CN101641406B - Polymeric material and its manufacture and use - Google Patents
Polymeric material and its manufacture and use Download PDFInfo
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- CN101641406B CN101641406B CN2008800024795A CN200880002479A CN101641406B CN 101641406 B CN101641406 B CN 101641406B CN 2008800024795 A CN2008800024795 A CN 2008800024795A CN 200880002479 A CN200880002479 A CN 200880002479A CN 101641406 B CN101641406 B CN 101641406B
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- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TXLMBPWQZULYHP-UHFFFAOYSA-N tert-butyl(dimethoxy)silane Chemical compound CO[SiH](OC)C(C)(C)C TXLMBPWQZULYHP-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08L23/06—Polyethene
-
- 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
- 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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Disclosed herein is a polymer composition, its manufacture and use, said composition may comprise greater than about 90 mole % propylene monomer, and having a unique combination of properties, including one or more of the following: a heat of fusion of more than about 108 J/g, a melting point of 165 DEG C or higher, a Melt Flow Rate so low that it is essentially not measurable and a molecular weight of greater than about 1.5 x 10<6>. Further disclosed herein are blends or mixtures of the present novel polymer composition and products, such as, for example, microporous film structures and the like comprising same.
Description
Technical field
The present invention relates to polymeric composition, it comprises the propylene monomer greater than about 90 moles of %, and 230 ℃ of melt flow rate(MFR)s that have less than about 0.2dg/ minute.This polymeric composition can be effective to prepare microporous membrane, comprises containing poly microporous membrane.
Background technology
Ultra-high molecular weight (" UHMW ") polymkeric substance has various important commercial purposes.For example, UHMW high density polyethylene(HDPE) (" UHMWPE ") can be used for many products, comprises shooting protection fabric, joint replacement materials and microporous membrane (WO 2004/026921A1 and United States Patent(USP) No. 4,734,196).What people required when as battery separator is: microporous membrane has well-balanced closing (shutdown) performance, temperature of fusion, perviousness and acupuncture disruptive strength.It is found that the UHMW Vestolen PP 7052 of certain form (" UHMWPP ") can be effective to spin with fixed attention HMP and high strength fibre, the additive that it controls the fusing rheology of low-molecular-weight polypropylene as the additive and the conduct of preparation microporous membrane.
The UHMW Vestolen PP 7052 can use Ziegler-Natta catalyst and dicyclopentyl dimethoxyl silane to prepare as electron donor.Referring to, for example JP 06234811A, JP06234812A and JP 07292021A.First reference discloses the product with limiting viscosity of 4 to 10dl/g, and second reference discloses has 5 to 10dl/g limiting viscosity and less than the product of 0.1g/10 minute melt flow rate(MFR) (" MFR ").It is said that two kinds of products can be effective to yarn, this yarn has good breaking strength and modulus.The 3rd product of top reference has 1x10
6Molecular-weight average.
JP 62022808A discloses use Ziegler-Natta catalyst (without the dicyclopentyl dimethoxyl silane electron donor) and has prepared and have 2x10
6To 5x10
6The UHMW Vestolen PP 7052 of molecular weight.Equally, JP 03007704A discloses use Ziegler-Natta catalyst (without the dicyclopentyl dimethoxyl silane electron donor) and prepares and have greater than 1x10
6The Vestolen PP 7052 of molecular weight and multipolymer.JP 02305809A also discloses with ziegler-natta catalyzed polymerization (without electron donor) and has prepared the UHMW Vestolen PP 7052.
US 4,413, and 110 disclose and have 2.1x10
6The Vestolen PP 7052 of molecular weight discloses it and can be used for high strength fibre.US 5,070, and 051 discloses UHMW Vilaterm and polyhexene, rather than Vestolen PP 7052, and it uses Ziegler-Natta catalyst (without the dicyclopentyl dimethoxyl silane electron donor) to prepare.
EP 0654476A and EP 0790076A disclose the Vestolen PP 7052 that uses metalloscene catalyst to prepare.In first reference, product has 786,500 molecular weight, 159 ℃ fusing point and 2.4 MWD (" Mw/Mn ").The product of second reference has 1.1x10
6Molecular weight, 2.5 MWD and 159 ℃ fusing point.
Although used metalloscene catalyst and Ziegler-Natta catalyst to prepare Vestolen PP 7052 (both can have and not have the dicyclopentyl dimethoxyl silane electron donor); But the Vestolen PP 7052 that obtains is difficult to prepare microporous membrane, especially contains Vestolen PP 7052 and poly microporous membrane.For example, United States Patent(USP) No. 6,096,213 disclose the microporous membrane by blend (comprising Vilaterm and the polyacrylic blend) generation of melt processable polymers.The disclosed content of this patent thinks to have only when Vestolen PP 7052 has the melt flow index that is higher than 0.2dg/min, and Vestolen PP 7052 just can melt-processed.
Therefore, also need can be used for preparing the UHMWPP of microporous membrane, for example contain Vilaterm and polyacrylic those, the Vestolen PP 7052 that especially wherein has 0.2dg/min or littler melt flow index.
Summary of the invention
In one embodiment, the present invention relates to a kind of UHMWPP, based on the weight of UHMWPP, it comprises the propylene monomer greater than about 90 moles of %.This UHMWPP has one or more following performance usually: greater than the limiting viscosity of about 10dl/g, and greater than the melting heat of about 108J/g, 165 ℃ or bigger fusing point, molecular weight is greater than about 1.5x10
6About 2.5 to about 7 MWD, promptly can not be measured less than approximately 0.01dg/ minute 230 ℃ melt flow rate(MFR)s basically; But based on the 0.5wt.% of UHMWPP weight or extract still less (can through UHMWPP contact with YLENE and by extracting) quantity; Greater than the meso five unit number of componentss of about 96mol%mmmm five unit groups and per 10,000 carbon atoms less than about 50 three-dimensional defects count.In related embodiment; Based on the weight of UHMWPP, UHMWPP comprises greater than about 90 moles of % propylene monomers, 230 ℃ of melt flow rate(MFR)s that have less than about 0.01dg/ minute; Has at least a following performance: greater than the limiting viscosity of about 10dl/g; Greater than the melting heat of about 108J/g, 165 ℃ or bigger fusing point, molecular weight is greater than about 1.5x10
6About 2.5 to about 7 MWD; But based on the 0.5wt.% of UHMWPP weight or extract still less (can through UHMWPP contact with YLENE and by extracting) quantity; Greater than the meso five unit number of componentss of about 96mol%mmmm five unit groups and per 10,000 carbon atoms less than about 50 three-dimensional defects count.
In another embodiment, the present invention relates to comprise the polymer compsn of aforementioned UHMWPP.In related embodiment, this polymer compsn further comprises: (a) second polymkeric substance (for example Vilaterm, for example high-density and/or High molecular weight polyethylene), and/or (b) thinner or solvent (for example whiteruss).In further related embodiment; Polymer compsn is the polyolefin compositions that comprises aforementioned UHMWPP and optional one or more following material: high density polyethylene(HDPE) (" HDPE "); Ultrahigh molecular weight polyethylene(UHMWPE) (" UHMWPE "); Second Vestolen PP 7052 (for example low Vestolen PP 7052) and thinner or solvent (it can be thinner, solvent or both mixtures) than UHMWPP molecular weight.In another related embodiment, the present invention relates to the polymer compsn and second polymer compsn.Second polymer compsn can comprise polyolefine for example Vilaterm and/or Vestolen PP 7052, for example HDPE, UHMWPE and second polyacrylic one or more.
In another embodiment, the present invention relates to prepare the method for aforementioned UHMWPP and polymer compsn.In another embodiment, the present invention relates to use aforementioned UHMWPP or polymer compsn to prepare the method for article, article are moulded products, sheet material or film for example, for example microporous membrane.Have been found that this microporous membrane for example can especially be used as battery separator in lithium ion galvanic cell and the lithium ion secondary accumulator battery.This battery can be used as Charge Source or electric charge pond.
Correspondingly, in another embodiment, the present invention relates to contain the microporous membrane or the film of aforementioned UHMWPP or polymer compsn.Have been found that contain aforementioned UHMWPP or polymer compsn have well-balanced performance, temperature of fusion, perviousness and the acupuncture disruptive strength of closing as the microporous membrane of battery separator.
Microporous membrane of the present invention can be unitary film or multilayer film.Therefore, in one embodiment, the present invention relates to prepare the method for microporous membrane or film; Comprise: first microporous layers that comprises the first layer material; Comprise the 3rd microporous layers of the first layer material and comprise second microporous layers of second layer material, second microporous layers is between the first and the 3rd microporous layers.First or second layer material at least a by the preparation of UHMWPP or polymer compsn.Except the molecular weight degradation that relatively small amount during processing, occurs,, comprise UHMWPP or the polymer compsn that produces it usually by the layer material of UHMWPP or combination of polymers deposits yields for example from shear thinning.In another embodiment, the present invention relates to prepare the method for microporous membrane or film, comprising: mix above-mentioned UHMWPP (or polymer compsn) to form first polyolefin solution with thinner (or process solvent) (1); (3) at least a portion first polyolefin solution is extruded through die head; Form extrudate, (4) form the refrigerative extrudate with the extrudate cooling; (5) from the refrigerative extrudate, remove at least a portion thinner; Form except that sheet material and (6) of desolvating and from sheet material, remove any volatile matter of at least a portion, form microporous membrane.In related embodiment, the present invention relates to prepare the method for multilayer film, comprising: mix above-mentioned UHMWPP or polymer compsn (1) with thinner (or process solvent); Form first polyolefin solution, mix second polyolefine or polymer compsn (the optional UHMWPP that comprises) (2) with second thinner (or process solvent), form second polyolefin solution; (3) at least a portion first polyolefin solution is extruded through die head, and extruded at least a portion second polyolefin solution jointly, so that form the multiwalled extrudate; (4) the multilayer extrudate is cooled off; Form refrigerative multilayer extrudate, at least a portion process solvent is removed in (5) from the refrigerative extrudate, forms to remove the sheet material that desolvates; (6) from sheet material, remove any volatile matter of at least a portion, form the multiwalled microporous membrane.In one embodiment, this method of continuous or semi-continuous operation.
