Polymodal-cure silicone composition, and method of making the same

• US 5,212,211 A
• Filed: 11/19/1990
• Issued: 05/18/1993
• Est. Priority Date: 11/19/1990
• Status: Expired due to Fees

• Current Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Inventors: Welch, Edward K. II, Cross, Robert P., Chu, Hsien-Kun, Crossan, David I.
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): BERMAN, SUSAN W
• Application Number:
  US07/615,185
• Time in Patent Office: 911 Days
• Field of Search: 522/99, 522/172, 522/37, 522/40, 522/44, 522/46, 528/31, 528/32, 528/34
• US Class Current: 522/37
• CPC Class Codes: C08G 77/50 by carbon 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
• CPC Class Codes: C09D 183/14 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms C09D183/10 takes precedence
• CPC Class Codes: C09K 2003/1062 UV-curable materials
• CPC Class Codes: C09K 2200/0247 Silica
• CPC Class Codes: C09K 2200/0625 Polyacrylic esters or derivatives thereof
• CPC Class Codes: C09K 3/1018 Macromolecular compounds having one or more carbon-to-silicon linkages

Abstract

An acryloxy-functional capped silicone formed as a reaction product of:

(i) a silyl diacrylate compound of the formula ##STR1## wherein: R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are independently selected from hydrogen, halo, and organo radicals; and n is an integer having a value of from 1 to 4; and

(ii) a silicone having (A) functionality which is reactive with an acryloxy functionality of the silyl diacrylate compound, and (B) additional functionality imparting (directly or by reaction with a co-reactant) further curability to the silicone by another modality (e.g., moisture curability, heat curability, etc.)

The capped polyfunctional silicone may suitably be formulated with (a) an effective amount of a photoinitiator for partial curing of the acryloxy-functional capped silicone under photoinitiating curing conditions, and (b) suitable curatives, initiators, accelerators, etc., as necessary or desirable for further curing by other cure mechanisms dissociated with the additional functionality (ii) (B). The compositions of the invention are usefully employed as adhesives, sealants, conformal coatings, potting materials, and the like.

Claims

1. An acryloxy-functional capped silicone, formed as a non-hydrolysis reaction product of:

(i) a silyl diacrylate compound of the formula;

##STR23## wherein;

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are independently selected from hydrogen, halo, and organo radicals; and

n is an integer having a value of from 1 to 4; and

(ii) a silicone having;

(A) functionality which is reactive with an acryloxy functionality of said silyl diacrylate compound to yield said acryloxy-functional capped silicone which is partially curable under first curing conditions comprising curingly effective radiation exposure optionally in the presence of a photoinitiator; and

(B) additional functionality which renders said acryloxy-functional capped silicone partially curable by second curing conditions different from the curingly effective radiation exposure of the first curing conditions.

2. A composition according to claim 1, wherein R₁, R₂, R₃, R₄, R₅, R₈, R₉, and R₁₀ are independently selected from hydrogen, halo, and organo radicals, and R₆ and R₇ are independently selected from hydrogen, halo, phenyl, and C₁ -C₈ alkyl radicals.

3. A composition according to claim 1, wherein n has a value of from 1 to 2.

4. A composition according to claim 1, wherein:

R₁, R₂, R₉, and R₁₀ are hydrogen;

R₃, R₄, R₅, and R₈, are independently selected from hydrogen and C₁ -C₈ alkyl;

R₆, and R₇ are independently selected from phenyl and C₁ -C₈ alkyl; and

n is 1.

5. A composition according to claim 1, wherein:

R₁, R₂, R₄, R₅, R₉ and R₁₀ are hydrogen;

R₃ and R₈ are independently selected from hydrogen and methyl;

R₆ and R₇ are methyl; and

n is 1.

6. A composition according to claim 1, wherein said silicone functionality, which is reactive with the acryloxy functionality of the silyl diacrylate compound, comprises a silicon-bonded functional group including a labile hydrogen constituent.

7. A composition according to claim 1, wherein said silicone functionality which is reactive with the acryloxy functionality of the silyl diacrylate compound, comprises a functionality selected from the group consisting of:

--OH;

--N(R'"'"')₂, wherein each of the R'"'"' substituents is independently selected from hydrogen and organo groups, with the proviso that at least one R'"'"' substituent is hydrogen;

--SH;

--SO₃ H; and

##STR24## wherein each of the R" and R"'"'"' substitutents is independently selected from hydrogen and organo groups;

with the proviso that said silicone functionality is ##STR25## only when the silyl diacrylate compound is present with residual acrylic acid groups deriving from the synthesis of the silyl diacrylate compound.

8. A composition according to claim 1, wherein said silicone having functionality (A) which is reactive with an acryloxy functionality of said silyl diacrylate compound, and additional functionality (B), comprises a linear polydiorganosiloxane.

9. A composition according to claim 8, wherein said reactive functionality of said silicone comprises a terminal reactive functional group.

10. A composition according to claim 1, wherein said silicone having functionality (A) which is reactive with an acryloxy functionality of said silyl diacrylate compound, and additional functionality (B), comprises a linear silicone with hydroxy functional groups at its termini.

