EP1274773A1 - Improvement of the dispersion of pigments in polypropylene - Google Patents
Improvement of the dispersion of pigments in polypropyleneInfo
- Publication number
- EP1274773A1 EP1274773A1 EP01925331A EP01925331A EP1274773A1 EP 1274773 A1 EP1274773 A1 EP 1274773A1 EP 01925331 A EP01925331 A EP 01925331A EP 01925331 A EP01925331 A EP 01925331A EP 1274773 A1 EP1274773 A1 EP 1274773A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- waxes
- polyolefin
- use according
- polypropylene
- polyolefin wax
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- the present invention relates to a process for the improved production of a colorant, consisting of at least one colorant which is distributed very finely in a meltable base material (matrix) which is solid at room temperature, and to the use of polyolefin waxes which coexist with Metallocene catalysts have been produced to improve the dispersion of the colorant in the polypropylene matrix, in particular for the production of polypropylene fibers.
- Pigment preparations that can be used for coloring polyolefins are known:
- DE-B-1 239 093 describes a carrier material for producing a pigment preparation which consists of a mixture of an amorphous ethylene-propylene block copolymer which has a viscosity of 5000 to 300,000 cps at 150 ° C. and a low molecular weight, crystalline polypropylene consists.
- DE-A-26 52 628 describes the use of a low molecular weight polypropylene wax with a viscosity of 500 to 5000 cP at 170 ° C. as a dispersing aid.
- DE-C-42 36 337 describes the use of polyacrylate esters as dispersants for pigments in plastic matrices.
- the object was therefore to provide a dispersing aid for pigments in polypropylene which effects a sufficient dispersion of the polymer particles, so that there are fewer strand breaks during fiber production.
- polyolefin waxes produced by metallocene catalysis ensure very good dispersion of pigments in polypropylene.
- the invention relates to the use of means
- Metallocene catalysts produced polyolefin waxes as dispersants for pigments in polypropylene.
- Another object of the invention is a process for the production of a masterbatch by mixing a polymer with a colorant, characterized by admixing at least one polyolefin wax obtained by metallocene catalysis.
- the pigments are preferably organic pigments.
- Suitable polyolefin waxes are homopolymers of ethylene or propylene or copolymers of both olefins or copolymers of ethylene or propylene with one or more further olefins. Linear or branched olefins having 4-18 C atoms are preferred as further olefins
- Examples include 1-butene, 1-hexene, 1-octene or 1-octadecene and styrene.
- the copolymers consist of 70-99.9, preferably 80-99% by weight of ethylene or propylene. Homopolymers of are preferred Ethylene or propylene and copolymers of ethylene and propylene.
- Polyolefin waxes with a dropping point between 90 and 165 ° C., preferably between 100 and 160 ° C., a melt viscosity at 170 ° C. between 5 and 10,000 mPa-s, preferably between 10 and 5000 mPa-s and a density at 20 are particularly suitable ° C between 0.86 and 0.98 g / cm 3 , preferably between 0.87 and 0.96 g / cm 3 .
- the waxes can be used both as such and in a polar modified form. Modifications known per se are, for example, oxidation with air or graft polymerization with polar monomers, for example maleic anhydride.
- the metallocene waxes used according to the invention are used in admixture with auxiliaries and additives which improve the dispersing action of the metallocene waxes.
- auxiliaries and additives include, for example
- Additive a) is polyethylene glycol, molecular weight range preferably 10 to 50,000 daltons, in particular 20 to 35,000 daltons.
- the polyethylene glycol can be mixed in amounts of preferably up to 5% by weight of the composition containing metallocene wax.
- additive b) is polyethylene homo- and copolymer waxes which were not produced by means of metallocene catalysis and which have a number average molecular weight of 700 to 10,000 g / mol at a dropping point between 80 and 140 ° C.
- additive c) is polytetrafluoroethylene with a molecular weight between 30,000 and 2,000,000 g / mol, in particular between 100,000 and 1,000,000 g / mol.
