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Title:
TRANSIENT POLYMER NETWORKS
Document Type and Number:
WIPO Patent Application WO/2020/243835
Kind Code:
A1
Abstract:
The present application provides a method for the preparation of sugar-modified siloxane oligomers or polymers that one their own, or after dilution in an appropriate solvent, become shear thickening and energy dissipating.

Inventors:
BROOK MICHAEL A (CA)
FEINLE ANDREA (CA)
Application Number:
CA2020/050771
Publication Date:
December 10, 2020
Filing Date:
June 04, 2020
Export Citation:
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Assignee:
UNIV MCMASTER (CA)
International Classes:
C09K3/00; B60R19/03; B64C3/00; F03D80/00; F41H1/02; C08G77/38
Domestic Patent References:
WO2014151720A12014-09-25
Foreign References:
JP3867898B22007-01-17
US20080318065A12008-12-25
Other References:
FAICZAK, KYLE, BROOK MICHAEL A., FEINLE ANDREA: "Energy-Dissipating Polymeric Silicone Surfactants", MACROMOLECULAR RAPID COMMUNICATIONS, vol. 41, no. 11, 6 January 2020 (2020-01-06), pages 1 - 6, XP055766559, DOI: 10.1002/marc.202000161
CESERACCIU, L. ET AL.: "Robust and Biodegradable Elastomers Based on Corn Starch and Polydimethylsiloxane (PDMS", ACS APPLIED MATERIALS AND INTERFACES, vol. 7, no. 6, 18 February 2015 (2015-02-18), pages 3742 - 3753, XP055484573, Retrieved from the Internet DOI: 10.1021/am508515z
Attorney, Agent or Firm:
BERESKIN & PARR LLP/S.E.N.C.R.L., S.R.L. (CA)
Download PDF:
Claims:
CLAIMS:

1. A use of a transient polymer network as an energy dissipation material, wherein the transient polymer network is formed from

(i) a compound of Formula II

wherein

R1 0 and R12-R14 are independently selected from Ci-ioalkyl, C2-ioalkenyl,

C2-ioalkynyl, linear and branched siloxanes;

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 R22, wherein the linker R22 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 R22 are substituted with O, NH, N(Ci-6alkyl) or S groups;

and

(ii) a saccharide which reacts with the amine of Y to form a covalent bond to form the transient polymer network.

2. The use of claim 1 , wherein R10 and R12-R14 are independently or simultaneously

selected from Ci ealkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl, linear and branched siloxanes.

3. The use of claim 1 or 2, wherein R10 and R12-R14 are independently or simultaneously selected from Ci salkyl or phenyl.

4. The use of any one of claims 1 to 3, wherein R10 and R12-R14 are methyl.

5. The use of any one of claims 1 to 4, wherein R23-R25 are methyl.

6. The use of any one of claims 1 to 5, wherein Y is -R22-NH2 or -R18-NHRa, wherein

Ra is Ci-ealkyl optionally substituted with amino (Nhte).

7. The use of any one of claims 1 to 5, wherein R22 is selected from Ci ealkyl, Ci- 6alkylene, C2-6alkenyl, C2-6alkenylene, C2-6alkynyl, C2-6alkynylene, C6-ioaryl, or C6- loarylalkyl, and wherein one or more carbons of R22 are substituted with NH, N(Ci-6alkyl) or S group.

8. The use of any claim 7, wherein R22 is selected from Ci-ealkyl, or Ci-6alkylene, wherein one or more of the carbon atom is replaced with one or more nitrogen or sulfur atoms.

9. The use of any one of claims 1 to 8, wherein Y is

10. The use of any one of claims 1 to 9, wherein the saccharide is selected from saccharides containing a lactone or ester group.

1 1 . The use of claim 10, wherein the saccharide is a monosaccharide.

12. The use of claim 10, wherein the saccharide is a disaccharide, oligo- or polysaccharide.

13. The use of any one of claims 1 to 10, wherein the saccharide is gluconolactone, maltonolactone, lactobionolatone, or dextran.

14. The use of any one of claims 1 to 13, wherein the transient polymer network formula comprises polymers of the formula (VIII)

wherein t is an integer from 20 to 2000.

15. The use of any claim 14, wherein t is an integer from 400-1000.

16. The use of any one of claims 1 to 14, wherein the transient polymer network is diluted in a suitable solvent.

17. The use of claim 16, where the solvent is a silicone.

18. The use of claim 17, where the solvent has a viscosity of 0.65-50 centiStokes.

19. The use of claim 18 where the silicone is a cyclic silicone including D4 ((Me2SiO)4), D5 ((Me2SiO)5), D6 ((Me2SiO)6) or a linear silicone Me3Si(OSiMe2)yOSiMe3 where y = 0- 50.

20. The use of any one of claims 1 to 19, wherein the transient polymer network exhibits increased energy dissipation under shear deformation or applied stresses.

21 . The use of any one of claims 1 to 20, wherein the transient polymer network attenuates the impact energy of an impact force.

