Poly(ether ketone ketone) (PEKK) polymer and composites
AssigneesSolvay Specialty Polymers USA, LLC, Cytec Industries Inc.
InventorsChantal Louis, James Pratte
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Abstract
The present invention relates to poly(ether ketone ketone) (PEKK) polymers, a method for the manufacture thereof, to articles and composites made therefrom, to methods of making the composites, and composite articles including the PEKK composites. It was surprisingly discovered that by synthesizing the PEKK polymers from low-metal monomers and selectively controlling the relative amounts of reactants during the synthesis, PEKK polymers having unexpectedly improved melt stability can be obtained. The PEKK composites including the PEKK polymers are especially well-suited for fabrication of thick composite parts where melt stability of the polymer matrix is important.
Claims14
A poly(ether ketone ketone) polymer [PEKKS polymer] comprising
- at least one recurring unit (RM*PEKK) of general formula -[Mm-O—]-;
- and
- at least one recurring unit (RP*PEKK) of general formula -[Mp-O—]-;
- Mm and Mp are represented by the following formulae, respectively:
- wherein
- each of R1 and R2 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- and
- each of i and j is independently selected from 0 or an integer from 1 to 4;
- said PEKKS polymer being characterized by % [F]>45 (μeq/g)/(g/10 min)0.29 and
- T/I ratio greater than 61/39,
- wherein
- % [F] is the ratio between [F], i.e. the concentration of fluorine end groups in the PEKK polymer measured by 19F-NMR, and MFI, i.e. the melt flow index of the PEKKS polymer determined according to ASTM D1238 at 360° C. with a 8.4 Kg weight to the 0.29 power, and
- T/I ratio is the ratio between recurring units (RP*PEKK) and recurring units (RM*PEKK).
A composite obtained by method (MC) of making a composite comprising a polymer matrix including a poly(ether ketone ketone) polymer [PEKKC polymer], said method comprising the following steps:
- (I*) preparing a poly(ether ketone ketone) (PEKKC) polymer by reacting, in a reaction mixture, at least one low-metal bis(hydroxybenzoyl) benzene monomer [monomer (HB)] and at least one low-metal bis(halobenzoyl) benzene monomer [monomer (FB)] in the presence of Na2CO3, K2CO3 and a solvent,
- wherein the relative amounts of the components reactants in step (I) are selected according the following Formulae:
- Σ=(% Na2CO3−105)+6*|% K2CO3−1|+0.25*|37−% Monomers|−(% XSDFDK) (EQ1)
- and
- 0%≤K2CO3<5 and (EQ2)
- 0%<% XSDFDK and (EQ3)
- 25%≤Monomers≤44% and (EQ4)
- wherein
- (a) Σ<6
- (b) % Na2CO3 is the concentration, in mol. %, of Na2CO3 relative to the number of moles of said monomer (HB);
- (c) % K2CO3 is the concentration, in mol. %, of K2CO3 relative to the number of moles of said monomer (HB) and where % K2CO3 ranges from 0 mol. % to less than 5 mol. %;
- (d) % Monomers is the total concentration, in wt. %, of said monomer (HB) and said monomer (FB), relative to the weight of said monomer (HB), of said monomer (FB) and solvent, and where % Monomers is from 25 wt. % to 44 wt. %;
- and
- (e) % XSDFDK is the concentration, in mol. %, of said monomer (FB) in excess of an equimolar concentration of said monomer (HB);
- said monomer (HB) and said monomer (FB) being independently represented by one of the following formulae:
- X5-Mm-X5 (13)
- X6-Mp-X6 (14)
- wherein
- X5 and X6 are —OH for said monomers (HB) and halogen for said monomers (FB), and
- Mm and Mp are represented by the following formulae, respectively:
- wherein
- each of R1 and R2 is independently selected from the group consisting of
- alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium;
- and
- each of i and j is independently selected from 0 or an integer from 1 to 4;
- to provide a polymer matrix comprising at least one PEKKC polymer comprising
- at least one recurring unit (RM*PEKK) of general formula -[Mm-O—]-;
- and
- at least one recurring unit (RP*PEKK) of general formula -[Mp-O—]-;
- wherein Mm and Mp are represented above formulae (3) and (4), respectively;
- and
- (II*) impregnating reinforcing fibers with the polymer matrix as obtained in step (I*) above, to form a composite.
Dependencies are inferred from the claim text.