Detailed description of the present invention
The present invention is based on the discovery of the polymer compsn that comprises above-mentioned UHMWPP, this polymer compsn can be used for preparing for example microporous membrane of goods usually.This polymer compsn comprises greater than about 90 moles of % propylene monomers usually; And has one or more following desirable performance: greater than the limiting viscosity of about 10dl/g; Greater than the melting heat of about 108J/g, 165 ℃ or bigger fusing point, molecular weight is greater than about 1.5x10
6About 2.5 to about 7 MWD 230 ℃ of melt flow rate(MFR)s that have less than about 0.01dg/ minute, promptly can not be measured basically; But based on the 0.5wt.% of polymer composition weight or extract still less (can through polymer compsn contact with boiling xylene and by extracting) quantity; Greater than the meso five unit number of componentss of about 96mol%mmmm five unit groups and per 10,000 carbon atoms less than about 50 three-dimensional defects count.In related embodiment; Polymer compsn comprises the propylene monomer greater than about 90 moles of %, and it has all following performances: greater than the limiting viscosity of about 10dl/g, greater than the melting heat of about 108J/g; 165 ℃ or bigger fusing point, molecular weight is greater than about 1.5x10
6About 2.5 to about 7 MWD 230 ℃ of melt flow rate(MFR)s that have less than about 0.01dg/ minute, promptly can not be measured basically; But based on the 0.5wt.% of polymer composition weight or extract still less (can through polymer compsn contact with boiling xylene and by extracting) quantity; Greater than the meso five unit number of componentss of about 96mol%mmmm five unit groups and per 10,000 carbon atoms less than about 50 three-dimensional defects count.Have been found that; This polymer compsn can be used to prepare microporous membrane, especially comprises Vilaterm and polyacrylic microporous membrane, though when the melt polypropylene flow rate be 0.2dg/min or more hour; Even or 0.1dg/min or littler, even or 0.01dg/min or littler.
The numbering of family can for example find in Hawley ' sCondensed Chemical Dictionary 852 (John Wiley & Sons, 13th ed.1997) in the periodic table of elements that this paper uses.
The term " polymer " that this paper uses " be meant the product of polyreaction, and comprise homopolymer, multipolymer, terpolymer or the like.
Unless otherwise mentioned, the term " multipolymer " of this paper use is meant the polymkeric substance that is formed by at least two kinds of different monomers polymerizations.For example, term " multipolymer " comprises that ethene and terminal olefin (terminal olefin) are for example through the example copolymerization product of propylene or 1-hexene only.Yet term " multipolymer " also comprises the for example copolymerization of the mixture of ethene, propylene, 1-hexene and 1-octene.
The term weight percentage (" wt.% ") (only if pointing out in addition) that this paper uses is meant the weight percent (based on the gross weight of the mixture that comprises component) of concrete component.For example, if mixture or blend comprise three pounds of compd As and one pound of compd B, compd A accounts for the 75wt.% of mixture so, and compd B accounts for 25wt.%.The performance of I.UHMWPP and polymer compsn
In one embodiment, polymer compsn comprises the propylene monomer greater than about 90 moles of %, for example greater than the propylene monomer of about 95 moles of % with up to the propylene monomer greater than about 99.99 moles of %.
In one form, the present invention relates to have the polymer compsn of one or more following performance.Be appreciated that this performance can be the characteristic of UHMWPP in characteristic or the compsn of polymer compsn, especially except that UHMWPP, polymer compsn also comprises under the situation of other species.
In one embodiment, the limiting viscosity of polymer compsn is greater than about 11dl/g, perhaps greater than about 12dl/g.The standard method of listing in below the limiting viscosity of polymer compsn (IV) can be utilized is measured: " PREPARATIVE METHODS OFPOLYMER CHEMISTRY "; W.R.Sorenson and T.W.Campbell book; The 43-50 page or leaf, second edition, Interscience Publishers publishes; 1968, or measure according to the ASTMD1601-78 method.
In one embodiment, the melting heat of polymer compsn is greater than about 108J/g, or greater than about 110J/g, or greater than about 112J/g.The melting heat of polymer compsn can utilize ordinary method to measure, for example dsc (DSC).
In one embodiment, polymer compsn has HMP (Tm), for example greater than about 166 ℃, or even greater than about 168 ℃, or even greater than about 170 ℃.Can utilize ordinary method to measure fusing point, for example dsc (DSC).Differential scanning calorimetric (DSC) data can obtain as follows: use PerkinElmer Instrument, model Pyris1 DSC.The sample of great about 5.5-6.5mg is sealed in the aluminium sample pot.Through at first sample being heated to 200 ℃ (being called first melt (n.d. record)) with 150 ℃/minute speed, record DSC data.Sample was kept 10 minutes at 200 ℃, then use cooling-heating cycle.With 10 ℃/minute speed sample is cooled to 25 ℃ (being called crystallization) from 200 ℃ then, then kept 10 minutes, be heated to 200 ℃ (are called two molten) with 10 ℃/minute speed at 25 ℃.Thermal phenomenon during record crystallization and two is melted.Fusing point (T
m) be the peak temperature of two molten curves, Tc (T
c) be the peak temperature of peak crystallization.
In one embodiment, and be generally used for preparing microporous membrane and compare with the Vestolen PP 7052 of film (especially also comprising poly microporous membrane), polymer compsn has than higher molecular weight.For example, polymer compsn can have greater than about 1.75x10
6Molecular weight, or even greater than about 2x10
6, or even greater than about 2.25x10
6, for example greater than about 2.5x10
6The MWD of polymer compsn can be for example within from about 2.5 to about 7 narrow relatively scope." molecular weight " that this paper uses is meant weight-average molecular weight (Mw).Mw can use the gel permeation chromatography that is described below.MWD (MWD) is meant that Mw is divided by number-average molecular weight (Mn).(for more information, referring to United States Patent(USP) No. 4,540,753, people and people such as reference of wherein quoting and Verstrate such as Cozewith, 21 Macromolecules 3360 (1998))." Mz " value is high molecular value; Method according to A.R.Cooper is discussed in Concise Encyclopedia of Polymer Science and Engineering 638-39 is calculated (J.I.Kroschwitz, ed.John Wiley & Sons 1990).Molecular weight distribution mw/mn (" MWD ") is the ratio of weight-average molecular weight (" Mw " that utilize GPC (" GPC " of hereinafter) to measure) and number-average molecular weight (GPC that utilization is described below measures " Mn ").
Molecular weight (weight-average molecular weight Mw and number-average molecular weight Mn) can use the high temperature size exclusion chromatography that is equipped with differential refractometer detector (DRI), and (GPC PL 220 PolymerLaboratories) measures.Use three PLgel mixing-B posts (PolymerLaboratories).Nominal flow rate is 1.0cm
3/ min, specified injection volume are 300 μ L.Various transfer limess, post and DR I detector are included in the baking oven (160 ℃ of maintenances).This technology is discussed in following: " Macromolecules, Vol.34, No.19, pp.6812-6820 (2001) " is attached to it among this paper as a reference.
The solvent of gpc analysis is 1,2 of a filtering Aldrich reagent grade, 4-trichlorobenzene (TCB), and it comprises～butylated hydroxytoluene (BHT) of 1000ppm.With online de-gassing vessel TCB is outgased, then get into SEC.Be prepared as follows polymers soln: in Glass Containers, put into dry polymer, add the above-mentioned TCB solvent of required quantity, then mixture was heated about 2 hours at 160 ℃, stir continuously simultaneously.The concentration of UHMWPP solution is 0.25mg/ml.
Use the MWD polystyrene standard sample of a series of narrow distributions to proofread and correct the separation efficiency of post group, it can reflect the exclusion limit of the expection MW scope and the post group of sample.18 independently polystyrene standard sample (Mp～580 are to 10,000,000) be used to make typical curve.The polystyrene standard sample is that (Amherst MA) obtains from Polymer Laboratories.Through the RV at the crest place in the DRI signal that writes down each PS standard, and, make typical curve (logMp is to RV) with this data set and second order polynomial match.Use WaveMetrics, Inc.IGOR Pro analytic sample.Following Mark-Houwink constant is respectively applied for and calculates PP basis Mw and PS basis MW.
| k(dL/g) | α | |
| PS | 1.75x10-4 | 0.67 |
| PP | 2.288x10-4 | 0.705 |
In one embodiment, polymer compsn the time has 0.2dg/min or littler melt flow rate(MFR) (MFR) at 230 ℃ with the 2.16kg load, perhaps less than about 0.1dg/min, or even less than about 0.01dg/min.0.01dg/min value be quite low, MFR can not measure basically.Melt flow rate(MFR) can be measured according to ordinary method, for example ASTM D 1238-95 condition L.
In one embodiment, polymer compsn has shown per 10,000 carbon atoms less than about 50 three-dimensional defective, or less than about 40, or less than about 30, or even per 10,000 carbon atoms less than about 20.For example, per 10,000 carbon atoms, polymer compsn can have than about 10 still less three-dimensional defectives, or than about 5 still less.Three-dimensional defective can be measured with ordinary method, and is for example following
13C NMR method:
13C NMR data are 125 ℃, acquisition on Varian VXR 400NMR spectrometer (100MHz).Use 90 ℃ of pulses, 3.0 seconds detection time and 20 seconds pulse delay.Spectrum is that broadband is decoupled, and do not obtain through gated decoupling.For polyacrylic methyl resonances (it normally is used for unique homopolymer resonances of quantitative purpose), similar relaxation time and nuclear-magnetism Euclidean effect are expected.The typical number of instantaneous collection is 2500.Be dissolved in tetrachloroethane-d with sample
2In, concentration is 15% weight.With respect to marking in the TMS, write down all spectral frequencies.Under the situation of HPP homopolymer polypropylene, with respect to the methyl resonances of 21.81ppm record mmmm, it is near target reported literature value 21.855ppm in the TMS.Employed five unit group ownership are confirmed preferably.
In one embodiment, polymer compsn has the meso five unit number of componentss greater than about 96mol%mmmm five unit groups.