22. The use of any one of claims 1 to 21 , wherein the transient polymer network is for use in a bullet proof vest, car bumpers, or leading edges of wings or wind turbine blades.

Description:
TRANSIENT POLYMER NETWORKS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application Nos. 62/857,034, 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 sugar-modified silicone polymers that exhibit shear thickening properties by forming transient polymer networks that can be tuned by type of sugar, type of silicone, fraction of sugar on the silicone, molecular weight of the polymer, sugar binding additives and morphology of the sugar substitution telechelic and/or pendant.

BACKGROUND

[0003] Shear thickening fluids (STF) are those for which the viscosity increases with shear rate. 1 Such materials are frequently created by forming colloidal dispersions, typically with solid materials at high solids content in fluids. Under stress, percolated particle/particle interactions lead to viscosity increases as discussed by Barnes in the Journal of Rheology 1989, 2 which is incorporated by reference in its entirety. In the limit, these materials at high shear behave like solids but, once the shear forces are reduced, regain their fluid properties. 3 4

[0004] Shear thickening behavior is of practical utility in many fields. For example, one strategy for body armor 5 · 6 or puncture resistant materials 7 uses shear thickening materials that also contain polymeric fibers. In the area of oil production, STFs may be used to stabilize oil wells. 8 STFs may also be used to increase the yield of recovery of oil from rock. 9

[0005] Transient polymer networks (TPNs) represent an alternative to traditional STFs because they do not require the addition of particles or a secondary phase. They are thus simpler to formulate and their properties are readily tuned. They are comprised of supramolecular polymer chains that reversibly connect via short-lived crosslinks that allow the polymer to flow while maintaining a certain mechanical integrity; 10 TPNs can act elastically under fast deformation but start to flow after the removal of the force, just like shear thickening fluids. Dynamic crosslinks include non-covalent interactions such as metal-ligand coordination, 11 · 12 hydrophobic interactions, 13 · 14 tt-p (pi-pi) stacking 1 1 · 15 or hydrogen bonding. 16 · 17

[0006] Silicone fluids are used in many applications because of their thermal and electrical stability, low surface energy, and ability to undergo degradation in the environment, among others. An STF derived from silicones is“Silly Putty” or“Funny Putty” that is prepared by reacting silicone fluids with boric acid. 18 In this case, the shear thickening properties have been reported to arise through hydrogen bonding interactions between boron-OH entities which may be chemically tethered to silicones oils, or dispersed within them.

[0007] Silicones may also be used as fluids into which associated colloids are dispersed to create STF. For example, silica particles (< 10 urn) may be dispersed in polyethylene glycol). When this mixture is dispersed in silicone oils it can create shear thickening emulsions. 19 Otherwise, there are relatively few references to silicone STF, most of which involve silicone fluids acting as thickening agents, rather than shear thickening fluids per se. 20-22

[0008] Silicones are readily modified by organic functional groups and polymers. Hydrophilically-modified silicone materials are well known in the art and widely available in commerce, and include those containing carboxy, amino and thiol groups. An important class of organically-modified silicone polymers are surfactants based on polyethers, which find use as wetting agents for agriculture, 23 foam stabilizers, 24 among other applications. Less well known are silicones modified with highly hydrophilic moieties based on saccharides. In the case of silicone polymers, Wagner et al. described a series of sugar-silicones that involved a sequence of protection/deprotection steps with an intervening step involving linkage to the sugar based using hydrosilylation. 25-34 Biocatalytic processes have also been exploited. 35 More recently, Fleury et al. described the use of copper-catalyzed, azide/alkyne click chemistry to create sugar silicones. 36 · 37 A more straightforward approach links sugars to silicones via amide bonds using a process that avoids protecting groups and catalysts. Such compounds are known in area of coupling agents, 38 and the same process has been used to create silicone surfactants. 39

SUMMARY

[0009] It has now been discovered that the attachment of sugar moieties to silicone polymers give products able to form transient polymer networks, that exhibit shear thickening behavior, and which provide tuneable energy absorption. The degree of thickening depends on the specific sugar utilized, the fraction of sugar in the molecules, and the morphology/distribution of the sugars on the silicone chain(s). In one embodiment, the sugar-siloxanes may, depending on sugar/silicone content, be thermoplastic elastomers, rigid resins, or viscous fluids. In other embodiments, responsive properties are further manipulated by dispersing the sugar silicones into fluids/solvents, particularly silicone oils. In another embodiment, the dynamic behavior of sugar silicones may be further adjusted through the physical interactions of metal oxides or non-metal oxides. In another embodiment, the hydrophobic behavior of the silicones is conveyed to polar substrates, such as paper; the paper/sugar interactions anchor the silicone to the substrate. In another embodiment, cellulose (for example, paper) has affinity for the saccharides in the sugar-siloxanes that anchors the sugar siloxane to the paper and repels the hydrophobic portion of the polymer.

