Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
CATALYST FREE SILICONE CURE
Document Type and Number:
WIPO Patent Application WO/2020/243834
Kind Code:
A1
Abstract:
The present application provides a method for the preparation of siloxane elastomers without the need for catalysts by the reaction of aminoalkyl- or hydroxyalkyl-modified silicones with cyanuric chloride or dianhydrides such as EDTA dianhydride or pyromellitic dianhydride.

Inventors:
BROOK MICHAEL A (CA)
FEINLE ANDREA (CA)
MORAN-MIRABAL JOSE (CA)
FATONA AYODELE (CA)
WONG MICHAEL YIN (CA)
Application Number:
CA2020/050770
Publication Date:
December 10, 2020
Filing Date:
June 04, 2020
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
UNIV MCMASTER (CA)
International Classes:
C08J3/24; C08G77/38; C08G77/388; C08K5/1539; C08K5/3492; C08K5/357
Domestic Patent References:
WO2012020068A22012-02-16
Foreign References:
US20130153261A12013-06-20
US20180230269A12018-08-16
US20110086204A12011-04-14
US4808686A1989-02-28
US5916688A1999-06-29
Other References:
PINTEALA, M. ET AL.: "Functional Polysiloxanes, 2. On the reaction of hydroxypropyl- and aminoalklyl-terminated polydimethysiloxanes with cyclic anhydrides", POLYMER BULLETIN, vol. 32, 1994, pages 173 - 178, XP000425948, DOI: 10.1007/BF00306385
Attorney, Agent or Firm:
BERESKIN & PARR LLP/S.E.N.C.R.L., S.R.L. (CA)
Download PDF:
Claims:
CLAIMS:

1 . A process for preparing siloxane elastomers by combining

(i) a compound of Formula I or a compound of Formula II:

wherein

R1-R5, R7-R9, R10, R12 and R14 are independently or simultaneously selected from Ci-

1 oalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, linear and branched siloxanes;

R6 and R13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl;

R11 is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, . linear and branched siloxanes, and Y;

R15-R17 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl; wherein n is 0-1000, and if n=0, m = 1 -60; if n>10, then m = 1 -60% of n; p is 0-1000;

Y is an amino-modified group, in which the amine is a primary or secondary amine connected to the silicone polymer through a linker R18, wherein the linker R18 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and wherein the nitrogen atom(s) of the primary or secondary amine is connected to the linker via a sp3 hybridized carbon, and wherein one or more carbons of R18 are substituted with NH, N(Ci-6alkyl) or S groups; or

Y is a hydroxy-modified group, in which the hydroxy group is a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R19, wherein the linker R19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and the hydroxy group is connected to the linker via a sp3 hybridized carbon; with

(ii) a crosslinker, wherein the crosslinker reacts with the compound of formula (I) or (II) to form the silicone elastomer without the need for a catalyst.

2. The process according to claim 1 , wherein R1-R5, R7-R9, R10, R12 and R14 are independently or simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl, C6-

ioaryl, linear and branched siloxanes.

3. The process according to claim 2, R1-R5, R7-R9, R10, R12 and R14 are independently or simultaneously selected from Ci-3alkyl.

4. The process according to claim 3, wherein R1-R5, R7-R9, R10, R12 and R14 are CH3 or phenyl.

5. The process according to any one of claims 1 to 4, wherein R6 and R13 are independently selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl.

6. The process according to claim 5, wherein R6 and R13 are CH3 or phenyl.

7. The process according to any one of claims 1 to 6, wherein R1 1 is selected from H,

Ci-6alkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl, , linear and branched siloxanes, and Y.

8. The process according to claim 7, wherein R11 is Y.

9. The process according to any one of claims 1 to 8, R15-R17 are independently or simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl.

10. The process according to claim 9, wherein R15-R17 are CH3 or phenyl.

11. The process according to any one of claims 1 to 10, wherein R18 is selected from

Ci-6alkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2-6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl.

12. The process according to any one of claims 1 to 11 , wherein Y is

13. The process according to any one of claims 1 to 11 , wherein Y is

wherein a, b are 0-30.

14. The process according to any one of claims 1 to 13, wherein the crosslinker is a compound having functional groups which are able to react with the amino or hydroxyl groups of the Y moiety to form the silicone elastomers.

15. The process according to claim 14, wherein the crosslinker is

16. The process of any one of claims 1 to 15, wherein the compound of formula (I) is a silicone polymer formed from a terminal monomer of formula (A)

a monomer of formula (B)

a monomer of formula (C)

R6

X-Si— X

Y (C);

and a terminal monomer of formula (D)

R7

X— Si— R8

R9 (D)

wherein each X is independently a leaving group, wherein the reaction is conducted in water to form a compound of formula (I),

wherein Y and R1-R9 are as defined above;

and wherein the monomers of formula (C) and (D) polymerize as random or block copolymers.

17. The process of any one of claims 1 to 15, wherein the compound of formula

(IIA) is a silicone polymer formed from a monomer of formula (E) R1 0

Y-Si- X

i

R1 2 (E);

a monomer of formula (F)

R1 3 X— Si X

R14 (F);

and a monomer of formula (G)

R1 3

X— Si Y

R14 (G)

wherein each X is independently a leaving group such, wherein the reaction is conducted in water to form a compound of formula (II), wherein Y and R10-R1 4 are as defined above.