In one embodiment; Weight based on polymer compsn; But polymer compsn comprise 0.5wt.% or extract still less (through polymer compsn contact with boiling xylene and by extracting) quantity, or 0.2wt.% or still less, or even 0.1wt.% or still less.According to following method, the solubleness when being utilized in 135 ℃, in YLENE, but the quantity of mensuration extract (for example relative lower molecular weight and/or amorphous substance, for example amorphous polypropylene).2 gram samples (pellet form of pellet or grinding) are claimed in the 300ml erlenmeyer flask.200ml YLENE is poured in the erlenmeyer flask that has stirring rod, flask is fixed in the heating oil bath.Begin to heat oil bath, flask in oil bath, about 15 minutes of 135 ℃ of placements, is made polymer melt.When fusion, end heating, but in whole process of cooling, continue to stir.The dissolved polymers naturally cooling is spent the night.With Teflon filter paper filtering deposition, then 90 ℃ of vacuum-dryings.Calculate the weight percent that at room temperature whole polymer samples (" A ") deduct throw out (" B "), the quantity of mensuration xylene soluble [meltage=((A-B)/A) x100].II. prepare UHMWPP and polymer compsn
Polymer compsn for example UHMWPP can prepare according to following method: use the common process condition of preparation alkene adoption compound, and for example solution polymerization, slurry polymerization or vapour phase polymerization technology, liquid polymerization is optimization technique.Similarly, can use suitable polyolefin catalyst system to prepare olefin polymer, comprise conventional system for example Ziegler-Natta catalyst or metalloscene catalyst.The example of suitable catalyst and processing condition is disclosed among the European patent No.0350170B2, and this paper combines it as a reference, does not only add hydrogen.
Ziegler-natta catalyst is a conventional catalyst; And in for example following, discuss: Concise Encyclopedia of Polymer Science andEngineering; 1087-1107 (Jacqueline I.Kroschwitz ed.; 1990) and F.A.Cotton & G.Wilkinson, Advanced Inorganic Chemistry, 1280-1282 (4th ed.1980).Typical solid magnesium carrier catalyst system and its preparation are listed in U.S. patent Nos.4,990,479 and 5,159,021 and WO 00/44795 in.For example, Ziegler-Natta catalyst typically is made up of the organometallic compound of the 11-13 family metal of the transistion metal compound of the 4-7 family of the periodic table of elements and the periodic table of elements.Known example comprises TiCl
3-Et
2AlCl, AlR
3-TiCl
4, wherein Et is an ethyl, R representes alkyl.These catalyzer comprise the mixture of the halogenide of transition metal and the organic derivative of nontransition metal (especially alkylaluminium cpd), and transition metal is titanium, chromium, vanadium and zirconium particularly.Common and the electron donor combination of Ziegler-natta catalyst.Electron donor can use in two processes that the Ziegler-Natta catalyst system forms.At first, internal electron donor can use in the formation reaction of solid catalyst.The example of internal electron donor comprises: amine, acid amides, ether, ester, aromatic ester, ketone, nitrile, phosphine, stibine, arsine, phosphoramide, thioether, thioesters, aldehyde, alcoholate and organic acid salt.Second purposes of electron donor in catalyst system is as the stereo-regulation agent in external electron donor and the polyreaction.Under two kinds of situation, can use same compound, but generally they are different.Silicoorganic compound (comprising conventional silicoorganic compound) can be used as electron donor.Conventional electron donor (organosilicon (or silane ") compound) example is disclosed in United States Patent(USP) Nos. 4,218, in 339,4,395,360,4,328,122,4,473,660,6,133,385 and 6,127,303.The explanation of two types electron donor is provided in United States Patent(USP) No. 4,535, in 068.
In one embodiment, be prepared as follows polymer compsn: in liquid phase, (comprise TiCl with Ziegler-Natta catalyst
4/ MgCl), comprise the internal electron donor of phthalic acid di-n-butyl ester, comprise the electron donor of dicyclopentyl dimethoxyl silane (DCPMS), add a little hydrogen or do not add hydrogen.This method comprises the following steps: that (1) makes Ziegler-Natta catalyst contact in advance with triethyl aluminum (TEAl) with the DCPMS donor; (2) polymerizing catalyst and propylene in advance; (3) polymer compsn is reclaimed in further polymerization pre-polymerized catalyst and (4) in one or more reactor drums, and it comprises the propylene monomer greater than about 90 moles of %; This polymer compsn has the combination of following performance: greater than the limiting viscosity of about 10dl/g; Greater than the melting heat of about 108J/g, 165 ℃ or bigger fusing point are greater than about 1.5x10
6Molecular weight; About 2.5 to about 7 MWD 230 ℃ of melt flow rate(MFR)s less than about 0.01dg/ minute, promptly can not be measured basically; But based on the 0.5wt.% of polymer composition weight or extract still less (through polymer compsn contact with boiling xylene and by extracting) quantity; Greater than the about meso five unit number of componentss of 96mol%mmmm five unit groups, per 10,000 carbon atoms are less than about 50 three-dimensional defective.In one embodiment, polymer compsn comprises UHMWPP of the present invention.In another embodiment, polymer compsn is made up of UHMWPP basically.In another embodiment, polymer compsn is made up of UHMWPP.(be used to prepare microporous membrane especially can be used for preparing polymer compsn (UHMWPP for example of the present invention); For example comprise poly those microporous membranes) an embodiment in; Can use following condition: in polymerization process, do not add hydrogen; Polymerizing catalyst is TOHO THC-135, and electron donor is a dicyclopentyl dimethoxyl silane; The residue processing condition are disclosed according to European patent No.0350170B2.
Except preferred above-mentioned DCPMS donor, other acceptable donor can include but not limited to: two (tertiary butyl) dimethoxy silane, cyclopentyl dimethoxy (tert.-butoxy) silane, (tertiary butyl) (tert.-butoxy) dimethoxy silane.III. use polymer compsn to prepare goods
In one embodiment, polymer compsn can combine with second polymer compsn, for example mixes or blend preparation goods, for example microporous membrane.For example, polymer compsn can mix or blend with Vilaterm (for example polyvinyl resin form).(a) starting raw material
When polymer compsn combined with second polymer compsn, the relative quantity of first and second polymer compsns was not critical.For example, in mixture or blend, based on the weight of first and second polymer compsns that merge, the percentage of the polymer compsn and second polymer compsn can for example be about 5 to about 95wt.%, or about 20 to about 80wt.%.Second polymer compsn can comprise polyolefine, for example high-density (HD) Vilaterm and/or High molecular weight polyethylene, for example, ultra-high molecular weight (UHMW) Vilaterm, or second polyacrylic one or more.In this mixture or blend, polymer compsn and HD Vilaterm and the HMW for example poly weight ratio of UHMW can be 5-95: 0-95: 0-95 for example, perhaps, and 20-80: 20-70: 0-20.The second polyacrylic amount (when existing) is not crucial, and in following scope: based on the gross weight of first and second polymer compsns, for example approximately 10wt.% to about 30wt.%.
In one embodiment, second polymer compsn comprises at least a in first Vilaterm, second Vilaterm or second Vestolen PP 7052.First Vilaterm can be for example to have 5X10
5Or the more Vilaterm of macromolecule, for example 1x10
6To 1.5x10
7Molecular weight, UHMWPE for example.This Vilaterm can be Alathon or the ethylene/alpha-olefin copolymer that comprises a small amount of nonvinylic terminal olefin.Nonvinylic terminal olefin can be a propylene, butene-1, hexene-1, amylene-1,4-methylpentene-1, octene, vinyl acetate, TEB 3K, vinylbenzene, or its mixture.
Second Vilaterm can be to have the Mw molecular weight at about 1x10
4To about 5x10
5Vilaterm in the scope.Second Vilaterm can be a high density polyethylene(HDPE) for example, medium-density polyethylene, side chain new LDPE (film grade) and straight-chain low density polyethylene.Second Vilaterm can be Alathon or the ethylene/alpha-olefin copolymer that comprises a small amount of nonvinylic terminal olefin.Nonvinylic terminal olefin can be a propylene, butene-1, hexene-1, amylene-1,4-methylpentene-1, octene, vinyl acetate, TEB 3K, vinylbenzene, or its mixture.Though be not critical, second Vilaterm can have the terminal unsaturation phenomenon, for example per 10,000 carbon atoms in the Vilaterm have two or more terminal unsaturations.Can utilize for example conventional method of infrared spectrophotometry to measure terminal unsaturation.
Second Vestolen PP 7052 can be to have less than about 7.5x10
5The Vestolen PP 7052 of weight-average molecular weight, about 1x10 for example
4To about 7.5x10
5, or about 4.5x10
5To about 7.5x10
5, or about 5x10
5To about 7x10
5Though be not crucial, second Vestolen PP 7052 can have for example about 5 to about 100 MWD, for example about 5 to about 50 and approximately 80J/g or higher melting heat, and for example about 80 to about 120J/g.Second Vestolen PP 7052 can be one or more in for example following: (i) alfon, or the (ii) multipolymer of propylene and one or more following material: terminal olefin, terminal olefin are ethene for example; Butene-1, amylene-1, hexene-1; 4-methylpentene-1, octene-1, vinyl acetate; TEB 3K and vinylbenzene or the like; And diene, diene is a divinyl for example, 1, and the 5-hexadiene, 1, the 7-octadiene, 1,9-decadiene or the like, based on 100 moles of % of whole multipolymer, its quantity is less than 10 moles of %.Multipolymer can be random or segmented copolymer.Randomly, second Vestolen PP 7052 has one or more following performance: (i) Vestolen PP 7052 is isotactic; (ii) Vestolen PP 7052 has at least approximately melting heat of 90J/g, and for example about 90 to about 120J/g; (iii) Vestolen PP 7052 has about at least 160 ℃ melting peak (two is molten); (iv) when about 230 ℃ temperature and 25 seconds
-1Strain rate under when measuring, Vestolen PP 7052 has about at least 15 Trouton's ratio; And/or (v) 230 ℃ temperature and 25 seconds
-1Strain rate under, it is about at least 50 that Vestolen PP 7052 has, the extensional viscosity of 000Pa second.
In one embodiment; The present invention relates to compsn, it comprises the polymer compsn of about 1wt.% to about 95wt.%, 0 to about 95wt.% first Vilaterm; 0 to about 95wt.% second Vilaterm and about 0 to about 50wt.% second Vestolen PP 7052.In related embodiment, the present invention relates to compsn, it comprises UHMWPP of the present invention, and quantity is in the scope of the extremely about 80wt.% of about 10wt.%, or about 20wt.% is to about 40wt.%; UHMWPE, its quantity is in about scope of 0 to about 20wt.%, or about 5wt.% is to about 15wt.%; HDPE, in about 10 to about 80wt.% the scope of its quantity, or about 20wt.% is to about 70wt.%; With second Vestolen PP 7052, the about 0wt.% of its quantity is to the scope of about 50wt.%, or about 10wt.% is to about 30wt.%.
