CN101563416A - Polypropylene compositions containing fillers and/or pigments - Google Patents
Polypropylene compositions containing fillers and/or pigments Download PDFInfo
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- CN101563416A CN101563416A CNA200780047410XA CN200780047410A CN101563416A CN 101563416 A CN101563416 A CN 101563416A CN A200780047410X A CNA200780047410X A CN A200780047410XA CN 200780047410 A CN200780047410 A CN 200780047410A CN 101563416 A CN101563416 A CN 101563416A
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Abstract
Polypropylene compositions having a MFR value (2.16 kg, 230 DEG C) from 15 to 200 g/10 min., comprising: A) a propylene polymer or polymer composition selected from propylene homopolymers or copolymers of propylene containing up to 5% by moles of comonomer(s), said homopolymers and copolymers having values of MFR, obtained without degradation treatments, from 500 to 2500 g/10 min., or combinations of the said homopolymers or copolymers; B) a filler or pigment, or their combinations; and optionally C) from 0.5 to 5% by weight, with respect to the total weight of A), B) and C), of a compatibilizer.
Description
The present invention relates to have the polypropene composition that contains filler and/or pigment of improved equilibrated workability and mechanical property.
Specifically, though exist significant quantity and even the very filler and/or the pigment of a large amount, but the present composition still has higher melt flow rate value (hereinafter being abbreviated as MFR), and this has brought the highly beneficial and thundering balance with mechanical property.
In order to improve the final MFR value of this kind composition, advised using propene polymer in this area with high MFR value.Specifically, according to U.S. Patent number 4997875, the 50wt% fiber enhancer is blended into the MFR value for obtaining improved melt flow characteristics and good mechanical performance in the amphoteric polymeric material of the polymerization state of the about 430g/10min of about 55-by inciting somebody to action at the most.
According to Application No. 20060264557, be blended into the Reinforced Polypropylene composition that acquisition has good impact property in the acrylic resin that MFR is the about 1500g/10min of about 20-by organic fibre and optional mineral filler with suitable a large amount.In fact, the highest MFR value of propene polymer that is used for the embodiment of described file is 400-430g/10min.
Have now found that, by filler and/or pigment and propene polymer blend with polymerization state of very high MFR value having been obtained the improvement balance of modulus in flexure, shock-resistance, tensile property and heat deflection temperature (HDT) (hereinafter HDT).
In addition, compare with the composition with low MFR as known in the art, high MFR composition of the present invention presents the ability of higher filling mould (even having somewhat complex design) inner chamber, and realizes the minimizing of cycling time in injection-molded application.
Use very the acrylic resin of high workability also to allow in composition, to load high-load filler (especially glass fibre), consequently, under the situation that realizes improved mechanical property, also may reduce the thickness of prepared molded article.
At length, the invention provides and have 15-200g/10min, preferred 20-200g/10min, the more preferably MFR value that under the load of 2.16kg and 230 ℃, records according to ISO 1133 of 50-200g/10min, and comprise:
A) be selected from alfon or contain 5 moles of % at the most, the propene polymer or the polymer composition of the propylene copolymer of preferred 3 moles of % comonomers at the most or the combination of described homopolymer or multipolymer, described homopolymer and multipolymer have 500-2500g/10min, preferred 1200-2500g/10min, more preferably 1500-2500g/10min, 1600-2500g/10min's most preferably in the MFR value that does not have to obtain under the situation of degradation treatment
B) filler or pigment, or their combination; With optional
C) with respect to A), B) and gross weight meter C), the 0.5-5wt% expanding material.
Component A) the alfon and the MFR of multipolymer record under the load of 2.16kg and 230 ℃ according to ISO 1133.
Preferably, composition of the present invention comprises 10wt%-80wt%, more preferably 20wt%-70wt%A) and 20wt%-90wt%, more preferably 30wt%-80wt%B), with respect to A) and gross weight meter B).
When also there being component C) time, composition of the present invention preferably comprises 10wt%-75wt%, more preferably 30wt%-67wt%A), 20wt%-89wt%, more preferably 30wt%-69wt%B) and 0.5wt%-5wt%, more preferably 0.5wt%-3wt%C), with respect to A), B) and gross weight meter C).
The top component A that limits) is to have very high MFR value, even is higher than propene polymer or the polymer composition of 1000g/10min.In addition, this kind MFR value is to obtain under the situation without any degradation treatment.In other words, component A) propene polymer by polymerization state constitutes, this polymkeric substance after polymerization not experience can change any processing of MFR value significantly.Therefore, molecular weight component A) also is those that directly obtain in being used for preparing the polymerization process of this propene polymer basically.