[0010] A variety of synthetic methods may be used to attach sugars to silicones. Among these are several methods that exploit aminoalkylsilicones, including addition of amines to saccharidic aldehydes created by oxidation of primary alcohols, using TEMPO, 40 43 for example, or of vicinal alcohols by periodate 44 or other oxidants. Improved stability of the resulting imine linkages is typically achieved by reduction to the amine. 45 A particularly convenient method involves the formation of an amide by reacting a sugar lactone, typically formed by oxidation of the reducing end of sugars, with aminoalkylsilicones, 38 39 which are widely available in commerce.

[001 1 ] In one embodiment, the present disclosure therefore includes a process for preparing transient polymer network sugar-siloxane oligomers or polymers by combining

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

wherein

R 1 -R 10 and R 12 -R 21 are independently selected from Ci-ioalkyl, C2-ioalkenyl,

C2-ioalkynyl, linear and branched siloxanes;

n is 0-1000, if n=0, m = 2-60, if n>10, then m = 1-60% of n but must be at least 2; 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 R 22 , 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 may be substituted with O, NH, NR or S groups;

with

(ii) a sugar (saccharide) or polyol having 5 or more OH groups, reacts with an amine to form a covalent bond.

[0012] In one embodiment, the sugar is or contains a lactone, which for example, may be prepared by oxidation of the reducing of native sugars with a variety of oxidants among which the most prominent one is iodine. 46 · 47 In one embodiment, examples of the saccharide lactones used to prepare the TPN include monosaccharides such as gluconolactone (GDL), and disaccharides like maltonolactone or lactobionolatone (see for example, Figure 1 ) or oligo- or polysaccharides, like dextran. 38 It will be understood by those skilled in the art that many mono-, oligo- and polysaccharides are available that already possess, or can be readily modified to contain, functional groups that are able to react with a primary or secondary amine.

[0013] In one embodiment, the polyol has 5-20 OH groups, or 5-10 OH groups, or 5-8 OH groups. [0014] In another embodiment, Y is an amino-modified group, wherein there may be more than one nitrogen in Y, or a sulfur atom. In one embodiment, Y is -R 22 -NH2, and for example

[0015] In another embodiment, the present disclosure includes the use of the transient polymer network sugar-siloxane oligomers or polymers in fluids (such as silicone fluids or oils) as energy dissipating materials.

[0016] The present disclosure also includes a method for the dispersion of sugar- modified silicones in fluids, for example silicone fluids.

[0017] The present disclosure also includes a method to modify the physical properties, particularly viscoelasticity, of sugar-siloxane materials by adding entities known to bind to sugars, including metal oxides, or non-metal oxides.

[0018] The present disclosure further demonstrates that elastomeric sugar- siloxanes are thermoplastic, which unlike thermosets, allows them to be readily reused or repurposed.

[0019] In another embodiment of the disclosure, the transient polymer network sugar-siloxane oligomers or polymers adhere to polar substrates, such as cellulosic substrates such as paper. In one embodiment, cellulosic paper is converted to a siliconized adhesive release paper.

[0020] 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

[0021] The embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0022] Figure 1 shows products of the described process in one embodiment of the disclosure derived from telechelic aminoalkylsilicones and various saccharide lactones. [0023] Figure 2 shows a comparison of energy dissipation as a function of dilution of the sugar-siloxanes in Ds (Me2SiO)s in one embodiment of the disclosure. The maximum bounce height is shown, which increases with increasing sugar-siloxane concentration. Over time gravity pulls the ball to the bottom, as shown at right.

[0024] Figure 3 shows a model of the sugar-siloxanes with additional physical crosslinkers including metal oxides like boric acid or non-metal oxides, such as T1O2 (left), and self-associating under compressive stress (right).

[0025] Figure 4 Temperature dependent dynamic viscosity of the sample DMSG- 63 measured at a constant shear rate of 0.1 s 1 . Inset: appearance of the solid after melting then solidification, or after grinding, respectively, demonstrating thermoplasticity.

DETAILED DESCRIPTION OF THE APPLICATION

(I) DEFINITIONS

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031 ] T erms 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.

[0032] 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.

[0033] 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.

[0034] The term“energy dissipation material” as used herein refers to a material which can attenuate, lessen or reduce the impact energy of an impact force.

[0035] 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.

[0036] 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 “CniV. 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. In the case of aminoalkenyl compounds, the N shall be bonded to the linker via an sp 3 hybridized carbon. [0037] 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“CniV. 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. In the case of aminoalkynyl compounds, the N shall be bonded to the linker via an sp 3 hybridized carbon.

[0038] The suffix“ene” as used herein, for example in“alkylene”, “alkenylene” means divalent hydrocarbon radicals having straight, branched or cyclic moieties or combinations thereof.

[0039] 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.

[0040] The term monomer is used to describe a silane or siloxane moiety that is possible of undergoing reactions to give siloxane products of increased molecular weight.

[0041] 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 <20.

[0042] The term “aminoalkylsilicone” as used herein, refers to a primary or secondary amine connected to the silicone polymer through a linker R 22 .

