Polycarbonate polymer with siloxane repeat units, compositions, and methods

Patent metadata

Field	Value
Publication number	US-12281199-B2
Application number	US-202318706766-A
Country	US
Kind code	B2
Filing date	Jan 18, 2023
Priority date	Feb 11, 2022
Publication date	Apr 22, 2025
Grant date	Apr 22, 2025

Abstract

Polycarbonate polymers comprising non-aromatic cyclic groups bonded with carbonate linking groups are described. A portion of the non-aromatic cyclic groups comprise a substituent having siloxane repeat units. Representative formulas of the substituents having siloxane repeat units include —CH 2 —CH 2 —Si(R 4 ) 2 —(OSi(R 4 ) 2 —R 5 , and —CH[Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 ]—CH 3 ; wherein m is the number of siloxane repeat units; and R 4 and R 5 are independently alkyl, aryl, aralkyl or aralkylene. The polycarbonate polymer C typically comprises a high concentration of carbonate linking group, for example in an amount of at least 85 or 90 mol % or greater N based on the total linking groups of the polymer. Also described are compositions comprising the polycarbonate polymer and methods of making.

First claim

What is claimed is:

1. A polycarbonate polymer comprising non-aromatic cyclic groups bonded with carbonate linking groups wherein a portion of the non-aromatic cyclic groups comprise a substituent
comprising siloxane repeat units having the formula:
—CH 2 —CH 2 —Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 , and

—CH[Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R]—CH 3

wherein m is the number of siloxane repeat units and R 4 and R 5 are independently alkyl, aryl, aralkyl or aralkylene,

wherein the polycarbonate polymer has a Tg of at least 50 and no greater than 100° C.

2. The polycarbonate polymer of claim 1 wherein the carbonate linking groups are present in an amount of at least 85 mol % based on the total linking groups of the polycarbonate polymer.

3. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer comprises non-carbonate linking groups in an amount less than 15 mol % based on the total linking groups of the polymer.

4. The polycarbonate polymer of claim 1 wherein the polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups is an amount ranging from 60 to 98.5 mol %.

5. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer comprises polymerized units of non-aromatic cyclic groups comprising a vinyl substituent in an amount ranging from 1 to 30 mol %.

6. The polycarbonate polymer of claim 1 wherein the polymer comprises polymerized units of non-aromatic cyclic groups comprising a substituent having siloxane repeat units in an amount ranging from 0.5 to 10 mol %.

7. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer has the formula:

wherein n independently ranges from 1 to 5,
R 1 is vinyl,
R 2 is hydrogen,
R 3 is independently —CH 2 —Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 or —[Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 ]—CH 3 ,
R 4 and R 5 are independently alkyl, aryl, aralkyl or aralkylene, and
u, V, W, x, y, and z are the number of each polymerized units.

8. The polycarbonate polymer of claim 7 wherein u+v+w are a value such that the polycarbonate polymer comprises less than 15 mol % of such polymerized units.

9. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer has a weight average molecular weight (Mw) ranging from 5,000 to 1,500,000 g/mol.

10. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer has a number average molecular weight (Mn) ranging from 5,000 to 750,000 g/mol.

11. The polycarbonate polymer of claim 1 wherein the polycarbonate polymer has a thermogravimetric mass loss onset temperature in the range from 220-300° C.

12. The polycarbonate polymer of claim 1 wherein the polymer has a higher receding contact angle with water than the same polymer without the siloxane substituents.

13. A composition comprising the reaction product of at least one ethylenically unsaturated material and a polycarbonate polymer comprising non-aromatic cyclic groups bonded with carbonate linking groups wherein a portion of the non-aromatic cyclic groups comprise a substituent
comprising siloxane repeat units having the formula:
—CH 2 —CH 2 —Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 , or

—CH[Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 ]—CH 3

wherein m is the number of siloxane repeat units and R 4 and R 5 are independently alkyl, aryl, aralkyl or aralkylene.

14. The composition of claim 13 wherein ethylenically unsaturated material is monofunctional, multifunctional, or a mixture thereof.

15. The composition of claim 14 wherein ethylenically unsaturated material is aromatic, aliphatic, or a mixture thereof.

16. The composition of claim 13 wherein the composition has a higher receding contact angle with water than the same composition without the polycarbonate polymer.

17. The composition of claim 1 wherein the polycarbonate polymer is the reaction product of a polycarbonate polymer comprising non-aromatic cyclic groups wherein a portion of the cyclic groups comprise a vinyl moiety and a hydride moiety of a compound comprising siloxane repeat units and a single hydride moiety.

18. A polycarbonate polymer comprising non-aromatic cyclic groups bonded with carbonate linking groups wherein a portion of the non-aromatic cyclic groups comprise a substituent
comprising siloxane repeat units having the formula:
—CH 2 —CH 2 —Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 , or

—CH[Si(R 4 ) 2 —(OSi(R 4 ) 2 ) m —R 5 ]—CH 3

wherein m is the number of siloxane repeat units and R 4 and R 5 are independently alkyl, aryl, aralkyl or aralkylene; wherein the polycarbonate polymer comprises polymerized units of non-aromatic cyclic groups comprising a vinyl substituent in an amount ranging from 1 to 30 mol %.

19. The polycarbonate polymer of claim 18 wherein the polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups in an amount ranging from 60 to 98.5 mol %.

Assignees

• 3M Innovative Properties Company

Inventors

• Laskowski Carl A
• Armstrong Paul B

Classifications

• C08G64/0291

  unsaturated · CPC title

• C08G64/0266

  containing silicon · CPC title

• C08F2/48

  by ultraviolet or visible light · CPC title

• C09D169/00

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

• C09D4/06

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00 · CPC title