DE1745939A1 - Verfahren zur Herstellung von ionisch vernetzten Mischpolymerisaten - Google Patents

Verfahren zur Herstellung von ionisch vernetzten Mischpolymerisaten

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Publication number
DE1745939A1
DE1745939A1 DE1965P0036184 DEP0036184A DE1745939A1 DE 1745939 A1 DE1745939 A1 DE 1745939A1 DE 1965P0036184 DE1965P0036184 DE 1965P0036184 DE P0036184 A DEP0036184 A DE P0036184A DE 1745939 A1 DE1745939 A1 DE 1745939A1
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acid
temperature
metal compound
extruder
nan
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DE1965P0036184
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DE1745939B2 (de
DE1745939C3 (de
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Rees Richard Watkin
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S260/00—Chemistry of carbon compounds
    • Y10S260/31—Ionic cross-link
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S36/00—Boots, shoes, and leggings
    • Y10S36/02—Plastic
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
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    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Description

1, Märs 1965 AD-2908/II
Ε» Ι» DU PONT DE NEMOUES AND COMPANY 10th and Market Streets, Wilmington, Del· 19898,
Verfahren zur Herstellung von ionisch vernetzten Mischpolymerisaten
(Zusatz zu Patent » ·<>. ..« Patentanmeldung P 30 096 IVo/39 b)
Das Hauptpatent · e«. ... (Patentanmeldung P 30 096 IVo/39 b) betrifft ein Verfahren zur Herstellung ionisch vernetzter Mischpolymerisate aus einem oder mehreren a-01efinen mit einer oder mehreren a,ß-äthylenisch ungesättigten Carbonsäuren durch Umsetzung mit einer oder mehreren wasserlöslichen ionischen Metallverbindung, das sich dadurch Kennzeichnet, dass man einwertige Metallionen, im Falle von durch Direktmisohpolymerisation aus einen oder mehreren a-Olefirien mit einer oder mehreren a,ß-äthylenisch ungesättigten Monocarbonsäuren hergestellten Mischpolymerisaten aber auch zwei- oder dreiwertige Me- * tallionen einsetzte
Bad j 00988^3/2022
AD-2908/IX
Haoh am Hauptpatent (Patentanmeldung P 30 096 XVo/59b)
kann dl· Vernetzung in der We ie β durchgeführt werden, dass mo dee CarbonsKuregruppen enthaltende Mischpolymerisat alt der Metall-Verbindung sehmelsalseht oder die Metallverbindung direkt oder in gelöster Fora einer Lösung der Misohpolymeriaat-Orundlage susetst und nach der Umsetzung das erhaltene Mischpolymerisat isoliert.
Gegenstand der Erfindung let ein Verfahren war Herstellung von
lonlsoh vernetzten Mischpolymerisaten naoh Patent (Pa-
tentanneldung P 30 096 IVo/39b), das eich dadureh kennselohnet, dass man kontinuierlich das MlsohpolyaMrieat alt der Metellverbindung la Extraktlonsextruder aisoht.
Als a-Olefin in den Mischpolymerisaten kann aan wenigstens «in ot-OlefIn der Forael RCB-CH2 verwenden, worin R Wasserstoff oder einen Kohlenwasserstoffreste besonders einen Alkylrest, ait I bis 8 Kohlenstoffatomen bedeutet. Vorzugsweise verwendet asu Äthylen, Propylen· Buten-(1), Styrol, Fenten-(l), Besen-(I), Hepten-(l), >Methylbuten-(X) und 4-Methylbuten-(l).
Vorzugswelse arbeitet man bei einer Temperatur von 100 bis 290 0C und unter einem Druck von 7 bis 700 kg/om2. Ansohllessend befreit man die Schmelze unter vermindertem Druck von flüchtigen Bestandteilen.
Bas Kationen bildend· Material gibt man sum Mischpolymerisat als wässrige Losung oder in einer la weeen ti lohen trocknen Form hinzu*
