EP2129720A1 - Procédé de production de mélanges polymères - Google Patents

Procédé de production de mélanges polymères

Info

Publication number
EP2129720A1
EP2129720A1 EP08714774A EP08714774A EP2129720A1 EP 2129720 A1 EP2129720 A1 EP 2129720A1 EP 08714774 A EP08714774 A EP 08714774A EP 08714774 A EP08714774 A EP 08714774A EP 2129720 A1 EP2129720 A1 EP 2129720A1
Authority
EP
European Patent Office
Prior art keywords
polymer
synthesized
polymers
reactor
post
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.)
Withdrawn
Application number
EP08714774A
Other languages
German (de)
English (en)
Inventor
Rolf Müller
Federico Innerebner
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.)
Innogel AG
Original Assignee
Innogel AG
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 Innogel AG filed Critical Innogel AG
Publication of EP2129720A1 publication Critical patent/EP2129720A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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

Definitions

  • the good mechanical properties of polymers are a consequence of the fact that the polymers are very long molecules.
  • Various properties such as strength, toughness and abrasion resistance typically increase with the length of the polymers and thus with their molecular weight.
  • the viscosity of polymer melts increases significantly with their molecular weight, so that the processability of the high-viscosity polymer melts is becoming increasingly difficult. For this reason, broad and bimodal or multimodal molecular weight distributions have been developed using appropriate synthesis, combining the advantages of high and low molecular weight polymers.
  • a broad molecular weight distribution of PE typically begins at about 10 1 OOO and ends slightly below 10'OOOOOO, wherein the weight average in the range 1 100 to 1 OOO 1 OOOO located.
  • the effort is greater than simple molecular weight distributions in all cases, so that polymers with optimized molecular weight distributions mean additional costs. Difficulties in the preparation of broad molecular weight distributions increase with their breadth.
  • the market offers a variety of substances, in particular of additives, which the flowability and thus the processing behavior of polymers can be improved.
  • additives such as fatty acid derivatives
  • these additives often have in addition to the additional costs also a negative impact on the final product and the plastic processor must evaluate various such additives on their suitability, which means a greater effort.
  • the present invention describes a technology whereby the flow properties of polymer melts can be markedly improved, whereby the end product is not impaired, and complicated and expensive syntheses can be avoided.
  • an independently prepared short-chain polymer P2 is mixed in a proportion of typically up to a few%, whereby various methods can be used. It is essential that the ready-prepared polymer P1 already contains the short-chain polymer P2. Frequently, a synthesized polymer is homogenized in the course of the treatment in the melt phase, so that this processing step can be used to mix in a short-chain polymer and to homogenize it with the long-chain polymer. The granules obtained therefrom then contain the short chain polymer and have markedly improved flow properties so that processing to final products, such as by extrusion or injection molding, is facilitated, e.g. by speeding up and optimizing the corresponding procedures.
  • novel short-chain polymers are similar in price to analogous long-chain polymers prepared in a simple manner and an additional processing step is not absolutely necessary for the combination of the two polymers, it is thus possible to obtain polymers having improved flow properties with an advantageous price / performance ratio to obtain.
  • the combination of improved flow properties with unchanged or even improved properties of the final product is obtained when the short-chain polymer P2 is compatible with the long-chain polymer P1.
  • Compatibility means that the two polymers are soluble in each other and in particular can crystallize together.
  • the polymer P2 participates in the semi-crystalline network formed by the polymer P1.
  • the number of connections between crystallites is somewhat reduced when a proportion of long-chain polymer is replaced with a short-chain polymer, the toughness theoretically decreasing somewhat, but the modulus of elasticity and the yield strength actually increasing due to the increased crystalline content.
  • the expected reduction in toughness is either low or non-existent in practice, as the tensions frozen in the final product are reduced due to the improved flow properties and thereby possible lower processing temperatures.
  • the thus advantageous short-chain polymers do not necessarily have to be mixed with the polymer products already by the polymer manufacturer; this could also be done by the processors of the polymer products.
