EP1511797A2 - Additif de nucleation beta hautement actif pour polypropylene - Google Patents

Additif de nucleation beta hautement actif pour polypropylene

Info

Publication number
EP1511797A2
EP1511797A2 EP03732345A EP03732345A EP1511797A2 EP 1511797 A2 EP1511797 A2 EP 1511797A2 EP 03732345 A EP03732345 A EP 03732345A EP 03732345 A EP03732345 A EP 03732345A EP 1511797 A2 EP1511797 A2 EP 1511797A2
Authority
EP
European Patent Office
Prior art keywords
polypropylene
iron oxide
melt
crystalline
temperature
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
Application number
EP03732345A
Other languages
German (de)
English (en)
Inventor
Detlef Busch
Petra HÄDE
Bertram Schmitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Treofan Germany GmbH and Co KG
Original Assignee
Treofan Germany GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Treofan Germany GmbH and Co KG filed Critical Treofan Germany GmbH and Co KG
Publication of EP1511797A2 publication Critical patent/EP1511797A2/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2268—Ferrous oxide (FeO)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to a method for increasing the proportion of the ⁇ -crystal modification in polypropylene.
  • the ⁇ , ⁇ , and ⁇ phases are known from polypropylene.
  • the ⁇ -crystalline PP When polypropylene melts cool down, the ⁇ -crystalline PP usually forms predominantly. A certain amount of ⁇ -crystalline phase can be generated by a certain temperature control when cooling a polypropylene melt. The proportion of ⁇ -crystalline PP produced in this way is less than 10%.
  • the hexagonal ⁇ -modification of the PP is distinguished from the monoclinic ⁇ -modification by better mechanical properties, in particular increased impact resistance and stress crack resistance.
  • the ⁇ -modification of polypropylene at 148-150 ° C has a significantly lower melting point compared to the ⁇ -modification with a melting point of 160 ° C.
  • ß-crystalline PP therefore has a favorable effect on certain usage properties of polypropylene in some applications.
  • some additives have been developed in the past which lead to even higher proportions of polypropylene in the ⁇ modification and are therefore generally referred to as ⁇ nucleators or ⁇ nucleating agents.
  • the ⁇ -quinacridone dye is described in German patent 1188278 as a ⁇ -nucleator with high activity.
  • the dye dihydroquinacridine is patented in German patent 344359 due to its ⁇ -nucleating effect.
  • the disadvantage of this nucleating agent is the intense red color and the lack of thermal stability, which often leads to decomposition of the nucleating agent and thus to a loss of its activity when compounding.
  • US Patent 3540979 the calcium salt of phthalic acid is considered to be thermally stable Nucleating agents described.
  • the disadvantage of this nucleating agent is the low activity.
  • the percentage of ß-crystalline PP thus obtained is at most 70% (K-0.5-0.7).
  • DE 3610644 describes a two-component nucleation system consisting of calcium carbonate and organic dicarboxylic acids. In practice, however, this nucleation system shows a fluctuating activity. Therefore, there is a lack of reproducibility.
  • the direct use of the calcium salts of the dicarboxylic acids described in DE 3610644 is described in patent DE 4420989.
  • EP-0557721 describes the ⁇ -nucleating effect of various dicarboxamides, in particular N, N-dicyclohexyl-2,6-naphthalene dicarboxamides. Disadvantages of this nucleator are the high cost of the starting material and complicated synthetic steps in the production.
  • the object of the present invention was to provide a process for producing ⁇ -crystalline polypropylene. This process is said to be able to reproducibly and reliably achieve high proportions of ⁇ . The process should be simple and efficient to carry out. Modification with a ß-nucleating agent must not impair the usual important properties of use of polypropylene.
  • This object is achieved by processes for producing a polypropylene mixture with an increased proportion of ⁇ -crystalline polypropylene, in which a polypropylene mixture of nanoscale iron oxide and polypropylene is melted at a temperature of at least 150 ° C. and then cooled in such a way that the cooled polypropylene melt has an increased proportion of ß-crystalline polypropylene.
