Polymers, processes, compositions and uses

Patent metadata

Field	Value
Publication number	US-11512165-B2
Application number	US-202016999043-A
Country	US
Kind code	B2
Filing date	Aug 20, 2020
Priority date	May 27, 2016
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

Polymers and methods of making the same are described whereby the polymers generically include one or more units each of which necessarily has a 1,2,4-substituted cyclohexane group or a 1,1,2,4-substituted cyclohexane group. According to specific disclosures herein, polymers and methods of making the same are described whereby the polymers have one or more S1 units represented by the formula:wherein n is an integer equal to or higher than 1, m is 0 or 1, A is H or CH3, and wherein each of X and Y is a specifically defined group.

First claim

The invention claimed is:

1. A polymer comprising one or more S1 units, wherein each S1 unit is represented by the following formula:

and wherein
i) m is either 0 or 1,
ii) A is either H or CH 3 ,
iii) n is an integer equal to or higher than 1, and
iv) X is selected from the group consisting of X3, X4, X5, X6, X7, X10 and X11 as each of X3 to X11 is defined below, and wherein the black bold dot shown in each of the formulae of any one of X3 to X11 represents an attachment point of each of X3 to X11 to the S1 unit, and wherein the attachment point is a carbon atom,

wherein
R 5 ′, R 7 ′, R 9 ′, R 11 ′, R 13 ′, R 15 ′, R 17 ′ is each independently selected from the group consisting of H and CH 3 ,
R 6 ′, R 8 ′ is each independently selected from the group consisting of H, CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl, and R 10 ′, R 12 ′, R 14 ′, R 16 ′ is each independently selected from the group consisting of CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl, and

v) Y is selected from the group consisting of Y1, Y5, Y10, Y11, Y12, Y13, Y14, Y15, Y16, Y17, Y18, Y19, and Y20, as each of Y1 to Y20 is defined below and wherein the black bold dots shown in each of the formulae of any one of Y1 to Y20 represent the attachment points of each of Y1 to Y20 to the S1, wherein each attachment point is a carbon atom,

wherein
R 1 , R 2 , R 3 , R 4 , R 13 , R 14 and R 21 is each independently selected from the group consisting of H, CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl, with the proviso that none of R 1 , R 2 , R 3 , R 4 , R 13 , R 14 and R 21 comprises any carboxyl group or any anhydride group, and

R 20 is a C 1 -C 34 optionally-substituted-hydrocarbyl.

2. The polymer according to claim 1 , further comprising one or more S2 units, wherein each S2 unit is represented by the following formula:

and wherein
S1 and S2 may or may not be directly connected to each other along the polymer's backbone,
w is an integer equal to or higher than 1,
Z is selected from the group consisting of Z1, Z2, Z3 and Z4 as each of Z1 to Z4 is defined below, and wherein each of the black bold dots shown in the formulae of any one of Z1 to Z4 represents an attachment point of each of Z1 to Z4 to the S2 unit, wherein the attachment point is a carbon atom, with the proviso that the O of the [—O—Z—] w group is connected to the a-carbon atom in any one of Z1 to Z4,

wherein
R 1 ′″, R 2 ′″, R 3 ′″, R 4 ′″, R 5 ′″, R 6 ′″, R 7 ′″, R 8 ′″, is each independently selected from the group consisting of H, CH 3 , and C 2 -C 202 optionally-substituted-hydrocarbyl, preferably a C 2 -C 36 optionally-substituted-hydrocarbyl, R 9 ′″, R 10 ′″, R 12 ′″, R 13 ′″ is each independently selected from the group consisting of H, CH 3 , and C 2 -C 34 optionally-substituted-hydrocarbyl, and R 11 ′″, R 14 ′″ is each independently selected from a C 1 -C 34 optionally-substituted-hydrocarbylene.

3. The polymer according to claim 1 , wherein X is selected from the group consisting of X10 and X11, and wherein
R 14 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 15 ′ is H or CH 3 ,
R 16 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl, and
R 17 ′ is H or CH 3 .

4. The polymer according to claim 1 , wherein m=1 and wherein X is selected from the group consisting of X10 and X11, and wherein
R 14 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 15 ′ is H or CH 3 , and
R 16 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 17 ′ is H or CH 3 , and wherein
Y is selected from the group consisting of Y16, Y17, Y18, Y19 and Y20.

5. The polymer according to claim 2 , wherein
each of R 1 ′″, R 2 ′″, R 3 ′″, R 5 ′″, R 6 ′″, R 7 ′″, R 9 ′″, R 10 ′″, R 12 ′″, R 13 ′″ is H,
each of R 4 ′″, R 8 ′″ is a C 2 -C 36 optionally-substituted-hydrocarbyl, and
each of R 11 ′″, R 14 ′″ is a C 1 -C 34 optionally-substituted-hydrocarbylene.

6. The polymer according to claim 5 , wherein X is selected from the group consisting of X10 and X11, and wherein
R 14 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 15 ′ is H or CH 3 ,
R 16 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl, and
R 17 ′ is H or CH 3 .

7. The polymer according to claim 5 , wherein m=1 and wherein X is selected from the group consisting of X10 and X11, and wherein
R 14 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 15 ′ is H or CH 3 ,
R 16 ′ is a C 11 -C 28 unsaturated-acyclic-hydrocarbyl,
R 17 ′ is H or CH 3 , and wherein
Y is selected from the group consisting of Y16, Y17, Y18, Y19 and Y20.

8. The polymer according to any one of claims 1 - 7 , wherein the polymer has a Molar Ratio Q (MRQ) determined via NMR spectroscopy of at least 1 and at most 10, where MRQ is:

MRQ
=

S
total

S
specific

=

S
specific

+

S
rest

S
specific

wherein
S total =S specific +S rest , and
S specific =(total moles S1)+(total moles S2), and
S rest =the total moles of all the units of a polymer wherein said units are not any one of S1, S2.

9. The polymer according to claim 8 , wherein the polymer has a MRQ of at most 4.

10. The polymer according to any one of claims 1 - 7 , wherein the polymer has:
i) a number average molecular weight (M n ) of at least 10 3 and at most 4×10 4 Da,
ii) a polydispersity (D) (D=M w /M n ) of at least 1,2 and at most 14,
iii) a glass transition temperature (T g ) of at least −10 and at most 150° C.,
iv) an acid value (AV) of at most 10 mg KOH/g,
v) a hydroxyl value (OHV) of at least 10 and at most 250, and
vi) a functionality (f) of at least 0.2 and at most 50, wherein
M w is weight average molecular weight measured via Gel Permeation Chromatography,
M n is measured via Gel Permeation Chromatography,
T g is measured via Differential Scanning Calorimetry
AV is measured titrimetrically via ISO 2114,
OHV is measured titrimetrically via ISO 4629, and
f is determined by the equation:

f
=

[

M
n

Assignees

• Covestro Netherlands Bv

Inventors

• Koning Cornelis Eme
• Veldhuis Theo
• Buijsen Paulus Franciscus Anna
• Drijfhout Jan Pieter
• Reuvers Albertus Johannes
• Sablong Rafael Jean
• Li Chunliang

Classifications

• C08G64/34

  and cyclic ethers · CPC title

• C08G64/025

  containing sulfur · CPC title

• C09D169/00

  Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates · CPC title

• C08G64/0208

  saturated · CPC title

• C08G63/6856

  Dicarboxylic acids and dihydroxy compounds · CPC title