11. A composition according to claim 10, wherein said linear silicone has a weight average molecular weight of from about 700 to about 300,000.

12. A composition according to claim 1, wherein said additional functionality is selected from the group consisting of:

amino;

vinyl;

hydrogen;

enoloxy;

hydroxy;

alkoxy;

aryloxy;

oxime;

--OOCR₁₃ ;

N,N-dialkylamino;

N,N-dialkylaminoxy;

N-alkylamido;

--O--NH--C(O)--R₁₃ ;

##STR26## --O--C(CH₃)═

CH₂ ; and

--S--C₃ H₆ Si(OCH₃)₃ ;

wherein R₁₃ is H or hydrocarbyl.

13. A composition according to claim 1, wherein said additional functionality (B) is selected from the group consisting of methoxy, oxime, and acetoxy.

14. A composition according to claim 1, wherein said silicone functionality (B) comprises silanol functionality, and said silanol functionality is reacted with a co-reactant comprising a silane of the formula:

##STR27## wherein;

R₁₄ is C₁ -C₈ alkyl, or ##STR28## and each R₁₅ is independently selected from hydrogen and C₁ -C₈ alkyl.

15. A composition according to claim 1, wherein said silicone functionality (B) comprises silanol functionality, and said silanol functionality is reacted with a co-reactant comprising ethyltriacetoxysilane.

16. A composition according to claim 1, wherein said additional functionality (B) is curable by curing conditions selected from the group consisting of:

(a) ambient temperature;

(b) moisture exposure;

(c) elevated temperature;

(d) reaction with curative species; and

(e) radiation exposure differing from the radiation exposure of the first curing conditions.

17. A composition comprising a capped silicone according to claim 1, and an effective amount of a photoinitiator for partial curing of said acryloxy-functional capped silicone under said radiation exposure first curing conditions.

18. A composition according to claim 17, wherein the photoinitiator comprises a compound selected from the group consisting of benzophenone, benzoin, acetophenone, benzil, and their substituted forms, and mixtures thereof.

19. A composition according to claim 17, wherein the photoinitiator comprises diethoxyacetophenone.

20. A composition according to claim 17, further comprising a stablizer.

21. A composition according to claim 17, further comprising a filler.

22. A composition according to claim 1, wherein said silyl diacrylate has the formula:

##STR29## wherein;

R is H or methyl; and

said silicone having functionality (A) which is reactive with an acryloxy functionality of said silyl diacrylate compound, and additional functionality (B), comprises a linear polydimethylsiloxane with terminal --OH groups.

23. A photocured silicone material produced by curing a composition comprising an acryloxy-functional capped silicone according to claim 1, under conditions curingly effective therefor.

24. A method of capping

(i) a silicone having

(A) functionality which is cappable by the silyl diacrylate compound of formula (I) below, and (B) additional functionality which renders, or is reactive with another component to yield a functionality which renders, the capped silicone partially curable by curing conditions other than radiation exposure,

with (ii) acrylic functionality to render the silicone photocurable in character,

said method comprising non-hydrolyzingly reacting the cappable functionality (A) of said silicone with a silyl diacrylate compound of the formula:

##STR30## wherein;

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are independently selected from hydrogen, halo, and organo radicals, and

n is an integer of from 1 to 4.

25. A method according to claim 24, wherein said silicone functionality (A) which is reactive with the silyl diacrylate compound, comprises a silicon-bonded functional group including a labile hydrogen constituent.

26. A method according to claim 24, wherein said silicone functionality (A) which is reactive with the silyl diacrylate compound, comprises a functionality selected from the group consisting of:

--OH;

--N(R'"'"')₂, wherein each of the R'"'"' substitutents is independently selected from hydrogen and organo groups, with the proviso that at least one R'"'"' substitutent is hydrogen;

--SH;

--SO₃ H; and

##STR31## wherein each of the R" and R"'"'"' substitutents is independently selected from hydrogen and organo groups;

with the proviso that said silicone functionality is ##STR32## only when the silyl diacrylate compound is present with residual acrylic acid groups deriving from the synthesis of the silyl diacrylate compound.

27. A method according to claim 24, further comprising forming a photocurable silicone composition by mixing said acryloxy-functional capped silicone with a photoinitiator.

28. A method according to claim 27, wherein said photoinitiator is selected from the group consisting of benzophenone, benzoin, acetophenone, benzil, and substituted forms thereof, and mixtures thereof.

29. A method according to claim 27, wherein the photoinitiator comprises diethoxyacetophenone.

30. A method according to claim 27, further comprising exposing said photocurable silicone composition to radiation curingly effective therefor, to yield a photocured silicone composition.

31. A method according to claim 30, wherein said radiation comprises ultraviolet radiation.

32. A method according to claim 24, wherein said silyl diacrylate has the formula:

##STR33## wherein;

R₁₉ and R₂₀ are independently selected from H and methyl; and

said silicone having functionality (A) which is cappable by the silyl diacrylate compound, and additional functionality (B), comprises a linear polydimethlysiloxane with terminal --OH groups.