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Nach einer anderen AusfUhrungeforn kann nan die für das erfindungsgemäeee Verfahren geeignete Metallverbindung a ten in situ erzeugen, indem nan eine im wesentlichen wasserunlösliche Metallverbindung in das gesohnolsene Mieohpolymeriaat einmischt, dann dieser gesohnolienen Masse eine Säurelöeung einverleibt und ansohlieesend die Schnelle unter vermindertem Druok von flüchtigen Bestandteilen befreit« Zn ■ ο lochen, in wesentlichen wasserunlöslichen Metallverbindungen, * gehören beispielsweise Metelloxyde, -hydroxyde und -carbonate. Zu geeigneten Säuren gehören beispielsweis· Essigsäure, Miloheäure, Propionsäure und Mischungen dieeer Säuren·
Unter den angegebenen Temperatur- und Druokbedingungtn erhält man durch die Mieohwirkung des Extrudere ein aneoheinend einphasiges Gemisch und demzufolge einen gleiohmäeeigen leutralisationagrad·
Dae Verfahren im Bxtraktionaextruder kann «an in vier Stufen *
entsprechend vier Zonen einteilen. In der ereten Zone wird das Mischpolymerisat bei hohen Druok gründlich genisoht und auf eine Temperatur oberhalb seines 8ohnslBpunktes gebraohtj
das Kationen bildende Material kann in die erete Zone gegs-.
ben werden« In der «weiten Zone findet die neutralisation der Carbonsäuregruppen statt· Falls das Kationen bildende Ma-
- 3 009883/2022 BAD
AD-2908/II
terial in der ersten Zone zugegen worden let, so fügt nan ea in der zweiten Zone zu* Das Mischpolymerisat leitet man dann in eine dritte Zone, In weloher ein yermlnderter Druok herrscht, und in weloher die fluchtigen Materialien, z. B. Waeaer und Säure (die eich bildet, wenn man.das Mischpolymerisat mit einen Salz umsetzt), verdampft und entfernt werden. Aus der vierten Zone wird das Polymerisat aua dem Extraktionsextruder entfernt« In dem Extruder können natürlich mehr als eine Zone des jeweiligen !Type vorliegen; auoh kunnen die Zonen unterschiedliche Abmessungen haben·
Der Vorteil des erflndungsgemässen Verfahrene gegenüber den Verfahren unter Verwendung eines Kauteohukmahlwerka liegt In der gruseeren aieiohmässlgkelt der Endprodukte und der viel kürzeren Reaktionszeit.
Die folgenden Beispiele erläutern die Erfindung, ohne sie einzuschränken·
Beispiele 1 bis 8
In die ZufUhrungeÖffnung eines 5-co-PlaetIfizierextrudere gibt nan in getrennten Strumen Pellets eines Mischpolymer!-
eats aus Äthylen und Methacrylsäure und eine Metallverbin- ,
0098ί34/3022
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dung, die' im wesentlichen in dem geschmolzenen Polymerisat unlöslich ist. Die ZufUhrungsgeaohwindlgkeit des Harzes variiert von .6,6 bis 10,0 kg/Std. Die Sohn ecke erstreckt sich über einen Plastifizierabschnitt, der 8aäl so lang ist wie der Durchmesser, einem lllachabsohnltt, wie er in der USA·» Patentschrift 3 006 029 beschrieben ist und der 13,Saal so lang ist wie der Durohmesser, einem Drosselring, der es erlaubt, in dem Mischabaohnitt einen Druck aufrechtzuerhalten, einem Extraktionaabsohnitt, der 5mal so lang ist wie der Durchmesser und einem Puüpabsohnltt, der 4aal so lang 1st wie der Durohmesser· Dort, wo der Mischabsohnitt beginnt, spritzt man in das gesohmolzene Bar«, eine Säurelösung ein· Die Schmelztemperatur beträgt an dieser Stelle 156 0O und der Druck 28,1 kg/om · Das Gemisch lässt man im Miaohabachnitt reagieren; ansohliessend leitet man das 210 0O heisse, ge* sohmolzene Gemisch Über den Drosselring in die Extraktionszone. Die Schmelze entdampft man im Vakuum (686 mm Eg)* Ansohliessend extrudiert man das getrocknete, gesohmolzene, durch Zonen vernetzte Harz; den erhaltenen Strang kühlt man in Wasser und zerschneidet ihn in Pellets· Die in Präge kommenden physikalischen Eigenschaften werden bestimmt»
Die einzelnen Arbeitsweisen, die eingesetzten Reagentieh und einige der beeinflussten Polymerisateigensohaften sind in Tabelle I angegebene
