CN1252824A - Compositions containing slip and anti-block agents - Google Patents

Compositions containing slip and anti-block agents Download PDF

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CN1252824A
CN1252824A CN98804203A CN98804203A CN1252824A CN 1252824 A CN1252824 A CN 1252824A CN 98804203 A CN98804203 A CN 98804203A CN 98804203 A CN98804203 A CN 98804203A CN 1252824 A CN1252824 A CN 1252824A
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benchmark
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alkyl
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L·K·摩根哈根
B·E·西蒙斯
R·维沃斯
B·菲尔
W·R·范沃肯伯格
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Dow Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—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
    • C08L23/0838—Copolymers of ethene with aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

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Abstract

Disclosed are resin compositions comprising: a homogeneous ethylene/ alpha -olefin interpolymer; and a saturated fatty acid amide or saturated ethylenebis(amide); and an unsaturated fatty acid amide or unsaturated ethylenebis(amide); and a finely divided inorganic compound. Also disclosed are compositions comprising a saturated fatty acid amide or saturated ethylenebis(amide), an unsaturated fatty acid amide or unsaturated ethylenebis(amide), and a finely divided inorganic compound and a substantially random interpolymer of one or more alpha -olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers or blend compositions therefrom. Also disclosed are compositions which comprise at least one homogeneous ethylene/ alpha -olefin interpolymer or substantially random interpolymer of one or more alpha -olefins with one or more vinylidene aromatic monomers and/or or more hindered aliphatic or cycloaliphatic vinylidene monomers, at least one slip agent, and at least one modifying agent comprising propylene homopolymers, propylene copolymers, nucleating agents, and mixtures thereof.

Description

The composition that contains slip(ping)agent and caking inhibiter
The present invention is directed to olefin polymer compositions, this polymer composition is used for anti stick and optical improved film.Theme of the present invention is a kind of composition, it comprises unsaturated fatty acid amide or saturated ethylene bisamides, unsaturated fatty acids acid amides or unsaturated ethylene bisamides and segmentation mineral compound, when the blend composition that is used to contain the homogeneous ethylene/alpha-olefin copolymer and obtains thus, these components are in conjunction with obtaining best anti-skidding and anti stick value.The present invention is also at such composition, it comprises unsaturated fatty acid amide or saturated ethylene bisamides, unsaturated fatty acids acid amides or unsaturated ethylene bisamides and segmentation mineral compound, when the composition of the random multipolymer basically that is used to contain one or more alpha-olefins and one or more vinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer or the blend composition that obtains thus, these components are in conjunction with obtaining best anti-skidding and anti stick value.The present invention is also at such composition, it comprises the random basically multipolymer of at least a homogeneous ethylene/alpha-olefin copolymer or one or more alpha-olefins and one or more vinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer, at least a slip(ping)agent, with at least a properties-correcting agent, described properties-correcting agent contains alfon, propylene/alpha-olefins multipolymer, nucleator, and their mixture.
Alathon and ethylene/alpha-olefin copolymer have importance for making various products.They comprise the film of blowing and curtain coating and individual layer and coextrusion, and the latter is used for many application, and for example multilayer and flexible package sealing material are particularly by means of vertical, level or thermoforming/seal-packed material.Be processed into such goods for this resinoid is easy to, the gained thin film layer must have good sliding and anti stick.
The sliding of polyolefin film or layer is one deck the measuring of slip ability on another layer, normally with frictional coefficient (COF) expression of film.Low sliding (or great friction coefficient) is harmful to the automatic high speed packaging operation.Low sliding usually causes equipment to stain, reduces the time greatly, and incomplete product.The film of sliding difference is difficult to dispose when producing with large-scale roller, and the friction process that causes because of processing units, when particularly making film and be out of shape.Typically, the density along with polyolefin compositions descends general raising of the viscosity of film and frictional coefficient increasing.
" bonding " of polyolefin film or layer is even property may be defined as film or layer owing to self the agglutinating proneness of slightly exerting pressure also.This " bonding " also more or less depends on or is decided by amount of pressurization and clamping time and temperature." destructive bonding " refers to the irreversible basically adherent proneness of formation, and it probably causes film deformation or tears.This " destructive bonding " even very little at moulding pressure, for example makes the film roller, also can occur when especially making roller, storage or transportation under very warm or awfully hot condition.Bonding can by add the segmentation mineral filler for example silicon-dioxide reduce.But, add the optical characteristics that too high-load filler is unfavorable for film.If film has very high bonding proneness, this adhesion also may cause deformation of thin membrane and tear in the course of processing so.
These problems have caused developing a large amount of additives or such reagent, when they are included in the polymer composition, can improve sliding and reduce the polymeric film agglutinating proneness of producing.Use this slip(ping)agent or caking inhibiter to become the theme of many open source literatures, this part is because multiple such additive, also may be because the kind of such additive and combination (and their absolute and relative amount) change according to the character of the polymkeric substance that mixes mutually with them.For example, when this century 70 and the eighties are sold with the low-pressure vapor phase of ziegler produced or liquid phase new LDPE (film grade) (LLDPE) merchant, with respect to before introducing LLDPE with regard to the polyolefine of widely used radical polymerization, these new LDPE (film grade)s require to keep sliding and anti stick with new additive packing.For example, United States Patent (USP) 4394474 (McKinney etc.) has been narrated a kind of method that reduces cohesiveness by the natural mineral component that adds a kind of secondary fatty acid amide and segmentation in polymkeric substance in the pressing mold film of LLDPE and improve sliding.United States Patent (USP) 4430289 (McKinney etc.) has been narrated a kind of method that reduces cohesiveness and raising sliding by the natural mineral component that adds a kind of secondary fatty acid amide with saturated alkyl and unsaturated thiazolinyl and segmentation in polymkeric substance in the blown film of LLDPE.United States Patent (USP) 4454272 (McKinney etc.) has been narrated the composition of the blend that comprises high molecular LLDPE, secondary fatty acid amide and segmentation natural mineral.United States Patent (USP) 4529764 (McKinney etc.) has been narrated a kind of extrusion blow film, and this film mainly is made up of the blend of high molecular LLDPE, secondary fatty acid amide and segmentation natural mineral.United States Patent (USP) 4751262 (Mckinney etc.) has been narrated the composition that comprises ethylene/acrylic acid copolymer or ionomer, saturated secondary fatty acid amide, unsaturated or mixing/unsaturated secondary fatty acid amide and segmentation natural mineral.United States Patent (USP) 4785042 (Azuma etc.) has been narrated polyethylene resin composition, comprises new LDPE (film grade), Buddhist stone, fatty acid amide and static inhibitor.United States Patent (USP) 5393814 (Chen etc.) has been narrated the composition of matter of the alkenyl monoamide that comprises polyolefine, dicarboxylic acid.At last, J610119644-A has narrated the linear low density polyethylene resin that contains LLDPE, fatty acid amide and/or silica gel particle.
In recent years, the metallocenyl catalyzer of introducing for the ethylene/alpha-olefin copolymerization causes producing the ethylene copolymer that makes new advances (term " multipolymer " refers to such polymkeric substance, and wherein at least two different monomer polymerizations obtain comprising the multipolymer of multipolymer, terpolymer etc.).These metalloscene catalysts comprise two (cyclopentadienyl).Catalyst system and single (cyclopentadienyl)-or the constrained geometry catalyst system.This class constrained geometry metal complexes and preparation method thereof is disclosed in United States Patent (USP) 545403, the applying date: July 3 nineteen ninety (european patent application 416815); European patent application 468651; Europe patent application 514828; U.S. Patent application 876268, May 1 1992 applying date (european patent application 520732) and U.S. Patent application 5374696; U.S. Patent application 5470993; U.S. Patent application 5055438; U.S. Patent application 5057475; U.S. Patent application 5096867; U.S. Patent application 5064802 and U.S. Patent application 5132380.In addition, open and claimed specific cationic derivative in U.S. Patent application 5132380 as the very useful aforementioned constrained geometry catalyzer of olefin polymerization catalysis.In U.S. Patent application 5453410, the combination of positively charged ion constrained geometry catalyzer and aikyiaiurnirsoxan beta is disclosed as suitable olefin polymerization catalysis.Wherein contained narration, aforementioned unsettled U.S. Patent application, the United States Patent (USP) and the disclosed european patent application of mandate are incorporated into this paper as a reference in this integral body.
The use of this class catalyst system has obtained new ethylene copolymer, therefore the composition that contains these materials has been had new requirement.Such polymkeric substance is called homogeneous copolymers, it is characterized in that with respect to catalytic its narrow molecular weight distributions of phase polyolefin polymkeric substance of for example traditional Ziegler and form distributing.Although do not wish to be bound by any theory, homogeneous copolymers is often greater than 0.92 gram per centimeter 3Be clamminess little than homologous heterophasic copolymer under the density; And less than about 0.92 gram per centimeter 3Density under be clamminess and want high.So, comprise that the new composition of these materials must be obtained purpose sliding and anti stick level, keep for example optical characteristics of other key properties simultaneously.
Homogeneous copolymers with improved strength characteristics and the trial that combines of the heterophasic copolymer inherent treatment characteristic homogeneous copolymers that also caused exploitation to comprise producing and with the composition of the blend of the heterophasic copolymer of traditional ziegler produced with metalloscene catalyst.Suitable blend composition and production method thereof are disclosed in U.S. Patent application 08/510527, the applying date: August 2 nineteen ninety-five; With 08/747419, the applying date: on November 12nd, 1996, the full content of these patent applications is incorporated into this paper as a reference at this.The composition that such blend also will be looked for novelty has and realizes purpose sliding and required improved sliding and the anti stick of anti stick level.
Except ethene/aliphatic alpha-olefin multipolymer, also can use the basic random copolymers of new constrained geometry catalyzer with the alpha-olefin/vinylidene monomer that is obstructed of preparation common species, comprise the material of alpha-olefin/binyl aromatic monomer multipolymer or the like.These materials, for example the ethylene/styrene multipolymer provides the very wide structure of matter and has made it be used for the characteristic of different application.Have again, particularly concerning the film of this material is used, need comprise that the composition of these materials is realized purpose sliding and bond level.
So, homogeneous copolymers composition or random substantially alpha-olefin and one or more vinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer composition are provided, and such composition has good anti stick and low COF, also keeps good physical property simultaneously; And keep good optical, and also have anti-abuse simultaneously, will be favourable.
In addition, the composition of the blend of the basic random copolymers that comprises homogeneous copolymers or alpha-olefin and one or more vinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer is provided, and such composition has good anti stick and low COF value, also keeps good physical property simultaneously; And keep good optical to comprise stopping property and anti-abuse, also be favourable.
Finish these and other advantage by following embodiment of the present invention.
The present invention relates to such composition, comprising:
(A) has homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; With
(B) unsaturated fatty acid amide or saturated ethylene bisamides; With
(C) unsaturated fatty acids acid amides or unsaturated ethylene bisamides; With
(D) segmentation mineral compound; And wherein the concentration sum of B component and C is greater than 1500ppm, with component A, and B, the combination weight meter of C and D, and when resin combination was made the blown film of thickness 2 mils, described film was characterised in that having the cohesiveness and the COF that are lower than 49 grams is lower than 0.31.
The invention still further relates to such composition, comprising: (A) a kind of copolymer blended compositions comprises:
(1) has homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; With
(2) second kinds of multipolymers comprise:
(a) has homogeneous ethylene/alpha-olefin copolymer that wide composition distributes; Or
(b) has different I 2Or density, or Mw, or the multipolymer of Mw/Mn; Or
(c) (a) or arbitrary combination (b); (B) unsaturated fatty acid amide or saturated ethylene bisamides; (C) unsaturated fatty acid amide or unsaturated ethylene bisamides; (D) segmentation mineral compound; And wherein the concentration sum of B component and C is greater than 1500ppm, with component A, and B, the combination weight meter of C and D, and when resin combination was made the blown film of thickness 2 mils, described film was characterised in that having the cohesiveness and the COF that are lower than 49 grams is lower than 0.31.
The inventor is surprised to find, during blend composition that three blend of components of unsaturated fatty acid amide or saturated ethylene bisamides, unsaturated fatty acids acid amides or unsaturated ethylene bisamides and segmentation mineral compound obtain at the composition that is used to comprise homogeneous ethylene/alpha-olefin copolymer or by it, this three component is in conjunction with obtaining sliding and close-burning optimum value.In addition, generally under the condition of not losing other key properties that comprise optical, stopping property and anti-abuse, can realize these advantages.The application of these resins comprises blowing and curtain coating and individual layer and co-extrusion film, and they can be used for multilayer and flexible package sealing material, particularly by means of vertical, horizontal or thermoforming filling/seal-packed material.
The invention still further relates to such composition, comprising:
(A) at least a random substantially multipolymer: wherein said multipolymer comprises:
(1) polymer unit of 0.5-65 mole %, derived from:
(a) at least a vinylidene aromatic monomer, or
(b) at least a hindered aliphatic vinylidene monomer, or
(c) at least a vinylidene aromatic monomer and the monomeric molectron of at least a hindered aliphatic vinylidene; With
(2) 35-99.5 mole % is derived from least a aliphatic C 2-C 20The alpha-olefinic polymer unit; With
(B) unsaturated fatty acid amide or saturated ethylene bisamides; Or
(C) unsaturated fatty acid amide or unsaturated ethylene bisamides; Or
(D) segmentation mineral compound; Or
(E) (B), (C) and (D) at least a molectron.
The invention still further relates to such composition, comprising:
(A) a kind of resin combination comprises:
(1) has homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; Or
(2) at least a basic random copolymers; Wherein said multipolymer comprises:
(a) polymer unit of 0.5-65 mole %, derived from:
(i) at least a vinylidene aromatic monomer, or
(ii) at least a hindered aliphatic vinylidene monomer, or
The inferior ethene of (iii) at least a vinylidene aromatic monomer and at least a hindered aliphatic
The base monomer; With
(b) 35-99.5 mole % is derived from least a aliphatic C 2-C 20The alpha-olefinic polymer unit; With optional
(3) alfon or propylene and one or more C 2-C 30The copolymerization of alpha-olefin
Thing; With
(B) one or more:
(1) unsaturated fatty acid amide or saturated ethylene bisamides; Or
(2) unsaturated fatty acid amide or unsaturated ethylene bisamides; Or
(3) molectron of B (1) and B (2); With
Choose wantonly,
(C) a kind of nucleator.
To understand these and other characteristics of the present invention better with appended claim with reference to the following drawings.
Element that belongs to certain family or metal that this paper is alleged all referred to CRC Press, and Inc. published and obtained the periodic table of elements of copyright in 1989.Alleged family is the family that adopts IUPAC name family system to react in the periodic table of elements.
Any numerical value described herein comprises all values of a unit increment of value from the low value to the height, and condition is the interval that at least 2 units are arranged between any low value and any high value.For example, be 1-90 for example if point out component concentration or process variable such as the numerical value of temperature, pressure and time, preferred 20-80, more preferably 30-70 just equals clearly to have enumerated 15-85,22-68,43-51,30-32 or the like in this specification sheets.For the numerical value that is lower than 1, it is believed that a unit is 0.0001,0.001,0.01 or 0.1 is very suitable.Only particularly point out, and be considered in the application's book, point out specially in a similar manner in cited Schwellenwert to the possible combinations of values between the maximum with an example.
Term " alkyl " means any aliphatic series herein, cyclic aliphatic, and aromatics, aryl replaces aliphatic series, aryl substituted ring aliphatic series, aliphatic series replaces aromatics, or aliphatic substituted ring aliphatic group.
Term "-oxyl " means the alkyl that an oxygen key is arranged between it and the carbon atom that connected herein.
Term " silyl " means the group that a silicon key is arranged between it and the carbon atom that connected.
Term " germyl " means the group that a germanium key is arranged between it and the carbon atom that connected.
Term " substituted cyclopentadienyl " is intended to comprise that the ring of cyclopentadienyl residue replaces or the multinuclear derivative, wherein substituting group is an alkyl,-oxyl, alkyl amino, cyano group, halo, silyl, germyl, siloxy or its mixture, or two such substituting groups are alkylene, and substituting group (or two substituting groups together) has 30 non-hydrogen atoms at the most.The object lesson of substituted cyclopentadienyl has indenyl, tetrahydroindenyl, fluorenyl and octahydro fluorenyl.
Term " bronsted acid positively charged ion " means a kind of positively charged ion that plays the protophobe effect.
Multipolymer used herein refers to such polymkeric substance, and wherein at least two different monomer polymerizations obtain multipolymer.This multipolymer comprises multipolymer, terpolymer, or the like.
For composition of the present invention, the COF value is measured after 24 hours according to ASTM D-1894 (use TMI directly to drive and monitor slip and rub(bing)test instrument).For the present invention, " good " sliding is that the COF value is lower than 0.31.
For composition of the present invention, cementing value is measured under off line according to ASTM D-3354-89 (using Kayeness cementation test instrument).For the present invention, " good " cohesiveness is that resin is lower than 49 grams.
The density that is used for polymer composition of the present invention is that ASTM D-792 measures.
The molecular weight that is used for polymer composition of the present invention adopts ASTM D-1238, and condition (normally is called ' condition (E) ', is also referred to as I for 190 ℃/2.16 kilograms 2) the melt index determination method represent easily.The molecular weight of melting index and polymkeric substance is inversely proportional to.So molecular weight is high more, melting index is just low more, although ratio is not linear.
Other useful physical characteristic measurements of using for the new copolymer compositions of this paper introduction comprise molten flow rate (MFR), that is: by measuring I 10(according to ASTM D-1238, condition 190 ℃/10 kilograms (normally being called ' condition (N) ') is also used I 2Remove gained I 10Measure.The ratio of these two melting index is molten flow rates, is defined as I 10/ I 2
Molecular weight of the present invention (Mw) and distribute (Mw/Mn) adopt gel permeation chromatography (GPC), and (the system operation temperature is 140 ℃) measured on the Waters 150C high temperature chromatogram arrangement of being furnished with mixing porous post.Its solvent is 1,2, the 4-trichlorobenzene, and the sample solution for preparing 0.3% weight thus is used for injection.Flow velocity is that 1.0 ml/min and injection are of a size of 100 microlitres.
The mensuration of molecular weight is to utilize the polystyrene standard of narrow molecular weight distributions (from PolymerLaboratories) to infer together with its effluent volume.The mensuration of the molecular weight of polyethylene that is equal to be utilize the suitable Mark-Houwink coefficient that is used for polyethylene and polystyrene (as described in Williams and the Ward at the polymer science magazine, Polymer Letters, the 6th volume (621) is described in 1968) obtain following equation:
M Polyethylene=a *(M Polystyrene) bIn this formula, a=0.4316 and b=1.0.Weight-average molecular weight Mw and number-average molecular weight Mn are calculated as follows in normal way:
M j=(∑ W i(M i j)) jW wherein iBe to be M by the molecular weight that GPC post wash-out goes out iThe weight fraction of the mark i of molecule, and when calculating Mw j=1, j=-1 when calculating Mn.
Except stock polymer, composition of the present invention can comprise unsaturated fatty acid amide or ethylene bisamides, unsaturated fatty acids acid amides or ethylene bisamides and segmentation mineral compound.
Be used for unsaturated fatty acid amide of the present invention and meet following empirical formula substantially:
R aC (O) NHR bR wherein aBe C 10-C 26Saturated alkyl, and R bBe hydrogen or C independently 10-C 26Saturated alkyl.The example of the compound that conforms to above empirical formula structure is palmitic amide, stearylamide, peanut acid amides, mountain Yu acid amides, stearyl stearylamide, palmityl palmitic amide, stearyl peanut acid amides and composition thereof.
Be used for saturated ethylene bisamides of the present invention and meet empirical formula substantially
R aC (O) NHCH 2CH 2NHC (O) R aR wherein aDefinition as above.The example of the compound that conforms to the following formula structure is a stearyl amido ethyl stearylamide, stearyl amido ethyl palmitic amide, palmityl amido ethyl stearylamide and composition thereof.
Be used for this R that conforms to following formula of unsaturated fatty acids amide group of the present invention c(CO) NHR dR wherein cBe C 10-C 26Unsaturated alkyl and R dBe hydrogen or C independently 10-C 26Unsaturated alkyl.The example of the compound that meets with above empirical formula is oleylamide, mustard acid amides, linolenamide and composition thereof.
Being used for unsaturated ethylene bisamides of the present invention meets with following empirical formula substantially:
R eC (O) NHCH 2CH 2NHC (O) R eR wherein eBe C 10-C 26Saturated or unsaturated alkyl, condition is at least one R eBe undersaturated.The compound that meets with above empirical formula structure comprises mustard amido-ethyl mustard acid amides, oleoyl amido ethyl oleylamide, mustard amido-ethyl oleylamide, oleoyl amido ethyl mustard acid amides; stearyl-ethyl mustard acid amides; mustard amido-ethyl palmitic amide, palmityl amido ethyl oleylamide and composition thereof.
Be used for segmentation mineral compound of the present invention and include but not limited to following material: clay, pure aluminium silicate, diatomite, silicon-dioxide, talcum, Wingdale, fumed silica, sal epsom, Magnesium Silicate q-agent, hibbsite, magnesium oxide, zinc oxide, titanium dioxide are good with siliceous material.Mineral compound preferably has the median size of 0.02-40 micron, the surface-area of 0.7-1000 meters squared per gram, and 21-175 part oil/100 parts of organic oil suction matter.