  • the mixing process already takes place centrally at the polymer manufacturer. There is no need for transport routes and intermediate trade, and it can be guaranteed that the mixture of polymer P1 and P2 is homogeneous, while otherwise the homogeneous mixture of the two polymers is not always possible with the equipment used by the processors, or only about 1 wt. % of polymer P1 a polymer P2 can be added sufficiently homogeneous.
  • the preparation of the mixture of polymer P1 and P2 centrally and directly by the polymer manufacturer also has the advantage that the better flowability can already be used there to optimize the preparation of synthesized polymer.
  • the preparation in particular the homogenization of the polymer, is facilitated by a proportion of short-chain polymer.
  • Development in processing equipment, which are typically extruders, is tending towards higher and higher throughput rates, currently around 70t / h, for polyolefins for cost optimization.
  • Limiting factors here are the high temperatures, temperature peaks and pressures resulting from the high-viscosity material with massive energy input, as a result of which the polymer can be damaged and technical problems arise, for example with the screen changer. Due to an improved flowability of the polymer, existing limits can be overcome and thus also costs can be saved. In view of the dimensions, throughput increases of only a few% are of great importance, all the more so since the product obtained with improved quality means a further added value.
  • the polymers P1 used, the short-chain polymers P2 and the combination of the two components and their processing have to meet certain conditions which are described below. Both logistical and material-technical aspects are used.
  • the addition of polymer P2 to polymer P1 occurs during the synthesis of polymer P1 or at a time in the subsequent processing, in particular in the homogenization of polymer P1, so that the finished product already contains the polymer P2.
  • the polymer P2 is contained therein and is thus converted into a final product by the processor receiving the polymer P1 + P2.
  • the polymer P1 may be any polymer. It is selected, for example, from the following group: polyolefins, in particular polyols of monomers having 2 to 10 C atoms, PE, in particular UHMWPE, HMWPE, HDPE, LDPE, LLDPE, VLDPE 1 PP, in particular isot. PP, syndiot. PP 1 atact. PP, PE-PP copolymers, PE copolymers, PP-PE copolymers, PP copolymers, PVA, PVC, PC, PA 1 PU, ABS, PS, SAN, POM, CA, PMMA, PPE, PPS, PSO, PTFE, PET , PBT.
  • polyolefins in particular polyols of monomers having 2 to 10 C atoms
  • PE in particular UHMWPE, HMWPE, HDPE, LDPE, LLDPE, VLDPE 1 PP, in particular isot. PP, syndiot. PP
  • the polyolefins are the most important group of substances.
  • P1 can also be a mixture of different types from the same plastic class, eg different PE types or different PP types.
  • the copolymers derived from the cited plastic classes and types (with a proportion of a second monomer type) and terpolymers (with a proportion of a second and third monomer type) and higher copolymers (with more than 3 monomer types) are also suitable wherein the additional monomers may be arranged randomly and / or in block form.
  • the proportion of additional monomers in wt.% Is ⁇ 40, preferably ⁇ 20, more preferably ⁇ 10, most preferably ⁇ 5, when used as the polymer P2 compatible with the predominant monomers of P1 polymer is, the proportion of copolymer in wt.% ⁇ 20, preferably ⁇ 15, more preferably ⁇ 10, most preferably ⁇ 5, wherein the monomers of the copolymer portion of polymer P1 and P2 need not be identical, but preferably identical.
  • the proportion of such additional monomers in weight percent is ⁇ 50, preferably ⁇ 30, more preferably ⁇ 20 , most preferably ⁇ 10, when the polymer P2 is a polymer compatible with the predominant monomers of P1, the copolymer content of which is% by weight ⁇ 20, preferably ⁇ 15, more preferably ⁇ 10, most preferably ⁇ 5 the monomers of the copolymer portion of polymer P1 and P2 need not be identical, but are preferably identical.
  • the polymer P1 is at least partially crystalline.
  • the crystalline fraction in% by weight is> 3, preferably> 5, more preferably> 7, most preferably> 10, the crystalline fraction being determined by means of density measurement according to the prior art.
  • the MFI of polymer P1 measured at standard temperature in g / 10min at 2.16kg is ⁇ 200, preferably ⁇ 50, more preferably ⁇ 35, most preferably ⁇ 20, since with increasing MFI of P1 the MFI is increased by addition of polymer P2 achievable relative improvement in the flow properties of the mixture M decreases, while the costs remain approximately the same.
  • the lower limit for the MFI of P1 in a preferred embodiment is> 0.005, preferably> 0.01, more preferably> 0.05, most preferably> 0.1, since with decreasing MFI of P1, homogenization with P2 becomes difficult.
  • the standard temperature is 19O 0 C.
  • the temperature is about 20-40 0 C above the melting point typical for the polymer.
  • the weight average molecular weight Mw in g / mol of P1 is> 20 1 000. In a preferred embodiment, this molecular weight> 30 1 OOO, preferably> 50o00, more preferably> 70 1 OOO, at Rushzugtesten> 90O00.
  • the upper limit for the molecular weight Mw for polymer P1 is given by the plasticizability and is ⁇ 6OOO 1 OOO. In a preferred embodiment, this limit is ⁇ 5 1 1 OOO OOO, more preferably ⁇ 4O00O00, Rushzugtesten on at ⁇ 3,000 1 OOO.
