EP4683952A1 - Polypropylene resin compositon - Google Patents
Polypropylene resin compositonInfo
- Publication number
- EP4683952A1 EP4683952A1 EP23782948.6A EP23782948A EP4683952A1 EP 4683952 A1 EP4683952 A1 EP 4683952A1 EP 23782948 A EP23782948 A EP 23782948A EP 4683952 A1 EP4683952 A1 EP 4683952A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- polypropylene resin
- resin composition
- ranges
- iso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/002—Organic membrane manufacture from melts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
Definitions
- the present disclosure relates to polypropylene resin composition
- polypropylene resin composition comprising an ultra- high-molecular-weight propylene homopolymer for use in the formation of a microporous membrane having good Gurley permeability, measured according to ISO 5636 and good mechanical properties.
- Microporous membranes made of polymeric materials are used in various applications, for example, filter membranes and separation membranes for medical and industrial use, and separators, such as battery separators and condenser separators.
- separators such as battery separators and condenser separators.
- EP 1 464669 relates to microporous membrane made substantially with high molecular weight polyethylene or a blend of polyethylene and polypropylene. However the air transmission rate (Gurley permeability) can be improved.
- the present disclosure is directed to a polypropylene resin composition
- a polypropylene resin composition comprising:
- the fraction soluble in xylene at 25°C , measured according to ISO 16 152 - 2005 is comprised between 6.0 wt% and 2.0wt%;
- component B) from 30 wt% to 90 wt% of an organic material selected from: organic acid esters; adipic acid esters, glyceric acid esters; phosphoric acid esters; paraffin; wax; and mineral oil; wherein the sum of the amounts of component A) and component B) in wt% is equal to 100 wt% .
- the present disclosure is directed to a polypropylene resin composition
- a polypropylene resin composition comprising:
- melting points are present in the DSC thermogram measured according to ISO 11357-3, with heating and cooling rate of 20°C/min; preferably the lower melting point ranges from 135°C to 150°C;
- heating and cooling rate of 20°C/min ranges from 155°C to 170°C; preferably from 157°C to 168°C;
- the fraction soluble in xylene at 25°C measured according to ISO 16 152 - 2005 is comprised between 6.0 wt% and 2.0wt%; preferably comprised between 5.0 wt% and 2.5wt%; more preferably comprised between 4.0 wt% and 2.8wt%;
- the isotactic pentads, mmmm %, measured with C 13 NMR as reported in the examples section ranges from 96.5 mol% to 90.0 mol%, .preferably from 96.0 mol% to 93.0 mol%; more preferably from 95.5 mol% to 93.5 mol%;
- the intrinsic viscosity (IV) measured in tetrahydronaphthalene at 135 °C ranges from 5.5dl/g to 12.0 dl/g; preferably from 7.0 dl/g to 11.0 dl/g; more preferably from 8.0 dl/g to 10.0 dl/g;
- melt strength measured measured according to ISO 16790-2005 at 250°C and applying an acceleration equal to 6 mm/s 2 , is higher than 0.070 N; preferably higher than 0.080 N; more preferably higher than 0.090 N;
- organic acid esters as dioctyl phthalate, diheptyl phthalate and dibutyl phthalate, adipic acid esters, glyceric acid esters; phosphoric acid esters, such as trioctyl phosphate; paraffin, such as liquid paraffin and solid paraffin; wax; and mineral oil
- the organic material component B) is selected from liquid paraffin, solid paraffin; wax; and mineral oil; more preferably the organic material component B) is a mineral oil; even more preferably the organic material component B) is white mineral oil (CAS 8042- 47-5).
- the propylene homopolymer of the present disclosure is not nucleated.
- the homopolymer of the present disclosure shows a value of melt strength lower than 0.30 N.
- the homopolymer of the present disclosure shows a polydispersity index, PI, measured according to ISO 6721-10, comprised between 4.5 and 7.5; more preferably between 5.0 and 7.2; more preferably from 5.5 to 6.5.
- PI polydispersity index
- the homopolymer of the present disclosure shows a tensile modulus ranging from 2100 MPa to 1100 MPa; preferably from 1800MPa, to 1200 Mpa.