Description:
CATALYST FREE SILICONE CURE

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001 ] This application claims the benefit of priority to U.S. Provisional Application Nos. 62/857,050, filed June 4, 2019 the contents of which are incorporated herein by reference in their entirety.

FIELD

[0002] The present application relates to the preparation of silicone elastomers without the need for catalysts.

BACKGROUND

[0003] Silicone elastomers are widely used because of the properties they possess, which are typically not matched by organic analogues, including low surface energy, low Tg, high thermal stability, etc. In commerce, silicone elastomers are created principally through three methods: radical cure at elevated temperature of silicone oils, or vinyl-modified silicone oils; condensation (moisture cure) crosslinking of telechelic silanol polymers with small organofunctional silanes (sometimes referred to as room temperature vulcanization); and hydrosilylation cure in which a vinylsilicone and HSi-containing silicone are combined to give a two carbon spacer between silicone chains (this process may be‘inhibited’ such that elevated temperatures are required for cure; in the case of hydrosilylation cure at room temperature, sometimes this process is also called RTV). 1

[0004] Catalysts are used for all three cure strategies. Radical cure often uses peroxides; RTV (moisture) typically exploits tin or titanium-derived catalysts, and hydrosilylation is mostly facilitated by platinum. There are significant disadvantages with the use of these catalysts. It is very challenging to remove untreated catalyst, catalyst by products or spent catalyst from the elastomer post production. Such resides may eventually leach from the product and the consequences of spontaneous release must be assessed. There are other practical disadvantages of catalysts. They are subject to poisoning through contamination of the starting material, they may have known toxicity - there is concern about tin catalysts in this regard 2 - and/or can be very expensive, as in the case of platinum. [0005] One strategy to reduce or avoid the use of catalysts for cure involves a greater reliance on organic chemistry to provide reactions that lead to cure. Organic chemistry has been widely used in the area of silicones. Figure 1 shows several reactions that have been exploited in the synthesis of silicone elastomers. These reactions require the use of catalysts; radical catalysts in the case of thiolene 3 and acrylate chemistry, 4 and acid, base or metal catalysts in the case of epoxy 5 and isocyanate chemistry. 6 The Lewis acid B(C6F5)3 catalyzes the Piers-Rubinsztajn reaction between SiH and ROSi-containing compounds. 7

[0006] There are certain organic chemical reactions that occur spontaneously, without the need for cataysts, and which are applicable to silicones. Selected examples are shown in Figure 2. Woodward-Hofmann allowed reactions, including the Diels Alder 8 and Huisgen reactions, 9 require heating, while conjugate addition - the azaMichael reaction - can occur spontaneously at room temperature with the appropriate starting materials. 10 These reactions can be disadvantageous because of the challenge, in the former cases, to cleanly synthesize dienylsilanes. Note that reactions catalyzed by strong acids or bases are normally not appropriate for silicone polymers because of the fragility of siloxane bonds to these conditions. 1

[0007] There remains a need to develop catalyst-free silicone crosslinking systems that involve readily available starting materials, are inexpensive, use reactions that are easy to control and which provide, at will, elastomers that have properties of typical silicones, or those that are more hydrophilic.

SUMMARY

[0008] The present application relates to the preparation of silicone elastomers without the need for catalysts. In particular, the present disclosure relates to treating silicone possessing SiH groups with heat and oxygen which leads to silicone elastomers via formation of both SiO bonds and ethers. In one embodiment, reaction of aminoalkyl- or hydroxyalkyl-modified organic chemical linkages with a crosslinker such as cyanuric acid, or anhydrides, bridges silicone chains at polymer termini and/or pendant to the chain to form elastomers. In some embodiments, the properties of the resulting elastomers, including modulus, extension at break, depend on the spacing between crosslinkers and the specific organic functional groups formed during cure. In other embodiments, small changes in the fraction of organic groups can significantly affect the physical properties of the elastomer product.

[0009] In one embodiment therefore, the present application includes a process for preparing elastomers comprising combining a compound of Formula I or a compound of Formula II:

wherein

R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-

1 oalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, linear and branched siloxanes;

R 6 and R 13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl;

R 11 is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, . linear and branched siloxanes, and Y;

R 15 -R 17 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl; wherein n is 0-1000, and if n=0, m = 1 -60; if n>10, then m = 1 -60% of n; p is 0-1000; q is 0-1000, and if q=0, r = 1 -60; if q>10, then r = 1 -60% of q; Y is an amino-modified group, in which the amine is a primary or secondary amine connected to the silicone polymer through a linker R 18 , wherein the linker R 1 8 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and wherein the nitrogen atom(s) of the primary or secondary amine is connected to the linker via a sp 3 hybridized carbon, and wherein one or more carbons of R 1 8 are substituted with NH, NR or S groups;

Y is a hydroxy-modified group, in which the hydroxy group is a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 , wherein the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and the hydroxy group is connected to the linker via a sp 3 hybridized carbon; or wherein the compound of Formula I or Formula II is reacted with a multifunctional organic molecule that crosslinks the compound of Formula I or Formula II to form the silicone elastomer.

