[go: up one dir, main page]

WO2009092721A1 - Procédés de production de polyoléfines à éléments structuraux syndiotactiques, polyoléfines et leur utilisation - Google Patents

Procédés de production de polyoléfines à éléments structuraux syndiotactiques, polyoléfines et leur utilisation Download PDF

Info

Publication number
WO2009092721A1
WO2009092721A1 PCT/EP2009/050638 EP2009050638W WO2009092721A1 WO 2009092721 A1 WO2009092721 A1 WO 2009092721A1 EP 2009050638 W EP2009050638 W EP 2009050638W WO 2009092721 A1 WO2009092721 A1 WO 2009092721A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymers
mass
polyolefins
solvent
butene
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
PCT/EP2009/050638
Other languages
German (de)
English (en)
Inventor
Hinnerk Gordon Becker
Walter Kaminsky
Matthias Hoff
Lutz Mindach
Thomas Wildt
Jürgen DERKS
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of WO2009092721A1 publication Critical patent/WO2009092721A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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

Definitions

  • the present invention relates to processes for the preparation of polyolefins, with syndotactic structural elements, polyolefins and their use, in particular as an adhesive or as a component of adhesives.
  • the polymerization of propene or its higher homologs may lead to the formation of different relative stereoisomers.
  • the regularity with which the configurational recurring units in the main chain of a macromolecule follow one another is called tacticity.
  • tacticity To determine the tacticity, consider the monomer units of a polymer chain and determine the relative configuration of each (pseudo) asymmetric chain atom relative to the previous one. Isotacticity is when the observed relative configuration of all (pseudo) asymmetric chain atoms is always the same, that is, the chain is built up from a single configurational repeating unit.
  • Syndiotacticity is used when the relative configuration of consecutive (pseudo) asymmetric chain atoms is straight is opposite, that is, the chain is constructed alternately from two different configurative Repetiertechniken. Finally, in atactic polymers, the various configurational repeating units are randomly arranged along the chain.
  • propylene polymers are primarily dependent on the structure of the macromolecules and thus also on the crystallinity, their molecular weight and the molecular weight distribution, and can be influenced by the polymerization process used, and in particular the polymerization catalyst used [R. Vieweg, A. Schley, A. Schwarz (eds); Plastic manual; Vol. IVf Polyolefins "; C. Hanser Verlag, Kunststoff 1969].
  • polypropylene polymers are thus subdivided into atactic, isotactic and syndiotactic polymers.
  • Special forms also include the so-called hemi-isotactic polypropylene polymers and the so-called stereoblock polymers.
  • the latter are usually polymers with isotactic and atactic stereo blocks, which behave like thermoplastic elastomers, since a physical crosslinking of the polymer chains takes place, which leads to a combination of different crystalline polymer regions (AF Mason, GW Coates in: "Macromolecular Engineering”; Wiley-VCH, Weinheim, 2007).
  • Atactic polypropylene has a low softening point, low density and good solubility in organic solvents.
  • Classic atactic polypropylene (aPP) is characterized by a very broad molecular weight distribution, which on the one hand leads to a broad melting range, and on the other hand brings high low molecular weight fractions, which tend more or less to migrate.
  • 1 PPa but has a very high elongation at break of up to 2000% (H.G. Elias, Makromoleküle, Vol. Due to the low softening point, the heat resistance of aPP formulations is correspondingly low, which greatly limits the range of application leads.
  • Pure atactic polypropylene polymers can also be prepared by metallocene catalysis, whereby both very low molecular weight and relatively high molecular weight polymers can be obtained (L. Resconi in: "Metallocenes based Polyolefins”; J. Scheirs, W. Kaminsky (ed.); J. Wiley & Sons Weinheim, 1999).
  • Syndiotactic polypropylene is highly transparent and is characterized by good heat resistance, with the melting temperature below that of isotactic polypropylene. It exhibits high breaking strength with moderate elongation at break (AF Mason, GW Coates in "Macromolecular Engineering", Wiley-VCH, Weinheim, 2007) Disadvantages are the slow melt crystallization observed in many cases due to physical entanglements, the melt viscosity syndiotactic polypropylene at comparable molecular weight is significantly higher than that of isotactic polypropylene, ie one can achieve the same melt viscosity with significantly lower molecular weights Syndiotactic and isotactic polypropylene are immiscible above a certain molecular weight, corresponding polymer blends are prone to phase separation, polymer blends of syndiotactic polypropylene with others Polyolefins exhibit a significantly higher elongation at break than blends with isotact
  • Isotactic polypropylene is characterized by a high melting temperature and good tensile strength.
  • the calculated melting temperature is 185 0 C and the enthalpy of fusion is about 207 J / g (J.Bicerano; JMS; Rev.Macromol.Chem.Phys .; C38 (1998); 391ff).
  • the tensile strength (fracture) is about 30 MPa, with virtually no elongation at break occurs.
  • the impact strength of the metallocene-based polymer is in a wide range of molecular weights over that of the Ziegler-Natta material.
  • the proportion of xylene-soluble constituents in isotactic poly (propylene) homopolymer which was obtained by metallocene catalysis is usually clearly ⁇ 1 ma-%; in random copolymers with ethylene, depending on the ethylene fraction, xylene-soluble fractions of not more than 5 ma-% are found (W. Spaleck in: "Metallocenes Based Polyolefins"; J. Scheirs, W. Kaminsky (ed.); J. Wiley & S .; Weinheim; 1999).
  • Tetrahydrofuran-soluble polypropylene oligomers have very low levels number average molecular weights of significantly less than 1500 g / mol to [H. El Mansouri, N. Yagoubi, D. Scholler, A. Feigbaum, D. Ferner; J.Appl.Polym.Sci .; 71 (1999); 371 ff.].
  • the different polymer types differ significantly in their material properties.
  • the crystallinity of highly isotactic or syndiotactic polymers is very high due to their high order.
  • atactic polymers have a higher amorphous content and consequently a lower crystallinity.
  • Polymers with high crystallinity show many material properties that are undesirable especially in the field of hot melt adhesives.
  • Organoaluminum compounds present may also lead to an uncontrolled change in the molecular structure of the alkylaluminoxane (eg., By building additional molecular weight).
  • the accessibility of the polymerization-active centers is sterically restricted by the support surface, so that in most cases the catalyst productivity decreases and polymers with a higher tacticity are formed, which is undesirable in the present case as described above.
  • such solids, both as such, as well as a slurry very difficult to dose evenly, because the density differences between the solid component and suspending medium usually very high and a stable homogeneous distribution of the solid particles in the suspension medium therefore can not be achieved.
  • fluctuations in the flow rate, z fluctuations in the flow rate, z.
  • WO 01/46278 describes 1-olefin copolymers of predominantly amorphous character, which are obtained by metallocene catalysis, wherein for their use as hot melt adhesives no or only minimal additions of tackifier resins should be necessary.
  • the copolymers consist of A: 60 to 94% of a C 3 -C 6 1-olefin, B: 6-40 mol% of one or more C 4 -C 0 1 - olefins and optionally C: 0-10 mol% another unsaturated monomer (preferably ethylene).
  • the random distribution of the comonomer B distorts the crystallinity of the polymers, since only a few regions still reach the minimum block length necessary for crystallization (see, for example, BS Davison, GL Taylor, Br.Polym.J., 4 (1972), 65ff). , This can be seen inter alia from the low melting point of the described polymers. Largely amorphous polymers also have a very unbalanced material behavior. In particular, the cohesion of such polymers in relation to the adhesion is clearly underdeveloped, which is why cohesive adhesive failure often occurs in the corresponding adhesive bonds. Such polymers with a low melting point also lead in bonds to a poor heat resistance, which precludes numerous applications.
  • the crystallinity of the described polymers is so low that a rather poor cohesion results.
  • Comonomers with more than 4 carbon atoms are also very expensive, which makes the products in terms of their applications and the product prices to be achieved uneconomical.
  • a freedom from aromatics is difficult to guarantee via the preparation process described, especially since it is preferably polymerized in aromatic solvents and used Cokatalystaor does not dissolve in aliphatic solvents.
  • the high reaction temperatures which are (in some cases far above) the melting points of the polymers produced, lead to very high reaction pressures, which make economical operation of the polymerization process difficult.
  • chlorinated solvents whether aromatic or aliphatic
  • the toxicological concern is the same in virtually all cases as for the non-halogenated aromatic solvents. Although they have in many cases a lower boiling point than the common aromatic solvents, but their toxicological concern is in many cases, especially with respect to carcinogenicity and reproductive toxicity even higher. Their use is therefore associated with a significant health risk for the end-users of the polymers produced or a significant financial risk for the polymer manufacturers and processors.
  • EP 480 390 describes an olefin polymerization process called "environmentally friendly" in which the use of aromatic solvents can be dispensed with by the choice of a specially designed system of metallocene catalyst and cocatalyst
  • the isotactic index of the examples is between 90 and 99%, the syndiotactic index is 96% .
  • the task is the search for a process for the production of polyolefins with high tacticity, high molecular weight and narrow molecular weight distribution high molecular weight polyolefins with high tacticity (and thus also high crystallinity) are, however, not suitable for use as adhesive raw materials, in particular not for the hotmelt adhesives commonly used in the packaging industry
  • Raw material polymers can not be sensibly produced in slurry and gas phase processes because of the inherent stickiness of the polymer particles produced.
  • Adhesive raw materials always have a certain surface tack due to their determination in order to be able to ensure good adhesion to the materials to be bonded.
  • This surface tack also occurs during the polymerization, provided that processes are chosen in which solid particles are formed during the polymerization.
  • the described phenomenon has a strongly negative effect, since the formation of a stable fluidized bed is necessary for carrying out a gas phase polymerization.
  • sticky polymers such.
  • EPDM is made by gas-phase polymerization, but a high amount of release agents (such as waxes or oils) must be used to prevent clumping.
  • release agents are very difficult or impossible to remove, and therefore lead to a product that can not be used as a sticky raw material.
  • gas-phase polymerization the formation of particles also takes place in the case of slurry polymerization which, in the case of adhesive raw materials, rapidly agglomerate and lead to blockage of pipelines.
  • sticky particles quickly accumulate on all non-moving reactor parts (such as the reactor walls) and lead to so-called reactor fouling (ie more or less rapid growth of the reactor).
  • the preparation is described directly in the suspending medium (for example monomer) used for the polymerization.
  • water is introduced into the polymerization vessel, which adversely affects the catalyst activity of the later added metallocene.
  • solvents for the aluminoxanes and for the likewise described preforming of metallocene and aluminoxane are alkanes of the formula CmH 2m +2 with m> 6 or so-called technical gasoline or diesel oil fractions having a boiling range of z. B. 100 - 120 0 C or 140 - 170 0 C used.
  • the present invention solves the complex requirement profile.
  • a first aspect of the present invention is a process for preparing polyolefins comprising contacting a metallocene compound, at least a first solvent, wherein the at least one first solvent is a non-halogenated aliphatic solvent, at least one alkyl group-modified methylaluminoxane component, optionally dissolved and / or suspended in a second solvent, wherein the second solvent may be the same or different from the first solvent, and at least one 1-olefin monomer in a reaction space and subsequent polymerization of the at least one 1-olefin monomer at a reaction temperature Formation of polyolefins, characterized in that the reaction temperature above the boiling point of the first or the first solvent (s) and more preferably below the softening point (determined by the ring and ball method) d it is polymer produced according to the invention.
  • the process according to the invention has the advantage that such a process enables, in particular, a simple direct and complete separation of the solvent used from the polymer.
