Injectable and moldable elastomers and medical devices

Abstract

In this invention synthetic bottlebrush and comb-like (multi) block polymers (copolymers) can be formulated to form on demand non leachable bottlebrush elastomers with tunable curing time as well as adjustable mechanical and optical properties. The disclosed formulations can be injected directly into the tissue followed up by curing at the physiological conditions. The curing process can be designed with and without using catalysts, initiators, and external stimuli. The cured polymer yield supersoft elastomer with tissue-mimetic mechanical properties.

Description

WSGR Docket No. Accolens-701.601 INJECTABLE AND MOLDABLE ELASTOMERS AND MEDICAL DEVICES INCORPORATION BY REFERENCE

[0001] This application claims the benefit of U. S. Provisional Application Serial No. 63 / 649,745 filed May 20, 2024 which is hereby incorporated by reference in its entirety. SUMMARY In one aspect, is a composition comprising a polymer network comprising a reaction product of copolymer A and reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, and wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, -N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

[0002] In some embodiments, copolymer A comprises siloxane, polyfluorosiloxane, or polybutyl acrylate. In some embodiments, copolymer A is a reaction product of one or more macromonomers. In some embodiments, copolymer A is a block copolymer or random copolymer. In some embodiments, each block of the copolymer can be a homopolymer or a random copolymer. In some embodiments, copolymer A is polymerized via a controlled radical polymerization process. In some embodiments, copolymer A comprises a random copolymer, a block copolymer, or a combination of random and block copolymers. In some embodiments, copolymer A has a multi- arm structure from 3 to 8 arms. In some embodiments, copolymer A comprises one or more -OH, - SH, -NH2, -N3, or furan groups. In some embodiments, copolymer A comprises one or more -OH groups. In some embodiments, the -OH group can be converted to an acrylate, methacrylate, allyl, vinyl, amine, or thiol group.

[0003] In some embodiments, reactant B is a copolymer, wherein the copolymer is a bottlebrush polymer, comb polymer, linear polymer with a branched, multi-arm, structure, or a combination thereof. In some embodiments, reactant B comprises more than one reactive moiety B, wherein reactive moiety B is -SH, -NH2, -N3, furan, maleimide, DBCO, acrylate, methylacrylate, allyl, or vinyl. In some embodiments, reactant B comprises more than one reactive moiety B, wherein the reactive moiety B is -NH2. In some embodiments, reactant B comprises a degradable site. In some embodiments, the degradable site is degraded using light or local high temperature. InWSGR Docket No. Accolens-701.601 some embodiments, the degradable site comprises nitro benzyl, diene, dienophile, peroxide, azo, or a combination thereof.

[0004] In some embodiments, the copolymer A is a reaction product of monomers that comprise a structure of Formula (Ia), Formula (Ib), and / or Formula (Ic):wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl; each R1’is independently hydrogen or C1-C3 alkyl; each R2is independently C1-C10alkyl group or phenyl; each R3is independently C1-C4alkyl group or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl group; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each a is independently 0 to 10; each b is independently 0 to 10; each c is independently 0 to 10; each d is independently 0 to 10; each e is independently 0 to 10; each f is independently 0 to 10; each g is independently 0 to 50; each a1 is independently 0 to 10; each b1 is independently 0 to 10; each c1 is independently 0 to 10; each d1 is independently 0 to 10; each e1 is independently 0 to 10; each f1 is independently 0 to 10; and each p is independently 0 to 10.

[0005] In some embodiments, wherein the copolymer A comprises a structure of Formula (II):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl; each R1’is independently hydrogen or C1-C3 alkyl; each R2is independently C1-C10 alkyl group or phenyl; each R3is independently C1-C4 alkyl group or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl group; each a is independently 0 to 10; each b is independently 0 to 4; each c is independently 0 or 1; each d is independently 0 to 4; each e is independently 0 to 9; each f is independently 0 to 4; each g is independently 0 to 50; each a1 is independently 0 to 10; each b1 is independently 0 to 4; each c1 is independently 0 or 1; each d1 is independently 0 to 4; each e1 is independently 0 to 9; each f1 is independently 0 to 4; each m is independently1 to 5000; each n is independently 1 to 5000; each o is independently 0 to 5000; and each p is independently 0 to 10.