  • the number average molecular weight Mn in g / mol of P1 is> 20 1 OOO. In a preferred embodiment, this molecular weight is> 30 1 000, more preferably> 40 1 000, more preferably> 50 1 000, most preferably> 70O00.
  • the weight fraction of polymer P1 having a molecular weight of ⁇ 10'000 is less than 40%, preferably less than 30%, more preferably less than 20%. , most preferably less than 10%.
  • the viscosity of the short-chain polymer P2 in mPas is ⁇ 10 1 000.
  • this viscosity is ⁇ 5'00O, preferably ⁇ 3 1 OOO, preferably ⁇ 1000, preferably ⁇ 500, preferably ⁇ 200, more preferably ⁇ 160, Elliszugtesten on at ⁇ 100.
  • the deeper this viscosity the greater the effect of improving the flow properties. Therefore, the viscosity of the polymer P2 can also be well below 100mPas, eg at 50 or 10mPas.
  • the lower limit of the viscosity of P2, when P1 is a semi-crystalline polymer and P1 and P2 can co-crystallize, is in mPas> 0.1, preferably> 0.5, more preferably> 1, most preferably> 2.
  • the reason for the lower limit lies in the fact that in P2 with too low viscosities, ie with too low molecular weight, the final properties in the final product can be affected.
  • the viscosity of P2 is measured at a temperature of about 10 ° C. above the melting point of the associated long-chain polymer P1. For short-chain PE this temperature is 140-150 °, for short-chain PP at 170-180 0 C.
  • the lower limit for the viscosity of P2 in mPas is> 1, preferably> 3, more preferably> 6, most preferably> 10, since the polymers P2 Increasing viscosity become heavier and less migrate.
  • the polymer P2 is predominantly linear, preferably completely linear, and has at least one block of> 10, preferably> 14, more preferably> 17, most preferably> 20 identical monomer units M2. In most cases, P2 consists exclusively of monomer units M2. The definition of monomer units is generally clear. For PE, a unit with 2 C atoms is understood as a monomer unit, both for short-chain and long-chain PE.
  • viscosity is expected to increase with Mw, the weight average molecular weight.
  • Mw the weight average molecular weight.
  • the viscosity is at significantly lower levels in comparison with linear polymers with the same Mw.
  • the polymer P2 has a branched, in particular hyperbranched, structure, most preferably a spheroidal shape. Then it is possible to obtain a low melt viscosity with comparatively heavy polymers P2 which may migrate little or no and have a positive impact on toughness.
  • polydispersity PD Mw / Mn of ⁇ 10, preferably ⁇ 5, more preferably ⁇ 3, most preferably ⁇ 2.
  • the vapor pressure in mbar at 25O 0 C of polymer P2 is ⁇ 100, preferably ⁇ 30, preferably ⁇ 10, preferably ⁇ 1, more preferably ⁇ 0.1, most preferably ⁇ 0.01. This ensures that during processing and processing of melts containing polymer P2, a vacuum can be applied without the polymer P2 is thereby withdrawn from the melt.
  • the short-chain polymer P2 can in principle be any polymer and is selected, for example, from the following group: short-chain PE, PVA, PVC, PC, PA, PU, ABS, PS, SAN, POM, CA, PMMA, PPE, PPS, PSO, PTFE, PET, PBT. They are prepared, for example, by degradation (e.g., thermal, metal-catalyzed) from the corresponding long-chain polymers, or synthesized a priori in short chain form, with various polymerization systems being available according to the prior art. Short chain polymers P2 may also be mixtures of different types of P2 from the same class of plastic, e.g. different types of PE waxes.
  • Short chain PEs are widely available on the market, for example selected from: n-alkanes C n H 2 n + 2 l isoalkanes C n ; cyclic alkanes C n Hk n ; Polyethylene waxes; Paraffins and paraffin waxes of mineral origin such as macrocrystalline, intermediate or microcrystalline paraffins, brittle, ductile, elastic or plastic microcrystalline paraffins; Paraffins and paraffin waxes of synthetic origin. Preference is given to PE waxes, Fischer-Tropsch waxes and hyperbranched polyolefins.
  • PE waxes examples are the Polywax products from Baker Petrolight, see Table 1.
  • PE and PP waxes are obtained by synthesis by means of polymerization, for example by Ziegler Natta polymerization, Philip's polymerization (chromium oxide catalysts), free-radical polymerization, metallocene polymerization, metalloid polymerization being particularly preferred.
  • polymer P1 and P2 must be compatible.
  • Compatibility means that P1 has at least one block with> 10 monomer units M1 and P2 at least one block with> 10 monomer units M2, where M1 is identical to M2.
  • P1 is a semi-crystalline polymer
  • compatibility between P1 and P2 means that both polymers can crystallize together. If the polymers P2 are incorporated in crystallites with P1, their migration is prevented and they can make a useful contribution to the mechanical properties.
  • P2 in the form of hyperbranched or hyperbranched or spheroidal short-chain polymers compatibility but not co-crystallization of P1 and P2 is mandatory and migration is prevented by a higher molecular weight of the spheroidal polymers. If polymer P1 is completely or predominantly amorphous, P2 of higher molecular weight may also be used to prevent migration. The condition of compatibility also allows a good miscibility of P1 and P2 in this case.