As will showing among the embodiment, when the degraded (viscosity breaking) of the propene polymer by having low MFR value obtains described MFR value, can not obtain the very favorable balance of the performance of the present composition.
Usually, may reside in component A) in propylene copolymer in comonomer be selected from ethene and/or C
4-C
8Alpha-olefin, for example butene-1, amylene-1,4-methylpentene-1, hexene-1 and octene-1.Preferred comonomer is ethene and butene-1.
Can in polymerization process, use Ziegler-Natta catalyst or metallocene-based catalyst systems to prepare component A) all propene polymers and multipolymer.
Described catalyzer and polymerization process are as known in the art.
Can use conventional molecular weight regulator as known in the art, for example chain-transfer agent (for example hydrogen or ZnEt
2).
The preferred embodiment of Ziegler-Natta catalyst is a load type catalyst system, this system comprises the trialkyl aluminium compound that loads on the Magnesium Chloride Anhydrous, optional electron donor and contain the halogenide of Ti or the ingredient of solid catalyst and the optional electron donor compound of halogen-alcoholate.Catalyzer with above-mentioned characteristic is to know in the patent documentation; Especially advantageously USP 4,399,054 and EP-A-45 977 in the catalyzer described.Other example can be referring to USP 4,472,524.
Be suitable for preparing component A) the concrete Ziegler-Natta catalyst of propene polymer and the example of polymerization process in EP0622380, disclose.
Preferably, when prepare component A with Ziegler-Natta catalyst) propene polymer the time, they have 100 under the MFR of 600-1000g/10min, 000-60,000 Mw value, be higher than under the MFR of 1000g/10min, having and be greater than or equal to 140000 Mz value, as described among the EP0622380 disclosed like that.
Other preferable feature with the described propene polymer of Ziegler-Natta catalyst preparation is:
The Mz/Mw value of-2.5-2.8;
-isotacticity index (according to the weight fraction that is insoluble to dimethylbenzene under room temperature (about 25 ℃)) is greater than or equal to 95%, more preferably is greater than or equal to 97%.
More preferably, propene polymer component A) directly obtains in the polymerization in the presence of the metallocene-based catalyst systems.
Polymerizing condition generally needn't be different from those that use under the situation of Ziegler-Natta catalyst.
Preferred metallocene-based catalyst systems can obtain by making following material contact:
A) Metallocenic compound of following general formula (I)
Wherein
M is the transition metal that belongs to the 3rd, 4,5,6 families in the periodic table of elements or lanthanon or actinide elements; Preferred M is titanium, zirconium or hafnium;
X, identical or different, be hydrogen atom, halogen atom or R, OR, OSO
2CF
3, OCOR, SR, NR
2Or PR
2Group, wherein R is straight or branched, ring-type or acyclic C
1-C
40Alkyl, C
2-C
40Thiazolinyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkaryl or C
7-C
40Aralkyl; Randomly comprise the heteroatoms that belongs to periodic table of elements 13-17 family; Preferred R is straight or branched C
1-C
20Alkyl; Or two X can randomly form and replace or unsubstituted butadienyl or OR ' O base, and wherein R ' is for being selected from C
1-C
40Alkylidene, C
6-C
40Virtue fork base, C
7-C
40Alkane virtue fork base and C
7-C
40The divalent group of virtue alkylidene; Preferred X is hydrogen atom, halogen atom or R group; More preferably X is chlorine or C
1-C
10Alkyl is as methyl or ethyl;
L is the optional heteroatomic divalence C that belongs to periodic table of elements 13-17 family that contains
1-C
40Alkyl or contain the divalence silicomethane fork base of maximum 5 Siliciumatoms; Preferred L is selected from randomly to contain the heteroatomic C that belongs to periodic table of elements 13-17 family
1-C
40Alkylidene, C
3-C
40Ring alkylidene, C
6-C
40Virtue fork base, C
7-C
40Alkane virtue fork base and C
7-C
40Virtue alkylidene and contain the silicylene such as the SiMe of maximum 5 Siliciumatoms
2, SiPh
2Preferred L is group (Z (R ")
