Functionalised polymers, process for producing them and their use in thermoplastic moulding compounds
Abstract
It is possible by the radical solid phase graft polymerisation of function monomers with at least one functional group selected from among mono and dicarboxylic groups or groups derived therefrom, especially anhydride groups, and hydroxy, epoxy, amino and silane groups, possible mixed with an additional comonomer in the proportion of 1 to 99% related to the total monomer mass, especially from the group of styrenes and/or (meth)acrylates, with a polymerised monomer porportion in relation to the graft product mass of 0.05 to 50% on an olefinic and/or dienic spinal polymer (compound), including hydrated conjugated dienic homopolymer, copolymer and especially block copolymer backbones which contain a quantity of a mineral and/or native oil added before the functionalisation reaction, to obtain functionalised polymers, preferably carboxylated thermoplastic elastomers (TPE-S, TPE-O) characterized by improved adhesive strength and especially impact resistance when used in a large number of thermoplastic moulding compounds, polymer blends and composites. Preference is given to (saturated) paraffinic/naphthenic process oils used in quantities of between 10 parts by mass and at maximum concentrations corresponding to 20 to 400 parts by mass, in relation to 100 parts by mass of the spinal polymer, taking account of the dry-flowing consistency of the spinal polymer to be maintained.
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5 claims: 5 independent, 0 dependent
- 1Claims of equivalent WO 9623011 A1 Translation of claims of equivalent WO 9623011 A1 1.) Functionalized polymers based on olefinic homo- and (block) copolymers and / or conjugated diene homo- and statistical or alternieren¬ the copolymers and block copolymers, including the corresponding selectively hydrogenated polymers having weight average molecular weights Mw from 10,000 to 1,000,000 as backbone polymers and from 0.05 to 50 parts by weight, based on 100 parts by weight of backbone polymer, at least one grafted molecular unit containing at least one functional Group selected from mono- and dicarboxylic groups, including groups derived therefrom, such as amide or Imide, half-ester and especially anhydride groups, hydroxy and epoxy groups, amino groups and silane groups, and optionally at least one further co-grafted molecular unit without the di .. mentioned functional groups, such as styrene or substituted styrene and / or (meth) acrylate-in-thienes, -n a mass ratio monomer (s) having functional groups (functional monomer (s)) to monomer (s) without said functional groups (additional comonomer (s)) 1 to 100% to 0 to 99%, wherein the total content of grafted-on functional plus plus comonomers, based on the backbone polymer composition, is 0.05 to 50%, contain a proportion of a mineral, added before the functionalizing grafting reaction, in particular paraffinic and / or naphthenic and / or aromatic oil and / or a native, in particular vegetable oil in an amount of 10 parts by mass up to a maximum concentration corresponding to the absorption capacity of the polymers used as backbone polymers, while maintaining their dry-flowable consistency within the limits of 20 to 400 parts by mass, in each case based on 100 parts by mass of backbone polymer. 2.) Functionalized polymers according to claim 1, comprising an added before the grafting portion of a mineral paraffinic and / or naphthenic and / or aromatic oil and / or vegetable oil in a be¬ to 100 parts by weight backbone polymer amount of 20 to 200 parts by weight according to Absorbency of the polymers used as backbone polymer while maintaining their dry flowable consistency. Patentansprüche 1.) Funktionalisierte Polymere auf Basis von olefinischen Homo- und (Block-)Copolymeren und/oder konjugierten dienischen Homo- sowie statistischen bzw. alternieren¬ den Copolymeren und Blockcopolymeren, einschließlich der entsprechenden selektiv hydrierten Polymeren, mit gewichtsmittleren Molekulargewichten Mw von 10.000 bis 1.000.000 als Rückgratpolymere und von 0,05 bis 50 Masseteilen, bezogen auf 100 Masseteile Rückgratpolymerisat, mindestens einer aufgepfropften Moleküleinheit, enthaltend mindestens eine funktioneile Gruppe, ausgewählt unter Mono- und Dicarboxylgruppen, einschließlich davon abgeleiteten Gruppen, wie Amid- bzw. Imid-, Halbester- und besonders Anhydridgruppen, Hydroxy- und Epoxygruppen, Aminogruppen und Silan- gruppen, sowie gegebenenfalls mindestens einer wei¬ teren cogepfropften Moleküleinheit ohne di.. genannten funktionellen Gruppen, wie Styren- bzw. substituierte Styren- und/oder (Meth-)Acrylateinhe-.ten, -n einem Massenverhältnis Monomer(e) mit funktioneilen Gruppen (Funktionsmonomer(e)) zu Monomer(e) ohne genannte funktioneile Gruppen (Zusatzcomonomer(e)) 1 bis 100 % zu 0 bis 99 %, wobei der auf die Rückgratpolymermasse bezogene Gesamtanteil an aufgepfropften Funktions¬ plus Zusatzcomonomeren 0,05 bis 50 % beträgt, enthal¬ tend einen vor der Funktionalisierungs-Pfropfreaktion hinzugefügten Anteil eines mineralischen, insbesondere paraffinischen und/oder naphthenischen und/oder aroma¬ tischen Öls und/oder eines nativen, insbesondere pflanzlichen Öls in einer Menge von 10 Masseteilen bis zu einer Maximalkonzentration entsprechend der Aufnahmefähigkeit der als Rückgratpolymerisate einge- setzten Polymeren unter Aufrechterhaltung ihrer trocken-fließfähigen Konsistenz in den Grenzen von 20 bis 400 Masseteilen, jeweils bezogen auf 100 Mas¬ seteile Rückgratpolymerisat. 2.) Funktionalisierte Polymere nach Anspruch 1, enthaltend einen vor der Pfropfung hinzugefügten Anteil eines mineralischen paraffinischen und/oder naphthenischen und/oder aromatischen Öls und/oder pflanzlichen Öls in einer auf 100 Masseteile Rückgratpolymerisat be¬ zogenen Menge von 20 bis 200 Masseteilen entsprechend der Aufnahmefähigkeit der als Rückgratpolymerisat eingesetzten Polymeren unter Aufrechterhaltung ihrer trocken-fließfähigen Konsistenz. 3.) Functionalized polymers according to claims 1 and 2, wherein the oil is paraffinic and / or relatively naphthenic and / or naphthenic process oils which have a carbon distribution CA, romat._ to CNap, ht.hen to CDraraifri.n from 0 to 10 to 20 to 45 to 45 to 80 and have a viscosity density constant (VDK) between 0.80 and 0.90. 3.) Funktionalisierte Polymere nach den Ansprüchen 1 und 2, wobei als Öl paraffinische und/oder relativ naphthe- nische und/oder naphthenische Prozeßöle, die eine Kohlenstoffverteilung C A,romat._ zu C.N.ap,ht.hen zu CDraraifri.n von 0 bis 10 zu 20 bis 45 zu 45 bis 80 und eine Viskositäts-Dichte-Konstante (VDK) zwischen 0,80 und 0,90 besitzen, eingesetzt werden. 4.) Functionalized polymers according to claims 1 to 3 based on olefinic homo- and / or (block) copolymers having weight-average molecular weights Mw of 20,000 to 500,000 as backbone polymers. 4.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3 auf Basis olefinischer Homo- und/oder (Block-)Copoly- merer mit gewichtsmittleren Molekulargewichten Mw von 20.000 bis 500.000 als Rückgratpolymere. 5.) Functionalized polymers according to claims 1 to 4 based on ethylene / propylene (EPM) and / or ethylene / propylene / diene rubbers (EPDM) with a molar ratio of ethylene to propylene units of 40 to 60 to 90 to 10 and in the EPDM up to a maximum of 20% by weight of unsaturated components, such as copolymerized dicyclopentadiene and / or 5-ethylidene-2-norbornene, including mixtures of 5 to 95% by mass of EPM and / or EPDM and 5 to 95% by mass of polyethylene (PE) and / or polypropylene (PP), as backbone polymers or Backbone polymer co pounds. 6.) Functionalized polymers according to claims 1 to 4 based on the prepared by means of metallocene catalysts ("single site" catalyst technology) ethylene copolymers of composition 50 to 97 mol% ethylene / 3 to 50 mol% comonomer units using cycloaliphatic monomers . (Meth) acrylates, Styrenes and especially higher ot-olefins, such as copolymers of the composition 80 to 97% by mass of ethylene / 3 to 20% by mass of 1-octene (POPs) and corresponding copolymers with --- 20% by mass of 1-octene (POEs), as backbone polymers or - With simultaneous use of other olefinic and / or dienic homo- and / or (block) copolymers - backbone polymer compound component. 5.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 4 auf Basis von Ethylen/Propylen- (EPM) und/oder Ethylen/Propylen/Dien-Kautschuken (EPDM) mit einem molaren Verhältnis von Ethylen- zu Propyleneinheiten von 40 zu 60 bis 90 zu 10 sowie im EPDM bis maximal 20 Masse-% ungesättigte Anteile, wie einpolymerisier- tes Dicyclopentadien und/oder 5-Ethyliden-2-norbornen, einschließlich Mischungen aus 5 bis 95 Masse-% EPM und/oder EPDM und 5 bis 95 Masse-% Polyethylen (PE) und/oder Polypropylen (PP), als Rückgratpolymere bzw. Rückgratpolymerco pounds. 6.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 4 auf Basis der mittels Metallocen-Katalysatoren ("Single Site"-Katalysatortechnologie) hergestellten Ethylencopolymeren der Zusammensetzung 50 bis 97 Mol-% Ethylen / 3 bis 50 Mol-% Comonomereinheiten unter Verwendung von cycloaliphatischen Monomeren, (Meth-) Acrylaten, Styrenen und besonders höheren ot-Olefinen, wie Copolymeren der Zusammensetzung 80 bis 97 Masse-% Ethylen / 3 bis 20 Masse-% l-0cten (POPs) und entsprechenden Copolymeren mit --- 20 Masse-% l-0cten (POEs), als Rückgratpolymere bzw. - unter gleichzei¬ tiger Verwendung von anderen olefinischen und/oder dienischen Homo- und/oder (Block-)Copolymeren - Rückgratpolymercompoundkomponente. 7.) Functionalized polymers according to claims 1 to 4 based on polar olefinic copolymers from the series of ethylene and / or x-olefin / vinyl esters and / or (meth) acrylate copolymers having a composition of 5 to 95% by weight. % Ethylene and / or C-- to C.2-01efineinheiten and 95 to 5 mass% vinyl ester and / or (meth) acrylate units, including Mi¬ mixtures of 30 to 97 mass% polar olefinic copolymer and 3 to 70 mass% PE and / or PP and / or EPM or EPDM, as backbone polymers or backbone polymer compounds. 7.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 4 auf Basis polarer olefinischer Copolymerer aus der Reihe der Ethylen und/oder «x -Olefin/Vinylester und/ oder (Meth-)Acrylat-Copolymeren mit einer Zusammen- setzung 5 bis 95 Masse-% Ethylen- und/oder C-- bis C.2-01efineinheiten und 95 bis 5 Masse-% Vinylester- und/oder (Meth-)Acrylateinheiten, einschließlich Mi¬ schungen aus 30 bis 97 Masse-% polarem olefinischen Copolymer und 3 bis 70 Masse-% PE und/oder PP und/oder EPM bzw. EPDM, als Rückgratpolymere bzw. Rückgrat- polymercompounds. 8.) Functionalized polymers according to claims 1 to 4 and 7 based on ethylene / vinyl acetate copolymers (EVA) of the composition 95 to 5% by mass of ethylene and 5 to 95% by mass of vinyl acetate units, including mixtures of 30 to 97% by mass of EVA and 3 to 70% by mass of PE and / or PP and / or EPM or EPDM, as backbone polymers or Backbone polymer compounds. 9.) Functionalized polymers according to claims 1 to 3 based on conjugated diene homo- and stati¬ stischer or alternating copolymer and block copolymer, including the corresponding selectively hydrogenated polymers having a degree of hydrogenation of the polydiene units of 20 to 100%, as Rückgratpo¬ polymers. 8.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 4 und 7 auf Basis von Ethylen/Vinylacetat-Copolymeren (EVA) der Zusammensetzung 95 bis 5 Masse-% Ethylen- und 5 bis 95 Masse-% Vinylacetateinheiten, einschlie߬ lich Mischungen aus 30 bis 97 Masse-% EVA und 3 bis 70 Masse-% PE und/oder PP und/oder EPM bzw. EPDM, als Rückgratpolymere bzw. Rückgratpolymercompounds. 9.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3 auf Basis konjugierter dienischer Homo- sowie stati¬ stischer bzw. alternierender Copolymerer und Block- copolymerer, einschließlich der entsprechenden selek- tiv hydrierten Polymeren mit einem Hydriergrad der Polydieneinheiten von 20 bis 100 %, als Rückgratpo¬ lymere. 10.) Functionalized polymers according to claims 1 to 3 and 9 based on selectively hydrogenated block copolymers of at least two monovinylsubstituierten aromati¬ rule hydrocarbon polymer blocks with a related to the aromatic double bonds Hydrier¬ degree• 20% and at least one polymer block obtained by polymerizing a conjugated diene or diene mixture, which is hydrogenated to a degree of ethylenic unsaturation * 20%, wherein the unhydrogenated precursor block copolymer has a weight-average molecular weight Mw of 20,000 to 1,000,000 and a content of vinylaromatic units of 5 to 95 mass%, and the unit consisting of the conjugated diene compound (s) has a vinyl group content of Contains 10 to 80%, optionally in admixture with 0 to 300 parts by mass of olefinic homo- and / or copolymer, based on 100 mass * selectively hydrogenated block copolymer, as backbone polymers or backbone polymer compounds. 10.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3 und 9 auf Basis selektiv hydrierter Blockcopolymerer aus mindestens zwei monovinylsubstituierten aromati¬ schen Kohlenwasserstoff-Polymerblöcken mit einem auf deren aromatische Doppelbindungen bezogenen Hydrier¬ grad .*=• 20 % und mindestens einem durch Polymerisation eines konjugierten Diens oder Diengemisches erhaltenen Polymerblock, der bis zu einem Grad der ethylenischen Unsättigung *£ 20 % hydriert ist, wobei das unhydrier- te Vorlaufer-Blockcopolymerisat ein gewichtsmittleres Molekulargewicht Mw von 20.000 bis 1.000.000 sowie einen Anteil an Vinylaromateinheiten von 5 bis 95 Masse-% besitzt und die aus der (den) konjugierten Dienverbindung(en) bestehende Einheit einen Vinyl- gruppengehalt von 10 bis 80 % enthält, gegebenenfalls in Abmischung mit 0 bis 300 Masseteilen olefinischem Homo- und/oder Copolymerisat , bezogen auf 100 Masse¬ * teile selektiv hydriertes Blockcopolymer, als Rück- gratpolymere bzw. Rückgratpolymercompounds. 11.) Functionalized polymers according to claims 1 to 3, 9 and 10 based on selectively hydrogenated radial block copolymers having an average number of starches of 3 to 16 and a degree of ethylenic unsaturation of the hydrogenated diene blocks. £ 10%, wherein the unhydrogenated precursor block copolymer has a weight-average molecular weight Mw of from 30,000 to 800,000 and a content of vinylaromatic units of from 5 to 75 Hasse-? and the unit formed from the conjugated diene (s) has a vinyl group content of 25 to 65%, optionally in admixture with 0 to 200 parts by mass of olefinic homo- and / or copolymer, based on 100 parts by weight of selectively hydrogenated radial block copolymer, as backbone polymers or Backbone polymer compounds. 11.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3, 9 und 10 auf Basis selektiv hydrierter radialer Block¬ copolymerer mit einer mittleren Sternastzahl von 3 bis 16 und einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke .£ 10 %, wobei das unhydrier- te Vorlaufer-Blockcopolymerisat ein gewichtsmittleres Molekulargewicht Mw von 30.000 bis 800.000 und einen Gehalt an Vinylaromateinheiten von 5 bis 75 Hasse-? besitzt und die aus dem (den) konjugierten Dien(en) gebildete Einheit einen Vinylgruppengehalt von 25 bis 65 % aufweist, gegebenenfalls in Abmischung mit 0 bis 200 Masseteilen olefinischem Homo- und/oder Copolymerisat, bezogen auf 100 Masseteile selektiv hydriertes radiales Blockcopolymer, als Rückgratpoly¬ mere bzw. Rückgratpolymercompounds. 12.) Functionalized polymers according to claims 1 to 3, 9 and 10 based on selectively hydrogenated linear block copolymers of at least two monovinyl-substituted aromatic hydrocarbon polymer blocks and at least one polymer block obtained by polymerizing a conjugated diene or diene mixture, which is hydrogenated to a degree of ethylenic unsaturation -x- 10%, wherein the unhydrogenated precursor block copolymer has a weight average molecular weight Mw of 20,000 to 1,000,000 and a content of vinylaromatic units of 5 to 75 mass%, and the unit formed of the conjugated diene compound (s) has a vinyl group content of 25 to Contains 65%, optionally in admixture with 0 to 200 parts by mass of olefinic homo- and / or copolymer, based on 100 parts by weight of selectively hydrogenated linear block copolymer, as backbone polymers or Backbone polymer compounds. 12.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3, 9 und 10 auf Basis selektiv hydrierter linearer Block- copolymerer aus mindestens zwei monovinylsubstituierten aromatischen Kohlenwasserstoff-Polymerblöcken und mindestens einem durch Polymerisation eines konjugier¬ ten Diens oder Diengemisches erhaltenen Polymerblock, der bis zu einem Grad der ethylenischen Unsättigung -x- 10 % hydriert ist, wobei das unhydrierte Vorläufer- Blockcopolymerisat ein gewichtsmittleres Molekular¬ gewicht Mw von 20.000 bis 1.000.000 und einen Gehalt an Vinylaromateinheiten von 5 bis 75 Masse-% besitzt und die aus der (den) konjugierten Dienverbindung(en) gebildete Einheit einen Vinylgruppengehalt von 25 bis 65 % enthält, gegebenenfalls in Abmischung mit 0 bis 200 Masseteilen olefinischem Homo- und/oder Copolymerisat, bezogen auf 100 Masseteile selektiv hydriertes lineares Blockcopolymer, als Rückgratpoly¬ mere bzw. Rückgratpolymercompounds. 