  • the proportion of polymer P2 in% by weight based on polymer P2 and polymer P1 is generally> 0.1, preferably> 0.2, more preferably> 0.3, most preferably> 0.4 or at ⁇ 25, preferably ⁇ 19, more preferably ⁇ 15, most preferably ⁇ 11.
  • the upper limit of this fraction is ⁇ H, preferably ⁇ G, more preferably ⁇ F, most preferably ⁇ E.
  • the lower limit of this fraction is> A, preferably> B, more preferably> C, most preferably> D.
  • a to H depend on the viscosity of polymer P2 and are listed in Table 2 for a wide range of viscosities.
  • the values of the limits for unrecognized viscosities are obtained by linear interpolation or extrapolation.
  • the limits given for each viscosity of polymer P2 reflect the situation that as the viscosity of P2 decreases, its efficiency in improving the flow properties increases, that is, less is needed, while for larger proportions the toughness of P1 + P2 can be compromised.
  • the difference in the crystallization temperatures of polymer P1 and polymer P2 is ⁇ 37 ° C, these crystallization temperatures are measured as onset temperatures by means of DSC at a cooling rate of 20 ° C / min.
  • this difference in the crystallization temperatures in 0 C is ⁇ 30, preferably ⁇ 20, more preferably ⁇ 15, preferably It is preferable that the crystallization temperature of P1 is higher than the crystallization temperature of P2.
  • HDPE injection molding type with MFI of 9.4g / 10min at 19O 0 C and 2.16kg
  • PW Polywax types from Baker Petrolight
  • Table 4 lists some useful combinations of polymer P1 and polymer P2.
  • wax is here understood in each case a corresponding short-chain polymer.
  • the MFI of the mixture of polymer P1 with 7% by weight of polymer P2 is increased by a factor of> 1.1, preferably of> 1.2, more preferably of> 1.3, most preferably of> 1.5.
  • the effect is the more pronounced the lower the MFI of Polymer P1 is.
  • An upper limit is a factor of about 6, especially 5, most especially 4.5. At lower or higher levels of P1 linear interpolation or extrapolation is performed.
  • Burn marks that may occur during injection molding are reduced or eliminated.
  • Masterbatches can be homogenized more easily, as well as pigments, whereby also an improved wetting behavior is observed.
  • Fillers may e.g. Talc, minerals, fibers, carbon, wood, etc., and these fillers each increase the viscosity, which suffers the processability of the filler-enriched polymers.
  • the use of mixtures of polymer P1 and P2 also allows a simpler and faster processing, whereby here, too, the improved wetting behavior of the polymer melt plays a role.
  • higher quantities are possible and thermally sensitive fillers such as wood and natural fibers can be processed.
  • Mixtures of polymer P1 and P2 can in principle be used advantageously in all plastic processing methods, e.g. Injection molding, blow molding, roto molding, film blowing, calendering, compounding, especially in the production of polymer blends and masterbatches, in the extrusion of films and profiles, in each case an increased productivity and / or a reduced energy consumption is obtained.
  • the extent of the advantage is process and machine dependent.
  • a process acceleration in% relating to the throughput of> 3, preferably> 5, more preferably 7, most preferably> 10 is generally obtained.
  • An increase in productivity of 10 to 30% is typical, with even better or slightly less good results, as the case may be. Very good is the process acceleration in the injection molding area where the process acceleration is typically in the range of 15 to 35%.
  • the modulus and / or strength of the mixture of polymer P1 with 7% polymer P2 is increased by a factor of> 1.03, preferably> 1.05, more preferably> 1.07, most preferably> 1.10. The effect is the more pronounced the lower the crystalline content of P1 is.
  • An upper limit is a factor of about 2, in particular of 1.85, in particular of 1.7.
  • the polymer P2 can basically
  • the polymer P2 in particulate form, or molten state, as a coherent melt or spray, wherein the polymer P2 is preferably supplied along with the additives normally required for the polymer P2. In this case, the dispersing of the additives by the polymer P2 is facilitated.
  • polymers are synthesized in the form of particles, powders or fine granules such as HDPE, LLDPE, PP. These powders are either plasticized directly in an extruder or kneader, homogenized and pelletized, or intermediate steps are used where, for example, monomers are removed and / or catalysts are deactivated.
  • the polymer P2 can be any polymer P2.
  • the polymer P2 is preferably used with a particle size which is comparable to the particle size of the powder of polymer P1. Since mixing typically takes place in the reactor and in the intermediate steps, the incorporation of polymer P2 does not require a fundamental change in the processes. The homogenization of polymer P2 with P1 at the molecular level then takes place during the plasticization and homogenization.