  • the present invention is based on the discovery that nanoscale iron oxides cool down a PP melt containing these iron oxides to form a lead to a high proportion of ß-crystalline polypropylene.
  • the cooled melt with a high proportion of ß forms a transparent PP matrix, since the particle size of the nanoscale iron oxides is significantly smaller than the wavelength of visible light.
  • Nanoscale iron oxides generally have an average particle size of 1 to 50 nm.
  • iron (II) and iron (III) oxides are particularly suitable as ⁇ -nucleating iron oxides.
  • those iron oxides with a cubically densest spherical packing are particularly suitable, in which the O 2 " ions form a cubic lattice in which the Fe 3+ ions are randomly distributed over the octahedral and tetrahedral gaps (Fe 2 0 3 ) or in the case of mixed oxides (Fe 3 0 4 ) which occupy Fe 2+ the octahedral gaps and Fe 3+ the tetrahedral gaps
  • nanoscale magnetite and nanoscale maghemite have proven to be particularly effective ß-nucleating agents in polypropylene.
  • the iron oxide powders can be added by adding surface-active substances, e.g. can be hydrophobized with higher-quality carboxylic acids, silanes, amines or sulfonates.
  • surface-active substances e.g. can be hydrophobized with higher-quality carboxylic acids, silanes, amines or sulfonates.
  • Such methods are known per se in the prior art, for example in Macromol. Mater. Closely. 275, 8-17 (2000) and in GAK 5/1988 volume 41, page 211 ff or Macromol. Rapid Commun, 2001, 22, 176-180.
  • Particularly preferred coatings of the nanoscale iron oxides consist of long-chain fatty acids, such as oleic acid or stearic acid.
  • nanocrystalline iron oxides can be carried out using conventional methods known per se, such as, for example, the sol-gel process, flame pyrolysis, EDOC or precipitation reactions. According to these processes, nanoscale iron oxides with a particle size in the range from 1 to 50 nm, preferably 5 to 30nm, in particular 10 to 20nm can be produced. Precipitation from brines containing Fe 2+ and / or Fe 3+ ions by addition of alkali is particularly suitable (Nouveau Journal De Chimie, Vol. 7, N ° 5-1983, p. 325).
  • the nanocrystalline iron oxides can optionally be subjected to a hydrothermal after-treatment step in order to increase the crystallinity by keeping the freshly precipitated nanoscale iron oxides for a certain time at elevated pressure and elevated temperature.
  • nanoscale iron oxides described above are incorporated into the polypropylene matrix using customary methods.
  • mechanical premixes are produced from propylene granules and the nanoscale iron powder and then compounded in a twin-screw extruder.
  • Such methods for compounding nanoscale additives are, for example, in Macromol. Rapid Commun, 2001, 22, 176-180. These methods are also suitable for the production of compounds for the present invention.
  • the mixture of polypropylene and nanoscale iron oxide generally contains at least 85% by weight, preferably 90 to ⁇ 100% by weight, in particular 98 to ⁇ 100% by weight, of a polypropylene.
  • the propylene polymer contains at least 90% by weight, preferably 94 to 100% by weight, in particular 98 to 100% by weight, of propylene.
  • the corresponding comonomer content of at most 10% by weight or 0 to 6% by weight or 0 to 2% by weight, if present, generally consists of ethylene and / or butylene. The percentages by weight relate to the propylene polymer.
  • Suitable copolymers which contain ethylene and / or butylene as comonomer are statistical copolymers or block copolymers.
  • Isotactic propylene homopolymers having a melting point of 140 to 170 ° C., preferably 155 to 165 ° C., and a melt flow index (measurement DIN 53735 at 21.6 N load and 230 ° C.) of 1.0 to 50 g / 10 min are preferred , preferably from 1.5 to 20 g / 10 min.
  • the n-heptane-soluble fraction of the polymer is generally 1 to 10% by weight, preferably 2-5% by weight, based on the starting polymer.
  • the molecular weight distribution of the propylene polymer can vary.
  • the ratio of the weight average M w to the number average M n is generally from 1 to 15, preferably from 2 to 10, very particularly preferably from 2 to 6.