- the homopolymer of the present disclosure shows a Charpy impact test at 23°C ranging from 4.0 kJ/m2 to 11.0 kJ/m2; preferably from 5.5 kJ/m2 to 9.0 kJ/m2.
- the propylene homopolymers disclosed herein can be prepared by a process comprising polymerizing propylene optionally with ethylene, in the presence of Ziegler-Natta catalysts.
- An essential component of said catalysts is a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron-donor compound, both supported on a magnesium halide in active form.
- Another essential component co-catalyst is an organoaluminium compound, such as an aluminium alkyl compound.
- An external donor is optionally added.
- Catalysts having the above mentioned characteristics are well known in the patent literature; particularly advantageous are the catalysts described in US patent 4,399,054 and European patent 45977. Other examples can be found in US patent 4,472,524.
- the solid catalyst components used in said catalysts comprise, as electron-donors (internal donors), compounds selected from the group consisting of ethers, ketones, lactones, compounds containing N, P and/or S atoms, and esters of mono- and dicarboxylic acids.
- electron-donor compounds are esters of succinic acid (succinates)
- succinates the succinate present in the solid catalyst component is selected from succinates of formula (I) below
- radicals Ri and R2 are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; and the radicals R3 and R4 equal to, or different from, each other, are Ci- C20 alkyl, C3-C20 cycloalkyl, C5-C20 aryl, arylalkyl or alkylaryl group with the proviso that at least one of them is a branched alkyl; said compounds being, with respect to the two asymmetric carbon atoms identified in the structure of formula (I), stereoisomers of the type (S,R) or (R,S) [0017] Ri and R2 are preferably Ci-Cs alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups.
- Ri and R2 are selected from primary alkyls and in particular branched primary alkyls.
- suitable Ri and R2 groups are methyl, ethyl, n- propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
- ethyl, isobutyl, and neopentyl are particularly preferred.
- R3 and/or R4 radicals are secondary alkyls like isopropyl, sec- butyl, 2-pentyl, 3 -pentyl or cycloakyls like cyclohexyl, cyclopentyl, cyclohexylmethyl.
- Examples of the above-mentioned compounds are the (S,R) (S,R) forms pure or in mixture, optionally in racemic form, of diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2- ethylbutyl)succinate, diethyl 2,3 -dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl
- Particularly suitable electron- donor compounds are esters of phtalic acid and 1,3- diethers of formula:
- R 1 and R n are the same or different and are Ci-Cis alkyl, C3-C18 cycloalkyl or C7-C18 aryl radicals;
- R 111 and R IV are the same or different and are C1-C4 alkyl radicals; or are the 1,3 -di ethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6, or 7 carbon atoms, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, O, S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structure), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl
- diethers are 2-methyl-2-isopropyl-l,3- dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-l,3- dimethoxypropane, 2-isopropyl-2-isoamyl-l,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene.
- Suitable electron-donor compounds are phthalic acid esters, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.
- a MgC12»nROH adduct (in particular in the form of spheroidal particles) wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol, is reacted with an excess of TiC14 containing the electron-donor compound.
- the reaction temperature is generally from 80 to 120° C.
- the solid is then isolated and reacted once more with TiC14, in the presence or absence of the electron-donor compound, after which it is separated and washed with aliquots of a hydrocarbon until all chlorine ions have disappeared.
- the titanium compound expressed as Ti
- the quantity of electron-donor compound which remains fixed on the solid catalyst component generally is 5 to 20% by moles with respect to the magnesium dihalide.
- the titanium compounds which can be used for the preparation of the solid catalyst component, are the halides and the halogen alcoholates of titanium. Titanium tetrachloride is the preferred compound.
- the Al-alkyl compounds used as co-catalysts comprise the Al-trialkyls, such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO4 or SO3 groups.
- Al-trialkyls such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO4 or SO3 groups.
- the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
- the electron-donor compounds that can be used as external donors include aromatic acid esters such as alkyl benzoates, and in particular silicon compounds containing at least one Si-OR bond, where R is a hydrocarbon radical.
- silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si (OCH3)2, (cyclopentyl)2Si(OCH3)2 and (phenyl)2Si(OCH3)2 and (1,1,2- tr imethy Ipropy 1) S i(OCH3 ) 3.
