DE4103140A1 - Macro-monomer(s) for prepn. of graft copolymers - partic. omega-(vinyl:benzoyl)-poly-(2,6-di:methyl)-1,4-phenylene] ethers] - Google Patents

Macro-monomer(s) for prepn. of graft copolymers - partic. omega-(vinyl:benzoyl)-poly-(2,6-di:methyl)-1,4-phenylene] ethers]

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Publication number
DE4103140A1
DE4103140A1 DE19914103140 DE4103140A DE4103140A1 DE 4103140 A1 DE4103140 A1 DE 4103140A1 DE 19914103140 DE19914103140 DE 19914103140 DE 4103140 A DE4103140 A DE 4103140A DE 4103140 A1 DE4103140 A1 DE 4103140A1
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Prior art keywords
ppe
poly
vinyl
macromonomers
benzoyl
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DE19914103140
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German (de)
Inventor
Klaus Dr Muehlbach
Friedrich Dr Seitz
Michael Wicker
Walter Prof Dr Heitz
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BASF SE
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BASF SE
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    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides

Abstract

Macromonomers of formula (I) are new., where R1, R2 are lower alkyl; R3 is H or lower alkyl; and n is polymerisation deg. of at least 5. Macromonomers of formula (Ia), partic. omega-(4-vinyl-)benzoyl-poly 2,6-dimethyl-1,4 phenylene ether (VB-PPE) of polymerisation deg. of the phenylene ether of 5-200 are specifically claimed. In (Ia), n = 5-200. USE/ADVANTAGE - Used for the prepn. of copolymers (claimed). Avoids prior art problems of sepg. copolymers and unreacted monomer. The graft polymers obtd. are useful as adhesives, compatabilisers in polymer alloys or rubber in materials. In an example, 30g poly-(2,6-dimethyl-1,4-phenylene ether) (PPE) (prepd. from p-chloro-2,6-dimethyl phenol) (Mn 13400) was dissolved in 350g pyridine. 10 mols. 4-vinyl benzoyl chloride were added at 0. deg. C, giving VB-PPE after 24 hrs.. 3g VB-PPE and 7g ethyl acrylate were dissolved in 50g toluene, 0.03 AIBN added and polymerisation occurred at 60 deg. C for 30 hrs.. The polymer was pptd. in 4 pts. vol. petroleum ether and 1 pt. vol. methanol and dried. The yield was 88%.

Description

Die Auffindung von Polymeren mit speziellen Strukturen und Eigenschaften ist eine zentrale Aufgabe der Forschung. Die Herstellung von Copolymeren durch Pfropfung unter Einsatz von Makromonomeren hat sich dabei zu einem effektiven Syntheseweg entwickelt. Makromonomere sind Polymere mit einer polymerisationsfähigen Endgruppe; sie können Molekulargewichte von einigen Hundert bis zu mehreren Tausend haben.The discovery of polymers with special structures and properties is a central task of research. The production of copolymers by grafting using macromonomers has become one effective synthetic route developed. Macromonomers are polymers with a polymerizable end group; they can have molecular weights of some Have a hundred to several thousand.

Die Makromonomeren lassen sich aufgrund der polymerisierbaren Endgruppe sowohl homo- als auch copolymerisieren. Durch Copolymerisation mit ge­ eigneten Comonomeren lassen sich Pfropfcopolymere herstellen, deren Haupt­ kette aus dem Comonomeren und der Endgruppe des Makromonomeren besteht. Die Seitenäste werden aus dem Strukturelement des Makromonomeren gebildet.The macromonomers can be because of the polymerizable end group both homo- and copolymerize. By copolymerization with ge Suitable comonomers can be prepared, the main graft copolymers chain consists of the comonomer and the end group of the macromonomer. The side branches are formed from the structural element of the macromonomer.