The separate polymer compsn or with second polymkeric substance or polymer compsn combination of polymers compsn, can choose the stablizer that further comprises significant quantity wantonly, form to prevent color.Those conventional stablizers known in the art are suitable stabilizers.This stablizer comprises phosphorus oxygen acid, acid organophosphate, acid organophosphate, acid phosphate metal salt, acid phosphatase metal-salt and its mixture.
The separate polymer compsn or with second polymkeric substance or polymer compsn combination of polymers compsn, can choose the coloured pigment that further comprises significant quantity wantonly.Conventional coloured pigment is suitable, comprises carbon black, phthalocyanine blue, phthalocyanine green, anthraquinone dye; Scarlet 2b Lake, azo cpd, acid azo pigment, quinacridone, chromium phthalocyanine (chromophthalocyanine) pyrroles; Halogenated phthalocyanines, quinoline, heterocyclic dye, purple cyclic ketones (perinone) dyestuff, amerantrone dyestuff; Thiaxanthene (thiozanthene) dyestuff, pyrazolone (parazolone) dyestuff, polymethine pigment and its mixture.
The separate polymer compsn or with second polymkeric substance or polymer compsn combination of polymers compsn, can choose wantonly and further comprise additive or compound, so that the compsn with concrete preferred feature to be provided.Conventional additives and compound are suitable, and their use is within the art technology scope.This example comprises the UV stablizer, inhibitor, photostabilizer, fire retardant, static inhibitor, sterilant, viscosity breaking agent, impact modifier, softening agent, filler, toughener, lubricant, releasing agent, pore forming material, nucleator or the like.(b) by the structure of the microporous membrane of UHMWPP or polymer compsn preparation
In one embodiment, microporous membrane is a unitary film.Preparing method's selection is not critical, can use any method that can be formed microporous membrane by the polyolefine starting raw material, comprises ordinary method; For example at United States Patent(USP) No. 5; 051,183 with United States Patent(USP) No. 6,096; Those methods described in 213 are attached to its integral body among this paper as a reference.In another embodiment, microporous membrane is a multilayer film, promptly has double-deck at least film.For the sake of brevity, can describe the preparation of microporous polyolefin film substantially, but, one skilled in the art will recognize that the film for preparing one deck or at least four layers film can use constructed according to double-deck and trilamellar membrane.
In one embodiment, three layers of microporous membrane comprises first and the 3rd microporous layers (constituting the skin of microporous polyolefin film) and second layer of (optional with its plane contact) between first and the 3rd layer.In one embodiment, first is prepared by first polyolefin solution with the 3rd layer, and second layer (or internal layer) prepared by second polyolefin solution.In another embodiment, first is prepared by second polyolefin solution with the 3rd layer, and second layer prepared by first polyolefin solution.
In one embodiment, the one deck at least in the layer of microporous membrane or multilayer microporous film shows with wide relatively pore size distribution to be the hybrid structure of characteristic.This microporous membrane can be according to the preparation of WO 2007/117042 disclosed method, and this paper is introduced into as a reference.When drawing, utilize the microporous membrane of method for preparing to have wide relatively pore size distribution with the form of differential pore volume curve.Pore size distribution can for example utilize ordinary method to measure, and for example mercury porosimetry is represented data with differential pore volume curve form.
When mercury porosimetry is used for measuring the distribution of hole size and pore volume of film, measure aperture, pore volume and the specific surface area of film usually.Measurement can be used for measuring the differential pore volume that is expressed as
; Wherein Vp is a pore volume; R is a pore radius, is assumed to cylindrical hole.When being that y axle, aperture are x axle when drawing with the differential pore volume, the differential pore volume is commonly referred to " pore size distribution ".For the film that shows hybrid structure, differential pore volume about at least 25% or about at least 30% or about at least 40% or about at least 50% or about at least 60% relevant with about 100 nanometers big or small (diameter) or bigger hole.In other words; For
curve to the aperture, below the curve from the area of about 100 nanometers to about 1,000 nano aperture be below the curve from about 10 nanometers to about 1; The hole size of 000 nanometer (or diameter; Be assumed to cylindrical hole) the total area about at least 25%, or about at least 30%, or about at least 40%; Or about at least 50%, or about at least 60%.In one embodiment; Below the curve aperture from about 100 nanometers to about 1; The area of 000 nanometer the total area about 25% to about 60% scope, or about 30% to about 55%, or about 35% to about 50%; The total area be below the curve aperture from the area of about 10 nanometers to about 1,000 nanometer.
A kind of pressure mercury void determination method that can be used for measuring microporous membrane structure is used PoreSizer 9320, and (Micromeritics Company, Ltd.), pressure range is from 3.6kPa to 207MPa, pond volume 15cm
3In order to measure, can use the contact angle of 141.3 mercury and the mercury surface tension of 484 dyne/cm.Thus obtained parameter comprises peak, mean pore size and the porosity in pore volume, surface-area ratio, aperture.Reference discloses this method, comprises Raymond P.Mayer and Robert A.Stowe, J.Phys.Chem.70,12 (1966); L.C.Drake, Ind.Eng.Chem., 41,780 (1949); H.L.Ritter and L.C.Drake, Ind.Eng.Chem.Anal., 17,782 (1945) and E.W.Washburn, Proc.Nat.Acad.Sci., 7,115 (1921).
Film can be used as battery separator.Film especially can be used as the dividing plate of lithium and lithium ion battery, for example lithium ion galvanic cell and lithium ion secondary accumulator battery.The representational battery and the battery separator that use in the present invention are described among the WO2007/117042.(c) use UHMWPP or polymer compsn to prepare the method for microporous membrane
In one embodiment, the present invention relates to prepare the method for microporous membrane, comprise the following steps: that (1) is with thinner or solvent (can be called film and form solvent) and first polyolefin compositions mixing that comprises UHMWPP or polymer compsn; To prepare first polyolefin solution, randomly (use when the needs multilayer film) (2), and second polyolefin compositions and second film are formed solvent; To prepare second polyolefin solution, (3) make first and second polyolefin solutions extrude (simultaneously preferred) through at least one die head, form extrudate; (4) randomly, with the extrudate cooling, form the refrigerative extrudate; Example gel shape sheet material, (5) are removed at least a portion film-formation solvent from refrigerative extrudate or extrudate, form to remove the sheet material that desolvates; (6) from sheet material, remove any volatile matter; For example, through drying, form microporous membrane.If necessary, the stretching step (7) that can between step (4) and (5), choose wantonly and optional hot solvent treatment step (8) or the like.If necessary, step (6) afterwards, the step (9) of the stretched multi-layer microporous membrane that can choose wantonly, optional heat treatment step (10), optional cross-linking step (use the ionization radiation) (11) and hydrophilic treatment step (12) of choosing wantonly or the like.The order of optional step is not critical.First and second solution are called " polyolefine " solution, because they comprise polyolefine.First and second solution that further comprise non-polyolefinic other material are within the scope of the invention.(1) preparation first polyolefin solution
First polyolefin compositions comprises UHMWPP or polymer compsn and other polyolefine (if necessary) (usually with aforesaid resin form); With itself and suitable diluent (for example; Film forms solvent) mix; For example through doing the method for mixed or melt-mixing, to prepare first polyolefin solution.Randomly, first polyolefin solution can comprise various additives for example one or more inhibitor, thin silicate powder (pore-creating material) or the like, and condition is to use these with the concentration range that does not significantly reduce the required performance of multi-layer microporous polyolefin film.In one embodiment, first polyolefin compositions comprises one or more in UHMWPP or polymer compsn and optional first Vilaterm, second Vilaterm and second Vestolen PP 7052.Select the polyolefin resin of first polyolefin compositions, to prepare needed microporous layers, for example one or more laminboard layers of microporous membrane or one or more top layer.
First thinner or solvent (for example process solvent or film form solvent) can be at room temperature to be the solvent of liquid.Do not it is believed that by any theory or model constraint using liquid solvent to form first polyolefin solution can be to carry out the stretching of gel sheet material than higher extensibility although do not hope.In one embodiment, first film forms solvent and can be at least one of following: aliphatics, alicyclic or aromatic hydrocarbon, nonane for example, decane, naphthane, p-Xylol, undecane, dodecyl, whiteruss or the like; Has MO distillment with the similar boiling point of boiling point of above-mentioned hydrocarbon; With the phthalic ester liquid under the room temperature, for example Witcizer 300, DOP or the like.Obtain to have in the embodiment of multilayer gel shape sheet material of stabilising liq solvent in hope, can use for example whiteruss of nonvolatile liquid solvent, use separately or use with other solvent combinations.Randomly, can use under the melt blending state can be miscible with Vilaterm but at room temperature be the solid solvent, can make up use separately or with other liquid solvent.This solid solvent can comprise for example stearyl alcohol, ceryl alcohol, paraffin or the like.Though be not critical, when solution does not comprise liquid solvent, evenly stretch the gel sheet material or the film that obtains maybe be more difficult.
The viscosity of liquid solvent is not key parameter.For example, at 25 ℃, the viscosity of liquid solvent can be at about 30cSt to the about scope of 500cSt, or approximately 30cSt to about 200cSt.Though it is not a key parameter, the viscosity when at 25 ℃ is during less than about 30cSt, and it is difficult to prevent that polyolefin solution from bubbling, and possibly cause the blend difficulty.On the other hand, when viscosity during, be difficult to from multi-layer microporous polyolefin film, remove liquid solvent greater than about 500cSt.
In one embodiment, resin that will be used for preparing first polyolefin compositions or the like carries out dry blending at for example twin screw extruder or mixing tank, or melt blending.For example, forcing machine (or mixing tank or mixing tank-forcing machine) commonly used for example twin screw extruder can be used for hybrid resin or the like, forms first polyolefin compositions.In the course of processing, the film formation solvent of can in officely how naming a person for a particular job easily joins in the polyolefin compositions and (perhaps joins the resin that is used for preparing polyolefin compositions).For example; Form in the embodiment of solvent melt blending at first polyolefin compositions and first film; Can solvent be joined in the polyolefin compositions (or its component) at any following time point: (i) before the beginning melt blending; (ii) during the melt blending of first polyolefin compositions, or (iii) after the melt blending, for example; At second forcing machine or be arranged in the extrusion molding zone in downstream, the employed extrusion molding of melt blending polyolefin compositions zone, provide first film to form solvent for polyolefin compositions melt blending or the partial melting blend.