[0006] In some embodiments, the copolymer A comprises a structure of Formula (III):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3alkyl group; each R6is independently H or C1-C10alkyl group; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each R8is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each g is independently 0 to 50; each m is independently1 to 5000; each n is independently 1 to 5000; each o is independently 0 to 5000; each q is independently 1 to 10; and each r is independently 1 to 10.

[0007] In some embodiments, the copolymer A comprises a structure of Formula (IV):wherein: each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl group; each R6is independently H or C1-C10 alkyl group; each m1 is independently 0 to 5000; each m2 is independently 0 to 5000; each n1 is independently 0 to 5000; each n2 is independently 0 to 5000; each q is independently 1 to 10; each p is independently 0 to 10; each s is independent 2 to 10; x is 1 to 6; and y is 1 to 6.

[0008] In some embodiments, each Z is -O-. In some embodiments, each Z is -NH-. In some embodiments, each R1is independently hydrogen or methyl. In some embodiments, each R1’isWSGR Docket No. Accolens-701.601 independently hydrogen or methyl. In some embodiments, each R2is independently C1-C10alkyl group. In some embodiments, each R2is independently C1-C3 alkyl. In some embodiments, each R3is independently C1-C4 alkyl. In some embodiments, each R4is independently C1-C5 alkyl. In some embodiments, each R5is independently -OH. In some embodiments, each R6is independently H or methyl. In some embodiments, each R6is independently H. In some embodiments, each R7is independently -OH. In some embodiments, each R8is independently -OH. In some embodiments, wherein each g is independently 0 to 10. In some embodiments, each a is independently 0 to 5; each b is independently 0 to 5; each c is independently 0 to 5; each d is independently 0 to 5; each e is independently 0 to 5; each f is independently 0 to 5; each g is independently 0 to 5; each a1 is independently 0 to 5; each b1 is independently 0 to 5; each c1 is independently 0 to 5; each d1 is independently 0 to 5; each e1 is independently 0 to 5; and each f1 is independently 0 to 5. In some embodiments, each m is independently 1 to 2000; each n is independently 1 to 2000; each o is independently 0 to 2000; and each p is independently 2 to 5. In some embodiments, each m is independently 1 to 1000; each n is independently 1 to 1000; each o is independently 0 to 1000; and each p is independently 2 to 5. In some embodiments, each q is independently 1 to 10; and each r is independently 1 to 5. In some embodiments, each q is independently 1 to 5; and each r is independently 1 to 4. In some embodiments, copolymer A is a reaction product of monomers that comprise Formula (Ia). In some embodiments, X is -O-, R1is methyl, each R3is methyl, R4is C4alkyl, a is 0, b is 3, c is 0, d is 0, e is 0, and f is 0. In some embodiments, copolymer A is a reaction product of monomers that comprise Formula (Ib). In some embodiments, X is -O-, R1is methyl, R5is -OH, a1 is 0, b1 is 1, c1 is 1, d1 is 1, e1 is 1, f1 is 1, and R2is methyl. In some embodiments, copolymer A is selected from Examples 1-20. In some embodiments, reactant B is (20-25% aminopropylmethylsiloxane)-dimethylsiloxane copolymer, (2-3% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (6-7% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, aminopropyl terminated polydimethylsiloxane, mercaptopropyl terminated polydimethylsiloxane, (30-35% dodecylmethylsiloxane)-[7-10% hydroxy(polyethyleneoxy(6- 9)propyl)methylsiloxane]-(55-65% dimethylsiloxane) terpolymer, (aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, acryloxy terminated ethyleneoxide dimethylsiloxane-ethyleneoxide aba block copolymer, or aminopropyl terminated polydimethylsiloxane. In some embodiments, reactive moiety B comprises -SH, -NH2 or a combination thereof. In some embodiments, reactive moiety B comprises -NH2.WSGR Docket No. Accolens-701.601