0098*3^2022
Tabelle I
Bei- Saorea MiaohPolyneriaat Metallverbindung Säurelöaung Ifrodulct
■p„ Metn- sonmels- stei- Typ zuniü- Typ waas- ZufUh- «roaur- eonaei»-stei-
Index, fig- rungs- rig· runge- tiona- Index, fig-
/10 i kl h Lö ta h g/10 Min keit
säure, g/10 Min. kelt,9 gesohw., Löag., gegctar., gesohw., g/10 Min. kelt»9 μ Gew.* kg/oaz kg/Std. Vol.* ojP/Min. kg/Std· kg/oa* M
861,3 ZnO 0,363 Propion- 50 5,29 7,48 1,52 3139,7
säure
861,3 ZnO 0,476 Basig- 100 6,0 8,39 0,28 3689,8
säure
861,3 ZnO 0,676 Meth- 60 9,17 7,94 0,19 3779,4
acrylsäure
861,3 ZnO 0,535 Milch- 60 5,85 7,17 0,29 4241,9
säure +)
1705,0 ZnO 0,508 Essig- 50 5,22 9,98 0,13 3728,8
2? O 15 71
3 O 15 71
(O
09		 15 71
OD
U *v
K) 45 71
5 O
Kt 45,3 6,3
KJ
6
7 15,3 6,3
BAD 10 Ή ►) 90
O 8
O 9 ++* ►) 178
Isopropanol
1705,0 ZnO 0,485 Heptan- 61,9 9,0 9,98 0,16 3168,1
säure Essig- 22,7
ZnO 0,404 Beeig- 50 4*83 8,66 2,46
säure
ZnO 0,163 Beeig- 50 5,5 6,12
aäure
+) Die Milchsäure löet toO unter den Reaktions- ++) Terpolymerisat au* 67 % Jtthylea, bedingungtn nicht voll*tanJIg. Blneweiterea 24 * Vinylacetat und 10 Ü Itothiicryl-
Misohen ergibt eine vollatändlge LOsungs. säure· .
lerpolyeerlsat aus 70~* Ithylen, 20 * Vinylacetat und 90 <Methao*yleiter·.
Α3)-29Οβ/ΐΙ
9 ti» 16
Xn dl· ZufUhrungeöffnung eines 8,9-oa-Plastlflslerextrttdere gibt man In getrennten Strumen Pallete eines Mieohpolymerieatee aue Äthylen und MetheoryIeäurβ und eine trockne pulverartige Mleohung (bezeichnet als Yorgealsoh), die aus einer oder mehreren Metallrerbindungen, feinsertsiltem Mieohpolymerisat und gleiohen Teilen Dilaurylthlodipropionat und Bode« oylpentaerythrltoL-Dlphoaphat als Stabilisator besteht. Ia Extruder «erden die Pellets geeohmolsen und gemelnsasi Bit dem grob eingelagerten Yorgemleoh In den Mlsohatsofcnitt gebraoht. Der erste PlastiflBlsrabsohnltt 1st 7mal so lang wie der Durchmesser und wird auf einer Temperatur Ton etwa 158 0C gehalten. Dort, wo der Misonabsohnltt beginnt, spritet man eine Säurelöeung In die geschmolzen· Masse mit Hilfe einer Düse, welohe die Extruderwand durchdringt· Der Misohabsolmitt ist von der Art, wie er in der U8A-Pat»nteohrift 5 0066029 besohriebon ist ι er 1st 1?aal so lang wie ABr1SUrObJIeSSSr. In dem Mlaohabsohnitt hält man eine Temperatur τοη 270 bis 260 0C aufrecht. Die rorgemisohts Hasse, die reagiert mit der Potymeriaateohaelse, um die Säuregruppen dee Polymerisates durch Bildung eines löslichen Metallealsea su neutralleieren·
009883/2022'
ORIGINAL
AD-2908/II
Vom Ende dee Miaohabaehnltta leitet man die Maaae, die aus ionisch vernetatem Mischpolymerisat und aua Nebenprodukten besteht, die ftioh infolge der Umaetsung gebildet haben, durch ein Druok-Lenkungeventil und ein Rohr in einen Extraktloheextruder, der einen Durchmesser ron 5 cm hat« Die Temperatür der Maeae vor den Ventil betragt 2Θ0 0O und der Druck 52,7 kg/om2. Dieser Extruder beaitat in Serie geschaltet «frei Extra*· P tlonaeonen, nobel jede etwa 4mal eo lang wie der Durchmesser let. In der eraten Extraktloneeone hält nan ein Vakuum Ton 666 und in der «weiten eine τοη 711 mm Hg aufrecht· Die Temperatur der Sohmelse hält can awiaohtn 270 und 280 0O* In der Extraktlonaaone werden die fluchtigen Bestandteile aua dem ge8ohmolaenen, duroh Ionen vernetaten Mischpolymerisat entfernt. Bas ansChilesβend in Font von 8trangen extrudlerte Polymerisat kühlt man in Wasser· Die Stränge aersohneidet man in Pellets.
Die eineeinen Arbeitebedingungen, die eingesetsten Reagentlen und einige der beelnflueaten Polymerisateigeneohaften ersieht man aus der nachstehend angeführten tabelle II.
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BAD ORIGINAL