The term“linear siloxane” as used herein refers to a group comprising units, wherein R, R', R" and R'" are independently selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl, arranged in linearfashion. The number of units may be

R

R""— Si-1- between 1 and 10 with the terminal group being R' , wherein R"" is selected from Ci-ioalkyl, C2-ioalkenyl, C2-ioalkynyl and aryl. [0044] The term“branched siloxane” as used herein refers to a group comprising

R R"

-i-Si-O-Si— :

< I I (

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

R

O-Si-jl·

I 1

at least one of R, R', R" and R'" is R' . The number of units may be between 1 and 10

R

R""— Si-|- i <

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

[0045] The term“saccharide” as used herein refers to any molecule comprising a saccharide moiety and encompasses both monosaccharides and polysaccharides such as di-, tri-, tetra-, oligo-saccharides, etc. A“monosaccharide”, for example, as would be known to a person skilled in the art, refers to any carbohydrate (“a simple sugar”), such as those, tetrose, pentose or hexose (including both aldose and ketose forms) that cannot be hydrolyzed to form simpler sugars, oligo- or polymeric saccharides, such as dextran.

(II) TRANSIENT POLYMER NETWORKS

[0046] In one embodiment, the present disclosure includes a process for preparing transient polymer network sugar-siloxane oligomers or polymers by combining

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

wherein R 1 -R 10 and R 12 -R 21 are independently selected from Ci-ioalkyl, C2-ioalkenyl,

C2-ioalkynyl, linear and branched siloxanes;

n is 0-2000 (or 0-1000), if n=0, m = 2-60, if n>10, then m = 1 -60% of n;

q is 0-2000 (or 0-1000), r = 0-60;

p is 0-2000 (or 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 R 22 , 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 may be substituted with O, NH, NR or S groups;

with

(ii) a sugar (saccharide) or polyol (having 5 or more OH groups) which reacts with an amine to form a covalent bond.

[0047] In one embodiment, the moieties

are randomly distributed throughout the compounds of formula (I) or (III) and the integers ‘n’,‘m’,‘q’ and Ύ represent the overall number of moieties throughout the compound. In another 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, but m must be at least 2.

[0048] 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.

[0049] In another embodiment, q is about 0-2000, or about 10-2000, or about 10- 1000, or about 50-1000, or about 100-1000. In one embodiment, r is 0-60, or 2-60, or 3- 60, or 2-40, or 2-20, or 2-10.

[0050] In another embodiment, p is about 0-2000, or about 10-2000, or about 10- 1000, or about 50-1000, or about 100-1000.

[0051] In one embodiment, R 1 -R 10 and R 12 -R 21 are independently or simultaneously

selected from Ci-ealkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl, linear and branched siloxanes.

[0052] In one embodiment, R 1 -R 10 and R 12 -R 21 are independently or simultaneously

selected from Ci ealkyl, C2-6alkenyl, C2-6alkynyl, C6-ioaryl, linear and branched siloxanes.

[0053] In one embodiment, R 1 -R 10 and R 12 -R 21 are independently or simultaneously selected from Ci salkyl or phenyl. In one embodiment, R 1 -R 10 and R 12 -R 21 are Chta.

[0054] In one embodiment, R 2 is Y.

[0055] In another embodiment, R 23 -R 25 are independently or simultaneously selected from Ci ealkyl, C2-6alkenyl, C2-6alkynyl and C6-ioaryl. In another embodiment, R 23 -R 25 are independently or simultaneously selected from Ci salkyl or phenyl. In one embodiment, R 23 -R 25 are Chb.

[0056] 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 22 , 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 22 may be replaced with one or more nitrogen atoms (NH or N-(Ci-6alkyl)) or sulfur atoms. In another embodiment, Y is -R 22 -NH2 or -R 18 -NHR a , wherein R a is Ci ealkyl optionally substituted with amino (NH2). In another embodiment, R 22 is selected from Ci- ealkyl, Ci-6alkylene, C2-6alkenyl, C2-6alkenylene, C2-6alkynyl, C2-6alkynylene, C6-ioaryl, or C6-ioarylalkyl. In another embodiment, R 22 is selected from Ci ealkyl, or Ci-6alkylene, wherein one or more of the carbon atom is replaced with one or more nitrogen or sulfur atoms.

[0057] In one embodiment, Y is -R 22 -NH2 or -R 22 -(NH2)2 and for example

[0058] In an embodiment, the addition of the aminoalkylsilicone (a compound of formula (I), (II) or (III), to a sugar lactone leads to sugar-siloxanes (for example, DMSG) that exhibit energy dissipating properties.

[0059] In one embodiment, the aminoalkylsilicones of the compounds of formula (I), (II) or (II) include the mono-, telechelic, and pendant aminopropylsilicones of the Formula IV, V and VI, where s, t, u + v are integers that range from 20 to 1000. In one embodiment, the compound of formula (II) is a compound of Formula V. In one embodiment, the mass ratio of sugar to silicone to form the shear thickening properties or transient polymer networks is 0.05% sugar:99.95% silicone up to 25% sugar:75% silicone. In some embodiments, at higher sugar concentrations it may be necessary to dilute the material before the TPN behavior is apparent. In one embodiment, the transient polymer networks are formed by, for example, grafting GDL onto the aminosilicones of formula (V), for example DMS A-35 (H 2 N(CH2)3SiMe2(OSiMe2)p)SiMe2(CH2)3NH2 MW ~ 50,000 g mol 1 , p ~ 675, -0.05% amine) converts the viscous liquid starting material into a TPN DMSG-671.

