Dual curing polymers and methods for their preparation and use

1. A polymer comprises, per molecule, an average of two or more groups of formula (I):

where Z is selected from the group consisting of one silicon atom, and a spacer group comprising two or more silicon atoms in which E, A, and R may be bonded to the same silicon atom or different silicon atoms in the spacer group; where

group A comprises a unit of formula

 at a terminus;

group E comprises a unit of formula

 at a terminus;

whereby when Z is a spacer, groups of formula (I) comprise two or more of units selected from R 2 2 SiO 2/2 , R 2 SiO 3/2 , SiO 4/2 , R 1′ , R 2 3 SiO 1/2 , (R 2 2 )ESiO 1/2 , (R 2 2 )ASiO 1/2 , (R 2 )(E)(A)SiO 1/2 , (R 2 )ESiO 2/2 , (A)ESiO 2/2 , (R 2 )ASiO 2/2 , ESiO 3/2 , and ASiO 3/2 with the proviso that the spacer has at least one unit containing group A and at least one unit containing group E, where group A and group E may be bonded to the same silicon atom or to different silicon atoms in the spacer;

each R is independently selected from the group consisting of R 1 , R 2 , E, A, and a covalent bond; and

where the two or more groups of formula (I) are spaced apart from one another in the polymer; and

each R 1 is independently a divalent hydrocarbon group;

each R 1′ is independently a divalent hydrocarbon group;

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation;

each X is independently a monovalent hydrolyzable group;

each J is independently a monovalent epoxy functional organic group;

each subscript s independently has a value of 1, 2, or 3; and

each subscript t independently has a value of 1, 2, or 3;

where group A has formula (II)

 where subscript x has a value of 1 or more; or

where group E has formula (III)

 where subscript y has a value of 1 or more;

with the proviso that substantially all of group X and group J are in formula (I).

2. The polymer of claim 1 , where group A has formula (II)

where subscript x has a value of 1 or more.

3. The polymer of claim 1 , where group E has formula (III)

where subscript y has a value of 1 or more.

4. The polymer of claim 1 , where the polymer has formula (IV):

or a derivative thereof,

where each R is independently selected from the group consisting of E and A, and

subscript h has a value ranging from 50 to 1000, wherein in the derivative of formula (IV), the h units of formula R 2 2 SiO 2/2 are replaced by units comprising (R 2 2 SiO 2/2 ) b′ , (R 2 SiO 3/2 ) c′ , (SiO 4/2 ) d′ , (R 1′ ) f′ , or (R 2 3 SiO 1/2 ) g′ or a combination thereof, wherein the quantity (b′+c′+d′+f′) may range from 50 to 1000, and g′ has a value of 0 or more.

5. A polymer comprises, per molecule, an average of two or more groups of formula (I):

where Z is selected from the group consisting of one silicon atom, and a spacer group comprising two or more silicon atoms in which E, A, and R may be bonded to the same silicon atom or different silicon atoms in the spacer group; where

group A comprises a unit of formula

 at a terminus;

group E comprises a unit of formula

 at a terminus;

whereby when Z is a spacer, groups of formula (I) comprise two or more of units selected from R 2 2 SiO 2/2 , R 2 SiO 3/2 , SiO 4/2 , R 1′ , R 2 3 SiO 1/2 , (R 2 2 )ESiO 1/2 , (R 2 2 )ASiO 1/2 , (R 2 )(E)(A)SiO 1/2 , (R 2 )ESiO 2/2 , (A)ASiO 2/2 , (R 2 )ASiO 2/2 , ESiO 3/2 , and ASiO 3/2 with the proviso that the spacer has at least one unit containing group A and at least one unit containing group E, where group A and group E may be bonded to the same silicon atom or to different silicon atoms in the spacer;

each R is independently selected from the group consisting of R 1 , R 2 , E, A, and a covalent bond; and

where the two or more groups of formula (I) are spaced apart from one another in the polymer; and

each R 1 is independently an oxygen atom or a divalent hydrocarbon group;

each R 1′ is independently a divalent hydrocarbon group;