When using melt blending, the melt blending temperature is not critical.For example, the melt blending temperature of first polyolefin solution can be at the fusing point Tm than first polyvinyl resin
1High about 10 ℃ to than Tm
1High about 120 ℃ scope.For for simplicity, this scope can be expressed as Tm
1+ 10 ℃ to Tm
1+ 120 ℃.Therein first polyvinyl resin have about 130 ℃ to the embodiment of about 140 ℃ of fusing points, the melt blending temperature can about 140 ℃ to about 250 ℃ of scopes, or about 170 ℃ to about 240 ℃.
When forcing machine when for example twin screw extruder is used for melt blending, the screw rod parameter is not critical.For example, the characteristics of screw rod are: spiro rod length L in the twin screw extruder and the ratio L/D of screw diameter D can be in about 20 to about 100 scopes, or about 35 to about 70.Though this parameter is not critical; But when L/D less than about 20 the time; Melt blending maybe be more difficult; And when L/D 100 the time, needs forcing machine speed faster greater than about, to prevent the overstand (overstand can cause undesirable molecular weight reduce) of polyolefin solution in twin screw extruder.Though it is not a key parameter, the machine barrel of twin screw extruder (or hole) for example can have the approximately interior internal diameter of the extremely about 100mm scope of 40mm.
The amount of first polyolefin compositions in first polyolefin solution is not critical.In one embodiment, based on the weight of polyolefin solution, the amount of first polyolefin compositions in first polyolefin solution can be in the scope of about 1wt.% to about 75wt.%, for example from the extremely about 70wt.% of about 20wt.%.Though the amount of first polyolefin compositions in first polyolefin solution is not critical,, be difficult to prepare multi-layer microporous polyolefin film with acceptable efficient when this quantity during less than about 1wt.%.In addition, when this quantity during less than 1wt.%, during extruding, die head exit be difficult to prevent swelling or in contract, make more to be difficult to form and carry multilayer gel shape sheet material (it is the precursor of formed film during the making processes).On the other hand, when the amount of the first polyolefin compositions solution during, possibly more be difficult to form multilayer gel shape sheet material greater than about 75wt.%.The preparation of (2) second polyolefin solutions
Can utilize with the same procedure for preparing first polyolefin solution institute method of use and prepare second polyolefin solution.For example, can be through second polyolefin compositions and second thinner or solvent melt blending be prepared second polyolefin solution.It can be to select from forming the solvent phase solvent together with first film that second film forms solvent.Solvent selects second film to form solvent although (usually) can be independent of the formation of first film; But second film form solvent can with first film form solvent phase with, and can use with first polyolefin solution in first film that uses form solvent phase with relative concentration.
Usually be independent of first polyolefin compositions and come second polyolefin compositions.Second polyolefin compositions comprises one or more in first Vilaterm, second Vilaterm, first Vestolen PP 7052 and second Vestolen PP 7052 usually.
Polyolefin compositions comprises in the second polyacrylic embodiment therein; The method for preparing second polyolefin solution is different from the method for preparing first polyolefin solution; Only be that mixing temperature is preferably in the scope of the second polyacrylic fusing point (Tm2) to Tm2+90 ℃; And polyolefin compositions content is the 1-50% quality, more preferably the 20-40% quality.When processing and preparing multilayer microporous film for example during trilamellar membrane; Film can comprise: first microporous layers that comprises the first layer material; Comprise the 3rd microporous layers of the first layer material and comprise second microporous layers of second layer material, second microporous layers is between first and the 3rd microporous layers.In one embodiment, the first layer material is prepared by first polyolefin solution, and second layer material is prepared by second polyolefin solution.In another embodiment, second layer material is prepared by first polyolefin solution, and the first layer material is prepared by second polyolefin solution.(3) extrude
In one embodiment, first polyolefin solution imports first die head from first forcing machine, and randomly, second polyolefin solution imports second die head from second forcing machine.If necessary, can and choose extruding sheet (that is, in-plane is bigger significantly than thickness direction) individual layer extrudate or multilayer extrudate second die head wantonly from first.Randomly, extrude first and second polyolefin solutions jointly from first and second die heads, the plane surface of formed first extrudate layer of first polyolefin solution contacts with the plane surface of formed second the extrudate layer of second polyolefin solution.The plane surface of extrudate can use second horizontal vector of first vector sum extrudate longitudinally of extrudate to define.
In another embodiment, use many die heads, each die head connects forcing machine, and forcing machine imports first or second polyolefin solution in the die head.For example, in one embodiment, first forcing machine that comprises first polyolefin solution is connected with the 3rd die head with first die head, and second forcing machine that comprises second polyolefin solution is connected with second die head.Under the situation of previous embodiments; Can be from first, second and the 3rd die head (for example simultaneously) extrude the layer extrudate that obtains jointly; Form three layers of extrudate, it comprise by first polyolefin solution that produce, that constitute top layer (for example T&B layer) first with the 3rd layer; With the middle part that constitutes extrudate or second layer in middle layer, its between two top layers and with two top layer plane contact, wherein second layer prepared by second polyolefin solution.
In another embodiment; Use identical die head; But polyolefin solution is opposite, and second forcing machine that promptly comprises second polyolefin solution is connected with the 3rd die head with first die head, and first forcing machine that comprises first polyolefin solution is connected with second die head.
In any previous embodiments, can use conventional die head extrusion equipment to carry out die head and extrude.For example, extrude and to utilize flat-die or inflation die head to carry out.In an embodiment of the co-extrusion that is used for multilayer gel shape sheet material, can use branch manifold to extrude, wherein first and second polyolefin solutions are imported in the manifold that separates of multilayer extrusion die, and carry out range upon range of at the die lip inlet.In another this embodiment, can use the piece material to extrude, wherein first and second polyolefin solutions at first are merged into laminar flow (in advance promptly), and laminar flow gets into die head then.Because branch manifold and the processing of piece material are known (for example, disclosed in JP06-122142 A, JP06-106599A) to the technician in processing of polyolefins film field, therefore, think that they are conventional, are not described in detail their operation.
It is not critical that die head is selected, and for example, can use flat or the inflation die head forms conventional multi-layer sheet.Die gap is not critical.For example, the flat-die of formation multi-layer sheet can have the die gap of about 0.1mm to about 5mm.Die head temperature and extruded velocity also are non-key parameters.For example, during extruding, can with die head be heated to about 140 ℃ to about 250 ℃ die head temperature scope.Extruded velocity can be in for example about 0.2m/ minute to about 15m/ minute scope.Can select the layer thickness of layer extrudate independently.For example, compare with the thickness in the middle layer of layer extrudate, the gel sheet material can have thick relatively upper layer (or " table " layer).
Although described according to the embodiment of one, two and three layer of extrudate and to have extruded processing, extrusion step is not limited.For example, use the extrusion molding of previous embodiments, many die heads and/or die head assembly can be used for preparation and have four or multiwalled multilayer extrudate more.In this layer extrudate, can use first polyolefin solution and/or second polyolefin solution to prepare each surface or middle layer.(4) formation of cooling extruded thing
Through for example cooling, extrudate can form the gel sheet material.Rate of cooling and cooling temperature are not critical especially.For example, can come cooling gel shape sheet material, till gelation temperature (or lower) approximately equal of the temperature (cooling temperature) of gel sheet material and gel sheet material with about at least 50 ℃/minute rate of cooling.In one embodiment, extrudate is cooled to about 25 ℃ or lower temperature, so that form the gel sheet material.Although do not hope to be it is believed that, the polyolefine microfacies tunicle formation solvent or the solvent of first and second polyolefin solutions are separated the cooling of layer extrudate by any theory or model constraint.It has been observed that slower rate of cooling (for example less than 50 ℃/minute) can provide and have the unitary multilayer gel shape of bigger psuedo-cell sheet material usually, produces more coarse higher structure.On the other hand, can produce fine and close structure cell unit than rate of cooling (for example 80 ℃/minute) faster.Though it is not a key parameter, when the rate of cooling of extrudate during, can in layer, produce the polyolefine percent crystallinity that increases less than 50 ℃/minute, this can more be difficult to process multilayer gel shape sheet material in stretching step subsequently.The selection of method of cooling is not critical.Can use for example conventional sheet cools method.In one embodiment, method of cooling comprises: for example cooling air, cold water or the like contact with heat-eliminating medium to make layer extrudate.Perhaps, can be through contact cooling extruded thing or the like with heat-eliminating medium refrigerative cylinder.(5) first and second films form removing of solvent
In one embodiment, at least a portion first and second films are formed solvent from the gel sheet material, remove (or displacement), remove the sheet material that desolvates so that form.Displacement (or " washing ") solvent can be used for removing (flushing or displacement) first and second films and forms solvent.Although do not hope by any theory or model constraint; It is believed that; Because can form the polyene hydrocarbon phase that separates the solvent phase in the gel sheet material that produces by first polyolefin solution and second polyolefin solution (i.e. first polyolefine and second polyolefine) from film; Film forms removing of solvent can provide porous-film, and this porous-film is made up of the protofibril that forms tiny three-dimensional net structure, and has the hole that can three peacekeepings connects brokenly.The selection of cleaning solvent is not critical, as long as it can dissolve or replace at least a portion first and/or second film formation solvent.Suitable cleaning solvent comprises for example one or more volatile solvent, stable hydrocarbon for example, pentane for example, hexane, heptane or the like; Chlorinated hydrocarbon, methylene dichloride for example, tetracol phenixin or the like; Ether, for example diethyl ether ， diox or the like; Ketone, for example methyl ethyl ketone or the like; The straight chain fluorohydrocarbon, HFC-143a for example, C
6F
14, C
7F
16Or the like; Ring-type hydrofluoric ether, for example C
5H
3F
7Or the like; Hydrogen fluoroether, for example C
4F
9OCH
3, C
4F
9OC
2H
5Or the like; With perfluoro ether, for example C
4F
9OCF
3, C
4F
9OC
2F
5Or the like.