[0060] In one embodiment, compound of formula (I), (II), or (III) is selected from

wherein s, t = 0-1000 and u=1 , v= 0; or v = 2-225 and u = at least 1 and up to 12% v.

[0061] In another embodiment, the compound of formula (II) is , wherein t is an integer that ranges from 20 to 1000.

[0062] In an embodiment, it is possible to modify all or only some of the available amine groups of the compounds of formula (I), (II) or (III). For example, both Formula VII and VIII are TPNs, but to different degrees depending on the value of t, where t is an integer from 20 to 2000 (or 20-1000):

[0063] In one embodiment, analogous aminoalkylsilcones that possess shorter silicone backbone (a lower value of t) may similarly be converted to GDL-modified aminosilicones DMSG. In one embodiment, the resulting products are resins or elastomers, where the minimum value of t is 20 (or about 20-50 for a resin, and about 50- 100 for an elastomer). In further embodiments, the maximum value is dependent on the nature of the sugar with higher values of permissible as the size of the saccharide is increased. In some embodiments, for sugar-siloxanes based on glucose, t is an integer up to about 1000 (20-1000, or 100-1000, or 500-1000). For example, t in a sugar-siloxane in which the size of the saccharide is doubled, for example, maltanolactone, t is an integer up to about 2000 (20-1000, 100-2000, 200-2000 or 500-2000). In another embodiment, t is an integer from 0-2000, or about 10-2000, or about 50-2000, or about 100-2000.

[0064] In an embodiment, the transient polymer network properties of the sugar- siloxanes are tuned by dilution with an appropriate solvent, such as silicone fluids or oils. In one embodiment, some sugar-silicones are converted into TPN (see Figure 3) by dilution in an appropriate solvent. In one embodiment, the solvent is silicone oils, including both cyclic silicone monomers and linear and branched silicone oligomers and polymers.

[0065] In one embodiment, the solvent is a silicone. In another embodiment, the solvent has a viscosity of 0.65-50 centiStokes. In another embodiment, the silicone is a cyclic silicone including D4 ((Me2SiO)4), Ds ((Me2SiO)s), D6 ((Me2SiO)6) or a linear silicone Me3Si(OSiMe2)yOSiMe3 where y = 0-50.

[0066] In another embodiment, the sugar moieties of the TPNs interact with compounds which have an affinity for saccharides, including non-metal oxides boron- derived compounds such as boric acid or boronic acids and metal oxides, including titanium dioxide (see Figure 3 for example). In one embodiment, these interactions act as weak to strong crosslinkers allowing one to increase the viscosity, or induce elasticity, by controlling the amount of additive.

[0067] In one embodiment, the present disclosure is also directed to transient polymer networks formed from the reaction of a compound of formula (I), (II) and/or (III) and a saccharide, further comprising a non-metal oxide, such as boric acid, boronic acid or other metal oxides such as titanium dioxide, which crosslinks the saccharide moieties. In one embodiment, the compounds are transient polymer networks which act as energy dissipation materials to lessen or reduce the impact energy of an impact force. In one embodiment, the present disclosure is directed to a transient polymer network comprising

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

wherein R 1 -R 10 and R 12 -R 21 are independently selected from Ci-ioalkyl, C2-ioalkenyl,

C2-ioalkynyl, linear and branched siloxanes;

n is 0-2000 (or 0-1000), if n=0, m = 2-60, if n>10, then m = 1 -60% of n;

q is 0-2000 (or 0-1000), r = 0-60;

p is 0-2000 (or 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 R 22 , 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 may be substituted with O, NH, NR or S groups;

with

(ii) a sugar (saccharide) or polyol (having 5 or more OH groups) which reacts with an amine to form a covalent bond;

(iii) a cross-linker such as a non-metal oxide, such as boric acid, boronic acid or other metal oxides such as titanium dioxide,

which forms a crosslinked transient polymer network.

[0068] In a further embodiment, sugar-siloxanes strongly interact with polar substrates including polysaccharides such as cellulose. In one embodiment, the sugar interacts to anchor the sugar-siloxane to the cellulose such that the surface is rendered low adhesion, as is required for release papers. In one embodiment, the low adhesion strength to sugar-siloxane paper is comparable to normal elastomer coated release papers (for example, address labels,“Hello my name is” stickers), and adhesive films may be contacted multiple times to either type of release papers without significant changing in the degree of adhesion. In another embodiment, the present disclosure is directed to the use of the transient polymer networks as adhesives for release papers. [0069] In an embodiment, energy dissipating materials may be used for protection against impact, for example, bullet proof vest, car bumpers, leading edges of wings or wind turbine blades, and also for energy recovery applications, such as energy recovering running shoes.