Makromonomere auf der Grundlage von Poly-(2,6-dimethyl-1,4-phenylenether) mit etherartig verknüpfter Vinylbenzylendgruppe werden von Percec (J. Polym. Sci., Part A, Polym. Chem. 25, 2605 (1987)) beschrieben. Es sind wohldefinierte Makromonomere. Es zeigt sich jedoch, daß die Copoly­ merisation dieser Makromonomeren unter Umständen zu einem unvollständigen Einbau der Makromonomeren führt. Dies wird insbesondere dann beobachtet, wenn das Molekulargewicht des Makromonomeren hoch ist. Der unvollständige Einbau führt zu uneinheitlichen Pfropfcopolymeren. Eine spätere Trennung von Pfropfcopolymer und nicht umgesetztem Makromonomer ist nicht möglich.Macromonomers based on poly (2,6-dimethyl-1,4-phenylene ether) with ether-linked vinylbenzyl end group are from Percec (J. Polym. Sci., Part A, Polym. Chem. 25, 2605 (1987)). It are well-defined macromonomers. However, it turns out that the Copoly meromerization of these macromonomers may be incomplete Incorporation of the macromonomers leads. This is particularly observed when the molecular weight of the macromonomer is high. The incomplete Installation leads to inconsistent graft copolymers. A later separation graft copolymer and unreacted macromonomer is not possible.

Es bestand somit die Aufgabe, Makromonomere auf der Grundlage von Poly­ 30 (2,6-dimethyl-1,4-phenylenether) zu schaffen, die sich durch Copolymeri­ sation vollständig in das Pfropfcopolymerisat überführen lassen.The task was therefore to develop macromonomers based on poly 30 (2,6-dimethyl-1,4-phenylene ether) to create, which by copolymers Allow the sation to be completely transferred to the graft copolymer.

Unmittelbarer Erfindungsgegenstand sind neue Makromonomere der allgemeinen Formel IImmediate subject matter of the invention are new macromonomers of the general Formula I.

in der R1 und R2 Niederalkyl und R3 Wasserstoff oder Niederalkyl und n einen Polymerisationsgrad von mindestens 5 bedeutet.in which R 1 and R 2 are lower alkyl and R 3 is hydrogen or lower alkyl and n is a degree of polymerization of at least 5.

Bevorzugt sind Makromonomere der allgemeinen Formel IaMacromonomers of the general formula Ia are preferred

mit n=5 bis 200.with n = 5 to 200.

Besonders bevorzugt ist ω-(4-Vinyl-)benzoyl-poly-(2,6-dimethyl-1,4- phenylenether) mit einem Polymerisationsgrad des Phenylenethers von 5 bis 200.Ω- (4-Vinyl) benzoyl-poly- (2,6-dimethyl-1,4- phenylene ether) with a degree of polymerization of the phenylene ether of 5 to 200.

Die Herstellung der erfindungsgemäßen Makromonomeren geschieht am ein­ fachsten dadurch, daß man zunächst in bekannter Weise einen Polyphenylen­ ether (PPE) geeigneten Molgewichts von z. B. etwa 500 bis 20 000 herstellt und dann dessen phenolische Endgruppe mit Hilfe eines Vinylbenzoyl­ halogenids verestert.The macromonomers according to the invention are produced on most skilled in that first a polyphenylene in a known manner ether (PPE) suitable molecular weight of z. B. produces about 500 to 20,000 and then its phenolic end group using a vinyl benzoyl halogenids esterified.

Der benötigte Polyphenylenether wird z. B. nach den Angaben in einer der US-Patentschriften 36 61 848, 32 19 625, 33 78 505, 33 06 874, 33 06 875 und 36 39 656 oder nach dem Verfahren ausgehend von 2,6-Dimethylphenolen, die in 4-Stellung ein Halogenatom tragen (vgl. W. Risse et al., Makromol. Chem. 186, 1835 (1985) oder V. Percec et al., J.Poly.Sci., Polym. Lett. Ed. 24, 439 (1986)) gewonnen.The required polyphenylene ether is e.g. B. according to the information in one of the U.S. Patents 36 61 848, 32 19 625, 33 78 505, 33 06 874, 33 06 875 and 36 39 656 or by the process starting from 2,6-dimethylphenols, which carry a halogen atom in the 4-position (cf. W. Risse et al., Makromol. Chem. 186, 1835 (1985) or V. Percec et al., J. Poly.Sci., Polym. Lett. Ed. 24, 439 (1986)).