- additive d) is polypropylene homo- and copolymer waxes, which were not produced by means of metallocene catalysis and which have a number average molecular weight of 700 to 10,000 g / mol at a dropping point between 80 and 160 ° C.
- additive e) is amide waxes which can be prepared by reacting ammonia or ethylenediamine with saturated and / or unsaturated fatty acids.
- the fatty acids are, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.
- additive f) is FT paraffins with a number average molecular weight of 400 to 800 g / mol at a dropping point of 80 to 125 ° C.
- Additive g) is preferably montan waxes including acid and ester waxes with a carbon chain length of the carboxylic acid from C 22 to C 36 .
- the ester waxes are preferably reaction products of the montanic acids with mono- or polyhydric alcohols having 2 to 6 carbon atoms, such as, for example, ethanediol, 1-butane, 3-diol or 1-propane, 2,3-triol.
- additive h) is carnauba wax or candelilla wax.
- Additive i) is paraffins and microcrystalline waxes which are obtained from petroleum refining.
- the dropping points of such paraffins are preferably between 45 and 65 ° C, those of such microcrystalline waxes preferably between 73 and 100 ° C.
- additive j) is polar polyolefin waxes, which can be prepared by oxidation of ethylene or propylene homopolymer and copolymer waxes or by grafting them with them
- additive k) is reaction products of sorbitol (sorbitol) with saturated and / or unsaturated fatty acids and / or montanic acids.
- the fatty acids are, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.
- Additive I) is preferably ground polyamides, for example polyamide-6, polyamide-6,6 or polyamide-12.
- the particle size of the polyamides is preferably in the range of 5-200 ⁇ m, in particular 10-100 ⁇ m.
- Additive m) is a polyolefin, for example polypropylene, polyethylene or copolymers of propylene and ethylene of high or low density with molecular weights of preferably 10,000 to 1,000,000 D, in particular 15,000 to 500,000 D as number average for the molecular weight, the particle size of which Grinding is in the range of preferably 5-200 ⁇ m, in particular 10-100 ⁇ m.
- Additive n) is thermoplastic PTFE with a molecular weight of preferably 500,000-10,000,000 D, in particular 500,000-2,000,000 D as the number average, the particle size of which is preferably 5-200 ⁇ m, in particular 10-100 ⁇ m, by grinding lies.
- Additive o is an amphiphilic compound that generally lowers the surface tension of liquids.
- the wetting agents are, for example, alkyl ethoxylates, fatty alcohol ethoxolates, alkyl benzene sulfonates or betaines.
- Additive p is a silicate which is not used as a filler for the pigment in the formulation. Preference is given to using silicic acids or talc.
- the mixing ratio of component a) to components b) to p) can be varied in the range from 1 to 99% by weight a) to 1 to 99% by weight b) to p). If a mixture of several of the components b) to p) is used, the quantity given applies to the sum of the quantities of these components.
- the waxes are used in micronized form for the purpose according to the invention.
- the use of polyolefin wax and optionally admixed auxiliaries and additives as ultra-fine powder with a particle size distribution dgo ⁇ 40 ⁇ m is particularly preferred.
- the use according to the invention is particularly preferred Polyolefin waxes for the production of color concentrates for polyethylene (LD) films.
- Metallocene catalysts for the preparation of the polyolefin waxes are chiral or nonchiral transition metal compounds of the formula M 1 L X.
- Transition metal compound M 1 L X contains at least one metal central atom M 1 to which at least one ⁇ ligand, for example a cyclopentadienyl ligand, is bonded.
- substituents such as halogen, alkyl, alkoxy or aryl groups can be bound to the metal central atom M 1 .
- M 1 is preferably an element of III., IV., V. or VI. Main group of the periodic table of the elements, such as Ti, Zr or Hf.
- Cyclopentadienyl ligand is understood to mean unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrolindenrofluoryl or octa-tetra-hydrofluoryl or octa-tetra-hydrofluoryl or octa-tetra-hydrofluoryl or octa.