2) n, wherein Z is carbon or Siliciumatom, n is 1 or 2, and R " for randomly comprising the heteroatomic C that belongs to periodic table of elements 13-17 family
1-C
20Alkyl; Preferred R is " for randomly comprising heteroatomic straight or branched, ring-type or the acyclic C that belongs to periodic table of elements 13-17 family
1-C
20Alkyl, C
2-C
20Thiazolinyl, C
2-C
20Alkynyl, C
6-C
20Aryl, C
7-C
20Alkaryl or C
7-C
20Aralkyl; More preferably group (Z (R ")
2) n is Si (CH
3)
2, SiPh
2, SiPhMe, SiMe (SiMe
3), CH
2, (CH
2)
2And C (CH
3)
2Even more preferably (Z (R ")
2) n is Si (CH
3)
2
R
1Be the optional heteroatomic C that belongs to periodic table of elements 13-17 family that contains
1-C
40Alkyl; Preferred R
1Be straight or branched, ring-type or acyclic C
1-C
40Alkyl, C
2-C
40Thiazolinyl, C
2-C
40Alkynyl, C
6-C
40Aryl, C
7-C
40Alkaryl or C
7-C
40Aralkyl; Randomly contain the heteroatoms that belongs to periodic table of elements 13-17 family; More preferably R
1Be straight or branched, saturated or unsaturated C
1-C
20Alkyl;
R
2, R
3, R
4And R
5Be same to each other or different to each other, for hydrogen atom or randomly contain the heteroatomic C that belongs to periodic table of elements 13-17 family
1-C
40Alkyl; Or R
2, R
3, R
4And R
5In the middle of two R groups to form can be the unsaturated or saturated heteroatomic C that belongs to periodic table of elements 14-16 family that randomly contains
4-C
7Ring; The ring of this formation can have C
1-C
20Hydrocarbon substituent;
B) aikyiaiurnirsoxan beta maybe can form the compound of alkyl metallocene cation at least.
Think that aikyiaiurnirsoxan beta is straight chain, side chain or the ring compound that contains at least one following type group:
Wherein substituting group U is identical or different, is hydrogen atom, halogen atom, C
1-C
20-alkyl, C
3-C
20-cycloalkyl, C
6-C
20-aryl, C
7-C
20-alkaryl or C
7-C
20-aralkyl randomly contains silicon or germanium atom, and condition is that at least one U is different from halogen.
Especially, under the situation of straight chain compound, can use aikyiaiurnirsoxan beta with following formula:
N wherein
1Be 0 or the integer of 1-40, substituting group U is as top definition; Or under the situation of ring compound, can use aikyiaiurnirsoxan beta with following formula:
N wherein
2Be the integer of 2-40, the U substituting group is as top definition.
Metallocenic compound specific examples a) is dichloro rac-dimetylsilyl two (2-methyl-4,5-benzo indenyls)-a close zirconium.
The example of the aikyiaiurnirsoxan beta that is fit to is methylaluminoxane (MAO), four-(isobutyl-) aikyiaiurnirsoxan beta (TIBAO), four-(2,4, the 4-tri-methyl-amyl) aikyiaiurnirsoxan beta (TIOAO), four-(2, the 3-dimethylbutyl) aikyiaiurnirsoxan beta (TDMBAO) and four-(2,3,3-trimethylammonium butyl) aikyiaiurnirsoxan beta (TIMBAO).
The examples for compounds that can form the alkyl metallocene cation is for having formula D
+E
-Compound, D wherein
+For
Acid, it can be supplied with proton and irreversibly react E with the substituent X of the metallocene of formula (I)
-Be compatible negatively charged ion, it can be stablized and starts from two kinds of compound reactive activity catalytic species, and enough unstable to being removed by olefinic type monomers.Preferably, negatively charged ion E
-Comprise one or more boron atoms.More preferably, negatively charged ion E
-For having formula BAr4
(-)Negatively charged ion, wherein substituent A r is identical or different, is aryl such as phenyl, pentafluorophenyl group or two (trifluoromethyl) phenyl.Four-pentafluorophenyl group borate is especially preferred compound, is described among the WO91/02012.In addition, can use easily and have formula BAr
3Compound.Such compound for example is described in the International Patent Application WO 92/00333.Other example of compound that can form the alkyl metallocene cation is for having formula BAr
3The compound of P, wherein P is for replacing or unsubstituted pyrryl.These compounds are described in WO01/62764.All these compounds of boracic atom can be with the mol ratio between the metal of boron and metallocene between about 1: 1 and about 10: 1; Preferred 1: 1 and 2.1; More preferably from about use at 1: 1.