Die Umsetzung zum erfindungsgemäßen Makromonomeren wird wie üblich in Gegenwart bzw. mit Hilfe eines säurebindenden Mittels bewerkstelligt; geeignet sind insbesondere organische Basen, die sich auch als Lösungs­ mittel eignen wie Pyridin oder Basen, die in einem Lösungsmittel für PPE (aromatische und/oder halogenierte nichtaromatische Kohlenwasserstoffe, Ether) wie Toluol, Xylol, Dichlormethan, THF ihrerseits löslich sind.The conversion to the macromonomer according to the invention is as usual in Presence or accomplished with the help of an acid-binding agent; organic bases which are also suitable as solutions are particularly suitable are suitable as pyridine or bases, which are in a solvent for PPE (aromatic and / or halogenated non-aromatic hydrocarbons, Ethers) such as toluene, xylene, dichloromethane, THF are in turn soluble.

Auch suspendierbare anorganische Basen oder Salze wie (Erd)alkalicarbonate sind verwendbar. Also suspendable inorganic bases or salts such as (earth) alkali carbonates are usable.  

Die Verwendung der Makromonomeren zur Polymerisation folgt den üblichen Regeln z. B. für die radikalisch ausgelöste Polymerisation:The use of the macromonomers for the polymerization follows the usual Rules z. B. for radical-initiated polymerization:

Zur Herstellung wohldefinierter Pfropfcopolymerer wird das Makromonomere mit geeigneten Comonomeren copolymerisiert. Das Gewichtsverhältnis von Makromonomer zu Comonomer kann beliebig sein und z. B. 1 : 99 bis 99 : 1, vor­ zugsweise von 1 : 99 bis 75 : 25 und insbesondere von 1 : 99 bis 50 : 50 sein.The macromonomer is used to produce well-defined graft copolymers copolymerized with suitable comonomers. The weight ratio of Macromonomer to comonomer can be any and z. B. 1:99 to 99: 1 preferably from 1:99 to 75:25 and in particular from 1:99 to 50:50.

Die Copolymerisation kann als Masse-, Suspensions-, Emulsions- oder Lösungspolymerisation geführt werden. Der Mechanismus der Copolymerisation ist an sich unerheblich, wenngleich die radikalische Polymerisation ggf. in Gegenwart geeigneter Starter bevorzugt wird.The copolymerization can take the form of bulk, suspension, emulsion or Solution polymerization are performed. The mechanism of copolymerization is in itself irrelevant, although the radical polymerization may is preferred in the presence of suitable starters.

Als Comonomere sind alle die Monomeren geeignet, die sich mit ω-(Vinyl­ benzoyl)-poly-(2,6-dimethyl-1,4-phenylenether) copolymerisieren lassen. Als copolymerisierbare Monomere können ethylenisch ungesättigte und/oder vinylisch ungesättigte Monomere und/oder Monomere mit einer Acrylat- und/ oder Alkylacrylateinheit verwendet werden.Suitable comonomers are all of the monomers which are compatible with ω- (vinyl allow to copolymerize benzoyl) poly (2,6-dimethyl-1,4-phenylene ether). As copolymerizable monomers, ethylenically unsaturated and / or vinyl unsaturated monomers and / or monomers with an acrylate and / or alkyl acrylate unit can be used.

Beispielhaft seien genannt:
Ethylen, α-Olefine, Vinylchlorid, Styrol, alkylsubstituierte Styrole, α-Methylstyrol, Vinyl- und Isopropenylnaphthalin, (Meth-)acrylnitril, (Meth-)acrylsäure, Maleinsäure, Maleinsäureanhydrid, Vinylacetat, Ester der Acrylsäure bzw. Methacrylsäure, deren Alkoholteil 1 bis 20 C-Atome trägt. Die Comonomeren können selbst weitere funktionelle Gruppen (z. B. Epoxi, Ester, Amid usw.) tragen.Examples include:
Ethylene, α-olefins, vinyl chloride, styrene, alkyl-substituted styrenes, α-methylstyrene, vinyl and isopropenylnaphthalene, (meth) acrylonitrile, (meth) acrylic acid, maleic acid, maleic anhydride, vinyl acetate, esters of acrylic acid or methacrylic acid, the alcohol part of which 1 up to 20 carbon atoms. The comonomers themselves can carry further functional groups (e.g. epoxies, esters, amides, etc.).