13.) Functionalized polymers according to claims 1 to 3, 9, 10 and 12 based on selectively hydrogenated linear block copolymers having a mass fraction of styrene units of 7 to 50% and a degree of ethylenic unsaturation of the hydrogenated diene blocks •* - 10%, its unhydrogenated precursor block copolymer of two terminal polystyrene blocks A having the same or different number average molecular weights Mn between 4,000 and 100,000 and a middle-term poly (butadiene and / or isoprene) -Block B having a number average molecular weight Mn between 10,000 and 200,000 (ABA triblock structure) and a vinyl group content of 25 to 65% exists as backbone polymers or backbone polymer compounds, respectively. 13.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3, 9, 10 und 12 auf Basis selektiv hydrierter linearer Blockcopolymerer mit einem Massenanteil an Styrenein- heiten von 7 bis 50 % und einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke •*-- 10 %, dessen unhydriertes Vorlaufer-Blockcopolymerisat aus zwei endständigen Polystyrenblöcken A mit gleichen oder unterschiedlichen zahlenmittleren Molekulargewichten Mn zwischen 4.000 und 100.000 und einem mittelstän- digen Poly(Butadien und/oder Isopren)-Block B mit einem zahlenmittleren Molekulargewicht Mn zwischen 10.000 und 200.000 (ABA-Dreiblockstruktur) und einem Vinylgruppengehalt von 25 bis 65 % besteht, als Rück- gratpolymere bzw. Rückgratpolymercompounds. 14.) Functionalized polymers according to claims 1 to 3, 9 10 and 12 based on selectively hydrogenated linear block copolymers having a mass fraction of styrene units of 7 to 50% and a degree of ethylenic unsaturation of the hydrogenated diene blocks of ≦ 10%, its unhydrogenated precursor block copolymer of two polystyrene blocks A having the same or different number average molecular weights Mn between 4,000 and 100,000 and two poly (butadiene and / or isoprene) blocks B having the same or different number average molecular weights Mn between 10,000 and 200,000 (ABAB four-block structure ) and a vinyl group content of 25 to 65%, as backbone polymers or Backbone polymer compounds. 14.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3, 9, 10 und 12 auf Basis selektiv hydrierter linearer Blockcopolymerer mit einem Massenanteil an Styrenein- heiten von 7 bis 50 % und einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke -≤ 10 %, dessen unhydriertes Vorlaufer-Blockcopolymerisat aus zwei Polystyrenblöcken A mit gleichen oder unterschiedli¬ chen zahlenmittleren Molekulargewichten Mn zwischen 4.000 und 100.000 und zwei Poly(Butadien und/oder Isopren)-Blöcken B mit gleichen oder unterschiedlichen zahlenmittleren Molekulargewichten Mn zwischen 10.000 und 200.000 (ABAB-Vierblockstruktur) und einem Vinyl¬ gruppengehalt von 25 bis 65 % besteht, als Rückgrat- polymere bzw. Rückgratpolymercompounds. 15.) Functionalized polymers according to one or more of claims 1 to 14, in which the olefinic and / or diene homopolymers and / or copolymers and / or block copolymers used as backbone polymers comprise 0 to 200 parts by weight of a fibrous and / or particulate filler , based on 100 parts by weight of polymer content. 15.) Funktionalisierte Polymere gemäß einem oder mehrerer der Ansprüche 1 bis 14, indem die als Rückgratpoly¬ mere eingesetzten olefinischen und/oder dienischen Homo- und/oder Copolymeren und/oder Blockcopolymeren 0 bis 200 Masseteile eines faserigen und/oder teil- chenförmigen Füllstoffs, bezogen auf 100 Masseteile Polymeranteil, enthalten. 16) Functionalized polymers according to one or more of claims 1 to 15, in which the used as Rückgratpoly¬ mers olefinic and / or dienic homo- and / or copolymers and / or block copolymers 10 to 100 parts by weight of a particulate filler based on calcium carbonate , based on 100 parts by weight of polymer content. 17.) Functionalized polymers according to claims 1 to 3, 9, 10, 12, 13, 15 and 16 based on selectively hydrogenated linear styrene / diene / styrene triblock copolymers having a weight-average molecular weight Mw of 40,000 to 800,000 and a mass fraction of styrene units of 7 to 50% and a degree of ethylenic unsaturation of the hydrogenated diene blocks _ = 5%. in the form of their backbone compounds added to the graft polymerization formulation of composition (a) from 30 to 95% by weight of styrene / ethylene-propylene or butylene / styrene triblock copolymer (SEPS or SEBS) (b) from 5 to 70% by weight of olefinic homo- and / or or copolymer and (c) 0 to 50% by weight of particulate filler, and at least one amount of 0.1 to 25 parts by weight of the grafted-in molecular unit in an amount of 100 parts by weight of backbone compound, this molecular unit being at least one functional group, selected from mono- and dicarboxyl groups, including groups derived therefrom (acid derivative groups), hydroxy, epoxy, Amino and silane groups, and optionally at least one further co-grafted molecular unit without the functional groups mentioned, selected under styrene or sub stituated styrene units and (meth) acrylate units, with a mass fraction of 0 to 95%, based on the total amount of grafted-on molecular units, containing a fraction of a mineral paraffinic and / or naphthenic and / or aromatic oil and / or a vegetable oil in an amount of 50 to 200 parts by weight, added before the functionalization-grafting reaction, based on 100 parts by weight of backbone compound, in accordance with the absorption capacity of the (non-functionalized) backbone compounds used while maintaining their dry-flowable consistency. 18.) Functionalized polymers according to one or more of claims 1 to 17 with at least one on the backbone polymers or Backbone polymer compounds Auf¬ grafted molecular unit having at least one mono- or dicarboxylic, including derived anhydride dehydro groups, which have been crosslinked by at least one mono- and / or divalent and / or trivalent metal ion to form ionomers. 16.) Funktionalisierte Polymere gemäß einem oder mehrerer der Ansprüche 1 bis 15, indem die als Rückgratpoly¬ mere eingesetzten olefinischen und/oder dienischen Homo- und/oder Copolymeren und/oder Blockcopolymeren 10 bis 100 Masseteile eines teilchenförmigen Füll- Stoffs auf Calciumcarbonat-Basis, bezogen auf 100 Masseteile Polymeranteil, enthalten. 17.) Funktionalisierte Polymere nach den Ansprüchen 1 bis 3, 9, 10, 12, 13, 15 und 16 auf Basis selektiv hydrierter linearer Styren/Dien/Styren-Dreiblockcopolymerer mit einem gewichtsmittleren Molekulargewicht Mw von 40.000 bis 800.000 und einem Massenanteil an Styren- einheiten von 7 bis 50 % sowie einem Grad der ethy¬ lenischen Unsättigung der hydrierten Dienblöcke _= 5 %. in Form ihrer dem Pfropfpolymerisationsansatz hinzugefügten Rückgrat-Compounds der Zusammensetzung (a) 30 bis 95 Masse-% Styren/Ethylen-Propylen oder Butylen/Styren-Dreiblockcopolymerisat (SEPS oder SEBS) (b) 5 bis 70 Masse-% olefinisches Homo- und/oder Copolymerisat und (c) 0 bis 50 Masse-% teilchenförmiger Füllstoff, und mindestens einer auf efpropften Moleküleinheit in einer auf 100 Masseteile Rückgrat-Compound bezo¬ genen Menge von 0,1 bis 25 Masseteilen, wobei diese Moleküleinheit mindestens eine funktionelle Gruppe, ausgewählt unter Mono- und Dicarboxylgruppen, ein¬ schließlich davon abgeleiteten Gruppen (Säurederivat¬ gruppen), Hydroxy-, Epoxy-, Amino- und Silangruppen, sowie gegebenenfalls mindestens eine weitere coge- pfropfte Moleküleinheit ohne die genannten funktio- nellen Gruppen, ausgewählt unter Styren- bzw. sub¬ stituierten Styreneinheiten sowie (Meth-)Acrylat- einheiten, mit einem Massenanteil von 0 bis 95 %, bezogen auf die Gesamtmenge an aufgepfropften Mole¬ küleinheiten, enthaltend einen vor der Funktionali- sierungs-Pfropfreaktion hinzugefügten Anteil eines mineralischen paraffinischen und/oder naphthenischen und/oder aromatischen Öls und/oder eines pflanzlichen Öls in einer Menge von 50 bis 200 Masseteilen, bezo¬ gen auf 100 Masseteile Rückgrat-Compound, entsprechend der Aufnahmefähigkeit der eingesetzten (nicht funk- tionalisierten) Rückgrat-Compounds unter Aufrechter¬ haltung ihrer trocken-fließfähigen Konsistenz. 18.) Funktionalisierte Polymere nach einem oder mehreren der Ansprüche 1 bis 17 mit mindestens einer auf die Rückgratpolymeren bzw. Rückgratpolymercompounds auf¬ gepfropften Moleküleinheit mit mindestens einer Mono- oder Dicarboxylgruppe, einschließlich davon abgelei¬ teter Anhydridgruppen, die durch mindestens ein ein- und/oder zwei- und/oder dreiwertiges Metallion unter Bildung von Ionomeren vernetzt worden sind. 19.) Ionically crosslinked functionalized polymers according to claim 18, wherein the ionic crosslinking of the functionalized polymers by at least one Metall¬ ion using a selected among the compounds of lithium, sodium, potassium, magnesium, calcium, zinc and aluminum crosslinking agent in a Molar ratio of metal in the crosslinking agent to grafted carboxyl group or an anhydride group derived therefrom in the functionalized polymer has been made from 0.1 to 3.0. 19.) Ionisch vernetzte funktionalisierte Polymere nach Anspruch 18, wobei die ionische Vernetzung der funk- tionalisierten Polymere durch mindestens ein Metall¬ ion unter Verwendung eines unter den Verbindungen des Lithiums, Natriums, Kaliums, Magnesiums, Calciums, Zinks und Aluminiums ausgewählten Vernetzungsmittels in einem Molverhältnis Metall im Vernetzungsmittel zur aufgepfropften Carboxylgruppe bzw. einer davon abgeleiteten Anhydridgruppe im funktionalisierten Polymer von 0,1 bis 3,0 durchgeführt worden ist.
- 220.) Process for the preparation of functionalized polymers according to claim 1, wherein as backbone polymers olefinic homo- and / or (block) copolymers and / or conjugated dienic homo- and statistical or alternating copolymers and / or block copolymers, including the corresponding selectively hydrogenated polymers, having weight-average molecular weights Mw of from 10,000 to 1,000,000 in oil-extended form using 10 parts by weight up to a maximum concentration corresponding to the absorption capacity of the abovementioned backbone polymers, in which their dry-flowable consistency is still maintained, within the limits of 20 to 400 parts by weight of mineral oil, in particular paraffinic and / or naphthenic and / or aromatic oil and / or native, especially vegetable oil, in each case based on 100 parts by weight of backbone polymer, with at least one .X. , fi ethylenically unsaturated Ver¬ bond in an amount of 100 parts by weight Rückgratpolymeri¬ sat amount of 0.05 to 50 parts by mass, said compound at least one functional group selected from mono- and dicarboxylic groups, ein¬ finally derived groups such as amide - or. Imide, half-ester and especially anhydride groups, hydroxyl and epoxy groups, amino groups and silane groups (functional monomers), and, if appropriate as a mixture with at least one none of these functional groups possessing cx, p> -ethylenically unsaturated compound, such as styrene or. Substituted styrenes and / or (meth) acrylates (additional comonomers), in a mass ratio of 1 to 100% functional monomer (s) to 0 to 99% additional comonomer (s), using a radical initiator having a ten-hour half-life of 40 to 80 * C are grafted. 20.) Verfahren zur Herstellung funktionalisierter Polymerer gemäß Anspruch 1 , wobei als Rückgratpolymere olefini¬ sche Homo- und/oder (Block-)Copolymere und/oder kon¬ jugierte dienische Homo- sowie statistische bzw. alter- nierende Copolymere und/oder Blockcopolymere, ein¬ schließlich die entsprechenden selektiv hydrierten Polymeren, mit gewichtsmittleren Molekulargewichten Mw von 10.000 bis 1.000.000 in ölgestreckter Form unter Verwendung von 10 Masseteilen bis zu einer Maxi- malkonzentration entsprechend der Aufnahmefähigkeit obengenannter Rückgratpolymerisate, bei der ihre trocken-fließfähige Konsistenz noch aufrechterhalten ist, in den Grenzen von 20 bis 400 Masseteilen mine¬ ralisches, insbesondere paraffinisches und/oder naphthenisches und/oder aromatisches Öl und/oder natives, insbesondere pflanzliches Öl, jeweils bezo- gen auf 100 Masseteile Rückgratpolymerisat, mit min¬ destens einer .X. , fi -ethylenisch ungesättigten Ver¬ bindung in einer auf 100 Masseteile Rückgratpolymeri¬ sat bezogenen Menge von 0,05 bis 50 Masseteile, wobei diese Verbindung mindestens eine funktioneile Gruppe, ausgewählt unter Mono- und Dicarboxylgruppen, ein¬ schließlich davon abgeleiteten Gruppen, wie Amid- bzw. Imid-, Halbester- und besonders Anhydridgruppen, Hydroxy- und Epoxygruppen, Aminogruppen und Silan- gruppen (Funktionsmonomere) , besitzt und, gegebenen¬ falls als Mischung mit mindestens einer keine dieser funktionellen Gruppen besitzenden cx , p> -ethylenisch ungesättigten Verbindung, wie Styren bzw. substi¬ tuierten Styrenen und/oder (Meth-)Acrylaten (Zusatz- comonomere), in einem Massenverhältnis 1 bis 100 % Funktionsmonomer(e) zu 0 bis 99 % Zusatzcomonomer(e) , unter Verwendung eines radikalischen Initiators mit einer Zehnstunden-Halbwertstemperatur von 40 bis 80 *C gepfropft werden. 21.) Process for the preparation of functionalized polymers according to claim 20, in which olefinic homopolymers and / or (block) copolymers having weight-average molecular weights Mw of from 20,000 to 500,000 in oil-extended form using 10 parts by mass are used as backbone polymers up to a maximum concentration corresponding to the absorption capacity of the abovementioned backbone polymers, in which their dry-flowable consistency is still maintained, within the limits of 20 to 200 parts by mass of mineral paraffinic and / or nonthenic and / or aromatic oil and / or vegetable oil, in each case based on 100 parts by weight of backbone polymer, be used. 22.) Process for the preparation of functionalized polymers according to claim 20, wherein conjugated dienic homo- and statistical or altering copolymers and / or block copolymers, including the corresponding selectively hydrogenated polymers, having weight-average molecular weights Mw of from 20,000 to 1,000,000 in oil-extended form using 20 parts by mass to a maximum concentration corresponding to the absorption capacity of the abovementioned backbone polymers, in which their dry-flowable consistency is still maintained, in the limits of 50 to 400 parts by weight of mineral paraffinic and / or naphthenic and / or aromatic oil and / or vegetable oil, in each case based on 100 parts by weight of backbone polymer, ein¬ be set. 21.) Verfahren zur Herstellung funktionalisierter Polymerer nach Anspruch 20, wobei als Rückgratpolymere olefi¬ nische Homo- und/oder (Block-)Copolymere mit gewichts¬ mittleren Molekulargewichten Mw von 20.000 bis 500.000 in ölgestreckter Form unter Verwendung von 10 Masse¬ teilen bis zu einer Maximalkonzentration entsprechend der Aufnahmefähigkeit obengenannter Rückgratpolymerer, bei der ihre trocken-fließfähige Konsistenz noch auf¬ rechterhalten ist, in den Grenzen von 20 bis 200 Masse- teilen mineralisches paraffinisches und/oder naphthe- nisches und/oder aromatisches öl und/oder pflanzliches Öl, jeweils bezogen auf 100 Masseteile Rückgratpoly¬ merisat, eingesetzt werden. 22.) Verfahren zur Herstellung funktionalisierter Polymerer nach Anspruch 20, wobei als Rückgratpolymere konju¬ gierte dienische Homo- sowie statistische bzw. alter¬ nierende Copolymere und/oder Blockcopolymere, ein- schließlich die entsprechenden selektiv hydrierten Polymeren, mit gewichtsmittleren Molekulargewichten Mw von 20.000 bis 1.000.000 in ölgestreckter Form unter Verwendung vcm 20 Masseteilen bis zu einer Maxi¬ malkonzentration entsprechend der Aufnahmefähigkeit obengenannter Rückgratpolymerer, bei der ihre trocken- fließfähige Konsistenz noch aufrechterhalten ist, in den Grenzen von 50 bis 400 Masseteilen minerali¬ sches paraffinisches und/oder naphthenisches und/oder aromatisches Öl und/oder pflanzliches Öl, jeweils bezogen auf 100 Masseteile Rückgratpolymerisat, ein¬ gesetzt werden. 23.) Process for the preparation of functionalized polymers according to claims 20 and 22, in which the backbone polymers are selectively hydrogenated block copolymers of at least two monovinyl-substituted aromatic hydrocarbon polymer blocks having a hydrogenation degree based on their aromatic double bonds ■ = 20% and at least one obtained by polymerizing a conjugated diene or mixture of at least two conjugated dienes polymer block which has been hydrogenated to a degree of ethylenic unsaturation of -20%, wherein the unhydrogenated precursor block copolymer has a weight-average molecular weight Mw of from 20,000 to 1,000,000 and a proportion of vinyl aromatic units of from 5 to 95% Hasse-? and the unit formed from the conjugated diene compound (s) contains a vinyl group content of 10 to 80%, optionally in admixture with 0 to 300 parts by mass of olefinic homo- and / or copolymer, based on 100 parts by weight of selectively hydrogenated block copolymer, be used. 79 24.) Process for the preparation of functionalized polymers according to claims 20, 22 and 23, wherein as Rückgrat¬ polymers selectively hydrogenated linear triblock copolymers having a mass fraction of styrene units of 7 to 50% and a degree of ethylenic unsaturation of the hydrogenated diene blocks ■£*-. 10%, whose unhydrogenated precursor block copolymer of two terminal polystyrene blocks A with the same or unterschiedli¬ chen number average molecular weights Mn between 4,000 and 100,000 and a central poly (butadiene and / or isoprene) block having a number average molecular weight Mn between 10,000 and 200,000 (ABA triblock structure) and a vinyl group content of 25 to 65%. 23.