[0010] In one embodiment, the multifunctional organic molecule is cyanuric chloride, EDTA anhydride or pyromellitic dianhydride:

[001 1 ] In another embodiment, when Y is an amino-modified group, there may be more than one nitrogen in Y, or a sulfur atom. In one embodiment, Y is -R 18 -NH2, and for example

[0012] In another embodiment, there may be more than one oxygen in Y. In another embodiment, Y is: where a, b are 0-30.

[0013] It has now been discovered that silicones bearing aminoalkyl or hydroxyalkyl groups can react with either di- or oligoanhydrides and/or cyanuric chloride 11 to form di-, tri- or higher order organic linkages at room temperature or slightly elevated temperatures (< 60 °C). In one embodiment, the network structure and resulting properties of the elastomer depends on the number of linkages to a given crosslinker. In one embodiment, in the case of anhydrides, carboxylic acids are generated that further affect the physical properties of the elastomer. In another embodiment, in the case of crosslinking by cyanuric chloride, the properties of the resulting elastomers are additionally affected by the presence of residual amines, and of ammonium ions.

[0014] Silicone polymers containing both aminoalkyl and hydroxyalkyl groups (for example, alkyl being propyl, which is used in commerce) are produced by several manufacturers. In one embodiment, these silicone polymers are readily crosslinked into silicone elastomers at room temperatures in the absence of catalyst. In one embodiment, the crosslinking molecules include cyanuric chloride, di-anhydrides, including pyromellitic dianhydride, EDTA dianhydride and others. 19

[0015] In other embodiments, triazines result from the reaction of monofunctional, telechelic, or pendant modified aminoalkylsilicones or hydroxypropylsilicones with cyanuric chloride. The reactions with amines are favored over alcohols, because the HCI produced in the reaction can be self-neutralized if sufficient amines are present (Figure 4). In one embodiment, the properties of the elastomers formed depend on total crosslink density, the number of linkages to the triazine moiety(ies), the fraction of residual amines or ammonium ions and the relative quantity of pendant, telechelic and monofunctional silicones used in the reaction. In some embodiments, it will be understood by those skilled in the art that each of these factors can be varied to change physical properties including modulus, and ability to absorb water. [0016] In other embodiments, dianhydrides also react spontaneously with monofunctional, telechelic, or pendant modified aminoalkylsilicones or hydroxyalkylsilicones. In one embodiment, network structures are formed with pendently modified functional silicones, and may be tuned by using telechelic silicones for chain extension and/or monofunctional entities to reduce the modulus (Figure 4). In some embodiments, crosslinking is accompanied by carboxylic acid formation which, in the acid form and even more in the carboxylate form, strongly influence the physical properties of the elastomer.

[0017] Other features and advantages of the present application will become apparent from the following detailed description. However, it should be understood that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments, but should be given the broadest interpretation consistent with the description as a whole.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0019] Figure 1 shows organic cure reactions of silicones using catalyzed organic chemistry.

[0020] Figure 2 shows organic cure reactions of silicones without catalysts.

[0021 ] Figure 3 shows silicone elastomer formation through crosslinking aminoalkyl and hydroxyalkyl-modified silicone polymers with dianhydrides or cyanuric chloride.

[0022] Figure 4. A: aminoalkylsilicones crosslinked with cyanuric chloride (HCI complexed with residual amines) and B: hydroxyalkylsilicone crosslinked with EDTA dianhydride in one embodiment of the disclosure.

DETAILED DESCRIPTION

(I) DEFINITIONS [0023] Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art.

[0024] The present application refers to a number of chemical terms and abbreviations used by those skilled in the art. Nevertheless, definitions of selected terms are provided for clarity and consistency.

[0025] As used herein, the words“comprising” (and any form of comprising, such as“comprise” and“comprises”),“having” (and any form of having, such as“have” and “has”), “including” (and any form of including, such as “include” and “includes”) or “containing” (and any form of containing, such as“contain” and“contains”), are inclusive or open-ended and do not exclude additional, unrecited elements or process/method steps.

[0026] As used herein, the word“consisting” and its derivatives, are intended to be close ended terms that specify the presence of stated features, elements, components, groups, integers, and/or steps, and also exclude the presence of other unstated features, elements, components, groups, integers and/or steps.

[0027] The term“consisting essentially of”, as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and/or steps as well as those that do not materially affect the basic and novel characteristic(s) of these features, elements, components, groups, integers, and/or steps.

[0028] Terms of degree such as“substantially”,“about” and“approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.

[0029] As used in this application, the singular forms“a”,“an” and“the” include plural references unless the content clearly dictates otherwise. For example, an embodiment including“a compound” should be understood to present certain aspects with one compound or two or more compounds. In embodiments comprising an “additional” or“second” component, such as an additional or second compound, the second component as used herein is chemically different from the other components or first component. A “third” component is different from the other, first, and second components, and further enumerated or“additional” components are similarly different.

[0030] The term“and/or” as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that“at least one of” or “one or more” of the listed items is used or present.

