Polyarylether ketone copolymer

Patent metadata

Field	Value
Publication number	US-11708457-B2
Application number	US-201716348224-A
Country	US
Kind code	B2
Filing date	Oct 24, 2017
Priority date	Nov 11, 2016
Publication date	Jul 25, 2023
Grant date	Jul 25, 2023

Abstract

The invention pertains to certain copolymers (PEDEK/PEEK), comprising a majority of “PEDEK”-type recurring units, which, thanks to the predominance of PEDEK-type units, their structural homogeneity and regularity, and absence of chlorinated end groups, possess a suitable molecular structure and crystallization behaviour so as to deliver improved mechanical properties and outstanding chemical resistance, and which are useful in numerous fields of endeavours, including notably in the oil&gas industry, and more specifically for the manufacture of parts used in oil and gas extraction systems.

First claim

The invention claimed is:

1. A polyaryl ether ketone copolymer (PEDEK-PEEK) comprising:
recurring units (R PEEK ) of formula (I):

and
recurring units (R PEDEK ) of formula (II):

wherein in above formulae (I) and (II), each of R′ and R″, equal to or different from each other, is independently selected at each occurrence from a C 1 -C 12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of j′ and k″, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4;
wherein the said recurring units are comprised in a molar ratio (R PEEK ):(R PEDEK ) of 45:55 to 15:85, and
wherein the said copolymer (PEDEK/PEEK):
(j) comprises an amount of chemically bound chlorine of less than 2.0 μeq/g, as determined by microcoulometry, and
(jj) possesses a narrow molecular weight distribution such that the following inequality is satisfied:

MV
⁡

(

kN

m
2

)

≤

6.62
·

[

RV
⁡

(

dl
g

)

]

0.20

Math
.

⁢
15

wherein:
MV is the melt viscosity measured pursuant to ASTM D3835 standard at 410° C. and at a shear rate of 46.3 sec −1 , using a conical die having a diameter of 1.016 mm a length of 20.32 mm and a cone angle of 120° C. and expressed in kNs/m 2 ; and
RV is the reduced viscosity measured pursuant to ASTM D2857 standard at 25° C. on 1.0 wt/vol % solution in concentrated H 2 SO 4 (96 wt %) and expressed in dl/g.

2. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 , wherein the molar ratio (R PEEK ):(R PEDEK ) is 40:60 to 20:80.

3. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 further comprising recurring units (RPAEK) different from recurring units (RPEEK) and (RPEDEK), wherein the amount of recurring units (RPAEK) is between 0 and 5% moles, with respect to the total number of moles of recurring units of copolymer (PEDEK/PEEK), and/or wherein said recurring units (RPAEK) comply with any of the following formulae (K-A) to (K-M) herein below:

wherein in each of formulae (K-A) to (K-M), each of R′, equal to or different from each other, is independently selected at each occurrence from a C1-C12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; and each of j′, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4.

4. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 , wherein in recurring units (R PEEK ) of formula (I), the connections among phenyl groups are in the para positions of each of the phenyl rings and/or each of j′ is zero, and wherein recurring units (R PEEK ) comply with formula (Ia):

5. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 , wherein in recurring units (R PEDEK ) of formula (II), the connections among phenyl groups are generally in the para positions of each of the phenyl rings and/or each of k″ is zero, and wherein recurring units (R PEDEK ) comply with formula (IIb):

6. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 , wherein the copolymer comprises end groups selected from the group consisting of:
benzo-phenone fluoride groups of formula:

hydroxyl-containing groups of formula (OH-1) or (OH-2) or salified groups thereof:

wherein the symbol

is intended to denote the polymer chain comprising recurring units (R PEEK ) and (R PEDEK ), wherein each of R, R′ and R″, equal to or different from each other, is independently selected at each occurrence from a C 1 -C 12 group optionally comprising one or more than one heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups; each of r, j′ and k″, equal to or different from each other, is independently selected at each occurrence from 0 and an integer of 1 to 4, and wherein end groups of formulae (F), (OH-1) and (OH-2) are more than 50% moles of the total moles of end groups of the copolymer (PEDEK/PEEK).

7. The polyaryl ether ketone copolymer (PEDEK/PEEK) of claim 1 comprising a narrow molecular weight distribution such that the following inequality is satisfied:

MV
⁡

(

kN

m
2

)

≤

6.60
⁡

[

RV
⁡

(

dl

Assignees

• Solvay Specialty Polymers Usa

Inventors

• Louis Chantal
• Thomas David B
• El-Hibri Mohammad Jamal
• Hammonds Ryan

Classifications

• C08G65/4012 Primary

  Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08G2650/40

  containing ketone groups, e.g. polyarylethylketones, PEEK or PEK · CPC title

• C08K7/14

  Glass · CPC title

• C08G65/40 Primary

  from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group · CPC title