Other preferred feature with the described propene polymer of metallocene-based catalyst systems preparation is:
-molecular weight distribution mw/mn is less than 4; Be more preferably less than 3; Most preferably less than 2.7;
-use
13The isotaxy pentads (mmmm) that C-NMR records are higher than 90%; More preferably be higher than 92%;
-xylene soluble part under 25 ℃ is more preferably less than 1.6wt% less than 2wt%;
-the fusing point that utilizes DSC to record is higher than 143 ℃.
Be ready to use in the filler component B of the present composition) can be organic or inorganic.
Fiber (organic and inorganic fibre) preferably, and mineral filler (being different from fiber), the for example glass of sheet metal, glass flake, grinding, glass sphere and mineral filler, as talcum, lime carbonate, mica, wollastonite or silicate, generally speaking, kaolin, barium sulfate, metal oxide and oxyhydroxide.
The another kind of filler that is fit to is a wood powder.
Pigment comprises organic and inorganic substance, for example carbon black, TiO
2, ZnO, chromic oxide, ferriferous oxide, azo pigment, phthalocyanine, quinacridone, perylene dye, naphthalene derivatives, isoindoline, anthraquinone pigment.
The fiber that the present composition is fit to comprises that for example aromatic poly constitutes the fiber that is the monofilament form by glass, metal, pottery, graphite and organic polymer for example polyester and nylon, and they are all commercially available.
Glass fibre is preferred.
Glass fibre can be to cut off glass fibre or long glass fibres, maybe can be the continuous monofilament fibers form, but preferred the use cut off glass fibre, also claims staple fibre or short chopping bundle.
Generally speaking, glass fibre can have the length of 1-50mm.
The cut-out or the short glass fiber that are used for the present composition preferably have 1-6mm, more preferably the length of 3-4.5mm and 10-20 μ m, the more preferably diameter of 12-14 μ m.
As previously mentioned, polypropene composition of the present invention can also comprise expanding material C).
Operable one type is the low-molecular weight compound with reactive polar groups, and they are used for making filler and pigment to become not too hydrophilic and are therefore more compatible with described polymkeric substance.The compound that is fit to for example is, silane is aminosilane, epoxy radicals silicone hydride, amido silane or acryl silane for example.
Yet expanding material preferably comprises modification (functionalized) polymkeric substance and the optional low-molecular weight compound with reactive polar groups.Modified olefine polymer, especially alfon and multipolymer, as ethene and propylene each other or with the multipolymer of other alpha-olefin be most preferred because the component A of they and the present composition) highly compatible.Also can use modified poly ethylene.
In configuration aspects, polymer-modified grafting or the segmented copolymer of being preferably selected from.
In this article, preferably contain polymer-modified derived from the group of polar compound, described polar compound especially is selected from acid anhydrides, carboxylic acid, carboxylic acid derivative, primary amine and secondary amine, oxy-compound ， oxazoline and epoxide, and ionic compound.
The specific examples of described polar compound is unsaturated cyclic anhydride and their aliphatic diester and two acid derivatives.Specifically, can use maleic anhydride and be selected from toxilic acid C
1-C
10Straight chain and side chain dialkyl, fumaric acid C
1-C
10Straight chain and side chain dialkyl, itaconic anhydride, C
1-C
10The compound of straight chain and side chain methylene-succinic acid dialkyl, toxilic acid, fumaric acid, methylene-succinic acid and their mixture.
Especially preferably the propene polymer that uses maleic anhydride graft is as polymer-modified.
Described low-molecular weight compound is used for filler or pigment is coupled to and polymer-modifiedly goes up and therefore it is bonded to propylene polymer component A securely) on.They are bifunctional compound normally, and in this case, a kind of functional group can participate in interacting with the keyed jointing of filler or pigment, and second kind of functional group can participate in interacting with polymer-modified keyed jointing.Described low-molecular weight compound is preferably amino-or epoxy radicals silicone hydride, more preferably aminosilane.
As filler B) when comprising glass fibre, aminosilane silane hydroxyl and glass fibre keyed jointing, and the stable amido linkage of amino formation, for example the polypropylene with maleic anhydride graft forms this key.
Especially advantageously before introducing glass fibre in the composition, described low-molecular weight compound is applied on this glass fibre.
Polymer-modifiedly can pass through polymkeric substance in a simple manner, for example extrude preparation with the reactivity of maleic anhydride in the presence of free-radical generating agent (as organic superoxide), for example among the EP0572028 disclosed like that.
Preferred amounts derived from the group of polar compound in polymer-modified is 0.5-3wt%.
The preferred value of polymer-modified MFR is 50-400g/10min.
Also may use the masterbatch that comprises filler and/or pigment and expanding material by the pre-mixing form.