Homopolymer of the present invention defined herein and multipolymer illustrate that its disclosure is incorporated into this paper as a reference in United States Patent (USP) 3645992 (Elston).Therefore, homopolymer and multipolymer are that wherein comonomer random distribution and wherein basic all copolymer molecules in the copolymer molecule of being given has identical ethene/comonomer ratio in this multipolymer.Such multipolymer is different with the catalytic multipolymer of typical Ziegler that is called homogeneous copolymers, and latter's copolymer molecule does not have identical ethene/comonomer ratio.This homopolymer is also different with the LDPE that the catalytic vinyl polymerization of high-pressure free radical obtains, and the high branched polyethylene that this polyreaction obtains is that this area professional is known, has a lot of long chain branches.
The comonomer distribution of homogeneous copolymers described in term used herein " narrow composition distribution ", mean according to dsc (DSC) and measure, this homogeneous copolymers only has single melting peak, and does not have " high-density " polymer fraction that can survey basically.
The homogeneous copolymers additional features that narrow composition distributes is SCBDI (short chain branch dispersion index) or CDBI (forming distribution branch index), its weight percentage that is defined as polymer molecule with co-monomer content average total mole co-monomer content 50% in.The CDBI of polymkeric substance is easy to the data computation that obtained by technology known in the art, elution fractionation (abbreviating TREF as) for example heats up, ' polymer science magazine ' referring to people such as for example Wild, the Poly.Phys.Ed.20 volume, 441 pages (1982), United States Patent (USP) 4798081 (people such as Hazlitt), or referring to United States Patent (USP) 5008204 (Stehling), it is for referencial use that its disclosed content is incorporated into this paper.The technology of CDBI illustrates that the content of all these patent disclosures is incorporated into this paper as a reference at this in United States Patent (USP) 5322728 (people such as Davey) and United States Patent (USP) 5246783 (people such as Spenadel) or United States Patent (USP) 5089321 (people such as Chum).The SCBDI or the CDBI of the ethylene/alpha-olefin copolymer of the narrow composition of using for the present invention of homogeneous phase are higher than 50%, preferably are higher than 70%, more preferably are higher than 90%.
According to the TREF technical measurement, being used for homogeneous copolymers that narrow composition of the present invention distributes does not have " high-density " (or homopolymer) cut that can survey substantially.Homogeneous copolymers and polymkeric substance preferably are lower than 10% weight in 15% weight or following, particularly are lower than the degree of branching that has in 5% weight and are less than or equal to 2 methyl/1000 carbon.
In the component of the present invention, also comprise the ethylene/alpha-olefin copolymer of substantially linear.The ethylene/alpha-olefin copolymer of substantially linear of the present invention has definition in United States Patent (USP) 5272236 and 5278272, it is for referencial use that described United States Patent (USP) is incorporated into this paper at this.The ethylene/alpha-olefin copolymer of substantially linear also is a homogeneous copolymers, because comonomer is a random distribution in the copolymer molecule of being given, and all copolymer molecules have identical/comonomer ratio substantially.
But, term " substantially linear " ethylene/alpha-olefin copolymer means polymkeric substance and also contains long chain branches.Long chain branches is defined herein as total carbon number in the comonomer and deducts two carbon and add the chain length of at least one, for example the long chain branches length of the ethylene copolymer of ethylene/octene substantially linear is 7 carbon (that is, 8 subtract 2 equal 6 and add 1 to equal 7 carbon long chain branches long) at least.Long chain branches can be isometric with main polymer chain.The long chain branches degree is to adopt 13(NMR) is spectrometric for the C-nucleus magnetic resonance, and with the qualitative (Rev.Macromol.Chem.Phys.C29 (2﹠amp of the method for Randall; 3) 285-297 page or leaf), it is for referencial use that its disclosure is incorporated into this paper.Certainly, the long chain branches degree is different with the short chain degree of branching, and the latter only obtains by adding comonomer, and for example the polymkeric substance of ethylene/octene substantially linear is that 6 carbon are long, and the long chain branches of same polymer is that at least 7 carbon are long.
More particularly, polymkeric substance is defined as 0.01 long chain branches/1000 carbon to 3 long chain branches/1000 carbon, more preferably 0.01 long chain branches/1000 carbon to 1 long chain branches/1000 carbon, preferred especially 0.05 long chain branches/1000 carbon to 1 long chain branches/1000 carbon.
The ethylene/alpha-olefin copolymer that is used for substantially linear of the present invention has good processibility astoundingly, even they are as narrow molecular weight distributions.The ethylene/alpha-olefin copolymer of substantially linear has the molecular weight distribution mw/mn of following formula definition:
Mw/Mn≤(I 10/I 2)-4.63
Even more surprised be the molten flow rate (I of substantially linear olefin polymer 10/ I 2) irrespectively change with heterogeneity index (Mw/Mn) in fact.This presents a contrast with the traditional heterogeneous ramose linear polyethylene resin with rheological, thereby along with polydispersity index improves, I 10/ I 2Value also improves.For the substantially linear ethene/alpha-olefinic polymer that is used for composition of the present invention, I 10/ I 2Than representing the long chain branching degree, that is: I 10/ I 2Higher than more, the long chain branching degree in the polymkeric substance is just high more.
" rheology processing index " is the apparent viscosity (thousand pools) that adopts the polymkeric substance of gas phase squeezing rheometer (GER) mensuration (PI).The gas phase squeezing rheometer by M.Shida.R.N.Shroff and L.V.Cancio at ' polymer engineering science ' the 17th volume, No. 11, in 770 pages (1977) and John Dealy, Van Nostrand Reinhold Co. (1982), illustrate that these two pieces of article integral body are incorporated this paper into as a reference in ' molten plastic rheometer ' 97-99 page or leaf that the 97-99 page or leaf is published.All GER tests all are at 190 ℃, and under the nitrogen pressure of 5250-500psig, use 0.0296 inch diameter and have 20 of 180 degree inlet angles: the 1L/D mould carries out.For substantially linear ethene/alpha-olefinic polymer as herein described, PI adopts GER 2.15 * 10 6The apparent viscosity (thousand pools) of the material that this measures down because of the apparent shearing stress of/square centimeter.The preferred PI of substantially linear ethene/alpha-olefinic polymer as herein described is 0.01-50 thousand pools, more preferably 15,000 pools or littler.The PI of substantially linear ethene/alpha-olefinic polymer be less than or equal to correlated substantially linear ethene/alpha-olefinic polymer PI 70%, described contrast substantially linear ethene/alpha-olefinic polymer does not contain long chain branches, but has identical I 2And Mw/Mn.
Use apparent shearing stress that apparent shearing rate curve is identified the melt fracture phenomenon.According to Ramamurthy in that ' 1986 is described for rheology magazine ' 30 (2), 337-357, is being higher than a specific critical flow velocity, and the extrudate irregularity of observation can broadly be divided into two big classes: surperficial melt fracture and melt fracture.
The surface melt fracture appears under the apparent steady flow condition, and concrete scope is that specular gloss is lost to harsher " shark skin ".In this article, the feature that surperficial melt fracture begins (OSMF) is to begin to lose extrudate gloss, and this moment, the surface roughness of extrudate can only be gone out by 40 times of amplification detection.Critical shear rate when the surperficial melt fracture of substantially linear ethene/alpha-olefin copolymer begins to occur is higher than and does not contain long chain branches, but has identical I 2Critical shear rate at least 50% when beginning to occur, wherein used here " identical " with the surperficial melt fracture of substantially linear ethene/alpha-olefinic polymer of Mw/Mn mean each value be the correlative value of contrast linear tetrafluoroethylene polymer 10% within.
Melt fracture appears under the unsettled flow condition, and concrete scope arrives random distortion by rule (the rough and smooth, spiral or the like are alternately).For commercial acceptable, (for example, in the blown film product), defective just should be minimum if not non-existent words.This paper is based on the surface roughness of the extrudate of being extruded by GER and the variation of configuration, the critical shear rate of (OGMF) when (OSMF) and whole melt fracture begin to occur when using surperficial melt fracture to begin to occur.
The illustrative metalloscene catalyst that is used to prepare the ethylene/alpha-olefin copolymer component that the narrow composition of homogeneous phase of the present invention distributes comprises:
A) satisfy the metal complexes of following formula:
L iMX pX ' qIt has had catalytic activity or afterwards by combine or use activating technology to give catalytic activity with active cocatalyst, wherein: M is the periodic table of elements 4 family's metals, have+2 ,+3 or+4 valency oxidation state, with η 5The keyed jointing mode is attached on one or more L groups;
The each appearance of L is cyclopentadienyl independently, indenyl, tetrahydroindenyl, fluorenyl, tetrahydro-fluorenyl or octahydro fluorenyl, described group can selectively be substituted with 1-8 substituting group arbitrarily, described substituting group is selected from: alkyl, halogen, halo alkyl, hydrocarbyl amino,-oxyl, dialkyl amino, dialkyl phosphino-, silyl, the-oxyl silyl, with contain the halo silyl of 20 non-hydrogen atoms at the most, or two further optional such L bases can link together by a divalent substituent, described substituting group is selected from hydrocarbon two bases, halohydrocarbon two bases, inferior-oxyl, inferior hydrocarbon amino, silane two bases, halogenated silanes two bases, with contain the divalence aminosilane base of 20 non-hydrogen atoms at the most;
It is the ligand group of univalent anion 6-bonding that X occurs at every turn, two valence links are all linked the ligand group of the dianion 6-bonding on the M, or valence link links that M goes up and another valence link is linked the ligand group of the dianion 6-bonding on the L group, and described X contains 60 non-hydrogen atoms at the most;
The each appearance of X ' is the ligand compound of the neutral Lewis base of 20 atoms at the most independently;
1 is 1 or 2;
P is 0,1, or 2, and when X is that the ligand group of univalent anion 6-bonding or valence link link that M goes up and another valence link when linking the ligand group of the dianion 6-bonding on the L group, normal oxidation attitude than M lacks 1, or when X be two valence links when all linking the ligand group of the dianion 6-bonding on the M, lack 1+1 than the normal oxidation attitude of M; With
Q is 0,1, or 2.
It is believed that, the catalyzer that is used to prepare the ethylene/alpha-olefin copolymer component that the narrow composition of homogeneous phase of the present invention distributes with one or more derived from the aforementioned metal title complex a) positively charged ion or the form of mixtures of zwitter-ion species occur.Complete positively charged ion or the isolating metal complexes of Partial charge, promptly the zwitter-ion metal complexes discloses in the United States Patent (USP) 5470993 and 5486632 in front, and its content of telling about is incorporated into this paper as a reference at this.
It is believed that cationic complexes meets following formula:
L iM +M P-1A -Wherein: M is 4 family's metals ,+4 or+3 normal oxidation attitudes; L, X, l and p definition are as above; And
A -Be derived from the compatible negatively charged ion of the non-coordination of active co catalyst.
Specifically, the zwitter-ion title complex is with Lewis acid activation promotor, particularly three (perfluor aryl) borine, obtain by 4 family's metal diene complexes (for the cyclopentenes form of metal replacement) activation, wherein metal be+4 normal oxidation attitudes (promptly, X is a 2-butylene-1,4-two bases, or the derivative of its alkyl replacement, two valence link is all linked on the M).These zwitter-ion title complexs it is believed that and meet following formula:
L iM -X P-1X *-A -Wherein
M is+4 family's metals of 4 normal oxidation attitudes;
L, X, l and p definition are as above;
X *Be the residue of divalent X ' of conjugated diolefine, it is that metallic bond open loop by the cyclopentenes that on a carbon metal is replaced forms; With
A -Be derived from active cocatalyst and the compatible negatively charged ion of non-coordination.
Terminology used here " non-coordination " mean negatively charged ion neither with a) coordination of component, also or only very weakly with its coordination, keep enough reactivity so that replace by Lewis base (comprising alpha-olefin).Specifically, non-coordination anion refers to a kind of like this negatively charged ion, do the time spent when it plays charge balance cation in catalyst system of the present invention, do not give described positively charged ion its fragment delivery, thereby form neutral four-coordination metal complexes and neutral by product.When " compatible negatively charged ion " do not influenced by the polymerization of required back for decomposing when the initial title complex that forms, be not degraded into the neutral negatively charged ion.
Preferred X ' group is a phosphine, particularly trimethyl-phosphine, triethyl phosphine, triphenylphosphine and two (1,2-dimethyl phosphino-) ethane; P (OR) 3, (wherein R is C 1-C 30Alkyl); Ether, particularly tetrahydrofuran (THF); Amine, particularly pyridine, dipyridyl, tetramethylethylened (TMEDA) and triethylamine; Alkene; And C 4-C 40Conjugated diolefine.The title complex that comprises conjugated diolefine X ' group has the title complex of those metals for+2 normal oxidation attitudes.
Be used for title complex of the present invention example a) and comprise aforementioned species: Wherein: M is a titanium, zirconium or hafnium, preferred zirconium or hafnium (+2 or+4 normal oxidation attitudes); In each the appearance, R 3Be independently selected from hydrogen, alkyl, silyl, first silicon Germanium based, cyano group, halogen and composition thereof, described R 3Have 20 non-hydrogen atoms at the most, or adjacent R 3Base forms divalent derivative (that is, hydrocarbon two bases, silane two bases or germane two bases) together, forms thus and condenses ring system.X " each appearance is the anion ligand group of 40 non-hydrogen atoms at the most independently; or two X " base is formed up to the dianion coordinating group of many 40 non-hydrogen atoms together or is the conjugated diolefine with 4-30 non-hydrogen atom together, form π-title complex with M, wherein M is+2 normal oxidation attitudes, R *Each appearance is C independently 1-4Alkyl or phenyl, the each appearance of E is carbon or silicon independently, and x is integer 1-8.
Metal complexes other example a) is to satisfy formula: LMX pX ' q(III) material,
L wherein, M, X, X ', p and q definition are as above.Preferred metal complexes belongs to preceding class (III) and satisfies following formula:
Wherein:
M is a titanium, zirconium or hafnium (+2 ,+3 or+4 normal oxidation attitudes);
R 3In each appearance, be independently selected from hydrogen, alkyl, silyl, first silicon Germanium based, cyano group, halogen and composition thereof, described R 3Have 20 non-hydrogen atoms at the most, or adjacent R 3Base forms divalent derivative (that is, hydrocarbon two bases, silane two bases or germane two bases) together, forms thus and condenses ring system, each X " be halogen, alkyl,-oxyl; hydrocarbon amino or silyl, described group have 20 non-hydrogen atoms at the most, or two X " base forms neutral C together 5-30Conjugated diolefine or its divalent derivative;
Y is-O--S-,-NR *-,-PR *-; Z is SiR * 2CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR *=CR *, CR * 2SiR * 2Or GeR * 2, R wherein *Define as above, and n is integer 1-3.
Being used for most preferred title complex of the present invention is the title complex that satisfies following formula a):
Figure A9880420300302
Wherein:
R 3Each appearance is following group independently, and be selected from: hydrogen, alkyl, halo alkyl, silyl, first silicon Germanium based, cyano group, halogen and composition thereof, described group have 20 non-hydrogen atoms at the most;
M is a titanium, zirconium or hafnium;
Z, Y, X and X ' definition are as above;
P is 0,1 or 2; And
Q is 0 or 1;
Condition is:
If p is 2, q is 0, and M is+4 normal oxidation attitudes, and X is an anion ligand, is selected from: halogenide, alkyl,-oxyl, dialkyl amide group, dialkyl phosphino-, alkyl sulfenyl and silyl, and halo, dialkyl amino,-oxyl, and the derivative of dialkyl phosphino-replacement, described X base contains 20 non-hydrogen atoms at the most
If p is 1, q is 0, and M is+3 normal oxidation attitudes, and X is a stable anion ligand group, be selected from allyl group, 2-(N, the N-dimethylaminomethyl) phenyl, and 2-(N, N-dimethyl)-aminobenzyl, or M is+4 normal oxidation attitudes, and X is the divalent derivative of conjugated diolefine, M and X form together cyclopentenyl that metal replaces and
If p is 0, q is 1, and M is+2 normal oxidation attitudes, and X ' is a neutral conjugation or non-conjugated diene, randomly replaces one or more alkyl, and described X ' base contains at the most 40 non-carbon atoms and forms a π-title complex with M.
Being used for preferred title complex of the present invention is the title complex that satisfies following formula a): Wherein:
R 3Each appearance is hydrogen or C independently 1-6Alkyl;
M is a titanium;
Y is-O--S-,-NR *-,-PR *-;
Z *Be SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR *=CR *, CR * 2SiR * 2Or GeR * 2
R *Each appearance is hydrogen independently, or is selected from alkyl,-oxyl, silyl, haloalkyl, halogenated aryl and combination thereof, described R *Have at the most 20 non-hydrogen atoms and randomly, from two R of Z *Base (is worked as R *When being not hydrogen), or from the R of Z *The R of base and Y *Base forms ring system; P is 0,1 or 2; Q is 0 or 1; Condition is:
If p is 2, q is 0, and M is+4 normal oxidation attitudes, and the each appearance of X is methyl or benzyl independently,
If p is 1, q is 0, and M is+3 normal oxidation attitudes, and X is 2-(N, a N-dimethyl) aminobenzyl; Or M be+4 normal oxidation attitudes and X are 2-butylene-1,4-two bases and
If p is 0, q is 1, and M is+2 normal oxidation attitudes, and X ' is 1,4-phenylbenzene-1,3-butadiene or 1,3-pentadiene.A kind of diene in back is asymmetric dienes, thus the metal complexes of producing actual be the mixture of geometrical isomer separately.
This title complex is to adopt known synthetic technology preparation.The preferred method of preparation metal complexes is disclosed in United States Patent (USP) 5491246, and its content is incorporated into this paper as a reference at this.This reaction is in suitable non-interference with solvent, and at-100 to 300 ℃, preferred-78 to 100 ℃, more preferably 0 to 50 ℃ temperature is carried out.Can use reductive agent, so that metal M drops to oxidation state at a low price from the high price oxidation state.The example of appropriate reductant is a basic metal, alkaline-earth metal, aluminium, and zinc, the alloy of basic metal and alkaline-earth metal, for example sodium/amalgam and sodium/potassium-sodium alloy, sodium naphthalene, graphite potassium, alkylation lithium, the refined reagent of dialkylene lithium or potassium and Green.
The suitable reaction medium that is used to form title complex comprises aliphatic series and aromatic hydrocarbon, ether and ring mystery, particularly branched-chain hydrocarbon, Trimethylmethane for example, butane, pentane, octane and their mixture; Cyclic hydrocarbon and alicyclic hydrocarbon, for example hexanaphthene, suberane, methylcyclohexane, methyl suberane and their mixture; The aromatic substance that aromatics and alkyl replace, for example benzene, toluene and dimethylbenzene, C 1-4Dialkyl ether, the C of (gathering) aklylene glycol 1-4Dialkyl ether, and tetrahydrofuran (THF).The mixture of above-mentioned substance also is suitable.
Be used for component a) active cocatalyst that bonded is suitable be can therefrom propose the X substituting group to form the non-interference counter ion of inertia or to form zwitter-ion ionic derivative compound a).Here used suitable active cocatalyst comprises perfluorination three (aryl) boron compound, most preferably three (pentafluorophenyl group) borine; Non-polymeric compatible non-coordination forms ionic compound (being included in the such compound of use under the oxidizing condition), especially uses ammonium, Phosphonium, oxygen, carbon, silicon or the sulfonium salt of compatible non-coordination anion, and the ferrocene salt of compatible non-coordination anion.Suitable activating technology comprises the use bulk electrolysis.Also can use the combination of aforesaid active cocatalyst and technology.Aforesaid active cocatalyst and technology are in front about introducing in the different metal complexess, referring to following document: european patent application 277003, U.S. Patent application 5153157, U.S. Patent application 5064802, european patent application 468651 and european patent application 520732 (the United States Patent (USP) series 07/876,286 that is equivalent to application on May 1st, 1992), with U.S. Patent application 5350723, the content of these patents is incorporated into this paper as a reference.
More particularly, the suitable formation ionic compound as catalyzer comprises the positively charged ion of the bronsted acid that can supply with proton and compatible non-coordination anion A -Terminology used here " non-coordination " mean negatively charged ion or material not with contain 4 family's metal precursor title complexs and match by the catalysis derivative that it obtains, or also or only very weakly with its coordination, keep enough reactivity so that replace by Lewis base (comprising alpha-olefin).When " compatible negatively charged ion " do not influenced by polymerization of required back or the application of other title complex for decomposing when the initial title complex that forms, be not degraded into the neutral negatively charged ion.
Preferred anionic surfactants is to contain only a kind of material of title complex, comprises a charged metal or metalloid nuclear, its negatively charged ion can two kinds of components of balance in conjunction with the time active catalytic species (metallic cation) that form electric charge.And described negatively charged ion should have enough handinesies, so that by olefinic diolefine and acetylenically unsaturated compound or other neutral Lewis base (for example ether or nitrile) displacement.Suitable metal includes but not limited to aluminium, gold and platinum.Suitable metalloid includes but not limited to boron, phosphorus and silicon.Certainly, it is known containing the anionic compound that comprises title complex (containing a metal or metalloid atom), and many, it is commercially available particularly containing a boron atomic compound at anionicsite.
Such promotor is preferably represented by following general formula:
(L *-H) d -(A) D-Wherein:
L *It is neutral Lewis base;
(L*-H) -It is bronsted acid;
A d -Be to have d -The negatively charged ion that the non-coordination of electric charge is compatible and
D is integer 1-3.