[0031 ] The term“alkyl” as used herein, whether it is used alone or as part of another group, means straight or branched chain, saturated alkyl groups. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the prefix “Cni-n2”. For example, the term Ci-ioalkyl means an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0032] The term“alkenyl” as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one double bond. The number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix“C ni -n 2”. For example, the term C2-ioalkenyl means an alkenyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one double bond.

[0033] The term“alkynyl” as used herein, whether it is used alone or as part of another group, means straight or branched chain, unsaturated alkyl groups containing at least one triple bond. The number of carbon atoms that are possible in the referenced alkylene group are indicated by the prefix“Cni-n2”. For example, the term C2-ioalkynyl means an alkynyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and at least one triple bond.

[0034] The suffix“ene” as used herein, for example in“alkylene”, “alkenylene” means divalent hydrocarbon radicals having straight, branched or cyclic moieties or combinations thereof. [0035] The term“aryl” as used herein, whether it is used alone or as part of another group, refers to cyclic groups containing from 6 to 20 carbon atoms and at least one aromatic ring. In an embodiment of the application, the aryl group contains from 6, 9 or 10 carbon atoms, such as phenyl, indanyl or naphthyl.

[0036] The term “aminoalkylsilicone” as used herein, refers to a primary or secondary amine connected to the silicone polymer through a linker R 18 .

[0037] The term “hydroxyalkylsilicone” as used herein, refers to a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 .

[0038] The term“monomer” is used to describe a silane or siloxane moiety that has the possibility of undergoing reactions to give siloxane products of increased molecular weight.

[0039] The term“oligomer” is used to describe a siloxane moiety that is prepared by reactions of lower molecular weight siloxanes or silanes (monomers). The number of monomers contained in an oligomer is about <20.

[0040] The term“linear siloxane” as used herein refers to a group comprising

R R"

s i I ,

-i-Si-O-Si— I-

5 I I ¾

R' R'" units, wherein R, R', R" and R'" are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl, arranged in linear fashion. The number of units may

R

be between 1 and 10 with the terminal group being R' , wherein R"" is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl.

[0041 ] The term“branched siloxane” as used herein refers to a group comprising

R R"

i I ,

-f-Si-O-Si-f- e I I ?

R' R'" units, wherein R, R', R" and R'" are as defined above, with the exception that

R

O— Si-1-

I <

at least one of R, R', R" and R'" is R' . The number of units may be between 1 and R

R""-Si-|-

I <

10 with any terminal group being R' , wherein R"" is selected from Ci-ioalkyl, C2- loalkenyl, C2-ioalkynyl and aryl.

(II) ELASTOMERS OF THE DISCLOSURE

[0042] In one embodiment of the disclosure, the present application includes a process for preparing elastomers comprising combining a compound of Formula I or a compound of Formula II:

wherein

R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-

1 oalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, linear and branched siloxanes;

R 6 and R 13 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl;

R 11 is selected from H, Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl, C6-2oaryl, . linear and branched siloxanes, and Y;

R 15 -R 17 are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and C6- 2oaryl; wherein n is 0-1000, and if n=0, m = 1 -60; if n>10, then m = 1 -60% of n; p is 0-1000; q is 0-1000, and if q=0, r = 1 -60; if q>10, then r = 1 -60% of q; Y is an amino-modified group, in which the amine is a primary or secondary amine connected to the silicone polymer through a linker R 18 , wherein the linker R 18 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and wherein the nitrogen atom(s) of the primary or secondary amine is connected to the linker via a sp 3 hybridized carbon, and wherein one or more carbons of R 18 are substituted with NH, NR or S groups; or

Y is a hydroxy-modified group, in which the hydroxy group is a primary, secondary or tertiary alcohol connected to the silicone polymer through a linker R 19 , wherein the linker R 19 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl, and the hydroxy group is connected to the linker via a sp 3 hybridized carbon; wherein the compound of Formula I or Formula II is reacted with a multifunctional organic molecule that crosslinks the compound of Formula I or Formula II to form the silicone elastomer.

[0043] In one embodiment, the moieties

are randomly distributed throughout the compound of formula (I) and the integers ‘n’ and ‘m’ represent the overall number of moieties throughout the compound. In one embodiment, the moieties are formed from block copolymers. In one embodiment, n is 0-1000 and m is 2-60, and where n is 0, m is 2-60, and wherein if n>10, then m = 1 -60% of n. In one embodiment, the minimum requirements for a covalent network are m=2 for a trifunctional or higher crosslinker or m=3 for a difunctional or higher crosslinker. In one embodiment, n is 0-2000 (or 0-1000), if n=0, m = 2-60, if n>10, then m = 1 -60% of n. In another embodiment, n is about 0- 2000, or about 10-2000, or about 10-1000, or about 50-1000, or about 100-1000. In one embodiment, m is 2-60, or 3-60, or 2-40, or 2-20, or 2-10.

[0044] In another embodiment, p is about 0-2000, or about 10-2000, or about 10- 1000, or about 50-1000, or about 100-1000. [0045] In one embodiment, R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or

simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl,

and linear and branched siloxanes.