Claims (1)

  1. Patentansprüche
    7erfahron aur Hero teilung von ionloch Tarnetaten Hleohpolymeriaaten naoh Patent . ... ··· (Patentanmeldung P 30 096 IVo/39 b), daduroh gekennzeichnet, daea nan kontlnulorlich das Uieohpolymerleat mit der Metallverbindung la Extraktione· extruder mlooht.
    P 2t Verfahren naoh Anspruch I, daduroh gekennselohnot, daaa man bei einer Temperatur zwischen 100 un
    Druok von 7 bla 7CO kg/on arbeitet.
    bei einer Temperatur zwischen 100 und 290 0C und unter einem
    3. Verfahren naoh Anopruoh 1 und 2» daduroh gekennaelohnet» daea nan die Hetallverbindung in situ erzeugt* indea man eine in weacntllohen waeeerunlöaUche Metallverblndung in das geaohmolaene illoohpolymerlaat einniacht, dann dieser geschmolzenen Maaae eine Säurelöoung einverleibt und anaohliee-Qend die Oohmolee unter veruindertea Druck von fluchtigen Bestandteilen befreit.
    009883/2022
    - 10 -
    BAD OWOINAL
DE1745939A 1961-08-31 1965-03-01 Verfahren zum Modifizieren von Carboxylgruppen enthaltenden Äthylenpolymeren Expired DE1745939C3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13514761A 1961-08-31 1961-08-31
US16883962A 1962-01-25 1962-01-25
US27147763 US3264272A (en) 1961-08-31 1963-04-08 Ionic hydrocarbon polymers
US34829364 US3404134A (en) 1961-08-31 1964-02-28 Process of crosslinking polymers

Publications (3)

Publication Number Publication Date
DE1745939A1 true DE1745939A1 (de) 1971-01-14
DE1745939B2 DE1745939B2 (de) 1973-07-19
DE1745939C3 DE1745939C3 (de) 1974-02-21

Family

ID=27495141

Family Applications (6)

Application Number Title Priority Date Filing Date
DE1962P0030096 Pending DE1520506B2 (de) 1961-08-31 1962-08-27 Verfahren zum modifizieren von carboxylgruppen enthaltenden aethylenpolymeren
DE1963P0031004 Pending DE1520518B2 (de) 1961-08-31 1963-01-24 Verfahren zur herstellung von modifizierten copolymerisaten aus ungesaettigten kohlenwasserstoffen und ungesaettigten carbonsaeuren
DE1520601A Granted DE1520601B2 (de) 1961-08-31 1964-04-08 Verfahren zum Modifizieren von Carboxylgruppen enthaltenden Äthylenpolymeren
DE1745939A Expired DE1745939C3 (de) 1961-08-31 1965-03-01 Verfahren zum Modifizieren von Carboxylgruppen enthaltenden Äthylenpolymeren
DE1965P0036183 Granted DE1745938B2 (de) 1961-08-31 1965-03-01 Verfahren zum modifizieren von carboxylgruppen enthaltenden aethylenpolymeren
DE1595112A Expired DE1595112C3 (de) 1961-08-31 1965-03-01 Verfahren zur Herstellung von modifizierten Copolymerisaten aus ungesättigten Kohlenwasserstoffen und ungesättigten Carbonsäuren

Family Applications Before (3)