More preferably, A D-Satisfy following formula: [M ' Q 4] -
Wherein:
M ' is boron or aluminium, is+3 normal oxidation attitudes; And
Hydride appears being independently selected from Q at every turn, the dialkyl amide base, halogenide, alkyl, hydrocarbyl oxide, halo alkyl, the halo-oxyl, with halo silyl alkyl (comprise perhalogeno alkyl-perhalogeno-oxyl-and perhalogeno silyl-oxyl), described Q has 20 carbon at the most, and condition is more than Q halogenide can not occur once.The example of suitable hydrocarbyl oxide Q base is disclosed in United States Patent (USP) 5296433, and its disclosure is incorporated into this paper as a reference at this.
In a preferred example, d is 1, that is: counter ion have a negative charge and are A -The active cocatalyst that is used in particular for preparing the boracic of catalyzer of the present invention can be represented by following general formula:
(L *-H) -(BQ 4) -Wherein:
L *Definition as above;
B is a boron, and the normal oxidation attitude is 3; With
Q is an alkyl,-oxyl, and the fluoro alkyl, fluoro-oxyl, or fluoro silyl-oxyl, they have 20 non-hydrogen atoms at the most, and condition is more than the Q alkyl can not occur once.
Most preferably, it is fluorinated aryl that Q occurs at every turn, particularly perfluorophenyl.
The non-limiting typical example that can be used as the boron compound of active cocatalyst of the present invention is: trisubstituted ammonium salt, for example: four (pentafluorophenyl group) boric acid TMA (TriMethylAmine), four (pentafluorophenyl group) boron triethylenetetraminehexaacetic acid ammonium, four (pentafluorophenyl group) boric acid, 3 third ammoniums, four (pentafluorophenyl group) boric acid, three positive fourth ammoniums, four (pentafluorophenyl group) boric acid, three Zhong Ding ammoniums, four (pentafluorophenyl group) boric acid N, N-dimethyl-N-dodecyl ammonium, four (pentafluorophenyl group) boric acid N, N-dimethyl-N-octadecyl ammonium, four (pentafluorophenyl group) boric acid N-methyl-N, the two dodecyl ammoniums of N-, four (pentafluorophenyl group) boric acid N-methyl-N, the two octadecyl ammonium of N-, four (pentafluorophenyl group) boric acid N, accelerine, normal-butyl three (pentafluorophenyl group) boric acid N, accelerine, benzyl three (pentafluorophenyl group) boric acid N, accelerine, four (4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluoro phenyl) boric acid N, accelerine, four (4-(triisopropyl silyl)-2,3,5,6-tetrafluoro phenyl) boric acid N, accelerine, penta fluoro benzene oxygen base three (pentafluorophenyl group) boric acid N, accelerine, four (pentafluorophenyl group) boric acid N, N-Diethyl Aniline, four (pentafluorophenyl group) boric acid N, N-dimethyl-2, four (2,3,4,6-tetrafluoro phenyl) the boric acid Trimethylamine, four (2,3,4,6-tetrafluoro phenyl) the boric acid triethylamine, four (2,3,4,6-tetrafluoro phenyl) the boric acid tripropylamine, four (2,3,4,6-tetrafluoro phenyl) the boric acid tri-n-butyl amine, four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl tert-butylamine, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N,-xylidine, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N ,-Diethyl Aniline, four (2,3,4,6-tetrafluoro phenyl) boric acid N, N,-dimethyl-2; Dibasic ammonium salt, for example: four (pentafluorophenyl group) boric acid two-sec.-propyl ammonium and four (pentafluorophenyl group) boric acid dicyclohexyl ammonium.Three replace the De phosphonium salt, for example: and four (pentafluorophenyl group) boric acid triphenyl phosphonium, four (pentafluorophenyl group) boric acid three (o-tolyl) Phosphonium and four (pentafluorophenyl group) boric acid three (2,6-two basic phenyl) Phosphonium; Dibasic oxonium salt, for example: four (pentafluorophenyl group) boric acid diphenyloxide, four (pentafluorophenyl group) boric acid, two (o-tolyl) oxygen and four (pentafluorophenyl group) boric acid two (2,6-two basic phenyl) oxygen; Dibasic sulfonium, for example: four (pentafluorophenyl group) boric acid phenylbenzene sulfonium, four (pentafluorophenyl group) boric acid, two (o-tolyl) sulfoniums and four (pentafluorophenyl group) boric acid two (2,6-two basic phenyl) sulfonium.
Preferred (L *-H) +Positively charged ion is N, accelerine, tributyl ammonium, N-methyl-N, the two dodecyl ammoniums of N-, N-methyl-N, two octadecyl ammonium of N-and their mixture.
Another kind of suitable formation ionic active cocatalyst comprises the compatible salt that negatively charged ion became of non-coordination that cationic oxygenant and following formula are represented:
(Ox E+) d(A D-) eWherein:
Ox E+It is cationic oxygenant with e+ electric charge;
E is integer 1-3; With
A D-Define as above with d.
The example of cationic oxygenant has ferrocene, the ferrocene that alkyl replaces, Ag +Or Pb + 2A D-Preferred embodiment be about containing active cocatalyst, the particularly positively charged ion of the above-mentioned definition of the boratory bronsted acid of four (pentafluorophenyl groups).
Another kind of suitable formation ionic active cocatalyst comprises a kind of compound, and it is the carbon ion anionic salt compatible with non-coordination, and its structural formula is:
+A -
Wherein
+Be C 1-20Carbon ion; With
A -Definition as above.Preferred carbon ion is a trityl group.
Further suitable formation ionic active cocatalyst comprises a kind of compound, and it is the compatible cationic salt with non-coordination of silicon, and its structural formula is:
R 3’Si +A -
Wherein
R ' is C 1-10Alkyl, and A -Definition as above.
Preferred silicon salt active cocatalyst is four (pentafluorophenyl group) boric acid trimethyl silicane, the adducts that four (pentafluorophenyl group) boric acid triethyl silicon and ether thereof replace.The former generally J.Chem Soc.Chem.Comm. of silicon salt, 1993,383-384, and Lambert, J.B. waits the people., Organometallics, 1994,13, open among the 2430-2443.The claimed purposes that is used for the above-mentioned silicon salt of addition polymerization catalyst as active cocatalyst of USSN08/304314 (application on September 12nd, 1994).
The specific title complex of alcohol, mercaptan, silanol and oxime and three (pentafluorophenyl group) borine also is effective catalyst activator, and can be used for the present invention.This class promotor is disclosed in United States Patent (USP) 5296433, and its related content is incorporated into this paper as a reference.
Most preferred active cocatalyst is three (pentafluorophenyl group) borines and four (pentafluorophenyl group) boric acid N, the two octadecyls of N--N-ammonium methyl.A kind of compound in back is that its mixture can be used as active cocatalyst derived from the main ingredient of the borate mixture of two (hydrogenated tallow) ammonium methyl compound.
The used metal complexes and the mol ratio of active cocatalyst are preferably 1: 10-2: 1, more preferably 1: 5-1.5: 1, most preferably 1: 5-1: 1.
Metalloscene catalyst can contain and not contain aluminum cocatalyst or only contain a small amount of (that is, 3: 1 Al: transition metal is than-100: 1 Al: transition metal compares) aluminum cocatalyst.For example, can be as the cationic complexes of homogeneous catalyst further with for example alkylaluminoxane activation of extra activator.Preferred activator promotor comprises methylaluminoxane, propyl group aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and their molectron.The methylaluminoxane (MMAO) of so-called modification also is suitable for and makes promotor.A kind of technology for preparing the aikyiaiurnirsoxan beta of this modification discloses in United States Patent (USP) 4960878 (people such as Crapo), its disclosure is incorporated into this paper as a reference at this, the preparation aikyiaiurnirsoxan beta also can be with reference to 4544762 people such as () Kaminsky, 5015749 (people such as Schmidt), 5041583 (Sangokoya), 5041584 (disclose among the people and 5041585 such as Crapo (people such as Deavenport), its disclosure is incorporated into this paper as a reference at this.
In general, polymerization can be used for carrying out under metallocene or the known condition of Kaminsky-Sinn type polyreaction in prior art, that is: temperature 0-250 ℃, and preferred 30-200 ℃ and pressure 1-30000 normal atmosphere (1 * 10 5-3 * 10 8Pa) or higher.Need, can use suspension, solution, slurry, gas phase, solid state powder polymerization or other processing condition.Can use carrier, particularly silicon-dioxide, aluminum oxide or polymkeric substance (particularly tetrafluoroethylene or polyolefine), and when this catalyzer is used for gaseous polymerization, preferably adopt.The preferable amount of carrier should be able to provide catalyzer (based on metal): the weight ratio of carrier is 1: 100000-1: 10, more preferably 1: 50000-1: 20, most preferably 1: 10000-1: 30.
In most polyreactions, the used catalyzer and the mol ratio of polymerizable compound are 10 -12: 1-10 -1: 1, more preferably 10 -9: 1-10 -5: 1.
The suitable solvent that polymerization is used is an inert liq.Example has side chain and straight chain hydrocarbon, Trimethylmethane for example, butane, pentane, hexane, heptane, octane and their mixture; Cyclic hydrocarbon and alicyclic hydrocarbon, hexanaphthene for example, suberane, methylcyclohexane, methyl suberane and their mixture; Perfluorinated hydrocarbon, for example C 4-C 10The aromatic hydroxy compound that alkane and aromatic hydrocarbons and alkyl replace, benzene for example, toluene, dimethylbenzene, and ethylbenzene.
Suitable comonomer also includes but not limited to ethene, propylene, butylene, divinyl, cyclopentenes, 1-hexene, 4 vinyl cyclohexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, vinylbenzene, Vinylstyrene, allyl benzene, Vinyl toluene (comprising all independent or blended isomer), the mixture of above-mentioned comonomer is also on probation.
Component in resin combination of the present invention also comprises: the ethylene/alpha-olefin copolymer that the narrow composition of homogeneous phase distributes with other include but not limited to ethylene/alpha-olefin copolymer that new LDPE (film grade) (LDPE), vinylacetate (EVA) and preferred heterogeneous wide composition distribute, most preferably with the blend polymer of the ethylene/alpha-olefin copolymer of the narrow composition distribution of the homogeneous phase of different molecular weight and/or density.
This multi-phase ingredients is different from equal phase component, that is: in equal phase component, basically all copolymer molecules all have identical ethene/comonomer ratio in multipolymer, and heterophasic copolymer is that wherein copolymer molecule does not have the multipolymer of identical ethene/comonomer ratio.The comonomer distribution of heterophasic copolymer narrated in term used herein " wide composition distributes ", mean heterophasic copolymer and have " high-density " part, and DVC measures, and heterophasic copolymer detects with DSC has multiple melting peaks (that is the melting peak that, has at least two uniquenesses).Heterophasic copolymer and polymkeric substance 10% (weight) or above, be preferably greater than 15% (weight), be preferably greater than especially and have the degree of branching of being less than or equal to 2 methyl/1000 carbon in 20% (weight).Heterophasic copolymer and polymkeric substance preferably are lower than 15% (weight) in 25% (weight) or lower, particularly are lower than also to have the degree of branching of being less than or equal to 25 methyl/1000 carbon in 10% (weight).
The heterophasic copolymer component of blend can be Alathon or optimal ethylene and at least a C 3-C 20Alpha-olefin and/or C 4-C 18The multipolymer of diolefine.The homogeneous copolymers of optimal ethylene and vinylbenzene, butene-1, hexene-1,4-methyl-1-pentene and octene-1, the multipolymer of special optimal ethylene and 1-octene.
The Mw/Mn that the used term " wide molecular weight distribution " of this paper heterophasic copolymer means multipolymer (or part) is greater than 3, preferred 3-5.
Be applicable to the catalyzer carrier Ziegler Natta catalyst typically of preparation multi-phase ingredients of the present invention, they are at the high polymerization temperature particularly suitable of solution polymerization process.The example of this based composition is by organo-magnesium compound, alkylogen or aluminum halide or hydrochlorinate aluminium, and transistion metal compound deutero-composition.The example of this catalyzer is disclosed in United States Patent (USP) 4314912 (Lowery, Jr wait the people), 4547475 (people such as Glass) and 4612300 (Coleman III), and its disclosure is incorporated into this paper as a reference at this.
Appropriate catalyst also can obtain from indifferent oxide carrier and transistion metal compound.The example that is applicable to this composition of solution polymerization process has explanation at United States Patent (USP) 5231151 and 5420090 (people such as Spencer.), and it is for referencial use that its content is incorporated into this paper.
If use the blend of second kind of ethylene/alpha-olefin copolymer, Shuo Ming each component can prepare in independent reactor so herein, and blend together subsequently, to prepare copolymer blend composition component of the present invention.Preferably, although homogeneous ethylene multipolymer that this paper introduces and extra blend component prepare with the staged reactor scheme, but also can parallel connection or serial operation, it is disclosed like that for example to press United States Patent (USP) 3914342 (Mitchell) and WO94/00500, and it is for referencial use that its disclosure is incorporated into this paper.In the staged reactor scheme, at least one reactor prepares the homogeneous ethylene multipolymer with metalloscene catalyst, at least one reactor uses single site catalysts to prepare second polymkeric substance, just different homogeneous ethylene multipolymers, or use Z-type catalyst to prepare heterogeneous ethylene copolymer.In the preferred operations scheme, with the serial operation reactor.When reactors in series connected, in one first reactor, polymeric reaction product and ethylene/alpha-olefin reactant by metalloscene catalyst obtains needed, and second catalyzer and solvent direct (that is, in proper order) together join in second reactor.
Each component that comprises resin combination of the present invention is generally mixed by the following method, that is: preparation contains the unsaturated fatty acid amide of institute's expense or ethylene bisamides, unsaturated fatty acids acid amides or ethylene bisamides and segmentation mineral compound and can be the homogeneous phase of ethene or the master batch of the high loading in the heterophasic copolymer.Then, mix master batch or allow it place each component concentrations that from the goods that resulting composition is made, reaches required to be implemented in the homogeneous copolymers of additional quantity or the blend that contains homogeneous copolymers.
In addition, the enriched material of each unsaturated fatty acid amide or ethylene bisamides, unsaturated fatty acids acid amides or ethylene bisamides and segmentation mineral compound also can prepare in the polyethylene matrix, and mix with the homogeneous copolymers of additional quantity or the blend that contains homogeneous copolymers, so that each component reaches desired concn.These required concentration mainly change with the difference of polymeric constituent density, but correct amount can adopt blending means as herein described and The test procedure to determine by experiment easily by this area professional.
So in typical case's preparation, Dow Chemical obtains and utilizes 94.7 kilograms of homogeneous ethylenes-octene copolymer AFFINITY  PL1880 (melting index, the I of metalloscene catalyst preparation 2=1.0 grams/10 minutes, density=0.9020 gram per centimeter 3) with enriched material (melting index, the I of 3.0 kilograms of 5wt% erucicamides in the matrix of ethylene-octene copolymer 2=6.0 grams/10 minutes, density=0.9110 gram per centimeter 3) and enriched material (melting index, the I of 1.0 kilograms of 5wt% stearylamides in the matrix of ethylene-octene copolymer 2=6.0 grams/10 minutes, density=0.9110 gram per centimeter 3) and 1.25 kilograms of 20wt% silicon-dioxide enriched material (melting index, I in the matrix of ethylene-octene copolymer 2=6.0 grams/10 minutes, density=0.9110 gram per centimeter 3) mix. obtain containing the final resin combination of 1500ppm erucicamide, 500ppm stearylamide and 2500ppm silicon-dioxide.
Although the significant quantity of each component and preferred concentration are in varying degrees with the density of homogeneous copolymers or blend components, the slickness of processing temperature and film surface and changing, but for the present invention, general preferred concentration, (i) unsaturated fatty acid amide or ethylene bisamides are 10-1250, preferred 100-1000, more preferably 250-750ppm, (ii) unsaturated fatty acids acid amides or ethylene bisamides are 250-10000, preferred 500-8000, more preferably 750-5000ppm and (iii) to segment mineral compound be 500-15000, preferred 1000-10000, the general weight ratio of more preferably 1250-7500ppm, and unsaturated fatty acids acid amides or ethylene bisamides and unsaturated fatty acid amide or ethylene bisamides is 10: 1-1: 10.Finally, unsaturated fatty acid amide and ethylene bisamides, and the concentration of unsaturated fatty acids acid amides or ethylene bisamides and be preferably greater than 1500ppm.
The density that joins the ethylene/alpha-olefin copolymer of the narrow composition distribution of homogeneous phase in the resin combination of the present invention is 0.870-0.940, preferred 0.890-0.920, more preferably 0.890-0.910 gram per centimeter 3
For the ethylene/alpha-olefin copolymer that the narrow composition of homogeneous phase distributes, its melting index I 2Be 0.2-100, preferred 0.4-50, more preferably the 0.5-20 gram is/10 minutes.
The I of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes 10/ I 2Ratio is greater than 5.6, preferred 5.6-13, more preferably 5.6-11.
The Mw/Mn ratio of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes is preferably 1.8-6.0.
The consumption that joins the ethylene/alpha-olefin copolymer that the narrow composition of first homogeneous phase in the blend components (comprising two kinds of homogeneous copolymers) of resin combination of the present invention distributes is 10-90wt%, preferred 15-85wt%, more preferably 20-80wt% is with the combination weight meter of each component of final resin combination.
In this blend, the density of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes is generally 0.870-0.940, preferred 0.870-0.920, more preferably 0.870-0.905 gram per centimeter 3
The melting index I of the ethylene/alpha-olefin copolymer that the narrow composition of described first homogeneous phase distributes 2Be generally 0.05-100, preferred 0.2-50, more preferably the 0.2-20 gram is/10 minutes.
The I of the ethylene/alpha-olefin copolymer that the narrow composition of described first homogeneous phase distributes 10/ I 2Ratio is greater than 5.6, preferred 5.6-13, more preferably 5.6-11.
The Mw/Mn ratio of the ethylene/alpha-olefin copolymer that the narrow composition of described first homogeneous phase distributes is preferably 1.8-6.0.
The consumption that joins the ethylene/alpha-olefin copolymer that the narrow composition of second homogeneous phase in the blend components of resin combination of the present invention distributes is 10-90wt%, preferred 15-85wt%, more preferably 20-80wt% is with the combination weight meter of each component of final resin combination.
The melting index of the ethylene/alpha-olefin copolymer that the narrow composition of described second homogeneous phase distributes, density, Mw/Mn, and I 10/ I 2Through selection, so that obtain the desired characteristic of final blend composition.
The consumption that joins the ethylene/alpha-olefin copolymer that the narrow composition of homogeneous phase in the blend group composition (comprising homogeneous phase and heterophasic copolymer) of resin combination of the present invention distributes is 10-90wt%, preferred 15-85wt%, more preferably 20-80wt% is with the combination weight meter of each component of final resin combination.
In this blend, the density of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes is generally 0.870-0.940, preferred 0.870-0.920, more preferably 0.870-0.905 gram per centimeter 3
The melting index I of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes 2Be generally 0.05-100, preferred 0.2-50, more preferably the 0.2-20 gram is/10 minutes.
The I of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes 10/ I 2Ratio is greater than 5.6, preferred 5.6-13, more preferably 5.6-11.
The Mw/Mn ratio of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes is preferably 1.8-6.0.
The consumption that joins the ethylene/alpha-olefin copolymer that the narrow composition of homogeneous phase in the blend composition of the present invention distributes is 10-90wt%, preferred 15-85wt%, and more preferably 20-80wt% is with the combination weight meter of final component A and B.
The melting index of the ethylene/alpha-olefin copolymer that the wide composition of described homogeneous phase distributes, density, Mw/Mn, and I 10/ I 2Through selection, so that obtain the desired characteristic of final blend composition.
The density that the present invention includes the final blend composition of two kinds of homogeneous copolymers or homogeneous phase or heterogeneous ethylene/alpha-olefin copolymer component is generally 0.870-0.940, preferred 0.890-0.920, more preferably 0.890-0.910 gram per centimeter 3
The melting index I of the ethylene/alpha-olefin copolymer of final blend of the present invention 2Be generally 0.2-100, preferred 0.4-50, more preferably the 0.5-20 gram is/10 minutes.
The I of the ethylene/alpha-olefin copolymer of final blend of the present invention 10/ I 2Ratio is greater than 5.6, preferred 5.6-13, more preferably 5.6-11.
The Mw/Mn ratio of the ethylene/alpha-olefin copolymer of final blend of the present invention is preferably 1.8-6.0.
Composition of the present invention also can comprise the multipolymer that one or more are random substantially.This paper used term " random substantially " in the random substantially multipolymer of the vinylidene monomer that comprises alpha-olefin and vinylidene aromatic monomer or hindered aliphatic or cyclic aliphatic means the monomer distribution of described multipolymer can be by the Bernoulli statistical model or by one-level or the explanation of secondary Markovian statistical model, determine referring to the polymkeric substance order, the 13C nuclear magnetic resonance method of J.C.Randall (AcademicPress New York, 1997, the 71-78 page or leaf).Preferably, the random substantially multipolymer that comprises alpha-olefin and vinylidene aromatic monomer does not contain in the block that is higher than 3 unitary vinylidene aromatic monomers and accounts for the vinylidene aromatic monomer of total amount more than 15%.More preferably, multipolymer is not just being spent with height isotaxy rule or syndiotaxy is a feature.This means in the 13C nuclear magnetic resonance spectrum of random substantially multipolymer, satisfy represent meso divalent radical order or racemize divalent radical in proper order the main chain methylene radical and the peak area of the methine carbon total peak area that should be no more than main chain methylene radical and methine carbon 75%.