[0046] In one embodiment, R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or

simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl,

and linear and branched siloxanes.

[0047] In one embodiment, R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are independently or simultaneously selected from Ci-3alkyl or phenyl. In one embodiment, R 1 -R 5 , R 7 -R 9 , R 10 , R 12 and R 14 are CH3.

[0048] In one embodiment, R 6 and R 13 are independently selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In one embodiment, R 6 and R 13 are independently selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In one embodiment, R 6 and R 13 are independently selected from Ci-3alkyl or phenyl. In one embodiment, R 6 and R 13 are Chb.

[0049] In one embodiment, R 1 1 is selected from H, Ci-6alkyl, C2-6alkenyl, C2-

6alkynyl, C6-ioaryl, , linear and branched siloxanes, and Y. In one

embodiment, R 1 1 is selected from H, Ci-6alkyl, , linear and branched siloxanes, and Y. In another embodiment, R 1 1 is selected from H, Ci-3alkyl, CH3, or phenyl.

[0050] In another embodiment, R 15 -R 17 are independently or simultaneously selected from Ci-6alkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In another embodiment, R 15 -R 17 are independently or simultaneously selected from Ci-3alkyl or phenyl In one embodiment, R 15 -R 17 are CH3.

[0051 ] In another embodiment, Y is an amino-modified group having one or more amine groups, in which the amine is a primary or secondary amine connected to the silicone polymer through a linker R 18 , wherein the linker R 18 is selected from Ci-ioalkyl, Ci-ioalkylene, C2-ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6- 2oarylalkyl, and wherein the nitrogen atom(s) of the primary or secondary amine is connected to the linker via a sp 3 hybridized carbon, and wherein one or more carbons in R 18 may be replaced with one or more nitrogen atoms (NH or N-(Ci-6alkyl)) or sulfur atoms. In another embodiment, Y is -R 18 -NH2 or -R 18 -NHR a , wherein R a is Ci-6alkyl optionally substituted with amino (Nhte). In another embodiment, R 18 is selected from Ci- 6alkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2-6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl. In another embodiment, R 18 is selected from Ci-6alkyl, or Ci-6alkylene, wherein one or more of the carbon atom is replaced with one or more oxygen atoms.

[0052] In one embodiment, Y is -R 18 -NH2 or -R 18 -(NH2)2 and for example

[0053] In another embodiment, Y is a hydroxy-modified group, in which the hydroxy group is a primary or secondary or tertiary alcohol connected to the silicone polymer through a linker R 23 , wherein the linker R 23 is selected from Ci-ioalkyl, Ci-ioalkylene, C2- ioalkenyl, C2-ioalkenylene, C2-ioalkynyl, C2-ioalkynylene, C6-2oaryl, or C6-2oarylalkyl and the hydroxy group is connected to the linker via a sp 3 hybridized carbon and wherein one or more carbons in R 23 may be replaced with one or more oxygen atoms. In another embodiment, R 23 is selected from Ci-6alkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2- 6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl. In another embodiment, R 23 is selected from Ci-6alkyl, or Ci-6alkylene, wherein one or more of the carbon atoms is replaced with one or more oxygen atoms. In another embodiment, Y is wherein a, b are 0-30.

[0054] In one embodiment, the multifunctional organic molecule crosslinker is an organic molecule having functional groups which are able to react with the amino or hydroxyl groups of the Y moiety to form the silicone elastomers. In one embodiment, the multifunctional organic molecule crosslinker has two or three functional groups (i.e. a difunctional or trifunctional crosslinker). In one embodiment, the functional groups are leaving groups, such as halo groups or anhydrides. In another embodiment, the multifunctional organic molecule is cyanuric chloride, EDTA anhydride or pyromellitic dianhydride:

[0055] In another embodiment, the cyanuric chloride is combined with amionalkylsilicone at a ratio such that there is at least one free amine is present for each amine that forms a bond with cyanuric chloride, such amine can act to neutralize HCI generated.

[0056] In another embodiment, the crosslinker is a dianhydride, selected from EDTA dianhydride and pyromellitic dianhydride.

[0057] In one embodiment, the compound of the formula (I) or (II) is

[0058] In another embodiment, the elastomer is

[0059] In one embodiment, the compound formula (II) is a compound of formula

(HA)

[0060] In a further embodiment, sufficient crosslinks must be obtained to create an elastomer, such number of crosslinks being achieved.

[0061 ] In another embodiment, the properties of the elastomer are controlled by varying the amount of Y groups on the compounds of formula (I) or (II), and by the amount and nature of the crosslinking.

[0062] In another embodiment of the disclosure, the compound of formula (I) is a silicone polymer comprised of a terminal monomer of formula (A)

monomers of formula (B)

monomers of formula (C)

R 6

X-Si— X

Y (C);

and a terminal monomer of formula (D) R 7

X— Si— R 8

R 9 (D)

wherein each X is independently a leaving group such that, after polymerization, X is replaced with 0 (oxygen) to form a compound of formula (I),

wherein Y and R 1 -R 9 are as defined above in any embodiment;

and wherein the monomers of formula (C) and (D) polymerize as random or block copolymers.

