Cross-linked composition and method of forming the same

• US 9,822,221 B2
• Filed: 10/29/2014
• Issued: 11/21/2017
• 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., Nguyen, Kimmai T., Zimmerman, Kenneth E.
• Primary Examiner(s): PENG, KUO LIANG
• Application Number:
  US14/912,174
• Publication Number:
  US 20160194456A1
• Time in Patent Office: 1,119 Days
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/48 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08G77/42 takes precedence
• CPC Class Codes: C08G 77/54 Nitrogen-containing linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C08L83/10 takes precedence

Abstract

A cross-linked composition comprises the reaction product of a first reactant having at least one hydroxyl or amine (functional) group, a second reactant having at least one hydroxyl or amine (functional) group, and a siloxane having at least two terminal anhydride groups reactive with the functional groups of the first and second reactants. The first reactant is selected from the group of first siloxanes having at least one hydroxyl or amine group, a first organic alcohol having at least one hydroxyl group, a first organic amine having at least one amine group, or combinations thereof. The second reactant is selected from the group of second siloxanes having at least one hydroxyl or amine group, a second organic alcohol having at least one hydroxyl group, a second organic amine having at least one amine group, or combinations thereof. If utilized, the first siloxanes and/or second siloxanes are different from the siloxane.

Claims

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

a first reactant having at least two hydroxyl groups;

a second reactant having at least two hydroxyl groups; and

a siloxane having at least two terminal anhydride groups reactive with the hydroxyl groups of said first and second reactants;

wherein said first reactant is selected from the group of;

i) a first siloxane different from said siloxane and having at least two hydroxyl groups,

ii) a first organic alcohol having at least two hydroxyl groups, or

iii) a combination thereof; and

wherein said second reactant is selected from the group of;

i) a second siloxane different from said siloxane and having at least two hydroxyl groups,

ii) a second organic alcohol having at least two hydroxyl groups, or

iii) a combination thereof.

2. The cross-linked composition as set forth in claim 1, wherein:

i) said first reactant comprises said first siloxane having at least two hydroxyl groups, alternatively at least two pendant hydroxyl groups;

ii) said second reactant comprises said second siloxane having at least two hydroxyl groups, alternatively at least two pendant hydroxyl groups;

or

iii) both i) and ii).

3. The cross-linked composition as set forth in claim 2, wherein:

i) said first siloxane has at least three hydroxyl groups, alternatively at least three pendant hydroxyl groups;

ii) said second siloxane has at least three hydroxyl groups, alternatively at least three pendant hydroxyl groups;

or

iii) both i) and ii).

4. The cross-linked composition as set forth in claim 1, wherein:

i) said first reactant comprises said first organic alcohol having at least two hydroxyl groups, alternatively at least three hydroxyl groups;

ii) said second reactant comprises said second organic alcohol having at least two hydroxyl groups, alternatively at least three hydroxyl groups;

or

iii) both i) and ii).

5. The cross-linked composition as set forth in claim 4, wherein:

i) said first organic alcohol has at least one pendant hydroxyl group;

ii) said second organic alcohol has at least one pendant hydroxyl group;

or

iii) both i) and ii).

6. The cross-linked composition as set forth in claim 1, wherein said siloxane has two terminal anhydride groups.

7. The cross-linked composition as set forth in claim 1, wherein said siloxane is of the following general formula (A):

R⁷R⁵₂Si—

O—

[SiR¹R⁴—

O-]_w[SiR¹R²—

O-]_x[SiR¹R⁴—

O-]_ySiR⁵₂R⁷ 

 

(A);

each R⁷ is a terminal anhydride group of the following general formula (B);

8. The cross-linked composition as set forth in claim 7, wherein said siloxane is of the following general formula (A1):

R⁷(CH₃)₂Si—

O—

[Si(CH₃)₂—

O—

]_w[Si(CH₃)₂—

O—

]_x[Si(CH₃)R⁴—

O—

]_ySi(CH₃)₂R⁷ 

 

(A1);

R³ of R⁷ is (CH₂)_n where n is an integer selected from 1 to 15, alternatively 3;

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

w is an integer selected from 0 to 200, alternatively 0 to 125;

x is an integer selected from 0 to 50, alternatively 0 to 5; and

y is an integer selected from 0 to 200, alternatively 0 to 5.