[0009] In some embodiments, the polymer network is formed via cross-linking between one or more reactive moiety A of copolymer A and one or more reactive moiety B of reactant B. In some embodiments one or more reactive moiety A and one or more reactive moiety B is randomly distributed. In some embodiments, reactant B is a copolymer, and one or more reactive moiety A and one or more reactive moiety B are randomly distributed or block distributed at the end of the copolymers. In some embodiments, the polymer network is formed spontaneously upon injection into or casting on a mold or a cavity. In some embodiments, the polymer network can be formed ex vivo. In some embodiments, the polymer network can be formed in vivo. In some embodiments, the polymer network is formed after injection into the body.

[0010] In some embodiments, wherein copolymer A has a glass transition temperature (Tg) of less than 20 ºC. In some embodiments, the Tgis less than -50 ºC. In some embodiments, the Tgis less than -100 ºC. In some embodiments, the Tg is about -150 ºC to about 0 ºC. In some embodiments, the Tg is about about -150 ºC to about -100 ºC. In some embodiments, the Tg is about -130 ºC to about -110 ºC. In some embodiments, the molecular weight of copolymer A is about 5000 g / mol to about 10,000,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 10,000 g / mol. In some embodiments, the ratio of copolymer A to reactant B is about 1000 to about 0.01. In some embodiments, n+m is at least 500. In some embodiments, n+m is 100 to 500. In some embodiments, the ratio of n to m is 1:10 to 1:20. In some embodiments, n is less than 5% of the polymer network. In some embodiments, n is about 1% to less than 5% of the polymer network. In some embodiments, n is about 1% of the polymer network. In some embodiments, n is about 2% of the polymer network. In some embodiments, n is about 3% of the polymer network. In some embodiments, n is about 3% of the polymer network. In some embodiments, n is about 4% of the polymer network. In some embodiments, n is about 5% to about 30% of the polymer network. In some embodiments, n is about 10% of the polymer network. In some embodiments, n is about 20% of the polymer network. In some embodiments, n is about 30% of the polymer network.

[0011] In some embodiments, the polymer network is cured from about 1 minute to about 100 hours. In some embodiments, the polymer network is cured from about 5 minutes to about 24 hours. In some embodiments, the polymer network is cured from about 30 minutes to about 12 hours. In some embodiments, the polymer network is cured from about 1 hour to about 6 hours. In some embodiments, the polymer network has a Young’s modulus of about 100 Pa to about 10 MPa. In some embodiments, wherein the polymer network has a Young’s modulus of about 0.5 kPa to about 10 kPa. In some embodiments, the polymer network has a viscosity below about 105cP. In some embodiments, the polymer network has strain-stiffening parameter from about 0.1 to aboutWSGR Docket No. Accolens-701.601 0.4. In some embodiments, the polymer network has elongation-at-break from about 1.5% to about 10%. In some embodiments, the polymer network has stress-at-break from about 0.05 MPa to about 1 MPa upon uniaxial extension and from about 0.05 MPa to about 1 MPa upon uniaxial compression. In some embodiments, the polymer network has a refractive index from about 1.4 to about 1.5 at a body temperature of about 37 ºC.

[0012] In some embodiments, the composition is for use in drug delivery, implantation, external and implantable contact lenses, or intraocular lenses. In some embodiments, the implantation is for breast implantation. In some embodiments, the polymer network is injected into a lumen. In some embodiments, the lumen is already implanted into the breast. In some embodiments, the composition is for use in intraocular lenses. In some embodiments, the polymer network is injected directly into a bag of crystalline lens implanted in an eye after extraction of cataract. In some embodiments, the polymer network is casted to a custom mold before implanting in an eye. In some embodiments, the polymer network is formed as a medical device. In some embodiments, the medical device is coated with a polymer. In some embodiments, the medical device is an implant, a microneedle array, a wound dressing pad, a tissue adhesive, a tissue sealant, a tissue filler, a dermal filler, a vascular graft, a catheter, an implantable contact lens, or an intraocular lens. In some embodiments, the implant is a breast implant. In some embodiments, the medical device is an intraocular lens. In another aspect, is a method of making a polymer network, the method comprising reacting copolymer A with reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, and wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, -N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