  • the advantage of the first two variants is that the plasticization and homogenization makes it unnecessary to supply polymer P2.
  • additives are already supplied in the reactor or in one of the intermediate steps, so that this possibility can be combined with the feeding of polymer P2.
  • ⁇ can also be used in powdery blend of polymer P2 with additives.
  • the sub-variant of A wherein the entire portion of polymer P2 is fed together with the polymer P1 to the preparation extruder (here, as with all dosages on the extruder is advantageously metered constant time, when polymer P1 and P2 are wholly or partially dosed together, they are preferred is metered into the extruder in at least partially mixed state), is particularly suitable for small amounts of P2 in the range in% by weight to 5, preferably 4, most preferably 3 and in particular for production lines, where additives are also fed together with polymer P1 to the extruder , Since the extrusion is almost completely adiabatic, the plasticization is achieved exclusively by mechanical energy input.
  • the plasticization of P1 is less affected by this, as shown by tests on smaller adiabatic systems.
  • the polymer P2 has a significantly lower melting point or melting range than the polymer P1
  • powders have a large surface area and are often porous, this problem arises only with relatively high proportions of polymer P2.
  • this undesirable lubricating effect can be at least partially inhibited if a polymer P2 is used whose melting point is similar to the melting point of polymer P1, or higher.
  • the sub-variant of A is used, after which optionally a first part is supplied together with polymer P1 and at least one further part at least at a later time of extrusion, preferably the remaining Part or the entire portion is fed at a later date.
  • a first part is supplied together with polymer P1 and at least one further part at least at a later time of extrusion, preferably the remaining Part or the entire portion is fed at a later date.
  • Subvision B is e.g. used when in the preparation of polymer P1, the additives are supplied at a later time than polymer P1, for example via a side extruder, or if the plasticization of the polymer P1 represents the bottleneck of the treatment.
  • polymer P1 is sprayed with polymer P2 before the post-reactor extrusion.
  • the homogenization of P1 and P2 is straightforward because the existing extruder configurations are designed to homogenize the polymer P2. Due to the proportion of polymer P2, this homogenization is now facilitated because the viscosity of the melt decreases with increasing homogenization of polymer P1 and P2.
  • polymer P1 and P2 are possible at low levels of P2 to about 2% even with many short and simple single screw extruders with low mixing efficiency, while in plastics processing longer extruders or two sequentially connected extruders are used and twin screw extruder with pronounced mixing action available .
  • the polymer P2 can be supplied in the first extruder, for example together with the polymer P1, or during the first extrusion with a side extruder or a pump, or at the beginning or during the second extrusion with a side extruder or a pump or a combination of these possibilities.
  • the same principles apply here as explained above for the single-stage process.
  • the use of polymer P2 also makes it possible to reduce two-stage treatment plants to single-stage, since the homogenization is substantially facilitated, especially at higher levels of polymer P
  • Various polymers such as LDPE, LLDPE, PP, EVA or PS are synthesized in the form of a melt in the synthesis.
  • the melt is here
  • Variant 1 optionally an additional extrusion for homogenization takes place (two-stage process), while in Variant 2 all process steps including homogenization with a single screw extruder with Maillefer screw geometry and about 24D and D from 300 to about 600mm, speeds from 80 to about 160 / min, outputs from 800 to about 4000kW and output rates from 4 to about 30to / h or with a close-meshed co-rotating twin screw extruder of about 21 D and D from 170 to about 350mm, speeds from 200 to 350 / min, powers from 600 to about 320OkW and discharge rates of 5 to about 35to / h are carried out (one-step process). Monomers are removed by degassing.
  • polymer P2 Compared to the powder process, the admixture of polymer P2 is facilitated insofar as the polymer P1 is already present in the form of a melt, that is, plasticization does not take place.
  • the polymer P2 can in principle be supplied in one or more steps at any time during the treatment, which is preferably carried out immediately after the synthesis, in particular even before the extrusion or melt pump, in particulate form, for example via an extruder or in a molten state Shape by means of a pump.
  • polymer P2 is supplied together with the additives and the already existing installations such as side extruders and / or pumps are used.
  • the polymer P2 can be metered into the single-screw extruder, for example, preferably in one of the first zones, in particular in front of the mixing part.