  • described method is an essential characteristic, since in this way a large part of the solvent can be separated already in the first evaporation stage.
  • the temperature limitation upwards (softening point of the polymer produced according to the invention) avoids excessive thermal loading of the polymers produced and ensures an optimum reaction temperature for the metallocene catalysts used according to the invention.
  • reaction temperature in the stationary reaction state is above the boiling point of the first solvent (s) and preferably at the same time below the softening point of the polymer produced according to the invention.
  • the at least one first solvent is selected from non-halogenated aliphatic solvents.
  • the solvent has a boiling point at atmospheric pressure of not more than 101 0 C.
  • the aliphatic solvents have a boiling point at atmospheric pressure of not more than 80 0 C, preferably not more than 60 0 C, more preferably not more than 40 0 C and particularly preferably not more than 20 0 C.
  • the non-halogenated aliphatic solvents are linear or cyclic aliphatic compounds having not more than 7 C atoms, preferably not more than 6 C atoms, and more preferably not more than 5 C atoms.
  • the non-halogenated aliphatic solvent is particularly preferably selected from the group consisting of propane, butane, pentane, cyclopentane, methylcyclopentane, hexane, cyclohexane, methylcyclohexane, heptane or mixtures thereof. Most preferably, the solvent is propane and / or n-butane.
  • Fluorenyl ligand connects, with R 1 selected from linear or branched alkyl groups with 1 to 6
  • R 4 , R 7 and R 12 are linear or branched alkyl groups having 1 to 10 carbon atoms and R 2 , R 3 , R 5 , R 6 , R 8 to R 11 and R 13 H. Die
  • Metallocene compound is preferably one of the formula II,
  • R 1 to R 13 have the abovementioned meaning.
  • Linear and branched alkyl groups having 1 to 10 C atoms are in particular substituents selected from the group comprising methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl.
  • Alkoxylalkyl groups having 1 to 6 C atoms are in particular selected from the group comprising methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl and ethoxypropyl.
  • Aryl groups are especially selected from the group comprising benzyl, phenyl and indenyl.
  • Alkoxyaryl groups are in particular selected from the group comprising methoxyphenyl, methoxybenzyl, dimethoxyphenyl, ethoxyphenyl, methoxy-ethoxyphenyl and methoxyindenyl, where at least one alkoxy group is in the para position for linking the aryl nucleus with the ligand bridge.
  • the metallocene compound in the present process according to the invention is most preferably dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (3-tert-butylcyclopentadienyl) hfluorenyl] zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene ( cyclopentadienyl) - (fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) - (fluorenyl) zirconium dichloride or di (paramethoxyphenyl) methylene (2,7-di-tert-butyl-fluorenyl) - (cyclopentadienyl) zirconium dichloride.
  • the compounds mentioned are preferably in the form of a racemic mixture of enantiomers and particularly preferably do not contain the enantiomorphic, optically inactive meso form to any significant extent.
  • the proportion of the meso-form in the present invention is not larger than 5% by mass, preferably not larger than 3% by mass, and particularly preferably not larger than 1% by mass.
  • the catalyst is preferably fed to the polymerization space together with a high excess of aliphatic hydrocarbon (s), more preferably the first solvent, more preferably in homogeneous form, i. H. completely dissolved is supplied.
  • aliphatic hydrocarbon more preferably the first solvent, more preferably in homogeneous form, i. H. completely dissolved is supplied.
  • the 1-olefin monomers used in the polymerization can in principle be selected from all 1-olefins known to the person skilled in the art.
  • the at least one 1-olefin monomer is selected from the group comprising ethylene and linear 1-olefins.
  • Suitable linear 1-olefins are in particular propene and / or 1-butene.
  • the metallocene compound and the at least one alkyl-modified methylaluminoxane component are preferably fed to the reaction space in homogeneous form.
  • the (metallocene) catalyst feed supplied to the polymerization space preferably contains no aluminum compounds. This has the advantage that no uncontrolled preforming and / or side reaction of metallocene catalyst and cocatalyst takes place, which can lead to poorly reproducible catalyst activities and polymerization results.
  • the at least one alkyl-modified methylaluminoxane component serves as cocatalyst in the process according to the invention.
  • the cocatalyst is a compound of formula III for the linear type
  • R 5 is methyl and / or iso-butyl and n is an integer from 2 to 50.
  • 15 to 45 mol% of the radicals R 5 are isobutyl, preferably 17 to 45 mol%, particularly preferably 19 to 43 mol% and particularly preferably 20 to 40 mol%.
  • iso-butyl radicals Only by the proportion of iso-butyl radicals is a solubility of the cocatalyst in non-aromatic solvents possible.
  • the cocatalyst is dissolved in a second solvent whose boiling point is particularly preferably at a maximum of 101 0 C.
  • the second solvent of the cocatalyst is preferably a non-halogenated solvent, more preferably a non-halogenated non-aromatic solvent, in particular selected from cyclic and / or linear alkanes having 3-7 C atoms, preferably 4-6 C atoms, preferably the Boiling temperature of the second solvent is well below the polymerization temperature, but this is not mandatory.
  • the second solvent is propane, n-butane, n-pentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane and / or n-heptane.
  • the proportion of the second solvent in the total amount of solvent in the polymerization is very low, preferably below 5 m%, in particular below 2 m%. Even if the second solvent should have a higher boiling temperature than the selected polymerization, the advantages of the invention described above are nevertheless achieved, since the proportion of the second solvent is very low, and thus has essentially no influence on the course of the polymerization.
  • the use of aromatic and / or halogenated, in particular chlorinated, solvents is dispensed with in the process according to the invention in the entire process sequence, and only unhalogenated, aliphatic solvents are used. During the entire polymerization process, no hydrocarbon compound having more than 7 carbon atoms is preferably used as solvent, suspending medium and / or monomer.
  • the reaction space for carrying out the process according to the invention may be a stirred tank, a stirred tank cascade with at least two stirred tanks, a flow tube and / or a forced-flow flow tube (eg a screw machine). act.
  • the above reactors can be used either as a single solution or in any combination.
  • the use of the raw-shaped reactor with forced delivery can take place either as the sole solution or in combination with a stirred tank or stirred tank cascade.
  • both a series and a parallel connection of the individual reactors are possible.
  • Preferred in the individual solutions is the stirred tank, particularly preferred is the continuous stirred tank.
  • a cascade of several continuous stirred tank is preferably used, particularly preferred is the continuous stirred tank in combination with the flow tube with forced delivery.
  • a discontinuous or continuous stirred tank, or a continuous stirred tank cascade or a continuous flow tube is / are used, is polymerized in the first solvent or in the monomer introduced, preferably in the first solvent.
  • continuous stirred tank or continuous stirred tank cascade and continuous flow tube with forced delivery is also polymerized in the first solvent or in the charged monomer, preferably in the monomer presented.
  • the solvent used and / or unreacted monomer components is preferably completely or partially removed.
  • the preferred reaction spaces have the advantage that an optimal adaptation of the process parameters to the different target polymers can take place.
  • Inventive polymers with very narrow molecular weight distribution can be z.
  • a stirred tank cascade or a combination of stirred tank / stirred tank cascade and flow tube is preferred.
  • the average residence time is adjusted so that in the steady state reaction, the average monomer conversion over all reaction spaces used at least 85%, preferably at least 90%, more preferably at least 92% and particularly preferably at least 95%.
  • the otherwise necessary separation of the release agent either at greatly elevated temperatures (risk of product discoloration) and / or very low pressures (expensive / expensive technology) or purification of the polymers by falling over and / or extraction (expensive / expensive technology) can be omitted.
  • the polymerization temperature is above the atmospheric boiling point of at least one solvent used. In the case of the polymerization in the initially charged monomer, the polymerization temperature is above the atmospheric boiling point of at least one monomer used. If a discontinuous or continuous stirred tank and / or a continuous stirred tank cascade and / or a continuous flow tube is used for the polymerization in a solvent or the polymerization in the monomer introduced, the polymerization temperature is preferably between 50 and 120 ° C., preferably 55 to 115 ° C. and more preferably at 60-110 0 C and most preferably at 65 to 105 0 C.
  • the polymerization temperature is in the steady state of reaction below the softening point (determined by the ring and ball method) of the polymers produced, preferably at least 10 K below the softening temperature, preferably at least 15 K, more preferably at least 20 K and particularly preferably at least 25 K.
  • the latter is a particularly outstanding characteristic of the method according to the invention, because despite this Temperature control when using the method according to the invention is not for the formation of macroscopic polymer particles (as they are present in a Slurrypolymehsation) in the polymerization, but polymehsiert in a homogeneous phase.
  • the polymerization temperature in this reactor / reactor part can also be above 120 ° C., in particular if degassing also takes place within this reactor / reactor part.
  • the residence time of the polymerization in regions with elevated temperature is very low in relation to the total residence time in the reaction part, which is why no negative influences occur.
  • polymerizations at higher temperatures than the invention are also disadvantageous because the metallocenes of the invention generally lose their polymerization activity at temperatures of> 120 0 C. The latter is due to the destruction of the polymerization-active metallocene cocatalyst complex at high temperatures. In addition, only very short polymer chains are formed at very high temperatures due to the then likewise accelerated chain termination reaction, which ensures good cohesion of the material is no longer sufficient (waxy character).
  • Another disadvantage is the high pressure level in the polymerization reactor at high temperatures, which requires high demands on the material used and thus greatly increases the cost of the process.
  • the pressure in the reaction space in the stationary reaction state is -5 to 40 bar, preferably 8, if evaporation cooling functions. 35 bar, particularly preferably at 10 to 30 bar and particularly preferably at 12-28 bar. It is particularly preferred in the present process that critical pressure and critical temperature of the solvents and monomers used are not exceeded at any time during the reaction. This has the advantage that the technical effort to control the reaction is limited, which contributes to the economic advantage of the method according to the invention in comparison with supercritical method.
  • the pressure within this reaction space can also be well above 30 bar and well below 5 bar, if this is necessary in terms of process engineering.
  • Lower pressures occur in particular when degassing takes place within this reactor / reactor part, for which case the (absolute) pressure in this reactor / reactor section is preferably ⁇ 4 bar, particularly preferably ⁇ 3 bar and particularly preferably ⁇ 1 bar ,
  • the residence time of the polymerization in areas with elevated pressure is very low in relation to the total residence time in the reaction part, which is why no negative influences occur.
  • the regulation of the molar mass can be carried out via the selected Polymehsationstemperatur and / or the addition and mixing of gaseous hydrogen in the polymerization, particularly preferably the control of the molecular weight without the use of gaseous hydrogen only by selecting the appropriate polymerization temperature.
  • hydrogen is used to control the molecular weight, this is preferably metered into the liquid reaction phase, wherein the dosage over the bottom of the reaction space and / or a mixing element used z.
  • B. a stirrer takes place.
  • toxic heavy chain chain transfer reagents eg tin organyls
  • the molar ratio of catalyst to cocatalyst (expressed by the molar ratio of the central transition metal atom of the metallocene to the cocatalyst constituent aluminum) is between 1: 1 and 1: 10,000.
  • the activity of the catalyst used is between 10,000 and 10,000,000 g of polymer / g of catalyst.