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20 und 22, wobei als Rückgratpoly- mere selektiv hydrierte Blockcopolymere aus mindestens zwei monovinylsubstituierten aromatischen Kohlenwasser- stoff-Polymerblöcken mit einem auf deren aromatische Doppelbindungen bezogenen Hydriergrad ■-=• 20 % und min¬ destens einem durch Polymerisation eines konjugierten Diens oder Gemisches aus mindestens zwei konjugierten Dienen erhaltenen Polymerblock, der bis zu einem Grad der ethylenischen Unsättigung von -- 20 % hydriert worden ist, wobei das unhydrierte Vorlaufer-Blockco¬ polymerisat ein gewichtsmittleres Molekulargewicht Mw von 20.000 bis 1.000.000 sowie einen Anteil Vinyl¬ aromateinheiten von 5 bis 95 Hasse-? besitzt und die aus der (den) konjugierten Dienverbindung(en) gebil¬ deten Einheit einen Vinylgruppengehalt von 10 bis 80 % enthält, gegebenenfalls in Abmischung mit 0 bis 300 Masseteilen olefinisches Homo- und/oder Copolymerisat, bezogen auf 100 Masseteile selektiv hydriertes Block- copolymerisat , eingesetzt werden. 79 24.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20, 22 und 23, wobei als Rückgrat¬ polymere selektiv hydrierte lineare Dreiblockcopolymere mit einem Massenanteil an Styreneinheiten von 7 bis 50 % und einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke ■£*-. 10 %, dessen unhydriertes Vorlaufer-Blockcopolymerisat aus zwei endständigen Polystyrenblöcken A mit gleichen oder unterschiedli¬ chen zahlenmittleren Molekulargewichten Mn zwischen 4.000 und 100.000 und einem mittelständigen Poly(Buta- dien und/oder Isopren)-Block mit einem zahlenmittle¬ ren Molekulargewicht Mn zwischen 10.000 und 200.000 (ABA-Dreiblockstruktur) und einem Vinylgruppengehalt von 25 bis 65 % besteht, eingesetzt werden. 25.) Process for the preparation of functionalized polymers according to claims 20, 22 and 23, wherein as Rückgrat¬ polymers selectively hydrogenated linear block copolymers having a mass fraction of styrene units of 7 to 50% and a degree of ethylenic desaturation - 10%, its unhydrogenated precursor block copolymer of two polystyrene blocks A having the same or different number average molecular weights Mn between 4,000 and 100,000 and two poly (butadiene and / or isoprene) blocks having the same or different number average molecular weights Mn between 10,000 and 200,000 ( ABAB four-block structure) and a vinyl group content of 25 to 65%, be used. 26.) Process for the preparation of functionalized polymers according to claims 20, 22 and 23, wherein as backbone polymers selectively hydrogenated radial block copolymers having an average number of starches of 3 to 16 and a degree of ethylenic unsaturation of the hydrogenated diene blocks .. = 10%, its unhydrogenated precursor block copolymer has a weight average molecular weight Mw of from 30,000 to 800,000 and a content of vinylaromatic units of from 5 to 75 mass%, and the unit formed from the conjugated diene (s) has a vinyl group content of from 25 to 65% ¬ points, be used. 25.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20, 22 und 23, wobei als Rückgrat¬ polymere selektiv hydrierte lineare Blockcopolymere mit einem Massenanteil an Styreneinheiten von 7 bis 50 % und einem Grad der ethylenischen Umsättigung — 10 %, dessen unhydriertes Vorlaufer-Blockcopoly¬ merisat aus zwei Polystyrenblöcken A mit gleichen oder unterschiedlichen zahlenmittleren Molekularge¬ wichten Mn zwischen 4.000 und 100.000 und zwei Poly(Bu- tadien und/oder Isopren)-Blöcken mit gleichen oder unterschiedlichen zahlenmittleren Molekulargewichten Mn zwischen 10.000 und 200.000 (ABAB-Vierblockstruk- tur) und einem Vinylgruppengehalt von 25 bis 65 % besteht, eingesetzt werden. 26.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20, 22 und 23, wobei als Rückgrat¬ polymere selektiv hydrierte radiale Blockcopolymere mit einer mittleren Sternastzahl von 3 bis 16 und einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke ..= 10 %, dessen unhydriertes Vorläufer- Blockcopolymerisat ein gewichtsmittleres Molekular¬ gewicht Mw von 30.000 bis 800.000 und einen Gehalt an Vinylaromateinheiten von 5 bis 75 Masse-% besitzt und die aus dem (den) konjugierten Dien(en) gebildete Einheit einen Vinylgruppengehalt von 25 bis 65 % auf¬ weist, eingesetzt werden. 27.) Process for the preparation of functionalized polymers according to one or more of claims 20 to 26, wherein the olefinic homo- and / or (block) copolymers used as backbone polymers and / or conjugated diene homo- and statistical or alternating copolymers and / or block copolymers, including the corresponding selectively hydrogenated polymers, 0 to 200 parts by weight of a fase¬ rigen and / or particulate filler, based on 100 parts by weight of polymer content added. 27.) Verfahren zur Herstellung funktionalisierter Polymerer nach einem oder mehreren der Ansprüche 20 bis 26, wobei den als Rückgratpolymere eingesetzten olefini¬ schen Homo- und/oder (Block-)Copolymeren und/oder konjugierten dienischen Homo- sowie statistischen bzw. alternierenden Copolymeren und/oder Blockcopoly- meren, einschließlich den entsprechenden selektiv hydrierten Polymeren, 0 bis 200 Masseteile eines fase¬ rigen und/oder teilchenförmigen Füllstoffes, bezogen auf 100 Masseteile Polymeranteil, hinzugefügt ist. 28.) Process for the preparation of functionalized polymers according to one or more of claims 20 to 27, wherein the olefinic homo- and / or (block) copolymers used as backbone polymers and / or conjugated diene homo- and statistical or alternating copolymers and / or Blockcopoly¬ mers, including the corresponding selectively hydrogenated polymers, 10 to 100 parts by weight of a particulate filler based on calcium carbonate, based on 100 parts by weight of polymer content added. 29.) Process for the preparation of functionalized polymers according to claims 20, 24, 27 and 28, wherein the graft polymerization batch selectively hydrogenated linear styrene / diene / styrene tri-block copolymers having a weight average molecular weight Mw of 40,000 to 800,000 and a mass fraction of styrene units of 7 to 50% and a degree of ethylenic unsaturation of the hydrogenated diene blocks £. 5 % in the form of backbone compounds of composition (a) from 30 to 95% by weight of styrene / ethylene-propylene or butylene / styrene triblock copolymer (SEPS or SEBS), (b) from 5 to 70% by weight of olefinic homo- and / or copolymer and (c) 0 to 50 by weight particulate filler. 28.) Verfahren zur Herstellung funktionalisierter Polymerer nach einem oder mehreren der Ansprüche 20 bis 27, wobei den als Rückgratpolymere eingesetzten olefini¬ schen Homo- und/oder (Block-)Copolymeren und/oder konjugierten dienischen Homo- sowie statistischen bzw. alternierenden Copolymeren und/oder Blockcopoly¬ meren, einschließlich den entsprechenden selektiv hydrierten Polymeren, 10 bis 100 Masseteile eines teilchenförmigen Füllstoffs auf Calciumcarbonat-Basis, bezogen auf 100 Masseteile Polymeranteil, hinzugefügt ist. 29.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20, 24, 27 und 28, wobei der Pfropfpolymerisationsansatz selektiv hydrierte lineare Styren/Dien/Styren-Dreiblockcopolymere mit einem ge- wichtsmittleren Molekulargewicht Mw von 40.000 bis 800.000 und einem Massenanteil an Styreneinheiten von 7 bis 50 % sowie einem Grad der ethylenischen Unsättigung der hydrierten Dienblöcke £. 5 % in Form von Rückgrat-Compounds der Zusammensetzung (a) 30 bis 95 Masse-% Styren/Ethylen-Propylen oder Butylen/Styren Dreiblockcopolymerisat (SEPS oder SEBS), (b) 5 bis 70 Masse-% olefinisches Homo- und/oder Copolymerisat und (c) 0 bis 50 Masse- teilchenförmiger Füllstoff enthält.
- 330.) Process for the preparation of functionalized polymers according to claims 20 to 29, wherein acrylic acid and / or methacrylic acid and / or maleic anhydride are used as functional monomers. 30.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20 bis 29, wobei als Funktions- monomere Acrylsäure und/oder Methacrylsäure und/oder Maleinsäureanhydrid verwendet werden. 31.) Process for the preparation of functionalized polymers according to claims 20 to 29, wherein the functional monomers used are glycidyl methacrylate and / or hydroxyethyl acrylate and / or hydroxypropyl methacrylate. 31.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20 bis 29, wobei als Funktions- monomere Glycidylmethacrylat und/oder Hydroxyethyl- acrylat und/oder Hydroxypropylmethacrylat verwendet werden. 32.) Process for the preparation of functionalized polymers according to claims 20 to 29, wherein as functional monomers (Nt-butylamino) ethyl methacrylate and / or (N, N-dimethylamino) ethyl acrylate and / or (N, N-dimethylamino) ethyl methacrylate and / or (N, N-diethylamino) ethyl acrylate. 33.) Process for the preparation of functionalized polymers according to claims 20 to 29, wherein as functional monomers (-y-methacryloyloxypropyl) -trimethoxysilane and / or tris- (2-methoxyethoxy) -vinylsilan be used. 32.) Verfahren zur Herstellung funktionalisierter Polymerer nach den Ansprüchen 20 bis 29, wobei als Funktions- monomere (N-t-Butylamino)ethylmethacrylat und/oder (N, N-Dimethylamino)ethylacrylat und/oder (N, N-Di- methylamino)ethylmethacrylat und/oder (N, N-Diethyl- amino)ethylacrylat verwendet werden. 33.) Verfahren zur Herstellung funktionalisierter Poly¬ merer nach den Ansprüchen 20 bis 29, wobei als Funk- tionsmonomere ( -y-Methacryloyloxypropyl)-trimethoxy- silan und/oder Tris-(2-methoxyethoxy)-vinylsilan ver- wendet werden. 34.) Process for the preparation of functionalized polymers according to one or more of claims 20 to 33, wherein as additional comonomers styrene and / or <κ-methyl styrene and / or ethyl acrylate and / or n-butyl acrylate and / or methyl methacrylate in a mass ratio of 1 to 99% functional monomer (s) to 99 to 1% additional comonomer (s). 34.) Verfahren zur Herstellung funktionalisierter Polymerer nach einem oder mehreren der Ansprüche 20 bis 33, wobei als Zusatzcomonomere Styren und/oder <κ -Methyl- styren und/oder Ethylacrylat und/oder n-Butylacrylat und/oder Methylmethacrylat in einem Massenverhältnis 1 bis 99 % Funktionsmonomer(e) zu 99 bis 1 % Zusatz- comonomer(e) verwendet werden. 35.) Thermoplastic molding composition of (a) 1 to 99% by weight of a thermoplastic polymer component, the at least one thermoplastic polymer, selected from among the polar thermopiles, polyoxymethylenes, polycarbonates, Polyphenylene ethers, polyphenylene sulfides, Polysulfones and nitrile polymers, including their mixtures with one another and using further polymers, having a weight-average molecular weight Mw between 20,000 and 1,000,000, and (b) from 1 to 99% by weight of at least one polymer functionalized according to one or more of claims 1 to 17 and / or at least one ionomer according to claims 18 and 19. 35.) Thermoplastische Formmasse aus (a) 1 bis 99 Masse-% einer thermoplastischen Polymer¬ komponente, die mindestens ein thermoplastisches Polymer, ausgewählt unter den polaren Thermopla¬ sten, Polyoxymethylenen, Polycarbonaten, Poly- phenylenethern, Polyphenylensulfiden, Polysulfonen und Nitrilpolymeren, einschließlich ihren Mi¬ schungen untereinander sowie unter Verwendung weiterer Polymerer, mit einem gewichtsmittleren Molekulargewicht Mw zwischen 20.000 und 1.000.000 enthält, und (b) 1 bis 99 Masse-% mindestens eines gemäß einem oder mehreren der Ansprüche 1 bis 17 funktiona- lisierten Polymeren und/oder mindestens eines Ionomeren gemäß den Ansprüchen 18 und 19. 36.) Thermoplastic molding composition according to claim 35, ent - holding - ^ 50 to 98% by mass (a) and -z 50 to 2% by mass (b). 37.) Thermoplastic molding composition according to claim 35, ent holding 2 to 50% by mass (a) and 50 to 98% by mass (b). 36.) Thermoplastische Formmasse gemäß Anspruch 35, ent¬ haltend -^ 50 bis 98 Masse-% (a) und -z 50 bis 2 Masse-% (b). 37.) Thermoplastische Formmasse gemäß Anspruch 35, ent¬ haltend 2 bis 50 Masse-% (a) und 50 bis 98 Masse-% (b). 38.) Thermoplastic molding composition according to claims 35 to 37, in which (a) is selected from the group of monovinylsubstituierter aromatic hydrocarbon homo- and / or copolymers modi¬ ficated polycarbonates and / or polyphenylene ethers and / or polyphenylene sulfides and / or polysulfones. 38.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37, in der (a) ausgewählt wird aus der Gruppe der mittels monovinylsubstituierter aromatischer Kohlenwasserstoff-Homo- und/oder -Copolymerer modi¬ fizierten Polycarbonate und/oder Polyphenylenether und/oder Polyphenylensulfide und/oder Polysulfone. 39.) Thermoplastic molding composition according to claims 35 to 37, in which (a) a polar thermoplastic having at least one polar functional group aus¬ selected from amino, hydroxyl, thiol, carboxyl, isocyanate and epoxy groups and of these derived groups. 39.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37, in der (a) ein polarer Thermoplast mit mindestens einer polaren funktionellen Gruppe, aus¬ gewählt unter Amino-, Hydroxyl-, Thiol-, Carboxyl-, Isocyanat- und Epoxygruppen sowie von diesen abgelei¬ teten Gruppen, ist.
- 440.) Thermoplastic molding compositions according to claims 35 to 37 and 39, in which the polar thermoplastics are polyamides. 40.) Thermoplastische Formmassen gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste Polyamide sind. 41.) Thermoplastic molding composition according to claims 35 to 37, 39 to 40, wherein the polyamide ausge¬ among the obtained from a dicarboxylic acid and a diol in and / or from an aminocarboxylic acid polycondensates and / or a polymer obtained by ring-opening polymerization of a cyclic lactam aus¬ is selected. 42.) Thermoplastic molding composition according to claim 41, wherein the polyamide is selected from polycaprolactam (PA 6), Polyhexamethylene adipamide (PA 66), Polyhexamethyleneazelaine amide (PA 69), Polyhexamethylene sebacinamide (PA 610), Polyhexamethylenedodecanamide (PA 612), Polytrimethylene hexamethylene terephthalamide (PA 6 3T), Poly-11-aminoundecanamide (PA 11), Polylaurolactam (PA 12), Poly (m-xylylene adipamide) (PA MXD 6), Polyhexamethylenisophthalamid (PA 61) and the copolymers of PA 6 and PA 66, PA 6 and PA 610 as well as PA 6 and PA 12 existing groups is selected. 41.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37, 39 bis 40, worin das Polyamid unter den aus einer Dicarbonsäure und einem Dia in und/oder aus einer Aminocarbonsäure erhaltenen Polykondensaten und/oder einem durch ringöffnende Polymerisation eines cyclischen Lactams erhaltenen Polymeren ausge¬ wählt ist. 42.) Thermoplastische Formmasse gemäß Anspruch 41, worin das Polyamid aus der aus Polycaprolactam (PA 6), Polyhexamethylenadipinamid (PA 66), Polyhexamethylenazelainamid (PA 69), Polyhexamethylensebacinamid (PA 610), Polyhexamethylendodecanamid (PA 612), Polytrimethylenhexamethylenterephthalamid (PA 6 3T), Poly-11-aminoundecanamid (PA 11), Polylaurinlactam (PA 12), Poly(m-Xylylenadipinamid) (PA MXD 6), Polyhexamethylenisophthalamid (PA 61) sowie den Copolymeren aus PA 6 und PA 66, PA 6 und PA 610 sowie PA 6 und PA 12 bestehenden Gruppen ausgewählt ist. 43.) Thermoplastic molding composition according to claims 35 to 37 and 39, in which the polar thermoplastics are thermoplastic polyesters. 43.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste thermoplastische Polyester sind. 44.) Thermoplastic molding composition according to claim 43, wherein the thermoplastic polyester is selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), including PET / PBT copolyester, the block copolyesters composed predominantly of PBT segments and PBT / polycarbonate Blends, existing group aus¬ selected. 44.) Thermoplastische Formmasse gemäß Anspruch 43, worin der thermoplastische Polyester aus der aus Polyethy¬ lenterephthalat (PET), Polybutylenterephthalat (PBT), einschließlich PET/PBT-Copolyester, den aus über- wiegend PBT-Segmenten aufgebauten Blockcopolyestern und PBT/Polycarbonat-Blends, bestehenden Gruppe aus¬ gewählt ist. 45.) Thermoplastic molding composition according to claims 35 to 37 and 39, in which the polar thermoplastics are thermoplastic polyurethanes. 45.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste thermoplastische Polyurethane sind. 46.) Thermoplastic molding composition according to claims 35 to 37 and 39, in which the polar thermoplastics are vinyl ester homo- and / or copolymers. 47.) Thermoplastic molding composition according to claim 46, in which the vinyl ester copolymers are ethylene / vinyl acetate copolymers having a vinyl acetate content of 5 to 90% by mass. 46.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste Vinylesterhomo- und/oder -copoLymere sind. 47.) Thermoplastische Formmasse gemäß Anspruch 46, in der die Vinylestercopolymerisate Ethylen/Vinylacetat-Copo- lymere mit einem Vinylacetatgehalt von 5 bis 90 Masse-% sind. 48.) Thermoplastic molding composition according to claims 35 to 37 and 39, in which the polar thermoplastics are vinyl alcohol homo- or copolymers. 48.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste Vinylalkoholhomo- uid/oder -copolymere sind. 49.) Thermoplastic molding composition according to claim 48, wherein the vinyl alcohol copolymers are ethylene / vinyl alcohol copolymers having a vinyl alcohol content of 40 to 90 mol%. 49.) Thermoplastische Formmasse gemäß Anspruch 48, worin die Vinylalkoholcopolymerisate Ethylen/Vinylalkohol- Copolymere mit einem Vinylalkoholgehalt von 40 bis 90 Mol-% sind.