[0063] In another embodiment of the disclosure, the monomers of formula (B) and (C) are present at a molar ratio of between about 1 : 1000 to about 1000: 1 , or about 1 :500 to about 500: 1 , or about 1 : 100 to about 100: 1.

[0064] In another embodiment, the compound of formula (I) is a silicone polymer formed from a monomer of formula (E)

R 1 0

Y-Si- x

i

R 1 2 (E);

a monomer of formula (F)

R 1 3 X— Si X

R 1 4 (F);

and a monomer of formula (G)

wherein each X is independently a leaving group such that, after polymerization, X is replaced with 0 (oxygen) to form a compound of formula (II), wherein Y and R 10 -R 14 are as defined above in any embodiment.

[0065] In another embodiment, any residual functional groups on the elastomer is used in a second step to link the elastomer to other materials, such as substrates or solid supports. In another embodiment, the degree of crosslinking is controlled by stoichiometry of the functional group to the crosslinker.

[0066] In one embodiment, the compound of formula (I) or (II) is crosslinked with the crosslinker without the need for a catalyst at an appropriate temperature, for example 0-100°C, or about room temperature.

[0067] In another embodiment, less than about 50% of the amines in the Y group in the compounds of formula (I) and/or (II) react with the crosslinker (such as cyanuric chloride).

EXAMPLES

[0068] The following non-limiting examples are illustrative of the present application. As is apparent to those skilled in the art, many of the details of the examples may be changed while still practicing the methods, compositions and kits described herein.

Materials

[0069] Telechelic 3-(aminopropyl)-terminated polydimethylsiloxanes: DMS-A1 1 (-850-900 g mo ), DMS-A21 (-5,000 g mol 1 ), DMS-A31 (-25,000 g mo ) and 3- (aminopropyl)methylsiloxane-dimethylsiloxane copolymer AMS-132 (2-3%mol aminopropyl-methylsiloxane, 4,500-6,000 g moM), MCR-H21 (HMe2Si0(SiMe20)zSiMe 2 Bu, MW-4759 g mol 1 ), DMS-H1 1 (HMe2Si0(SiMe 2 0)tSiMe 2 H (MW ~ 1050 g mol 1 ): HMS-082 (Me 3 Si(OSiMe2)s(OSiHMe)tOSiMe3, MW ~ 6000 g mol 1 , SiH ~ 7-8%): PMS-H03 (HMe2Si0(PhMeSi0)20SiMe 2 H), AMS-162

(Me3Si(OSiMe2)s(OSiMe(CH2)3NH2)tOSiMe3, Mw ~ 4500 g mol 1 , 6-7% amine) were purchased from Gelest. Ethylendiaminetetraacetic dianhydride (98%), cyanuric chloride and 2-propanol were purchased from Sigma Aldrich. All compounds were used as received.

Methods

[0070] FTIR data was collected on a Nicolet 6700 FTIR using Thermo Electron’s OMNIC software

[0071 ] 1 FI and 29 Si NMR spectra were recorded on a Bruker Advance 600 MFIz nuclear magnetic resonance spectrometer using deuterated solvent chloroform -c/.

[0072] Polymer molecular weights were established by gel permeation chromatography (GPC) using a Waters Alliance GPC System 2695 calibrated with a polystyrene calibration kit S-M-10 (Lot 85) from Polymer Laboratories.

[0073] GC-MS analyses were performed using an Agilent 6890N gas chromatograph (Santa Clara, CA, USA), equipped with a DB-17ht column (30 m c 0.25 mm i.d. x 0.15 pm film, J & W Scientific) and a retention gap (deactivated fused silica, 5 m x 0.53 mm i.d.), and coupled to an Agilent 5973 MSD single quadruple mass spectrometer. One microliter of sample was injected using Agilent 7683 autosampler with a 10: 1 split and slit flow of 7.0 ml/min. The injector temperature was 250 °C and carrier gas (helium) flow was 0.7 ml/min. The transfer line was 280 °C and the MS source temperature was 230 °C. The column temperature started at 50 °C and raised to 300 °C at 8 °C/min, and then held at 300 °C for 10 min for a total run time of 41 .25 min. Full scan mass spectra between m/z 50 and 800 were acquired after five min solvent delay.

[0074] A Shore OO durometer (Rex Gauge Company, Inc. U.S.) was used to characterize the hardness of the elastomer.

[0075] Example 1 : Full crosslinking of both anhydride groups: [0076] Crosslinked silicone elastomers were prepared from telechelic 3- (aminopropyl)-terminated polydimethylsiloxane or pendant 3-

(aminopropyl)methylsiloxane-dimethylsiloxane copolymer and ethylendiaminetetraacetic dianhydride (EDTAD) in IPA at room temperature.

[0077] In a typical preparation, EDTAD (0.04 g, 0.17 mmol) was dispersed in IPA (0.51 g) and stirred with a magnetic stir bar (450 rpm) for 3 h. The aminopropylpolydimethylsiloxane (DMS A-21 , 0.83 g, 0.17 mmol)) was added and the mixture was again stirred with a magnetic stir bar (450 rpm) for 4 h followed by mixing with a dual asymmetric centrifuge SpeedMixer DAC 150FVZ-K at 3500 rpm for 30 s. IPA (0.5 g) was added on top of the thus obtained viscous mixture and the sample was placed into an oven at 60 °C for 24 h. Subsequently, the cured elastomer was cooled to room temperature and characterized.