Substantially random alpha-olefin/vinylidene aromatic copolymer blend component of the present invention includes but not limited to by one or more alpha-olefins of polymerization and one or more vinylidene aromatic monomers/or the multipolymer of one or more be obstructed aromatics or cycloaliphatic vinylidene monomer and optional other polymerisable monomer preparations.
For instance, suitable alpha-olefin comprises and contains 2-20, preferred 2-12, the more preferably alpha-olefin of 2-8 carbon atom.Particularly preferably be ethene, vinylbenzene, butene-1,4-methyl-1-pentene, hexene-1, and octene-1.These alpha-olefins do not contain the aromatics part.Preferably ethene and C 3-C 8The alpha-olefin mixture.Be more preferably ethene.
The suitable vinylidene aromatic monomer that can be used for preparing multipolymer includes but not limited to the monomer that for example is expressed from the next: R wherein 1Be selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Ar is phenyl or the phenyl that replaced by 1-5 substituting group, and described substituting group is selected from: halogen, C 1-4Alkyl, and C 1-4Haloalkyl; With n be 0-4, preferred 0-2, most preferably 0.The example of monovinylidene aromatic monomer comprises vinylbenzene, vinyl benzene, and alpha-methyl styrene, t-butyl styrene, chlorostyrene comprises all isomer of these compounds.Specially suitable this monomer comprise vinylbenzene and low alkyl group thereof-or halogen-replacement derivative.Preferred monomer comprises vinylbenzene, alpha-methyl styrene, cinnamic low alkyl group (C 1-4) or phenyl ring replace derivative, for example adjacent-, partially-, and p-methylstyrene, the ring halogenated styrenes is to Vinyl toluene or its mixture.Preferred aromatics monovinylidene monomer is a vinylbenzene.
Term " hindered aliphatic or cycloaliphatic vinylidene compound " but mean the vinylidene monomer of the addition polymerization that satisfies following formula:
Figure A9880420300441
A wherein 1Be the huge aliphatic series or the cyclic aliphatic substituting group in space of 20 carbon at the most, R 1Be to be selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Or R 1And A 1Also can become ring system together.Used term " space is huge " mean have this substituent monomer usually can not with the comparable speed of vinyl polymerization under carry out addition polymerization by standard metallocene polymerizing catalyst.Preferred hindered aliphatic or cycloaliphatic vinylidene compound are that one of carbon atom of wherein having ethylenic unsaturated bond is the monomer that replaces in uncle or season.This substituent example comprises cycloaliphatic groups, cyclohexyl for example, and cyclohexenyl, cyclooctene base, or the derivative that replaces of its cycloalkyl or aryl comprise the tertiary butyl, and norcamphyl.Most preferred hindered aliphatic or cycloaliphatic vinylidene compound are the different cyclosubstituted derivatives of isomery vinyl of the tetrahydrobenzene of tetrahydrobenzene and replacement, and 5-ethylidene-2-norbornene.Specially suitable is 1-, 3-, and 4 vinyl cyclohexene.
Other optional polymerizable ethylenically unsaturated monomers comprise strained (strained) cycloolefin, for example norbornylene and C 1-10Alkyl or C 6-10The norbornylene that aryl replaces, its multipolymer of giving an example has ethylene/styrene/norbornene.
Substantially random multipolymer can be by typical grafting, hydrogenation, functionalized or known other reaction modifying of this area professional.Polymkeric substance sulfonation easily or chlorination are so that provide functional derivative according to the technology of establishing.The method for preparing basic random copolymers is with the polymerization of mixtures of polymerisable monomer in the presence of metallocenes or constrained geometry catalyzer and active cocatalyst.
Basic random copolymers can prepare according to the method that european patent application 0416815 and United States Patent (USP) 5703187 (Francis Timmers) are introduced, and it is for referencial use that described patent is incorporated into this paper at this.The preferred operations condition of this polyreaction is that pressure is from normal atmosphere (1 * 10 5Pascal) to 3000 normal atmosphere (3 * 10 8Pascal), temperature is from-30 ℃ to 200 ℃.Random isotactic polystyrene is for example produced in polymerization and remove the homopolymer polymerisate that unreacted monomer can cause forming some quantity under the temperature that is higher than each monomeric autopolymerization temperature.
The example of method of appropriate catalyst and the basic random copolymers of preparation is at U.S. Patent application 545403, the applying date: July 3 nineteen ninety (european patent application 416815); U.S. Patent application 702475, the applying date: on May 20th, 1991 (european patent application 514828); U.S. Patent application 876268, the applying date: on May 1st, 1992 (european patent application 520732); U.S. Patent application 241523, the applying date: on May 12nd, 1994; And U.S. Patent application 5055438; 5057475; 5096867; 5064802; 5132380; 5189192; 5321106; 5347024; 5350723; 5374696; With 5399635, it is for referencial use that all these patent documentations and patent application are incorporated into this paper at this.
Substantially random alpha-olefin/vinylidene aromatic multipolymer also can use the compound shown in the following general formula to prepare by the method that JP07/278230 introduces:
Figure A9880420300451
Cp wherein 1And Cp 2Be cyclopentadienyl independently of one another, indenyl, fluorenyl, or their substituent, R 1And R 2Be hydrogen atom independently of one another, halogen atom, C 1-12Alkyl, alkoxyl group, or aryloxy; M is an IV family metal, preferred Zr or Hf, most preferably Zr; R 3Be to be used for crosslinked Cp 1And Cp 2Alkylidene group or silane two bases.
Substantially random alpha-olefin/vinylidene aromatic multipolymer also can pass through John G, (W.R.Grace ﹠amp such as Bradfute; Co.) at WO95/32095; R.B.Pannell (ExxonChemical Patents.Inc.) is at WO94/00500; With at plastics technology, the method preparation of introducing 25 pages (in September, 1992), the disclosed content of all these documents is incorporated into this paper as a reference at this.
Substantially random multipolymer also is suitable, described multipolymer comprises at least a alpha-olefin/binyl aromatics/aromatic vinyl/alpha-olefin tetravalence group, referring to people's such as Francis J.Timmers U.S. Patent application 08/708809, the applying date: on September 4th, 1996.These multipolymers contain additional signal in 13C nuclear magnetic resonance spectrum, intensity is greater than 3 times of peak-peak noises.These signals appear at chemical shift range 43.70-44.25 and 38.0-38.5ppm.Particularly, 44.1,43.9 and 38.2ppm observe main peak.Proton test nmr experiments points out that the signal at chemical shift zone 43.70-44.25ppm is a methine carbon, and the signal in regional 38.0-38.5ppm is a mesomethylene carbon.
It is believed that, these signals are because such order causes, that is: two statures-tail vi-ny l aromatic monomers is leading inserts, then be that at least one alpha-olefin inserts, ethylene/styrene/styrene/ethylene tetravalence group for example, the insertion of the styrene monomer of wherein said tetravalence group is carried out in 1,2 (head-tail) mode specially.This area the professional all know, not cinnamic vi-ny l aromatic monomers and be not such tetravalence group of the alpha-olefin of ethene for comprising, ethylene/vinyl base aromatic monomer/vi-ny l aromatic monomers/ethene tetravalence group will improve similar 13C nuclear magnetic resonance peak, but slightly different with chemical shift.
In the presence of the catalyzer that following formula is represented,
Figure A9880420300461
Wherein the each appearance of each Cp is π-the be bonded to cyclopentadienyl of the replacement on the M independently; E is C or Si; M is an IV family metal, preferred Zr or Hf, most preferably Zr; The each appearance of each R is hydrogen independently, alkyl, and silicon alkyl, or hydrocarbon silyl, they contain 30, preferred 1-20, more preferably 1-10 carbon or Siliciumatom at the most; The each appearance of each R ' is hydrogen independently, halogen, and alkyl,-oxyl, silicon alkyl, or hydrocarbon silyl, they contain 30, preferred 1-20 at the most, more preferably 1-10 carbon or Siliciumatom or two R ' bases are C together 1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2; And randomly, but preferably in the presence of a kind of active cocatalyst,, prepare these multipolymers by polymerization at 30-250 ℃.Specially suitable substituted cyclopentadienyl comprises the group that following formula is represented: Wherein the each appearance of each R is hydrogen independently, alkyl, and silicon alkyl, or hydrocarbon silyl, they contain 30, preferred 1-20 at the most, more preferably 1-10 carbon or Siliciumatom or two R bases constitute the divalent derivative of this group together.Preferably, the each appearance of R is (if suitable, comprising all isomer) hydrogen independently, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, two such R bases of phenyl or silyl or (if suitable) connect together to form and condense ring system, for example indenyl, fluorenyl, tetrahydroindenyl or octahydro indenyl.
Particularly preferred catalyzer comprises for example racemize (dimethylsilane two bases-two-(2-methyl-4-phenyl indenyl) zirconium dichloride, racemize (dimethylsilane two bases-two-(2-methyl-4-phenyl indenyl) zirconium 1,4-phenylbenzene-1, the 3-divinyl, racemize (dimethylsilane two bases-two-(2-methyl-4-phenyl indenyl)-C 1-4The alkyl zirconium, racemize (dimethylsilane two bases-two-(2-methyl-4-phenyl indenyl) two-C 1-4Zirconium alkoxide.
Also comprise titanium base constrained geometry catalyzer, and [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η-)-1,5,6,7-tetrahydrochysene-s-indenes-1-yl] silane ammino (2-)-N] the titanium dimethyl; (1-indenyl) (tert-butylamides base) dimethyl-silane titanium dimethyl; ((the 3-tertiary butyl) (1,2,3,4,5-η-)-the 1-indenyl) (tert-butylamides base) dimethylsilane titanium dimethyl; ((3-sec.-propyl) (1,2,3,4,5-η-)-the 1-indenyl) (tert-butylamides base) dimethylsilane titanium dimethyl, or its any combination.
Other preparation method who is used for multipolymer of the present invention has introduction in the literature.Longo and Grassi (Makromol.Chem.191 volume, 2387-2396 page or leaf [1990]) and people's (journal of applied such as D ' Anniello, 58 volumes, 1701-1706[1995]) reported and used based on methylaluminoxane (MAO) and cyclopentadienyl titanous chloride (CpTiCl 3) catalyst system prepare ethylene-styrene copolymer.Xu and Lin (Polymer Preprints, Am.Chem.Soc.Div.Polym.Chem.), 35 volumes, 686-687 page or leaf [1994] has been reported and has been used MgCl 2/ TiCl 4/ NdCl 3/ Al (iBu) 3Catalyzer carries out copolymerization to obtain vinylbenzene and cinnamic random copolymers.People such as Lu (journal of applied, 53 volumes, 1453-1460 page or leaf [1994]) have reported and have used TiCl 4/ NdCl 3/ MgCl 2/ Al (Et) 3Catalyzer copolymerization of ethylene and vinylbenzene.Sernetz and Mulhaupt. (Macromo1.Chem.Phys., 197 volumes, 1071-1083 page or leaf, 1997) have introduced polymerizing condition to using Me 2Si (Me 4Cp) (the N-tertiary butyl) TiCl 2The influence of/methylaluminoxane ziegler natta catalyst vinylbenzene and ethylene copolymerization.With the ethene of bridged metallocents Catalyst Production and styrol copolymer at Arai, Toshiaki and Suzuki (PolymerPreprints, Am.Chem.Soc.Div.Polym.Chem.), 38 volumes, the 349-350 page or leaf is introduced in [1997].Produce alpha-olefin/binyl aromatic monomer multipolymer for example propylene/styrene and butylene/styrene at United States Patent (USP) 5244996 (licensing to Mitsui PetrochemicalIndustries Ltd) or United States Patent (USP) 5652315 (also licensing to Mitsui PetrochemicalIndustries Ltd) or be disclosed in German Patent 197 11 339A1 (Denki KAGAKU KogyoKK.).The aforesaid method that all are disclosed to be used to prepare copolymer component is incorporated into this paper as a reference.
The multipolymer that is used for one or more alpha-olefins of the present invention and one or more monovinylidene aromatic monomers and/or one or more be obstructed aromatics or cycloaliphatic vinylidene monomers is unregulated polymer substantially.These multipolymers contain 0.5-65 usually, preferred 1-55, the more preferably at least a vinylidene aromatic monomer of 2-50 mole % and/or hindered aliphatic or cycloaliphatic vinylidene monomer and 35-99.5, preferably 45-99, more preferably at least a C of 50-98 mole % 2-20Aliphatic alpha-olefin.
The number-average molecular weight of these multipolymers (Mn) generally is higher than 1000, preferred 5000-1000000, more preferably 10000-500000.
Melting index (the I that can be used for multipolymer of the present invention 2) be 0.01-1000, preferred 0.1-100, most preferably the 0.5-30 gram is/10 minutes.
The polydispersion that can be used for multipolymer of the present invention is 1.5-20 than Mw/Mn, preferred 1.8-10, more preferably 2-5.
When the basic random copolymers of preparation,, can form the homopolymer of a certain quantity for example owing to the homopolymerization of vinylidene aromatic monomer at high temperature.In general, exist the vinylidene aromatic homopolymer can not destroy purpose of the present invention, can tolerate.If desired, for example from solution, use non-solvent (concerning multipolymer or vinylidene aromatic homopolymer) selective precipitation, can from multipolymer, isolate the vinylidene aromatic homopolymer by abstraction technique.For the present invention, atactic vinylidene aromatic homopolymer amount preferably is not higher than 20 weight %, more preferably less than 15 weight % (with total restatement of multipolymer).
The character that is used to contain the saturated and unsaturated amides of composition of basic random copolymers and segmentation mineral compound as previously mentioned.
Although the significant quantity of each component and preferred concentration are more or less with the composition of basic random copolymers, make temperature and film surface slickness and change, but for the present invention, the preferred concentration of ethylbenzene is: (i) unsaturated fatty acid amide or ethylidene-bisamide are 0-5000, preferred 250-2500, more preferably 500-1500ppm, (ii) unsaturated fatty acids acid amides or ethylidene-bisamide are 0-10000, preferred 500-7500, more preferably 1000-3000ppm, (iii) segmenting mineral compound is 0-20000, preferred 1000-15000, more preferably 2000-10000ppm.
Also comprise the composition that contains homopolymer or basic random copolymers and properties-correcting agent in the present invention.Properties-correcting agent comprises alfon or propylene/alpha-olefins multipolymer and/or nucleator.The inventor finds that density is the 0.885-0.905 gram per centimeter 3The refractive index of homogeneous copolymers and the refractive index of alfon or propylene alpha-olefin copolymer similar.This makes this alfon or multipolymer can be dispersed in the described homogeneous copolymers and can not destroy optical characteristics, plays a part caking inhibiter simultaneously.The inventor finds that also when the adding nucleator improved the optical quality of described homogeneous copolymers, the bonding tendency of also observing the film of being made by it descended astoundingly.
The polypropylene that is used for membrane structure of the present invention generally is the homopolymer polypropylene of isotaxy form, although other forms of polypropylene also can use (for example, syndyotactic polypropylene).But also can use propylene and C 2-C 20The multipolymer of alpha-olefin, include but not limited to impact-resistant copolymer (for example using wherein, the second copolymerization step is the multipolymer of ethene and propylene reaction) and random copolymers (also as the reactor modification and contain 1.5-7 weight % ethene and propylene copolymer usually).The complete discussion of different polyacrylic polymers is included in distribution in modern plastics macropaedia/89,1998 years 10 months, 65 volumes, and No. 11, the 86-92 page or leaf, it is for referencial use that its whole explanation is incorporated into this paper at this.Be used for polyacrylic molecular weight of the present invention and be easy to use the D-1238 according to ASTM, condition (was called condition (L) in the past, was also referred to as condition I for 230 ℃/2.16 kilograms 2) the indication of molten flow rate measuring method.The molecular weight of molten flow rate and polymkeric substance is inversely proportional to.So molecular weight is high more, molten flow rate is just low more, although its relation is not linear.
When the specific refractory power of the ethylene/alpha-olefin polymer of even linearity or substantially linear in specific refractory power 0.005 specific refractory power unit, when particularly in 0.002 specific refractory power unit, (measuring in 589 nanometers typically) from polyacrylic polymer, realize the good transparency.In general, polyacrylic specific refractory power is 1.470-1.515, and the specific refractory power of for example transparent homopolymer polypropylene is 1.5065, and the specific refractory power of transparent polypropylene random copolymer is 1.5044 (in 589 nanometers).
Specific refractory power is to make and measure at the Abbe-3L refractometer of 589 nanometers (sodium " d " line) operation with Milton Roy company.By the polymkeric substance in the BOY 30T injection moulding forming machine being injection molded into about 0.125 inch of thickness (0.317 centimetre), preparation is used for the sample tested at refractometer.Be used to test the sample of physical property with the same manner and about 0.125 inch (0.317 centimetre) preparation of thickness.
Chum, Silvis and Kao have proposed the curve of the specific refractory power of substantially linear ethene polymers to density being entitled as ' to be used for the INSITE technology of impact modified polyolefin elastomer ' in SPO ' 93 1 literary compositions.Curve thus, they obtain following equation:
RI=Q.69694 (density)+0.87884
Wherein RI is the specific refractory power of polymkeric substance.Therefore, when needs use when having 1.5044 transparent polypropylene random copolymer, preferred evenly linear and substantially linear ethene polymers has 0.898 gram per centimeter 3
In order to improve the transparency, the viscosity of polyacrylic polymer should be lower than even linearity or substantially linear ethene polymers.Viscosity and melting index are inversely proportional to (under the situation of even linearity or substantially linear ethene polymers), also are inversely proportional to molten flow rate (under the situation of polyacrylic polymer).The estimated value that poly melting index and polyacrylic molten flow rate compare is that the polypropylene melt flow rate is divided by 4.For example, having molten flow rate is that a bit to resemble melting index be/10 minutes polyethylene of 3 grams for 12/10 minutes its viscosity of polypropylene of gram or flow behavior.So, use the polypropylene of/10 minutes molten flow rates of 2 or 4 grams and the ethene polymers of/10 minutes melting index of 1.6 grams may cause such blend, wherein the component of viscosity higher has constituted the minimum component of blend, therefore, obtain the membrane structure of low turbidity and high-clarity, this is not preferred.By contrast, using molten flow rate/10 minutes polypropylene of 12 grams and melting index is that/10 minutes ethene polymers of 1.6 grams may cause such blend, wherein more low viscous component has constituted the low viscosity component of blend, minimum component is improved in the dispersiveness of homogeneous phase linearity or substantially linear ethene polymers principal phase, good optical characteristics is provided thus.
Term ' nucleator ' is defined as and means a kind of material that is used to control particle diameter and is formed crystallisation process by liquid, supersaturated solution or saturation steam.Two class nucleators are arranged, comprising: (1) is dispensed into the premolding particle in the polymer composition under high-shear; (2) crystallization under than the high temperature of other components of polymer composition of the particle that forms on the ground, melt Central Plains of other components of polymer composition, this particle forms the fibrous reticulum of the nucleation position effect that plays homogeneous polymer and wax.
The premolding particulate example that is dispensed under high-shear in the polymer composition comprises organically multilayer particle of parent.This particle can adopt method well known in the art, is prepared by the hydrophilic silicic salts substances.The illustrative examples of this material is the smectic clays ore deposit, for example polynite, montmorillonite, beidellite, volkonskoite, hectorite, bentonite, sauconite, magauigite, fibrous morphology crystals, and vermiculite.Other multilayer particles that are suitable for comprise illite class mineral, for example the admixture of the clay pit of illite and illite class and above name.The multilayer particle that other are suitable, the multilayer particle that especially is used in anionic polymer are double-deck oxyhydroxide, for example Mg 6Al 3.4(OH) 18.8(CO 3) 1.7H 2O (referring to W.T.Reichle, J.Catal., 94 volumes, 547 pages (1985)).Other multilayer particles of not loading on the layer or loading seldom can be used for the present invention.This material comprises muriate, for example ReCl 3And FeOCl, chalkogenide, for example TiS 2, MoS 2, and MoS 3Prussiate, for example Ni (CN) 2, and oxide compound, for example H 2Si 2O 5, V 5O 13, HTiNbO 5, Cr 0.5V 0.5S 2, W 0.2V 2.8O 7, Cr 3O 8, MoO 3(OH) 2, VOPO 4-2H 2O, CaPO 4CH 3-H 2O, MnHAsO 4-H 2O, and Ag 6Mo 10O 33
Hydrophilic multilayer particle is by making for example water-soluble polymers of sodium, potassium or calcium positively charged ion and suitable material, quaternary ammonium salt, and zwitterionics and chlorine compound or analogue exchange, and can give its close organic property.The typical example of tradable water-soluble polymers has the water-soluble polymers (polyvinyl alcohol for example of vinyl alcohol, polyalkylene glycol is polyoxyethylene glycol for example, water-soluble cellulose polymer is methylcellulose gum and carboxymethyl cellulose for example, the polymkeric substance of ethylenically unsaturated carboxylic acids is polyacrylic acid and salt thereof for example, and Polyvinylpyrolidone (PVP).