[0070] In another embodiment, the present disclosure relates to the use of the transient polymer networks as energy dissipation material, wherein the transient polymer network is formed from

(i) a compound of Formula I, II or III as defined above; and

(ii) a saccharide or polyol (having more than 5 OH groups) which reacts with the amine of the compound of formula (I), (II) or (III), to form a covalent bond resulting in the transient polymer network.

[0071] In one embodiment, the polyol has 5-20 OH groups, or 5-10 OH groups, or 5-8 OH groups.

[0072] In another embodiment, the transient polymer network exhibits increased energy dissipation under shear deformation or applied stresses. In another embodiment, the transient polymer network attenuates the impact energy of an impact force.

[0073] In another embodiment, the disclosure also includes a method of reducing or attenuating the impact energy of an impact force on a substrate, the method comprising coating the substrate with a transient polymer network as defined herein, wherein the transient polymer network attenuates or lessens the impact energy when substrate is contacted with an impact force.

[0074] 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)

wherein each X is independently a leaving group such that, after polymerization, X is replaced with O (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.

[0075] 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 .

[0076] In another embodiment, compounds of the formula (III) are obtained in a similar manner when R 2 is Y.

[0077] 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.

EXAMPLES Materials

[0078] Telechelic 3-(aminopropyl)-terminated polydimethylsiloxanes: DMS-A1 1 (850-900 g mo ), DMS-A15 (3,000 g moM), DMS-A21 (5,000 g mol 1 ), DMS-A31 (25,000 g mol 1 ), DMS-A35 (50,000 g mol 1 ), octamethyltetracyclosiloxane (D4, (Me2SiO)4), and decamethylcyclopentasiloxane (Ds, (Me2SiO)s), dodecamethylcyclohexasiloxane (D6, (Me2SiO)6), and the linear silicones Me3Si(OSiMe2)wOSiMe3 DMS-T02 w ~ 7, DMS-T03 w ~ 10, DMS-T05 w ~ 13 were purchased from Gelest. Octamethyltrisiloxane, titanium (IV) isopropoxide (>97%), titanium (IV) diisopropoxide bis(acetylacetonate) (75% in isopropyl alcohol), d-gluconolactone, and isopropanol were purchased from Sigma- Aldrich. All compounds were used as received.

Methods

[0079] 1 H-NMR spectra were recorded on a Bruker Advance 600 MHz nuclear magnetic resonance spectrometer using the deuterated solvent chloroform-d.

[0080] Rheology measurements were performed using a TA Instruments HR-2 Rheometer equipped with a 40 mm 1.0° cone and a Peltier plate. The gap between the two plates was set to 200 pm for all experiments. T emperature dependent measurements were conducted between 100 and -10 °C using a heating or cooling ramp of 15 °C min 1 . For the oscillation test, the strain was set to 5% and the time dependent measurements were performed at a constant angular frequency of 100 rad * s 1 . For the creep and creep- recovery test, a 1000 Pa strain was used and the creep as well as recovery time was set to 10 s.

[0081] Dynamic Scanning Calorimetry was performed on a TA-instruments DSC Q20 calorimeter.

[0082] FTIR data was collected a Thermo Scientific Nicolet 6700 FT-IR spectrometer equipped with a Smart iTX attenuated total reflectance (ATR) attachment

Example 1 : Synthesis of GDL-modified aminosilicones

[0083] GDL-modified aminosilicones DMSG were prepared using telechelic 3- (aminopropyl)-terminated polydimethylsiloxane and D-gluconolactone in IPA at room temperature. In a typical synthesis shown for the bis-modification of a telechelic aminopropylsilicone DMS-A15 (MW ~ 3000 g mol 1 , 1-1.2% amine), 4 mmol (0.71 g) of D- gluconolactone was added to a solution of DMS-A15 (2 mmol, 6.0 g) in IPA (V = 20 mL) (Figure 1 , compound VIII). The mixture was stirred at room temperature until the suspension turned into a transparent solution. Reaction completion was confirmed by FT- IR spectroscopy, as shown by the disappearance of the lactone signal at 1700 cm 1 and the formation of two new peaks at 1644 cm 1 and 1539 cm 1 , respectively. After evaporation of the solvent at 40 °C in vacuum, DMSG-36 was obtained as a white solid (1.65 mmol, 82% recovered yield).

[0084] 1 H-NMR (600 MHz, chloroform-d, ppm) d = 0.05 (Si-CHs (1 )), 0.51 (4H, Si- CH 2 (2), 0.86 (4H, CH 2 (3)), 3.14 (2H, CH (d)), 3.26 (2H, CH (c)), 3.69 (4H, CH 2 (4)), 3.78 (4H, CH 2 (e)), 4.1 1 (m, 2H, CH (b)), 4.29 (m, 3H, CH (a)). IR (ATR-IR, cm-1 ): 3360, 2962, 2904, 1644, 1539, 1412, 1257, 1079, 1009, 863, 787, 684; note: without wishing to be constrained by theory, the specific signals in the spectrum assigned as shown below.

[0085] All other GDL-modified aminosilicones (Table 1 ) were synthesized following the synthesis procedure described above. Physical and thermal properties are shown in Table 2.