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation;

each X is independently a monovalent hydrolyzable group;

each J is independently a monovalent epoxy functional organic group;

each subscript s independently has a value of 1, 2, or 3; and

each subscript t independently has a value of 1, 2, or 3;

with the proviso that substantially all of group X and group J are in formula (I);

and with the proviso where the polymer has formula (V):

 or a derivative thereof,

where each R is independently selected from the group consisting of E and A,

subscript h has a value ranging from 50 to 1000, and

each subscript i has a value ranging from 1 to 10;

where group A has formula (II)

 where subscript x has a value of 1 or more; or

where group E has formula (III)

 where subscript y has a value of 1 or more;

wherein:

in the derivative of formula (V), the h units of formula R 2 2 SiO 2/2 are replaced by units comprising (R 2 2 SiO 2/2 ) b″ , (R 2 SiO 3/2 ) c″ , (SiO 4/2 ) d″ , (R 1′ ) f″ , or (R 2 3 SiO 1/2 ) g″ , or a combination thereof, wherein the quantity (b″+c″+d″+f″)=50 to 1000 and g″ has a value of 0 or more; or

in the derivative of formula (V), the i units of formula R 2 2 SiO 2/2 may be replaced by units comprising (R 2 2 SiO 2/2 ) b′″ , (R 2 SiO 3/2 ) c′″ , (SiO 4/2 ) d′″ , (R 1′ ) f′″ , or (R 2 3 SiO 1/2 ) g′″ , or a combination thereof, wherein the quantity (b′″+c′″+d′″+f′″)=1 to 25 and g′″ has a value of 0 or more; or

in the derivative of formula (V), both the h units of formula R 2 2 SiO 2/2 and the i units of formula R 2 2 SiO 2/2 are replaced as described above.

6. A polymer comprises, per molecule, an average of two or more groups of formula (I):

where Z is selected from the group consisting of one silicon atom, and a spacer group comprising two or more silicon atoms in which E, A, and R may be bonded to the same silicon atom or different silicon atoms in the spacer group; where

group A comprises a unit of formula

 at a terminus;

group E comprises a unit of formula

 at a terminus;

whereby when Z is a spacer, groups of formula (I) comprise two or more of units selected from R 2 2 SiO 2/2 , R 2 SiO 3/2 , SiO 4/2 , R 1′ , R 2 3 SiO 1/2 , (R 2 2 )ESiO 1/2 , (R 2 2 )ASiO 1/2 , (R 2 )(E)(A)SiO 1/2 , (R 2 )ESiO 2/2 , (A)ESiO 2/2 , (R 2 )ASiO 2/2 , ESiO 3/2 , and ASiO 3/2 with the proviso that the spacer has at least one unit containing group A and at least one unit containing group E, where group A and group E may be bonded to the same silicon atom or to different silicon atoms in the spacer;

each R is independently selected from the group consisting of R 1 , R 2 , E, A, and a covalent bond; and

where the two or more groups of formula (I) are spaced apart from one another in the polymer; and

each R 1 is independently an oxygen atom or a divalent hydrocarbon group;

each R 1′ is independently a divalent hydrocarbon group;

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation;

each X is independently a monovalent hydrolyzable group;

each J is independently a monovalent epoxy functional organic group;

each subscript s independently has a value of 1, 2, or 3; and

each subscript t independently has a value of 1, 2, or 3;

with the proviso that substantially all of group X and group J are in formula (I);

and with the proviso where the polymer has formula (VI):

or a derivative thereof, where subscript h has a value ranging from 50 to 1000,

each subscript u independently has a value ranging from 0 to 22;

where group A has formula (II)

 where subscript x has a value of 1 or more; or

where group E has formula (III)

 where subscript y has a value of 1 or more;

wherein:

in the derivative of formula (VI), when u is greater than 0, then the silicon atoms to which group A and group E are bonded need not be adjacent in the ring; or

in the derivative of formula (VI), groups A and E are bonded to the same silicon atom in the ring, and the remaining silicon bonded groups in the ring are R 2 ; or

in the derivative of formula (VI), the h units of formula R 2 2 SiO 2/2 are replaced by units comprising (R 2 2 SiO 2/2 ) b″″ , (R 2 SiO 3/2 ) c″″ , (SiO 4/2 ) d″″ , (R 1′ ) f″″ , or (R 2 3 SiO 1/2 ) g″″ , or a combination thereof, wherein the quantity (b″″+c″″+d″″+f″″) has a value ranging from 50 to 1000 and g″″ has a value of 0 or more.