Polypropene composition of the present invention can obtain by fusion and blending ingredients, and this is blended in the mixing tank at general 180-320 ℃, preferred 200-280 ℃, more preferably carries out under 200-260 ℃ the temperature.
Can use any known equipment and technology for this reason.
Useful in this article mixing tank is forcing machine or kneader especially, especially preferred twin screw extruder.Pre-mixing component in mixing tank at room temperature also.
Preferably originally make component A) and optional component C) fusion, subsequently with B component) and this melt-mixing, to reduce wearing and tearing and the fibre breakage (when fiber is used as filler) in the mixing tank.
During the preparation of polypropene composition of the present invention, except that two kinds of main ingredient A) and B) and some possible expanding material C), also might introduce the additive that is usually used in this area, for example stablizer (to heat, light, U.V.), softening agent, static inhibitor and water-resisting agent.
The especially preferred feature of the present composition is:
-density: 1.1-4.5kg/dm
3, more preferably 1.1-1.8kg/dm
3
-modulus in flexure: 2500-19000MPa, more preferably 5000-16000MPa;
-tensile modulus: 2500-20000MPa, more preferably 5000-17000MPa;
-unnotched card is finished (charpy): 30-200kJ/m under 23 ℃
2, more preferably 35-65kJ/m
2
-unnotched card is complete down at-30 ℃: 30-150kJ/m
2, more preferably 40 arrive 65kJ/m
2
-card jaggy is complete down at 23 ℃: 5-200kJ/m
2, more preferably 10-20kJ/m
2
-card jaggy is complete down at-30 ℃: 5-150kJ/m
2, more preferably 8-25kJ/m
2
-fracture tensile strength: 50-150MPa, more preferably 80-135MPa;
-elongation at break: 1-200%, more preferably 1-3%;
-HDT 1.82MPa:60-155 ℃, more preferably 135-155 ℃.
When use was different from the filler of glass fibre, the preferred feature of the present composition was:
-density: 1.1-4.5kg/dm
3, more preferably 1.1-1.9kg/dm
3
-modulus in flexure: 2500-12000MPa, more preferably 4000-10000MPa;
-tensile modulus: 2500-20000MPa, more preferably 5000-10000MPa;
-unnotched card is complete down at 23 ℃: 2-15kJ/m
2, more preferably 3-12kJ/m
2
-card jaggy is complete down at 23 ℃: 1-10kJ/m
2, more preferably 1-7kJ/m
2
Because their favourable performance balances, the present composition can be used for many application, as injection-molded item, especially the parts of automobile, electrical equipment, furniture, or moulded products, generally speaking, especially sheet material, the parts of electrical equipment, furniture, household utensil, or as the superfill masterbatch.
Specifically, work as B component) amount especially high, illustrative ground, with respect to A) and gross weight meter B), when being 60%-90wt%, composition of the present invention can also be advantageously used for enriched material, by with additional polymer blending filler and/or pigment being introduced polymer composition, especially polyolefin compositions, and obtain having according to demand filler content and the molded articles of modulus.
Following examples for illustration purposes and non-limiting purpose provides.
Following analytical procedure is used for measuring the performance of reporting among specification sheets and the embodiment.
Melt flow rate (MFR) (MFR): ISO 1133, and the load that adopts 2.16kg is at 230 ℃;
Intrinsic viscosity: in tetraline, measure down at 135 ℃;
Density: ISO 1183;
Modulus in flexure (secant): ISO 178, T-shape rod ISO527-1 Class1 A's
On 80 * 10 * 4mm rectangular specimen;
Tensile modulus (secant): ISO 527/-1 ,-2, adopt on specimen types 1A
The speed of 1mm/min, the span of 50mm;
The non-notch card is finished: ISO 179 (Class1 is along the limit), at T-shape rod ISO527-1
On 80 * 10 * 4mm rectangular specimen of Class1 A;
The breach card is finished: ISO 179 (Class1, along the limit, breach A), T-shape
80 * 10 * 4mm rectangular specimen of rod ISO527-1 Class1 A
On;
Fracture tensile strength: ISO 527/-1 ,-2, adopt on specimen types 1A
The speed of 50mm/min, the span of 50mm;
Elongation at break: ISO 527/-1 ,-2, adopt on specimen types 1A
The speed of 50mm/min, the span of 50mm;
HDT (1.80MPa): (heat deflection temperature (HDT)) ISO 75A-1.-2, at sample clause 6
On.
T-shape rod preparation (injection moulding)
According to test method ISO 1873-2 (1989) injection moulding sample.