  • the monomer ethene is used in gaseous form, while the monomers propene and 1-butene can be used both gaseous and liquid. Higher homologs are used liquid. If propene and / or 1-butene are used in liquid form, a pressure corresponding to the reaction conditions must be maintained in the reactor used, which ensures a sufficient monomer concentration in the liquid phase.
  • the mass ratio of polymer to solvent in the case of polymerization in a stationary state solvent is between 1: 100 and 1: 0.01, preferably between 1:50 and 1: 0.1 and particularly preferably between 1:10 and 1: 0.2.
  • it is preferably between 1: 1 and 1: 0.01.
  • Catalyst and cocatalyst are decomposed at the end of the reaction in a suitable manner, for example by the addition of water or steam, or aliphatic alcohols in liquid and / or gaseous form wherein the decomposed catalyst components either remain in the polymer or are removed via a washing step.
  • the decomposition usually takes place in such a way that the decomposed catalyst components converted into unreactive constituents remain at least partly in the polymer.
  • the polymer is not colored by the decomposed catalyst components converted into unreactive constituents in the production process according to the invention.
  • the proportion of catalyst decomposition products is so low that no appreciable macroscopic effects are present.
  • the polymers prepared according to the invention can be chemically stabilized either in the form of their reaction solution or at a later time in order to protect them from the influence of solar radiation, atmospheric moisture and oxygen.
  • stabilizers containing hindered amines HALS stabilizers
  • hindered phenols hindered phenols
  • phosphites hindered phenols
  • aromatic amines can be used.
  • the effective amount of stabilizers is in the range of 0.1 to 3 wt .-%, based on the polymer.
  • antifogging substances can be used as additives.
  • This z. B. fatty acid esters are used; the effective concentration is usually in the range of 0.1 to 2 wt .-%, based on the polymer.
  • the polymer obtained according to the invention is obtained after polymerization either by precipitation in a counterpolar precipitant (for example water and / or alcohols such as, for example, ethanol, isopropanol or butanol) or by direct degassing with subsequent melting.
  • a counterpolar precipitant for example water and / or alcohols such as, for example, ethanol, isopropanol or butanol
  • stirred tank and stirred tank cascades or flow tubes or tubular reactors with forced delivery for example, a screw machine
  • forced delivery for example, a screw machine
  • the polymer produced can be subjected to a further formulation, wherein the formulation is an additization and / or a pulverization and / or a pelleting and / or a granulation.
  • the formulation is an additization and / or a pulverization and / or a pelleting and / or a granulation.
  • granulation it is a strand granulation or an underwater granulation, in particular the underwater strand or underwater Vorkopfgranulmaschine.
  • a surfactant and / or dispersing agent or a release agent emulsion is necessary in this case.
  • liquefied or cryogenic gases such as CO2 and / or N 2
  • Pulverization can be done either by a separate milling step or by using a spraying method.
  • supercritical fluids such as CO 2 , water or propane possible.
  • PGSS Packet-S (Particle from Gas Saturated Solutions)
  • the polymer melt is mixed with a supercritical medium and then atomized in a spray tower using cryogenic gases, such as CO2 and / or N 2 .
  • the flow aids commonly used in the polymer field can be used. These can be both inorganic and organic in nature and contain both low and high molecular weight components, in which case both crystalline and amorphous flow aids can be used.
  • the flow aids may be both compatible and incompatible with the polymers according to the invention in terms of thermodynamic miscibility. Particularly preferred are flow aids which are compatible with the polymers according to the invention and the adhesive properties of the polymers due to their chemical nature and / or their low content with respect to the mass of the polymer according to the invention. As flow aids z.
  • polyolefin waxes both polyethylene and polypropylene-based
  • Fischer-Tropsch waxes are used.
  • Polyolefin waxes based on 1-butene can also be used.
  • micro waxes is possible.
  • waxes and olefin polymers such as polyethylene, polypropylene and / or poly (I-buten), in particular isotactic or syndiotactic polypropylene can be used. Both waxes and polymers can also be used in modified form (eg modified with maleic anhydride).
  • crosslinked polymers such.
  • crosslinked polyolefins or crosslinked styrene-divinylbenzene polymers in the powdered state is possible.
  • inorganic materials z. As MgO, talc, silica, etc. in question.
  • the polymers of the present invention are obtainable by methods as previously described in the present invention.
  • the use of the process according to the invention for the preparation of the polymers according to the invention is particularly preferred and allows easy access to the desired polymers.
  • the triad distribution determined by 13 C-NMR has Propentriads (provided that the polymer contains propynes) have a syndiotactic content of 32-90% by mass, preferably 34-88% by mass, particularly preferably 36-86% by mass and in particular 38-85% by mass, based on the Propentriaden, on.
  • the propylene triad distribution determined by 13 C-NMR (assuming that the polymer contains propene triads) has an isotactic content of not more than 25% by mass, preferably not more than 23% by mass, more preferably from 1 to 20% by mass in particular from 2 to 18% by mass, based on the propene triages.
  • the propylene triad distribution determined by 13 C-NMR preferably has an atactic content of not more than 65% by mass, preferably from 1 to 63% by mass, more preferably from 5 to 61% by mass. and in particular from 7 to 60 m%, based on the propene triages.
  • the polymers according to the invention depending on the (co) polymer composition and selected polymerization conditions with high transparency, also have specifically adjustable adhesive properties in addition to the dominant flexible and cohesive properties.
  • the propylene triad distribution determined by 13 C-NMR (assuming that the polymer contains syndiotactic and atactic propene triads) has a ratio of syndiotactic to atactic propene diions between 1: 0.1 and 1: 2, preferably between 1: 0.12 and 1: 1, 75, more preferably between 1: 0.14 and 1: 1.5, and particularly preferably between 1: 0.16 and 1: 1.35.
  • the polymers according to the invention have an optimum balance between the dominating flexible and cohesive material properties and the specifically adjustable adhesive material properties with high to extremely high transparency, whereby a certain basic adhesion is always guaranteed.
  • the triad distribution determined by 13 C-NMR for 1-butene triad (provided that the polymer contains 1-butene triad) has a syndiotactic content of not more than 96% by mass, preferably not more than 94% by mass, more preferably from 1-92 ma-% and in particular from 2 to 90 ma-%, based on the 1-butene triads, with further preferred ranges between 2 and 20 m% and 75 to 90 m%.
  • the polymers according to the invention have> 60 m% atactic triads.
  • the triad distribution determined by 13 C-NMR for 1-butene triads (assuming that the polymer contains 1-butene triads) has an atactic proportion of not more than 100% by mass, preferably 4%. 99% by mass, more preferably from 6 to 98% by mass and in particular from 8 to 96% by mass, based on the 1-butene triads, with further preferred ranges of between 9 and 35% by mass and between 60 and 95% by mass. lie.
  • the triad distribution determined by 13 C-NMR in the investigation of poly (ethylene-co-propylene-co-1-butene) terpolymers according to the invention for ethylene contents of up to 20% by mass has a content of ethylenes of ⁇ 1% by mass. , preferably ⁇ 0.8% by mass, more preferably ⁇ 0.6% by mass, particularly preferably ⁇ 0.5% by mass, so that the monomer ethylene is thus incorporated essentially in a statistically distributed manner.
  • the polymers according to the invention preferably contain not more than 20% by mass, preferably not more than 18% by mass and more preferably not more than 15% by mass of ethylene.
  • the polymers of the invention preferably contain either 50-
  • the polymers according to the invention preferably contain either 85-100% by mass or at most 55% by mass of 1-butene, particularly preferred ranges being 87-99% by mass, 89% -97% by mass and 90% -96% by mass not more than 54mA%, 1-50mA%, 2-45mA%, 5-35mA% and 37-44mA%.
  • the polymers according to the invention contain 100% by mass of propylene.
  • the polymers according to the invention contain 100% by mass of 1-butene.
  • the polymers according to the invention are copolymers of ethylene, propylene and / or 1-butene, in particular either a poly (ethylene-co-propylene) copolymer to a poly (ethylene -co-1-butene) copolymer, or a poly (propylene-co-1-butyne) copolymer.
  • the polymers according to the invention contain not more than 25% by mass, preferably from 1 to 23% by mass, more preferably from 2 to 20% by mass, and particularly preferably from 3 to 15% by mass of ethylene.
  • the proportion of propylene is accordingly, so that in total 100 ma-% present (100 ma-% minus ethylene content).
  • the polymers according to the invention contain not more than 17% by mass, preferably 1-15% by mass, more preferably 2-13% by mass, and particularly preferably 3-11% by mass of ethylene ,
  • the proportion of butene is correspondingly, so that in total 100% by mass are present (100% by mass minus ethylene content).
  • the polymers according to the invention contain either not more than 47% by mass, preferably 1-45% by mass, more preferably 2-43% by mass and especially preferably 3-40% by mass. %, or 85-99mA%, preferably 87-98mA%, and more preferably 89-97mA% 1 -butene.
  • the proportion of propylene results accordingly, so that in total 100 ma-% are present (100 ma-% minus butene content).
  • the copolymers contain two comonomers selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-hexene, 3-methyl-1-heptene, 4-methyl 1 -pentene and 6-methyl-1-heptenes wherein the maximum proportion of the branched 1-olefin in the copolymer is not more than 50% by mass, preferably not more than 40% by mass and particularly preferably not more than 30% by mass.
  • this contains in particular ethylene, propylene and 1-butene, with a maximum of 25% by mass, preferably 1-20% by mass, particularly preferably 2-18% by mass and especially preferably 3-15% by mass.
  • this contains three comonomers selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-hexene, 3-methyl-1-heptene, 4-methyl-1 -pentene and 6-methyl-1 -hepten wherein the maximum proportion of the branched 1-olefin in the copolymer is not more than 50% by mass, preferably not more than 40% by mass and more preferably not more than 30% by mass.
  • the polymers according to the invention are preferably present in the form of a powder after preparation, in the form of pellets or in the form of granules. Particularly preferred are powders, pellets and / or granules which are free-flowing and can be metered automatically.
  • powders, pellets and / or granules which are free-flowing and can be metered automatically.
  • the direct further processing of molten polymer to the products of the invention is also possible.
  • the polymers of the invention preferably contain no aromatic compounds (ie, ⁇ 100 ⁇ g / g). In addition, they contain substantially no organic halogenated compounds derived from the polymerization process. Also preferred is that the polymers (with the exception of the decomposition products derived from the catalyst decomposition) no impurities by suspending oils (release agents), no residues of inorganic support materials, in particular no inorganic oxides and / or alkaline earth halides (such as MgC ⁇ ), no inorganic or organic boron compounds, no talcites and / or hydrotalcites and / or their degradation products, no contaminants by alcohols, in particular by methanol.
  • suspending oils release agents
  • inorganic support materials in particular no inorganic oxides and / or alkaline earth halides (such as MgC ⁇ )
  • no inorganic or organic boron compounds no talcites and / or hydrotalcites and / or their degradation products, no contaminants by alcohols, in particular by
  • the polymers of the invention are free of toxic compounds and optimally suitable for use in sensitive areas such.
  • food packaging, medical supplies, children's toys, clothing, carpet / floor coverings, automotive interior applications, etc. are suitable.
  • the negative effects of the above-mentioned auxiliaries and accompanying substances on the thermal stability (in particular color stability) and the adhesive properties of the polymers are excluded.
  • the molecular weight distribution of the polymers according to the invention can be monomodal or bimodal, with a narrow molar mass distribution having a polydispersity (quotient of number average and weight average molecular weight) of ⁇ 3 also present in bimodally dispersed polymers. Most preferably, the molecular weight distribution is monomodal. Polymers with a narrow molecular weight distribution are characterized by a low variance of the material properties. For example, they have a clearly defined melting and setting behavior.