Es versteht sich, daß auch Mischungen verschiedener Comonomerer verwendet werden können.It is understood that mixtures of different comonomers are also used can be.

Die Polymeren können durch Fällung, Entgasen des Lösungsmittels in einem Entgasungsextruder oder einem Dünnfilmverdampfer isoliert werden.The polymers can be obtained by precipitation, degassing of the solvent in one Degassing extruder or a thin film evaporator can be isolated.

Die Pfropfcopolymeren können für viele Zwecke eingesetzt werden. Anwendungsbeispiele sind Haftvermittler, Verträglichkeitsvermittler in Polymerlegierungen oder Kautschuke in Werkstoffen.The graft copolymers can be used for many purposes. Application examples are adhesion promoters, compatibility promoters in Polymer alloys or rubbers in materials.

Herstellung von Poly-(2,6-dimethyl-1,4-phenylenether)Preparation of poly (2,6-dimethyl-1,4-phenylene ether)

Ausgehend von p-Chlor-2,6-dimethylphenol wurden nach dem in Makromol. Chem. 186, 1838 (1985) beschriebenen Verfahren zwei unterschiedliche Produkte hergestellt. Mittels GPC wurde das Molekulargewicht bestimmt.Starting from p-chloro-2,6-dimethylphenol according to the in Makromol. Chem. 186, 1838 (1985) described two different methods Products manufactured. The molecular weight was determined by means of GPC.

PPE-1: Mn= 3 000
PPE-2: Mn=13 400PPE-1: M n = 3,000
PPE-2: M n = 13,400

Beispielexample Herstellung von ω-(4-Vinylbenzoyl)-poly-(2,6-dimethyl-1,4-phenylenether) (VB-PPE)Preparation of ω- (4-vinylbenzoyl) poly (2,6-dimethyl-1,4-phenylene ether) (VB-PPE)

VB-PPE-1 bzw. VB-PPE-2
30 g PPE-1 bzw. PPE-2 werden unter Stickstoff in jeweils 350 g Pyridin gelöst. Bei 0°C wird ein 10molarer Überschuß an 4-Vinylbenzoylchlorid unter Rühren zugegeben. Nach 24 h wird das jeweilige Produkt durch Fällung aus Methanol isoliert.VB-PPE-1 or VB-PPE-2
30 g of PPE-1 and PPE-2 are dissolved in 350 g of pyridine under nitrogen. A 10 molar excess of 4-vinylbenzoyl chloride is added at 0 ° C. with stirring. After 24 h, the respective product is isolated by precipitation from methanol.

Vergleichsversuch: VP-PPEComparison test: VP-PPE

Die polymerisierbare Endgruppe wird über eine Etherbindung anstelle der erfindungsgemäßen Esterbindung eingeführt.The polymerizable end group is replaced by an ether bond instead of the introduced ester bond according to the invention.

25 g PPE-2 wurden unter Stickstoff in 250 ml Toluol gelöst. Bei Raumtemperatur wird ein 10molarer Überschuß an 4-Vinylbenzylchlorid, 10,6 g 3n NaOH und 1,08 g Tetrabutylammoniumhydrogensulfat als Phasentransferkatalysator unter Rühren zugegeben. Nach 24 h wird das Produkt durch Fällung aus Methanol isoliert.25 g of PPE-2 was dissolved in 250 ml of toluene under nitrogen. At A 10 molar excess of 4-vinylbenzyl chloride, 10.6 g of 3N NaOH and 1.08 g of tetrabutylammonium hydrogen sulfate as Phase transfer catalyst added with stirring. After 24 hours it will Product isolated from methanol by precipitation.

Der Nachweis der vollständigen Umsetzung erfolgte jeweils mittels 1H-NMR- Spektroskopie, GPC und UV-Spektroskopie (vgl. Makromol. Chem. 88, 215 (1965) und J. Polym. Sci., Part A, Polym. Chem. 25, 2605 (1987)).The complete conversion was verified in each case by means of 1 H-NMR spectroscopy, GPC and UV spectroscopy (cf. Makromol. Chem. 88, 215 (1965) and J. Polym. Sci., Part A, Polym. Chem. 25, 2605 (1987)).