It is not critical removing the method that striping forms solvent, can use any method that can remove remarkable quantity solvent, comprises that routine removes solvent method.For example, can spray detergent gel shape sheet material with cleaning solvent through sheet material being immersed in the cleaning solvent and/or with sheet material.The amount of employed cleaning solvent is not critical, depends on the selected method that striping forms solvent of removing usually.For example, based on the quality of gel sheet material, the amount of employed cleaning solvent can be in about 300 scopes to about 30,000 parts (by quality).Although it is not critical especially that the film of removing forms the amount of solvent, when first and second films of from the gel sheet material, removing most of quantity form solvent, can obtain the more film of high quality (more porous) usually.In one embodiment, from the gel sheet material, remove striping and form solvent (for example through washing), till amount that remaining film in the gel sheet material forms solvent is less than 1wt.% (based on the weight of gel sheet material).(6) with dried
In one embodiment, will form the dried of desolvating of removing that solvent obtains through removing at least a portion film, so that remove cleaning solvent.Can use any method that can remove cleaning solvent, comprise ordinary method, for example heat drying, dry up (fluidizing air) or the like.The temperature of gel sheet material during drying (being drying temperature) is not critical.For example, drying temperature can equal crystalline dispersion temperature T cd or lower than it.Tcd is the crystalline dispersion temperature T cd of first polyvinyl resin
1Crystalline dispersion temperature T cd with second polyvinyl resin (when using)
2In lower temperature.For example, drying temperature can be at least than low 5 ℃ of crystalline dispersion temperature T cd.The crystalline dispersion temperature of first and second polyvinyl resins can be according to ASTM D 4065, measure through the viscoelastic temperature profile of kinetics of measuring polyvinyl resin.In one embodiment, at least one in first or second polyvinyl resin has about 90 ℃ of crystalline dispersion temperature to about 100 ℃ of scopes.
Although drying is not critical, can carry out drying, up to the amount of residue cleaning solvent be approximately 5wt.% or still less till (being on dry matter basis) promptly based on the weight of dry microporous polyolefin film.In another embodiment, carry out drying, up to the residue cleaning solvent amount be approximately 3wt.% or still less till (being on dry matter basis).Can distinguish inadequate drying, because it causes undesirable reduction of the porosity of microporous membrane usually.If observe this phenomenon, should use the drying temperature of rising and/or increase time of drying.Remove cleaning solvent, for example, can cause the formation of microporous membrane through dry or other mode.(7) stretch
Before the step of removing striping formation solvent (promptly before step 5), can sheet material be stretched, so that obtain tensile gel sheet material.It is believed that, in the gel sheet material, exist first and second films to form solvent and can cause extensibility relatively uniformly.The gel sheet material is heated, particularly when stretching beginning or in relative draw stage (for example accomplishing before 50%) early, also helpful to the tensile homogeneity in stretching.
The selection of drawing process and the degree of extensibility are not crucial especially.For example, can use any method (comprising any optional heating) that can the gel sheet material be stretched to predetermined extent.In one embodiment, stretching can realize through one or more mode in expanding-stretching, cylinder-stretching or the inflation stretching (for example using air).Though it is not critical selecting, stretches and singly axially to carry out (promptly vertical or horizontal) or two axially carry out (vertical or horizontal both direction).In one embodiment, use biaxial stretching.Under the situation of biaxial stretching (being also referred to as diaxial orientation); Stretching can be a biaxial stretching, along axle center, a plane then along the sequence stretching of other direction (for example simultaneously; At first horizontal; Then vertical) or multistage stretching (for example, the coupling of biaxial stretching and sequence stretching simultaneously).In one embodiment, use biaxial stretching simultaneously.
Extensibility is not critical.In using an embodiment of uniaxial extension, the linear stretch rate can be for example about 2 times or more, or about 3 to about 30 times.In using an embodiment of biaxial stretching, the linear stretch rate on any in-plane can be for example about 3 times or more.In another embodiment, the area magnification that is caused by stretching is at least about 9 times, or about at least 16 times, or about at least 25 times.Though area magnification is not a key parameter, when causing about at least 9 times area magnification when stretching, multi-layer microporous polyolefin film has high relatively acupuncture disruptive strength.When area magnification during, more be difficult to operate stretching device greater than about 400 times.
The temperature of the gel sheet material during stretching (being draft temperature) is not critical.In one embodiment, the temperature of the gel sheet material during stretching can be approximately (Tm+10 a ℃) or lower, or chooses wantonly than the high but scope lower than Tm of Tcd, and wherein Tm is the first poly fusing point Tm
1Fusing point Tm with second Vilaterm (when using)
2In less one.Though this parameter is not critical, when draft temperature was roughly high than fusing point Tm+10 ℃, at least a in first or second Vilaterm possibly be molten state, and this can make the orientation of the molecular polyolefin chain in the gel sheet material during the stretching more difficult.And when draft temperature was roughly low than Tcd, at least a in first or second Vilaterm maybe be therefore softening not enough, and the multilayer gel shape sheet material that very difficult stretching is not ruptured or torn possibly cause obtaining needed extensibility.In one embodiment, the draft temperature scope is from about 90 ℃ to about 140 ℃, or from about 100 ℃ to about 130 ℃.
Although do not hope to be it is believed that by any theory or model constraint this stretching can cause division between polyethylene sheets, make that Vilaterm is thinner mutually and form a large amount of fibrils.Fibril forms three-dimensional net structure (three-dimensional irregular connected network structure).Thereby when using stretching, stretching to make the microporous membrane of the high relatively physical strength of preparation easier usually, has big relatively aperture simultaneously.Think that this multilayer microporous film is especially suitable for use as battery separator.
Randomly, stretching can be in the presence of thermograde, carry out at thickness direction (that is, direction roughly the plane surface with microporous polyolefin film is vertical).The microporous polyolefin film that can prepare in this case, physical strength easily with raising.The detailed content of this method is described in the Japanese Patent 3347854.(8) hot solvent treatment step
Though do not require, can between step (4) and (5), handle multilayer gel shape sheet material with hot solvent.When using, it is believed that hot solvent is handled can provide fibril with thick relatively leaf texture spline structure (those that are for example formed by stretched multi-layer gel sheet material).Think that this structure can make the difficulty of preparation multilayer microporous film (have big hole, the hole has high relatively intensity and perviousness) littler.Term " leaf texture appearance " is meant that the fibril in the network structure has thick trunk and from extended fibril wherein.The detailed content of this method is described among the WO2000/20493.(9) stretching of multilayer microporous film (" dry method tension ")
In one embodiment, the dry microporous membrane of step (6) can singly axially stretch at least.The drawing process of selecting is not critical, can use conventional drawing process, for example uses expanding method or the like.Although it is not critical, can during stretching, film be heated.Although it is not critical selecting, stretching can be single shaft or biaxial stretch-formed.When using biaxial stretching, stretching can be carried out on axially at two simultaneously, perhaps, and can the multi-layer microporous polyolefin film of sequence stretching, for example, at first longitudinal stretching, cross directional stretch then.In one embodiment, use biaxial stretching simultaneously.When sheet material is stretched (like what describe in the step (7)), in step (9) stretching of dry microporous membrane can be called dry method tension, again stretch or dry method directed.
The temperature of the dry microporous membrane during stretching (" dry draft temperature ") is not critical.In one embodiment, the dry method tension temperature is approximately equal to fusing point Tm or lower, for example in the scope of the extremely about fusing point Tm of about crystalline dispersion temperature T cd.When the dry method tension temperature is higher than Tm, more be difficult to prepare and have than higher crushing resistance, the relatively even microporous membrane of breathable characteristics, particularly when the multi-layer microporous polyolefin film of cross directional stretch drying transversely.When draft temperature is lower than Tcd, more be difficult to fully soften first and second polyolefine, this can cause tearing during stretching, and lacks evenly stretching.In one embodiment, the dry method tension TR is from about 90 ℃ to about 135 ℃, or from about 95 ℃ to about 130 ℃.
When using dry method tension, extensibility is not critical.For example, on the direction of at least one plane (for example horizontal), the extensibility of multilayer microporous film can about 1.1 times to about 1.8 times scope.Thus, under the situation of uniaxial extension, in axially (i.e. " vertically ") or transversely, extensibility can be in about 1.1 times of about 1.8 times scopes extremely, and this depends on that film is longitudinal stretching or cross directional stretch.Uniaxial extension can also be realized along the axle center, plane between the vertical and horizontal.
In one embodiment, use biaxial stretching (promptly stretching) along two planar axes, about 1.1 times to about 1.8 times along the extensibility of two tensile axis, for example, along the vertical and horizontal both direction.The longitudinal stretching rate need be not identical with the cross directional stretch rate.In other words, in biaxial stretching, can select extensibility independently.In one embodiment, the dry method tension rate is identical on two draw directions.If necessary; Can film be stretched to the extensibility greater than 1.8 times, particularly when during the following process when (for example thermal treatment), film loose on draw direction (or contraction); The size compared of the film when beginning with dry orientation step obtains about 1.1 to about 1.8 times final extensibility.(10) thermal treatment
In one embodiment, in step (6) afterwards, can the exsiccant microporous membrane be heat-treated.It is believed that thermal treatment can make the polyolefin crystal in the exsiccant multilayer microporous film stable, forms even platelet.In one embodiment, thermal treatment comprises heat setting type and/or annealing.When using heat setting type, can use ordinary method to carry out, for example expanding method and/or cylinder method.Though be not critical, the temperature of exsiccant microporous membrane during the heat setting type (i.e. " heat setting temperature ") can be in the scope from Tcd to about Tm.In one embodiment, the scope of heat setting temperature in dry method tension temperature ± 5 of multi-layer microporous polyolefin film ℃, or the scope of dry method tension temperature ± 3 of multi-layer microporous polyolefin film ℃.
Annealing is different from heat setting type, because the thermal treatment of its to be no-load be applied to multi-layer microporous polyolefin film.The selection of method for annealing is not critical, can carry out through using the heating chamber or the air flotation type heating chamber that for example have rotary conveyor.Perhaps, annealing can be carried out after with tentering cloth clamp relaxation heat setting.The temperature of the microporous polyolefin film during the annealing (being annealing temperature) is not critical.In one embodiment, annealing region is about fusing point Tm or lower, or in about 60 ℃ of scopes to (Tm-10 ℃).It is believed that it is littler than the difficulty of the microporous membrane of higher permeability and intensity that annealing can make preparation have.(11) crosslinked
In one embodiment, can be in step (6) afterwards with multi-layer microporous polyolefin film crosslinked (for example, utilizing the ionizing rays ray, for example α-ray, beta-rays, gamma-radiation, electron beam or the like).For example, when the radiating electron bundle is used for when crosslinked, the amount of electron beam irradiation can be about 0.1Mrad to about 100Mrad, uses the acceleration voltage of about 100kV to the about 300kV scope.It is believed that it is littler than the difficulty of the microporous membrane of higher melting temperature that crosslinking Treatment can make preparation have.(12) wetting ability is handled
In one embodiment, can carry out wetting ability to microporous membrane and handle (that is, can make microporous polyolefin film have more hydrophilic processing).It can be for example monomer-grafted processing, surfactant treatment, Corona discharge Treatment or the like that wetting ability is handled.In one embodiment, after crosslinking Treatment, use monomer-grafted processing.