The typical example that can be used for quaternary ammonium salt of the present invention (cats product) comprise have octadecyl, the quaternary ammonium salt of hexadecyl, tetradecyl or dodecyl, preferred quaternary ammonium salt comprises dimethyl dihydro fat ammonium salt, the octadecyl leptodactyline, two octadecyl dimethyl ammoniums, cetyltrimethyl ammonium salt, double hexadecyl dimethyl ammonium, tetradecyl leptodactyline and two tetradecyl dimethyl ammonium.
Preferred close organic multilayer particle is the material by the preparation of ion-exchange quaternary ammonium cation.Preferred close organic multilayer particle is the montmorillonite clay of handling with quaternary ammonium salt, dimethyl dihydro fat ammonium salt most preferably, and it is with Claytone TMHY (trade mark of Southern Clay Products) sells.
Parent's organic multilayer particle also can be by with inorganics, by the polymerisable metal alkoxide of hydrogenation Si (OR) for example 4, Al (OR) 3, Ge (OR) 4, Si (OC 2H 5) 4, Si (OCH 3) 4, Ge (OC 3H 7), or Ge (OC 2H 5) 4The polymkeric substance that obtains separately or arbitrary combination and sodium, potassium or calcium positively charged ion exchange and prepare.In addition, inorganics can be the colloid mineral compound.Can be separately or arbitrary combination use the typical example of colloid mineral compound that SiO is arranged 2, Sb 2O 3, Fe 2O 3, Al 2O 3, TiO 2, ZrO 2, and SnO 2
Parent's organic multilayer material also can be according to WO93/11190, the method that the 9-21 page or leaf is introduced, and the exchange by functionalized organic silane compound prepares, and the content of described document is incorporated into this paper as a reference.
The example of nucleator (being the particle that forms on the ground, melt Central Plains of other components of polymer composition) has acetals, trinaphthylenyl sorbyl alcohol for example, three (4-methyl isophthalic acid-naphthylidene) sorbyl alcohol, three-(4-methoxyl group-1-naphthylidene) sorbyl alcohol and dibenzylidene zylitol.Preferred material is the acetal of the condensation product of sorbyl alcohol and phenyl aldehyde, it can comprise for example blended aldehyde, just it can comprise a unsubstituting phenenyl formaldehyde substituting group and a substituted benzaldehyde substituting group, or it can comprise two unsubstituting phenenyl formaldehyde substituted benzaldehyde substituting groups.The neighbour of substituted benzaldehyde residue,, and/or the spendable substituting group in any position of contraposition comprises the low alkyl group that for example has 1 to 5 carbon atom, hydroxyl, and methoxyl group, single-and dialkyl amido and halogen fluorine for example, bromine, and chlorine.The example of introducing in United States Patent (USP) 4419473 and 5001176 (whole contents of its patent is incorporated into this paper as a reference) includes but not limited to Sorbitol dibenzal, 3, and 4-dimethyl Sorbitol dibenzal, 1,3-benzylidene-2,4-is to the methyl benzylidene sorbitol, 1,3-benzylidene-2,4-is to the ethyl benzylidene sorbitol, 1,3-is to methyl benzylidene-2, the 4-benzylidene sorbitol, 1,3-is to ethyl benzylidene-2, the 4-benzylidene sorbitol, 1,3-is to methyl benzylidene-2, and 4-is to the ethyl benzylidene sorbitol, 1,3-is to ethyl benzylidene-2, and 4-is to the methyl benzylidene sorbitol, 1,3,2,4-two-(to the methyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the ethyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the n-propyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(p-isopropyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the normal-butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the sec-butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(aligning tertiary butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(2 ', 4 '-dimethyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the methoxyl group benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the oxyethyl group benzylidene) sorbyl alcohol, 1,3-benzylidene-2,4-chlorine benzylidene sorbitol, 1,3-is to chlorine benzylidene-2,4-benzylidene sorbitol, 1,3-is to chlorine benzylidene-2,4-is to the methyl benzylidene sorbitol, and 1,3-is to chlorine benzylidene-2,4-is to the ethyl benzylidene sorbitol, 1,3-is to methyl benzylidene-2, and 4-is to the chlorine benzylidene sorbitol, 1,3-is to ethyl benzylidene-2, and 4-is to chlorine benzylidene sorbitol and 1,3,2,4-two-(to the chlorine benzylidene) sorbyl alcohol.Most preferred material is 3,4-dimethyl dibenzyl sorbyl alcohol, and it can be by Milliken Chemical, and Inc. is with Millad TM3988 have bought, and it also can Millad TM5L71-10 and Millad TM3905P dibenzyl sorbyl alcohol has been bought as the mixture of 10% weight in the new LDPE (film grade) of 90% weight.
Alfon or the multipolymer content in final composition is 0-5, preferred 0.3-3, more preferably 0.5-2% (weight).
Melting index (the I of alfon or multipolymer 2, 230 ℃) and be 0.2-10, preferred 0.3-5, more preferably the 0.5-2 gram is/10 minutes.
The density of alfon or multipolymer is 0.880-0.920, preferred 0.890-0.910, more preferably 0.895-0.905 gram per centimeter 3
Nucleator content in final composition is 0-3000, preferred 500-2500, more preferably 1000-2000ppm.
The density that joins the ethylene/alpha-olefin of the narrow composition distribution of homogeneous phase in the resin combination of the present invention is 0.855-0.960, preferred 0.870-0.915, more preferably 0.885-0.905 gram per centimeter 3
The melting index of the ethylene/alpha-olefin copolymer that the narrow composition of described homogeneous phase distributes is 0.02-100, preferred 0.2-50, more preferably 0.2-5 and most preferably 0.5-4 restrain/10 minutes.
The I of the ethylene/alpha-olefin that the narrow composition of homogeneous phase distributes 10/ I 2Ratio is greater than 5.6, preferred 5.6-13, more preferably 5.6-11.
The Mw/Mn ratio of the ethylene/alpha-olefin that the narrow composition of homogeneous phase distributes is preferably 1.8-6.0.
The multipolymer that is used for one or more alpha-olefins of the present invention and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatics or cycloaliphatic vinylidene monomer is random substantially polymkeric substance.These multipolymers generally contain 0.5-65, preferred 1-55, the more preferably at least a vinylidene aromatic monomer of 2-50 mole % and/or hindered aliphatic or cycloaliphatic vinylidene monomer and 35-99.5, preferred 45-99, the more preferably at least a aliphatic alpha-olefin of 50-98 mole % with 2-20 carbon atom.
The number-average molecular weight of these multipolymers is generally greater than 1000, preferred 5000-1000000, more preferably 10000-500000.
Can be applicable to the melting index (I of multipolymer of the present invention 2) be 0.01-1000, preferred 0.1-100, more preferably the 0.5-30 gram is/10 minutes.
The polymolecularity that can be applicable to multipolymer of the present invention is 1.5-20 than Mw/Mn, preferred 1.8-10, more preferably 2-5.
When preparing random substantially multipolymer, may form the homopolymer of a certain quantity, for instance, this is because the equal polymerization reaction of vinylidene aromatic monomer at high temperature causes.In general, exist the vinylidene aromatic homopolymer can not influence purpose of the present invention, can tolerate.The vinylidene aromatic homopolymer can be isolated by multipolymer, needs, by abstraction technique, for example with non-solvent selective precipitation from solution of multipolymer or vinylidene aromatic homopolymer.For the present invention, the preferred existence is not more than 20 weight %, more preferably less than the multipolymer of the random vinylidene aromatic homopolymer of 15 weight %.
For the present invention, although the significant quantity of each component and preferred concentration are more or less with the density of homogeneous copolymers and blend components, change with the composition of basic random copolymer component and the slickness of processing temperature and film surface etc., but general preferred concentration is: (i) unsaturated fatty acid amide or ethylene bisamides are 0-5000, preferred 250-2500, more preferably 500-1500ppm, (ii) unsaturated fatty acids acid amides or ethylene bisamides are 0-10000, preferred 500-7500, more preferably 1000-3000ppm.
For all above-mentioned compositions, additive for example oxidation inhibitor (for example, Hinered phenols is (as, Irganox TM1010 or 1076), phosphite (as, Irgafos TM168 PEP Q TM, or three nonyl phenyl phosphites, the antiskid additive (as, PIB), polymer processing aids, pigment, filler also can to a certain degree be included in the prescription, and they do not disturb the formula property of the improvement of being found by the inventor.Irganox TMAnd Irgafos TMIt all is the trade mark of Ciba-Geigy company.Irgafos TMThe 168th, phosphites stabilizers, Irganox TMThe 1010th, the polyphenol stablizer that is obstructed (as, four [methylene radical 3-(3,5-di-t-butyl-4 hydroxy phenyls-propionic ester)] methane.PEPQ is the trade mark of SandozChemical, and its major ingredient it is believed that it is four-(2, the 4-di-tert-butyl-phenyl)-4,4 ' phenylbenzene phosphites.
In embodiment 1-14, provide additive with the form of enriched material, for this reason, stock polymer is substantially linear ethene/1-octene copolymer (being sold by Dow Chemical), is to use metalloscene catalyst preparation, its melting index I 2=6.0 grams/10 minutes, density=0.9110 gram per centimeter 3And contain 50ppm Irganox TM1076 and 800ppm PEPQ TM
Embodiment 1
Resin combination mixes following composition preparation by doing:
(a) raw material substantially linear ethene/1-octene copolymer (being sold by Dow Chemical) is to make
With metalloscene catalyst preparation, its melting index I 2=1.0 grams/10 minutes, close
Degree=0.902 gram per centimeter 3, I 10/ I 2=9 and contain 500ppm Irganox TM1076
With 800ppm PEPQ TM,
(b) erucicamide of Witco, 5 weight % enriched materials are to obtain ultimate density in resin
Be 1500ppm,
(c) stearylamide of Witco, 5 weight % enriched materials are to obtain ultimate density in resin
Be 250ppm,
(d) the White Mist of silicon-dioxide-Celite, 20 weight % enriched materials are to obtain
The ultimate density of 2500ppm in the resin.
Use is furnished with 2.5 inches forcing machines of 6 inches Gloucester die heads and 70 mil mould pins, is prepared the blown film of 2 mil thick by resin combination.Extruding parameter is:
Output rating-120 Pounds Per Hours (1.51 * 10 -2Kilograms Per Second)
Target melt temperature-450 (232 ℃)
Blow-up ratio-2.5: 1
Frost line height-25 inch (63.5 centimetres)
Embodiment 2
Identical with embodiment 1, but have the 1500ppm erucicamide, the 500ppm stearylamide.
Embodiment 3
Identical with embodiment 1, but have the 1500ppm erucicamide, the 750ppm stearylamide.
Embodiment 4
Identical with embodiment 1, but have the 1250ppm erucicamide, the 250ppm stearylamide.
Embodiment 5
Identical with embodiment 1, but have the 1250ppm erucicamide, the 500ppm stearylamide.
Embodiment 6
Identical with embodiment 1, but have the 1250ppm erucicamide, the 750ppm stearylamide.
Embodiment 7
Identical with embodiment 1, but have the 500ppm erucicamide, the 1500ppm stearylamide.
Embodiment 8
Identical with embodiment 1, but have the 1500ppm erucicamide, the 500ppm stearylamide.
Comparison test 1
Identical with embodiment 1, but have the 0ppm erucicamide, 0ppm stearylamide and 0ppm silicon-dioxide.
Comparison test 2
Identical with embodiment 1, but have the 750ppm erucicamide, the 0ppm stearylamide.
Comparison test 3
Identical with embodiment 1, but have the 750ppm erucicamide, the 250ppm stearylamide.
Comparison test 4
Identical with embodiment 1, but have the 750ppm erucicamide, the 500ppm stearylamide.
Comparison test 5
Identical with embodiment 1, but have the 750ppm erucicamide, the 750ppm stearylamide.
Comparison test 6
Identical with embodiment 1, but have the 250ppm erucicamide, the 250ppm stearylamide.
Comparison test 7
Identical with embodiment 1, but have the 250ppm erucicamide, the 750ppm stearylamide.
Comparison test 8
Identical with embodiment 1, but have the 500ppm erucicamide, the 500ppm stearylamide.
Comparison test 9
Identical with embodiment 1, but have 2500ppm silicon-dioxide.
COF value and the cementing value of these embodiment are summarized in the table 1.
Embodiment 9
The blown film sample of 1 and 2 mil thick adopts the used similarity condition of embodiment 1, mixes the resin that following composition prepares and prepares by doing:
(a) substantially linear ethene/1-octene copolymer, Dow Chemical sells, and it is to use metallocene catalyst
The agent preparation, its melting index I 2Be 1.6 grams/10 minutes, density is 0.8965 gram per centimeter 3,
And I 10/ I 2Be 10, contain 500ppm Irganox TM1076 and 800ppm PEPQ TM,
(b) erucicamide of Witco, 5 weight % enriched materials are to obtain ultimate density in resin
Be 2000ppm,
(c) stearylamide of Witco, 5 weight % enriched materials are to obtain ultimate density in resin
Be 1000ppm,
(d) the White Mist of silicon-dioxide-Celite, 20 weight % enriched materials are to obtain the ultimate density of 4000ppm in resin.
Embodiment 10
Identical with embodiment 9, but have the 1250ppm erucicamide, the 500ppm stearylamide.
Embodiment 11
Identical with embodiment 9, but have the 1500ppm erucicamide, the 750ppm stearylamide.
Embodiment 12
Identical with embodiment 9, but have the 1000ppm erucicamide, the 1000ppm stearylamide.
Embodiment 13
Identical with embodiment 9, but have the 1000ppm erucicamide, the 2000ppm stearylamide.
Comparison test 10
Identical with embodiment 9, but have the 1500ppm erucicamide, the 250ppm stearylamide.
Comparison test 11
Identical with embodiment 9, but have the 1250ppm erucicamide, the 250ppm stearylamide.
Comparison test 12
Identical with embodiment 9, but have the 0ppm erucicamide, 0ppm stearyl and 0ppm silicon-dioxide.
Comparison test 13
Identical with embodiment 9, but have the 1000ppm erucicamide, the 0ppm stearylamide.
Comparison test 14
Identical with embodiment 9, but have the 750ppm erucicamide, the 0ppm stearylamide.
Comparison test 15
Identical with embodiment 9, but have the 750ppm erucicamide, the 250ppm stearylamide.
Comparison test 16
Identical with embodiment 9, but have the 750ppm erucicamide, the 500ppm stearylamide.
Comparison test 17
Identical with embodiment 9, but have the 750ppm erucicamide, the 750ppm stearylamide.
Comparison test 18
Identical with embodiment 8, but have the 500ppm erucicamide, the 500ppm stearylamide.
Comparison test 19
Identical with embodiment 9, but have the 500ppm erucicamide, the 1000ppm stearylamide.
COF value and the cementing value of these embodiment are summarized in the table 2.
Embodiment 14
The blown film sample of 2 mil thick adopts the used similarity condition of embodiment 1, mixes the resin that following composition prepares and prepares by doing:
(a) ethylene-butene copolymer EXACT TM3028, obtain (its melting index I by exxon chemical company 2Be 1.2 grams/10 minutes, density is 0.900 gram per centimeter 3), it is with the metalloscene catalyst preparation,
(b) erucicamide of Witco, the 5 weight % enriched materials that provided by Ampacet company (produce
Article Number 100329), ultimate density is 1500ppm in resin to obtain,
(c) stearylamide of Witco, the 5 weight % enriched materials that provide by Bayshore company,
Ultimate density is 500ppm in resin to obtain,
(d) the White Mist of silicon-dioxide-Celite, the 20 weight % enriched materials (production number 100342) that provided by Ampacet company are to obtain the ultimate density of 3000ppm in resin.
Comparison test 20
Identical with embodiment 14, but have the 750ppm erucicamide, 0ppm stearylamide and 2500ppm silicon-dioxide.
Comparative experiments 21
Identical with embodiment 13, but have the 2000ppm erucicamide, the 0ppm stearyl.
COF value and the cementing value of these embodiment are summarized in the table 3.