[0078] All other EDTAD-crosslinked silicone elastomers were produced following the preparation procedure described above. The formulations are given in Table 1 .

[0079] Example 2: Partial crosslinking of the anhydride groups:

[0080] Crosslinked silicone elastomers comprising anhydride groups were prepared using telechelic 3-(aminopropyl)-terminated polydimethylsiloxane and EDTAD in IPA at room temperature. In a typical preparation, EDTAD (0.08 g, 0.34 mmol) was dispersed in IPA (0.51 g) and stirred with a magnetic stir bar (450 rpm) for 3 h. The aminopropylpolydimethylsiloxane (DMS A-21 , 0.83 g, 0.17 mmol)) was added and the mixture was again stirred with a magnetic stir bar (450 rpm) for 4 hours followed by mixing with a dual asymmetric centrifuge SpeedMixer DAC 150.1 at 3500 rpm for 30 s. IPA (0.5 g) was added on top of the thus obtained viscous mixture and the sample was placed into an oven at 60°C for 24 h. Subsequently, the cured elastomer was cooled to room temperature and characterized as shown in Table 2.

[0081 ] Example 3: Molecular Characterization: Full crosslinking of both anhydride groups:

[0082] An equimolar ratio between the aminosilicone and the EDTAD leads to elastomers that contain amide, carboxylic acid as well as carboxylate groups, as seen in the FT-IR spectra. The FT-IR data for an elastomer that was prepared with an equimolar ratio between DMS-A21 and EDTAD is exemplarily given below.

IR (ATR-IR, cm- 1 ): 2962, 2904, 1714, 1677, 1648, 1577, 1444, 1412, 1257, 1077, 1009, 864, 786, 699, 685, 660.

[0083] The Shore OO hardness was determined five times at five different position of the sample. The average value and the deviations are given in 3.

[0084] Example 4: Partial crosslinking of the anhydride groups:

[0085] An excess amount of EDTAD leads to crosslinked silicone elastomers that contain amide, carboxylate as well as residual anhydride groups. The FT-IR data for an elastomer that was prepared with an excess amount of EDTAD is exemplarily given below.

IR (ATR-IR, cm- 1 ): 2962, 2906, 1805, 1745, 1680, 1653, 1572, 1465, 1443, 1413, 1345, 1321 , 1257, 1009, 927, 864, 786, 701 , 685, 661 , 614.

[0086] The Shore OO hardness was determined five times at five different position of the sample. The average value and the deviations are given in 4.

[0087] Example 5: Elastomer preparation using triazinyl-crosslinked silicones

[0088] A representative curing procedure for the synthesis of amino-triazinyl functional silicone networks based on cyanuric chloride, is provided below. (Aminopropyl)methylsiloxane-dimethylsiloxane copolymer (PDMS-NFte, AMS-162, 1 g, 0.876 mmol of amino groups) was weighed into a polypropylene mixing cup (FlackTek, size 10) followed by the addition of cyanuric chloride (27 mg, 0.146 mmol dissolved in 500 pL of dichloromethane). After mixing using the Speedmixer (3500 rpm, 1 min), the transparent and homogeneous silicone mixture was allowed to cure at room temperature for 24 h or at 60 °C for 4 h. Characterization of elastomers by FTIR showed changes in functional groups as curing occurred (Table 5).

[0089] Example 6: Elastomer preparation using pre-grafted triazinyl crosslinked silicones a) Synthesis of 4,6-dichloro-s-triazinyl modified aminosilicones

[0090] To a solution of cyanuric chloride (203 mg, 1 .1 mmol) dissolved in tetrahydrofuran (15 ml_) cooled to 0 °C was added a mixture of aminopropyl terminated polydimethylsiloxane (DMS-A1 1 , 1 g, 1 .1 mmol of amino groups) and triethylamine (153 pl_, 1 1 1 mg, 1 .1 mmol) in tetrahydrofuran (15 ml_) dropwise over 30 min. The reaction mixture was stirred for additional 12h after which the precipitate formed was filtered and solvent removed under reduced pressure to afford crude 4,6-dichlor-s-triazinyl modified silicone oil partitioned between acetonitrile and hexane. The acetonitrile extract was recovered and concentrated to give pure product as a colorless silicone oil. Yield (90%).

b) Elastomer formation with 4,6-dichloro-s-triazinyl modified aminosilicones

[0091 ] A representative curing procedure for the synthesis of amino-triazinyl functional silicone networks based on 4,6-dichloro-s-triazinyl modified aminosilicones, is provided, as shown below. To (aminopropyl)methylsiloxane-dimethylsiloxane copolymer (PDMS-Nhte, AMS 152, 1 g, 0.467 mmol of amino groups) weighed into a polypropylene mixing cup (FlackTek, size 10) 4,6-dichloro-s-triazinyl modified aminosilicones (94.6 mg, 0.31 1 mmol of chloro groups dissolved in 500 pl_ of dichloromethane) was added. After mixing using the Speedmixer (3500 rpm, 1 min), the transparent and homogeneous silicone mixture was allowed to cure at room temperature for 24 h or at 60 °C for 4 h. Elastomers prepared using pre-grafted triazinyl silicones can be achieved in the presence or absence of organic solvent (dichloromethane or toluene). Characterization of elastomers by FTIR showed changes in functional groups as curing occurred (Table 6).