- the ⁇ ligands can be bridged or unbridged, whereby single and multiple bridging - also via ring systems - are possible.
- metallocene also includes compounds with more than one metallocene fragment, so-called multinuclear metallocenes. These can have any substitution pattern and bridging variant.
- the individual metallocene fragments of such multinuclear metallocenes can be of the same type or different from one another. Examples of such multinuclear metallocenes are described, for example, in EP-A-632 063.
- the melt viscosities of the waxes used below were determined using a rotary viscometer in accordance with DGF-M-Ill 8 (57), the dropping points in accordance with DGF-M-Ill 3 (75) (standards of the German Society for Fat science), the densities determined according to DIN 53479.
- the filter value is used below, which is defined as follows:
- the filter value according to this definition thus reflects the extent of the pressure increase due to filtration of a certain dispersed amount of pigment, hence the degree of "blocking" of the filter by undispersed or poorly dispersed pigment, based on the amount of pigment used.
- a Henschel mixer FM 10 is used, which typically provides a statistical distribution of the feed components for 4 to 10 minutes (at room temperature) at 600 to 1500 revolutions / min.
- the actual dispersion (typically one in an iPP matrix) takes place in a co-rotating twin-screw extruder with a partial process length of 30 to 48 D, which works with a temperature profile of 30 to 230 ° C (feed -> nozzle).
- the number of revolutions is between 100 and 550 revolutions / minute, and a throughput of 4 to 30 kg / h is used.
- the following table shows the examples according to the procedure according to the invention or corresponding comparative examples according to the prior art:
Abstract
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2000109751 DE10009751A1 (en) | 2000-03-01 | 2000-03-01 | Improving dispersion of pigments in polypropylene, using polyolefin waxes produced by metallocene catalysis, especially for preparing master batches for fiber preparation |
DE10009751 | 2000-03-01 | ||
DE2000163421 DE10063421A1 (en) | 2000-12-20 | 2000-12-20 | Process for improving the dispersion of pigments in polypropylene using metallocene catalysts and giving extremely good dispersion of the pigments |
DE10063421 | 2000-12-20 | ||
PCT/EP2001/001669 WO2001064776A1 (en) | 2000-03-01 | 2001-02-15 | Improvement of the dispersion of pigments in polypropylene |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1274773A1 true EP1274773A1 (en) | 2003-01-15 |
Family
ID=26004599
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01925331A Ceased EP1274773A1 (en) | 2000-03-01 | 2001-02-15 | Improvement of the dispersion of pigments in polypropylene |
Country Status (6)
Country | Link |
---|---|
US (1) | US20030050381A1 (en) |
EP (1) | EP1274773A1 (en) |
JP (1) | JP2003525329A (en) |
CN (1) | CN1406264A (en) |
HK (1) | HK1052520A1 (en) |
WO (1) | WO2001064776A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1238026B2 (en) * | 1999-12-13 | 2007-01-24 | Basf Aktiengesellschaft | Pigment concentrates and methods for production thereof |
DE10224845A1 (en) * | 2002-06-05 | 2003-12-24 | Clariant Gmbh | Wax mixtures of finely ground waxes |
RU2006107436A (en) * | 2003-08-12 | 2007-09-20 | БЕРИНГЕР ИНГЕЛЬХАЙМ ИНТЕРНАЦИОНАЛЬ ГмбХ (DE) | 1-CARBOMOYLICYCLOalkylcarboxylic acids, methods for their preparation and use |
JP5223165B2 (en) * | 2005-05-13 | 2013-06-26 | 東洋インキScホールディングス株式会社 | Colored resin composition for polypropylene resin and colored resin molded product |
US20070100056A1 (en) * | 2005-10-31 | 2007-05-03 | Mitsui Chemicals, Inc. | Process for producing thermoplastic resin composition |