Table 1
Embodiment # Resin # Erucicamide (ppm) Stearylamide (ppm) SiO 2(ppm) Erucicamide adds stearyl amine (ppm) Thickness (mil) The E/S ratio Cementing value (g) ??COF
Embodiment 1 ??PL?1880 ??1500 ??250 ?2500 ????1750 ????2 ????6∶1 ??45.4 ??0.25
Embodiment 2 ??PL?1880 ??1500 ??500 ?2500 ????2000 ????2 ????3∶1 ??43.7 ??0.10
Embodiment 3 ??PL?1880 ??1500 ??750 ?2500 ????2250 ????2 ????2∶1 ??47.7 ??0.20
Embodiment 4 ??PL?1880 ??1250 ??250 ?2500 ????1500 ????2 ????5∶1 ??47.4 ??0.25
Embodiment 5 ??PL?1880 ??1250 ??500 ?2500 ????1750 ????2 ??2.5∶1 ??44.1 ??0.20
Embodiment 6 ??PL?1880 ??1250 ??750 ?2500 ????2000 ????2 ??1.7∶1 ??44.2 ??0.18
Embodiment 7 ??PL?1880 ??500 ??1500 ?2500 ????2000 ????2 ????1∶3 ??47.8 ??0.19
Embodiment 8 ??PL?1880 ??1500 ??500 ?3000 ????2000 ????2 ????3∶1 ??36.9 ??0.19
Comparative experiments 1 * ??PL?1880 ????0 ????0 ????0 ??????0 ????2 ??99.3 ???＞1
Comparative experiments 2 * ??PL?1880 ??750 ????0 ?2500 ????750 ????2 ??92.0 ??0.10
Comparative experiments 3 * ??PL?1880 ??750 ??250 ?2500 ????1000 ????2 ????3∶1 ??84.1 ??0.10
Comparative experiments 4 * ??PL?1880 ??750 ??500 ?2500 ????1250 ????2 ??1.5∶1 ??58.2 ????1
Comparative experiments 5 * ??PL?1880 ??750 ??750 ?2500 ????1500 ????2 ????1∶1 ??70.8 ????1
Comparative experiments 6 * ??PL?1880 ??250 ??250 ?2500 ????500 ????2 ????1∶1 ??93.7 ??0.31
Comparative experiments 7 * ??PL?1880 ??250 ??750 ?2500 ????1000 ????2 ????1∶3 ??78.9 ??0.24
Comparative experiments 8 * ??PL?1880 ??500 ??500 ?2500 ????1000 ????2 ????1∶1 ??80.7 ??0.13
Comparative experiments 9 * ??PL?1880 ????0 ????0 ?2500 ??????0 ????2 ??94 ??CNA
*Not embodiments of the invention (' good ' cementing value＜49 grams, ' good ' COF＜0.31)
Table 2
Embodiment # Resin # Erucicamide (ppm) Stearylamide (ppm) SiO 2(ppm) Erucicamide adds stearyl amine (ppm) Thickness (mil) The E/S ratio Cementing value (g) ??COF
Embodiment 9 ?PF?1140 ??2000 ??1000 ?4000 ????3000 ????2 ????2∶1 ??33.4 ??0.16
Embodiment 10 ?PF?1140 ??1250 ??500 ?4000 ????1750 ????2 ??2.5∶1 ??39.8 ??0.25
Embodiment 11 ?PF?1140 ??1500 ??750 ?4000 ????2250 ????2 ????2∶1 ??29.5 ??0.20
Embodiment 12 ?PF?1140 ??1000 ??1000 ?4000 ????2000 ????2 ????1∶1 ??36.4 ??0.18
Embodiment 13 ?PF?1140 ??1000 ??2000 ?4000 ????3000 ????2 ????1∶2 ??37.3 ??0.24
Comparative experiments 10 * ?PF?1140 ??1500 ??250 ?4000 ????1750 ????2 ????6∶1 ??39.4 ??0.35
Comparative experiments 11 * ?PF?1140 ??1250 ??250 ?4000 ????1500 ????2 ????5∶1 ??50.7 ??0.35
Comparative experiments 12 * ?PF?1140 ????0 ????0 ????0 ??????0 ????2 ??112.6 ??＞1
Comparative experiments 13 * ?PF?1140 ??1000 ????0 ?4000 ????1000 ????2 ??63.8 ??0.15
Comparative experiments 14 * ?PF?1140 ??750 ????0 ?4000 ????750 ????2 ??103.1 ??＞1
Comparative experiments 15 * ?PF?1140 ??750 ??250 ?4000 ????1000 ????2 ????3∶1 ??82.3 ??＞1
Comparative experiments 16 * ?PF?1140 ??750 ??500 ?4000 ????1250 ????2 ??1.5∶1 ??83.6 ??＞1
Comparative experiments 17 * ?PF?1140 ??750 ??750 ?4000 ????1500 ????2 ????1∶1 ??43.5 ??＞1
Comparative experiments 18 * ?PF?1140 ??500 ??500 ?4000 ????1000 ????2 ????1∶1 ??75.7 ??0.34
Comparative experiments 19 * ?PF?1140 ??500 ??1000 ?4000 ????1500 ????2 ????1∶2 ??40.6 ??0.32
* not embodiments of the invention (' good ' cementing value＜49 grams, ' good ' COF＜0.31)
Table 3
Embodiment # Resin # Erucicamide (ppm) Stearylamide (ppm) SiO 2(ppm) Erucicamide adds stearyl amine (ppm) Thickness (mil) The E/S ratio Cementing value (g) ??COF
Embodiment 14 ??EXACT TM??3028 * ??1500 ??500 ?3000 ????2000 ????2 ????3∶1 ??25.1 ??0.22
Comparative experiments 20 * ??EXACT TM??3028 * ??750 ????0 ?2500 ????750 ????2 ??35.3 ??1.0
Comparative experiments 21 * ??EXACT TM??3028 * ??2000 ????0 ?3000 ????2000 ????2 ??23.7 ??0.40
* not that embodiments of the invention (' good ' cementing value＜49 gram, ' good ' COF＜0.31) # is that the trade mark embodiment 15-17 of exxon chemical company uses ethylene/styrene multipolymer ESI#1-3 preparation embodiment 15-17 respectively.The preparation catalyst A preparation of ESI#1-(dimethyl [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl] silane ammino 2-)-N] titanium).1) preparation 3,5,6,7-tetrahydrochysene-s-indane-1 (2H)-ketone
1,2-indane (94.00 grams, 0.7954 mole) and 3-chlorpromazine chloride (100.99 grams, 0.7954 mole) are at CH 2Cl 2Stir in 0 ℃ in (300 milliliters), under nitrogen gas stream, slowly add AlCl simultaneously 3(130,00 grams, 0.9750 mole).Mixture left standstill two hours in room temperature.Remove fugitive constituent then.Mixture is cooled to 0 ℃, slowly adds the vitriol oil (500mL).Because do not stir when this step begins, the solid of formation will often stir with spatula.Then, be placed under the nitrogen in mixture under the room temperature and spend the night.Afterwards, mixture heating up is reached 90 ℃ until temperature reading.These conditions kept 2 hours, between this, regularly stirred the mixture with spatula.After the reaction, trash ice is placed mixture and mobile all around.Afterwards, mixture is transferred in the beaker, water and ether washing is incessantly filtered then and is merged all cuts.Washing mixture (2 * 200 milliliters).Separate organic layer, remove fugitive constituent.By using hexane, isolate light yellow required product (22.36 grams, 16.3% productive rate) in 0 ℃ of recrystallization. 1H NMR (CDCl 3): d2.04-2.19 (m, 2H), 2.65 (t, 3JHH=5.7Hz, 2H), 2.84-3.0 (m, 4H), 3.03 (t, 3J HH=5.5Hz, 2H), 7.26 (s, 1H), 7.53 (s, 1H). 13C NMR (CDCl 3): d25.71,26.01,32.19,33.24,36.93,118.90,122.16,135.88,144.06,152.89,154.36,206.50.GC-MS:C 12H 12The calculated value 172.09 of O, measured value 172.052) preparation 1,2,3,5-tetrahydrochysene-7-phenyl-s-indenes
3,5,6,7-tetrahydrochysene-s-indane-1 (2H) ketone (12.00 grams, 0.06967 mole) stirs in 0 ℃ of ether (200 milliliters), slowly adds PhMgBr (0.105 mole, 35.00 milliliters of 3.0M solution in ether) simultaneously.Then, at room temperature this mixture stirring is spent the night.After reaction period, the mixture method Quench of pouring ice cube into.Use hcl acidifying mixture (pH=1) and strong mixing 2 hours then.Afterwards, tell organic layer, dried over mgso is used in washing (2 * 100 milliliters) again.After the filtering fugitive constituent, isolate the required product of dark buttery (14.68 grams, 90.3% productive rate). 1H NMR (CDCl 3): δ 2.0-2.2 (m, 2H), 2.8-3.1 (m, 4H), 6.54 (s, 1H), 7.2-7.6 (m, 7H) .GC-MS:C 18H 16Calculated value 232.13, measured value 232.053) preparation 1,2,3,5-tetrahydrochysene-7-phenyl-s-indenes, dilithium salt
1,2,3,5-tetrahydrochysene-7-phenyl-s-indane (14.68 grams, 0.06291 mole) stirs in hexane (150 milliliters), slowly adds n-Butyl Lithium (0.080 mole, 40.00 milliliters in the 2.0M of hexanaphthene solution) simultaneously.Afterwards, this mixture stirs and spends the night.After reaction period, collect yellow solid by the method for suction strainer, use hexane wash, vacuum-drying need not be further purified or analyze just and can use (12.2075 grams, 81.1% productive rate).4) preparation Chlorodimethyl (1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl) silane
In 0 ℃, 1,2,3 among the THF (50 milliliters), 5-tetrahydrochysene-7-phenyl-s-indenes, dilithium salt (12.2075 grams, 0.05102 mole) is added drop-wise to Me 2SiCl 2In THF (100 milliliters) solution of (19.5010 grams, 0.1511 mole).This mixture is in stirred overnight at room temperature.After reaction period, remove fugitive constituent, extracted residues is also filtered with hexane.Except that the required product of isolating yellow oily behind the hexane (15.1492 grams, 91.1% productive rate). 1H NMR (CDCl 3): d0.33 (s, 3H), 0.38 (s, 3H), 2.20 (p, 3J HH=7.5Hz, 2 H), 2.9-3.1 (m, 4H), 3.84 (s, 1H), 6.69 (d, 3J HH=2.8Hz, 1H), 7.3-7.6 (m, 7H), 7.68 (d, 3J HH=7.4 Hz, 2H). 13C NMR (CDCl 3): d0.24,0.38,26.28,33.05,33.18,46.13,116.42,119.71,127.51,128.33,128.64,129.56,136.51,141.31,141.86,142.17,142.41,144.62.GC-MS:C 20H 21ClS: calculated value 324.11, measured value 324.055) preparation N-(1, the 1-dimethyl ethyl)-1.1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl) silanamines
Chlorodimethyl (1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl) silane (10.8277 grams, 0.03322 mole) stirs (150 milliliters) in hexane, add NEt simultaneously 3(3.5123 grams, 0.03471 mole) and TERTIARY BUTYL AMINE (2.6074 grams, 0.03565 mole).Mixture stirred 24 hours.After reaction period, filtering mixt is removed fugitive constituent, thereby isolates required product, is red-yellow sticking oil (10.6551 grams, 88.7% productive rate). 1H NMR (CDCl 3): d0.02 (s, 3H), 0.04 (s, 3H), 1.27 (s, 9H), 2.16 (p, 3J HH=7.2Hz, 2 H), 2.9-3.0 (m, 4H), 3.68 (s, 1H), 6.69 (s, 1H), 7.3-7.5 (m, 4H), 7.63 (d, 3J HH=7.4 Hz, 2H). 13C NMR (CDCl 3): d-0.32 ,-0.09,26.28,33.39,34.11,46.46,47.54,49.81,115.80,119.30,126.92,127.89,128.46,132.99,137.30,140.20,140.81,141.64,142.08,144.83.6) preparation N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl) silanamines, dilithium salt
N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-indane-1-yl) silanamines (10.6551 grams, 0.02947 mole) stir in hexane (100 milliliters), slowly add n-Butyl Lithium (0.070 mole, 35.00 milliliters of 2.0M solution in hexanaphthene) simultaneously.Afterwards, this mixture stirs and spends the night, and between this, does not separate out salt from dark red solution.After reaction period, remove fugitive constituent, resistates is used hexane wash (2 * 50 milliliters) rapidly.Afterwards, scarlet resistates pump is done, and need not be further purified or analyze just to use (9.6517 grams, 87.7% productive rate).7) preparation dichloro [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl] silane ammino (2-)-N] titanium
N-in THF (50 milliliters) (1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl) silicon amine, dilithium salt (4.5355 grams, 0.01214 mole) is added drop-wise to TiCl 3(THF) 3In the slurry of the THF (100 milliliters) of (4.5005 grams, 0.01214 mole).This mixture stirred 2 hours.Afterwards, add PbCl 2(1.7136 grams, 0.006162 mole), mixture left standstill 1 hour again.After reaction period, remove fugitive constituent, extracted residues is also filtered with toluene.Remove toluene, thereby isolate dark resistates.Afterwards, this resistates slurrying and be cooled to 0 ℃ in hexane.Then, by filtering to isolate required product, be reddish-brown crystalline solid (2.5280 grams, 43.5% productive rate). 1H NMR (CDCl 3): d0.71 (s, 3H), 0 97 (s, 3H), 1.37 (s, 9H), 2.0-2.2 (m, 2H), 2.9-3.2 (m, 4H), 6.62 (s, 1H), 7.35-7.45 (m, 1H), 7.50 (t, 3J HH=7.8Hz, 2H), 7.57 (s, 1H), 7.70 (d, 3J HH=7.1Hz, 2H), 7.78 (s, 1H). 1H NMR (C 6D 6): d0.44 (s, 3H), 0.68 (s, 3H), 1.35 (s, 9H), 1.6-1.9 (m, 2H), 2.5-3.9 (m, 4H), 6.65 (s, 1H), 7.1-7.2 (m, 1H), 7.24 (t, 3J HH=7.1Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H), 7.77-7.8 (m, 2H). 13C NMR (CDCl 3): d1.29,3.89,26.47,32.62,32.84,32.92,63.16,98.25,118.70. 121.75,125.62,128.46,128.55,128.79,129.01,134.11,134.53,136.04,146.15,148.93. 13C NMR (C 6D 6): d0.90,3.57,26.46,32.56,32.78,62.88,98.14,119.19,121.97,125.84,127.15,128.83,129.03,129.55,134.57,135.04,136.41,136.51,147.24,148.96.8) [N-(1 for the preparation dimethyl, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl] silane ammino (2-)-N] titanium
Dichloro [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl] silane ammino (2-)-N] titanium (0.4970 gram, 0.001039 mole) stirs in ether (50 milliliters), slow simultaneously adding MeMgBr (0.0021 mole, 0.70 milliliter of 3.0M solution in ether.Afterwards, this mixture stirred 1 hour.After reaction period, remove fugitive constituent, extracted residues is also filtered with hexane.Remove hexane, thereby isolate required product, be golden yellow solid (0.4546 gram, 66.7% productive rate). 1H NMR (C 6D 6): d0.071 (s, 3H), 0.49 (s, 3H), 0.70 (s, 3H), 0.73 (s, 3H), 1.49 (s, 9 H), 1.7-1.8 (m, 2H), 2.5-2.8 (m, 4H), 6.41 (s, 1H), 7.29 (t, 3J HH=7.4Hz, 2H), 7.48 (s, 1H), 7.72 (d, 3J HH=7.4Hz, 2H), 7.92 (s, 1H). 13C NMR (C 6D 6): d2.19,4.61,27.12,32.86,33.00,34.73,58.68,58.82,118.62,121.98,124.26,127.32,128.63,128.98,131.23,134.39,136.38,143.19,144.85. polymerization
In 6 gallons of (22.7 liters) oil jacket layer box reactors of autoclave continuously stirring (CSTR), the preparation multipolymer.Be furnished with Lightning A-320 blade magnetic couple agitator mixing is provided.Reactor is in the full liquid operation of 475psig (3.275 kPas).Working fluid is in the bottom, and flowed out by the top.Heat-transfer oil is taken some reaction heat out of by the circulation of reactor jacket layer.Reactor outlet is micro-mobile under meter, is used to measure flow and density.All pipelines on the reactor outlet are along road 50psi (344.7 kPas) and adiabatic.
Toluene solvant offers reactor with 30psig (207 kPas).Reactor feed is measured with micro-moving mass under meter.Speed change orifice plate pump control input speed.At the solvent pump discharge port, taking out side liquid stream provides racing current to catalyzer injection tube (1 Pounds Per Hour (0.45 kilogram/hour)) and reactor agitator (0.75 Pounds Per Hour (0.34 kilogram/hour)).These fluids are measured by difference formula differential pressure flow meter and are controlled by the mobile needle-valve of manual regulation trace.The styrene monomer of Yi Zhiing does not offer reactor with 30psig (207 kPas).Reactor feed is measured with micro-moving mass under meter.Speed change orifice plate pump control input speed.Vinylbenzene liquid stream mixes with the solvent liquid stream that is left.Ethene offers reactor with 600psig (4137 kPas).Ethene liquid stream was just measured with micro-moving mass under meter before this search valve (Research valve) dominant discharge.Hydrogen is transferred to the ethene liquid stream in ethene control valve exit with Brooks under meter/controller.At room temperature, ethene/hydrogen mixture merges with/vinylbenzene liquid stream.-5 ℃ of glycol carry out heat exchange on reactor and the jacket layer when solvent/monomer enters, and its temperature descends about 5 ℃.This liquid flows to the bottom into reactor.Three component catalyst systems and solvent washing lotion thereof also enter reactor bottom, but by flowing different ports with monomer liquid.The preparation of catalyst component is carried out in the inert atmosphere protection box.The dilution component is put into the cylinder of nitrogen protection and is added the catalyzer work box in the operational zone.From these work boxs, catalyzer pressurizes with piston pump, and with micro-moving mass flow measurement constant flow.These liquid streams merge each other, and just merge with it before the catalyzer washing lotion enters reactor by independent filling tube.
After micro-moving mass under meter was measured solution density, by catalyzer lethal (with the water of solvent) is added the reactor product pipe, polyreaction stopped.(catalyst kill) also can add other polymeric additive with the catalyzer lethal.Static mixer in the pipeline provides catalyzer lethal and the dispersion of additive in reactor waste liquid stream.This liquid stream then enters the post-reactor well heater, provides extra energy for desolventizing flash.This flash is along with waste liquid is discharged this post-reactor well heater appearance, and at reactor pressure control valve place, pressure drops to about 250 millimeters (absolute pressures) from 475psig (3275 kPas).The polymkeric substance that washes out enters the liquefier of deep fat jacket layer.Remove in the polymkeric substance of about 85% fugitive constituent from liquefier.Fugitive constituent is discharged the top of liquefier.Liquid stream enters vacuum pump negative pressure section, and is discharged in ethylene glycol solvent jacket layer and the styrene/ethylene separator by means of the condensation of glycol jacket layer interchanger.Shift out solvent and vinylbenzene from reactor bottom, shift out ethene from the top.Measure ethene liquid stream and analyze its composition with micro-moving mass under meter.The gas dissolved of measuring the ethene of discharging and calculating in solvent/vinylbenzene liquid stream calculates conversion of ethylene.During isolating polymkeric substance liquefies vacuum-extruder with the toothed gear pump pump to ZSK-30 in the liquefier.The polymkeric substance of doing is discharged forcing machine with sub-thread.Along with pulling out by water-bath, this strand be cooled.With air from then on thigh blow excessive water off, with the Odd Lot machine this strand is split into particle.
Preparation ESI#2
Catalyst B preparation-(1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base)-silane titanium 1, the 4-diphenyl diethylene
1) preparation 1H-ring penta [1] phenanthrene-2-base lithium
To 250 milliliters 1.42 gram (0.00657 mole) 1H-are housed and encircle in the round-bottomed flask of penta [1] phenanthrene and 120 milliliters of benzene, drip the mixing hexane solution of 4.2 milliliters of 1.60M n-Butyl Lithiums.This solution stirring is spent the night.Filter to isolate lithium salts, with 25 milliliters of benzene washings twice, and vacuum-drying.Isolated yield is 1.426 grams (97.7%).1H NMR analysis revealed is substituted at 2 main isomer.
2) preparation (1H-encircles penta [1] phenanthrene-2-yl) dimethylchlorosilane
To 500 milliliters 4.16 gram (0.0322 mole) dimethyldichlorosilane(DMCS) (Me are housed 2SiCl 2) and the round-bottomed flask of 250 milliliters of tetrahydrofuran (THF)s (THF) in drip the THF solution of 1.45 gram (0.0064 mole) 1H-rings, penta [1] phenanthrene-2-base lithium.About 16 hours of solution stirring, decompression afterwards desolventizes.Remaining oily solid extracts with toluene, filters by super-cell (CeliteTM), and with toluene wash twice, and drying under reduced pressure.Isolated yield is 1.98 grams (99.5%).
3) preparation (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl amino) silane
In 500 milliliters of round-bottomed flasks that 1.98 gram (0.0064 mole) (1H-encircles penta [1] phenanthrene-2-yl) dimethylchlorosilanes and 250 milliliters of hexanes are housed, add 2.00 milliliters of (0.0160 mole) tert-butylamines.Reaction mixture stirred several days, used super-cell (Celite afterwards TM) filter, with hexane wash twice, remove residual solvent by decompression and isolate product.Isolated yield is 1.98 grams (88.9%).
4) preparation two lithiums close (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silanization titanium
To 250 milliliters 1.03 gram (0.0030 mole) (1H-encircle penta [1] phenanthrene-2-yl) dimethyl (tertiary butyl) silane are housed) and the round-bottomed flask of 120 milliliters of benzene in the mixing hexane solution of 3.90 milliliters of 1.6M n-Butyl Lithiums of dropping.Reaction mixture stir about 16 hours.Product is isolated with filtering method, with benzene washing twice, and drying under reduced pressure.Isolated yield is 1.08 grams (100%).
5) preparation (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silane
To 250 milliliters 1.17 gram (0.0030 mole) TiCl are housed 3: 1.08 grams, two lithiums that add about 50 milliliters of THF with the speed of quick dropping in the round-bottomed flask of 3THF and 120 milliliters of THF close (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silane.Mixture adds 0.55 gram (0.002 mole) solid PbCl this moment in about 20 ℃ of stirrings 1.5 hours 2After stirring 1.5 hours again, vacuum is removed THF, uses the toluene extracted residues, filters and drying under reduced pressure, obtains orange solids.Output is 1.31 grams (93.5%).
6) preparation (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silane titanium 1, the 4-diphenyl diethylene
To (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silane titanium dichloride (3.48 grams, 0.0075 mole) and 1.551 gram (0.0075 moles) 1, add 9.9 milliliters of 1.6M n-Butyl Lithiums (0.0150 mole) solution in the slip (70 ℃) of 4-diphenyl diethylene in about 80 milliliters.Solution is deepening at once.The temperature raising is made the mixture backflow and is incubated 2 hours in this temperature.Mixture is cooled to-20 ℃ approximately.Fugitive constituent is removed in decompression.In about 20 ℃, resistates was mixed in the hexanes slurrying 16 hours at 60 milliliters.It is about 1 hour that mixture is cooled to-25 ℃ of pacts.By vacuum filtration with solid collection on frit and drying under reduced pressure.The exsiccant solid places glass fibre sleeve and uses hexane extraction continuously with Soxhlet's extractor.After 6 hours, in the ebullient jar, observe crystalline solid.Mixture is cooled to-20 ℃ approximately,, obtains the dark crystalline solid of 1.62 grams by the cold organic drying under reduced pressure of mixture filtering separation.Drain filtrate.Solid in the stirring extractor, and, obtain other 0.46 gram desired product with the mixing hexane continuous extraction of additional quantity, be dark crystalline solid.
Polymerization
Carry out polymerization according to ESI#1, just use catalyst B under promotor, processing condition are summarized in the table 4.
Preparation ESI#3
Used catalyzer is identical with ESI#1 with polymerization process and have promotor, and processing condition are summarized in the table 4.
Table 4 ethylene/styrene multipolymer ESI#1-3 ePreparation condition
ESI# Temperature of reactor ℃ Solvent flux Pounds Per Hour (kg/s) Ethylene stream octarius/hour (kg/s) Hydrogen flowing quantity Pounds Per Hour (kg/s) Styrene stream octarius/hour (kg/s) Conversion of ethylene % Promotor Catalyzer d ??MMAO dTi ratio
ESI#1 ??92.7 ???34.8 ??(4.4E -3) ???3.1 (3.9E -4) 16(2.0E -1) 5.4(6.8E -???? 4) ??95.3 ????C c ????A a ????7.0
ESI#2 ??68.9 ???30.0 ??(3.8E -3) ???1.3 (1.6E -4) ????0 ???10.0 (1.2E -3) ??87.1 ????C c ????B b ????5.0
ESI#3 ??71.6 ???30.0 ??(3.8E -3) ???1.3 (1.6E -4) ????0 ???15.6 (2.0E -3) ??96.6 ????C c ????A a ????4.0
This catalyzer of a be dimethyl [N-(and 1,1-dimethyl ethyl-1,1-dimethyl-1-[(1,2,3,4,5-
η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-indenes-1-yl] silane ammino (2-)-N]-titanium b catalyzer is (1H-encircles penta [1] phenanthrene-2-yl) dimethyl (tert-butylamides base) silane titanium 1,4-
The methylaluminoxane e of the diphenyl diethylene c promotor c modification that to be three (pentafluorophenyl group) borine d Akzo Nobel sell with MMAO-3A B/Ti mol ratio in all cases is 3.0: 1
Embodiment 15-17
In embodiment 15-17, additive is that the form with enriched material provides, and its stock polymer is the ethylene/styrene multipolymer of substantially linear, is sold by Dow Chemical, adopts the metalloscene catalyst preparation, and its melting index I 2=6.0 grams/10 minutes contain 70 weight % (38.6 moles) vinylbenzene.Used acid amides is stearylamide (Crodamide SR pellet, stearylamide refining, CAS 124-26-5) and erucicamide (Crodamide ER pellet, erucicamide refining, CAS 112-84-5), and Croda international corporation produces.
Embodiment 15
Do mixed following composition and prepare resin combination:
(a) the ethylene/styrene multipolymer of substantially linear, i.e. the described ESI#1 of table 4, fusion
Index I 2=1.4 grams/10 minutes, the multipolymer styrene content is 40.3 weight %
(35.4 moles of %), the dried 5000ppm talcum that is mixed with on pellet,
(b) erucicamide of Croda international corporation product, 5 weight % enriched materials are at resin
In final concn be 2000ppm,
(c) stearylamide of Croda international corporation product, 5 weight % enriched materials are at resin
In final concn be 1000ppm.