In allen drei Fällen war die Umsetzung quantitativ.In all three cases the implementation was quantitative.

Copolymerisation des VB-PPE-2 mit Ethylacrylat 3 g VB-PPE-2 und 7 g Ethylacrylat werden in 50 g Toluol unter Stickstoff gelöst. Nach Zusatz von 0,03 g AIBN als Starter wurde 30 h bei 60°C poly­ merisiert. Copolymerization of VB-PPE-2 with ethyl acrylate 3 g of VB-PPE-2 and 7 g of ethyl acrylate are dissolved in 50 g of toluene under nitrogen solved. After the addition of 0.03 g of AIBN as a starter, poly was 30 h at 60 ° C. merized.  

Das entstandene Polymere wurde in einer Mischung aus 4 Vol.-Teilen Petrol­ ether und 1 Vol.-Teil Methanol gefällt und getrocknet. Ausbeute: 88%.The resulting polymer was in a mixture of 4 parts by volume of petroleum ether and 1 part by volume of methanol precipitated and dried. Yield: 88%.

Der Vergleichsversuch wurde wie vorstehend beschrieben, jedoch durch Copolymerisation des VB-PPE* mit Ethylacrylat angestellt.The comparison experiment was as described above, but by Copolymerized the VB-PPE * with ethyl acrylate.

Die Ausbeute beim Vergleichsprodukt war 85%.The yield of the comparison product was 85%.

Beide Proben wurden mittels GPC und DSC untersucht: Beide Proben weisen in der DSC zwei Glasstufen auf: -11°C und 206°C. Unterschiede ergeben sich dagegen im GPC-Diagramm: während in der erfindungsgemäßen Probe im Endprodukt kein VB-PPE-2 mehr enthalten ist erkennt man in der Vergleichsprobe ein deutliches Signal von nicht umgesetztem VB-PPE*.Both samples were examined using GPC and DSC: Both samples have two glass levels in the DSC: -11 ° C and 206 ° C. However, there are differences in the GPC diagram: while in the sample according to the invention is no longer contained in the end product VB-PPE-2 one recognizes a clear signal of not in the comparison sample implemented VB-PPE *.

Claims (4)

1. Makromonomere der allgemeinen Formel I in der R1 und R2 Niederalkyl und R3 Wasserstoff oder Niederalkyl und n einen Polymerisationsgrad von mindestens 5 bedeutet.1. Macromonomers of the general formula I in which R 1 and R 2 are lower alkyl and R 3 is hydrogen or lower alkyl and n is a degree of polymerization of at least 5. 2. Makromonomere der allgemeinen Formel Ia mit n=5 bis 200.2. Macromonomers of the general formula Ia with n = 5 to 200. 3. ω-(4-Vinyl-)benzoyl-poly-(2,6-dimethyl-1,4-phenylenether) mit einem Polymerisationsgrad n des Phenylenethers von 5 bis 200.3. ω- (4-vinyl) benzoyl-poly- (2,6-dimethyl-1,4-phenylene ether) with one Degree of polymerization n of the phenylene ether from 5 to 200. 4. Verwendung der Makromonomeren nach Anspruch 1 zur Herstellung von Copolymeren.4. Use of the macromonomers according to claim 1 for the preparation of Copolymers.
DE19914103140 1991-02-02 1991-02-02 Macro-monomer(s) for prepn. of graft copolymers - partic. omega-(vinyl:benzoyl)-poly-(2,6-di:methyl)-1,4-phenylene] ethers] Withdrawn DE4103140A1 (en)

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US7655734B2 (en) 2003-10-03 2010-02-02 Sabic Innovative Plastics Ip B.V. Capped poly(arylene ether) composition and process
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US7067595B2 (en) 2003-10-03 2006-06-27 General Electric Company Poly (arylene ether) composition and method
US7329708B2 (en) 2004-08-18 2008-02-12 General Electric Company Functionalized poly(arylene ether) composition and method
US7781537B2 (en) 2004-08-18 2010-08-24 Sabic Innovative Plastics Ip B.V. Functionalized poly(arylene ether) composition and method

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