  • a defined melting / setting behavior can also be achieved with bimodally distributed polymers, in particular if longer open times are required and / or sharp melting peaks are not allowed to occur (for example in the case of long joining times or fluctuating application temperatures).
  • the polymers of the invention have a polydispersity, determined by high-temperature gel permeation chromatography with universal calibration, of 1, 3-3, preferably from 1.4 to 2.7. This area is particularly advantageous, especially for use in the adhesive sector.
  • the crystallization or melting behavior in polymers, in particular in polyolefins is known to be a function of the molar mass, in linear polyolefins, in particular the chain length.
  • So z. B. of classical amorphous polyolefins, as they are currently used in the field of hot melt adhesive known that a polydispersity of 4-6 (or even higher) to a very wide Aufschmelz Symposium one hand and a delayed physical curing / crystallization on the other hand leads.
  • the latter is particularly disadvantageous for hot melt adhesives which are to be used in the packaging sector, because the polymers thereby have a partially extremely long open time (this is the time when there is a strong stickiness of the polymer as a result of not yet or not completely crystallized constituents). exhibit. Such polymers are not suitable for processing in high-speed packaging machines.
  • An additional disadvantage of the known systems is that polymers with a broad molecular weight distribution often also show poor tensile strengths as a result of the described crystallization deficiencies, which is likewise undesirable for packaging adhesives. In general, a broad molecular weight distribution is an indication that no uniform polymer but rather a polymer blend (or a polymer blend) is present, which leads to known limitations in the material properties.
  • the weight-average molar mass of the polymers according to the invention is usually in the range from 15,000 to 400,000 g / mol, preferably from 17,000 to 200,000 g / mol, more preferably in the range from 20,000 to 100,000 g / mol, and in particular preferably in the range of 22,000 to 95,000 g / mol. This range is particularly advantageous, especially for use in the adhesive sector. Due to their molecular weight and their molecular weight distribution, the polymers according to the invention have an optimum melt viscosity in the relevant application window, so that optimum wetting of the surface to be bonded can take place.
  • the relatively low melt viscosity also allows for penetration into macroscopic and microscopic surface structures, which significantly improves the adhesion of the adhesive layer.
  • the polymers according to the invention having weight-average molar masses of> 75,000 g / mol are also particularly suitable for use in molding compositions, geomembranes and films. Polymers of higher molecular weight show, especially in the case of linear polyolefins, a high to very high melt viscosity. This is for many applications, such as. As the production of moldings or the production of films and films quite desirable, because they give the products a high rigidity and high tensile strength. However, such materials are completely unsuitable for use as raw materials for hot melt adhesives, particularly those intended for use in packaging applications.
  • the polymers according to the invention are distinguished by having an ALPHA value, determined by high-temperature gel permeation chromatography with universal calibration, in the range from 0.6 to 1.2, preferably in the range from 0.62 to 1.17, particularly preferably in the range from 0.65 to 1, 15 and particularly preferably in the range of 0.7 to 1, 12 have.
  • the polymers according to the invention are thus distinguished by a low branching tendency, in particular they preferably do not contain any long chain branching. Branched polymers show a highly complex theological behavior due to their molecular structure, which leads to a poor applicability from the melt and a poor flow, especially in doctor blade and spray application.
  • the proportion of low molecular weight constituents having a molecular weight of 500 to 1000 daltons found in the investigation by high-temperature gel permeation chromatography with universal calibration is at most 0.75% by mass, preferably at most 0.5% by mass, particularly preferably at most 0.4% -%, in particular at most 0.3 ma-%.
  • the described method can not detect constituents having a molecular weight of 500 to 1000 daltons. It is thereby achieved that the polymers according to the invention contain no polymer constituents which are responsible for the migration z. B. tend to the surface and / or the interface.
  • Such migration results in a strong weakening of an adhesive bond containing this polymer due to the release effect of low molecular weight polymer constituents, and in the area of food packaging (especially in direct and / or indirect food contact) fabrics with migrating Components may not be used due to legal regulations.
  • the proportion of low molecular weight constituents with a molecular weight ⁇ 500 daltons found in the investigation by high-temperature gel permeation chromatography with universal calibration is at most 0.75% by mass, preferably maximum 0.5% by mass, more preferably at most 0.4% by mass, especially at most 0.3% by mass.
  • no components with a molecular weight ⁇ 500 daltons can be detected by the method described.
  • polymers containing low molecular weight components with low molar masses are therefore unsuitable The same applies to the area of food packaging.
  • the polymers of the invention are characterized in that they at a temperature of 190 0 C, a maximum deformation of 1% and a measurement frequency of 1 Hz, a complex melt viscosity of 700 to 400,000 mPa * s, preferably from 800 to 300,000 mPa * s , particularly preferably from 900 to 250,000 mPa * s and particularly preferably from 1,000 to 150,000 mPa * s, with further preferred ranges between 1100 and 25,000 mPa * s, between 26,000 and 65,000 mPa * s and between 66,000 and 140,000 mPa * s.
  • different regions are very particularly preferred. So z. B. for use in the field of spray application and for naps and Filraitinitati the polymers of the invention having a melt viscosity of 700 to 10,000 mPa * s particularly preferred, while for use in molding compositions polymers having a melt viscosity of
  • the ratio of the melt viscosity measured at 190 0 C and a maximum deformation of 1% at a shear rate of 10 Hz and a shear rate of 0.1 Hz serve. This ratio is for the polymers according to the invention between 1: 1 and 1: 100, preferably between 1: 1, 05 and 1:50, particularly preferably between 1: 1, 075 and
  • the polymers according to the invention thus have an optimum balance between processability and flow properties and are distinguished by a moderate intrinsic viscosity.
  • the viscosity in the application tool eg spray gun
  • the viscosity when the shear disappears is important, so that no course of the polymer melt takes place beyond the sprayed area.
  • the increase must be within narrow limits, since otherwise no coagulation of the individual spray particles takes place.
  • thermo-dependent theological behavior An important parameter for hotmelt adhesives or adhesive raw materials is the temperature-dependent theological behavior. This is accessible, for example, by measuring a cooling curve in the oscillation rheometer, paying attention to a very small deformation (max 1%) and a slow cooling rate (1, 5 K / min).
  • the measured values obtainable from the cooling curve are clearly superior to those obtained from heating curves (in particular from curves during the first heating), since the previous history of melting on the one hand levels the thermal history of the polymer sample, and on the other hand optimum wetting of the measuring body surface by the melt , whereby friction and slip effects between measuring body and sample are excluded.
  • the deformation susceptibility ie the risk of irreversible morphology change
  • the rheological material states can in any case be realistically imaged during a bonding by means of hot melt adhesives only via a cooling curve, since this is the present state during the bonding.
  • the ratio of storage and loss modulus in the temperature range from the end of the melting point to about 220 0 C can be used.
  • the loss modulus G " (as a synonym for the viscous material properties) must lie clearly above the storage modulus G ' (as a synonym for the elastic material properties) in the processing window
  • the ratio of storage modulus G ' to loss modulus G " lies for the claimed polymers at a shear rate of 1 Hz and a deformation of 1% in the temperature range from the end of the highest melting peak (offset / DSC) to about 220 0 C between 1: 1 and 1: 10000, preferably between 1: 1, 25 and 1: 5000, more preferably between 1: 1, 5 and 1: 2500, and most preferably between 1: 2 and 1: 1000.
  • the minimum shear rate determined by oscillation rheometry at a deformation of 1% is above the loss modulus above the storage modulus (crosspoint) and thus a rheological processability of the melt is present at a maximum of 1 Hz, preferably at a maximum of 0.5 Hz preferably at a maximum of 0.1 Hz and more preferably at a maximum of 0.01 Hz.
  • a rheological processability of the melt is present at a maximum of 1 Hz, preferably at a maximum of 0.5 Hz preferably at a maximum of 0.1 Hz and more preferably at a maximum of 0.01 Hz.
  • Particularly preferred is the frequency-dependent measurement of storage modulus G ' and loss modulus G " by oscillatory rheometry (sample deformation maximum 1%) at processing temperature in the frequency range 0.1 to 10 Hz no intersection (so-called "crosspoint") of G ' and G " , where G " is greater than G ' over the entire frequency range.
  • the needle penetration of the polymers according to the invention is in the range from 1 to 50 * 0.1 mm, preferably from 2 to 45 * 0.1 mm, particularly preferably from 3 to 30 * 0.1 mm and particularly preferably from 4 to 28 * 0, 1 mm., With value ranges between 5 and 15 * 0.1 mm and between 16 and 27 * 0.1 mm are very particularly preferred. This ensures that the polymers according to the invention, despite high strength, have a sufficient degree of plasticity. This is particularly important in applications in which a dynamic stress of the bond takes place. Highly crystalline polyolefins have a needle penetration of ⁇ 1 * 0.1 mm and are therefore very hard and in the unmelted state not plastically deformable so inflexible. Predominantly amorphous polyolefins have a needle penetration of> 60 * 0.1 mm and therefore do not show sufficient strength.
  • the polymers according to the invention are predominantly semicrystalline in nature, that is to say they have a significant crystalline fraction. This manifests itself in melt peaks on first and / or second heating of the polymers in the DSC. All of the polymers according to the invention exhibit at least one melting peak at least during the first melting in the DSC. Independent of The number and nature of the melting peaks in the differential calorimetry (DSC) are those at the first heating for the polyolefins according to the invention between 40 and 140 0 C. It is preferred that during the measurement in the differential calorimeter (DSC) during the first heating 1 -.
  • melting peaks can be detected, wherein in the case of three melt peaks, the first melting peak maximum at temperatures of 40 - 60 0 C, the second at temperatures of 65 - 110 0 C and the third at temperatures of 80 - 140 0 C, particularly preferably at temperatures from 85 to 130 0 C. With only two melting peaks, as is the first melting peak maximum 40-115 0 C, the second between 50 and 140 0 C, particularly preferably 55-135 0 C. If only one melting peak on, so the melting peak maximum is between 40 and 140 0 C.
  • the polymers according to the invention preferably 0, 1 or 2 melting peaks, wherein in the case of two melt peaks, the first melting peak maximum at 80 to 125 0 C, the second melting peak maximum at 90 - 140 0 C, more preferably from 95 - 135 0 C. If only one melting peak is present, the melting temperature is from 80 to 145 0 C, particularly preferably 85-142 0 C.
  • the polymers have a pronounced tendency to cold crystallization, where (if any) of the exothermic cold crystallisation peak at the second Heating between 30 and 75 0 C is. If the polymers according to the invention have no melting peak on the second reflow, this in no way means that they have no crystallinity. Rather, only the crystallinity present is not detectable by the DSC standard measurement method used.
  • the polymers according to the invention have an optimum ratio of crystalline and non-crystalline units and show optimum thermal properties both in the loading and in the processing case.
  • a more or less pronounced partial melting occurs before the adhesive bond melts on the whole.
  • a plastic deformation is possible even without complete dissolution (melting) of the adhesive bond, which is particularly advantageous in structural bonding and temporary fixation.
  • the polymers according to the invention can be modified by changing the polymer composition and
  • Polymerization conditions are also carried out so that takes place until shortly before the melting point no significant partial melting. In the latter case, very high heat resistance of the bond can be realized, the heat deflection temperature is very close to the softening temperature.