- 1,3 -diethers having the formulae described above can also be used advantageously. If the internal donor is one of these diethers, the external donors can be omitted.
- the component A) are preferably prepared by using catalysts containing a phthalate as internal donor and (cyclopentyl)2Si(OCH3)2 as outside donor, or the said 1,3 -di ethers as internal donors.
- the polymerization is generally carried out at temperatures of from 20 to 120°C, preferably of from 40 to 80°C.
- the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
- the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
- Hydrogen is typically used as a molecular weight regulator.
- the polymerization can be in gas phase or in slurry or in solution. In one or more reactors. Preferably the polymerizaiotn is carried put in two slurry reactors operating in series.
- composition of the present disclosure can be obtained with a process comprising the step of mixing component A) and component B) to perform a granulation in a mixer.
- composition of the present disclosure can be used in the formation of a microporous membrane having good Gurley permeability and good mechanical properties.
- a method most suitably employed for obtaining the microporous membrane in accordance with the present disclosure comprises the steps of mixing organic material component B) with component A), heating and melting the mixture, extruding the melt into a sheet, orientating the sheet biaxially, either simultaneously or sequentially, and then extracting the liquid with a volatile solvent (dichloromethane for example).
- a volatile solvent dichloromethane for example
- the membrane can be subjected to a heat-setting process, this last step enhances the dimensional stability and prevents shrinkage or wrinkle formation upon heating, which is important for safety and control of the final performance.
- microporous membrane obtained with the composition of the present disclosure shows a good Gurley permeability, measured according to ISO 5636.
- the porosity measures according to the method described in the examples is particularly good, the porosity preferably ranges from 30.0% to 60.0%, more preferably from 33.0% to 51.0%; more preferably from 34.0% to 45.0%.
- the puncture resistance of microporous membrane normalized for 20pm ranges from 700 g/20pm to 1200 g/20pm; preferably from 750 g/20pm to 1050 g/20pm; more preferably from 800 g/20pm to 998 g/20pm
- Tm melting points of the polymers
- the weighted sample was sealed into aluminium pans and heated to 200°C at 20°C/minute.
- the sample was kept at 200°C for 2 minutes to allow a complete melting of all the crystallites, then cooled to 5 °C at 20°C/minute.
- the sample was heated for the second run time to 200°C at 20°C/min. In this second heating run, the peak temperature (Tp,m) was taken as the melting temperature.
- the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
- the distance from the capillary outlet to the center of the transducer pulley is 150 mm.
- the monofilament is stretched at each temperature test applying an acceleration equal to 6 mm/s 2 and, passing through an angular transducer, its tension is measured.
- the draw ratio (dimensionless value) and force (cN) values are recorded as the final result in addition to the entire curve.
- the value of the melt strength is the maximum force value of the curve.
- Tensile Modulus is measured according to ISO 527-2, and ISO 1873-2 on compression sample
- Porosity is measured by measuring the mass and thickness of a film sample of 5 cm x 5 cm calculating the free volume in relation to the standard density given in equation below.
- m is the mass of the sample
- p is the density of the base material (0.915 g/cm 3 )
- A is the area of the sample and d is the measured thickness.
- the polymerization run is carried out in continuous mode in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
- the two reactors are liquid phase loop reactors.
- Propylene is the main solvent, hydrogen is used as molecular weight regulator.
- the gas phase is continuously analyzed via gaschromatography.
- Gurley permeability has been measured according to ISO 5636, the value has been normalized for 20pm sheet.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23163204 | 2023-03-21 | ||
| PCT/EP2023/077252 WO2024193834A1 (en) | 2022-11-07 | 2023-10-02 | Polypropylene resin compositon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4683952A1 true EP4683952A1 (en) | 2026-01-28 |
Family
ID=85771999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23782948.6A Pending EP4683952A1 (en) | 2023-03-21 | 2023-10-02 | Polypropylene resin compositon |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP4683952A1 (en) |
| CN (1) | CN120787241A (en) |
-
2023
- 2023-10-02 EP EP23782948.6A patent/EP4683952A1/en active Pending
- 2023-10-02 CN CN202380094433.5A patent/CN120787241A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN120787241A (en) | 2025-10-14 |
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Free format text: CASE NUMBER: UPC_APP_0005957_4683952/2026 Effective date: 20260218 |