is filtered on fast grade filter paper.By 100cm
3filtrate pour into before in the load weighted aluminum container heated on hot plate under nitrogen flowing to pass through evaporation of solvent.Then till making this container be retained in the vacuum drying oven of 80 DEG C to obtain constant weight.Then the weight percentage of the polymkeric substance be at room temperature dissolved in dimethylbenzene is calculated.
The weight percentage being at room temperature insoluble to the polymkeric substance in dimethylbenzene is considered to the isotactic index of polymkeric substance.This value substantially with extract determined isotactic index (being defined as polypropylene isotactic index) with the normal heptane seethed with excitement and be consistent.
embodiment 1-2 and comparing embodiment 1
Ingredient of solid catalyst for being polymerized is be carried on the titanium comprising about 2.2% weight on magnesium chloride and the diisobutyl phthalate Ziegler-Natta catalyst component as the highly stereoregular of interior electron donor(ED), by preparing this ingredient of solid catalyst to the similar method described in patent application disclosed in Europe 395083 embodiment 3.
Catalyst system and prepolymerization process
Above-mentioned ingredient of solid catalyst is made at-5 DEG C, to contact 5 minutes with the amount of the TEAL/ ingredient of solid catalyst weight ratio equaling 5 with the TEAL/DCPMS weight ratio equaling about 5 with dicyclopentyl dimethoxyl silane (DCPMS) with triethyl aluminum (TEAL) causing before in polymerization reactor.Then, before catalyst system is introduced the first polymerization reactor, at 25 DEG C, keep being suspended in liquid propene about 30 minutes by making it prepolymerization is carried out to it.
Polymerization
By by the hydrogen (as molecular weight regulator) of pre-polymerized catalyst system, gaseous state and propylene (embodiment 1) or propylene and ethene (embodiment 2) with continuously and steady flow form be supplied in the first gas-phase polymerization reactor and prepare propylene copolymer (component (A)).
The propylene copolymer prepared in the first reactor is discharged with Continuous Flow form, and after removing unreacted monomer, it is introduced in the second gas-phase polymerization reactor with quantitatively constant gaseous hydrogen, ethene with Continuous Flow form together with flow of propylene.
Propylene/ethylene copolymer (component (B)) is prepared in the second reactor.The mol ratio of polymerizing condition, reactant and the composition of resulting polymers are shown in Table 1.
Steam treatment is carried out to remove reactive monomer and volatile matter to the polymer beads leaving the second reactor, then dry.
By polymer beads and conventional stabilizer twin screw extruder Berstorff ZE 25 (length of screw rod: mix and extrude in a nitrogen atmosphere according to following condition 33):
Rotating speed: 250rpm;
Forcing machine extrusion capacity: 6-20kg/ hour;
Melt temperature: 200-250 DEG C.
The character relevant to polymer composition recorded in table 2 carries out measurement gained by extruded each polymkeric substance.
At the Luperox of 0.015% weight (embodiment 1) and 0.03% weight (embodiment 2)
tXunder the existence of 101 (2,5-dimethyl-2,5-two (t-butyl peroxy) hexanes), in Werner 58 twin screw extruder, also/granulating is extruded to each polymer composition of gained thus.Extrude in a nitrogen atmosphere according to following condition:
Rotating speed: 200rpm;
Forcing machine extrusion capacity: 150kg/ hour;
Melt temperature: about 240 DEG C.
By resulting polymers performance inventory in table 3.
In order to contrast, table 2 and 3 have recorded the performance by the polyolefin compositions (comparing embodiment 1C) prepared by sequential polymerization, and described polyolefin compositions comprises:
A) 31% weight comprise the propylene of about 3.5% weight percent ethylene and the random copolymers of ethene;
B) 69% weight comprise the propylene of about 27% weight percent ethylene and the elastocopolymer of ethene.
Table 1
Note: C3-=propylene; C2-=ethene; The amount of the polymkeric substance shunt=prepared in paid close attention to reactor; C2-content (multipolymer)=relative to the ethylene content of the multipolymer prepared in paid close attention to reactor.
Table 2
| Embodiment is numbered | 1 | 2 | 1C | |
| MFR L | G/10 minute | 0.24 | 0.1 | 0.6 |
| Xylene soluble part | % weight | 63.2 | 62.95 | 64 |
| C2-content | % weight | 45.6 | 46.4 | 19.7 |
| X.S.I.V. | dl/g | 3.87 | 4.36 | 3.2 |
Note: X.S.I.V=is dissolved in the limiting viscosity of the fraction in dimethylbenzene; MD=longitudinally; TD=laterally.