[0013] In some embodiments, copolymer A is polymerized via a controlled radical polymerization process. In some embodiments, the controlled radicalization polymerization process is free radical polymerization (FRP), atom transfer radical polymerization (ATRP), SARA ATRP, anionic polymerization, or reversible addition-fragmentation chain-transfer polymerization (RAFT). In some embodiments, the controlled radicalization polymerization process is ATRP. In some embodiments, the controlled radicalization polymerization process is RAFT. In some embodiments, copolymer A and reactant B form the polymer network without a catalyst. In someWSGR Docket No. Accolens-701.601 embodiments, copolymer A and reactant B form the polymer network without a stimuli. In some embodiments, the stimuli is heat or light. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG.1A shows exemplary copolymer A blocks according to one or more embodiments of the present invention. FIG.1B shows exemplary copolymer A wherein it can be a random block. FIG.1C shows exemplary copolymer A wherein it can be blocks of linear / comb and bottlebrush monomers.

[0015] FIG.2A shows how the polymer network can form with copolymer A, with all active blocks, and reactant B, and how the polymer network can degrade accordingly to one or more embodiments of the present invention. FIG.2B shows how the polymer network can form with copolymer A, with active and inactive blocks, and reactant B, and how the polymer network can degrade accordingly to one or more embodiments of the present invention.

[0016] FIG.3A shows how the polymer network can form with copolymer A and reactant B, wherein the polymer network is crosslinked for formation and can also be degraded. FIG.3B shows how the polymer network can form with copolymer A and reactant B, with less reactive moieties, wherein the polymer network is crosslinked for formation and can also be degraded.

[0017] FIG.4 shows how copolymers and linear polymer chains with same or different active moieties can make network integrated with or without bottlebrush network.

[0018] FIG.5 shows how the copolymers can combine to form the polymer network.

[0019] FIG.6A shows how breast implants can be injected with the polymer network described in one or more embodiments of the present invention, and how external stimuli can cleave the polymer network. FIG.6B shows how the polymer network described in one or more embodiments of the present invention can be injected in a fascial implant.

[0020] FIG.7A and FIG.7B shows examples of biomedical devices that the polymer network described herein can be. FIG.7A shows breast implants and FIG.7B shows intraocular lens (IOL).

[0021] FIG.8A shows accommodative IOL. FIG.8B shows coating layer of the IOL coating the polymer network. FIG.8C shows different coating methods for IOL.

[0022] FIG.9A to FIG.9K show mechanical property measurements and kinetic of polymer network formation. FIG.9A, FIG.9C, FIG.9E, FIG.9F, and FIG.9I shows time sweep. FIG. 9B, FIG.9D, FIG.9G and FIG.9H shows frequency sweep. FIG.9J and FIG.9K show the curing time.

[0023] FIG.10 shows active adhesives and polymer network formation with crosslinkers.

[0024] FIG.11 shows synthesis for PBA macromonomer and ONB-PBA crosslinker.WSGR Docket No. Accolens-701.601

[0025] FIG.12 shows coating of biomedical device surfaces of one or more embodiments described herein. DETAILED DESCRIPTION

[0026] The present invention relates to new compositions of brush like copolymers with ability to form polymeric network for biomedical applications including but not limited to, implants, microneedle arrays, wound dressing pads, tissue adhesives, tissue sealants, dermal fillers, vascular grafts, catheters, implantable contact lenses, tissue fillers, intraocular lenses.