- 550.) Thermoplastic molding composition according to claims 35 to 37 and 39, in which the polar thermoplastics of ionomers of from 0.1 to 50% by mass u, fi-ethylenically unsaturated carboxylic acids and / or acid anhydrides and from 50 to 99.9% by mass of olefin and / or styrene and / or (meth) acrylate units of existing copolymers, wherein in the ionomers Carb oxylgruppen via at least one 1-valent and / or 2- and / or 3-valent metal ion are networked. 50.) Thermoplastische Formmasse gemäß den Ansprüchen 35 bis 37 und 39, in der die polaren Thermoplaste Ionomere von aus 0,1 bis 50 Masse-% u , fi -ethyle¬ nisch ungesättigten Carbonsäuren und/oder -säure- anhydriden und aus 50 bis 99,9 Masse-% Olefin- und/oder Styren- und/oder (Meth-)Acrylateinheiten bestehenden Copolymeren darstellen, wobei in den Ionomeren Carb- oxylgruppen über mindestens ein 1-wertiges und/oder 2- und/oder 3-wertiges Metallion vernetzt sind.
Independent claims5
369 paragraphs in 27 sections, as filed
Translation of description of equivalent WO 9623011 A1
Functionalized polymers, processes for their preparation and their use in thermoplastic molding compositions of
The invention relates to functionalized polymers by radical FestphasenpfropfPolymerisation of <x>, - ethylenically unsaturated functional groups besitzen¬ the compounds to olefinic and / or dienic Ther¬ tics and elastomers, the method of their preparation and their use in thermoplastic molding compositions.
It is known, both olefin homopolymers and copolymers and dienic homopolymers and statistical or alter¬ nating copolymers and especially copolymers, often to also selectively hydrogenated form, for a wider applicational range, ie from the usual thermoplastics up technically significant rubbers and thermoplastic elastomers (TPE) is present, for several important application areas by turning on or subsequent grafting propertied of special funktio¬ Neile groups monomers (so-called Funkt- tionsmonomere) in the trunk or on the Rückgratpoly¬ mer chain targeted chemical to modify.
As can Rückgratpolymerisate except the homopolyolefins (PO) such as polyethylenes (PE) and polypropylenes (PP), especially olefinic and / or dienic copolymers and Block¬ copolymers, in particular ethylene / propylene copolymers (EPM), ethylene / propylene / diene ( dicyclopentadiene and / or norbornene) - terpolymers (EPDM), ethylene / vinyl acetate copolymers (EVA, EVM), ethylene / (meth) acrylate copolymers (EAM), styrene / ethylene-butylene / styrene (SEBS) and styrene / ethylene-propylene / styrene-block copolymers (SEPS), including their mixtures with one another, such as EPM and EPDM / PO (PE and / or PP) and
SEBS and SEPS / PO and / or EPM and EVA, and not least the classic rubbers based conjugated Dienes such as 1,4-cis polybutadiene (BR), polyisoprene (IR) or natural rubber (NR), random styrene / butadiene copolymers (SBR), acrylonitrile / butadiene copolymers (NBR) and styrene / butadiene or isoprene two-block copolymers (SB, SI) and the corresponding three- and Vierblock- copolymers (SBS, SIS or SBSB and the like.) or radial styrene / butadiene block copolymers ((SB) X with n = 3-12, X = coupling agent) be used. Besides Verwen¬ the functionalized base polymer formation as adhesion-resistant film and coating material (US 4,394 485), they are primarily a well-bonded or compatible component in composite foils, laminates and preferably suitable in different thermoplastic molding compositions.
The particularly on the automotive, household appliances and
Electric or (micro) electronics sector used technical grade thermoplastics generally require an adhesive or compatibilizer, especially compared to other polymer components but also non-polymeric materials, the same mostly significant (notched) Schlagzähver- causes improvement.
Of the for the above mentioned application areas usually ver¬ used thermoplastics which are often chemically due to their final pendant reactive groups well modifiable, have especially polyamides and saturated polyesters, further thermoplastic polyurethanes, poly phenyl ethers, polyphenylene sulfides, among others, including their combinations themselves and blends styrene under inclusion of other thermoplastics, in particular PO, poly (PS) or Styrencopolymerer, the most important. (DE 2,622,973 and US 4,174 358, US 4172 859, EP 0279 578, EP 0234 819, EP 0180 302; US 4,628 072, US 4657 970, US 4657 971, EP 0415 344; US 3,668 274, US 3972 961, US 4,017 557;. Ide and Hasegawa, J. Appl Polym Sei.18 (1974). 963, US 4,427 828, US 4508 874, US 3972 961, US 4017 557, US 4,863 996; WO 87/00540, WO 86/04076; US 4,594 386; WO 88/07065).
The modification of the olefin and also (ungesät¬-saturated) dienic polymers may for various Pfropf¬ polymerization processes carried out.
Because of their inefficiency and the low overall achievable degrees of modification have solvents and dispersion Pfropftechnologien that beru¬ on the use of liquid organic and / or aqueous carrier phase hen (EP 0074811, EP 0187659, DE 2023154, DE 2329780, DE 2420942), for the functionalization olefinic backbones little or no commercial importance. Even non-hydrogenated and selectively hydrogenated styrene / conjugated diene block copolymers can - similar to Maleini- capitalization of polyisoprene (JP 20294/74) - by grafting of mono- and dicarboxylic acids and their derivatives, more particularly special maleic anhydride (MA), in a be functionalized organic solvent (US 4308 353, EP 0173 380).
But this has to work with large amounts of solvents, including their recovery / recycling, and taking account of physiological and fire protection aspects, emerged as an obstacle to commercial use.
The vast number of used functionalized olefinic thermoplastics / elastomers is on an industrial scale by means of radical Schmelzepfropfung, are generally employed in an extruder or kneader at temperatures zwi¬ 150 and 300 ° C, produced (EP 0128775, EP 0235876, EP 0266221, EP 0287140, EP 0299499, EP 0371001, DE 1694126, DE 2242324, DE 2326589, DE 2401149, US 3873643, US 3987122, US 4578429, US 4927889). Unsaturated styrene / butadiene / styrene polymers Dreiblockcopoly- (SBS) are formed by grafting of unsaturated mono- or dicarboxylic acids or derivatives thereof, more particularly special MSA, under melt mixing conditions in the absence of a radical initiator using Radi¬ kalinhibitoren order to suppress unwanted Vernet ¬ tions or gel formation functionalized (US 4,292 414). To such an addition "functionalization, also called" ENE "reaction referred to perform, requires a minimum proportion of unsaturated bonds in the dienic Weich¬ segments necessary.
Since the selectively hydrogenated styrene / diene / block copolymers mers but have a generally low (between 0.2 and 20%) sufficient degree of residual unsaturation in their Olefinblöcken, these means of "ENE" reaction functionalize (US 4427 828, US 4508 874, EP 0155995). When using MSA as Funktionsmonomer the MSA addition leads to steinsäureanhydridgruppen preferably attached allylic Bern¬ that are thermally extremely unstable and can be relatively easily removed again ( "counterparty ENE" reaction).
The modified melt SBS or SIS triblock copolymer, including their by mono-, di- or trivalent metal ion cross-linked products, can contribute to the processing and application technical Aus¬ armor of polystyrene (PS) (US 4,308 353), PS / PO mixtures (DE 4217470, DE 3643008, US 4518 681, EP 0289926, EP 0310051), and tics for the modification of technical Ther¬ and Hochleistungskunststoffe how special polyamides (PA), thermoplastic polyesters such as polyethylene and polybutylene terephthalate (PET and PBT ), polycarbonates (PC) and polyester (PEC), polyphenylene ether (PPE), polyphenylene sulfides (PPS), thermoplastic polyurethanes (TPU), polyoxymethylenes (P0M), polymethacrylates (PMMA), saponified ethylene-vinyl acetate copolymers / ethylene-vinyl alcohol copolymers with different degrees of hydrolysis be (EVAL) and others, including their blends with styrenic polymers and PO, used (GB 2053238). Thermally stable and essentially non-crosslinked (gel¬ free) graft with improved overall processed beitungs- and performance properties by grafting carboxyl-containing monomers and their derivatives, in particular MSA, and block copolymers having low ethylenic unsaturation in the polymerised diene block, especially SEBS SEPS with a generally high 1, 2-configuration corresponding high vinyl group or decorate the diene midblock in unhydrogenated Aus¬ base product (SBS and SIS), generally under Schmelze¬ grafting using a radical initiator peracetic oxide in the extruder obtained (EP 0173380 , EP 0262691, EP 0371001, EP 0282664, US 4578 429, US 4628 072, US 4657 970, US 4657 971). In this case, place the grafting of the MSA or other Funktionsmonomeren - in contrast to the "ENE" - Addition - mainly at the tertiary and secondary carbon atoms of the olefin (EB or EP) segments instead (US 4,578 429).
The functionalization in the form of a maleination or carboxylation melt is fraught lems despite their many technical use with a number of general Pro¬. That's structures mainly due to the high Tempera¬, crosslinking generally between 200 and 300 C in the extruder or compounder under high shear forces, and thus ver¬ affiliated adverse reactions, in particular polymer and -abbaureaktionen and side reactions (homopolymer formation) and / due or low or only partial polymerization (escape of volatile monomers) of Funktionsmonomeren. Since the Schmelzepfropfung must be under conditions mentioned above, takes place generally in short reaction periods, generally between about 3 and a maximum of 20 minutes, the possible SchmelzepfropfSysteme limited to those reactants and components - under gleichzei¬ term assurance of their chemical stability, the weitest- continuous preventing their escape from the Reaktions¬ zone and to avoid its corrosive effect on the tool material - spreads easily in the reaction medium, not abruptly (risk of high homopolymer formation or low grafting yield and a very low degree of grafting) but in the short available reaction time almost must be fully implemented.
From the above it can be concluded that higher monomer and initiator concentrations in order to achieve higher degrees of functionalization ban from the outset. Therefore, in practice only a few Funktionsmonomere except the MSA preferably used mostly only higher unsaturated (di) carboxylic acids or their anhydrides, suitable for grafting to the different backbone polymers.
Thus the possibility of variation is in terms of adjustability Ein¬ the concentration of carboxyl or acid anhydride groups or on other functional groups and thus the adhesive (pressure-sensitive or compatibility) very limited effect.
If the graft below the polymer backbone melting temperature, in generally between 40 and 130 ° C. in the absence of liquid aqueous and / or organic suspension (emulsion) - or solvent phase, finally ein¬ of monomer (s) themselves as independent liquid phase, carried out may particularly from predominantly styrene and a Funktionsmonomer such as acrylic acid, composite monomer in specially ausgebil¬ Deten PO or olefin / monomer Gelmischphasen (DD 135 622), or - if the monomers in gas¬ like state (IT 867 340, US 3162 697) - in the form of a Gasphasenpfropfung (JP 03,285,936, JP 03,285,937 , JP 03285938), the latter in particular for producing intermediaries Verträglichkeits¬ be polymerized for PA / PO, PC / PBT and PO / PO blends copolymerizable.
In contrast to the in the polymer melt or in the liquid aqueous and / or organic media durchge resulted graft functionalization of thermoplastics and elastomers, used as backbone polymers, this Pfropf¬ polymerization process because of the "fixed" consistency of the reaction mixture until the Monomerendumsatz as Fest¬ phasenpfropfung are designated.
A number of grund¬ for melt functionalization additional disadvantages is pfropftechnologie avoided or mitigated by the application of highly economically feasible radical Festphasen¬, the various possible backbone polymers - practically from the thermoplastics (PO, such as PE and PP or EVA) over the thermoplastic elastomers (TPE), especially those based on hard PS-segment / soft (elastic) Dien¬ or olefin oligomer segment / hard PS-segment (TPE-S) or crosslinked EP (D) M / P0 compounds ( TPE-0) to the elastomers (EPM, EPDM, EVM, BR, IR, SBR, NBR, SB, SI) - and the various graft monomers or graft monomer mixtures, including compositions comprising functional and non-functional additives comonomers can be used taking into account the specific for each PfropfSysteme conditions (DD 136971, DD 275 159, DD 275 160, DD 275 161, DD 266 358, DD 290 431, DD 290 432, DD 300977, DE 4123972, DE 4217469, DE-A P 4342605.0 , EP 0469693, EP 0263887, EP 0265527). A not or systems for a number of interesting Pfropf¬ insufficiently resolved problem of the resultant by Festphasenpfropftechnologie functionalized thermoplastics / elastomers are their generally very high degrees of crosslinking, although for different applications can be advantageous even, but applications for other Verwen¬ are very disadvantageous , This applies particularly challenging to functionalizing while significantly more expensive rubbers and TPE, especially those (_i Hw 100,000) with higher molecular weights, and the use of monomers containing carboxyl groups at higher concentrations (- ^ 2 mass%), whilst ensuring a high monomer conversions and grafting, both essential conditions for highly effective impact-modifiers, especially in the temperature range Tie
(0 C. to about -50 C), levels in consideration of a total ins¬ high mechanical and thermal Eigenschafts¬ and a good processability of the modified with the functionalized polymers see thermoplastic molding compositions.
The invention is therefore based on the object funktiona¬ ized polymers using olefinic and / or polymeric backbone dienischer and different, j3 - ethylenically unsaturated compounds with functional
Groups (Funktionsmonomere) based on a ökono¬ mix Pfropftechnologie while eliminating the disadvantages occurring under graft polymerization conditions in liquid aqueous and / or organic phase or in the melt, in particular with regard to the very limited choice of functionality setting olefini¬ rule and / or diene graft substrates and thus restricted Pfropfproduktkennwertniveaus, with a preserved against the organization by known Festphasenpfropfpolymeri- graft higher Adhäsionsfestig¬ speed or modifying effect when used as an adhesion promoter / Impact modifier to develop in a large number of thermo¬ plastic molding compositions.
According to the invention contain functionalized polymers based on olefin homopolymers and / or (block) copolymers mers and / or conjugated diene homo- and stati¬-elastic or alternating copolymers and / or block copolymers, including the respective selectively hydrogenated polymers, with weight average Molekularge¬ weights Mw of 10,000 to 1,000,000 as a backbone polymer and from 0.05 to 50 parts by weight based on 100 parts Masse¬ Rückgratpolymerisat, at least one grafted molecular unit containing at least one functional group selected from mono- and dicarboxyl, including groups derived therefrom, such as amide or imide, Halbester- and especially anhydride groups, hydroxy and epoxy groups, amino groups and silane groups, and optionally at least one further molecular unit cografted without the aforementioned functional groups, such as styrene or substituted styrene and / or (meth) acrylate, in a mass ratio of monomer (s) with functional groups (Funktionsmonomer (e)) to monomer (s) without said functional groups (additional comonomer (s)) 1 to 100% 0 to 99%, said related to the backbone polymer composition total amount of up graft function plus Zusatzcomonomeren is 0.05 to 50%, an added before functionalizing graft portion of a mineral, in particular paraffinic and / or naphthenic and / or aromati¬ rule oil and / or a native, particularly vegetable oil in an amount of 10 parts by weight up to a Maximal¬ concentration corresponding to the absorption capacity of the polymers used as Rückgratpolymerisate under Auf¬ maintaining their dry-flowable consistency within the limits of 20 to 400 parts by mass, in particular to 200 parts by mass, respectively based on 100 parts by mass return gratpolymerisat. The addition of a - considering the Aufnahme¬ capacity of individual Rückgratpolymerisates - selectable within wide limits amount of oil, which is especially a kosten¬ reducing action led to functionalized graft products with a surprisingly wide variable modifying effect during their incorporation in unterschied¬ Liche thermoplastic molding compositions, including polymer blends and -Composites.