(solubleness in dimethylbenzene at room temperature with wt% is the mensuration of isotacticity index
Unit)
With 2.5g polymkeric substance and 250cm
3Dimethylbenzene is introduced the glass flask that is equipped with refrigerator and magnetic stirring apparatus.In 30 minutes, temperature is increased to the boiling point of solvent.Keep the clear solution obtained under refluxing and restir 30 minutes then.Then the flask of sealing was remained in ice and the water-bath 30 minutes and remained in 25 ℃ the water bath with thermostatic control same 30 minutes.Filtering formed solid on the filter paper fast.With 100cm
3Filtered liquid is poured in the aluminum container of weighing in advance, is heating this container on the hot-plate to desolvate by evaporating to remove under nitrogen gas stream.Then this container is remained in 80 ℃ baking oven under the vacuum up to reaching constant weight.Calculate the weight percent of the polymkeric substance that at room temperature dissolves in dimethylbenzene then.
The weight percent that at room temperature is insoluble to the polymkeric substance of dimethylbenzene is thought the isotacticity index of this polymkeric substance.This value is substantially equal to by the isotacticity index with the boiling n-heptane extraction and determination, and the latter constitutes polyacrylic isotacticity index according to definition.
MWD measures
Use down at 145 ℃ that to be equipped with three particle sizes be that Alliance GPCV 2000 instruments (Waters) of the mixed bed column TosoHaasTSK GMHXL-HT of 13 μ m are measured Mn and Mw value via gel permeation chromatography (GPC).The size of this post is 300 * 7.8mm.The moving phase of using is 1,2 of vacuum distilling, 4-trichlorobenzene (TCB), and flow velocity remains on the 1.0ml/ branch.Prepared this sample solution in two hours by when in TCB, stirring under 145 ℃, heating this sample.Concentration is 1mg/ml.In order to prevent degraded, add 2 of 0.1g/l, 6-di-t-butyl-p-cresol.326.5 μ L solution are injected in this column device.Using 10 molecular weight is that 580 to 7500000 polystyrene standard sample (the EasiCal kit of Polymer Laboratories) obtains working curve; Comprise that also two kinds of other peak molecular weights from same manufacturer are 11600000 and 13200000 standard model.The K value of supposing the Mark-Houwink relation is:
For the polystyrene standard sample, K=1.21 * 10
-4DL/g, α=0.706
For polypropylene specimen, K=1.90 * 10
-4DL/g, α=0.725
For the polypropylene copolymer sample, K=1.93 * 10
-4DL/g, α=0.725
Use three grades of polynomial fitting insertion experimental datas and obtain this working curve.Data acquisition and processing (DAP) is undertaken by the Empower with GPCV option 1.0 that uses Waters.
Melt temperature
Measure according to the heating rate that ISO 3146 adopted 20K/ minute by DSC.
13
C-NMR (for the propene polymer of metallocenes preparation)
NMR analyzes.Under 120 ℃ and 100.61MHz, obtain PP's on the DPX-400 spectrograph of Fourier transform mode work
13The C-NMR spectrum.The peak value that uses this mmmm pentads carbon is as the interior mark under 21.8ppm and 29.9ppm respectively.120 ℃ of following concentration that this sample is dissolved in the 5mm test tube are among sym.-tetrachloroethane-d2 of 8%wt/v.Utilize 90 ° of pulses, postponed to obtain each spectrum in 12 seconds between pulse and the CPD (WALTZ 16) to eliminate the 1H-13C coupling.Use the spectral window of 6000Hz in the 32K data point, to store about 2500 transient states.
According to " Selectivity in Propylene Polymerization with MetalloceneCatalysts ", L.Resconi, L.Cavallo, A.Fait, F.Piemontesi, Chem.Rev., 100,1253, (2000)) PP spectrum is carried out assignment.
Adopt mapping position model will test the pentads distributed modelization and obtained mmmm content.The following acquisition of mmmm content with PP of high-content 2,1 (E) and 1,3 (H) error:
[mmmm]＝100(∑[CH
3]-5[mrrm]-5[E]-5[H])/(∑[CH
3])
∑ [CH wherein
3] be all CH
3The summation of group
The amount of following acquisition 2,1 and 3,1 errors:
[E]＝100(E
9/∑[CH
2])
[H]＝100(0.5H
2/∑[CH
2])
E wherein
9Be the peak value under 42.14ppm, H
2Be the peak value under 30.82ppm, ∑ [CH
2] be all CH
2The summation of group.