Use is furnished with 1.25 inches (3.17 centimetres) forcing machines of 3 inches (7.6 centimetres) Killion die heads and 60 mil die gap, is prepared the blown film sample of 3.5 mils by this resin combination.Extruding parameter is:
Screw speed ... 50rpm
The target melt temperature ... 415 °F (213 ℃)
Flat width ... 9 inches (23 centimetres)
Frost line height ... 20 inches (51 centimetres)
Embodiment 16
Identical with embodiment 15, but have ethylene/styrene multipolymer ESI#2, it is to prepare its melting index I by the method for narrating in the table 4 2=0.9 the gram/10 minutes, the styrene content of multipolymer is 70 weight % (38.6 moles of %), and on pellet the dried 5000ppm talcum that is mixed with.Thick 5.5 mils of sample of preparation.
Embodiment 17
Identical with embodiment 15, but have ethylene/styrene multipolymer ESI#3, it is to prepare its melting index I by the method for narrating in the table 4 2=1.3 the gram/10 minutes, the styrene content of multipolymer is 75 weight % (44.7 moles of %), and on pellet the dried 5000ppm talcum that is mixed with.Thick 5 mils of sample of preparation.
The cementing value of these embodiment is listed in table 5.The significance of these samples is their not being destroyed property ground bondings, as not having additivated this class material usually.And the COF of at least one sample can survey, and the COF of this class material is immesurable usually.
Table 5
Embodiment number Resin number Erucicamide (ppm) Stearylamide (ppm) Talcum (ppm) Erucicamide+stearylamide (ppm) Thickness (mils) The F/S ratio Cementing value (g) ?COF ?1-1
Embodiment 15 ?ESI#1 ?2000 ?1000 ?5000 ?3000 ?3.5 ?2∶1 ?50 Can not survey
Embodiment 16 ?ESI#2 ?2000 ?1000 ?5000 ?3000 ?5 ?2∶1 ?156 Can not survey
Embodiment 17 ?ESI#3 ?2000 ?1000 ?5000 ?3000 ?5 ?2∶1 ?52 ?1.8
Embodiment 18-22
For embodiment 18-22, adopt ASTM D-3354 to measure cohesiveness, adopt ASTM D-1894 to measure COF, adopt ASTM D-1003 to measure turbidity, adopt ASTM D-2457 to measure glossiness, and adopt ASTM D1746 to measure transparency or clarity.The evaluation of used composition in the composition of embodiment
POP1 is substantially linear ethene/1-octene copolymer, and its density is 0.902 gram per centimeter 3, melting index (I 2) be/10 minutes (in 190 ℃) of 1 gram, I 10/ I 2Being 9.0, is to be sold with trade(brand)name Affinity PL1880 by Dow Chemical.
POP2 is substantially linear ethene/1-octene copolymer, and its density is 0.902 gram per centimeter 3, melting index (I 2) be/10 minutes (in 190 ℃) of 3 grams, I 10/ I 2Being 8.0, is to be sold with trade(brand)name Affinity FW1650 by Dow Chemical.
POP3 is substantially linear ethene/1-octene copolymer, and its density is 0.896 gram per centimeter 3, melting index (I 2) be/10 minutes (in 190 ℃) of 1.6 grams, I 10/ I 2Being 9.9, is to be sold with trade(brand)name Affinity PF1140 by Dow Chemical.
POP4 is substantially linear ethene/1-octene copolymer, and its density is 0.903 gram per centimeter 3, melting index (I 2) be/10 minutes (in 190 ℃) of 1.0 grams, I 10/ I 2Be 9.0, it has 750ppm erucicamide and 2500ppm silicon-dioxide, is to be sold with trade(brand)name AffinityPL1881 by Dow Chemical.
PP1 is isotactic alfon, is sold with the T1001 trade mark by Amoco, and its molten flow rate is 0.5 gram/10 minutes in 230 ℃.
PP2 is isotactic styrene homopolymers, is sold with the Moplen Q30P trade mark by Monter, and its molten flow rate is 0.7 gram/10 minutes in 230 ℃.
MB1 is the master batch of being sold by Ampacet (the commercial coding of Ampacet 100329-E), is 0.910 gram per centimeter by density 3, melting index (I 2) be the erucicamide that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 5 weight %.
MB2 is the master batch of being sold by Ampacet (the commercial coding of Ampacet 100371-E), is 0.910 gram per centimeter by density 3, melting index (I 2) be the silicon-dioxide caking inhibiter that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 20 weight %.
MB3 is the master batch of being sold by Ampacet (the commercial coding of Ampacet LR-87476), is 0.910 gram per centimeter by density 3, melting index (I 2) be the stearylamide slip(ping)agent that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 5 weight %.
MB4 is the master batch of being sold by Ampacet (the commercial coding 100342 of Ampacet), is 0.910 gram per centimeter by density 3, melting index (I 2) be the White Mist caking inhibiter that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 20 weight %.
MB5 is a master batch, is 0.910 gram per centimeter by density 3, melting index (I 2) be erucicamide and 15% lime carbonate that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 6 weight %.This master batch prepares by each composition of melting mixing, and adds in the polymkeric substance by means of the side arm charging in expressing technique.
MB6 is a refining glue, is 0.910 gram per centimeter by density 3, melting index (I 2) be erucicamide and 15% talcum that the 6 ethene/1-octene copolymers (being sold by Dow Chemical) that restrain the substantially linear of/10 minutes (in 190 ℃) prepare and contain 6 weight %.This master batch prepares by each composition of melting mixing, and adds in the polymkeric substance by means of the side arm charging in expressing technique.
MB7 is the molten mixture of 1200 gram POP2 and 800 gram POP1 (as mentioned above) and 4 gram Millad 3988 nucleators (sale of Milliken company).MB7 is at Werner ﹠amp in 200 ℃; To do on the Pfleiderer ZSK30 (twin screw extruder is furnished with the single thread die head, cooling bath and single thread knife mill) and mix thing and be extruded into ball and prepare.
Embodiment 18-20 and comparative experiments 22-24
Being furnished with 90 mm dia die heads and die gap is this group blown film of preparation on 1.2 millimeters the Davo blown film forcing machine of 40 millimeters screw rods.The system bar technology that is used to prepare film is 50rpm, 2.5 blow-up ratios, 50 microns thickness, 240 ℃ of melt temperatures, about 15 kilograms/hour.
Embodiment 18-20 and comparative experiments 22-24 extrude as POP1 after rotating cylinder mixes each composition and suitable master batch and/or the dry mixture of nucleator.
In each example, the quantity sum of POP1 and master batch is 100, different additives, and for example slip(ping)agent, caking inhibiter and nucleator are to exist with its amount of indicating in master batch.But, notice in embodiment 18-19, use the nucleator that is higher than and surpasses the content in master batch; In embodiment 20, all nucleators provide separately, rather than provide by means of master batch MB7.
The cohesiveness of evaluation group compound, COF, glossiness, turbidity and clarity.The characteristic of composition and mensuration is listed in table 6.
Table 6
Embodiment Comparative experiments 22 Comparative experiments 23 Comparative experiments 24 Embodiment 18 Embodiment 19 Embodiment 20
Raw material POP1 ?POP1 ?POP1 ?POP1 ?POP1 ?POP1
?MB1(wt.％) 0 ?0 ?1.6 ?1.6 ?1.6 ?1.6
?MB2(wt.％) 0 ?0 ?1 ?0 ?0 ?0
?MB5(wt.％) 0 ?1.33 ?0 ?0 ?0 ?0
?MB7(wt.％) 0 ?0 ?0 ?5 ?2.5 ?0
Slip(ping)agent content (ppm) 0 ?800 ?800 ?800 ?800 ?800
AB content (ppm) 0 ?2000 ?2000 ?20000 ?10000 ?0
The AB class - ?CaCO 3 ?SiO 2 ?PP1 ?PP1 ?0
Nucleator (ppm) 0 ?0 ?0 ?1100 ** ?1050 * ?1000
Bonding (N) + n.m. * ?0.47 ?0.55 ?0.26 ?0.35 ?0.27
?COF n.m. * ?1.14 ?0.35 ?0.18 ?0.83 ?n.m. *
Glossiness 112 ?120 ?110 ?70 ?107 ?119
Turbidity (%) 3.7 ?4.8 ?3.8 ?7 ?3.8 ?2.8
Clarity 70 ?63.5 ?49.7 ?65.4 ?62.4 ?72.5
*N.m.=Yin Taigao and can not measuring
*100ppm is owing to used MB7
* *50ppm is owing to used MB7
+ the cementing value (newton number) measured according to ASTM 1893 (225 millimeters films are wide)
The performance of the pure POP1 of comparative experiments 22 representatives.Comparative experiments 23 and the traditional performance that increases sliding anti stick system of 24 representatives.These embodiment show, compare with unmodified resin POP1, turbidity and or clarity worse.
Embodiment 18,19 and 20 represents the present invention.Embodiment 18 shows that not only anti stick and COF are very good, and clarity is good.Embodiment 19 shows good clarity, turbidity and glossiness and good anti stick and C0F result.Embodiment 20 has shown best optical and good anti stick; But COF does not have embodiment 19 good like that.
Embodiment 21 and comparative experiments 25-27
At the forcing machine identical with use identical system bar technology, the blown film of preparation embodiment 21 and comparative experiments 25-27 with embodiment 18.Composition is extruded as the dried blend of POP1 after rotating cylinder mixes and suitable master batch.In each example, the quantity sum of POP1 and master batch is 100, different additives, and for example slip(ping)agent, caking inhibiter and nucleator are to exist with its amount of indicating in master batch.Cohesiveness, the COF of assessment film, glossiness, turbidity and clarity.The characteristic of composition and mensuration is listed in table 7.
Table 7
Embodiment Comparative experiments 25 Comparative experiments 26 Comparative experiments 27 Embodiment 21
Raw material POP1 ?POP1 ?POP1 ?POP1
?MB1(wt.％) 0 ?1.6 ?4 ?4
?MB4(wt.％) 0 ?1.25 ?1.5 ?0
?MB7(wt.％) 0 ?0 ?0 ?1.25
Slip(ping)agent content (ppm) 0 ?800 ?2000 ?2000
AB content (ppm) 0 ?2500 ?3000 ?5000
The AB class - ?White?Mist + ?White?Mist + ?PP1
Nucleator (ppm) 0 ?0 ?0 ?25 **
Bonding (N) ++ 0.827 ?0.4 ?0.185 ?0.106
?COF n.m. * ?0.161 ?0.145 ?n.m. *
Glossiness 133 ?98.3 ?95.7 ?126.7
Turbidity (%) 2.44 ?3.85 ?4.2 ?2.47
Clarity 79.1 ?34.7 ?32.7 ?76.4
*N.m.=Yin Taigao and can not measuring *25ppm is owing to used MB7+White Mist TMBe white cigarette-calcification diatomite of selling by Celite Corp..++ according to the cementing value (newton number) of ASTM 1893 (225 millimeters films are wide) mensuration
The performance of the unmodified POP1 of comparative experiments 25 representatives.On behalf of tradition, comparative experiments 26 and 27 increase the performance of sliding anti stick system.Turbidity that comparative experiments 26 and 27 film have and/or clarity are lower than unmodified POP1 film.The film that embodiment 21 representatives are made by composition of the present invention.This film shows good clarity, turbidity and anti stick.
Embodiment 22 and comparative experiments 28-30
The film of embodiment 22 and comparative experiments 28-30 prepares on blowing coextrusion streamline.The new LDPE (film grade) of density 0.924 and melting index 1.75 is as outer, and this polyethylene is non-stabilization, sells (trade(brand)name LD320) by Dow Chemical.Heterogeneous branching linear low density ethylene/1-octene copolymer is as sandwich layer, and the density of this multipolymer is 0.919 gram per centimeter 3, melting index (I 2) be 1.05 grams/10 minutes, and sell (trade(brand)name DowlexNG 5056.01E) by Dow Chemical.POP1 that illustrates or POP4 are as inner sealant layer.Each composition is extruded by automatic feed by weight as POP1 layer and suitable master batch and/or the dried blend of PP1.In each example, the quantity sum of POP1 and master batch is 100, different additives, and for example slip(ping)agent, caking inhibiter and nucleator are to exist with its amount of indicating in master batch.
Cohesiveness, the COF of assessment film, glossiness, turbidity and clarity.The characteristic of composition and mensuration is listed in table 8.
Table 8
Embodiment Comparative experiments 28 Comparative experiments 29 Comparative experiments 30 Embodiment 22
Raw material ????POP4 ????POP1 ????POP1 ????POP1
MB1 ????％ ????0 ????0 ????1.2 ????3
MB3 ????％ ????0 ????0 ????1 ????1
MB4 ????％ ????0 ????2.2 ????2.2 ????0
PP1 ????％ ????0 ????0 ????0 ????1
Slip(ping)agent content ??ppm ????750 ????990 ?2090(1590Er+500St) 2000(1500Er+500St)
AB content ??ppm ????3000 ????2750 ????2750 ????10000
The AB class White?Mist + Talcum Talcum ????PP
The nip rolls design temperature ????℃ ????35 ????43 ????42 ????42
Comment Wrinkling Wrinkle resistant Wrinkle resistant Wrinkle resistant
COF (initial inch/inch) ????0.44 ????0.64 ????0.32 ????0.32
Glossiness 20 ????89.94 ????81.62 ????95.6 ????91.92
Glossiness 60 ????116.04 ????114.54 ????119.48 ????115.4
Turbidity (%) ????5.54 ????5.62 ????5.66 ????5.9
Clarity ????78.6 ????65.8 ????70.6 ????83.4
*N.m.=Yin Taigao and can not measuring+White Mist TMBe white cigarette-calcification diatomite of selling by Celite Corp..
Comparative experiments 28 and the traditional performance that increases sliding and anti stick system of 29 representatives.Temperature required on the nip rolls according to the co-extrusion-blown moulding film streamline is judged adhesive property.If it is too low to open the required temperature of bubble, then film curls, and causes the bad order of film roller.If temperature is higher, then observe no wrinkling problem.At comparatively high temps, operator notice and bonding phenomenon (audiovisual observation poor separation) occurs.Comparative experiments 29 shows acceptable anti stick.Comparative experiments 28 does not show sufficient anti stick.
Embodiment 22 represents the present invention.It shows with comparative experiments 29 compares with 30, and anti stick is with to increase sliding property identical.Embodiment 22 represents the preferred embodiments of the invention, compares with 30 with comparative experiments 28, and clarity is improved.

Claims (35)

1. composition comprises: (A) have homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; (B) unsaturated fatty acid amide or saturated ethylene bisamides; (C) unsaturated fatty acids acid amides or unsaturated ethylene bisamides; (D) segmentation mineral compound; And wherein the concentration sum of B component and C is greater than 1500ppm, with component A, and B, the combination weight meter of C and D, and when resin combination was made the blown film of thickness 2 mils, described film was characterised in that having the cohesiveness and the COF that are lower than 49 grams is lower than 0.31.
2. the composition of claim 1, wherein the density of (A) component A is the 0.870-0.940 gram per centimeter 3, melting index (I 2) for 0.2-100 restrains/10 minutes, I 10/ I 2Greater than 5.6; (B) B component meets empirical formula R substantially a-C (O) NHR bOr R a-C (O) NHCH 2CH 2NHC (O)
R a, R wherein aBe saturated C 10-C 26Alkyl and R bBe hydrogen or saturated C independently 10-C 26Alkyl and
The concentration of wherein said B component is with component A, and B, the combination weight of C and D are benchmark, for
10ppm-1250ppm, (C) component C meets empirical formula R substantially cC (O) NHR d, R wherein cBe unsaturated C 10-C 26Alkyl and
R dBe hydrogen or unsaturated C independently 10-C 26Alkyl, or empirical formula
R e-C (O) NHCH 2CH 2NHC (O) R e, R wherein eBe saturated or unsaturated C 10-C 26Alkyl, condition are at least one R eBe unsaturated C 10-C 26Alkyl, and the concentration of wherein said component C is with component A, and B, the combination weight of C and D are benchmark, are 250ppm-10000ppm; (D) component D comprises silicon oxide, aluminum oxide, talcum, Wingdale, clay, diatomite, dioxy
Change at least a in titanium or the lime carbonate, and concentration is with component A, B, the combination weight of C and D
Be benchmark, be 500ppm-15000ppm.
3. the composition of claim 1, wherein the density of (A) component A is the 0.890-0.920 gram per centimeter 3, melting index (I 2) be that 0.4-50 restrains
/ 10 minutes, I 10/ I 2Be 5.6-13; (B) B component is a stearylamide, mountain Yu acid amides or peanut acid amides, and its concentration is with component A, B, C and
The combination weight of D is a benchmark, for 100ppm-1000ppm and (C) component C be erucicamide, oleylamide, erucicamide base ethyl erucicamide or oleoyl amido second
The two oleylamide of base, and its concentration is with component A, and B, the combination weight of C and D are benchmark, for
500ppm-8000ppm; (D) component D is a silicon-dioxide, and its concentration is with component A, and B, the combination weight of C and D are benchmark, for
1000ppm-10000ppm。
4. the composition of claim 1, wherein the density of (A) component A is the 0.890-0.910 gram per centimeter 3, melting index (I 2) be that 0.5-20 restrains
/ 10 minutes, I 10/ I 2For 5.6-11 and Mw/Mn are 1.8-6.0; (B) B component is a stearylamide, and its concentration is with component A, and B, the combination weight of C and D are benchmark,
Be 250ppm-750ppm; (C) component C is an erucicamide, and its concentration is with component A, and B, the combination weight of C and D are benchmark,
Be 750ppm-5000ppm; (D) component D is a silicon-dioxide, and its concentration is with component A, and B, the combination weight of C and D are benchmark, for
1250ppm-7500ppm。
5. the composition of claim 1, wherein component A is substantially linear ethene/alpha-olefin copolymer, the feature of wherein said multipolymer is: A) melt rate I 10/ I 2〉=5.63; And B) molecular weight distribution mw/mn is defined by following formula: Mw/Mn≤(I 10/ I 2)-4.63; With C) critical shear rate when melt surface destroys beginning is than having identical I 2Critical shear rate height at least 50% when destroying beginning with the linear ethylene of Mw/Mn/alpha-olefinic polymer melt surface; With D) processing index is less than or equal to has identical I 270% and E with linear ethylene/alpha-olefinic polymer PI of Mw/Mn) have 0.01-3 long chain branches/1000 carbon.
6. reduce the method for film and fine sheet bonding and raising sliding, this method comprises by the composition of claim 1 makes described film and sheet material.
7. composition, comprising: (A) a kind of copolymer blended compositions comprises:
(1) has homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; With
(2) second kinds of multipolymers comprise:
(a) has homogeneous ethylene/alpha-olefin copolymer that wide composition distributes; Or
(b) has different I 2Or density, or Mw, or the multipolymer of Mw/Mn (1); Or
(c) (a) or arbitrary combination (b); (B) unsaturated fatty acid amide or saturated ethylene bisamides; (C) unsaturated fatty acids acid amides or unsaturated ethylene bisamides; (D) segmentation mineral compound; And wherein
The concentration sum of B component and C is greater than 1500ppm, with component A, and B, the combination weight meter of C and D, and when resin combination was made the blown film of thickness 2 mils, described film was characterised in that having the cohesiveness and the COF that are lower than 49 grams is lower than 0.31.
8. the composition of claim 7, wherein the density of component A is the 0.870-0.940 gram per centimeter 3, melting index (I 2) for 0.2-100 restrains/10 minutes, and I 10/ I 2Greater than 5.6; A wherein) concentration of component (A) (1) in copolymer compositions is with component A, and B, the combination weight of C and D are that benchmark is a 10-90% weight, and density is the 0.870-0.940 gram per centimeter 3, melting index (I 2) for 0.05-100 restrains/10 minutes, I 10/ I 2Greater than 5.6; And B) concentration is with component A in copolymer compositions for component (A) (2), and B, the combination weight of C and D are that benchmark is a 10-90% weight; And wherein said component (A) (2) has corrected density, I 2, I 10/ I 2, and Mw/Mn, and exist with corrected concentrations, to obtain the desired characteristic of final blend components (A), C) B component meets empirical formula R substantially a-C (O) NHR bOr R a-C (O) NHCH 2CH 2NHC (O)-R a, R wherein aBe saturated C 10-C 26Alkyl and R bBe hydrogen or saturated C independently 10-C 26The concentration of alkyl and wherein said B component is with component A, and B, the combination weight of C and D are benchmark, are 10ppm-1250ppm; And D) component C meets empirical formula R substantially cC (O) NHR d, R wherein cBe unsaturated C 10-C 26Alkyl and R dBe hydrogen or unsaturated C independently 10-C 26Alkyl, or empirical formula R e-C (O) NHCH 2CH 2NHC (O) R e, R wherein eBe saturated or unsaturated C 10-C 26Alkyl, condition are at least one R eBe unsaturated C 10-C 26Alkyl, and the concentration of wherein said component C is with component A, and B, the combination weight of C and D are benchmark, are 250ppm-10000ppm; And E) component D comprises silicon oxide, aluminum oxide, talcum, Wingdale, clay, diatomite, dioxy
Change at least a in titanium or the lime carbonate, and its concentration is with component A, B, the combination of C and D is heavy
Amount is 500ppm-15000ppm for benchmark.