With a suitable choice of PfropfSystems, especially using special thermoplastic elastomers with higher molecular weights (Mw _≥200.000) polymers as Rückgrat¬ which can generally be no additional oil is difficult, especially with lower graft, functionalized lisieren, and acrylic and / or methacrylic acid or their Hoirologen and / or MSA and other Funktionsmono¬ mers to graft degrees - 2% by weight are grafted onto the backbone ^, functionalized, preferably carboxyiierte polymers are obtained, the ther¬ a variety moplastic molding compositions high often give erratic anstei- rising low temperature toughness by securing all other major application and processing properties at the required level for anspruchs¬ application fields. Herein is revealed in a surprising manner, the inventive solution, which indirectly speeds un- to the specific technological Möglich¬ the solid phase graft modification Verwen¬ training a fairly broad range of usable Rück¬ gratpolymeren and Funktionsmonomeren and optionally Zusatzcomonomeren is due. In addition to the general utility of the native oils, ins¬ particular of vegetable oils (glycerides of predominantly unsaturated fatty acids), such as rapeseed oil or rapeseed oils, soy oils, etc., and also animal oils (glycerides of predominantly saturated fatty acids) (ULLMANN Vol. 11, pp 455-524 "fats and oils"; Verlag Chemie Weinheim 1976), are particularly the known saturated mineral belonging to the paraffinic, naphthenic or for relatively thenischen naphthenic, for relatively aromatic or aromatic process oil type and are widely used in rubber products as mineral oil softeners, suitable for the inventive functionalized polymers. Other oily hydrocarbon products, such as liquid polybutenes, are in the Pro¬ invention ucts used. Particular preference mineral oils, paraffins from African or relatively naphthenic or naphthenic
Process oil type, the carbon distribution a<sup>ö</sup> CA.roma_t. to
C<sub>B</sub>N / A<sub>O</sub>p.ht..hen. to C<sub>D</sub>Para <sub>c</sub>f<sub>c</sub>fi.n. from 0 to 10 to 20 to 45 to
are 45 to 80 and those having viscosity-density constants (VDK) from 0.80 to 0.90 assign
(E. Balint, rubber, fibers, plastics (GAK) (1993) 6, pp 286-290).
Possible oil additives to melt or Lösungspfropf- are polymerization indeed known (EP 0173380, EP 0266221), but have only a subordinate role or provide any compelling, the Pfropfprozeβ and beson¬ DERS the properties of functionalized Pfropfpro¬ products significantly influencing measure constitutes . this is not to be expected because of the inherent melt and Lösungspfropfbedingungen such an addition is not effective or only to a limited extent, as the oil, especially when using high proportions, largely außer¬ half is the reaction phase, moreover leads to sensitive technical and technological disturbances within the overall process.
In addition, in the production of melt in the maleated selectively hydrogenated styrene / diene block copolymers meren the effectiveness of oil as a Pfropfpolymeri- the sationsansatz hinzusetzbarer flow improvers at any point occupies (EP 0173380). And also the potential mineral additive to Schmelzepfropf¬ approach in the preparation solely peroxide highly crosslinked (hochgelhaltiger) pfropffunktionalisierter Olefinelastomerer that act as polyamide impact modifiers (EP 0266221), is a limited and purchased only on the Schmelzepfropfung, no connection with the present invention task standing action.
In general, the more costly thermopla¬-elastic elastomers such as TPE-S saturated based on unge¬ and selectively hydrogenated (saturated) styrene / diene block copolymers, optionally, not used directly in funktiona¬ ized form, but taking into account optimum use properties and a significantly more cost-effective deployment with underside various aggregates "blended", with a broad range of TPE-S in hardness settings -MZ 30 Shore a to ^ 65 Shore D can be adjusted or added as elasticizing component or impact modifier thermoplastic molding compositions.
Known in this context is also the mere for Elasto¬ conventional oil extension, ie the addition of a mineral process oil - not sationsansatzes as part of Polymeri¬, but directly in the production of processable rubber mixture - in quantities of 50 to 300 parts by mass of 100 parts by weight of elastomer, eg TPE-S in the form of a mixture of SEBS and SEBS maleini- dized, which optionally as further component a PO (US H 1022) or in general may contain other elastomers and resins (EP 0085115, EP 0216347). The inventive functionalized polymers, ins¬ particular the carboxylated thermoplastic elastomers of the type TPE-S and TPE-O, are distinguished from known functionalized thermoplastics / elastomers, prepared by the Schmelze¬ commercially applied pfropftechnologie or extremely uneconomic Pfropffunktionalisierung organic liquid or aqueous phase or solid phase Pfropffunktiona¬ tion without oil additive in Pfropfpolymerisationsansatz, and to those obtained by these processes functionalized products which have been oil extended only after the functionalization reaction by a significantly higher modifying effect. This is reflected especially - considering the achievable only by means of inventive solution Zu¬ accessibility of wide backbone polymer palette beson¬ DERS regarding high molecular TPE (Hw -ϊ 200,000) - also in the sharp increase in toughness, in particular notched impact strength characteristics at low temperatures (0 C to about -50 C), which finished with the erfindungsge¬ Maessen pfropffunktionalisierten polymer thermoplastic molding compositions - taining while Auf¬ or even mostly increase in the total mechanical level (strength and stiffness and hardness characteristics ) and the heat resistance to the equipped with known comparable modifiers polymer molding compositions - from.
Since when using especially the functionalized TPE invention with significantly lower proportions - in comparison to the known, about the same or similar functionalization having TPE - the wish ge modifying effect is achieved, resulting from the use of the products according to the invention except through the oil stretching inherently reached verbesser¬ th Wirtschafftlichkeit an additional cost saving. Possible backbone polymers for the production of the inventive functionalized polymers, the wide range of known olefin homopolymers, gesättig¬ and unsaturated copolymers and block copolymers are used.
The main usable polyolefins (PO) are:
Low density polyethylenes (from 0.900 to 0.932 g / cm<sup>3</sup>), Including small amounts ( <sup>■</sup>* = 3 mass%) of higher olefins comprising, after the high-pressure method (PE-LD);
3 linear polyethylenes of low density (0.915 to 0.935 g / cm) by means of low-pressure (PE-LLD)
(H. Münstedt u H.-J. Walter, Plastics 83 (1993) 10, pp 725-728).;
high density polyethylene (0.940 to 0.980 g / cm) by means of different polymerization process low-pressure or Mitteldruckpolymeri-, optionally using small amounts of higher olefins obtained (PE-HD)
(C. Gondro, Plastics 83 (1993) 10, pp 729-732);
isotactic polypropylenes (PP), including those obtained by incorporating higher olefins random or block copolymers, preferably produced by suspension sion (slurry) -, gas phase process or a combination of mass (bulk) - and gas-phase polymerization, whereby in addition to the standard products, including those that can be the engineering plastics in key properties match and under the designation "PP based Advanced Materials" (PPAM) traded, used (... Kunststoffe 83 (1993) 10, pp 732-737);
more olefinic homopolymers such as polybutene-1 (PB), polyisobutylene (PIB) and C ..- up ^ <sub>2</sub>~ Polyolefins. The main olefin copolymers are:
Nonpolar copolymers and terpolymers based on the polymerization of olefin, optionally with the addition of non-conjugated diene (dicyclopentadiene, 5-ethylidene-2-norbornene, etc.), such as the elastomeric peroxide-crosslinkable ethylene / propylene copolymers (EPM) and the sulfur cross-linkable ethylene / propylene / diene terpolymers (EPDM), including the corresponding EP (D) M / P0 (PE, PP) - compounds, representatives of the TPE-0 class
(W. Hofmann, Plastics 84 (1994) 2, pp 109-111; ibid
80 (1990) 10, S.1204-1209, 1210-1212),
ester units constructed polar olefinic copolymers are used as Rückgratpolymerisate and / or (meth) acrylic acid - except the non-polar olefin copolymer may also consist of olefin - as well as vinyl esters.
Preferably suited the wide range is ethylene /
Vinyl acetate (VA) copolymer (EVA) with a different composition according VA contents of about 5 to
95 mass, including the portion of the ethylene /
Vinyl acetate rubbers (EVM) having a VA content of between about 40 and 80% by mass
(H. Streib Others Plastics 67 (1977) 3, pp 118-121;.. E. Rohde, couch + Gum.-Plaids 45 (1992) 12, pp 1044-1051;
K. Adler u. K.-P. Paul; Plastics 70 (1980) 7, pp 411-418;
DE 1126613, DE 1495660, DE 1495767, DE 2927088).
Furthermore, according to the broad EVA / EVM pallet composite ethylene / acrylate rubbers (AEM), for example ethylene / ethyl acrylate (EEA), ethylene / n-butyl acrylate (EBA) as well as ethylene / (methyl-) methacrylate copolymers ( EMA), are used as backbone polymers. A relatively new and very promising olefin polymer product class with a targeted control and variable microstructures and molecular weights indicated by use of metallocene catalysts, also with respect to their mode of action as a "single-site" catalysts, have been developed.
(EP 0416,815; J. Okuda, msgs Chem Tech Lab 41 (1993) 1, S. 8-14;........ R. Mühlhaupt, msgs Chem Tech Lab 41 (1993) 12, S. 1341- 1351).
The metallocene technology particularly Olefinco- can polymers of ethylene (propylene) and higher oC-olefins, preferably octene whose proportionate amount decided in the reactor of the number of C, side chains, can be obtained. The backbone polymers according to the present invention preferably several already sold commercially or soon-to-launch olefin copolymers of this new product class may be used. This concerns mainly consisting mainly of ethylene and up to 20% obtained from octene copolymers known as polyolefin plastomers (POPs), and the corresponding "softer" copolymers with more than 20% octene and as polyolefin elastomers (POEs) called to continue the cycloaliphatic olefin homopolymers and mers -copoly- and styrene / ethylene copolymers with high styrene share and high molecular weight and also - analog syndiotactic polystyrenes (SPS) - the syndiotactic Poly propylene (SPP)
(J. Wolters, Plastics 83 (1993) 12, pp 985-987).
Another useful class of polymeric backbone are located in contrast to the amorphous POPs and POEs in the market partly crystalline thermoplastic Block¬ copolymers consisting of crystalline (hard) PO blocks, mostly PE blocks with melt temperatures of about
95 and 110 ° C, and amorphous (soft) PO blocks transformation temperatures with Glas¬ consist -40 to -60 C. Ultimately, chlorinated polyethylenes (PE-C, CM) and chlorosulfonated polyethylene rubber (CSM) can be used as the backbone polymers and the backbone polymer components.
In general, as the backbone material compounds consisting moplastics from at least two different olefinic Thermo¬ and / or (crosslinked or uncrosslinked) Elasto¬ mers, possibly with the addition of a fibrous or more particulate filler from the series of the known ranges in the usual concentrations of about 5 to 100 parts by mass, preferably from 10 to 50 parts by weight based on polymeric each 100 parts by weight of backbone material used.
A preferred position as usable Rückgratmateria¬ lien take the olefin / vinyl aromatic Blockcopo¬ a mers. They are prepared by selective hydrogenation (GB 1030306, US 3700633) of differently structured (linear and radial) block copolymers of monovinyl substituted aromatic hydrocarbon segments (Polyvinylarylblöcken), preferably composed of styrene or alkylated and / or halogenated styrenes blocks (S), and conjugated diene segments, preferably from butadiene (1, 3) or Methylbutadien- (1, 3) (isoprene) blocks built (B or I), wherein the unterschiedli¬ chen blocks be sharply separated from each other or "smeared" transitions ( tapered section) may have, with olefinic UnSättigungsgraden of the general -≤ 20%, preferably. * =. 5% was obtained. Particularly suitable are the by selective hydrogenation of styrene / butadiene / styrene three-block copolymer (SBS), the butadiene midblock rule a vinyl group content zwi¬ 10 and 80%, preferably between 25 and 65%, having obtained styrene / ethylene-butylene / styrene
Triblock copolymers (SEBS) and the corresponding obtained from the styrene / isoprene / styrene three-block copolymers styrene / ethylene-propylene / styrene triblock copolymer (SEPS) with weight average molecular weights Mw from 20,000 to 1,000,000.
behavior blocks Because of thermodynamically incompatible Phasenver¬ between hard fusible vinylaryl and olefinblöcken the soft elastic polydiene or poly-, these three and possibly
Multiblock typical TPE (TPE as polystyrenhaltige coded TPE-S) represents.
The group of TPE-S, which can be employed particularly advantageously in the form of Rückgratpolymer- compounds include especially SEBS / P0 or SEPS / PO blends using as PO component preferably PP, LDPE, LLDPE and EPM are well suited and the compounds optionally also a filler for adjusting certain curing while achieving a cost reduction can contain.
The basic morphological characteristics of TPE-S is not or only slightly changed by the said polymeric and / or inorganic additives.
In general, fibrous filler and particulate fillers may particularly in an amount up to about 70% by weight, preferably between 5 and 50% by mass, hinzu¬ be joined, wherein in addition to the preferred spherical calcium carbonates, in particular chalks, optionally also platy potassium aluminum silicates, such as Mica, feldspar and kaolin, or magnesium silicates, such as talc, and needle-shaped calcium silicates, such as wollastonite, are used. In addition to said olefinic backbone polymers may also be unsaturated, substantially polymerized
Diene units based backbone polymers, partly already mentioned among the olefin copolymers with, be used mers for the Preparation of Functionalized Poly invention, especially Olefinterpolymere, such as non-network EPDM, and styrene / conjugated diene block copolymers (SBS, SIS) as well as the corresponding ¬ the two-block copolymers (SB, SI) and Mehrfachblockcopoly- mers, with different structures, symmetric or asymmetric, linear and star-shaped branched (radial) up (GB 985,614, DE 2,125,344, DE 1,959,922, US 3,281,383), the block copolymers only sharp Über¬ courses have between segments or "ver¬ smeared", ie essentially random copolymer segments (tapered section) may contain (DE 2,550,226, DE 2,550,227, GB 888 624, GB 1044862, NL 6713383).
The vinyl group content of the conjugated diene formed from ge segment unit may be 10 to 80%, preferably 25 to 65%, respectively. The weight average molecular weight Mw of the styrene / diene block copolymer is 20,000 to 1,000,000, preferably 50,000 to 500,000. In this case, any PS block S is the same or underside schiedliches number average molecular weight M<sup>*</sup>n 4000-100000 and each polydiene B or I have a Mn 10000-200000. The backbone polymers may continue polydienes and sta¬ tical diene elastomers, in particular the commercially available butadiene rubbers (BR), natural rubber (NR), Isoprenkaut¬ rubbers (IR), butyl rubber (IIR), styrene / butadiene caoutchouc rubbers (SBR), acrylonitrile / butadiene rubbers (NBR),
Chloroprene rubbers (CR) and the like., Including the corresponding hydrogenated rubbers (BR-H, H-NBR, etc.), may be used.
Moreover, by grafting of olefinic and / or vinyl group-containing monomers, in particular styrenes, (meth) acrylonitrile and (meth) acrylates, obtained on diene rubbers and olefin or acrylate rubbers Copfropfpolymerprodukte as especially those corresponding to the monomer acrylonitrile /
Butadiene / styrene (ABS), methyl methacrylate / butadiene / styrene (MBS), methyl methacrylate / acrylonitrile / butadiene / styrene (MABS) and acrylate / styrene / acrylonitrile (ASA), are suitable as inventively employable backbone polymers. The thermoplastics used as Rückgratpolymerisate and elastomers, in particular TPE, are pfropffunktionali- Siert using the following preferred Funk¬ tionsmonomerer:
1) at least a mono- or dicarboxyl or a group derived therefrom (corresponding derivatives), in particular an anhydride, have, said representative of this class of compounds acrylic acid (AA), methacrylic acid (MAS), fumaric acid (FS) and maleic anhydride (MA ) and the corresponding higher molecular weight homologues are mentioned,
2.) that have at least one epoxy or hydroxy, said representative of this class of compounds glycidyl methacrylate (GMA), hydroxyethyl acrylate (HEA) and hydroxypropyl methacrylate (HPMA) are to be mentioned, 3.) which have at least one amine, amide or imidic group (both latter einzu¬ well as derivatives of the above 1. Function monomer class organize), wherein acrylamide and as 2-dimethylaminoethyl methacrylate (DMAEMA) are typical representatives of this class of compounds, and
4.) the minimum one silanische group such as (y-MethacryloyloxypropyD trimethoxysilane and especially tris (2-methoxyethoxy) -vinylsilane as selected representative Funktionsmonomertyps.
The functionalization - generally up to a maximum of about 33% by weight of grafted functional monomer content - is of course also possible with the corresponding two or more different polar functional groups enacting monomers.
Equally can after graft functionalization secondary reactions or on the aufgepfropf¬ th functional groups, such as a radical or especially by reaction with metal salts or hydroxides ionic crosslinking reaction (EP 0086159) as well as a follow-up reaction of the functional groups with low molecular weight substances that can react with the grafted polar groups, for example with an N-substituted imide, amide or N-substituted Hydroxyethylmonomer (EP 0,128,775) or with bis or tris-carbodiimides (US 4,689,372 ), be performed.
The Funktionmonomeren can be used alone or as a mixture of two or more Funktionsmonomeren and günstiger¬ example with the addition of one or more, preferably be used on any reactive functional groups or only significantly weaker polar groups, such as ester groups, verfü¬ lowing comonomers. Particularly through the use of styrenes as comonomer, with the mass ratio Funktionsmonomer to comonomer within a very wide range, preferably 90 to 10% 10 to 90%, is varied, can - independent of the other selectable Pfropfprozeß- and
Product characteristic control variables such as initiator type and concentration -konzen-, ratio monomer submitted to Rückgratpoly¬ mer content and not least by the addable within wide limits oil content - important performance properties of the functionalized polymers are highly influenced.