When using surfactant treatment, can use any non-ionics, cats product, AS and amphoterics, for example, be used alone or in combination.In one embodiment, use non-ionics.The selection of surfactant is not critical.For example, can multi-layer microporous polyolefin film be immersed in the solution of surfactant and water or lower alcohol (for example methyl alcohol, ethanol, Virahol or the like), or be coated with stain with solution (for example through scraping gluing method).
Embodiment
With reference to following embodiment, can understand present description and desired polymkeric substance more fully, these embodiment are not intended to limit the scope of this claim.
Successive polymerization EXAMPLE Example 1 prepares sample through successive polymerization in the loop slurry pilot plant.The device design comprises: on-the-spot prepolymerization device, two 6 inches loop reactors (series connection) and particle operating equipment.(TOHO THC-135) is injected in the preparatory contacting container through syringe pump with catalyst solid, and therein, catalyst solid mixes with electron donor-dicyclopentyl dimethoxyl silane (DCPMS) and triethyl aluminum (TEAl).The mole of feed ratio of three catalyst components is provided in the table 1.After 65 ° of F prepolymerizations, pre-polymerized catalyst is input in the principal reaction device.The reaction conditions that is used for preparing all samples is provided at table 1.The characterization result of sample is provided in the table 2.Table 1: the polymerizing condition that is used to prepare the UHMW-PP sample
Table 2: characterization result 
Embodiment 2
The product (sample 8-3) that is prepared as follows embodiment 1 (has 2.5 * 10 with the UHMW Vilaterm
6Molecular weight) and the HD Vilaterm (have 3.0 * 10
5Molecular weight) blend: 100 parts of (by quality) polyolefine (PO) compsn (product (sample 8-3) of embodiment 1 of HD Vilaterm and 50% quality that comprises UHMW Vilaterm, 49% quality of 1% quality) and 0.5 part of (by quality) butylated hydroxytoluene (as inhibitor) are carried out blend through dry method.Independently take off data shows, the polyethylene compsn of this blend has 135 ℃ fusing point and 90 ℃ crystalline dispersion temperature.
The blend that 35 parts (by quality) are obtained joins in the intensively stirred twin screw extruder (having the internal diameter of 58mm and 42 L/D), to twin screw extruder 65 parts of (by quality) whiterusss [40cst (40 ℃)] is provided through the side feed appliance.210 ℃ with the 200rpm condition under carry out melt blending, with the preparation polyolefin solution.Make this polyolefin solution form the gel sheet material.
Use the laboratory tenter machine, 114 ℃ with gel sheet material biaxial stretching simultaneously, be 5 times at vertically (MD) with extensibility on horizontal (TD) both direction.The tensile film is fixed on the aluminium sash of 20cmx20cm, and is dipped in the methylene dichloride [surface tension: 27.3mN/m (25 ℃), boiling point: 40.0 ℃] that is controlled at 25 ℃, washing (vibrating with 100rpm simultaneously) 3 minutes.The film that obtains is at room temperature carried out air cooling,, be fixed to simultaneously on the aluminium sash, with the preparation microporous membrane 125 ℃ of heat setting types 10 minutes.
Utilize following method to measure the performance of the microporous membrane of this embodiment.(1) mean thickness (μ m) i. utilizes contact thickness gauge (5mm MD at interval on the width of 30cm) to measure the thickness of microporous membrane, averages, and obtains 33 μ m.(2) ventilation property (sec/100cc/20 μ m): i. utilizes formula P
2=(P
1X20)/T
1, will have thickness T according to JIS P8117
1Microporous membrane on the ventilation property P that measures
1Ventilation property P when changing 20 μ m thickness into
2, obtain 233sec/100cc/20 μ m.(3) porosity (%): i. utilizes gravimetric determination, obtains 41%.(4) acupuncture disruptive strength (mN/20 μ m): i. is when (when spherical end surface (radius R of curved part: 0.5mm)) stings the microporous membrane with T1 thickness with the speed of 2mm/ second, measuring maximum load with the pin of 1mm diameter.Utilize formula L
2=(L
1X20)/T
1, with the maximum load L that measures
1Maximum load L when changing 20 μ m thickness into
2, and as the acupuncture disruptive strength.Obtain 1893mN/20 μ m.(5) closing temperature
i. uses hot machine analyzer (TMA/SS6000; Be obtained from Seiko InstrumentsInc.); The test film of 10mm (TD) x3mm (MD) is begun heating with the speed of 5 ℃/min from room temperature; With the load longitudinal stretching test film of 2gf, the temperature at the point of inflection place of the sample length that will near the test film fusing point time, be observed is defined as " closing temperature " simultaneously.Obtain 133 ℃.(6) temperature of fusion (℃): with the block clamping of the microporous membrane sample of 5cmx5cm, the wolfram varbide abrading-ball of 10mm diameter is placed on the microporous membrane in the annular opening with annular opening with 12mm diameter.Heat simultaneously the temperature when measuring microporous membrane and breaking with 5 ℃/minute rate of rise in temperature.Obtain 178 ℃.Comparative Examples 1
The polyolefin solution that has same combination and concentration with the solution among the embodiment 2; Only use methyl-cyclohexyl base dimethoxy silane (MCMS) and triethyl aluminum (TEAL) as outside electron donor and promotor, the alfon that obtains through polymerization has 8.4 * 10
5Molecular weight and the melting heat of 83.9J/g.
The performance of the microporous membrane of this Comparative Examples is following.
The mean thickness that obtains, ventilation property, porosity, acupuncture disruptive strength, closing temperature and temperature of fusion are respectively: 30 μ m, 4830sec/100cc/20 μ m, 25%, 4437mN/20 μ m, 133 ℃ and 174 ℃.Embodiment 3 table 1.Lab UHMW iPP polymerization and characterization datas
aThe DCPMS=dicyclopentyl dimethoxyl silane
bGPC is 160 ℃ of operations.
cLimiting viscosity=12.28dl/g
dLimiting viscosity=13.61dl/g embodiment 3 shows that UHMW high-crystallinity PP can use Ziegler-Natta catalyst and dicyclopentyl dimethoxyl silane external donor to prepare.
Propylene polymerization
| Sample ID | Catalyzer/donor a | Activity, g/g/hr | Mw, k b | Mw/Mn | Tm, ℃ | Δ H, J/g |
| 24186-181 | C-133/DCPMS | 9584 | 2440 | 5.88 | 165.79 | 112.03 |
| 24186-182 | C-133/DCPMS | 5015 | 2400 | 5.55 | 164.62 | 108.34 |
| 24186-183 | C-135/DCPMS | 13550 | 2410 | 5.15 | 166.80 | 112.05 |
| 24186-184 | C-133/DCPMS | 6372 | 2413 | 5.28 | 164.63 | 111.78 |
| 24186-185 c | C-135/DCPMS | 8538 | 2477 | 5.00 | 165.65 | 108.48 |
| 24186-188 | C-135/DCPMS | 14351 | 2406 | 4.64 | 167.17 | 111.55 |
| 24186-189 | C-135/DCPMS | 7756 | 2657 | 4.54 | 166.67 | 111.00 |
| 24186-190 d | C-135/DCPMS | 16010 | 2273 | 4.53 | 167.00 | 108.81 |
| 24186-191 | C-135/DCPMS | 14680 | 2450 | 4.41 | 166.50 | 109.74 |
| 24186-192 | C-135/DCPMS | 9574 | 2145 | 4.11 | 166.76 | 108.66 |
| 24186-193 | C-135/DCPMS | 7840 | 2304 | 3.45 | 166.08 | 111.27 |
| 24186-194 | C-135/DCPMS | 10099 | 166.10 | 109.92 | ||
| 24186-195 | C-135/DCPMS | 6553 | 166.09 | 109.59 |
THC-C-133 and THC-C-135 are commercial Ziegler-Natta catalysts, are produced by Toho Catalyst Company.Make propylene carry out purifying through the R3-11 copper catalyst of reductive R3-11 copper catalyst, dehydration, the 3A molecular sieve of dehydration and the Selexsorb COS alumina post of dehydration.At 100-120 ℃, 2L Zipperclave reactor drum was purged 1 hour with nitrogen gas stream, then temperature of reactor is reduced to room temperature.Usually, add the hexane solution of 2-4mL1.0M triethyl aluminum, the hexane solution and the 1000mL propylene of 2-12mL 0.1M dicyclopentyl dimethoxyl silane.Begin to stir.Through adding the 250mL propylene, about 10-30mg solid catalyst (in the 5wt% mineral oil slurry) is injected in the reactor drum, in about 5 minutes, reactor drum is heated to 60 or 70 ℃.Injecting catalyst 60 minutes afterwards through stopping heating and emptying volatile matter, stops polymerization.
Dsc (DSC)Use ASTM D 3418-03 document as a reference, measure peak fusing point (Tm), peak Tc (Tc) and melting heat (Δ H).Use PerkinElmer Instrument, model Pyris 1DSC obtains differential scanning calorimetric (DSC) data.The sample of great about 5.5-6.5mg is sealed in the aluminium sample pot.Through at first sample being heated to 200 ℃ (being called first melt (n.d. record)) with 150 ℃/minute speed, record DSC data.Sample was kept 10 minutes at 200 ℃, then use cooling-heating cycle.With 10 ℃/minute speed sample is cooled to 25 ℃ (being called crystallization) from 200 ℃ then, then kept 10 minutes, be heated to 200 ℃ (are called two molten) with 10 ℃/minute speed at 25 ℃.Thermal phenomenon during record crystallization and two is melted.Fusing point (T
m) be the peak temperature of two molten curves, Tc (T
c) be the peak temperature of peak crystallization.