Example 2: Preparation of DMSG dispersions in cyclopentasiloxane

[0086] For the preparation of the DMSG dispersions in Ds, the respective amount of the DMSG (T able 3) was weighed into a polypropylene cup and the solvent was added. The mixture was stirred until the DMSG was dispersed in the solvent and no phase separation was visually observed anymore.

Example 3: Energy Dissipation

[0087] T o investigate energy dissipation properties, 2.5 g of the sample was placed into a 14 mm glass diameter test tube. Steel balls with different diameters and different weights (6 mm, 0.43 g; 8 mm, 1 .37 g, 10 mm, 2.91 g; 12 mm, 6.95 g) were dropped from two different heights (10 cm, 75 cm) onto the sample and the height of the bouncing balls after hitting the sample for the first time was measured (Figure 2, Table 4). The degree of energy absorption can be tailored simply by controlling the sugar/silicone ratio. [0088] The effect of different silicone fluids (Table 5) to affect the ability of DMSG- 63 dispersions in silicone oils to dissipate energy was measured via constant strain oscillatory frequency rheology measurements. The measured tan(delta) values are given in Table 6, which show that the energy dissipation can also be tuned by nature of the dissolving medium.

[0089] In the absence of a solvent DMSG-63 (VIII, t = 63) is not a TPN, but dilution of the material with Ds ((Me2SiO)s) turns it into one. The magnitude of energy dissipation may also tuned for viscous fluids made less viscous by dilution. The impact of dilution on the TPN properties is demonstrated in Figure 2 (Table 4).

Example 4: Thermal behavior

[0090] Temperature dependent viscosity measurements of solid samples DMSG- 36 and DMSG-63 were taken using rheology at a constant shear rate of 0.1 s 1 . A high thermal dependency of the viscosity and, thus, thermoplastic behaviour was observed for both samples; they immediately turn into pliable and moldable fluids upon heating but solidified upon cooling (inset Figure 4). No significant changes in the curves were detected after repeated heating and cooling (DMSG-63 Figure 4). The melting temperature depended on sugar content (Table 7). See also Table 2.

Example 5: Tuning viscoelastic properties by use of sugar binding agents boric acid (BA) of T1O2 behavior

Preparation of BA crosslinked DMSG

[0091] Boric acid (BA) crosslinked DMSG elastomers were prepared by the addition of DMSG-n (with n being the average silicone chain length, 3.0 g) in I PA (V = 2 mL) to a solution of boric acid (H3BO3, m = 0 -0.216 g, see Table 8) in IPA (V = 2 mL). The mixture was mixed in a capped polypropylene container (Flacktek size 10) using a SpeedMixerTM (FlackTek) to ensure homogeneity (3500 rpm, 30 s). Thereafter the cap was removed, and the solvent evaporated. The determined Young ' s moduli of elastomers containing DMSG with different molecular weights or different amount of BA are given in Table 9 and show an increase in modulus with increasing BA content.

Preparation of Ti02-crosslinked DMSG elastomers [0092] TiCte-crosslinked DMSG elastomers were prepared by dissolution of the respective DMSG in I PA and addition of a solution of titanium (IV) isopropoxide (TTIP) or titanium (IV) diisopropoxide bis(acetylacetonate) in isopropanol in open air. The respective amounts are given in Table 10. After mixing, isopropanol was evaporated, and elastomers were obtained. The materials all exhibit higher crosslinking properties than the DMSG precursors.

Hydrophobizing hydrophilic surfaces

[0093] The ability of sugar silicones to interact with hydroxy-terminated compounds, e.g., cellulose via hydrogen bonding was investigated by soaking commercial copy paper (5 cm x 2 cm) for 2 s in a 1 wt% solution of DMSG-63 in isopropanol (10 ml_). After drying of the coated copy paper at room temperature, commercial adhesives were contacted to the coated copy paper. The adhesion strength was comparable (low) to normal elastomer coated release paper. The adhesives could be contacted multiple times to both release papers without changing the subsequent adhesion of the label to uncoated copy paper.

[0094] 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. Ring-opening amide formation (Figure 1 - > VIII) gives DMSG of different silicone chain lengths.

DMSG-n Mw DMS-n DMS-n (g) GDL GDL (g) Yield

(g.mol 1 ) (mmol) (mmol) (%)

_ (h in cSt) _

DMSG-36 3,000 DMS-15 6.00 4.00 0.71 82

(50-60) (2.00)

DMSG-63 5,000 DMS-21 10.00 4.00 0.71 83

(100-120) (2.00)

DMSG-333 25,000 DMS-31 5.00 0.40 0.07 77

(900- (0.20)

1 , 100)

DMSG-671 50,000 DMS-35 5.00 0.20 0.04 74

(4,000- (0.10)

6,000)

a The volume of I PA used in all cases was 20 ml_.