A central role for the Pfropfpoly erisationsprozeß and the functionalized graft takes the process a zeßöl. For the functionalized thermoplastics and elastomers according to the invention a variety of different oils that stage the backbone polymer or -polymeicompound (unfilled / filled) before Pfropffunktionaiisierungs- has to be added - optionally in a spe- cial Vorcompoundierungsstufe - proved to be suitable. This primarily concerns the known hochausraffi- ned high-boiling mineral oils, preferably those with paraffinic and / or naphthenic but also gege¬ appropriate aromatic structure, generally below 300 C is not corrosive, clear and odorless, without toxic components (for the food sector suitable).
Furthermore, - taking into account the vorge provided specific intended use, including the use of functionalized products in the ver¬ different thermoplastic molding compositions - also natural oils, such as in particular the known vegetable oils (rapeseed oil, Soja¬ oil, etc.), as an inventive component in Pfropf¬ polymerization are used. Initiators are particularly the known organic peroxides and diazo compounds, including entspre¬ sponding initiator mixtures, with a ten-hour Halb¬ worth temperature (measured in 1.0 m-Benz solution) between 40 C and 90 C, preferably the known diacyl such as dilauroyl (DLPO) and dibenzoyl (BPO), and Dialkylperoxidicarbonate Perneodecanoate suitable.
The entire Pfropfpolymerisationsansatz consisting of backbone polymer (-Compound), oil content, monomer (s) (Funktionsmonomer and optionally Zusatzco onomer) and radical initiator is presented tor at room temperature in Reak¬ in which in a first, generally ten minutes to half an hour dispersion phase the Reak¬ tion mix, substantially in a virtually dry up "oil wet" powdery and / or crumbly and / or flaky or flake-like to lamellar and / or coarse-grained (granular) state, is brought into a pfropfpolymeri- sationsgünstige form.
At this point it should be noted that for the purpose of improving the dispersing effect - as well as for possible Vorcompoundierungsstufen (eg mixture of the residue gratpolymerisates, optionally polymeric the addition of a Zweit¬ and / or a filler, with the oil) - in a Inertwasser -medium can be worked, said Inertwasseranteil between 20 and 500 parts by mass, be¬ subjected to 100 parts by mass of solid / oil, can be selected.
In principle, also the subsequent stage, the eigent¬ Liche Pfropffunktionalisierung, in the presence of water as Inert¬ Dispergierhilfsmedium and / or additional heat transfer and Wärmeabfühungsmedium (taking into account the specific reactor design, einschlie߬ Lich the agitator) feasible without fundamentally the grafting process something changes. In the second phase, the reaction phase, is under Ein¬ pose a dependent of the reaction components temperature-time regime and the fixed Reaktions¬ end temperature at which also corresponds to the currently selected radi- Kara initiator, generally for a period between 1 and 10 hours, preferably between 2 and 5 hours, the chemical grafting reaction carried out.
A characteristic feature of this type of grafting Festphasen¬ - water added without the aforementioned possible Inert¬ - is to maintain the dry to optionally oil moist consistency of Reaktions¬ medium.
As a technology and product specific particularly vor¬ geous have functionalization that at Ver¬ use from 0.2 to 10 parts by weight of AS and / or MAS and / or MSA or GMA or HPMA as Funktionsmonomere, based on 100 parts by mass of the backbone material, and of graft onomermischungen mers from the corresponding Funktionsmono¬ and a non-polar or less reactive polar groups owning comonomers, preferably styrene and / or .alpha.-methyl styrene and / or an alkyl (meth) acrylate with a mass ratio function / comonomer from 1 to 5 are obtained at 5-1, proved.
The inventive functionalized polymers, because of their excellent adhesive properties as coatings coordinates on different documents in Lami¬ and the like. (Adhesivs) are used. The main use - both for economic reasons and because of their particularly high activity - but as impact modifiers for a variety of thermoplastics, in particular for a number of technical and wichtig¬ first Hochleistungskunststof e. The most important group of engineering thermoplastics, particularly by the addition of the functionalized elastomer according to the invention - depending on their concentrations - increased impact can be set low from high impact to low temperatures (-40 to -50 C) to room temperature, are the polyamides ( PA).
As PA component for the invention equipped molding compositions are particularly the linear and partially aromatic semicrystalline and amorphous thermoplastically processable polyamides having a relative intensity Visko¬ 2-5, preferably from 2.2 to 4.0 (measured in a one percent solution in cresol or in 96-pro¬ zentiger H, S0, at 25 C), corresponding to weight average molecular weights Mw 5000-80000, preferably zwi¬ rule 15,000 and 60,000 (US 2,071,250, US 2,071,251, US 2,130. 523, US 2,241,322, US 2,312,966, US 2,512,606, US 3,393,210, EP 0039524).
Apart from the main usable semicrystalline line¬ aren polyamides, especially polycaprolactam (PA6) and polyhexamethyleneadipamide (PA66), further Polyunde- canolactam (PAH), polylaurinlactam (PA12), polyhexamethylene methylenazelainamid (PA69), Polyhexamethylensebacinamid (PA 610) and last but not least Polytetra ethylenadipinamid (PA46) (EP 0038094, EP 0038582), can also Mi¬ mixtures of PA or Copolya ide, preferably those which are both units of ζ, caprolactam and units of adipic acid and hexamethylenediamine (PA 66/6) gege be appropriate, as the dicarboxylic acid partially an aromatic acid such as terephthalic and / or isophthalic acid (PA 6 / 6T, PA 66 / 6T, PA 66/61, PA 66/6 / 6T, etc.) (EP 0129195, EP 0129196), used - , Also the products obtained by reaction of isophthalic acid or isophthalic acid-terephthalic acid-hexamethylenediamine mixtures with amorphous PA such as poly (hexamethylene isophthalamide) (PA 61) and the corresponding Polycokondensat (PA 6IT) are as well as the carboxylic acids by reaction of aliphatic di- , in particular adipic acid, with equimolar amounts of diamine to aromatic diamines, especially m-xylylene, obtained semi-crystalline partially aromatic polyamides (polyarylamides), such as. for example, poly (m-Xylylenadi- Pamid) (PA XMD6), according to the invention as impact auszu¬ rüstende polymers or part corresponding thermo¬ plastic molding compounds used.
A second, functionalized by means of inventive polymers effectively modifying thermoplastic Poly noticeable leave are the saturated polyesters (SP), especially the high molecular weight linear aromatic polyester (intrinsic viscosity of 0.4 to 1.2 dl / g), the equimolar by polycondensation compositions from terephthalic acid or its esters are obtained and alkanediols (Becker / Braun, Kunststoff-Handbuch 3/1, pp 7-113, Carl Hanser Verlag, Munich 1992).
Preferred polyesters are polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), including those obtained by additional Cocondensation aliphatic tri- or tetrabasic carboxylic acids or diol mixtures of copolyesters (DE 1,900,270, DE 2,407,674, DE 2,407,776, DE 2,715,932; US 3,692,744), in particular statistical PET / PBT copolyester and constructed from predominantly PBT segments block-copolyester (DE 2756167, DE 3040999) was used. Furthermore, the built-up from higher more Molecular aromati¬ rule dicarboxylic acid and glycol units polyesters such as polyethylene naphthalate (PEN), suitable for the invention auszurüstende molding compositions. As esters of carbonic acid, the aromatic polycarbonates (PC) practically the simplest conventional polyester (Brown / Becker, Plastics Handbook, Carl Hanser Verlag, Munich, 1992, pp 177-288; lapping, M., plastic and rubber 37 (1990) 11, p 361).
Besides the main, by reacting the under Be¬ drawing Bisphenol A (BPA) known 2,2- (4, 4'-dihydro xydiphenyl) propane (Dian) obtained with phosgene BPA-PC, the standard PC (DE 1570703, DE 2063050, DE 2211956; FR 1561518; US 2970131, US 2991273, US 3028365, US 3062781, US 3148172, US 3275601), may also be further developed PC, especially trimethyl cyclohexanone (TMC) -Bisphenol- PC or the TMC-BP / use BPA copolycarbonates or blends of BPA-PC and TMC-BP-PC, in the to be modified molding compounds (W. Uerdingen, plastics 83 (1993) 10, pp 760-763).
In a broader sense are the polycarbonates not only by substitution of BPA by others, in particular halogenated and alkylated (methylated) BPA derivatives, but also obtained and according to the invention by replacing the phosgene by chlorides higher dicarboxylic ein¬ settable polyester (PEC ) expected (M. Schnell "Chemistry and Physics of Polycarbonates", New York, London, Sidney; Intersc Publ 1964)... The polyesters including copolyesters can be quite advantageously used also in the form of known polymer blends, such as on the basis of Kombi¬ nations PBT / PC (C. Plachetta, Plast Europe (1992) 5, 610); SP (PBT vzw.) / PC (DD 290431; EP 469 404; DE 1569448,
DE 2035390, DE 2248242, DE 2659338; US 3130177, US 4264437, US 4257937); PBT / ASA (P. Beer & D. Rempel, Autec '88, S. 1485th); PC / ABS (Plastics Handbook 3/1, S. 155, Carl Hanser Verlag, Munich 1992).
The inventively modifiable thermoplastics include the acetate from vinyl acetate homopolymers, in particular poly, and olefin / vinyl ester copolymers, insbeson particular ethylene / vinyl acetate copolymers of different composition (EVA and EVM), and vinyl alcohol polymers existing polymer group. The vinyl alcohol polymers are even those from vinyl alcohol units exclusively zu¬ sammengesetzten polymers and especially composed of Vinylal- kohol- and olefin copolymers, in general, the products obtained by complete or partial Versei¬ tion of vinyl ester polymers in an alkaline medium to you,.
Accordingly, the present invention especially ethylene can len / vinyl alcohol copolymers (EVAL), prepared from the corresponding ethylene / vinyl acetate copolymer (vinyl acetate between 40 and 90 mol%) having saponification degrees of generally from 10 to 100%, wherein EVAL with
Ethylene content of from 10 to 60 mol%, in particular of
20 to 50 mol%, are preferred in accordance with densities from 1.30 to 3 1.10 g / cm, are used. The part as inventively modifiable Formmassenbestand¬ usable polyacetals, to which the homo- and Co¬ polymeric aldehydes and acetals, consisting of -CHR-O-blocks belong, are primarily the homopolymers obtained from formaldehyde and / or trioxane (Polyformaldehyd , polytrioxane) with identical -CH "-0- structures, ie polyoxymethylenes (POM), further polymers corresponding to the higher molecular weight cyclic ethers homo- as polydioxolane, poly-1, 3-dioxepane and poly-1, 3,6-trioxocane , as well as consisting of formaldehyde and / or trioxane together with another polymerizable monomer or prepolymer having acetalic structure, for example, dioxolane, obtained copolymer with random or block-like structure (K. Weissermel, inter alia, plastics 54 (1964), p 410; W. core among others, Angew. Chem. 73 (1961), p 183) and also the terpolymers, obtained with the addition, in most cases at lower levels, a third monomer, such as Butandiolglycidether (Becker / Braun, Kunststoff-Handbuch 3/1, Carl Hanser Verla g, Munich 1992, pp 300 et seq .: H.-D. Saber and Others "4th polyacetals").
As low impact auszurüstende molding component, the members of the family of polymers of polyether polyphenylene ether (PPE) obtained by oxidative coupling of 2,6-di-substituted phenols with reduced spe¬ cific viscosities •<sup>■</sup>"/, From 0.2 to 0.9 dl / g, preferably from 0.4 to 0.7 dl / g (measured in a einprozen- term solution in chloroform at 25 ° C, according to DIN 53726), according to weight average molecular weights Mw from 10,000 to 80,000, preferably 20,000 to 60,000, are used.
Examples of substituents are halogen atoms (chlorine, bromine) and alkyl radicals having 1 to 4 carbon atoms, which can in turn be substituted by halogen atoms or by a hydroxyl group, be mentioned. Preferably the known representative poly (2,6-diphenyl-l, 4-phenylene) ether (PPE), often due to its compatibility with vinylaro- matic polymers (A. Noshay, "block copolymer", pp 8-10, Academic Press, 1977; 0. Olabisi, "polymer-polymer Misci- bility", 1979, p 117-189) as PPE / PS blend or in his means of grafting "sour" functional monomers modi fied form as a polymer blend with PA and other Poly mers (DE 3908408, WO 86/02086, WO 87/00540; EP 0222246, EP 0282664, EP 0223116, EP 0254048, EP 0416435, EP 0415344, US 3379792, US 4315086, US 4338421, US 4970272) used. Representing the usable copolymers based on various substituted phenols are selected from 2,6-
Dimethylphenol / 2,3,6-trimethylphenol mixtures to mention the copolymers obtained.
Analog PPE have the thermoplastic component in the Erfin modified according molding materials also thermoplastic aromatic polysulfone (PSU), including polyether sulfone (PES), with the general formula Ph-S0 m, .-> m or pH'-X-Ph be - 'n, i wove P, h SO -.-)?' a phenylene or alkyl and / or halogen-substituted phenylene sur and X represent a 0 or S atom or an aromatic diol residue, used.
As an example of a usable PES Poly is to name (4,4-bisphenol ether sulfone).
Furthermore, in this particular group of Hochlei- stungskunststoffe the Phenylensulfidhomo- and copolymers of the general formula fPh-S-, wherein Ph is a phenylene or alkylphenylene or substituted alkyl phenylene means to classify.
As inventively suitable polymers particularly poly phenylene sulfide (PPS) and poly (, '-diphenylensulfid) are mentioned. Especially this Hochleistungskunststoffe (PPE, PSU / PES, PPS) can be used in the erfindungs¬ be modified according to molding compositions directly in the form of polymer blends, as noted already for PPE. As blend component polymers are preferred, which consist of at least 50% by weight of a monovinyl substituted aro¬ matic hydrocarbon, preferably styrene (S) and / or oo-methyl styrene (MS), such as poly- styrene (PS), S / MS-copolymers (S / MS), butadiene / styrene
Block copolymers, by means of various unsaturated or saturated rubbers toughened polystyrene rene (PS-HI), also SAN, S / MMA, ASA, AES and S / MSA and last but not least - using a diene rubber as graft - copolymer obtained (ABS, MBS, MABS), with a related to the polymer blend mass An¬ part between about 10 and 70%, preferably between 15 and 50%. Other useful, low modifiable thermoplastics having average molecular weights Mw between 5,000 and
500,000, vzw. 10,000 to 300,000, are the ther¬ tic polyurethanes (TPU), the diisocyanate-block are generally composed of a polyol (polyester or polyether) and a diisocyanate as a soft segment glycol block as a hard segment and corresponding to the at its synthesis Syn¬ present molar ratio of the NCO group of the diisocyanate to the OH group of start-ending bifunctional polyol or glycol in full TPU (0.95 -. NC0 / 0H tx l) or incomplete TPU (1 - NC0 / 0H - 1, 1) used to be divided.
The range of modifiable thermoplastics ranging from mass polymers (especially PO and PS) on the samsten on wirk¬ be equipped engineering plastics to high-performance plastics, should at this point, without laying claim to completeness, are concluded with the nitrile polymers. Including the '-ethyle- of at least 50% by mass ix ,, / unsaturated, optionally substituted mono- are nitrile, preferably acrylic, methacrylic and Bromacryl- nitrile to understand existing homopolymers and especially copolymers. As copolymerizable compounds can
Olefins, vinyl esters, lower alkyl esters of <sub>J</sub> , / 3 -ethyle- unsaturated carboxylic acids and especially Vinylaro- mate, especially Styrem and αo-methyl styrene employed. The preferred nitrile polymers are the corresponding zu¬ sammengesetzten styrene / acrylonitrile copolymers (SAN). The previously mentioned possible inventively modifi¬ ducible thermoplastics, including their mixtures / blends themselves and under use fertil further molding material components, in particular from the class of PO and PS or Styrencopolymeren, can also in the form of recyclable waste materials, where they to main components include and where gege¬ appropriate further conventional molding composition ingredients are contained, successfully modified by the addition of the inventive functionalized polymers are brought in particular a required for re-use of mechanical properties.
Last is still an interesting for the invention auszu¬ equip the thermoplastic molding compositions Stoff¬ class, the ionically crosslinked polymers prepared by ionic crosslinking of carboxyl groups in the from min¬ least one i, P-ethylenically unsaturated carboxylic acid and at least one other monomer existing substrate copoly erisaten be obtained, go einzu¬ with at least one mono- and / or di- and / or trivalent metal ion. Preferred are acid Substratcopolymere of an olefin (ethylene, propylene or butylene) or styrene and an unsaturated monocarboxylic acid, preferably acrylic and / or methacrylic acid, or an unsaturated dicarboxylic such as maleic acid and its anhydride particularly MSA, with an olefin or styrene content of at least 50 mol%, and preferably an unsaturated acid (anhydride) - content of 0.2 to 25 mole% composed.
Some of the major ionically crosslinkable Substratcopoly- merisate are:
Ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / itaconic acid copolymers, ethylene / maleic acid copolymers,
Ethylene / acrylic acid / methacrylic acid copolymers, ethylene / propylene / methacrylic acid copolymers and the corresponding styrene / acid monomer copolymers.
One-, two- and trivalent ions of metals, particularly of Groups I, II, III of the periodic table, are used for the production of ionomers, so beispiels¬, the monovalent ions of sodium, lithium and potassium, the divalent ions of magnesium, calcium and zinc, and the trivalent ions of Alu¬ miniums.
The ionic crosslinking takes place in that the substrate copolymer be reacted with the hydroxides, alcoholates or carboxylic acid salts above mentioned metals.