  • the incorporation of polymer P2 also improves the mixing effect and gives a better homogenised material, so that if the second stage is unnecessary for homogenization.
  • the polymer P2 can also be fed to the homogenization extruder, again preferably in one of the first zones.
  • the polymer P2 is preferably supplied in one of the first zones and allows additionally improved homogenization, as well as a gentler process at lower temperatures and pressures or an optimized process with improved throughput.
  • a degassing is carried out in one of the variants, it is possible to initiate the polymer P2 after this degassing, if the polymer P2 is significantly removed at the vacuum used, but preferably a polymer P2 is used with sufficiently low vapor pressure at the current mass temperature.
  • originating from solution polymers such as PE or LLDPE degassing extruders are used with multiple degassing
  • the withdrawal of the solvent is preferably supported with water (water stripping).
  • Throughput rates in the range of 1 to 20 to / h are achieved.
  • the polymer P2 can already be admixed to the solution prior to extrusion and homogeneously distributed here or added together with the solution or in one of the following zones of the extruder.
  • it must be ensured that the vapor pressure at the current temperature is sufficiently low so that the polymer P2 is not appreciably removed together with the solvent during intensive degassing.
  • Corresponding polymers P2 are available. Nevertheless, it is in most cases advantageous to feed the polymer P2 after the last degassing stage, where normally the additives and masterbatches are supplied. In the following extrusion stages, in turn, lower mass temperatures, lower pressures and better homogenization are achieved, while the throughput by means of Polymer P2 can be increased less well, as this is determined primarily by the concentration of the fed into the extruder solution.
  • the processing extruders are typically non-intermeshing counter-rotating twin screw extruders with up to 6OD and D from 150 to about 500mm, speeds of about 60 to 200 / min, outputs from 250 to about 3500 kW and throughputs in the range 1 to about 20to / h, as well as closely intermeshing co-rotating Twin screw extruder with up to 3OD and D from 130 to around 350mm, speeds from about 150 to about 300 / min, powers from 300 to about 2500 kW and throughputs ranging from 1 to about 20to / h used.
  • the work-up step by post-reactor extrusion can be omitted and the corresponding polymers come in powder form, optionally agglomerated in the trade.
  • the powder is a particle size of ⁇ 2 mm. Above it is granules.
  • the polymer P1 can be treated with polymer P2 to a homogeneous mixture, wherein the two particle types are homogeneously mixed at the particle level.
  • the bulk densities and particle sizes of the two polymers should preferably satisfy the following conditions:
  • the difference in bulk density of polymer P1 and polymer P2 in% is ⁇ 50, preferably ⁇ 30, more preferably ⁇ 20, most preferably ⁇ 10.
  • the difference of the average particle size of polymer P1 and polymer P2 in% is ⁇ 50, preferably ⁇ 30, more preferably ⁇ 20, most preferably ⁇ 10.
  • the homogenization at the molecular level is carried out later in the processing of the particulate polymer mixture, this process is much easier compared to the Ho Mogenmaschine of polymer P1 and P2 on processing equipment, if they are in granular form, wherein typically only 1 to at most 2% of polymer P2 can be homogenized.
  • simple processing extruders such as, for example, single-screw extruders, which are frequently used, can still be homogenized in proportions of polymer P2 to about 6% by weight.
  • Mixtures with proportions of polymer P2 in% by weight are preferred ⁇ 5, more preferably ⁇ 4.5, most preferably ⁇ 4.
  • the agglomeration is preferably carried out together with polymer P2, whereby the condition concerning the bulk density of the two components can be dispensed with. It is preferred to use at least partially polymer P2 in the molten state as an agglomerator, it being still possible to homogenize about 1% higher amounts of polymer P2 on simple processing extruders.
  • the post-reactor extrusion processing step may be dispensed with, wherein the powder or granules of polymer P1 are at least partially coated with polymer P2, for example by Polymer P2 is sprayed in liquid form or as a dispersion on the powder or granules, for example in a fluidized bed.
  • the homogenization at the molecular level will be carried out later in the processing of the particulate polymer mixture, which process is also significantly easier compared to the homogenization of polymer P1 and P2 on processing equipment, if these be present in granular form, wherein typically only 1 to at most 2% of polymer P2 can be homogenized.
  • simple processing extruders such as, for example, single-screw extruders with poor mixing action, as frequently used.
  • Shares of polymer P2 to about 4.5 wt.% Still be homogenized, preferably mixtures are used with proportions of polymer P2 in wt.% Of ⁇ 4.0, more preferably of ⁇ 3.7, most preferably ⁇ 3.5.