Embodiment 1 and 2 and comparative example 1 and 2
Following material is as component A), B) and C).
Component A)
PP-1: alfon, MFR are 550g/10min, and Mw/Mn is 2.3, at room temperature isotacticity index was 98.7% (isotaxy pentads (mmmm) is higher than 92%) in dimethylbenzene, the DSC temperature of fusion is 145.3 ℃, and intrinsic viscosity is 0.69dl/g, is pellet;
PP-2: alfon, MFR are 2300g/10min, and Mw/Mn is 2.6, and isotacticity index is 98.5%, and the DSC temperature of fusion is 146 ℃, and intrinsic viscosity is 0.47, is pellet;
PP-3: alfon, MFR are 12g/10min, and Mw/Mn is 5.4, and isotacticity index is 96.7%, is pellet;
PP-4: alfon, MFR are 800g/10min, and Mw/Mn is 4.3, and isotacticity index is 96%, and is spherical in shape, from MFR 400 viscosity breakings.
With obtaining PP-1 and PP-2 by using dichloride rac-dimetylsilyl two (2-methyl-4,5-benzo indenyl) to close zirconium as the described catalyst system of PCT/EP2004/007061.
To infeed pre-contacting container as the catalyst system that is catalyzer mud form of acquisition as described in the PCT/EP2004/007061, wherein it be diluted with about 5kg/h propane.This catalyst system is supplied with the prepolymerization endless tube from this pre-contacting container, wherein supply with propylene simultaneously.The residence time of catalyzer in the prepolymerization endless tube is 8 minutes.Continuously the pre-polymerized catalyst that obtains in the prepolymerization endless tube is infeeded annular-pipe reactor then, wherein under the situation of PP-1,, under the situation of PP-2, supply with propylene with the speed of 340kg/h with the speed of 329kg/h.Polymerization temperature is 70 ℃.Discharge polymkeric substance from this annular-pipe reactor, with unreacted monomer separation and dry.By the MFR of hydrogen supply control product, through regulating to obtain desired polymkeric substance MFR.Under the situation of PP-1, density of hydrogen is 550ppm, and under the situation of PP-2, density of hydrogen is 1080ppm.
B component)
GF: glass fibre White ECS O3T 480 (Nippon Electric Glass CompanyLtd), staple length is 3mm, diameter is 13 μ m.
Component C)
PP-MA: maleic anhydride (MA) grafted propylene homopolymer, MFR is 115g/10min, MA content is 1wt% (Polybond 3200, sold by Chemtura).
Component A) also contains the conventional anti-oxidant additives of about 0.3wt%.
Use twin screw extruder (model Werner﹠amp; Pfleiderer ZSK40SC) by extruding the preparation composition.
This production line has the processing length of about 43L/D and is equipped with the gravity feeding device.Via forcing the side charging with component A) and C) infeed first barrel, with B component) infeed the 5th barrel.
Tow template with cooling bath and tow cutting machine Scheer SGS 100 is used for forming pellet; Also apply vacuum stripping (barrel number 8) to extract flue dust and degradation production.
Operational conditions:
Screw speed: 200rpm;
Capacity: 50-60kg/h;
Barrel temperature: 200-220 ℃.
The final performance of the composition that is obtained is reported in Table I together with the relative quantity of component.
Table I
Footnote: Comp.=contrast
Spiral flow test
Use has the single chamber toroidal helical stream mould of the 2.5mm degree of depth, and under 230 ℃ constant melt temperature at different injection pressures (2,4,6,8,10MPa) injection embodiment 2 and comparative example's 1 composition down.
Injection molding machine is the Sandretto Model 190 with 190 tons of holding forces; Die temperature is 40 ℃.
Under these conditions, for each injection pressure, measurement flow channel length (representing with millimeter), it is directly proportional with the flowable of material.
Outcome record is in following Table II.
Table II
| Pressure | 2MPa | 4MPa | 6MPa | 8MPa | 10MPa |
| Ex.2: flow channel length | 770 | 1270 | 1690 | 2000 | ＞2000 |
| Comp.Ex.1: flow channel length | 80 | 260 | 425 | 600 | 720 |
As above shown in the table, the composition of embodiment 2 presents much higher helical flow length with respect to comparative example 1 composition for each injection-molded pressure.
This means that composition of the present invention can more easily fill mold cavity, even have those mold cavities of somewhat complex design, and allow to reduce injection-molded pressure, and produce still less warpage issues, with the minimizing molding cycle time, and aspect productivity, has economical advantage.