Ionomers can also be prepared by saponification of a of an olefin and a C (<sup>j</sup> unge¬ ethylenically saturated carboxylic acid ester compound copolymer such as an ethylene / methyl (meth) acrylate copolymer, with a hydroxide of a monovalent, divalent or trivalent metal. By partial neutralization some of the carboxylate can be converted into the corresponding free carboxylic acid in the resulting saponification. The so prepared ionomer are also known as thermoplastic component according to the invention can be used in the molding compositions. The inventively equipped molding compositions are prepared by known technologies by the starting components (functionalized polymers Thermo¬ plast or thermoplastic blends, optionally chamfer engined and / or particulate fillers and Funktions¬ additives, including processing aids in the usual concentrations) in the known melt ¬ mixing devices, in particular in and twin-screw kneaders or -extrudern be compounded. In general, mean mixing times of from 0.5 to 30 minutes preferably 1 to 10 minutes, and Massetem¬ are temperatures from 180 to 350 C, preferably between 200 and 300 C, are required as homogeneous as possible to obtain molding compositions.
On the basis of the following embodiment herge¬ easily selected functionalized thermoplastics / elastomers (modifiers) and different with the inventively functionalized polymers, finally ein¬ corresponding comparative modifiers, impact equipped molding compositions is documented, the invention in its range of variation.
embodiment
Preparation of functionalized polymers
In a temperature and equipped with a stirrer, oxygen free purged reactor are 100 parts by weight of a polymer or polymer compounds from the series of results summarized in Table 1 Rückgrat¬ polymers, each having a specific, likewise indicated in Table 1 share of a process oil (oil characteristic values in Table 2 ) included, submitted. At room temperature, the monomer or Monomerge ish (Funktionsmonomer and additional comonomer) in accordance with Table 3, auf¬ out species and units together with the rule radikali¬ initiator, in most cases, a diacyl for Polymerisationsendtemperaturen Tpm of 70 to 90 C optionally for lower TPM (55 to 75 C) a Dialkylperoxidicarbonat or a diazo compound, hinzu¬ together.
Specifically subsequent Einsatz¬ are out in Tables 1 and 2 specified backbone polymers and oils have been used substances:
Funktionsmonomer
Acrylic acid (AA), maleic anhydride (MSA), Hydroxypropy1- methacrylate (HPMA), glycidyl methacrylate (GMA), 2-dimethylaminoethyl methacrylate (DMAEMA) and tris (2-methoxyethoxy)<sup>■</sup> vinylsilane (V-silane) Additional comonomers
Styrene (S), methyl styrene (MS) and ethyl acrylate (EA)
initiators
Mostly dibenzoyl peroxide and dilauroyl in Kon¬ concentrations between 0.1 and 3%, preferably between 0.2 and 1.5%, based on the backbone polymer composition, in some cases Dicetylperoxidicarbonat or 2,2-azobis (isobutyronitrile) within the said Konzentra¬ tion area.
filler
Chalk (coated) with an average particle diameter of 2.5 microns (in the backbone of the polymer compound included) (s. Table 1).
After about 30 minutes mixing of the starting substances (dispersion phase) is carried out according to one of the zelkonzentrationen Ein¬ of Pfropfpolymerisationsansatzes ab¬ dependent, generally about 2 to 5 hours fixed temperature-time program, the functionalization of the Rück¬ gratpolymeren (reaction phase). The reaction is stopped after reaching a monomer conversion which is in dependence on the respective Pfropfsystem between 50 and almost 100%, terminated by the reactor cooled, contains a nitrogen flushed (if separate recovery of unreacted and expelled residual monomers) and is emptied.
The graft usually free of monomers obtained are directly analytically characterize (s. Table 3). Be determined:
- Functionalization FG (percentage mass fraction of-polymerized Funktionsmonomer, based on the total Pfropfproduktpolymermasse), determined by
Back titration with 0.1 M HC1 by the carboxylic acid level (AS, MSA) unneutralized 0.1M potassium hydroxide solution or by elemental analysis of oxygen (control determination AS and MSA and solely for HPMA and GMA), nitrogen (for DMAEMA) and of silicon ciums (for V-silane);
- Gel content π><sub>Ge</sub>n as a measure of the degree of crosslinking, ie selected in boiling xylene and in mass% specified insoluble fraction of the functionalised Poly mer.
In Table 3, taken from Table 1 backbone systems (backbone polymer or -polymercompound / oil additive) with the YTD specified in Column 1 of Table 1. No. (1 to 70) listed.
In addition, some representative comparison Pro¬ products (See. No. / Column 1 of Table 3) indicated that the respective same product number. - However herge¬ sets without oil additive - correspond. In addition, not specified, according to the technology used to compare products - either analog Festphasenpfropfung without oil (FP) or by Schmelzepfropfung (SP 190 - 210 ° C / twin screw extruder) - have been obtained.
An essential feature of the characterization graft is their degree of functionalization (FG). After separating the Homopolymerisat- formed from the Funktionsmonomeren or from functional / comonomer mixtures formed copolymer shares by fractional precipitation, the graft can be used as the ratio of the mass of grafted Funktionsmonomer the entire polymerizable th Funktionsmonomermasse or grafting than the submitted backbone polymer composition grafted related Funktionsmonomermasse be determined.
Particularly high grafting (- .. 90%) are for ole¬ finischen backbone polymers, especially LDPE, EPM, EVA, SEBS, SEPS and SEPS / PO compounds, obtained the correspondingly invention Pfropfrezeptur (oil content, type and concentration of monomers and initiator) characteristics result in functionalized polymers with highly effective modifier.
Based on the gel content specified as a second important characteristic in Table 3 can be seen that with appropriate choice of from Pfropfrückgrat / Oil and Funktionsmonomer /
Additional comonomer existing PfropfSysteme gel-free
(5%) or functionalized graft gelarme
( <img id="imgf000040_0001" he="12" wi="18" file="imgf000040_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> obtained 20%) (exception is only PE
LD backbones). On the other hand but also targeted high gel-containing functionalized polymers can be prepared.
In this context, departures assign again to a previously mentioned advantage of Pfropftechnologie invention and thus obtained functionalized polymers, namely, that high molecular mass backbones (Mw -. ^ 200,000), such as for present invention technically interesting styrene / olefin / styrene three-block polymer (s. particularly the SEPS used or ent speaking SEPS compounds as the backbone), the pfropftechnologie by the addition of oil, and then by applying the Festphasen¬ the first place in a very sensible graft- can be brought form suitable and functionalized without any technical technolo¬ logical difficulties (including any internal reactor wall-product approaches / Pfropf¬ products with a very uniform particle).
Furthermore, the inventive technology disclosed other advantages, some of which were taken into account in the individual examples in Table 3 below. Thus, especially when using MSA monomeric as functional without any additional comonomer in excess is vor¬, due to the oil content significantly higher Pfropfaus¬ yields (about 70 - 80% vs. about 50 to a maximum of 60% without oil in Pfropfansatz) receive. Analog causes of er¬ inventive oil content - in contrast to the use of oil in the same concentration after Pfropffunk- nationalization - a decrease in gel content m ,. , Which is otherwise achieved by increasing the additional Comonomeranteiles, particularly in the form of a significant styrene surplus. Higher Styrenanteile turn generally lead to a lower backbone functionality and thus a ge ringeren adhesion (Adhäisivität) or impaired Modifikatorwirksamkeit particularly in molding compositions (blends, composites) based on polar thermoplastics. On the other hand allows the erfindungsgemäβe technology functionalization with very significant excess of additional comonomers, in particular of styrene, in order Her¬ provision of only very low or in the limiting case of non-functionalized, styrengepfropften olefinic and / or diene backbone polymers.
The Pfropfpolymerprodukte thus obtained, which practically comprise a graft PS block structure include particularly for the modification of blends based PS / PO and optionally suitable other thermoplastics. Preparation of ionically crosslinked functionalized polymers
The neutralization and hence the ionic crosslinking of some listed in Table 3 carboxylated polymers or polymer compound was technology by conventional Extrusionstech- (s. See also US 3,969,434) using a salt combination of ZnO, Zn acetate and zinc stearate (in the form a previously% from 50 mass carboxylated polymer and 50% by mass of salt combination produced concentrate) corresponding to a Zn cation concentration, which allowed a degree of neutralization of the grafted acrylic acid between 30 and 80 mol%, phen in a Brabender Plastogra- performed ( s. data in Table 4).
Similarly, the ionic crosslinking reaction was carried out by means of K0H (s. Also US 4,308,353).
Using a 43 mm twin screw extruder
(L = 38 D) with a degassing zone has a selected carbo- xyliertes TPE ionically crosslinked by Mg (0H) "(s. Also US 4,666,988, US 4,774,290).
Table 4 shows the thus obtained crosslinked ionically functionalized polymers, including two are without oil in graft functionalization approach produced easily comparison-ionomer listed.
Preparation and characterization of the modified with the functionalized polymers according erfindungs¬ thermo¬ plastic molding compositions
From the series inventively modifiable thermoplastics, including polymer blends, a selection correspondingly was taken Table 5 below. Similarly, the number of usable functionalized polymers at 19, including appropriate comparative modifiers, the total presented in Table 3170 special modifiers limited (marking in further detail by the product number. / Table 3). Was This selection was made taking into account the highest possible toughness improvements, detectable especially with reference to the corresponding low-temperature notched impact strength, while securing an overall high mecha¬ African and thermal characteristic levels of the modified molding compositions.
The modified thermoplastic molding compositions were generally divide by melt mixing 79-97 Masse¬ thermoplastic or thermoplastic-filler composite with 3 to 21 parts by weight of functionalized polymer or polymer compound (hereinafter referred to as modifier), wherein the molding compositions of the known processing auxiliaries and other additives, such as antioxidants, heat, light and UV stabilizers and, if required Farb¬ materials / pigments, plasticizers and flow agents, lubricants and release agents and others may be added, in a twin-screw extruder (DSE with diameter D = 43 mm, length = 38 D) were prepared.
The measures for the characteristic value determination test specimens (ISO test specimens, dumbbell specimens) were sprayed on a Spritz¬ molding machine under the conditions customary for the individual thermoplastics conditions. In the following tables 6 to 14 both Modi¬ fizierungsbreite and the high Modifikatorwirksamkeit is based ver¬ various thermoplastic molding compositions tics for a number of important, listed in Table 5 thermal, including thermoplastic polymer blends, demonstrated without anywhere near the variety of to detect possible applications of functionalized polymers of the invention.
According to the shown in Table 6 notched impact strengths of the modified thermoplastics / polymer blends can be seen that the modification of the invention used indicators over the corresponding Vergleichsmodifika¬ tors generally significantly higher toughness increase, especially for low temperatures cause.
In the following tables 7 to 14 is based erwei¬ terter characteristic summaries for a number of important tech¬ cal plastics and polymer blends which he impressively confirmed indungsgemäße effect of modifiers, particularly those containing petrochemical-based TPE-S backbone materials ein¬.
Accordingly, has been found to be surprising that, using the invention modifiers, taking into account the special Modifikatorart and concentration, overall than comparable modified ther¬ tic compounds / blends improved toughness / stiffness / strength level is obtained In Tables 7-14 the following characteristic values are aufge¬ leads:
Melt index, determined according to DIN ISO 1133; Impact / impact strength according to Charpy a / a, determined according to ISO 179;
Yield stress (tensile speed: 50 mm / min) -r, determined according to DIN 53 455;
3.5% bending stress / flexural strength, "/ (Jl • determined according to DIN 53 452;
Flexural modulus of elasticity E., determined according to DIN 53 457;
Vicat softening temperature (method B / heating rate
50 K / h; Medium: Air) VST / B 50, determined according to ISO 306th
In addition to the modification used in the molding compositions indicators (designation:.. Mod./Vgl.-Mod with appropriate product number in Table 3) were also not operational tionalisiertes oily Rückgratpolymerisat or redemption gratpoly ercompound (backbone number . 34, no. 48 in Table 1) and the four ionomers according to the invention
II to V together with the comparative ionomers II and III of Table 4 compositions used in the selected thermoplastic molded bodies.
Table 1
YTD .nr. Backbone polymer / backbone backbone characteristics additional v. Oil (re backbone Compound charac. Molar mass density hardening (Ma-Tle. On grat number.) Zus. (% By mass) Mw (g / cm) form 100 Ma-Tle . backbone)
HDPE ethylene (E) / 3% 51,000 0.956 powder min 01 I 20 butylene (B) 50 min oil I
3 HDPE granules 147,000 0,952 20 Mi n. -Ö L II 4 50 Mi n. -01 I 5 20 fl. -Oil IV
6 LLDPE 81,000 0.933 granule 20 min oil I 7 40 Min Oil II
8 LDPE 33.000 0.918 powder 20 min Oil I 9 50 Min Oil I 10 50 Pfl. oil IV
11 PP propylene (P) 190,000 0,910 powder 20 min oil III 12 50 Min Oil I
13 PP 159.000 0.912 flakes 20 min Oil II 14 50 Min Oil I 15 20 Pfl. oil IV
<img id="imgf000046_0001" he="26" wi="235" file="imgf000046_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
Table 1, page 2
YTD .nr. RUckgratpolymer / backbone backbone characteristics additional v. Oil
(Re backbone Compound charac. Molar mass density hardening (Ma-Tle. On grat number.) Zus. (% By mass) Mw (gm) form 100 Ma-Tle.
Backbone)
<sup>"</sup>21 EPM / PP / 63% EPM / 0.885 granule 30 min 01 III
22 HDPE 27% PP 10% PE / 50 min Oil I
23 EVA E / 14% vinyl 151,000 0,934 powder 30 min Oil I
24 acetate 50 min Oil I
25 POE E / 25% l-0cten Tm ': 0.872 granule 20 min Oil I
76/80 ° C
26 SEBS 29% PS / 38% E 81,000 0,910 crumbs 120 min oil I
27 33% B 150 min oil I
28 60 Pfl. oil IV
29 SEBS / EVA 70% SEBS / 0.921 powder 60 min Oil I
30 30% EVA 120 min Öi III x --- - -
31 SEPS<sup>"</sup> 11% PS / 46% E 66,000 0,890 granule 60 min Oil I
32 43% P 120 min oil I
33 SEPS 30% PS / 38% E- 280.000 0.920 crumbs 60 min Oil I
34 32% P 120 min oil I
35,150 min-oil I
36,180 min-oil I
37 SEPS 30% PS / 38% E 280,000 0,920 granule 60 min Oil II
38 32% P 120 min oil III
39 50 Pfl. oil IV
40 100 Pfl. oil IV
Table 1, page 3
YTD .nr. Backbone polymer / backbone backbone characteristics additional v. Oil (re backbone Compound charac. Molar mass density hardening (Ma-Tle. On grat number.) Zus. (% By mass) Mw (g / t) form 100 Ma-Tle . backbone)
41 SEPS / LDPE 40% LDPE granules 60 min Oil I
42 60 Pfl. oil IV
43 SEPS / PP 33% PP granules 100 min Oil I 44 100 min oil III
45 SEPS / PP 20% PP granules 100 min Oil I 46 100 min Oil II 47 100 Pfl. oil IV
48 SEPS / PP 15% PP granules 110 min Oil I 49 110 min Oil II 50 110 Pfl. oil IV
51 SEPS / PP / chalk 55% SEPS / 10% PP / granule 35 min Oil I 52 35% chalk 25 Pfl. oil IV
53 SEPS / EPM 25% EPM granules 100 min Oil I 54 60 Pfl. oil IV
55 SEPS / P0E 25% POE granules 100 min Oil I 56 EPDM E / P = 65 / 35th 130,000 0.882 granule 50 min Oil I 8% Norb<sup>1</sup>
57 EPDM / PP 30% PP granules 50 min Oil II
Table 1, page 4
YTD .nr. RUckgratpolymer / backbone backbone characteristics additional v<sup>"</sup>, Oil
(Re backbone Compound charac. Molar mass density hardening (Ma-Tle. On grat number.) Zus. (% By mass) Mw (gλm) form 100 Ma-Tle.