  • the inventive polymers in the 2nd heating curve exhibit the DSC measurement at a heating rate of 10 K / min, either a melting peak or two melting peaks, these melting peaks having different intensities , If at least one melting peak is detectable in the second heating curve of the DSC, then the end of the melting range (so-called peak offset) is particularly preferred for the polymers according to the invention between 85 ° C. and 150 ° C., preferably between 87 ° C. and 148 ° C. between 89 0 C and 146 0 C and particularly preferably between 90 0 C and 145 0 C. If the end of the melting range at low temperatures, this is especially for the bonding of thermolabile materials of advantage. On the other hand, if the end of the melting range is high, the result is a particularly high heat resistance.
  • the polymers preferably have an endothermic enthalpy of fusion of at most 35 J / g, preferably from 1 to 33 J / g, more preferably from 2 to 30 J / g and especially preferably from 3 to 28 J / g, measured in the DSC during the second heating with the ranges of 1-15 J / g and 16-28 J / g being most preferred.
  • This ensures that the polymers of the invention have a crystallinity which, although high enough to ensure a high initial strength of a bond, but remains so low that the flexibility of the polymers of the invention is not impaired.
  • the exothermic cold crystallization enthalpy measured in the second heating in the DSC is preferably not more than 20 J / g, preferably not more than 18 J / g, particularly preferably 1-17 J / g. It is thereby achieved that polymers can be made available whose use in bonds allows completely new possibilities with regard to the joining techniques used. Thus, depending on the polymer composition and the polymerization conditions used, it is possible, after the joining and cooling, to plastically deform the adhesive bond for a certain period of time and then to cure by storage at elevated temperature (recrystallization). On the other hand, the recrystallization can also be accelerated by tempering (i.e., storage at elevated temperature) immediately after the joining.
  • tempering i.e., storage at elevated temperature
  • the means of DSC (2.Avemsammlungkurve, 20K / min.) Determined glass transition temperature of the polymers of the invention is a maximum of 0 0 C, preferably -2 to -50 0 C, particularly preferably from -3 to -45 0 C, in particular, the ranges of values between -3 and -25 0 C and between -26 and -45 0 C are particularly preferred. It is thereby achieved that, depending on the polymer composition and selected polymerization conditions, the inventive compositions can also be used in applications which require high low-temperature flexibility and therefore remain closed to highly crystalline polyolefins (such as, for example, isotactic polypropylene). It is particularly noteworthy that for the polymers of the invention low glass transition temperatures without the use of expensive comonomers such. 1-pentene, 1-hexene, 1-octene, 1-nonene and / or 1-decene.
  • a maximum of 160 0 C preferably at 80 to 155 0 C, particularly preferably at 83 to 145 0 C and in particular at 85-140 0 C.
  • the softening temperature found differs from the uppermost melting temperature (maximum melting peak) determined in the DSC during the second melting by 1-40 K, preferably 2-35 K, more preferably 3 - 30 K from.
  • the softening temperature found is 1 to 40 K, preferably 2 to 35 K, particularly preferably 3 to 30 K, above the uppermost melting temperature (maximum melting peak) determined in the DSC during the second melting. This ensures that polymers can be made available which have a good material cohesion even above their melting point, so that high heat resistance can be achieved.
  • the inventive polymers have in the 2nd heating curve of the DSC no detectable melting peak on, however, a certain after Ring and Ball softening point of at least 80 0 C preferably at least 83 0 C, more preferably of at least 85 0 C, and particularly preferably from 85 ° to 160 ° C.
  • a certain after Ring and Ball softening point of at least 80 0 C preferably at least 83 0 C, more preferably of at least 85 0 C, and particularly preferably from 85 ° to 160 ° C.
  • the polymers of the invention preferably have a solubility in XyIoI at room temperature of up to 100% by mass, preferably from 60 to 100% by mass, more preferably from 70 to 100% by mass, and most preferably from 80 to 100% by mass.
  • This has the advantage that polymers having good to very good solubility in xylene are made available, which, in contrast to previously known systems having this property, has a very narrow molecular weight distribution with extremely low low molecular weight fraction and high crystallinity in terms of solubility, as well as have a high softening point and moderate needle penetration.
  • the polymers according to the invention having high solubility in xylene enable the preparation of solution formulations having good handleability and low toxic endangering potential.
  • the polymers according to the invention furthermore preferably have a solubility in tetrahydrofuran at room temperature of up to 100% by mass, preferably at least 10% by mass, preferably at least 25% by mass, more preferably at least 40% by mass and most preferably at least 50% -% on.
  • the polymers according to the invention are distinguished by the fact that they have an adhesive shear strength of at least 0.2 MPa, preferably at least 0.4 MPa, more preferably of at least 24 hours storage time without further additions on untreated isotactic polypropylene have at least 0.5 MPa and more preferably greater than 0.6 MPa.
  • an adhesive shear strength is present after at least 24 hours storage time of at least 0.1 MPa, preferably at least 0.15 MPa, more preferably at least 0.2 MPa, and most preferably greater than 0.25 MPa ,
  • the adhesive shear strength without further additives after at least 24 hours storage time is at least 1.0 MPa, preferably at least 1.5 MPa, more preferably at least 2.0 MPa and particularly preferably more than 2.5 MPa.
  • the open time of the polymers according to the invention can be up to 30 minutes, depending on the polymer composition and the polymerization conditions used.
  • the open time without further additives is not more than 300 seconds, preferably not more than 250 seconds, more preferably not more than 200 seconds and particularly preferably from 1 to 180 seconds.
  • the polymers according to the invention are distinguished by the fact that they have a tensile strength of from 1 to 25 MPa, preferably from 1.5 to 23 MPa, more preferably from 2 to 21 MPa and in particular from 2, without further additives after at least 24 hours of storage in the tensile test. 5 to 20 MPa and / or have an absolute elongation at break of at least 10%, preferably of at least 15%, more preferably from 20 to 1500% and most preferably from 25 to 1250%, wherein the ranges of 50 - 750%, 100 - 650% and 150-600% as well as the ranges of 150-1200%, 250-1100% and 350-1000% are also particularly preferred.
  • Another object of the present invention is the use of the polymers of the invention in molding compositions, as or in adhesives, in marking materials, coating compositions, geomembranes or roofing membranes, as primers or in primer formulations and / or in aqueous dispersions, suspensions and / or emulsions.
  • molding compositions, adhesives, marking compounds, coating compositions, geomembranes or roofing membranes, primers or primer formulations, aqueous dispersions, suspensions and / or emulsions comprising the polymers according to the invention are likewise provided by the present invention.
  • molding compositions these essentially contain the polymer according to the invention.
  • the molding compositions may contain other ingredients.
  • the other constituents may in particular comprise other polymers, these other polymers being one or more ethylene polymers, and / or isotactic propylene polymers and / or syndiotactic propylene polymers and / or isotactic poly-1-butene polymers and / or syndiotactic poly-1 Butters Polymehsate can act.
  • melt viscosity measured by Oszillationsrheometrie at 190 0 C, particularly preferably between the inventive polymers contained and polymers additionally contained, wherein the additional polymers contained at least twice as high melt viscosity as the polymers of the invention, preferably at least 3 times have such high, more preferably at least 4 times as high, and particularly preferably at least 5 times higher melt viscosity.
  • the molding compositions mentioned can be used for the production of finished parts (eg by injection molding) or for the production of films and / or films.
  • the polymers according to the invention are preferably used as or in adhesives, particularly preferably in adhesive formulations.
  • the preferred adhesive formulations according to the invention contain the polymer according to the invention.
  • constituents may be present in the adhesive formulations according to the invention.
  • the other constituents may be in particular solution formulations to cyclic and / or linear aliphatic and / or aromatic hydrocarbons, including corresponding halogenated hydrocarbons. This proves the good solubility of the polymers of the invention in different solvents such.
  • the abovementioned hydrocarbons have a formulation proportion of not more than 90% by mass, preferably not more than 80% by mass, more preferably not more than 75% by mass, and particularly preferably not more than 50% by mass.
  • the adhesive formulation according to the invention is very particularly preferably a hot-melt adhesive formulation which can be used for all types of adhesive bonds known to the person skilled in the art, for example for the bonding of packaging materials.
  • the hot melt adhesive formulation according to the invention may contain further constituents which are suitable for achieving special properties, such as, for example, Deformability, adhesiveness, processability, (melt viscosity) viscosity, strength, crystallization rate, tackiness, storage stability, etc. are necessary.
  • the proportion of the further constituents in a particular embodiment of the present invention is particularly preferably not more than 10% by mass. This has the advantage that the material properties of the adhesive formulation are substantially the same as the polymer of the invention used. Such an adhesive formulation can be produced with very little effort.
  • the proportion of the further constituents can be> 10% by mass.
  • the further constituents make up at most 80% by mass of the total formulation, preferably at most 60% by mass, particularly preferably at most 50% by mass, in particular preferably at most 40% by mass.
  • the other constituents may be inorganic and / or organic fillers, which may optionally be electrically conductive or insulating, inorganic and / or organic pigments, which may optionally be electrically conductive or insulating, synthetic and / or natural resins, in particular adhesive resins, synthetic and / or natural oils, inorganic and / or organic, synthetic and / or natural polymers, which may optionally be electrically conductive or insulating, inorganic and / or organic, synthetic and / or natural fibers, which may optionally be electrically conductive or insulating , inorganic and / or organic stabilizers, inorganic and / or organic flame retardants.
  • inorganic and / or organic fillers which may optionally be electrically conductive or insulating, inorganic and / or organic pigments, which may optionally be electrically conductive or insulating, synthetic and / or natural resins, in particular adhesive resins, synthetic and / or natural oils, inorganic and / or organic, synthetic and
  • the other constituents comprise resins, the resins being used to adapt certain properties of the adhesive layer, in particular the tackiness and / or adhesion, the flow and creep behavior of the adhesive layer and / or the adhesive viscosity, to particular requirements.
  • resins may be natural resins and / or synthetic resins. In the case of natural resins, these natural resins contain abietic acid as the main component (eg rosin).
  • the resins may be terpene or polyterpene resins, petroleum resins and / or cumarone-indene resins, in particular so-called C 5 resins and / or Cg resins and / or copolymers of C5- / C9 resins act.
  • the proportion of the resins in the hot-melt adhesive formulation according to the invention is in particular at most 45% by mass, preferably between 1 and 40% by mass, more preferably between 2 and 30% by mass, and particularly preferably between 3 and 20% by mass, based on the total formulation.
  • amorphous poly ( ⁇ -olefins) (so-called APAOs) as further constituents.
  • the abovementioned amorphous poly ( ⁇ -olefins) may be homo- / co- and / or terpolymers of ethylene, propylene, 1-butene or linear and / or branched 1-olefins having 5 to 20 carbon atoms, which may be, for example , B. by classical Ziegler-Natta catalysis or metallocene catalysis are available.
  • the proportion of amorphous poly ( ⁇ -olefins) is in particular at most 50% by mass, preferably at most 40% by mass and particularly preferably at most 30% by mass, based on the total formulation.
  • the other constituents are preferably crystalline or partially crystalline polyolefins, in particular isotactic polypropylene, syndiotactic polypropylene, polyethylene (HDPE, LDPE and / or LLDPE), isotactic poly (I-butene), syndiotactic poly (I-butene), and copolymers thereof and / or their copolymers with linear and / or branched 1-olefins having 5 to 10 carbon atoms.