  • Such a narrow molecular weight distribution of the propylene homopolymer is achieved, for example, by its peroxidic degradation or by the preparation of the polypropylene using suitable metallocene catalysts.
  • the polypropylene used in the base layer is highly isotactic.
  • the chain isotaxy index of the n-heptane-insoluble portion of the polypropylene determined by means of 13 C-NMR spectroscopy, is at least 95%, preferably 96 to 99%.
  • a mixture of polypropylene and nanoscale iron oxide is first melted at suitable temperatures. This temperature is generally in the range of 150 to 165 ° C.
  • the melting is preferably carried out in a suitable extruder, for example in a twin-screw extruder, which at the same time ensures good mixing of the nanoscale iron oxide in the polypropylene.
  • the melted mixture is extruded and cooled at suitable temperatures.
  • the mixture is produced in other process variants or the compound as described above in a preceding step. These compounds are then used together with pure polypropylene in the process according to the invention.
  • the compounds can be melted in any extrusion tool or in a kneader and mixed with polypropylene. It is essential to the invention that after the extrusion the iron oxide-containing melt is cooled in such a way that the ⁇ -nucleating effect of the nanoscale iron oxides comes into play. For this purpose, it is preferred to cool the melt slowly at a temperature in a range from 60 to 130 ° C., preferably at 80 to 125 ° C. The closer this temperature is to the crystallization temperature of the ß-crystalline polypropylene (approx. 139 ° C), the more favorable the conditions for the formation of the ß-crystalline modification.
  • ⁇ -polypropylene can be generated by the selection of the temperature during cooling.
  • the dwell time of the cooling melt at the respective temperature has an influence on the ß fraction achieved.
  • the melt should be slowly cooled at higher temperatures (120-130 ° C), the necessary dwell time at the given temperature depending on the shape during extrusion.
  • ß-nucleating iron oxides have a positive effect in these cases, since the cooling rate can be increased, i.e. faster take-off speeds can be used.
  • DSC method DSC measurements (method described below) of isotactic polypropylene with 1% by weight of nanoscale iron oxide accounted for ß-crystalline polypropylene of 92%.
  • the method according to the invention can advantageously be used in the production of films, moldings, in particular tubes and hoses, fibers and other extrusions.
  • the increased ⁇ -content in polypropylene has a favorable effect in a wide variety of extrusion applications, for example because the extrusion temperatures can be reduced.
  • an increased proportion of ß-crystalline polypropylene is advantageous since this improves the properties of the polypropylene, e.g. one achieves a higher notched impact strength and stress crack resistance of the polypropylene.
  • the high proportion of ⁇ in polypropylene is used for the production of porous films by converting the ⁇ -modification into the alpha modification when stretching films or for producing rough surfaces of a stretched film.
  • nanoscale iron oxide and polypropylene are mixed and melted in an extruder at a temperature of at least 150 ° C.
  • the melt is extruded through a flat die and cooled and solidified into a pre-film in such a way that the desired proportion of ⁇ -crystalline polypropylene is formed in the pre-film.
  • a proportion of at least 40%, preferably 60 to 80%, of ⁇ -polypropylene (measured according to DSC) in the prefilm is generally sought, whereas smaller proportions of, for example, 10 to 40% are sufficient to produce surface roughness could be.
  • the pre-film is then heated in a manner known per se and stretched in the longitudinal direction, preferably at a temperature less than 140 ° C., preferably 90 to 125 ° C. and with a stretch factor of 3: 1 to 5: 1.
  • the longitudinally stretched film is heated again and stretched in the transverse direction, preferably at a temperature greater than 140 ° C. from 145 to 160 ° C. and with a Stretch ratio from 3: 1 to 6: 1.