[0092] All publications, patents and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety. Where a term in the present application is found to be defined differently in a document incorporated herein by reference, the definition provided herein is to serve as the definition for the term. Table 1 Formulations for the preparation of EDTAD-crosslinked silicones without anhydride groups.

Table 2: Formulations for the preparation of EDTAD-crosslinked aminosilicones comprising anhydride groups.

* Curing time in oven: 64 h.

Table 3 Shore 00 hardness of EDTAD-crosslinked silicones without anhydride groups.

Table 4: Shore 00 hardness of EDTAD-crosslinked silicones comprising anhydride groups.

Table 5 Silicone aminotriazinyl elastomer formulations

Table 6 Silicone aminotriazinyl elastomer formulations using 4,6-dichloro-s- triazinyl modified aminosilicone

REFERENCES

1. Brook, M. A., Chapter 9. In Silicon in Organic, Organometallic, and Polymer Chemistry, John Wiley & Sons, Inc.: New York, 2000; p 256.

2. Boyer, I. J., Toxicity of dibutyltin, tributyltin and other organotin compounds to humans and to experimental animals. Toxicology 1989, 55 (3), 253-298.

3. Hoyle, C. E.; Bowman, C. N., Thiol-Ene Click Chemistry. Angew. Chem. Int. Edit. 2010, 49 (9), 1540-1573.

4. Treat, N. J.; Fors, B. P.; Kramer, J. W.; Christianson, M.; Chiu, C.-Y.; Read de Alaniz, J.; Hawker, C. J., Controlled Radical Polymerization of Acrylates Regulated by Visible Light. ACS Macro Lett. 2014, 3 (6), 580-584.

5. Jin, F.-L.; Li, X.; Park, S.-J. , Synthesis and application of epoxy resins: A review. J. Ind. Eng. Chem. 2015, 29, 1 -11.

6. Silva, A. L.; Bordado, J. C., Recent Developments in Polyurethane Catalysis: Catalytic Mechanisms Review. Catalysis Reviews 2004, 46 (1 ), 31 -51.

7. Brook, M. A., New Control Over Silicone Synthesis using SiH Chemistry: The Piers-Rubinsztajn Reaction. Chem. Eur. J. 2018, 24 (34), 8458-8469.

8. LaRonde, F. J.; Ragheb, A. M.; Brook, M. A., Controlling silica surfaces using responsive coupling agents. Colloid Poly m. Sci. 2003, 281 (5), 391-400.

9. Pascoal, M.; Brook, M. A.; Gonzaga, F.; Zepeda-Velazquez, L., Thermally controlled silicone functionalization using selective Huisgen reactions. Eur. Polym. J. 2015, 69 (0), 429-437.

10. Genest, A.; Binauld, S.; Pouget, E.; Ganachaud, F.; Fleury, E.; Portinha, D., Going beyond the barriers of aza-Michael reactions: controlling the selectivity of acrylates towards primary amino-PDMS. Polym. Chem. 2017, 8 (3), 624-630.

11. Yu, N.; Zhang, S.; Tang, B.; Ma, W.; Qiu, J., Synthesis of Novel Reactive Disperse Silicon-Containing Dyes and Their Coloring Properties on Silicone Rubbers. Molecules 2018, 23 (1 ), 127.

12. Larson, G. L., Silicon-Based Reducing Agents. Gelest 2004.

13. Eaborn, C., Organosilicon compounds. Butterworths: 1960; p p. 210 of 530.

14. Lickiss, P. D., The Synthesis and Structure of Organosilanols. In Advances in

Inorganic Chemistry, Sykes, A. G., Ed. Academic Press: 1995; Vol. 42, pp 147-262.

15. Lickiss, P. D., Polysilanols. In The Chemistry of Organic Silicon Compounds, Rappoport, Z.; Apeloig, Y., Eds. Wiley: New York, 2001 ; Vol. 3, pp 695-744.

16. Brook, M. A., Silicones. In Silicon in Organic, Organometallic and Polymer

Chemistry, Wiley: New York, 2000; pp 256-308.

17. Reich, L.; Jadrnicek, B. R.; Stivala, S. S., Kinetics of thermal oxidation of polyolefins— A review. Polym. Eng. Sci. 1971 , 11 (4), 265-273.

18. Khatri, A.; Peerzada, M. H.; Mohsin, M.; White, M., A review on developments in dyeing cotton fabrics with reactive dyes for reducing effluent pollution. Journal of Cleaner Production 2015, 87, 50-57.

19. Zheng, H. B.; Wang, Z. Y., Polyimides Derived from Novel Unsymmetric Dianhydride. Macromolecules 2000, 33 (12), 4310-4312.