[0027] In one embodiment, said composition can be injected in the tissue or molded in vivo and ex vivo in a casing bag and then injected to the living tissue. For example, for IOL (intraocular lenses), the polymeric composition can be injected directly to the capsular bag to form the super soft accommodative IOL. Alternatively, the polymer composition can be casted / molded in the mold with the custom crystalline lens feature or rods that need to be milled to the custom shape, or in the capsular-like bag that already custom made and then injected to the natural capsular bag. This material has the appropriate mechanical, physical, and optical properties such as modulus, relaxation time, transparency and refractive index that is to match the needs of implant. Hence, it is compatible with the surrounded living tissue with high performance to reduces any potential interference of implanting devices such as IOLs. Shape forming (cross linking) time and final mechanical properties are adjustable based on the composition of the selected composition and cross-linker percentage. The formed polymer network can be a combination of linear polymer chain networks and brush like polymer networks such that it can be called a hybrid or interpenetrated double network. The formed polymer network as an implant can be degradable using external stimuli such as light, heat and mechanically due to available cleavable bonds in the cross-linker polymer chains. The surface of ex vivo implants can be treated or coated in nano or macro scale to improve the surface of implants in terms of bio compatibility and administration.

[0028] Mimicking soft biological tissues has always been a goal for material engineers because of its applications in biomedical engineering (e.g., implants, wearable electronics, and robotics). Current strategies for mimicking very low modulus of soft tissues for making implants as medical devices with relies solely on adding solvent, which allows tuning Young's modulus at small deformations; however, the addition of solvent fails to replicate the stress-strain behavior at large strains. Further, the constituting solvent may leak upon deformation, over-swell (i.e., shape change) in contact with bodily fluids, and evaporate or freeze under variable environmental conditions. Therefore, a new strategy to prepare solvent-free and tissue-mimicking soft polymer material has been desirable. Plus, the existing materials for biomedical applications (and beyond) would need to be adaptable with various processing techniques, such as milling, were not available that couldWSGR Docket No. Accolens-701.601 allow them to have a modulus variable by more than three orders of magnitude from hard to ultrasoft polymer networks.

[0029] Bottlebrush polymers and elastomers has been developed as the next-generation material candidate for biomedical applications to address the challenges from solvent-swollen polymers and elastomers mentioned in the previous paragraph. Bottlebrush polymers utilized high density of grafting long side chains to reduce the flexibility of polymer backbones, thus minimizing the physical entanglements between polymer chains to reach the tissue-like stress-strain properties. The naturally low modulus properties of bottlebrush polymer elastomers allow this method to be a solvent-free alternative to the conventional solvent-swelling elastomers.

[0030] Bottlebrush polymer elastomers have demonstrated tissue-mimicking mechanic properties (U.S Patent US2020 / 0399414A1 and US 2021 / 0077659 Al), low leachable (US Patent US 2018 / 0201785 A1) in various type of biomedical applications.