backbone)
<sup>"</sup>58 SBS 29% PS / 71% PB 120,000 0.941 granule 80 min. -Oil I
59 80 Pfl. oil IV
60 (SB) (radial) 20% PS / 80% PB 180,000 0.930 crumbs 20 min Oil I
61 "40 min Oil I
62,100 min-oil I
63 (SB) (radial) 30% PS / 70% PB 160,000 0.939 crumbs 20 min oil III
64 "40 min Oil II
65,100 min-oil I
66 (SB) (radial) 38% PS / 62% PB 125,000 0.960 crumbs 45'-oil I
67 "45'-Oil II
68 45'-Oil III
69 SBR 30% styrene / 85.000 0.930 crumbs 60 min Oil I
70 70% butadiene 60 min oil III
1) Norb .: 5-ethylidene-2-norbornene 2) Tm: melting temperature
Table 2: process oils used (in Pfropfpolymerisationsansatz included) and their characteristics (at room temperature)
Ol-type density Brechungs¬ Dynamic distribution of carbon (g / cm), number n<sub>n</sub> Viscosity (% by mass) (DIN 51378) (DIN 51757) (DIN 51432) (Pa 's) or composition (DIN 51562) (% by mass)
'Arom naphth. paraffin
Oil I 0,865 1 476 0.28 0 32 68
Mineral II 0.880 1.485 0.36 6 37 57
Petroleum III 0.939 1.521 0.43 20 31 49
(Min-Oil)
Proportion of saturated fatty acids
Rape IV 0,917 1.473 0.60 7 (Pfl.Öl) <sup>C</sup>16<sup>"</sup> to rnn "G CS
Proportion of unsaturated fatty acids oleic acid 59 21 linoleic
9.5 linolenic
2.5 Gadolinsäure
1, 0 erucic
Table 3: Production of functionalized polymers (used PfropfSysteme, characterization of graft)
Lfd.Nr. Backbone / oil mono erzugabe in Ma.-Tln. on characteristics (product system 100 Ma.-Tle. backbone (solid)<sup>FG m</sup>r<sub>0</sub>, . No.) (statement:. Funktionsmonomere Zusatzcomon (wt .-%) (Hai-5 Lfd.Nr. Tab.l) AS MSA other S other
1 HDPE 1 2.5 2.1 2 2 2 2.5 1.9 1 3 2 2.5 2.5 2.1 4
4 2 5 4.2 6
5 2 5 5 4.6 20
6 3 2.5 1.7 28
7 4 2.5 1.9 11
8 4 5 23 3.8
9 4 5 5 4.0 39 See HDPE (FP) 5 5 2.6 55 10 HDPE 5 5 5 1.5 9 11 LLDPE 6 2.5 1.3 2 12 6 2.5 2 , 5 1.4 3 13 6 5 3.4 6 14 6 5 5 2.2 17 15 7 1.5 0.8 4 16 7 2.5 1.6 11 17 PE-LD 8 4.6 49 18 9 2.5 1.8 47
<img id="imgf000051_0001" he="17" wi="247" file="imgf000051_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
<img id="imgf000052_0001" he="227" wi="151" file="imgf000052_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000053_0001" he="227" wi="147" file="imgf000053_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000054_0001" he="227" wi="150" file="imgf000054_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000055_0001" he="228" wi="143" file="imgf000055_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Table 3, page 6
Lfd.Nr. Riickgrat / oil- monomer in Ma.-Tln. on characteristics
(Product system 100 Ma.-Tle. Backbone (solid) FG m<sub>tappet</sub>
. No.) (statement:. Funktionsmonomere Zusatzcomon (wt .-%) (wt .-%)
Lfd.Nr. Tab.l) AS MSA other S other
SEPS 116 / PP 48 2.5 1.25 2.4 32 SEPS Vgl.116 / PP (SP / 200 ° C) 1.25 2.5 1.7 31
117 SEPS / PP 48 2.5 2.5 2.2 11
118 48 2.5 5 2.45 3
119 48 2.5 7.5 2.45 2
120 48 5 4.2 41
121 48 5 5 4.5 36 Vgl.121 SEPS / PP (FP) 5 5 2.7 30
122 SEPS / PP 48 5 10 4.3 11
123 48 5 15 4 4, 44 2 2
124 49 2.5 2 2,, 33 3366
125 49 2.5 5 2.4 2
126 49 5 3.8 5 GMA
127 49 2.5 2.0 1 DMAEMA
128 50 2.5 2.5 2.4 13
129 50 5 5 3.9 34 EA
130 SEPS / PP / chalk 51 2.5 7.5 2.1 4
131 51 2.5 2.0 8 GMA
132 51 2.5 2.5 2.0 25
133 51 5 5 4.1 42 Vgl.133 SEPS / PP / chalk 5 5 2.6 35
(SP / 210 ° C)
134 SEPS / PP / chalk 52 5 3.8 53
135 52 2.5 1.4 41
136 SEPS / EPM 53 2.5 2.4 38
137 53 5 10 4.6 5
138 53 2.5 2.0 29 <img id="imgf000056_0001" he="9" wi="233" file="imgf000056_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
<img id="imgf000057_0001" he="227" wi="164" file="imgf000057_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Table 4 Ionic crosslinking
A functionalized polymer crosslinking agents (VM) reaction Identification of the backbone / oil / AS (Ma.-Tle.VM per 100 Ma.-Tle. Temperature ionomer
Graft on.-Ratio, proportion function. Polymer) (° C) (Nr.Tabelle 3) (% by mass)
66.7 EPM / 33.3 Oil I 4.0 AS 1.0 ZnO / 0.08 Zn acetate / ionomer 210 I-5-g AS / 5 S 0.004 Zn stearate (Prod No .: 44)
77 EVA / 23 oil I 2.35 AS 0.6 Zn0 / 0.05 Zn acetate / ionomer 210 II-g-2.5 AS 0.0025 Zn stearate (Prod No .: 52)
100 EVA - 1.2 AS 0.3 Zn0 / 0.025 Zn acetate / 210 See. Ionomer II-g-2.5 AS 0.0015 Zn stearate Prod : Vgl.52)
40 SEBS / 60 oil I 4.4 AS 0.5 K0H 205 ionomer III-g-5 AS / S 5 (Prod No .: 64)
100 SEBS - 2.6 AS 0.3 K0H 205 Comp Ionomerlll -g-5 AS / S 5 (Prod: V<sub>G</sub>1.64)
50 SEPS (80%) / 4.3 AS 1.5 Mg (0H), 220 ionomer IV PP (20%) / 50 oil I-5-g AS / S 5 (Prod: 103
Table 4, page 2
A functionalized polymer crosslinking agents (VM) reaction Identification of the backbone / oil / AES (Ma.-Tle.VM per 100 Ma.-Tle. Temperature ionomer Pfropfmon.-Ratio. Share function. Polymer) (° C) (Nr.Tabelle 3) (% by mass)
47.6 SEPS (85%) / 2.4 AS 0.7 Zn0 / 0.06 Zn acetate / ionomer 220 V PP (15%) / 52.4 oil 0.003 Zn stearate 2.5 -g-AS ( Prod: 116)
69 (SB) (38% PS) / 1.8 AS 0.5 ZnO / 0.04 Zn acetate / ionomer 210 VI 31 oil l "-g-2 AS / 2 S 0.002 Zn stearate (Prod No. .: 165)
Table 5: thermoplastics / polymer blends
(Used as a thermoplastic polymer component in the molding compositions)
Thermoplastic density mittl .Molekular- notched impact strength (kJ / m)
Polymer component (g / cm<sup>J</sup>) Weight Mw n. Charpy (ISO 179/2 C)
+ 23 ° C - 30 ° C
PA 6 1 13 45,000 4 .8 2.5
PA 66 1.13 36,500 4 .1 1.8
PA MXD 6 1.17 49,000 3 .8 2.8
PET 1.37 45,000 3 .0 1.6
PBT 1.31 52,000 2 .8 1.7
BPA-PC 1.20 28,000 65 15
POM 1:41 38,000 11 2 8.0
TPU 1.21 42,000 3, 3 2,2
PE-HD 0,952 147,000 12 2 8.6
PP 0.912 159,000 5, 8 4.5
PS 1, 02 55,000 2 5 1.8
ABS (20% BR) 1 05 72,000 21 6.0
EVAL (40 mole% E) 1.14 122,000 2, 0 1.2
EVAL (50) / PA 6 (50) 1.13 3 3 2.5
PA 6 (40) / PP (60) 1 07 4 5 2.8
PA 6 (80) / ABS (20) 1.11 4 8 5.4
PBT (60) / PC (40) 17.1 6 4.5 1
PPE (40) / PA 6 (60) 1.09 51,000 10 6 5.1 <img id="imgf000060_0001" he="6" wi="5562" file="imgf000060_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
PPE (50) / PS (50) 1.06 46,000 12 3 4.3
<img id="imgf000061_0001" he="5" wi="4" file="imgf000061_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
Table 6: Toughening thermoplastics / polymer compound (s Table 5 below.) With functionalized polymers
(Juxtaposition of invention and Vergleichsmodifikatoren according to Table 3)
Thermoplast.Polymer- share Modlfikator (mass%) Charpy notched impact strength (kJ / IRT) comp. (Mass%) invention Comp Mod. + 23 ° C - 20 ° C - 30 ° C - 40 ° C acc. Mod.
85 PA 6 15 no. 121 81 47 38.3 35.7
15 Nr.Vgl.121 48 13 11.5 9.5
80 PA 6 20 no. 75 66 38.7 36.3 31.5 20 Nr.Vgl. 75 65 19 12.5 11 8
80 PA 66 20 no. 69 27.3 20.4 13.4 9.2 20 Nr.Vgl. 69 18.8 9.9 7.2 5.1
85 PA MXD 6 15 no. 133 64 33 30 27 15 31 10.5 8.7 6.5 Nr.Vgl.133
90 PA 6 10 no. 116 31.4 21.5 23.5 19.0 10 no. Gl.116 22.5 10.8 9.5 7.6
75 PA6 / 10 HDPE 15 Nr. 9 19.5 13.6 11.5 15 Nr.Vgl. 9 16.1 11.5 10.2
75 PA6 / 10 PP 15 no. 33 20.3 15.1 15.0 15 Nr.Vgl. 33 14.5 8.6 7.7
74 PA6 / ABS 18.5 7.5 no. 121 10.8 7.8 7.4 7.2 <img id="imgf000061_0002" he="10" wi="4" file="imgf000061_0002.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" /> 7,5 8,1 5,6 4,8 4,5 Nr.Vgl.121
36 PA6 / 54 PP 10 no. 96 12.1 8.7 8.5 7.8 10 Nr.Vgl. 96 6.6 4.1 3.6 2.9
<img id="imgf000062_0001" he="227" wi="163" file="imgf000062_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Table 7: characteristic map for modified PA 6 molding compositions
<img id="imgf000063_0001" he="6" wi="228" file="imgf000063_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
Composition 1 Vgl.2 3 Cf.. 5 Vgl.6 7 Vgl.8
Yae<sup>~</sup>6% by mass 95 95 90 90 85 85 80 80
Model no 121! "5 - 10 - 15-20 -
Comp Mod.121 "- 5 10-15
Backbone number. 48<sup>»</sup> _ _ _ _ _ _ _ 20
characteristics
MFI (235 / 2.16) g / 10 min 11 7 13.0 4.1 3.5 1.3 5.3 0,4i 18 at (23 ° C) kJ / m<sup>2</sup> NB NB NB NB NB NB NB 48 a kJ / m<sup>2</sup> NBB 6622 NNBB n N (-40 ° C) kJ / m "N NBB NBB N N N NBB NBB 5500 %% 7788 // NNBB a<sub>k</sub> (23 ° C) kJ / m<sup>2</sup> 18.7 14.7 41.5 27.8 81 48 66 9.4 a<sub>k</sub> (-20 ° C) kJ / m<sup>2</sup> 13.6 5.0 25.5 8.5 47 13 42 8.8 a<sub>k</sub> (-40 ° C) kJ / m<sup>2</sup> 11.9 4.2 21.6 4.7 35.7 9.5 28 6 9.1
(Ts N / mm 72 68 70 62 76 60 53 45
(7b 3.5 N / mm 84 71 77 67 71 52 72 57
<sup>e</sup>b N / mm 2400 2100 2050 1950 2030 1360 2100 1600
VST / B 50 ° C 197 196 194 192 183 166 174 148 <img id="imgf000063_0002" he="7" wi="4" file="imgf000063_0002.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
NB = not broken
Table 8; Characteristic map for modified PA 6 molding compositions
Components / unit Example number. Composition 10 11 12 Vgl.13 Vgl.14 Vgl.15 Vgl.16
PA 6 mass% 80 80 80 80 80 80 80 80
Model no 75 1 "20 -
Model no 77 II - 20
Model no 82 II _ _ 20
Model no 86 II - - 20
Backbone number .34% by mass 20 Comp Mod. 64 II 20 Comp Mod. 69 20 Comp-Mod. 85 - - - 20 l *
Kennwer e MFI / 240/5) g / 10 min 1. 3 1, 2 2, 5 1, 4 16 8 17.5 5.4 a (23<sup>υ</sup>C) n kJ / m<sup>2</sup> NB NB NB NB NB NB NB NB A (- 30 ° C) kJ / m<sup>2</sup> NB NB NB NB NB NB NB NB
(23 ° C) kJ / m<sup>2</sup> 66 56 52 47 10 70 66 34 a<sub>k</sub> (-20 ° C) kJ / m<sup>2</sup> 39 30 28 22 7 2 28 19 15 a<sub>k</sub> ° C) kJ / m<sup>2</sup> 36 26 15 18 8 6 18 12 10 CT <img id="imgf000064_0001" he="10" wi="241" file="imgf000064_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" /> N / mm 1600 2000 2100 2000
<sup>e</sup> b 1500 1400 1400 1500
VST / B 50 ° C 171 171 170 175 164 166 166 165
<img id="imgf000065_0001" he="228" wi="148" file="imgf000065_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Table 10: characteristic map for modified chalk filled PA 6 molding compositions <img id="imgf000066_0001" he="5" wi="2" file="imgf000066_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" />
Component / unit Example number. Composition 25 26 27 28 Vgl.29 Vgl.30
PA 6 Mass 49 49 49 49 49 49
Model no 77 II 21
Model no 96 II 21
Mod-II No.103 21
Mod-II No.121 21
Comp-Mod. 69 mass 21
Comp-Mod. 54 II 21
Chalk mass% 30 30 30 30 30 30
characteristics
MFI (240/5) g / 10 min 1.3 4.8 1.8 0.5 3.5 7.8
(23 ° C) kJ / m "NB NB NB NB NB NB (-30 ° C) kJ / m. NB NB NB NB NB NB (-40 ° C) kJ / NB NB NB NB NB NB
(23 ° C) kJ / m "30 20 50 55 29 25 (-20 ° C) kJ / m 14.6 10.5 20.9 24 5.5 4.8 (-30 ° C) kJ / m "11.6 9.4 16.5 19.9 4.5 4.2 <img id="imgf000066_0002" he="18" wi="6" file="imgf000066_0002.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" /> (-40 ° C) kJ / m "<sup>1</sup> 10.3 7.7 15.4 17.3 3.9 4.0 b 3.5 N / mm 57 45 47 45 48 53
N / mm 2030 1800 1700 1600 1600 1650
VST / B 50 ° C 156 140 137 137 133 132
Table 11: characteristic map of the modified polybutylene terephthalate (PBT) - and polyethylene terephthalate (PET) molding materials
Components / unit Example number. Composition 31 32 33 35 Vgl.34 Vgl.36 37 Vgl.38
PBT mass -% 95 90 90 90 80 80
PET it 80 80
Mod. -No. 77 II 10
Mod. -Nr.103 1 "10 20 20
See. -Mod. 69 mass -% 10 20 See -Mod.103 II 20th
characteristics
<img id="imgf000067_0001" he="12" wi="214" file="imgf000067_0001.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" /> kJ / m "8.1 9.7 10.5 7.9 11.6 8.7 14.2 9.0 kJ / m ~ 6.6 8.7 9.1 3.0 9.8 5.0 11.5 8.2 kJ / rn <img id="imgf000067_0002" he="16" wi="28" file="imgf000067_0002.tif" img-format="tif" img-content="drawing" orientation="landscape" inline="no" /> 6.1 8.3 8.5 2.7 9.5 4.2 10.1 5.5 Xs N / mm, 49 41 39 44 30 35 38 38
^ B 3.5 N / mm 66 62 59 62 46 49 52 50
N / mm '2050 1850 1800 2000 1500 1600 1650 1700
VST / B 50 176 165 162 168 125 128 121 122
<img id="imgf000068_0001" he="227" wi="144" file="imgf000068_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /><img id="imgf000069_0001" he="227" wi="136" file="imgf000069_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> Table 14 Kennwer outline of PA 6 / ionomer molding compositions
Components / unit Example number. Composition 55 Vgl.56 57 Vgl.58 59 Vgl.60 61 62
PA 6% by mass 95 95 88 88 85 85 90 90
Ionomer II mass% 5 12 See. Ionomer II 12 III 15 ionomer See. Ionomer III 15 IV 10 ionomer ionomer V 10
Kennwer e a. (23 ° C) kJ / m 14.8 12.6 32 22 48 33 30 27 <sup>k</sup> (-20 ° C) kJ / π 11.6 8.5 19 13 21 17 18.6 16.6
(-30 ° C) kJ / m '10.5 8.0 17.2 11.3 17.5 14 15.8 14.2
Xs N / mm 79 75 70 68 72 70 72 73
63.5 N / mm 86 81 75 76 70 68 71 75
N / mm '2500 2400 2060 1950 2050 1900 2100 2070
VST / B 50 195 192 191 190 187 182 194 193
Contents27
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| US10189933B2 | Cited by | United States of America | Applicant |
| WO2004048426A3 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| WO2004048426A2 | Cited by | World Intellectual Property Organization (WIPO) | International search |
7 members in 4 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 19502206 | Germany | A | |
| 19502206 | Germany | A | |
| 19951002206 | Germany | – | |
| 9600087 | Germany | W | |
| 9600087 | Germany | W | |
| 19502206 | – | – | – |
| DE1995102206 | – | – | – |
| DE9600087 | – | – | – |
| WO1996DE00087 | – | – | – |
Members7
| Document | Office | Kind | |
|---|---|---|---|
| DE19502206A1 | Germany | A1 | |
| WO9623011A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP0805827A1This record | European Patent Office (EPO) | A1 | |
| EP0805827B1 | European Patent Office (EPO) | B1 | |
| AT187970T | Austria | T | |
| ATE187970T1 | Austria | T1 | |
| DE59603980D1 | Germany | D1 |
31 legal events, as 2 offices reported them to INPADOC
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Numbers
- Publication
- 0805827
- Publication, DOCDB
- 0805827
- Publication, EPODOC
- EP0805827
- Application
- 96900838
- Application, DOCDB
- 96900838
- Application, EPODOC
- EP19960900838
Titles3
- English
- FUNCTIONALISED POLYMERS, PROCESS FOR PRODUCING THEM AND THEIR USE IN THERMOPLASTIC MOULDING COMPOUNDS
- French
- POLYMERES FONCTIONNALISES, LEUR PROCEDE DE PRODUCTION ET LEUR UTILISATION DANS DES MATIERES DE MOULAGE THERMOPLASTIQUES
- German
- FUNKTIONALISIERTE POLYMERE, VERFAHREN ZU IHRER HERSTELLUNG UND IHRE VERWENDUNG IN THERMOPLASTISCHEN FORMMASSEN
Classification
- CPC, 3
- C08F291/00
- C08F8/00
- C08F8/04
- IPC, 5
- C08F2 44
- C08F8 00
- C08F8 04
- C08F291 00
- C08F255 00
Designated states5
- Contracting states, 5
- Austria
- Germany
- France
- Italy
- Netherlands (Kingdom of the)