Application Number Title Priority Date Filing Date
DE1962P0030096 Pending DE1520506B2 (de) 1961-08-31 1962-08-27 Verfahren zum modifizieren von carboxylgruppen enthaltenden aethylenpolymeren
DE1963P0031004 Pending DE1520518B2 (de) 1961-08-31 1963-01-24 Verfahren zur herstellung von modifizierten copolymerisaten aus ungesaettigten kohlenwasserstoffen und ungesaettigten carbonsaeuren
DE1520601A Granted DE1520601B2 (de) 1961-08-31 1964-04-08 Verfahren zum Modifizieren von Carboxylgruppen enthaltenden Äthylenpolymeren

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DE1965P0036183 Granted DE1745938B2 (de) 1961-08-31 1965-03-01 Verfahren zum modifizieren von carboxylgruppen enthaltenden aethylenpolymeren
DE1595112A Expired DE1595112C3 (de) 1961-08-31 1965-03-01 Verfahren zur Herstellung von modifizierten Copolymerisaten aus ungesättigten Kohlenwasserstoffen und ungesättigten Carbonsäuren

Country Status (9)

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US (2) US3264272A (de)
BE (2) BE621846A (de)
CH (2) CH445861A (de)
DE (6) DE1520506B2 (de)
DK (1) DK125713B (de)
FR (1) FR1430478A (de)
GB (4) GB1011981A (de)
NL (4) NL282755A (de)
SE (2) SE311229B (de)

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DE3108983A1 (de) * 1981-03-10 1982-09-23 Gebr. Sträb GmbH & Co, 7317 Wendlingen Rolladensicherung
US4517330A (en) * 1983-03-30 1985-05-14 Rohm And Haas Company Floor polish composition having improved durability
EP0193110A2 (de) * 1985-02-26 1986-09-03 BASF Aktiengesellschaft Verfahren zur ionischen Vernetzung eines Ethylencopolymerisats
EP0193110A3 (en) * 1985-02-26 1988-03-30 Basf Aktiengesellschaft Ionic cross-linking process for ethylene copolymers
EP0349828A2 (de) * 1988-06-30 1990-01-10 BASF Aktiengesellschaft Verfahren zur ionischen Vernetzung eines Ethylencopolymerisates.
EP0349826A2 (de) * 1988-06-30 1990-01-10 BASF Aktiengesellschaft Verfahren zur Herstellung von ionisch vernetzten Ethylencopolymerisaten.
EP0349828A3 (en) * 1988-06-30 1990-03-21 Basf Aktiengesellschaft Process for the ionic crosslinking of an ethylene copolymer, ionically crosslinked ethylene copolymers and their use as coupling agents, injection-moulded articles or coating foils
EP0349826A3 (en) * 1988-06-30 1990-03-21 Basf Aktiengesellschaft Process for the manufacture of ionically crosslinked ethylene copolymers, ionically crosslinked ethylene copolymers and their use as foils, cable insulating materials and coupling agents

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Publication number Publication date
NL282755A (de) 1900-01-01
NL288151A (de) 1900-01-01
DE1520506B2 (de) 1971-06-09
FR1430478A (fr) 1966-03-04
CH435741A (de) 1967-05-15
CH445861A (de) 1967-10-31
SE311229B (de) 1969-06-02
NL128027C (de) 1900-01-01
GB1063436A (en) 1967-03-30
DK125713B (da) 1973-03-26
GB1011981A (en) 1965-12-01
DE1520506A1 (de) 1970-02-19
DE1745938B2 (de) 1973-07-19
US3404134A (en) 1968-10-01
DE1520518A1 (de) 1969-07-03
DE1595112B2 (de) 1973-07-05
DE1595112A1 (de) 1970-04-09
DE1520518B2 (de) 1971-07-22
NL129542C (de) 1900-01-01
US3264272A (en) 1966-08-02
DE1745939B2 (de) 1973-07-19
BE621846A (de) 1900-01-01
SE303882B (de) 1968-09-09
DE1520601B2 (de) 1973-01-04
DE1745938A1 (de) 1971-01-14
DE1520601A1 (de) 1970-05-14
DE1745939C3 (de) 1974-02-21
DE1595112C3 (de) 1974-03-14
GB1029035A (en) 1966-05-11
GB1034268A (en) 1966-06-29
DE1745938C3 (de) 1974-02-21
BE627537A (de) 1900-01-01

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