7. A method of making the polymer of claim 1 comprising:

combining ingredients comprising

(A) a polyorganohydrogen siloxane having an average, per molecule, of one silicon-bonded hydrogen atom and one to three terminal hydrolyzable groups;

(B) a polyorganohydrogen siloxane having an average, per molecule, one silicon-bonded hydrogen atom and one to three terminal epoxy functional organic groups; and

(C) a polymer having an average, per molecule, of at least 4 aliphatically unsaturated organic groups; and

(D) a hydrosilylation catalyst.

8. The method of claim 7 , where ingredient (A) comprises a unit of formula

at a terminus, a silicon bonded hydrogen atom at another terminus, where the unit

and the hydrogen atom are separated by 1 to 10 additional units selected from the group consisting of R 2 2 SiO 2/2 , R 2 SiO 3/2 , SiO 4/2 , R 2 3 SiO 1/2 , R 1′ , and combinations thereof; where

each R 1 is independently a divalent hydrocarbon group,

each R 1′ is independently a divalent hydrocarbon group,

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation,

each X is independently a monovalent hydrolyzable group,

subscript t has a value of 1, 2, or 3.

9. The method of claim 8 , where ingredient (A) has formula (VII):

where subscript x has a value of 1 or more.

10. The method of claim 7 , where ingredient (B) comprises a unit of formula

at a terminus, a silicon bonded hydrogen atom at another terminus,

where the unit

 and the hydrogen atom are separated by 1 to 10 additional units selected from the group consisting of R 2 2 SiO 2/2 , R 2 SiO 3/2 , SiO 4/2 , R 2 3 SiO 1/2 , R 1′ , and combinations thereof; where

each R 1′ is independently a divalent hydrocarbon group,

each R 2 is independently a monovalent organic group that is free of terminal aliphatic unsaturation,

J is a monovalent epoxy functional organic group, and

subscript s has a value of 1, 2, or 3.

11. The method of claim 10 , where ingredient (B) has formula (VIII):

where

subscript y has a value of 1 or more.

12. The method of claim 7 , where ingredient (C) has formula (IX):

or a derivative thereof,

where subscript h has a value ranging from 50 to 1000,

each R 1 is independently a divalent hydrocarbon group,

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation,

each R 3 is independently an organic group having terminal aliphatic unsaturation.

13. The method of claim 7 , where ingredient (C) has formula (X):

or a derivative thereof, where

subscript i has a value ranging from 1 to 10,

subscript h has a value ranging from 50 to 1000,

each R 1 is independently an oxygen atom or a divalent hydrocarbon group,

each R 2 is independently a monovalent substituted or unsubstituted hydrocarbon group that is free of terminal aliphatic unsaturation,

each R 3 is independently an organic group having terminal aliphatic unsaturation.

14. The method of claim 7 , where ingredient (C) has formula (XII):

subscript h has a value ranging from 50 to 1000,

each subscript u has a value ranging from 0 to 22,

each R 1 is independently an oxygen atom or a divalent hydrocarbon group,

each R 2 is independently a monovalent organic group that is free of terminal aliphatic unsaturation,

each R 3 is independently an organic group having terminal aliphatic unsaturation.

15. A composition comprising:

(a) the polymer of claim 1 , and

(b) a photoinitiator.

16. A method comprising:

(i) applying the composition of claim 15 to a substrate, and

(ii) exposing the composition to ultra-violet radiation or atmospheric moisture, or both.

17. A method comprising:

(i) applying the composition of claim 15 to a substrate, and

(ii) exposing the composition to heat or atmospheric moisture, or both.

18. The method of claim 16 , where the substrate is selected from the group consisting of an electronic device and a circuit board.

19. The composition of claim 15 , further comprising one or more additional ingredients selected from the group consisting of (c) a filler, (d) a filler treating agent, (e) solvent, (f) a condensation reaction catalyst, (g) an adhesion promoter, (h) a colorant, (i) a reactive diluent, (j) a radical generator, (k) a shelf life extender, (l) an antioxidant, (m) a crosslinker, (n) a corrosion inhibitor, and a combination thereof.

20. The method of claim 17 , where the substrate is selected from the group consisting of an electronic device and a circuit board.