Table 3
| Embodiment is numbered | 1 | 2 | 1C | |
| MFR L | G/10 minute | 0.5 | 0.7 | 0.6 |
| Xylene soluble part | % weight | 61 | 62.5 | 64 |
| X.S.I.V. | dl/g | 2.8 | 2.3 | 3.2 |
| Shore A | 75 | 73 | ＞90 | |
| Modulus in flexure | MPa | 80 | ||
| Rupture stress MD/TD | MPa | 4.8/3.5 | 3.8/2.6 | 21.4/20.3 |
| Elongation at break MD/TD | % weight | 510/472 | 378/261 | 723/762 |
| Glossiness | % weight | 4.9 | 4.5 | 73.5 |
Claims (8)
1. the polyolefin compositions with low-luster is manufacturing the purposes in goods, and described polyolefin compositions comprises:
A) alfon of 10-25% weight or propylene and one or more be selected from ethene and CH
2the multipolymer of the comonomer of=CHR alpha-olefin or the combination of described polymkeric substance, wherein R is the alkyl of 2-8 carbon, and this multipolymer comprises one or more comonomers of 8% weight at the most;
B) ethene of 75-90% weight and (i) propylene or (ii) CH
2the multipolymer of=CHR alpha-olefin or (iii) its combination, wherein R is the alkyl of 2-8 carbon, and optional containing a small amount of diene, this multipolymer comprises 55 to 63% weight percent ethylene;
Wherein be dissolved in the fraction XS of dimethylbenzene all based on the total weight of (A)+(B) under the content B of copolymer component (B) and room temperature, its weight ratio B/XS is 1.40 or less, and the limiting viscosity [η] of wherein said XS fraction is 2.9-1.5dl/g, described polyolefin compositions has modulus in flexure lower than 200MPa and by comprising the same composition (A) of same ratio and (B) but the precursor composition superoxide that the viscosity [η] of described XS fraction is 3dl/g or higher carries out chemical viscosity reduction obtains.
2. the purposes of claim 1, is wherein dissolved in described fraction XS and the ethylene total content C of dimethylbenzene under room temperature
2all based on the total weight of (A)+(B), its weight ratio XS/C
2be 1.15 or larger.
3. the purposes of claim 1, the MFR value of described polyolefin compositions is 0.01 to 10g/10min.
4. the purposes of claim 1, the Flexural Modulus values of described polyolefin compositions is equal to or less than 120MPa.
5. the purposes of claim 1, the shore A value of described polyolefin compositions is equal to or less than 90.
6. goods, described goods comprise the polyolefin compositions as defined in claim 1 with low-luster.
7. the goods of claim 6, described goods are by extruding preparation.
8. the goods of claim 6 or 7, the form of described goods is sheet material, film and trolley part.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06125609 | 2006-12-07 | ||
| EP06125609.5 | 2006-12-07 | ||
| US87456306P | 2006-12-13 | 2006-12-13 | |
| US60/874563 | 2006-12-13 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800447634A Division CN101583661A (en) | 2006-12-07 | 2007-10-24 | Polyolefin compositions having low hardness and low gloss |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104710691A true CN104710691A (en) | 2015-06-17 |
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ID=41365186
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800447634A Pending CN101583661A (en) | 2006-12-07 | 2007-10-24 | Polyolefin compositions having low hardness and low gloss |
| CN201510056331.1A Pending CN104710691A (en) | 2006-12-07 | 2007-10-24 | Polyolefin compositions having low hardness and low gloss |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800447634A Pending CN101583661A (en) | 2006-12-07 | 2007-10-24 | Polyolefin compositions having low hardness and low gloss |
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|---|---|
| CN (2) | CN101583661A (en) |
| AT (1) | ATE511529T1 (en) |
| TW (1) | TWI433884B (en) |
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| CN114350058A (en) * | 2014-05-28 | 2022-04-15 | 巴塞尔聚烯烃股份有限公司 | Ethylene polymer compositions and their use in polyolefin compositions |
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- 2007-10-24 CN CNA2007800447634A patent/CN101583661A/en active Pending
- 2007-10-24 CN CN201510056331.1A patent/CN104710691A/en active Pending
- 2007-10-24 AT AT07821747T patent/ATE511529T1/en not_active IP Right Cessation
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| CN101583661A (en) | 2009-11-18 |
| TWI433884B (en) | 2014-04-11 |
| ATE511529T1 (en) | 2011-06-15 |
| TW200837125A (en) | 2008-09-16 |
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