Table 2. Physical properties of DMSG

Product 3 Appearance DMSG-n Dynamic Melting Crossover Yield viscosity 13 temperature frequency 0 (%)

DMSG-36 Translucent solid _d 89 °C - 82

DMSG-63 5700 Pa.s 98 °C - 83

DMSG-333 Highly viscous, 550 Pa.s -44 °C 39 rad. s 1 77 transparent fluid

DMSG-671 1700 Pa.s -43 °C 22 rad. S 1 74 a The DMSG-number reflects the DP of the telechelic polymer. Thus, DMSG-671 = SugarN(CH2)3Si(OSiMe2)67iSi(CH2)3NSugar. b Dynamic viscosity at a shear rate of 0.1 s _ 1 and 25 °C. Crossover frequency where G’=G”. d Viscosity too high to be measured at

25 °C.

Table 3. Weight masses of GDL-mod. silicones and Ds for the preparation of various dispersions of GDL-modified silicones in Ds shown for the bis-modified telechelic aminopropylsilicone derived from DMS-A21 (DMSG-63).

mass DMSG-63 in g mass Ds in g

Table 4. Energy absorbance of a sugar-siloxane as a function of dilution in silicone oil (Ds)

a Dropping height: 10 cm, weight of steel ball: 0.430 g. See Figure 2.

b Dropping height: 10 cm, weight of steel ball: 1 .369 g

c Dropping height: 10 cm, weight of steel ball: 2.907 g

d Dropping height: 10 cm, weight of steel ball: 6.953 g

e Dropping height: 50 cm, weight of steel ball: 0.430 g Table 5. Weight masses of DMSG-63) and the respective silicone oil (Octamethyltrisiloxane, DMS T02, DMS T03, DMS T05, D4, Ds, De) for the preparation of various dispersions of DMSG-63) in silicone oil.

m (DMSG-63) in g m (silicone oil) in g

10.0 wt% 0.21 2.25

20.0 wt% 0.50 2.00

25.0 wt% 0.63 1.87

30.0 wt% 0.75 1.75

40.0 wt% 1 .00 1.50

50.0 wt% 1 .25 1.25

Table 6. tan(delta) values for the DMSG-63 dispersions in various linear and cyclic silicone oils.

tan(delta)

20 wt% 25 wt% 30 wt% 40 wt% 50 wt%

Octamethyltrisiloxane 9.4 674 - 2.7

T02 7.3 4.6 2.6

T03 5.1 3.1 2.2

T05 3.5 2.5 1 .9

D 4 9.3 7.9 5.0 1 .9

Ds 9.8 8.3 5.1 1 .9

Ds 9.7 8.2 5.5 3.2

Table 7. Crystallization (T c ) and melting (T m ) temperatures of aminopropylsilicones and gluconamidosilicones determined by DSC.

_ Tc (° C) _ Tm (° C)

DMS-36 - -51

DMSG-36 - 89

DMS-63 - -49, -43

DMSG-63 - 98

DMS-333 - -48, -37

DMSG-333 -74 -44

DMS-671 -80 -45, -37

DMSG-671 -71 -43 Table 8. Selected examples and required amounts for the preparation of boric-acid crosslinked GDL-modified aminosilicone elastomers.

Sample Name m n (OH) m (HsBOs) n (HsBOs) [OH]:[H 3 BOs]

(DMSGn)

BA3- DMSG- 3.0 g 10.50 mmol 216 mg 3.50 mmol 3 : 1

36

BA3- DMSG- “ “ 120 mg 1.94 mmol 3 : 1

63

BA3- DMSG- “ 24 mg 0.39 mmol 3 : 1

333

BA10- DMSG- “ 5.60 mmol 33 mg 0.53 mmol 10 : 1

63

BA3- DMSG- “ “ 120 mg 1.94 mmol 3 : 1

63

BA2- DMSG- “ “ 180 mg 2.91 mmol 2 : 1

63

Table 9. Young’s moduli of BA crosslinked DMSG elastomers prepared with different aminopropylsilicones of different molecular weights or different amounts of BA.

Sample Name wt% BA [0H]:[H 3 B0 3 ] Young ' s Modulus

BA3- DMSG-36 7 3 ~ n 5.93

BA3- DMSG-63 4 3 : 1 2.79

BA3- DMSG-333 1 3 : 1 0.22

BA0- DMSG-63 0 1 .19

BA10- DMSG-63 1 10 : 1 1 .52

BA3- DMSG-63 4 3 : 1 2.79

BA2- DMSG-63 6 2 : 1 2.99

Table 10. Preparation of crosslinked DMSG elastomers with TTIP or TAA. The GDL- modified aminosilicones were dissolved in isopropanol (V = 4 mL) before a solution of TTIP or TAA in isopropanol (V = 4 mL) was added.

Sample Name m (DMSG-n) n (DMSG-n) m (TTIP) n (TTIP)

Ti-GAS36 750 mg 0.22 mmol 63.5 mg 0.22 mmol

Ti-GAS63 750 mg 0.14 mmol 39.8 mg 0.14 mmol Ti-GAS333 750 mg 0.03 mmol 8.4 mg 0.03 mmol

Ti-GAS671 750 mg 0.01 mmol 4.2 mg 0.01 mmol

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