  • the selected temperature during stretching converts the ß-crystalline polypropylene of the pre-film into the alpha modification of the polypropylene and, depending on the process conditions, creates a continuous porous network structure in the film or at least a surface roughness due to crater-like depressions that arise during the conversion processes.
  • Two methods can be used to determine the ⁇ -crystalline content in polypropylene which can be achieved by means of the method according to the invention.
  • the ß component can be determined by means of DSC and on the other hand by means of wide-angle X-ray scattering.
  • Heating rate from 20 ° C / min to 220 ° C and melted (1st heating).
  • Heating is determined from the ratio of the enthalpies of fusion of the ß-crystalline phase (H ß ) to the sum of the enthalpies of fusion of ß- and ⁇ -crystalline phases (H ß + H ⁇ ) the degree of crystallinity K ß , D sc.
  • Kß, X- ay [kßi] / [k ß1 ] / [k ß ⁇ + (k ⁇ ⁇ + k ⁇ 2 + k chair3)]
  • K ß , ⁇ - Ra y is the ß component, ß ⁇ the height of the peak of the ß phase and k administrat ⁇ , k ⁇ , k ⁇ the height of the three peaks of the ⁇ phase.
  • X-ray wide-angle scattering always has a higher ⁇ component than found using the DSC method.
  • a nanocrystalline iron oxide (Fe304) was compounded into an isotactic polypropylene in a ZSK 30 twin-screw extruder at a temperature of 200 ° C.
  • the polypropylene was an isotactic homopolymer with a melting point of 162 ° C and an MFI of ... (Exxon Escorene PP 4352 F1).
  • the nanocrystalline iron oxide had an average particle size of 13 nm. It was magnetite, which had a characteristic black color. An amount of 3% by weight of the iron oxide was incorporated into the polypropylene.
  • Example 2 A nanocomposite was produced as described in Example 1. In contrast to Example 1, the nanoscale iron oxide was surface-modified before compounding with stearic acid and the concentration of magnetite was reduced from 3 to 1% by weight.
  • a nanocomposite was produced as described in Example 2.
  • the nanoscale iron oxide was subjected to a hydrothermal after-treatment before the surface modification with stearic acid and the concentration was increased from 1 to 2% by weight.
  • the respective ⁇ -proportion of the nanocomposites according to Examples 1 to 3 was determined as described using DSC from the 2nd heating curve.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé permettant d'augmenter la proportion de la modification cristalline ß du polypropylène par l'incorporation de substances nanocristallines. Avec ce procédé, on obtient une proportion ß de 50-100 %. Ces composés se caractérisent par des propriétés mécaniques améliorées. Les poudres nanocristallines peuvent être soit directement incorporées soit compatibilisées avec des substances tensioactives pour une meilleure dispersion dans la matrice PP.
EP03732345A 2002-05-14 2003-05-12 Additif de nucleation beta hautement actif pour polypropylene Ceased EP1511797A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10221310A DE10221310A1 (de) 2002-05-14 2002-05-14 Hochaktives beta-Nukleierungsadditiv für Polypropylen
DE10221310 2002-05-14
PCT/EP2003/004931 WO2003094832A2 (fr) 2002-05-14 2003-05-12 ADDITIF DE NUCLEATION β HAUTEMENT ACTIF POUR POLYPROPYLENE

Publications (1)

Publication Number Publication Date
EP1511797A2 true EP1511797A2 (fr) 2005-03-09

Family

ID=29413782

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03732345A Ceased EP1511797A2 (fr) 2002-05-14 2003-05-12 Additif de nucleation beta hautement actif pour polypropylene

Country Status (7)

Country Link
US (1) US6992128B2 (fr)
EP (1) EP1511797A2 (fr)
JP (1) JP4332110B2 (fr)
CN (1) CN1274745C (fr)
AU (1) AU2003240222A1 (fr)
DE (1) DE10221310A1 (fr)
WO (1) WO2003094832A2 (fr)

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Also Published As

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CN1653122A (zh) 2005-08-10
AU2003240222A1 (en) 2003-11-11
DE10221310A1 (de) 2003-12-11
WO2003094832A2 (fr) 2003-11-20
JP2005525444A (ja) 2005-08-25
CN1274745C (zh) 2006-09-13
JP4332110B2 (ja) 2009-09-16
AU2003240222A8 (en) 2003-11-11
US6992128B2 (en) 2006-01-31
US20050182175A1 (en) 2005-08-18
WO2003094832A3 (fr) 2004-07-22

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