[0031] Another feature of living tissue is a strain stiffening property. Initially soft and compliant tissues such as skin stiffen rapidly during deformation to prevent injury. Within narrow intervals of strain, their elastic moduli increase by several orders of magnitude at rates far beyond those observed in conventional elastomers, gels, and thermoplastics. The mechanics of biological tissues arise from their composite nature, defined by the distinct mechanical response of two proteins— collagen and elastin (Yu et al. (2016) Nature Mater.15: 911-918). A scaffold of stiff collagen fibers resists deformation, while an interwoven elastin network ensures elastic recoil. This structural duet produces a characteristic, two-phase mechanical response (Yu et al. (2016) Nature Mater.15: 911- 918): (i) exponential stiffening that switches to a (ii) linear response ( ) halfway before rupture as exhibited by plotting differential modulus ∂σtrue / ∂λ as a function of λ. The resulting sigmoid shape of the ∂σtrue / ∂λ curves contrasts with the steady increase in stiffness displayed by synthetic elastomers and gels. While various molecular and macroscopic constructs implement the basic principles of strain-stiffening (Grindy et al. (2015) Nat. Mater.14: 1210-1216; Yu et al. (2016) Nature Mater.15: 911-918; So et al. (2014) Adv. Funct. Mater.24: 7197-7204; Yang et al. (2014) Nature Comm.6, 6649 / 1-10; Jaspers et al. (2017) Nature Comm.8: 15478; Ducrot (2014) Science 344: 186-189), none replicate entire tissue's deformation response. For example, various silicone rubbers, such as Ecoflex® and Dragon Skin®, which are widely used in orthotics and cinematography (Yu et al. (2016) Nature Mater.15: 911-918), possess skin-like softness but lack its strain-stiffening characteristics. Polymeric gels are similarly incapable of replicating tissue mechanics and further suffer from solvent leakage upon deformation (Yu et al. (2016) Nature Mater.15: 911-918). Softness and strain-stiffening were simultaneously enhanced by employing brush-like architecture in solvent-free elastomers (Yu et al. (2016) Nature Mater.15: 911-918). TheWSGR Docket No. Accolens-701.601 attachment of side chains to network strands yielded a dual mechanical effect: (i) moduli reduced to 100 Pa via chain disentanglement and (ii) strain-stiffening increased by an order of magnitude via strand extension due to side-chain steric repulsion (Yu et al. (2016) Nature Mater.15: 911-918). This enables mechanical replicas of gel-like tissues such as lung and jellyfish (Vantankhah- Varnosfaderani et al. (2017) Nature 549: 497-501), that of these systems pales when compared to that of soft connective tissues like skin. In parallel, various chromogenic polymers have been created (Yu et al. (2016) Nature Mater.15: 911-918; So et al. (2014) Adv. Funct. Mater.24: 7197- 7204) but fail to incorporate tissue-like mechanical properties. The issue was addressed by designing by strain-stiffening materials A-B-A block copolymer architecture. (Vantankhah- Varnosfaderani et al. (2018) Science 359 (6383) 1509-1513) however self-assembly of ABA polymers requires casting followed by solvent evaporation. Additionally, as the systems are not flowable in the absence of solvent (not injectable), its applications (in a solvent free condition and shape changing during casting and evaporation almost make is not applicable) for in vivo implantation is limited. Injectable elastomers (Dashtimoghadam et al (2021) Nature communication 12 (1) 3961) address the issue of injectability of implantable materials, however they require external stimuli or catalyst to form network leading to shelf-life stability problems. The other challenge that most of implants faced with is they need to be prepared ex vivo using external stimuli such as photo, thermal that make the administration route of the implant very difficult or they need to use external as mentioned external stimuli in vivo that is harmful for surrounded living tissue and in some cases is not applicable. The other challenge is removing or replacing the implant from / in the body due to integrating of implant and living tissue around in cases that the implant need to replaced due to failure. Thus, a spectrum of properties must be addressed to create the prefect implant. Soft elastomer with controllable mechanical properties such as modulus and rouse time, stimuli and catalyst free curable, solvent less injectable, moldable with strain stiffening property and on demand degradable capability and in some chemistry lathe-able. These needs and others are met by the present invention.

[0032] In accordance with the purpose of the invention, as embodied and broadly described herein, the invention, in one aspect, relates to low glass transition and melting temperatures, one to four arm branched polymers, one to multi block copolymers composed of linear, comb, and brush blocks that can be useful in, for example, drug delivery, tissue augmentation, body countering, and tissue reconstruction / replacement such as a drug depots, breast implant, external and implantable contact lens, intraocular lens with and without coating a layer from nano to micron scale thickness.WSGR Docket No. Accolens-701.601 Polymer Molecules (Building Blocks for Polymer Networks)

[0033] Disclosed are copolymer blocks comprising a polymer block, wherein the Tg of polymer block is lower than processing temperature to allow injection, casing, molding (custom mold) at ambient or body temperature. Also disclosed are copolymer blocks having Tm higher than the processing temperature to provide the material with the lathe ability to make custom final shape.

[0034] We disclose polymer blocks that are poly(dimethylsiloxane). In various aspects, copolymer blocks may include polyacrylates and polyolefins such as poly(n-butyl acrylate) (PBA) and poly(isobutylene) (PIB) and any phenyl and hexyl ethylene glycol (meth)acrylate to tune the refractive index. In other embodiments, copolymer blocks may include hydrophilic moieties such as poly(ethylene oxide), polyacrylamide, PVP, POx to control water uptake and lubriciousness.