Embodiment 3 and 4 and comparative example 3
With identical PP-1, PP-2 and the PP-3 polymkeric substance (component A) that uses in the previous embodiment) with talcum HM05 (supplier IMI Fabi S.p.A) (B component)) extrude the composition that preparation is filled, this talcum HM05 visual inspection is tenderly white toner end, compacted density=0.31g/mL and have size less than 5 μ m more than the 95wt% particle.
In single screw extrusion machine (be total to kneader Buss model MDK70, have the screw rod of 70mm diameter, the 17L/D processing length), extrude.
Supply with component A via first opening for feed), and preferably via two vertical feed openings with B component) supply with the fusion phase.
Operating parameters is as follows:
Screw speed: 270rpm;
Capacity: 50-60kg/h;
Barrel temperature: 200-230 ℃.
Tow template with cooling bath and tow cutting machine is used for forming pellet; Also apply vacuum stripping to extract flue dust and degradation production.
The final performance of the composition that is obtained is noted down in Table III together with the relative quantity of component.
The spiral flow test that carries out as discussed previously.
Table III
Claims (9)
1. polypropene composition, it has the MFR value that records according to ISO 1133 of 15-200g/10min under the load of 2.16kg and 230 ℃, and comprises:
A) be selected from alfon or contain the propylene copolymer of 5 moles of % comonomers at the most or the propene polymer or the polymer composition of the combination of described homopolymer or multipolymer, described homopolymer and multipolymer have 500-2500g/10min in the MFR value that does not have to obtain under the situation of degradation treatment
B) filler or pigment, or their combination; With optional
C) with respect to A), B) and gross weight meter C), the 0.5-5wt% expanding material.
2. the composition of claim 1, wherein component A) alfon and multipolymer be in the polymerization in the presence of the metallocene-based catalyst systems, directly to obtain.
3. the composition of claim 1, wherein component A) alfon and multipolymer have molecular weight distribution according to the Mw/Mn ratio less than 4.
4. the composition of claim 1 comprises 10wt%-80wt%A) and 20wt%-90wt%B), with respect to A) and gross weight meter B).
5. the composition of claim 1 comprises 10wt%-75wt%A), 20wt%-89wt%B) and 0.5wt%-5wt%C), with respect to A), B) and gross weight meter C).
6. the composition of claim 1, wherein B) be selected from mineral filler and fiber or their combination.
7. the composition of claim 5, wherein B) form by glass fibre basically.
The composition of claim 1 by injection-molded, extrude or thermoforming prepares the purposes of goods.
9. the composition of claim 1 is as the purposes of enriched material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310716906.9A CN103739949B (en) | 2006-12-20 | 2007-12-12 | Polypropene composition containing filler and/or pigment |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06126677.1 | 2006-12-20 | ||
| EP06126677 | 2006-12-20 | ||
| US60/876,741 | 2006-12-22 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310716906.9A Division CN103739949B (en) | 2006-12-20 | 2007-12-12 | Polypropene composition containing filler and/or pigment |
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| Publication Number | Publication Date |
|---|---|
| CN101563416A true CN101563416A (en) | 2009-10-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200780047410XA Pending CN101563416A (en) | 2006-12-20 | 2007-12-12 | Polypropylene compositions containing fillers and/or pigments |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN101563416A (en) |
| AT (1) | ATE543868T1 (en) |
| ES (1) | ES2381625T3 (en) |
| TW (1) | TW200833714A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110291139A (en) * | 2017-01-10 | 2019-09-27 | 国际人造丝公司 | The propylene compositions of long fiber reinforcement for thin part |
| CN110291140A (en) * | 2017-01-10 | 2019-09-27 | 国际人造丝公司 | The propylene compositions of high flow fiber enhancing with low emission |
-
2007
- 2007-12-05 TW TW96146216A patent/TW200833714A/en unknown
- 2007-12-12 AT AT07857483T patent/ATE543868T1/en active
- 2007-12-12 ES ES07857483T patent/ES2381625T3/en active Active
- 2007-12-12 CN CNA200780047410XA patent/CN101563416A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110291139A (en) * | 2017-01-10 | 2019-09-27 | 国际人造丝公司 | The propylene compositions of long fiber reinforcement for thin part |
| CN110291140A (en) * | 2017-01-10 | 2019-09-27 | 国际人造丝公司 | The propylene compositions of high flow fiber enhancing with low emission |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE543868T1 (en) | 2012-02-15 |
| ES2381625T3 (en) | 2012-05-30 |
| TW200833714A (en) | 2008-08-16 |
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