Cross-linked composition and method of forming the same

• US 9,714,323 B2
• Filed: 10/29/2014
• Issued: 07/25/2017
• Est. Priority Date: 10/31/2013
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow Corning Corporation (Dow, Inc.)
• Inventors: Kadlec, Donald A., Zimmerman, Kenneth E., Nguyen, Kimmai T.
• Primary Examiner(s): ZIMMER, MARC S
• Application Number:
  US14/912,177
• Publication Number:
  US 20160200876A1
• Time in Patent Office: 1,000 Days
• Field of Search: None
• CPC Class Codes: A61K 2800/10 General cosmetic use
• CPC Class Codes: A61K 8/89 Polysiloxanes
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/46 containing polyether sequences
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence

Abstract

A cross-linked composition comprises the reaction product of siloxanes having pendant anhydride groups and a reactant having hydroxyl and/or amine functional groups. The cross-linked composition can be of the following general formula (I): (I). Refer to formula (1) Each X can be of the following general formula (i): (i). Refer to formula (i) Each of W and W* is independently an oxygen atom or N—R, with R independently being a hydrogen atom or R¹. Each of Y, R³, and R¹³ is an independently selected divalent group. Each of R¹, R¹¹, R⁴, R¹⁴, R⁵, and R¹⁵ is an independently selected substituted or unsubstituted hydrocarbyl group. Each of w and ww, and each of y and yy, is an independently selected integer from 0 to 1,000. Each of x and xx is an independently selected integer from 1 to 100. Typically, w and y are not simultaneously 0, and ww and yy are not simultaneously 0.

Claims

1. A cross-linked composition comprising the reaction product of:

a first siloxane having at least one pendant anhydride group;

a second siloxane having at least one pendant anhydride group; and

a reactant comprising a polyol having at least two carbon-bonded hydroxyl groups reactive with the pendant anhydride groups of said first and second siloxanes.

2. The cross-linked composition as set forth in claim 1, wherein said polyol is selected from the group of:

i) an organic polyol having at least two carbon-bonded hydroxyl groups reactive with the pendant anhydride groups of said first and second siloxanes;

ii) a third siloxane having at least two carbon-bonded hydroxyl groups reactive with the pendant anhydride groups of said first and second siloxanes;

iii) combinations thereof.

3. The cross-linked composition as set forth in claim 2, wherein said polyol is said organic polyol and wherein:

i) said organic polyol has two terminal carbon-bonded hydroxyl groups;

ii) said organic polyol is free of silicon;

or

iii) both i) and ii).

4. The cross-linked composition as set forth in claim 2, wherein said polyol is said third siloxane and said third siloxane has two terminal carbon-bonded hydroxyl groups.

5. The cross-linked composition as set forth in claim 1, wherein each of said first and second siloxanes comprise at least one [SiR¹R²—

O—

] unit, R¹ is an independently selected substituted or unsubstituted hydrocarbyl group, R² is a pendant anhydride group of the following general formula (A);

6. The cross-linked composition as set forth in claim 5, wherein each of said first and second siloxanes is individually of the following general formula (B):

R⁵₃Si—

O—

[SiR¹R⁴—

O—

]_w[SiR¹R²—

O—

]_x[SiR¹R⁴—

O—

]_ySiR⁵₃ 

 

(B);

each of R¹ and R² are as defined above, alternatively each R¹ is an independently selected alkyl group;

R³ is a hydrocarbylene, heterohydrocarbylene, or organoheterylene group, alternatively R³ is (CH₂)_n where n is an integer selected from 1 to 30;

R⁴ is a substituted or unsubstituted hydrocarbyl group, alternatively R⁴ is an independently selected alkyl group, aryl group, or polyether group;

each R⁵ is an independently selected substituted or unsubstituted hydrocarbyl group, alternatively each R⁵ is R¹;

w is an integer selected from 0 to 1,000, alternatively 1 to 300;

x is an integer selected from 1 to 100, alternatively 1 to 75; and

y is an integer selected from 0 to 1,000, alternatively 1 to 300;

with the proviso that w and y are not simultaneously 0.

7. The cross-linked composition as set forth in claim 6, wherein each of said first and second siloxanes is individually of the following general formula (B1):

(CH₃)₃Si—

O—

[Si(CH₃)₂—

O—

]_w[Si(CH₃)R²—

O—

]_x[Si(CH₃)R⁴—

O—

]_ySi(CH₃)₃ 

 

(B1);

R³ of R² is (CH₂)_n where n is an integer selected from 1 to 15, alternatively 3;

R⁴ is an independently selected alkyl group having from 2 to 20 carbon atoms;

w is an integer selected from 50 to 200, alternatively 75 to 125;

x is an integer selected from 1 to 50, alternatively 1 to 5; and

y is an integer selected from 1 to 200, alternatively 1 to 5.