9. The cross-linked composition as set forth in claim 1, wherein each of said first and second siloxanes is individually of the following general formula (C):

R¹¹₃Si—

O—

[SiR⁸R¹⁰—

O-]_a[SiR⁸R⁹—

O-]_b[SiR⁸R¹⁰—

O-]_cSiR¹¹₃ 

 

(C);

each R⁹ is of the following formula (D);

—

[Z]_d—

V 

 

(D);

V is OH;

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

each of R⁸ and R¹¹ is an independently selected substituted or unsubstituted hydrocarbyl group, alternatively each of R⁸ and R¹¹ is an independently selected alkyl group;

each R¹⁰ is an independently selected alkyl group, aryl group, or polyether group having from 2 to 49 ether linkages and terminated with —

OR⁶, wherein R⁶ is an alkyl group or aryl group;

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; and

each d is independently 0 or 1, alternatively 1.

10. The cross-linked composition as set forth in claim 9, wherein d is 1 and Z comprises at least one structural unit selected from the group consisting of:

i) [(CH₂)_i]_k;

ii) [(CH₂)_iO]_k;

iii) [(CH₂)_i(CH)(CH₃)O]_k;

iv) [(CH₂)_i(CH)(CH₂)_j(CH₃)O]_k;

v) [(CH)OH]_k;

vi) [(CH)(CH₂)_iOH]_k;

vii) [(CH₃)₂COH(CH₂)_i]_k;

viii) [(CH₃)(CH₂)_iCOH(CH₂)_j(CH₃)]_k;

ix) [(CH₂)_iNH(CH₂)_i]_k;

x) [(CH₂)_iN(CH₂)_j(CH₃)]_k; and

xi) combinations thereof;

where i is an integer selected from 1 to 100;

j is an integer selected from 1 to 100; and

k is an integer selected from 1 to 100.

11. The cross-linked composition as set forth in claim 1, wherein each of said first and second siloxanes is individually a resin of the general formula R*_SSiO_(4-s)/2 where R* is an independently selected substituted hydrocarbyl group, unsubstituted hydrocarbyl group, or hydroxyl group, and s is from greater than 0 to 3.

12. The cross-linked composition as set forth in claim 1, wherein:

i) at least one of said organic alcohols has the following general formula;

HO—

R⁸—

OH, where R⁸ is a hydrocarbylene group having from 1 to 40 carbon atoms, alternatively 1 to 10 carbon atoms; and

/or

ii) at least one of said organic alcohols is a polyether diol.

13. The cross-linked composition as set forth in claim 12, wherein each of said organic alcohols independently has the following general formula:

HO—

R⁸—

OH;

where R⁸ is a hydrocarbylene group having from 1 to 40 carbon atoms, alternatively 1 to 10 carbon atoms.

14. The cross-linked composition as set forth in claim 1, wherein each of said organic alcohols is free of silicon.

15. The cross-linked composition as set forth in claim 1, having free carboxyl groups provided by said siloxane and optionally, a carboxyl equivalent of from 100 to 50,000 g/mol.

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

17. The cross-linked composition as set forth in claim 16, wherein each of R¹, R², R⁵, R⁸, R¹⁸, R¹¹, and R²¹ 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, or aryl group;

each of R¹⁰ and R²⁰ is an independently selected alkyl group, or aryl group;

each of a and aa is an independently selected integer from 0 to 500;

each of b and bb is an independently selected integer from 2 to 100;

each of c and cc is an independently selected integer from 0 to 500;

w is an integer selected from 0 to 300;

x is an integer selected from 0 to 75; and

y is an integer selected from 0 to 300.

18. The cross-linked composition as set forth in claim 16, wherein d is 1 and Z comprises at least one structural unit selected from the group consisting of:

i) [(CH₂)_i]_k;

ii) [(CH₂)_iO]_k;

iii) [(CH₂)_i(CH)(CH₃)O]_k;

iv) [(CH₂)_i(CH)(CH₂)_j(CH₃)O]_k;

v) [(CH)OH]_k;

vi) [(CH)(CH₂)_iOH]_k;

vii) [(CH₃)₂COH(CH₂)_i]_k;

viii) [(CH₃)(CH₂)_iCOH(CH₂)_j(CH₃)]_k;

ix) [(CH₂)_iNH(CH₂)_i]_k;

x) [(CH₂)_iN(CH₂)_j(CH₃)]_k; and

xi) combinations thereof;

where i is an integer selected from 1 to 100;

j is an integer selected from 1 to 100; and

k is an integer selected from 1 to 100.