  • the crystalline or partially crystalline polyolefins are chemically modified polyolefins, the chemical modification in particular comprising those by maleic anhydride, itaconic anhydride, acrylic acid, acrylates, methacrylates, unsaturated epoxy compounds, silane acrylates, silanes and hydroxyalkylsilanes.
  • the other ingredients may include polymers having polar groups.
  • Polymers containing polar groups include polystyrene copolymers (eg, with maleic anhydride, acrylonitrile, etc.), polyacrylates, polymethacrylates, (co) polyesters, polyurethanes, (co) polyamides, polyether ketones, polyacrylic acid, polycarbonates, and chemically modified polyolefins (such as, for example).
  • the other constituents may include homopolymers and / or copolymers based on ethylene, propylene, acrylonitrile, butadiene, styrene and / or isoprene, in particular, these polymers are block copolymers, in particular rubbers such as. Example, natural and Synthetic rubber, poly (butadiene), poly (isoprene), styrene-butadiene rubber and nitrile rubber.
  • the proportion of the polymers based on butadiene, styrene, and / or isoprene is not more than 20% by mass, preferably 1-15% by mass, more preferably 1.5-10% by mass and in particular 2-9% by mass on the hot melt adhesive formulations.
  • elastomeric polymers based on ethylene, propylene, a diene and / or c / s, c / s-1, 5-cyclooctadiene, exo-dicyclopentadiene, enc / o-dicyclopentadiene u. 1, 4-hexadiene and 5-ethylidene-2-norbornene, in particular these are ethylene-propylene rubber, EPM (double bond-free, ethylene content 40-75 m%) and / or EPDM.
  • the proportion of polymers based on ethylene, propylene, a diene and / or ice, c / s-1, 5-cyclooctadiene, exo-dicyclopentadiene, enc / o-dicyclopentadiene and 1, 4-hexadiene and 5-ethylidene-2 norbornene is usually not more than 20% by mass, preferably 1-15% by mass, more preferably 1.5-10% by mass and in particular 2-9% by mass, based on the hot-melt adhesive formulations.
  • the further components may comprise waxes, in particular modified and unmodified waxes, these preferably being crystalline, partially crystalline and / or amorphous polyolefin waxes based on polyethylene, polypropylene and / or poly (l-butene), paraffin waxes, metallocene waxes, Micro waxes, polyamide waxes, polytetrafluoroethylene waxes and / or Fischer-Tropsch waxes.
  • the proportion of waxes is at most 50% by mass, preferably 1-40% by mass, more preferably 2-30% by mass, and particularly preferably 3-20% by mass, based on the hot-melt adhesive formulations.
  • the further constituents may include fillers, wherein the fillers are used to specific property profiles of the adhesive layer, such. As the temperature application range, the strength, the shrinkage, the electrical conductivity, the magnetism and / or the thermal conductivity specifically adapted to specific requirements.
  • the fillers are inorganic and / or organic fillers.
  • the inorganic fillers are in particular selected from silicic acids (including hydrophobized silicas), quartz flour, chalks, barite, glass particles (in particular spherical particles to increase light reflection), glass fibers, carbon fibers, asbestos particles, asbestos fibers and / or metal powders.
  • Organic fillers are, for example, carbon black, bitumen, crosslinked polyethylene, crosslinked rubber. Rubber compounds synthetic fibers such.
  • polyethylene fibers polypropylene fibers, polyester fibers, polyamide fibers, aramid fibers, saran fibers, MP fibers or natural fibers such as straw, wool, cotton, silk, flax, hemp, jute, and / or sisal.
  • the proportion of fillers is at most 80% by mass, preferably 1-60% by mass, more preferably 5-40% by mass, and particularly preferably 7-30% by mass, based on the hot-melt adhesive formulations.
  • the other ingredients may include stabilizers, which are used to prevent the adhesive formulation from external influences such. B. the influence of (processing) heat, shear stress, solar radiation, humidity and oxygen to protect.
  • Suitable stabilizers are, for example, hindered amines (HALS stabilizers), hindered phenols, phosphites and / or aromatic amines.
  • HALS stabilizers hindered amines
  • hindered phenols hindered phenols
  • phosphites / or aromatic amines.
  • the proportion of stabilizers is at most 3% by mass, preferably between 0.05 and 2.5% by mass, and particularly preferably between 0.1 and 2% by mass, based on the hot-melt adhesive formulations.
  • the other ingredients may include one or more oils, which may be natural and / or synthetic oils. These one or more oils preferably have a viscosity at the processing temperature of from 1 to 1000 mPa * s, preferably from 2 to 750 mPa * s, most preferably from 3 to 500 mPa * s.
  • Suitable oils are, for example, mineral oils, (medicinal) white oils, isobutene oils, butadiene oils, hydrogenated butadiene oils and / or paraffin oils.
  • the proportion of one or more oils is not more than 50% by mass, preferably 1-45% by mass, more preferably 3-40% by mass and in particular 5-38% by mass on the hot melt adhesive formulations.
  • inorganic and / or organic pigments, UV-active substances, organic and / or inorganic nucleating agents which accelerate the crystallization of the polymers and thus reduce the open time of the bond can be contained in the hot melt adhesive formulations.
  • the formulations described above are multiphase blends.
  • hot-melt adhesive formulations according to the invention can be applied to the surface to be bonded in particular by means of spray application, as bead (s) and / or by doctoring. Particularly preferably, the order is carried out by spray application.
  • adhesions containing one or more polymers of the present invention are, in particular, packaging adhesions, adhesions of hygiene articles, wood bonds, adhesions of glass surfaces, label adhesions, laminating bonds, carpet or artificial turf bonding, shoe bonding, pressure-sensitive adhesions, book bonding or textile adhesives.
  • the packaging materials may include the materials wood, cardboard, paper, plastic, metal, ceramics, glass, synthetic and / or natural fibers and / or textiles.
  • the packaging materials are preferably non-polar plastics, in particular polyethylene, polypropylene, poly (I-butene) or their copolymers with linear and / or branched C 2-20 olefins, for example uncrosslinked polyethylene, such as, for example, As LDPE, LLDPE and / or HDPE, and / or to (eg silane) crosslinked polyolefin, in particular to silane-crosslinked polyethylene.
  • nonpolar plastics may in particular be polystyrene, polybutadiene, polyisoprene homopolymers and / or copolymers, and / or their copolymers with linear and / or branched C 2 -C 20 -olefins or dienes, such as, for example, As EPDM, EPM or EPR, and / or synthetic or natural rubber.
  • polar plastics these are in particular polyacrylates, in particular polyalkyl methacrylates, polyvinyl acetate, polyesters and / or copolyesters, in particular polyethylene terephthalate and / or polybuthylene terephthalate, polyamides and / or copolymamides, acrylonitrile copolymers, in particular acyl nitrile / butadiene / styrene Copolymers and / or styrene / acrylonitrile copolymers to maleic anhydride copolymers, in particular to S / MSA copolymers and / or MSA-grafted polyolefins such.
  • polyacrylates in particular polyalkyl methacrylates, polyvinyl acetate, polyesters and / or copolyesters, in particular polyethylene terephthalate and / or polybuthylene terephthalate, polyamides and / or copolymamides,
  • the packaging materials can be present as a box, box, container, sheet, disc, film and / or film.
  • corresponding plastic films may be made via extrusion, calendering, blow molding, casting, solvent drawing, thermoforming, or a combination of several of these techniques.
  • the plastic films are single-layer films that are oriented or unoriented. In the case of an orientation of the monolayer film, a one-, two- or multi-axis orientation may be present, wherein the orientation axes may be at any angle to the film take-off direction.
  • the plastic films may be multilayer films, wherein the film layers may be made from the same as well as from different materials.
  • the multilayer films may be oriented or unoriented. In the case of an orientation of the multilayer plastic films, a one-, two- or multi-axis orientation may be present, wherein the orientation axes may be at any angle to the film take-off direction.
  • the bonds are adhesions of transparent plastic films.
  • the multilayer plastic film is a composite film.
  • one or more of the film layers may consist of composite material, the composite materials being in continuous form (eg paper, aluminum foil or the like) and / or discontinuous form (eg particles and / or fibers). may be present.
  • the wood packaging may be solid wood, real wood laminates, plastic laminates, MDF boards and / or similar woody materials. Both resin and oil-poor woods such. B. beech, oak, etc., but also resin or oil-rich woods such as teak, pine, etc. are used.
  • At least one of the polymers according to the invention contained has an open time of less than 30 seconds.
  • bonds according to the invention are structural wood bonds, in particular Kantenumleim Institute and / or Dekorpapierummantelungen and / or Dekorfolienamamin isten and / or Assembly bonding.
  • the bond can moisture-absorbing substances such. As silica gel, polyacrylic acid particles, etc. included.
  • This is preferably a multi-pane insulating glass composite. All types of multi-pane insulating glass composites known to those skilled in the art are suitable for this purpose, regardless of the individual structure, for example with or without further spacers.
  • the glass surface may be the surface of glass fibers, such as the surface of a fiber optic cable, such as e.g. B. is used for data and / or telephone lines.
  • the object to be bonded is a label.
  • the label may in this case consist of a paper, plastic, metal and / or multilayer film and in particular for the marking of coated, coated, anodized and / or otherwise surface-treated metal, in particular tinplate cans and glass or plastic (in particular PET). ) Bottles are used.
  • the adhesive for label bonds may be a so-called "pressure-sensitive" adhesive (PSA).
  • the bonds are a lamination
  • the surface to be laminated may be the surface of an inorganic and / or organic substance, preferably of metals (eg steel, aluminum, Brass, copper, tin, zinc, enamel), glass, ceramics and / or inorganic building materials such.
  • the surface may be wood, paper, cardboard and / or plastics.
  • the surface can itself Composite of inorganic and organic materials (eg glass fiber composites).
  • the laminated laminating material may be inorganic and / or organic in nature.
  • Examples of counter-laminated inorganic laminating materials are ultrathin glass sheets, ceramic membranes and / or metal foils (eg aluminum foil).
  • counter-laminated organic laminating materials are paper, cardboard, wood veneer, plastics, natural and / or synthetic textiles, nonwoven artificial leather and / or natural leather.
  • bonds according to the invention may also be an adhesive bond in the vehicle interior (eg screens, headliners, etc.).
  • the present invention are adhesives for the production of carpets and / or artificial turf.
  • the bond is used for nubs and filament binding.
  • the fibers or fiber composites to be incorporated may be natural and / or synthetic fibers. Examples of natural fibers or fiber composites are wool, cotton, sisal, jute, straw, hemp, flax, silk and / or mixtures of these fibers.
  • synthetic fibers or fiber composites to be incorporated are (co) polyamide fibers, polyethylene fibers, co (polyester fibers), polypropylene fibers and / or mixtures of these fibers.
  • the bonded by the bonding filaments are selected from polypropylene filaments, polyethylene filaments, polyamide filaments, polyester filaments or mixed filaments of the listed plastics.
  • the bond is used for carpet backing.
  • a textile substrate can additionally be counter laminated.
  • the carpet elements obtained are, for example, carpet tiles or a subsequently deformable car carpet.
  • the polyolefin according to the invention contained a melt viscosity at 190 0 C of not more than 10,000 mPa * s, preferably from 500 to 8,000 mPa * s, more preferably from 600 to 6000 mPa * s and particularly preferably from 750 to 4000 mPa * s on.
  • the proportion of polyolefins according to the invention is in particular 60 to 98% by mass.
  • the application weight is in particular 20-1500 g / m 2 . Other examples are within the skill of one of ordinary skill in the art.
  • adhesions according to the invention can be shoe adhesions which can be used, for example, in the field of sports shoes and / or for the production of so-called split leathers.
  • Adhesive bonds according to the invention are also known as "pressure-sensitive adhesives” (PSA), in which case it is advantageous if at least one of the polymers and / or formulation constituents according to the invention has a “cold flow” (ie a melting point below room temperature).
  • Cold flow formulation ingredients include, for example, poly (I-hexene), poly (I-octene), poly (1-hexene-co-1-octene), polyacrylates, etc.
  • a plurality of textile layers can be connected to one another selectively or in a planar manner, wherein textile elements to be bonded can comprise natural or synthetic materials.