  • short-chain polymer P2 By mixing the short-chain polymer P2 in the preparation of synthesized polymers with them, compared to the fact that the polymer P2 is mixed by the plastics processors during processing, on the one hand economic advantages for logistical reasons and due to the low prices of polymers P2, resulting in the required huge tonnages. On the other hand, the potential of short-chain polymers can only be optimally and completely implemented since average processing equipment is only able to sufficiently homogenize smaller amounts of such polymers.
  • the extruder had an opening where, where appropriate, polymer P2 could be metered in, in this area the screw was equipped with conveying elements with a gradient of 1.5D. From the middle of the 5th zone until the middle of the 6th zone, the screw was configured over a length of 3 L / D with neutral kneading blocks of 90 ° slope, completed with a recirculating kneading block, as a homogenization area. For the discharge of the pressure build-up with conveying elements with a slope of 1 D was generated. The nozzle used was a strand die with 17 holes a 5 mm. The strands were granulated via a conventional strand granulation system with water bath.
  • polymer P1 For polymer P1 an injection molding HDPE with an MFI of 9.4 g / 10 min in granular form was used and the temperatures of the housing and the nozzle were in 0 C. 180/220/220/200/200/195/205, the screw speed set to 300 / min and the solids metering time constant total to 300kg / h.
  • Polywax 3000, Polywax 1000 and Polywax 500 which give a broad range of advantageous polymers P2 in a homologous series, are used in each case in a proportion of 3 and 5 and 7 wt.%, These short-chain polymers are shown in Table 1 characterized.
  • polymer P2 was metered in via the opening in the 4th zone, thus producing the series of experiments 1.
  • the mass temperature in front of the nozzle of 218 ° C at the reference without polymer P2 was reduced to about 212/211/209 0 C at 3% polymer P2 for Polywax 3000/1000/500, at 5% polymer P2 at 207/205/204 0 C and at 7% polymer P2 to 203/201 / 200 ° C.
  • polymer P2 was metered together with polymer P1 to study the influence of polymer P2 on the plasticization of polymer P1, after a start-up time of 15 minutes the heaters and coolers were turned off to produce adiabatic ratios, i. Simulate large-scale production plants as practically as possible. In this state, the experimental series 2 produced. It was found that at 3% of polymer P2 no plasticization problems occurred, in zone 4, where the melt could be observed through the orifice, a macroscopically homogeneous mass appeared and no unmelted particles of polymer P1 were observed. However, with 5% of polymer P2, Polywax 500 detected some unmelted particles, but at the nozzle, a homogeneous melt was also obtained in this case. At 7%, only Polywax 3000 did not give unmelted particles, but at all times a homogenous melt was obtained at the die.
  • the products were sprayed on various injection molding machines to form various moldings and the cycle times and material properties of the molded parts were examined.
  • the reduction of the cycle times compared to polymer P1 without the proportion of polymer P2 were the same in the test series 1 within the scatter range as in the test series 2 and averaged about 26% on average of the various molded parts with a proportion of polymer P2 of 3%, at around 34% at 5% and at around 37% at 7%, with a decrease in the molecular weight from Polywax 3000 to Polywax 500, a marked increase in cycle time reduction was noted.
  • the properties of the molded parts were unchanged to better within the range of scattering at 3% polymer P1 (higher modulus of elasticity due to higher crystallinity and better toughness due to reduced frozen stresses), compared to the reference without polymer P2, also at 5% polymer P2 Polywax 500, which has been found to reduce to about 5% toughness.
  • Polywax 3000 were unchanged or better than the reference, while polywax 1000 was found to have about 5% and Polywax 500 reduced toughness by about 10%.
  • the injection molding HDPE of the above test series was comminuted into a powder with a mean particle size of 1 mm and with a powder of Polywax 1000 with the same mean particle size in mixed with a tumble mixer, wherein the densities and bulk densities of the two polymers differed by 3 and 8%.
  • the proportion of polymer P2 was 3, 5 and 7%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de production avantageuse de mélanges polymères à répartitions des masses moléculaires spécifiques, présentant une faible quantité de polymère à chaîne courte et une aptitude à la transformation sensiblement améliorée. Selon l'invention, les étapes de préparation se déroulant pendant ou après la synthèse de la majeure partie du mélange polymère sont utilisées pour produire lesdits mélanges.
EP08714774A 2007-03-23 2008-03-20 Procédé de production de mélanges polymères Withdrawn EP2129720A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007014621A DE102007014621A1 (de) 2007-03-23 2007-03-23 Verfahren zur Herstellung von Molekulargewichtsverteilungen mit kurzkettigem Anteil mittels Post-Reaktor Extrusion
PCT/CH2008/000124 WO2008116336A1 (fr) 2007-03-23 2008-03-20 Procédé de production de mélanges polymères