9. the composition of claim 7, wherein A) density of component A is the 0.890-0.920 gram per centimeter 3, melting index (I 2) for 0.4-50 restrains/10 minutes, I 10/ I 2Be 5.6-13; And B) concentration of component (A) (1) in copolymer compositions is with component A, and B, the combination weight of C and D are that benchmark is a 15-85% weight, and density is the 0.870-0.920 gram per centimeter 3, melting index (I 2) for 0.2-50 restrains/10 minutes, I 10/ I 2Be 5.6-13; And C) concentration is with component A in copolymer compositions for component (A) (2), and B, the combination weight of C and D are that benchmark is a 15-85% weight; And D) B component is to be selected from stearylamide, and at least a and its concentration in mountain Yu acid amides or the peanut acid amides is with component A, and B, the combination weight of C and D are that benchmark is 100ppm-1000ppm; And E) component C is selected from erucicamide, oleylamide, and the two oleylamide of erucicamide base ethyl erucicamide or oleoyl amido ethyl, and its concentration is with component A, and B, the combination weight of C and D are benchmark, are 500ppm-8000ppm; And F) component D is a silicon-dioxide, and its concentration is with component A, and B, the combination weight of C and D are benchmark, are 1000ppm-10000ppm.
10. the composition of claim 7, wherein A) density of component A is the 0.890-0.910 gram per centimeter 3, melting index (I 2) for 0.5-20 restrains/10 minutes, I 10/ I 25.6-11; Mw/Mn is 1.8-6.0; And B) concentration of component (A) (1) in copolymer compositions is with component A, and B, the combination weight of C and D are that benchmark is a 20-80% weight, and density is the 0.870-0.905 gram per centimeter 3, melting index (I 2) for 0.2-20 restrains/10 minutes, I 10/ I 25.6-11 and Mw/Mn is 1.8-6.0; And C) concentration is with component A in copolymer compositions for component (A) (2), and B, the combination weight of C and D are that benchmark is a 20-80% weight; And D) B component is a stearylamide, and its concentration is with component A, and B, the combination weight of C and D are that benchmark is 250ppm-750ppm; And E) component C is an erucicamide, and its concentration is with component A, and B, the combination weight of C and D are benchmark,
Be 750ppm-5000ppm; And F) component D is a silicon-dioxide, and its concentration is with component A, and B, the combination weight of C and D are benchmark,
Be 1250ppm-7500ppm.
11. the composition of claim 7, the homogeneous copolymers that wherein has narrow composition distribution is substantially linear ethene/alpha-olefin copolymer, and wherein the feature of substantially linear ethene/alpha-olefin copolymer is to have: a) melt rate I 10/ I 2〉=5.63; And b) molecular weight distribution mw/mn is defined by following formula: Mw/Mn≤(I 10/ I 2)-4.63; With c) critical shear rate when melt surface destroys beginning is than having identical I 2Critical shear rate height at least 50% when destroying beginning with the linear ethylene of Mw/Mn/alpha-olefinic polymer melt surface; With d) processing index is less than or equal to has identical I 2With 70% of linear ethylene/alpha-olefinic polymer PI of Mw/Mn; And e) has 0.01-3 long chain branches/1000 carbon.
12. reduce the method for film and fine sheet bonding and raising sliding, this method comprises by the composition of claim 7 makes described film and sheet material.
13. the composition of claim 1, it is laminar, and thickness is the 10-20 mil.
14. the composition of claim 7, it is laminar, and thickness is the 10-20 mil.
15. the composition of claim 1, it is film like, and mean thickness is the 0.3-8 mil.
16. the composition of claim 7, it is film like, and mean thickness is the 0.3-8 mil.
17. the composition of claim 1, it is blown film, cast film, single thin film, or co-extrusion film shape.
18. the composition of claim 7, it is blown film, cast film, single thin film, or co-extrusion film shape.
19. composition comprises: (A) at least a random substantially multipolymer: wherein said multipolymer comprises:
(1) polymer unit of 0.5-65 mole %, derived from:
(a) at least a vinylidene aromatic monomer, or
(b) at least a hindered aliphatic vinylidene monomer, or
(c) at least a vinylidene aromatic monomer and the monomeric molectron of at least a hindered aliphatic vinylidene; With
(2) 35-99.5 mole % is derived from least a aliphatic C 2-C 20The alpha-olefinic polymer unit; (B) unsaturated fatty acid amide or saturated ethylene bisamides; Or (C) unsaturated fatty acid amide or unsaturated ethylene bisamides; Or (D) segmentation mineral compound; Or (E) (B), at least a molectron (C) and (D).
20. the composition of claim 19, (1) described basic random copolymers wherein, component A comprises 1-55 mole % polymer unit, spreads out
Be conigenous:
(a) at least a described vinylidene aromatic monomer, component A (1) (a), it is by following logical
Formula is represented:
Figure A9880420300071
R wherein 1Be selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Ar is phenyl or the phenyl that replaced by 1-5 substituting group, and described substituting group is selected from: halogen, C 1-4Alkyl, and C 1-4Haloalkyl; With n be 0-4; Or
(b) at least a described hindered aliphatic vinylidene monomer, component A (1) (b), it is represented by following general formula:
Figure A9880420300072
A wherein 1Be the substituting group that big aliphatic series in space or cyclic aliphatic have 20 carbon at the most, R 1Be selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Or other R 1And A 1Become ring system together; Or (2) described basic random copolymers, component A contains 45-99 mole % derived from least a
Be selected from the polymer unit of at least a described aliphatic alpha-olefin in the molectron of ethene or ethene and propylene, 4-methylpentene, butene-1, hexene-1 and octene-1; (3) described basic random copolymers, component A has the melting index (I of 0.01-1000 2); (4) described basic random copolymers, component A has the molecular weight distribution (Mw/Mn) of 1.5-20; (5) described unsaturated fatty acid amide or saturated ethylene bisamides, B component meets empirical formula R respectively substantially a-C (O) NHR bOr R a-C (O) NHCH 2CH 2NHC (O) R a, R wherein aBe saturated C 10-C 26Alkyl and R bBe hydrogen or saturated C independently 10-C 26The concentration of alkyl and wherein said B component is with component A, and B, the combination weight of C and D are benchmark, are 0-5000ppm, (6) described unsaturated fatty acids acid amides or saturated ethylene bisamides, and component C meets empirical formula R respectively substantially cC (O) NHR d, R wherein cBe unsaturated C 10-C 26Alkyl and R dBe hydrogen or unsaturated C independently 10-C 26Alkyl, or empirical formula R e-C (O) NHCH 2CH 2NHC (O) R e, R wherein eBe saturated or unsaturated C 10-C 26Alkyl, condition are at least one R eBe unsaturated C 10-C 26Alkyl, and the concentration of wherein said component C is with component A, and B, the combination weight of C and D are benchmark, are 0-10000ppm; (7) described segmentation mineral compound, component D comprises silicon oxide, aluminum oxide, talcum, Wingdale, clay, diatomite, at least a in titanium dioxide or the lime carbonate, and concentration is with component A, and B, the combination weight of C and D are benchmark, are 0-20000ppm.
21. the composition of claim 19, (1) described basic random copolymers wherein, component A comprises 2-50 mole % polymer unit, derived from:
(a) vinylbenzene, alpha-methyl styrene, adjacent-,-, p-methylstyrene, and ring
Halogenated vinylbenzene; Or
(b) 5-ethylidene-2-norbornene or 1-vinyl cyclohexene, the 3-vinyl cyclohexene,
And 4 vinyl cyclohexene; Or
(c) a) and b) at least a combination; (2) described basic random copolymers, component A contains 50-98 mole % derived from ethylene polymer unit; (3) described basic random copolymers, component A has the melting index (I of 0.1-100 2); (4) described basic random copolymers, component A has the molecular weight distribution (Mw/Mn) of 1.8-10; (5) described unsaturated fatty acid amide or unsaturated ethylene bisamides, B component, it is stearylamide, mountain Yu acid amides or peanut acid amides, and its concentration is with component A, and B, the combination weight of C and D are benchmark, be 250ppm-2500ppm, (6) described unsaturated fatty acids acid amides or unsaturated ethylene bisamides, component C is an erucicamide, oleylamide, the two oleylamide of erucicamide base ethyl erucicamide or oleoyl amido ethyl, and its concentration is with component A, B, the combination weight of C and D is a benchmark, is 500ppm-7500ppm; (7) described segmentation mineral compound, component D is silicon oxide or talcum, and concentration is with component A, B, the combination weight of C and D are benchmark, are 1000-15000ppm.
22. the composition of claim 21, (1) described basic random copolymers wherein, component A has the melting index (I of 0.5-30 2); (2) described basic random copolymers, component A has the molecular weight distribution (Mw/Mn) of 2-5; (3) described vinylidene aromatic monomer, component A1 (a) is a vinylbenzene; (4) described aliphatic alpha-olefin, component A2 is an ethene; (5) described unsaturated fatty acid amide or unsaturated ethylene bisamides, component C is a stearylamide, and its concentration is with component A, and B, the combination weight of C and D are benchmark, be 500ppm-1500ppm, (6) described unsaturated fatty acid amide or unsaturated ethylene bisamides, component C is an erucicamide, and its concentration is with component A, B, the combination weight of C and D are benchmark, are 1000ppm-3000ppm; (7) described segmentation mineral compound, component D is silicon oxide or talcum, and concentration is with component A, B, the combination weight of C and D are benchmark, are 2000-10000ppm.
23. composition comprises (A) a kind of resin combination, comprising:
(1) has homogeneous ethylene/alpha-olefin copolymer that narrow composition distributes; Or
(2) at least a basic random copolymers; Wherein said multipolymer comprises:
(a) polymer unit of 0.5-65 mole %, derived from:
(i) at least a vinylidene aromatic monomer, or
(ii) at least a hindered aliphatic vinylidene monomer, or
(iii) at least a vinylidene aromatic monomer and at least a hindered aliphatic Asia
The vinyl monomer molectron; With
(b) 35-99.5 mole % is derived from least a aliphatic C 2-C 20The alpha-olefinic polymer unit; With optional
(3) alfon or propylene and one or more C 2-C 20The multipolymer of alpha-olefin; (B) one or more following materials:
(1) unsaturated fatty acid amide or saturated ethylene bisamides; Or
(2) unsaturated fatty acid amide or unsaturated ethylene bisamides; Or
(3) molectron of B (1) and B (2); With
Choose wantonly, (C) a kind of nucleator.
24. the composition of claim 23, (1) described homogeneous ethylene/alpha-olefin copolymer wherein, the density of component (A) (1) is 0.855-
0.960 gram per centimeter 3, melting index (I 2) for 0.02-100 restrains/10 minutes, I 10/ I 2
Greater than 5.6; (2) described basic random copolymers, component (A) (2) contain 1-55 mole % polymer unit, derived from:
(a) at least a described vinylidene aromatic monomer, component (A) (2) is (i) (a), and it is represented by following general formula:
Figure A9880420300101
R wherein 1Be selected from hydrogen and C 1-4Alkyl, preferred hydrogen or methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen or methyl; Ar is phenyl or the phenyl that replaced by 1-5 substituting group, and described substituting group is selected from: halogen, C 1-4Alkyl, and C 1-4Haloalkyl; With n be 0-4; Or
(b) at least a described hindered aliphatic vinylidene monomer, component (A) (2) (a) is (ii) represented by following general formula: A wherein 1Be the substituting group that has 20 carbon at the most of big aliphatic series in space or cyclic aliphatic, R 1Be selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Each R 2Be independently selected from hydrogen and C 1-4Alkyl, preferred hydrogen and methyl; Or other R 1And A 1Become ring system together; (3) described basic random copolymers, component (A) (2) contains the polymer unit of 45-99 mole % derived from least a described aliphatic alpha-olefin at least a molectron that is selected from ethene or ethene and propylene, 4-methylpentene, butene-1, hexene-1 and octene-1; (4) described basic random copolymers, component (A) (2) has the melting index of 0.01-1000; (5) described basic random copolymers, component (A) (2) has the molecular weight distribution (Mw/Mn) of 1.5-20; (6) described cinnamic homopolymer or multipolymer, the concentration of component (A) (3) are 0-5 weight % (with component A, the combination weight meter of B and C), melting index (I 2, 230 ℃) for 0.2-10 gram/10 minutes and density be the 0.880-0.920 gram per centimeter 3(7) described unsaturated fatty acid amide or saturated ethylene bisamides, B component (1) meets empirical formula R respectively substantially a-C (O) NHR bOr R a-C (O) NHCH 2CH 2NHC (O) R a, R wherein aBe saturated C 10-C 26Alkyl and R bBe hydrogen or saturated C independently 10-C 26The concentration of alkyl and wherein said B component (1) is with component A, and the combination weight of B and C is a benchmark, is 0-5000ppm; (8) described unsaturated fatty acid amide or saturated ethylene bisamides, B component (2) meets empirical formula R respectively substantially cC (O) NHR d, R wherein cBe unsaturated C 10-C 26Alkyl and R dBe hydrogen or unsaturated C independently 10-C 26Alkyl, or empirical formula R e-C (O) NHCH 2CH 2NHC (O) R e, R wherein eBe saturated or unsaturated C 10-C 26Alkyl, condition are at least one R eBe unsaturated C 10-C 26Alkyl, and the concentration of wherein said B component (2) is with component A, and the combination weight of B and C is a benchmark, is 0-10000ppm; (9) described nucleator, component C comprises the smectic clays ore deposit, Erie's stone ore, stratification double-hydroxide, prussiate, and oxide compound, chalkogenide, metal chloride, or acetal or its mixture; With wherein said nucleator, the concentration of component C is with component A, and the combination weight of B and C is a benchmark, is 0-3000ppm.
25. the composition of claim 23, (1) described homogeneous ethylene/olefin copolymer wherein, the density of component (A) (1) is the 0.870-0.915 gram per centimeter 3, melting index (I 2) for 0.2-50 restrains/10 minutes, I 10/ I 2Be 5.6-13; (2) described basic random copolymers, component (A) (2) contain 2-50 mole % polymer unit, derived from:
(a) vinylbenzene, alpha-methyl styrene, adjacent-,-, p-methylstyrene and encircle halogenated vinylbenzene; Or
(b) 5-ethylidene-2-norbornene or 1-vinyl cyclohexene, 3-vinyl cyclohexene, and 4 vinyl cyclohexene; Or
(c) a) and b) at least a combination; (3) described basic random copolymers, component (A) (2) contains the polymer unit of 50-98 mole % derived from ethylene; (4) described basic random copolymers, component (A) (2) has the melting index (I of 0.1-100 2); (5) described basic random copolymers, component (A) (2) has the molecular weight distribution (Mw/Mn) of 1.8-10; (6) homopolymer of described propylene or multipolymer, the concentration of component (A) (3) are 0.3-3 weight % (with component A, the combination weight meter of B and C), melting index (I 2, 230 ℃) for 0.3-5 gram/10 minutes and density be the 0.890-0.910 gram per centimeter 3(7) described unsaturated fatty acid amide or saturated ethylene bisamides, B component (1), it is stearylamide, mountain Yu acid amides or peanut acid amides, and its concentration is with component A, the combination weight of B and C is a benchmark, be 250ppm-2500ppm and (8) described unsaturated fatty acids acid amides or unsaturated ethylene bisamides, B component (2), it is erucicamide, oleylamide, the two oleylamide of erucicamide base ethyl erucicamide or oleoyl amido ethyl, and its concentration is with component A, the combination weight of B and C is a benchmark, is 500ppm-7500ppm; (9) described nucleator, component C comprises polynite, montmorillonite, beidellite, volkonskoite, hectorite, bentonite, sauconite, magauigite, fibrous morphology crystals, and vermiculite, illite and crud thereof, Mg 6Al 3.4(OH) 18.8(CO 3) 1.7H 2O, ReCl 3, FeOCl, TiS 2, MoS 3, and MoS 3Ni (CN) 2, H 2Si 2O 5, V 5O 13, HTiNbO 5, Cr 0.5V 0.5S 2, W 0.2V 2.8O 7, Cr 3O 8, MoO 3(OH) 2, VOPO 4-2H 2O, CaPO 4CH 3-H 2O, MnHAsO 4-H 2O, Ag 6Mo 10O 33, Sodium Benzoate, lithium benzoate, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) sodium phosphate, Sorbitol dibenzal, methyl-Sorbitol dibenzal, trinaphthylenyl sorbyl alcohol, three (4-methyl isophthalic acid-naphthylidene) sorbyl alcohol, three-(4-methoxyl group-1-naphthylidene) sorbyl alcohols, dibenzylidene Surrey Extra Old (zylitol), Sorbitol dibenzal, 3,4-dimethyl Sorbitol dibenzal, 1,3-benzylidene-2,4-is to the methyl benzylidene sorbitol, 1,3-benzylidene-2,4-is to the ethyl benzylidene sorbitol, 1,3-is to methyl benzylidene-2, the 4-benzylidene sorbitol, 1,3-is to ethyl benzylidene-2, the 4-benzylidene sorbitol, 1,3-is to methyl benzylidene-2, and 4-is to the ethyl benzylidene sorbitol, 1,3-is to ethyl benzylidene-2, and 4-is to the methyl benzylidene sorbitol, 1,3,2,4-two-(to the methyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the ethyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the n-propyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(p-isopropyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the normal-butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the sec-butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(aligning tertiary butyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(2 ', 4 '-dimethyl benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the methoxyl group benzylidene) sorbyl alcohol, 1,3,2,4-two-(to the oxyethyl group benzylidene) sorbyl alcohol, 1,3-benzylidene-2,4-is to the chlorine benzylidene sorbitol, and 1,3-is to chlorine benzylidene-2, the 4-benzylidene sorbitol, 1,3-is to chlorine benzylidene-2, and 4-is to the methyl benzylidene sorbitol, 1,3-is to chlorine benzylidene-2, and 4-is to ethyl benzylidene sorbitol, 1,3-is to methyl benzylidene-2,4-is to the chlorine benzylidene sorbitol, and 1,3-is to ethyl benzylidene-2,4-is to chlorine benzylidene sorbitol hexamethylene or 1,3,2,4-two-(to the chlorine benzylidene) sorbyl alcohol, or its mixture, and its concentration is with component A, and the combination weight of B and C is a benchmark, is 500-2500ppm.
26. the resin combination of claim 25, wherein the density of (1) described homogeneous ethylene/alpha-olefin copolymer is the 0.885-0.905 gram per centimeter 3, melting index (I 2) for 0.5-4 restrains/10 minutes, I 10/ I 2For 5.6-11 and Mw/Mn are 1.8-6.0; (2) described vinylidene aromatic monomer is a vinylbenzene; (3) described aliphatic alpha-olefin is an ethene; (4) melting index (I of described basic random copolymers 2) be 0.5-30; (5) molecular weight distribution of described basic random copolymers (Mw/Mn) is 2-5; (6) described alfon or multipolymer are isotactic propylene homopolymer or multipolymer, and its concentration is 0.5-2 weight % (with component A, the combination weight of B and C is a benchmark); And melting index (I 2, 230 ℃) and for 0.5-2 restrains/10 minutes, density is the 0.895-0.905 gram per centimeter 3(7) described unsaturated fatty acid amide or saturated ethylene bisamides are stearylamides, and concentration is with component A, and the combination weight of B and C is that benchmark is 500-1500ppm; (8) described unsaturated fatty acids acid amides or unsaturated ethylene bisamides are erucicamides, and concentration is with component A, and the combination weight of B and C is that benchmark is 1000-3000ppm; (9) described nucleator is Millad TM3988 and concentration with component A, the combination weight of B and C is that benchmark is 1000-2000ppm.
27. the resin combination of claim 23, wherein said homogeneous ethylene/alpha-olefin copolymer, component (A) (1) is substantially linear ethene/alpha-olefin copolymer, the feature of wherein said multipolymer is to have: (A) molten flow rate, I 10/ I 2〉=5.63; (B) molecular weight distribution, Mw/Mn presses the following formula definition: Mw/Mn≤(I 10/ I 2Critical shear rate when)-4.63 (C) melt surface destroys beginning is than having identical I 2Critical shear rate height at least 50% when destroying beginning with the linear ethylene of Mw/Mn/alpha-olefinic polymer melt surface; (D) processing index is less than or equal to and is had identical I 2With 70% of linear ethylene/alpha-olefinic polymer PI of Mw/Mn; (E) has 0.01-3 long chain branches/1000 carbon.
28. reduce the method for film and fine sheet bonding and raising sliding, this method comprises by the resin combination of claim 19 makes described film and sheet material.
29. the resin combination of claim 19, it is laminar, and thickness is the 10-20 mil.
30. the resin combination of claim 19, it is film like, and mean thickness is the 0.3-8 mil.
31. the resin combination of claim 19, it is blown film, cast film, single thin film or co-extrusion film.
32. reduce the method for film and fine sheet bonding and raising sliding, this method comprises by the composition of claim 23 makes described film and sheet material.
33. the resin combination of claim 23, it is laminar, and thickness is the 10-20 mil.
34. the resin combination of claim 23, it is film like, and mean thickness is the 0.3-8 mil.
35. the resin combination of claim 23, it is blown film, cast film, single thin film or co-extrusion film.
CN98804203A 1997-04-16 1998-04-15 Compositions containing slip and anti-block agents Pending CN1252824A (en)

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CN109219634B (en) * 2016-05-24 2021-09-28 科莱恩国际有限公司 Anti-adhesive component for improving anti-adhesive properties of thermoplastic packaging material

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