Polyarylether ketone polymers
The present invention relates to novel polyaryl ether ketone copolymers, a method for their preparation, polymer compositions including the same and shaped articles manufactured from said polymer compositions.
1 . A polymer (polymer (P)) comprising:
from more than 60 to 85 mol. % based on 100 mol. % of said polymer (P) of recurring units (R PEDEK ) of formula (I):
wherein each R1 is independently selected from Ci-C12 alkyl group optionally comprising one or more heteroatom(s), sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups, each R3 is independently halogen, 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 each a and each c is independently 0 or an integer from 1 to 4;
recurring units (R PEoEK ) of formula (II):
wherein each R1 is independently selected from Ci-C12 alkyl group optionally comprising one or more heteroatom(s), sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups; and each a is independently 0 or an integer from 1 to 4,each R2 is independently selected from the group consisting of halogen, 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 b is independently 0 or an integer from 1 to 4;
wherein the polymer (P) has a heat of fusion higher (ΔH) higher than 40 J/g (determined according to ASTM D3418-03).
2 . The polymer (P) according to claim 1 , wherein said polymer (P) comprises:
from 61 mol. % of said recurring units (R PEDEK ) of formula (I), based on 100 mol. % of said polymer (P) and up to 85 mol. % of said recurring units (R PEDEK ) of formula (I), based on 100 mol. % of said polymer (P).
3 . The polymer (P) according to claim 1 , wherein said polymer (P) comprises:
from 15 to 40 mol. % of said recurring units (R PEoEK ) of formula (II), based on 100 mol. % of said polymer (P).
4 . The polymer (P) according to claim 1 , wherein:
in said recurring units (R PEDEK ) of formula (I), a and c are 0; and/or
in said recurring units (R PEoEK ) of formula (II), a and b are 0.
5 . A method for the synthesis of polymer (P) according to claim 1 , said method comprising:
(a) contacting at least one compound of formula (III)
wherein
each R1 is independently selected from C 1 -C12 alkyl group optionally comprising one or more heteroatom(s), sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amine and quaternary ammonium groups; and each a is independently 0 or an integer from 1 to 4,
with a mixture of compounds of formula (IV) and (V):
wherein each R2 is independently selected from the group consisting of halogen, 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; each R3 is independently halogen, 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; each b and each c is independently 0 or an integer from 1 to 4,
such that the ratio of (IV) and (V) is from 85/15 to 60/40;
in the presence of a base (base (B)) and in a polar organic solvent (solvent(S)), so as to obtain a reaction mixture;
(b) optionally, terminating the reaction in step (a) by contacting said reaction mixture with a suitable agent, so as to obtain a product mixture; and
(c) recovering said polymer (P) from said reaction mixture or from said product mixture.
6 . The method according to claim 5 , wherein said step (a) is performed:
in the presence of base (B) selected from Na 2 CO 3 , K 2 CO 3 , or a combination thereof; and/or
in a solvent(S) comprising diphenyl sulfone; and/or
at a temperature of at least 130° C. for about 0.5 to 15 hours.
7 . The method according to claim 5 , wherein:
in formula (III), a is 0 and said compound is 4,4′-difluorobenzophenone (DFBP); and/or
in formula (IV), c is 0 and said compound is 4,4′-dihydroxybiphenyl;
in formula (V), b is 0 and said compound is catechol.
8 . The method according to claim 5 , wherein said step (b) is performed in the presence of at least one end-capping agent.
9 . The method according to claim 8 , wherein the at least one end-capping agent complies with the following formula (F):
wherein
R 6 is F, Cl, or OH,
R 7 is —C(O)—Ar—R 10 , —O—Ar—R 10 , —SO 2 —Ar—R 10 , —Ar—R 10 , an alkyl or —H, with Ar being an arylene group
comprising at least one benzene ring, and with R 10 being F, Cl or H.
10 . A composition (composition (C)) comprising polymer (P) as defined in claim 1 and at least one additional ingredient (ingredient (in)).
11 . The composition (C) according to claim 10 , wherein said ingredient (in) is selected from the group consisting of (i) reinforcing fillers; (ii) colorants; (iii) pigments; (iv) light stabilizers; (v) heat stabilizers; (vi) antioxidants; (vii) acid scavengers; (viii) processing aids; (ix) nucleating agents; (x) internal lubricants and/or external lubricants; (xi) flame retardants; (xii) smoke-suppressing agents; (xiii) anti-static agents; (xiv) anti-blocking agents; (xv) conductivity additives; (xvi) plasticizers; (xvii) flow modifiers; (xviii) extenders; and (xix) metal deactivators.
12 . The composition (C) according to claim 11 , wherein said composition (C) comprises less than 80 wt. % and at least 10 wt. % of said reinforcing filler, based on the total weight of the composition (C).
13 . The composition (C) according to claim 11 , wherein said at least one nucleating agent is selected from talc or boron nitride.
14 . A shaped article comprising: the polymer (P) as defined in claim 1 and/or a composition (C) comprising the polymer (P) and at least one additional ingredient, ingredient (in).
15 . The shaped article according to claim 14 , said article being an article for oil and gas recovery, for automotive, for aerospace, for electronics, for semi-conductor industry, for industrial or consumer applications.
16 . A method of making at least one part included in a shaped article as defined in claim 13 , including at least one step of moulding, extruding or coating said polymer (P) and/or said composition (C), to make said at least one part.
17 . The polymer (P) according to claim 1 , wherein said polymer (P) comprises:
from 62 mol. % of said recurring units (R PEDEK ) of formula (I), based on 100 mol. % of said polymer (P) and up to 84 mol. % of said recurring units (R PEDEK ) of formula (I), based on 100 mol. % of said polymer (P).
18 . The polymer (P) according to claim 1 , wherein said polymer (P) comprises from 15 to 39 mol. % of said recurring units (R PEoEK ) of formula (II), based on 100 mol. % of said polymer (P).
19 . The polymer (P) according to claim 1 , wherein said polymer (P) has:
(i) a glass transition temperature (Tg) higher than 153° C. (measured according to ASTM D3418-03); and
(ii) a ratio of the storage modulus measured at 165° C. to the storage modulus measured at 140° C. higher than 15% (measured according to ADTM D5279-13).
20 . The polymer (P) according to claim 1 , wherein said polymer (P) has
a melt viscosity in the range from 0.20 to 9.00 KN/m2 (measured according to ASTM D3835).