[0035] In various aspects, some of the monomers in one block or more than one block of the disclosed copolymers contain active moieties that can react together or with complimentary reactive moieties from other polymeric system with the same structure or different one. In various aspects, the polymer blocks are homopolymer or copolymer. In various aspects, each block can be randomly composed of different monomers not necessarily similar to the monomers in the other blocks. In various aspects, these blocks can be linear, branched, or brush-like such as comb and bottlebrush). In various aspects, these copolymer blocks can be located (placed, incorporated) in each arm of multifunctional initiator from 1 initiation site to 2, 3, 4 initiation sites.

[0036] Also disclosed are methods of making a disclosed copolymer blocks, the method comprising the step of synthesizing the copolymer block from a first residue of any block, via free radical polymerization (FRP), atom transfer radical polymerization (ATRP), SARA ATRP, anionic polymerization, or reversible addition-fragmentation chain-transfer polymerization (RAFT), ring opening polymerization (ROMP), and click reactions such as azide / alkyne-TCO, thiol / alkene or combination of these techniques.

[0037] Also disclosed are compositions of making a disclosed copolymer blocks reactive. There functional groups from the monomers in the blocks can converted to reactive functional groups such as acrylate, methacrylate, aldehyde, azide, isocyanate, amine, alkylene, DBCO, etc.

[0038] Also disclosed are polymer blocks and final composition has glass temperature lower room temperature and in some formulations they have Tm higher than processing temperature to form network lathe ability to make custom final shape.

[0039] Also disclosed are polymer blocks has monomers that can control refractive index from 1.4 to 1.54 and the copolymer and final compositions are transparent and optically clear.

[0040] Also disclosed are copolymers blocks can contain monomers with moieties that control filtering of UVA, UVB and HEVL (high energy visible light) to protect eye.WSGR Docket No. Accolens-701.601

[0041] Also disclosed that polymer formulations have low viscosity without adding diluents and solvents to facilitate injection, casting, molding, and 3D printing. Polymer melts have a viscosity below about 105cP, preferably, below about 104cP, and more preferably below about 103cP. Polymer Network

[0042] Disclosed are polymer networks comprising a plurality of the disclosed copolymer blocks.

[0043] We disclose polymeric networks based on one of the above-mentioned copolymer block or a combination of the above-mentioned copolymer blocks and another copolymer (secondary part) similar to the first part but with complimentary reactive groups or polymer chains with other structure such as linear and brush-like copolymers with complementary functional groups.

[0044] We disclose that the block copolymers or secondary part of network may contain cleavable bonds that can dissociate upon using external stimuli such as heat, light, and ultrasound.

[0045] We disclose that the polymer network can be formed spontaneously without external stimuli and catalyst upon injection to, casting on, or filling a mold or cavity.

[0046] We disclose that the polymer network can be formed both ex vivo and in vivo. The disclosed formulations can be injected into the body either directly into tissue or into a pre-made and pre-inserted lumen. In a different embodiment, the disclosed formulations can be molded outside the body by filling a mold of a defined shape.

[0047] We disclose that the polymer network can be formed with or without external stimuli and catalyst in the mold that already coated using spray, drop, and spin or printed using inject print or pad print with hydrophilic or hydrophobic layer.

[0048] We disclose that the polymer network can be formed using external stimuli and / or catalyst in the mold or cavity ex vivo and in vivo.