8. The cross-linked composition as set forth in claim 1, wherein said polyol has the following general formula:

HO—

R⁷—

OH;

where R⁷ comprises at least one of a hydrocarbylene, a heterohydrocarbylene, or an organoheterylene group, alternatively is a hydrocarbylene group having from 1 to 40 carbon atoms, alternatively 1 to 10 carbon atoms.

9. The cross-linked composition as set forth in claim 2, wherein said reaction product is further derived from a polyamine having at least two amine groups reactive with the pendant anhydride groups, and/or derivatives thereof, of said first and second siloxanes.

10. The cross-linked composition as set forth in claim 2, wherein said polyol comprises said third siloxane and said third siloxane is a polysiloxane of the following general formula:

HO—

[Z]_d—

[SiR⁸R¹⁰—

O—

]_a[SiR⁸R⁹—

O—

]_b[SiR⁸R¹⁰—

O—

]_cSi—

[Z]_d—

OH

wherein each of R⁸, R⁹, and R¹⁰ is an independently selected substituted or unsubstituted hydrocarbyl group;

each Z independently comprises at least one of a hydrocarbylene, heterohydrocarbylene, or organoheterylene group, alternatively each Z is a hydrocarbylene group having from 1 to 20 carbon atoms;

a is an integer selected from 0 to 1,000;

b is an integer selected from 1 to 200;

c is an integer selected from 0 to 1,000, alternatively 0 to 400; and

each d is 1.

11. The cross-linked composition as set forth in claim 3, wherein:

i) said organic polyol has two terminal carbon-bonded hydroxyl groups; and

ii) said organic polyol is free of silicon.

12. The cross-linked composition as set forth in claim 1, wherein said polyol is a polyether diol.

20. The cross-linked composition as set forth in claim 1, having:

i) free carboxyl groups and optionally, free anhydride groups, provided by said first and/or second siloxane(s);

ii) a carboxyl equivalent of from 100 to 50,000 g/mol;

or

iii) both i) and ii).

13. A cross-linked composition of the following general formula (I):

14. The cross-linked composition as set forth in claim 13, wherein each of R¹ and R¹¹ is an independently selected alkyl group;

R³ is (CH₂)_n where n is an integer selected from 1 to 30, alternatively 1 to 15;

R¹³ is (CH₂)_nn where nn is an integer selected from 1 to 30, alternatively 1 to 15;

each R⁴ is an independently selected alkyl group, aryl group, or polyether group, alternatively each R⁴ is an independently selected alkyl group having from 2 to 20 carbon atoms;

each R¹⁴ is an independently selected alkyl group, aryl group, or polyether group, alternatively each R¹⁴ is an independently selected alkyl group having from 2 to 20 carbon atoms;

each R⁵ is R¹;

each R¹⁵ is R¹¹;

each of w and ww is an independently selected integer from 1 to 300, alternatively 75 to 125;

each of x and xx is an integer selected from 1 to 75, alternatively 1 to 5; and

each of y and yy is an integer selected from 1 to 300, alternatively 1 to 5.

15. The cross-linked composition as set forth in claim 13, wherein Y comprises at least one of a hydrocarbylene, heterohydrocarbylene, or organoheterylene group.

16. The cross-linked composition as set forth in claim 13, wherein Y is of the following general formula (ii):

—

[Z]_d—

[SiR⁸R¹⁰—

O—

]_a[SiR⁸R⁹—

O—

]_b[SiR⁸R¹⁰—

O—

]_cSi—

[Z]_d—

 

 

(ii);

wherein each of R⁸, R⁹, and R¹⁰ is an independently selected substituted or unsubstituted hydrocarbyl group;

Z comprises at least one of a hydrocarbylene, heterohydrocarbylene, or organoheterylene group;

a is an integer selected from zero to 1,000;

b is an integer selected from 1 to 200;

c is an integer selected from 0 to 400; and

each d is 1.

17. The cross-linked composition as set forth in claim 13, wherein said polyol has the following general formula:

HO—

R⁷—

OH;

where R⁷ comprises at least one of a hydrocarbylene, a heterohydrocarbylene, or an organoheterylene group, alternatively is a hydrocarbylene group having from 1 to 40 carbon atoms, alternatively 1 to 10 carbon atoms.

18. The cross-linked composition as set forth in claim 13, wherein said polyol is a polyether diol.

19. The cross-linked composition as set forth in claim 13, wherein said polyol comprises a polysiloxane of the following general formula:

HO—

[Z]_d—

[SiR⁸R¹⁰—

O—

]_a[SiR⁸R⁹—

O—

]_b[SiR⁸R¹⁰—

O—

]_cSi—

[Z]_d—

OH;

wherein each of R⁸, R⁹, and R¹⁰ is an independently selected substituted or unsubstituted hydrocarbyl group;

each Z independently comprises at least one of a hydrocarbylene, heterohydrocarbylene, or organoheterylene group, alternatively each Z is a hydrocarbylene group having from 1 to 20 carbon atoms;

a is an integer selected from 0 to 1,000;

b is an integer selected from 1 to 200;

c is an integer selected from 0 to 1,000, alternatively 0 to 400; and

each d is 1.