Claims (13)
1. microporous membrane that comprises Vilaterm and polymer compsn; Said polymer compsn comprises the propylene monomer greater than 90 moles of %; Said compsn has the limiting viscosity of measuring according to ASTM D1601-78 method greater than 10dl/g; Greater than the melting heat of 108J/g, 165 ℃ or bigger fusing point, use gel permeation chromatography greater than 1.5x 10
6Weight-average molecular weight; 2.5 MWD to 7; This MWD is to use the weight-average molecular weight of gel permeation chromatography and the ratio of the number-average molecular weight of using gel permeation chromatography; 230 ℃ with 2.16kg when load melt flow rate(MFR) less than 0.01dg/ minute, but based on the 0.5wt.% of polymer composition weight or extract quantity still less, per 10; 000 carbon atom is less than 50 three-dimensional defective with greater than the meso five unit number of componentss of 96mol%mmmm five unit groups.
2. the microporous membrane of claim 1, wherein polymer compsn comprises the propylene monomer greater than 99.99mol%.
3. the microporous membrane of claim 1, wherein polymer compsn has greater than 1.75x 10
6Weight-average molecular weight.
4. the microporous membrane of claim 1, wherein polymer compsn has the limiting viscosity greater than 11dl/g, and greater than the melting heat of 110J/g, 166 ℃ or bigger fusing point are greater than 1.5x10
6Weight-average molecular weight, 2.5 to 7 MWD, in the time of 230 ℃ less than 0.01dg/ minute melt flow rate(MFR) and per 10,000 carbon atoms less than 40 three-dimensional defective.
5. the microporous membrane of claim 1, wherein polymer compsn comprises the propylene monomer greater than 95 moles of %.
6. claim 3 or 4 microporous membrane, wherein polymer compsn comprises the propylene monomer greater than 95 moles of %.
7. the microporous membrane of claim 1, wherein this film is the multilayer film with at least one layer that comprises said polymer compsn.
8. battery separator film, it comprises the microporous membrane of claim 1.
9. battery, it comprises the battery separator film of anode, negative electrode, ionogen and claim 8, wherein the battery separator film is between anode and negative electrode.
10. prepare the method for microporous membrane, comprise the following steps:
(1) with thinner, the mixture of the Vilaterm and first polyolefin compositions is extruded, and first polyolefin compositions comprises the propylene monomer greater than 90 moles of %, and has following performance:
(a) the limiting viscosity of measuring according to ASTM D1601-78 method greater than 10dl/g,
(b) greater than the melting heat of 108J/g, 165 ℃ or bigger fusing point,
(c) use gel permeation chromatography greater than 1.5x 10
6Weight-average molecular weight,
(d) 2.5 to 7 MWD, this MWD are to use the weight-average molecular weight of gel permeation chromatography and the ratio of the number-average molecular weight of using gel permeation chromatography,
(e) 230 ℃ with 2.16kg when load melt flow rate(MFR) less than 0.01dg/ minute,
(f) but based on the 0.5wt.% of polyolefin compositions weight or extract quantity still less,
(g) greater than the meso five unit number of componentss of 96mol%mmmm five unit groups and
(h) per 10,000 carbon atoms are less than 50 three-dimensional defects count; Then
(2) from the extruded product of step (1), remove at least a portion thinner.
11. the method for claim 10 further comprises the one or more steps in following: stretching extrudate and/or microporous membrane; With microporous membrane heat setting type; Microporous membrane is carried out hot solvent to be handled; And/or microporous membrane carried out crosslinking Treatment.
12. the method for claim 10; Further comprise: second mixture of second polyolefin compositions and second thinner extruded; Wherein microporous membrane is a multilayer film, and it has one deck at least that comprises first polyolefin compositions and the one deck at least that comprises second polyolefin compositions.
13. the method for claim 10 further comprises: before removing thinner, extrudate is cooled off.
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|---|---|---|---|
| US88124707P | 2007-01-19 | 2007-01-19 | |
| US60/881,247 | 2007-01-19 | ||
| PCT/US2008/051352 WO2008140835A1 (en) | 2007-01-19 | 2008-01-17 | Polymeric material and its manufacture and use |
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|---|---|
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| EP (1) | EP2104711A1 (en) |
| JP (1) | JP2010516842A (en) |
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|---|---|---|---|---|
| US8916644B2 (en) * | 2009-01-07 | 2014-12-23 | Toray Battery Separator Film Co., Ltd | Polypropylene resin composition for use in formation of microporous membrane |
| US9449761B2 (en) * | 2009-03-17 | 2016-09-20 | Prime Polymer Co., Ltd. | Polypropylene for film capacitor, polypropylene sheet for film capacitor, method for producing the same, and uses of the same |
| JP5536871B2 (en) | 2009-03-30 | 2014-07-02 | 東レバッテリーセパレータフィルム株式会社 | Microporous membrane and methods for making and using such membranes |
| KR20110139279A (en) | 2009-04-23 | 2011-12-28 | 도레이 토넨 기노우마쿠 고도카이샤 | Thermoplastic film, methods for making such film, and the use of such film as battery separator film |
| WO2010123687A1 (en) | 2009-04-23 | 2010-10-28 | Toray Tonen Specialty Separator Company | Thermoplastic film, methods for making such film, and the use of such film as battery separator film |
| US8951677B2 (en) | 2009-06-19 | 2015-02-10 | Toray Battery Separator Film Co., Ltd. | Microporous membranes, methods for making such membranes, and the use of such membranes as battery separator film |
| JP5728473B2 (en) | 2009-06-19 | 2015-06-03 | 東レバッテリーセパレータフィルム株式会社 | Multilayer microporous film |
| EP2512641A1 (en) | 2009-12-18 | 2012-10-24 | Toray Battery Separator Film Godo Kaisha | Microporous membranes, methods for making same and their use as battery separator films |
| WO2011086823A1 (en) | 2010-01-13 | 2011-07-21 | Toray Tonen Specialty Separator Godo Kaisha | Microporous membranes and methods for producing and using such membranes |
| US20110223485A1 (en) | 2010-03-15 | 2011-09-15 | Toray Tonen Specialty Separator Godo Kaisha | Microporous membranes, methods for making these membranes, and the use of these membranes as battery separator films |
| US9136517B2 (en) | 2010-08-12 | 2015-09-15 | Toray Battery Separator Film Co., Ltd. | Microporous film, process for production of the film, and use of the film |
| CN102148346B (en) * | 2011-03-11 | 2013-04-24 | 河南义腾新能源科技有限公司 | Polyolefin microporous diaphragm and preparation method thereof |
| CN109810398A (en) * | 2017-11-21 | 2019-05-28 | 中国石油天然气股份有限公司 | A kind of super high molecular weight isotactic polypropylene resin combination and preparation method thereof |
| CN109876362A (en) * | 2019-02-22 | 2019-06-14 | 滁州市超顺装备科技有限公司 | A kind of processing method of crosslinked foaming gymnastics pad |
| CN112724509B (en) * | 2020-12-18 | 2022-08-09 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242785A (en) * | 1996-10-18 | 2000-01-26 | Ppg工业公司 | Very thin microporous material |
| CN1271184A (en) * | 1999-04-20 | 2000-10-25 | 思凯德公司 | Structure stable meltable cell disphragm and its making method |
| CN1362892A (en) * | 2000-01-10 | 2002-08-07 | Lg化学株式会社 | High crystalline polypropylene microporous membrane, multi-component microporous membrane and methods for preparing same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2691023B2 (en) * | 1989-03-20 | 1997-12-17 | 株式会社トクヤマ | Ultra high molecular weight polypropylene and method for producing the same |
| US5430119A (en) * | 1991-06-11 | 1995-07-04 | Mitsui Petrochemical Industries, Ltd. | Stretched molded article of ultra-high-molecular weight polypropylene and process for the preparation of the same |
| JP3070694B2 (en) * | 1991-06-11 | 2000-07-31 | 三井化学株式会社 | Ultra-high molecular weight stretched polypropylene article and method for producing the same |
| JPH06234811A (en) * | 1993-02-10 | 1994-08-23 | Mitsui Petrochem Ind Ltd | Production of ultra-high-molecular weight polyolefin |
| US6214949B1 (en) * | 1993-12-29 | 2001-04-10 | Fina Technology, Inc. | Polymerization of polyolefins having low melt flow and high molecular weight |
| WO1995027740A1 (en) * | 1994-04-11 | 1995-10-19 | Mitsui Petrochemical Industries, Ltd. | Process for producing propylene polymer composition, and propylene polymer composition |
| JP2001072792A (en) * | 1999-09-06 | 2001-03-21 | Tonen Chem Corp | Microporous polyolefin film and its production |
| EP1803742B1 (en) * | 2004-08-30 | 2010-06-23 | Mitsui Chemicals, Inc. | Process for producing propylene polymer |
-
2008
- 2008-01-14 CN CN2008800024795A patent/CN101641406B/en active Active
- 2008-01-17 WO PCT/US2008/051352 patent/WO2008140835A1/en active Application Filing
- 2008-01-17 KR KR1020097017189A patent/KR101126916B1/en active IP Right Grant
- 2008-01-17 EP EP08795784A patent/EP2104711A1/en not_active Ceased
- 2008-01-17 JP JP2009546513A patent/JP2010516842A/en active Pending
- 2008-01-17 CA CA2675424A patent/CA2675424C/en active Active
- 2008-01-18 TW TW097102024A patent/TW200904883A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242785A (en) * | 1996-10-18 | 2000-01-26 | Ppg工业公司 | Very thin microporous material |
| CN1271184A (en) * | 1999-04-20 | 2000-10-25 | 思凯德公司 | Structure stable meltable cell disphragm and its making method |
| CN1362892A (en) * | 2000-01-10 | 2002-08-07 | Lg化学株式会社 | High crystalline polypropylene microporous membrane, multi-component microporous membrane and methods for preparing same |
Non-Patent Citations (1)
| Title |
|---|
| JP平3-7704A 1991.01.14 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008140835A1 (en) | 2008-11-20 |
| CN101641406A (en) | 2010-02-03 |
| JP2010516842A (en) | 2010-05-20 |
| KR101126916B1 (en) | 2012-03-21 |
| KR20090116745A (en) | 2009-11-11 |
| WO2008140835A8 (en) | 2009-08-20 |
| CA2675424A1 (en) | 2008-11-20 |
| EP2104711A1 (en) | 2009-09-30 |
| CA2675424C (en) | 2012-04-03 |
| TW200904883A (en) | 2009-02-01 |
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