  • the natural textile elements are wool, horsehair, cotton, linen fabric, hemp, jute, sisal, flax, straw and / or leather.
  • Preferred synthetic textile elements as constituents polypropylene, polyethylene, (co) polyamides, (co) polyester, nylon, perlon and / or Kevlar ®.
  • one or more of the elements to be bonded may be an insert.
  • the adhesive formulation according to the invention is introduced in the form of a powder between the textile layers to be bonded and activated by thermal energy (for example with the aid of an ironing press).
  • the polymers according to the invention can be used in marking compositions, coating compositions, geomembranes or roofing membranes.
  • the marking compositions according to the invention may contain the other constituents already mentioned in the description of the molding compositions or adhesive formulations.
  • the marking compositions according to the invention can be used as road marking compounds.
  • coating compositions it may be, for example, a coating material for cardboard or paper coating.
  • the polymers according to the invention are suitable for use in geomembranes.
  • further constituents may be present in the geomembranes, in particular the other constituents are other polymers, fillers and bitumen.
  • the proportion of the polymers according to the invention is at most 30% by mass, preferably at most 27% by mass, more preferably at most 25% by mass and particularly preferably at most 22% by mass, based on the geomembrane.
  • the geomembranes are roofing membranes.
  • At least one of the polymers according to the invention has a glass transition temperature of not more than -10 0 C, preferably not more than -15 0 C, particularly preferably not more than -18 0 C and particularly preferably not more than -20 0 C.
  • the polymers according to the invention are suitable for use as primers, adhesion promoters or in primer formulations and / or in adhesion promoter formulations, in particular the absence of halogenated organic constituents is beneficial.
  • primer and adhesion-promoting formulations containing the polymers according to the invention are used in order to achieve adhesion of organic coatings and / or adhesives to untreated polyolefin surfaces, in particular to untreated polypropylene.
  • the primer and / or primer formulations are used as a primer on polypropylene moldings such. As vehicle bumpers and / or trim parts applied to achieve better adhesion of the subsequent painting.
  • the polymers according to the invention are suitable for use in aqueous dispersions, suspensions and / or emulsions.
  • surface-active substances eg inorganic and / or organic surfactants of ionic and / or nonionic nature
  • other polymers in particular those with polar monomer units
  • the preparation of the aqueous dispersions, suspensions and / or emulsions is preferably carried out using a solution of the polymers according to the invention, in particular in tetrahydrofuran or xylene.A production using a melt of the polymers according to the invention is also possible. in which case polymers having a melting / softening temperature of ⁇ 100 ° C.,
  • the proportion of the polyolefins according to the invention is more than 10% by mass, based on the total formulation.
  • the polymer composition is determined by high temperature 13 C NMR.
  • the 13 C NMR spectroscopy of polymers is described, for example, in the following publications:
  • the determination of the molecular weight is carried out by high-temperature GPC.
  • the solvent used is trichlorobenzene.
  • the measurement is carried out at a column temperature of 160 ° C.
  • the universal calibration used for the evaluation of the elution curves is carried out on the basis of polyolefin standards. The results are not comparable with measurements whose calibrations based on non-related polymers - eg. B. on polystyrene basis - was carried out, or which have been done without universal calibration, otherwise there is an impermissible comparison of different three-dimensional polymer structures or hydrodynamic radii. Also, the comparison with measurements using other than the specified solvent, is not allowed, since in different solvents different three-dimensional polymer structures or hydrodynamic radii may be present, leading to a different result in the molecular weight determination.
  • the polydispersity P d is defined as the quotient of number average and weight average molecular weight. In particular, it is a measure of the width of the present molecular weight distribution, which in turn allows conclusions to be drawn about the present polymerization behavior. It is determined by high temperature GPC.
  • the polydispersity is characteristic within certain limits for a particular catalyst-cocatalyst combination. The polydispersity has a relatively strong influence on the tackiness of the material at room temperature and on the adhesion.
  • [ ⁇ ] K v Mv ⁇ describe (H. -G. Elias, macromolecules, Volume 2, 6th edition, Wiley-VCH, Weinheim 2001, pp 411-413).
  • K v and ⁇ are constants which are influenced by the constitution, configuration and molar mass of the polymer as well as by the solvent and the temperature.
  • the essential meaning of the alpha value in the present invention is that of the hydrodynamic radius, which depends more or less on the branching sites on the polymer chains. With a low branch the alpha value is high, with a higher branch the value is low.
  • the rheological measurements are carried out according to ASTM D 4440-01 ("Standard Test Method for Plastics: Dynamic Mechanical Properties Measurement Rheology") using an Anton Paar MCR 501 rheometer with a plate-plate geometry (plate diameter: 50 mm) as the oscillation measurement
  • the maximum sample deformation used is 1% in all measurements, the temperature dependent measurements are carried out at a measuring frequency of 1 Hz and a cooling rate of 1, 5 K / min
  • the melt viscosity is determined by oscillatory rheometry using a shear rate of 1 Hz
  • the maximum deformation of the sample is chosen so that the sample is in the linear viscoelastic region during the entire measurement period
  • Viscoelastic materials are characterized by their ability to dissipatively dissipate stresses resulting from a deformation over a certain time compared to Hook's solids (relaxation) In the Gege
  • viscoelastic fluids may recover some of the de
  • the melting enthalpy, the glass transition temperature and the melting range of the crystalline fraction are determined by differential calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min.
  • DSC differential calorimetry
  • a mixture of xylene isomers is used whereby the polymer is dissolved under reflux and then the solution is cooled to room temperature.
  • 2 g of polyolefin are dissolved in 250 ml of xylene with stirring and heating to the boiling point of xylene. After refluxing for 20 minutes, the polymer solution is allowed to cool to 25 ° C. Undissolved or precipitated polyolefin is filtered off with suction (15 cm suction filter, Sartohus 390 filter paper) and dried. The remaining polymer solution is precipitated in a ⁇ -fold excess of methanol (added with a drop of 37% aqueous HCl). The resulting precipitate is filtered off and dried at 80 0 C in a drying oven (vacuum).
  • the adhesive shear strength is determined in accordance with DIN EN 1465.
  • Examples of Metallocene Polyolefins Having Syndiotactic Structural Elements 1. Preparation (Polymerization) of the Polymers According to the Invention:
  • one or more 1-olefin monomers will be at different temperatures and reaction pressures polymerized in a laboratory autoclave under protective gas (argon), wherein hydrogen is used as molecular weight regulator.
  • the monomer ethene (if used) is added continuously during the reaction time of 3 h.
  • the monomers propene and / or 1-butene are presented partially or completely in an autoclave. After 3 hours, the reaction mixture is mixed with isopropanol, whereby the reaction is stopped.
  • acetone solution of a stabilizer eg Irganox 1010 from Ciba
  • a stabilizer eg Irganox 1010 from Ciba
  • unreacted monomers and solvent (s) are evaporated.
  • the melt of the polyolefin produced is discharged at a temperature of about 190 0 C.
  • a catalyst solution or a catalyst suspension and a cocatalyst or a cocatalyst solution ethene, propene and 1-butene at different reaction temperatures in a laboratory autoclave polymehsiert, with hydrogen is used as molecular weight regulator.
  • the monomer ethene (if used) is added continuously during the reaction time of 3 h.
  • the monomers propene and / or 1-butene (if used) are partially or completely im Autoclaves submitted. After 3 hours, the reaction mixture is mixed with isopropanol, whereby the reaction is stopped. Then an acetone solution of a stabilizer (eg Irganox) is added. In an evaporator, unreacted monomers and solvent (s) are evaporated.
  • the melt of the polyolefin produced is discharged at a temperature of about 190 0 C.
  • titanium-aluminum mixed contact (aluminum-reduced TiCl 2): TiCl 3 * 0.33
  • the polymer composition and the microstructure of the polymers produced are determined by high-temperature 13 C-NMR.
  • muiii ei iiiiuuiiyäytMiicm 1 manufacturer Mitsui Chemicals; 2: manufacturer Dow Chemicals; 3: Manufacturer: Clariant; 4: manufacturer ExxonMobil Chemicals; 5: manufacturer Eastman Chemicals; 6 : Manufacturer Huntsman Polymer Chemicals
  • the determination of the molecular weight is carried out by high-temperature GPC. The determination is carried out according to ASTM D6474-99, but at a higher temperature (160 0 C instead of 140 0 C) and a lower injection volume of 150 ul instead of 300 ul.
  • the determination of the low molecular weight components is carried out from the molecular weight distribution curves obtained by integration of the corresponding surfaces. Examples of molecular weight distributions according to the invention and not according to the invention with or without a low molecular weight fraction can be found in the drawings.
  • nb not determined
  • the determination of the enthalpy of fusion, the glass transition temperature and the melting range of the crystalline fraction is carried out by Differentialkalohmetrie (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min.
  • the inflection point of the heat flow curve is evaluated as the glass transition temperature.
  • the thermograms of the first heating are taken from the same measurement and evaluated.
  • An exemplary DSC thermogram for a polyolefin according to the invention can be found in the drawings.
  • the determination of the adhesive shear strength according to DIN EN 1465.
  • the polymer samples (etc. z., Nitrogen, argon) melted for one hour at 190 0 C in a drying oven under a protective gas atmosphere and then at a temperature of 170 0 C (with the aid of a temperature sensor) applied to a test specimen. This is simply overlapped in 20 seconds with another test piece of the same material on a surface of 4 cm 2 and pressed together for 5 minutes with a weight of 2 kg. Supernatant adhesive polymer is removed. Subsequently, the bond pattern stored for 7 days at 20 0 C / 65% rel. Humidity in the climatic chamber and is then tested by tensile test for its mechanical properties.
  • test materials are untreated beech wood (thickness: 2 mm), untreated isotactic polypropylene (thickness: 2 mm, isotactic polypropylene, "PP-DWST7 manufacturer: Simona AG), untreated polyethylene (thickness: 2 mm,” PE-HWST “, manufacturer: Simona AG) and untreated poly (vinylchlohd) (thickness: 2 mm, hard PVC "Kömmadur ES", manufacturer Kömmerling-Profine)) used.
  • n.b . not determined; n.bb .: not determinable
  • the formulation ingredients are added, optionally melted and then mixed with a suitable mixing apparatus (eg on a hot plate with an IKA stirrer with kneader) homogeneously mixed:
  • a suitable mixing apparatus eg on a hot plate with an IKA stirrer with kneader
  • silane-modified polyolefin eg. B. VESTOPLAST ®
  • microwax for example MULTIWAX 180 HM
  • polymer stabilizer for example IRGANOX 1010, Ciba
  • low-viscosity oil for example PRIMOL 352
  • plasticizer for example INDOPOL H100, from Ineos
  • polymer stabilizer for example IRGANOX 1010, Ciba
  • low-viscosity oil eg PRIMOL 352
  • polymer stabilizer for example IRGANOX 1010, Ciba
  • hydrocarbon resin eg ESCOREZ 1102, Fa.
  • Hotmelt adhesive for packaging material: polypropylene
  • Hotmelt adhesive for packaging moisture-curing
  • polyolefin according to the invention according to Example 1 9.7 parts by weight of partially crystalline polyolefin z. B. VESTOPLAST ® 891,
  • isotactic polypropylene eg SABIC PP579S, Sabic
  • MSA-grafted polypropylene wax eg., MSA-grafted polypropylene wax
  • aromatic hydrocarbon resin eg NOVARES TN150, Rütgers Chemicals GmbH
  • ELVAX210 12 parts by weight calcite 0.3 parts by weight polymer stabilizer (eg IRGANOX 1010, Ciba)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des procédés de production de polyoléfines, des polyoléfines et leur utilisation, en particulier en tant qu'adhésif ou plus précisément en tant que constituant d'adhésifs.
PCT/EP2009/050638 2008-01-24 2009-01-21 Procédés de production de polyoléfines à éléments structuraux syndiotactiques, polyoléfines et leur utilisation Ceased WO2009092721A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008005945A DE102008005945A1 (de) 2008-01-24 2008-01-24 Verfahren zur Herstellung von Polyolefinen mit syndiotaktischen Strukturelementen, Polyolefine und deren Verwendung
DE102008005945.5 2008-01-24