JP2008088389A (en) * | 2005-10-31 | 2008-04-17 | Mitsui Chemicals Inc | Method for manufacturing thermoplastic resin composition |
WO2007052367A1 (en) | 2005-10-31 | 2007-05-10 | Mitsui Chemicals, Inc. | Method for producing thermoplastic resin composition |
US7605208B2 (en) | 2005-10-31 | 2009-10-20 | Mitsui Chemicals, Inc. | Process for producing thermoplastic resin composition |
CN101291983A (en) * | 2005-10-31 | 2008-10-22 | 三井化学株式会社 | Method for producing thermoplastic resin composition |
DE102006039913A1 (en) * | 2006-08-12 | 2008-02-14 | Clariant International Limited | Highly filled colorant composition for coloring and modifying olefinic and non-olefinic plastics |
DE102007028308A1 (en) * | 2007-06-20 | 2008-12-24 | Clariant International Limited | Micronized wax mixtures with reduced dust development containing polyethylene glycol compounds (PEG) |
DE102008039279A1 (en) * | 2008-08-22 | 2010-02-25 | Clariant International Limited | Transparency improvement of polypropylene with metallocene waxes |
US8022154B2 (en) * | 2008-11-06 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Ethylene polymers, their production and use |
WO2013028453A1 (en) * | 2011-08-24 | 2013-02-28 | Flowchem, Ltd. | Fuel additive and fuel composition |
JP7399183B2 (en) * | 2019-11-11 | 2023-12-15 | 株式会社プライムポリマー | Polyolefin resin composition containing pigment, colored resin pellets and manufacturing method thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2652628C2 (en) * | 1976-11-19 | 1984-08-23 | Hoechst Ag, 6230 Frankfurt | Pigment preparations based on polypropylene wax |
ES2100388T3 (en) * | 1992-05-26 | 1997-06-16 | Hoechst Ag | PROCEDURE FOR PREPARING POLYOLEFIN WAXES. |
DE4446923A1 (en) * | 1994-12-28 | 1996-07-04 | Hoechst Ag | Polyolefin wax |
DE19516387A1 (en) * | 1995-05-04 | 1996-11-07 | Huels Chemische Werke Ag | Dispersant and pigment formulation e.g. preventing fibre break |
JPH0943891A (en) * | 1995-08-02 | 1997-02-14 | Hoechst Ind Kk | Electrophotographic toner |
ES2227747T3 (en) * | 1997-07-11 | 2005-04-01 | Clariant Gmbh | USE OF POLYOLEFIN WAXES. |
DE19729833A1 (en) * | 1997-07-11 | 1999-01-14 | Clariant Gmbh | Polypropylene wax |
DE19750663A1 (en) * | 1997-11-15 | 1999-05-20 | Clariant Gmbh | Use of polyolefin waxes in solvent pastes |
DE19860174A1 (en) * | 1998-12-24 | 2000-06-29 | Clariant Gmbh | Polymer oxidates and their use |
-
2001
- 2001-02-15 JP JP2001564268A patent/JP2003525329A/en not_active Withdrawn
- 2001-02-15 CN CN01805579A patent/CN1406264A/en active Pending
- 2001-02-15 EP EP01925331A patent/EP1274773A1/en not_active Ceased
- 2001-02-15 WO PCT/EP2001/001669 patent/WO2001064776A1/en not_active Application Discontinuation
- 2001-02-15 US US10/220,076 patent/US20030050381A1/en not_active Abandoned
-
2003
- 2003-07-09 HK HK03104914.2A patent/HK1052520A1/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0164776A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20030050381A1 (en) | 2003-03-13 |
JP2003525329A (en) | 2003-08-26 |
HK1052520A1 (en) | 2003-09-19 |
CN1406264A (en) | 2003-03-26 |
WO2001064776A1 (en) | 2001-09-07 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HOHNER, GERD Inventor name: HESS, REINER Inventor name: BOTT, RAINER |
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RBV | Designated contracting states (corrected) |
Designated state(s): DE ES FR GB IT NL |
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17Q | First examination report despatched |
Effective date: 20050117 |
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RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
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18R | Application refused |
Effective date: 20060410 |