US 11,879,036 B2
Poly(ether ketone ketone) (PEKK) polymer and composites
Chantal Louis, Alpharetta, GA (US); and James Pratte, Wilmington, DE (US)
Assigned to SOLVAY SPECIALTY POLYMERS USA, LLC, Alpharetta, GA (US); and Cytec Industries Inc., Princeton, NJ (US)
Appl. No. 17/055,234
Filed by SOLVAY SPECIALTY POLYMERS USA, LLC, Alpharetta, GA (US); and CYTEC INDUSTRIES INC., Princeton, NJ (US)
PCT Filed Jun. 19, 2019, PCT No. PCT/EP2019/066227
§ 371(c)(1), (2) Date Nov. 13, 2020,
PCT Pub. No. WO2019/243433, PCT Pub. Date Dec. 26, 2019.
Claims priority of provisional application 62/782,725, filed on Dec. 20, 2018.
Claims priority of provisional application 62/688,047, filed on Jun. 21, 2018.
Claims priority of application No. 18184038 (EP), filed on Jul. 17, 2018; and application No. 19153019 (EP), filed on Jan. 22, 2019.
Prior Publication US 2021/0253792 A1, Aug. 19, 2021
Int. Cl. C08G 65/40 (2006.01); C08G 65/46 (2006.01); C08J 5/04 (2006.01); C08J 5/24 (2006.01)
CPC C08G 65/4012 (2013.01) [C08G 65/4093 (2013.01); C08G 65/46 (2013.01); C08J 5/042 (2013.01); C08J 5/043 (2013.01); C08J 5/24 (2013.01); C08G 2650/40 (2013.01); C08J 2371/10 (2013.01)] 11 Claims
OG exemplary drawing
 
1. A method [method (MS)] of making a poly(ether ketone ketone) polymer [PEKKS polymer], said method comprising the following steps:
(I) in a reaction mixture, reacting 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 said monomer (FB) and said monomer (HB) are in a molar ratio of at least 1.007:1
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)
0.7%<% 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:

OG Complex Work Unit Chemistry
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 mixture comprising at least one 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—]—;
wherein Mm and Mp are represented above formulae (3) and (4), respectively;
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 the concentration of fluorine end groups in the PEKK polymer, as measured by 19F-NMR, and 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);
(II) contacting the mixture comprising at least one PEKK polymer obtained in step (I) with a solution containing sodium dihydrogen phosphate and disodium hydrogen phosphate, to isolate said at least one PEKKS polymer.