Publications (1)

Publication Number Publication Date
WO2009092721A1 true WO2009092721A1 (fr) 2009-07-30

Family

ID=40535796

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/050638 Ceased WO2009092721A1 (fr) 2008-01-24 2009-01-21 Procédés de production de polyoléfines à éléments structuraux syndiotactiques, polyoléfines et leur utilisation

Country Status (4)

Country Link
CN (1) CN101560274A (fr)
DE (1) DE102008005945A1 (fr)
TW (1) TW201000505A (fr)
WO (1) WO2009092721A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821971B2 (en) 2008-01-24 2014-09-02 Evonik Degussa Gmbh Use of polyolefins having atactic structural elements in floor coverings
US10214600B2 (en) 2014-02-07 2019-02-26 Eastman Chemical Company Amorphpus propylene-ethylene copolymers
US10308740B2 (en) 2014-02-07 2019-06-04 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US10647795B2 (en) 2014-02-07 2020-05-12 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10696765B2 (en) 2014-02-07 2020-06-30 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
US10723824B2 (en) 2014-02-07 2020-07-28 Eastman Chemical Company Adhesives comprising amorphous propylene-ethylene copolymers
US11267916B2 (en) 2014-02-07 2022-03-08 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
CN115996798A (zh) * 2020-06-03 2023-04-21 E·丰特查·奎托斯 用于从罐和其它容器中选择性提取粘性烃的系统和方法
US12312509B2 (en) 2019-12-20 2025-05-27 3M Innovative Properties Company Adhesive article comprising polymer and polymerizable cyclic olefins, adhesive compositions and methods
US12338316B2 (en) 2019-10-14 2025-06-24 3M Innovative Properties Company Compositions comprising cyclic olefins and thermally conductive filler

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009027447A1 (de) 2009-07-03 2011-01-05 Evonik Degussa Gmbh Modifizierte Polyolefine mit besonderem Eigenschaftsprofil, Verfahren zu deren Herstellung und deren Verwendung
JP5736139B2 (ja) * 2010-09-16 2015-06-17 日東電工株式会社 粘着テープ
JP5689269B2 (ja) * 2010-09-16 2015-03-25 日東電工株式会社 粘着テープ
JP5685118B2 (ja) * 2011-03-17 2015-03-18 日東電工株式会社 粘着テープ
CN104077956B (zh) * 2013-03-28 2017-05-17 优泊公司 模内成型用标签及使用其的带标签的塑料容器
CN108473622A (zh) * 2016-01-13 2018-08-31 道达尔研究技术弗吕公司 包括间同立构聚丙烯的管道
CN108570121A (zh) * 2017-03-07 2018-09-25 常州市五洲环保科技有限公司 一种预分散橡胶助剂的高聚物载体的制备方法
JP7327815B2 (ja) * 2018-03-14 2023-08-16 国立研究開発法人理化学研究所 極性オレフィン系重合体からなる成形品とその物性
CN108440954B (zh) * 2018-03-15 2020-10-16 湖南格林美映鸿资源循环有限公司 一种pa6基复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387690A1 (fr) * 1989-03-11 1990-09-19 Hoechst Aktiengesellschaft Procédé de préparation d'une polyoléfine syndiotactique
DE19850898A1 (de) * 1998-11-05 2000-05-11 Bayer Ag Verfahren zur Herstellung von EP(D)M
EP1661924A1 (fr) * 2003-08-22 2006-05-31 Mitsui Chemicals, Inc. Copolymeres aleatoires propylene et utilisations

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272279A (en) 1980-06-19 1981-06-09 Gulf Oil Corporation Semicarbazidyl phthalides and use as plant growth regulators
KR100197327B1 (ko) 1988-07-15 1999-06-15 치어즈 엠. 노우드 신디오택틱 폴리프로필렌
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US6255425B1 (en) 1989-04-28 2001-07-03 Mitsui Chemicals, Inc. Syndiotactic polypropylene copolymer and extruded polypropylene articles
US5206324A (en) 1989-10-06 1993-04-27 Mitsui Toatsu Chemicals, Inc. Butene-1 copolymer and resin composition containing the same
DE3942366A1 (de) 1989-12-21 1991-06-27 Hoechst Ag Verfahren zur herstellung eines syndiotaktischen propylen-copolymers
JP2927885B2 (ja) 1990-05-24 1999-07-28 三井化学株式会社 シンジオタクチックポリα―オレフィンの製造方法
DE4032266A1 (de) 1990-10-11 1992-04-16 Hoechst Ag Verfahren zur herstellung eines polyolefins
US5571880A (en) 1991-05-09 1996-11-05 Phillips Petroleum Company Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process
EP0516018B1 (fr) 1991-05-27 1996-03-27 Hoechst Aktiengesellschaft Procédé de préparation de polyoléfines à large distribution de poids moléculaire
US5459117A (en) 1993-08-27 1995-10-17 Ewen; John A. Doubly-conformationally locked, stereorigid catalysts for the preparation of tactiospecific polymers
JPH09230791A (ja) 1996-02-22 1997-09-05 Kao Corp 熱活性型ラベル及びラベル付き成形体の製造方法
US6265512B1 (en) 1997-10-23 2001-07-24 3M Innovative Company Elastic polypropylenes and catalysts for their manufacture
CA2356667A1 (fr) 1998-12-21 2000-06-29 Exxonmobil Chemical Patents Inc. Compositions ramifiees semi-cristallines a base d'ethylene-propylene
WO2001046277A2 (fr) 1999-12-22 2001-06-28 Exxonmobil Chemical Patents, Inc. Compositions adhesives a base de polypropylene
EP1833939B1 (fr) 2004-12-21 2011-03-16 Dow Global Technologies Inc. Compositions adhésives à base de polypropylène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387690A1 (fr) * 1989-03-11 1990-09-19 Hoechst Aktiengesellschaft Procédé de préparation d'une polyoléfine syndiotactique
DE19850898A1 (de) * 1998-11-05 2000-05-11 Bayer Ag Verfahren zur Herstellung von EP(D)M
EP1661924A1 (fr) * 2003-08-22 2006-05-31 Mitsui Chemicals, Inc. Copolymeres aleatoires propylene et utilisations

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821971B2 (en) 2008-01-24 2014-09-02 Evonik Degussa Gmbh Use of polyolefins having atactic structural elements in floor coverings
US10214600B2 (en) 2014-02-07 2019-02-26 Eastman Chemical Company Amorphpus propylene-ethylene copolymers
US10308740B2 (en) 2014-02-07 2019-06-04 Eastman Chemical Company Amorphous propylene-ethylene copolymers
US10647795B2 (en) 2014-02-07 2020-05-12 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US10696765B2 (en) 2014-02-07 2020-06-30 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and propylene polymer
US10723824B2 (en) 2014-02-07 2020-07-28 Eastman Chemical Company Adhesives comprising amorphous propylene-ethylene copolymers
US11267916B2 (en) 2014-02-07 2022-03-08 Eastman Chemical Company Adhesive composition comprising amorphous propylene-ethylene copolymer and polyolefins
US11390701B2 (en) 2014-02-07 2022-07-19 Synthomer Adhesive Technologies Llc Amorphous propylene-ethylene copolymers
US12338316B2 (en) 2019-10-14 2025-06-24 3M Innovative Properties Company Compositions comprising cyclic olefins and thermally conductive filler
US12312509B2 (en) 2019-12-20 2025-05-27 3M Innovative Properties Company Adhesive article comprising polymer and polymerizable cyclic olefins, adhesive compositions and methods
CN115996798A (zh) * 2020-06-03 2023-04-21 E·丰特查·奎托斯 用于从罐和其它容器中选择性提取粘性烃的系统和方法

Also Published As

Publication number Publication date
DE102008005945A1 (de) 2009-07-30
TW201000505A (en) 2010-01-01
CN101560274A (zh) 2009-10-21

Similar Documents

Publication Publication Date Title
WO2009092721A1 (fr) Procédés de production de polyoléfines à éléments structuraux syndiotactiques, polyoléfines et leur utilisation
WO2009092752A9 (fr) Polyoléfines à éléments structuraux isotactiques, procédé de production desdites polyoléfines et leur utilisation
WO2009092757A1 (fr) Polyoléfines à éléments structuraux atactiques, procédés de production desdites polyoléfines et leur utilisation
EP2277931B1 (fr) Polyoléfines modifiées dotées d'un profil de propriétés spécifique, leur procédé de fabrication et d'utilisation
EP2272933A2 (fr) Polyoléfines modifiées dotées d'un profil de propriétés spécifique, leur procédé de fabrication et d'utilisation
DE60110071T2 (de) Polyolefinharz für heissschmelzklebstoff
EP2270111A2 (fr) Polyoléfines modifiées dotées d'un profil de propriétés spécifique, leur procédé de fabrication et d'utilisation
WO2010018027A1 (fr) Polyoléfines modifiées par un silane, ayant un degré élevé de fonctionnalisation
EP3781638B1 (fr) Adhésifs de contact de longue tenue à impact réduit sur l'environnement
US20240034869A1 (en) Propylene-ethylene copolymers and adhesives containing propylene-ethylene copolymers
WO2024026173A1 (fr) Copolymères de propylène-éthylène et adhésifs contenant des copolymères de propylène-éthylène
EP1871814B1 (fr) Polyolefine fortement visqueuse et largement amorphe
EP4562067A1 (fr) Copolymères de propylène-éthylène et adhésifs contenant des copolymères de propylène-éthylène
WO2024026175A1 (fr) Copolymères de propylène-éthylène et adhésifs contenant des copolymères de propylène-éthylène

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09703188

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09703188

Country of ref document: EP

Kind code of ref document: A1