Publications (1)

Publication Number Publication Date
EP2129720A1 true EP2129720A1 (fr) 2009-12-09

Family

ID=39446205

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08714774A Withdrawn EP2129720A1 (fr) 2007-03-23 2008-03-20 Procédé de production de mélanges polymères

Country Status (6)

Country Link
US (1) US20100168335A1 (fr)
EP (1) EP2129720A1 (fr)
CN (1) CN101679693A (fr)
DE (1) DE102007014621A1 (fr)
WO (1) WO2008116336A1 (fr)
ZA (1) ZA200906624B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110206882A1 (en) * 2010-02-24 2011-08-25 Norman Scott Broyles Injection stretch blow molding process
EP2939814B1 (fr) * 2014-04-30 2016-06-15 Scg Chemicals Co. Ltd. Composition polymère pour la fermeture d'un récipient
US20220380583A1 (en) * 2021-05-25 2022-12-01 Rachel PRATO Machinable wax with plastic additive and method of manufacture

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1057728A (en) 1963-11-21 1967-02-08 Shell Int Research Olefin polymerisation and polyolefins produced thereby
US4525322A (en) 1983-06-28 1985-06-25 E. I. Du Pont De Nemours And Company Ethylene polymer composition for blow molding
FR2577558B1 (fr) 1985-02-19 1987-03-06 Bp Chimie Sa Polymerisation en plusieurs etapes d'alpha-olefines en phase gazeuse
SE9603683L (sv) * 1996-10-09 1998-02-09 Borealis Polymers Oy Sätt för kompoundering av en multimodal polymerkomposition
EP1739126A1 (fr) * 2000-07-12 2007-01-03 Japan Polychem Corporation Composition à base de polypropylène, film préparé avec la composition et film de résine laminée
US6639003B2 (en) * 2001-09-11 2003-10-28 Gregory G. Borsinger Rubber additive
US6875828B2 (en) 2002-09-04 2005-04-05 Univation Technologies, Llc Bimodal polyolefin production process and films therefrom
DE10259458A1 (de) 2002-12-19 2004-07-01 Tesa Ag Bimodale Acrylathaftklebemassen
US7172987B2 (en) 2002-12-31 2007-02-06 Univation Technologies, Llc Bimetallic catalyst, method of polymerization and bimodal polyolefins therefrom
US20050063622A1 (en) * 2003-09-12 2005-03-24 Rengan Kannabiran Blended polymeric draw tapes
US20060068085A1 (en) 2004-07-13 2006-03-30 David Reece Electrical cable having a surface with reduced coefficient of friction
GB0418581D0 (en) * 2004-08-20 2004-09-22 Solvay Polymer composition
ATE541898T1 (de) * 2004-10-19 2012-02-15 Innogel Ag Polymermischungen für spritzguss anwendungen
EP1807456B1 (fr) 2004-11-04 2012-07-11 Chevron Phillips Chemical Company Lp Catalyseurs de combinaison d'organochrome/metallocene pour produire des resines bimodales

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008116336A1 *

Also Published As

Publication number Publication date
DE102007014621A1 (de) 2008-09-25
US20100168335A1 (en) 2010-07-01
ZA200906624B (en) 2010-07-28
WO2008116336A1 (fr) 2008-10-02
CN101679693A (zh) 2010-03-24

Similar Documents

Publication Publication Date Title
EP1240209B1 (fr) Procede pour reduire la teneur en polymere d'eaux usees lors du drainage de melanges matiere plastique/eau
EP1613700B1 (fr) Reseaux polymeres
DE60204312T2 (de) Verfahren zum compoundieren einer multimodalen polyäthylenzusammensetzung
EP2129719B2 (fr) Mélange polymère à faible viscosité
DE102008015782A1 (de) Verfahren zur Herstellung einer Phasenwechselmaterial-Zusammensetzung
EP1421140A1 (fr) Corps moules en matiere synthetique a base d'alcool polyvinylique, leurs procedes de fabrication par traitement thermoplastique et leur utilisation
WO2008025446A1 (fr) Procédé de compoundage de polymères
WO1992010539A1 (fr) Materiaux et/ou pieces moulees a base d'amidon modifie par des composes polymeres synthetiques et leur procede de production
EP1814953B1 (fr) Melanges polymeres pour applications de moulage par injection
DE2901776A1 (de) Verfahren zum herstellen kleinteiliger, mit leitfaehigkeitsruss versehener polyolefin-formmassen und deren verwendung zur herstellung von formkoerpern
EP2129720A1 (fr) Procédé de production de mélanges polymères
DE4402943C2 (de) Polymerwerkstoff und Verfahren zu dessen Herstellung
EP0988338B1 (fr) Procede de production de pvc souple
DE4115531A1 (de) Verfahren zum emulgieren einer thermoplastischen harzmischung
DE4111739A1 (de) Verfahren und vorrichtung zur kontinuierlichen herstellung von schmelzklebstoffen
AT413268B (de) Verfahren zum auf- und/oder zubereiten einer thermoplastischen masse und vorrichtung zur durchführung des verfahrens
DE69530358T2 (de) Reaktive Extrusion von Polymergelen
DE102018124523B4 (de) Verfahren zur Herstellung von Polymeren, in welchen Füllstoffe mit Partikelgrößen kleiner 10 μm eingearbeitet und homogen verteilt sind.
DE4433273A1 (de) Verfahren zur Herstellung von Mischungen aus hochmolekularem Polyisobutylen und thermoplastischen Polymeren
EP3356101B1 (fr) Procédé et dispositif de modification continue d'un polymère en fusion à partir d'un polyamide 6 non extrait pourvu d'un ou plusieurs additifs
DE2557832A1 (de) Verfahren zur herstellung schlagfester styrolpolymerisate
EP0013752B1 (fr) Procédé pour la préparation de masses à mouler finement divisées de polyoléfines ayant des propriétés améliorées et leur application dans la fabrication d'objets moulés
DE10331451A1 (de) Verfahren zur Herstellung von Styrolpolymeren mit hohem Mineralölgehalt
DE2037784C2 (de) Einarbeiten von Kautschuk in thermoplastische Kunststoffe
CH616171A5 (en) Process for incorporating additives into polymers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091015

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20121002