[0049] We disclose that the curing time can be tuned from minutes to hours based on molecular structure of polymer system and concentration of active moieties without using catalyst and external stimuli. Formulations 1) The disclosed formulations are two-component polymeric (modular) systems 2) The first component is a (A-r-B)-b-(B-r-C)-b-(A-r-B) copolymer 2-1) type of reactive monomers should be broad 2-2) A and C can have reactive functional group 2-3) Tg of blocks are important and need to be mentioned) 3) The second component is a di-functional crosslinker 3-1) End groups need to be mentioned broadly 3-2) Cross linker can have cleavable (one or more) links thermally, photo 4) The disclosed formulations are solvent-free (do not contain solvent) It is important in vivo injection and moldingWSGR Docket No. Accolens-701.601 5) The disclosed formulations are injectable (liquid) and moldable 6) The disclosed formulations have high shelf lifetime (>3 year) 7) The disclosed solvent-free (A-r-B)-b-(B-r-C)-b-(A-r-B) copolymeric system can flow at any ratio of the constituting monomeric units. 8) Solubility parameters of monomers, their size, and glass transition temperature (Tg) were adjusted to ensure that the disclosed copolymers either do not phase separate or form weak domains that readily dissociate upon flow. 9) The disclosed formulations have low viscosity (down to 103cP) due to the brush structure Synthesis and chemical composition 1) The disclosed copolymers can be prepared by one-pot synthesis using any control radical polymerization technique (ATRP, RAFT, nitroxide-mediated) and their combinations. 2) A broad range of monomers that form polymers with low Tg or Tm such as PDMS, PBA, PEG, PIB, PCL, PVL …. 3) Monomers with functional groups have low Tg 4) The disclosed compositions are biocompatible Curing (for a non-limiting example. for formation of a biomedical device) 1) The crosslinking process is spontaneous 2) No need for external stimuli (such as temperature and light) to form network. 3) No need for catalyst and initiator to induce and facilitate the curing process 4) Curing time is tunable from minutes to hours at both physiological (body) temperature of 37C (for in vivo curing) 5) Curing time is also tunable at ambient temperature (for ex vivo curing) 6) The tunability is implemented through the polymeric structure (without using external stimuli) Application (for a non-limiting example, for formation of a biomedical device) 1) The disclosed formulations can be cured both in vivo and ex vivo 2) In vivo: The disclosed formulation can be injected into the body either directly into tissue or into a lumen 3) Ex vivo: The disclosed formulation can be molded outside the body by filling a mold of a defined shape 4) The disclosed formulation can be used in additive manufacturing (3D-, 4D- printing) 5) The disclosed formulations can be applied in mold that surface already treated using spray, deep coating or pad printing Features of cured biomedical deviceWSGR Docket No. Accolens-701.601 1) After curing, the final product replicates mechanical properties of living tissue 2) Tunable mechanical properties: modulus down to 0.1 kPa, strength up to 1 MPa, elongation at break up to 10^, compressibility up to 5^, strain-stiffening up to ^^ = 0.9, elasticity at 1Hz (Rouse time < 1Hz) 3) Coating can be applied to a surface of a molded and cured product (device) to enhance lubriciousness, provide anti-fouling, and hinder posterior calcification opacification. 4) If needed, an implanted device can be removed through its degradation by applying external stimuli such as light, heat, and ultrasound. 5) On demand property change to post tune mechanical properties 6) In some chemistry: Lath-able to make customized biomedical device such as ICL or IOL with specific features Biomedical device fabrication

[0050] We disclose that the invented curable polymeric system can be prepared in the container using speed mixed or any other type of mixer or double series syringes by pushing composition back and forth or double parallel syringes and dispenser (screw mixer).

[0051] We disclose that the shelf life of the prepared curable mixer can be from seconds to hours.

[0052] We disclose that for making breast implant, the prepared curable above mentioned polymeric system can be injected to the lumen and cure then implanted or injected to the lumen that already implanted to the body.

[0053] We disclose that for making facial implant, the prepared curable above mentioned polymeric system can be injected directly to the body or injected to the custom mold and then implanted to the body.

[0054] We disclose that for making accommodative IOL the above mentioned curable polymeric system can inject directly to the capsular bag of crystalline lens after extraction of cataract.

[0055] We disclose that for making accommodation IOL the above mentioned curable polymeric system can be casted to the custom mold and then cure it and without surface modification or surface treatment such as plasma treatment, dip coating and spray coating is implanted using shuttle to the capsular bag of natural lens.

[0056] We disclose that for making accommodation IOL the above mentioned curable polymeric system can be casted to the custom mold that already coated with a layer of polymer using pad printing for custom coating such as do nut, spin coating, dip coating and then cure it and without surface modification or surface treatment such as plasma treatment, dip coating and spray coating is implanted to the capsular bag of natural lens using shuttle.WSGR Docket No. Accolens-701.601

[0057] We disclose that for making accommodation IOL the above mentioned curable polymeric system with Tm higher than milling or lathing temperature can be cast to the rod shape mold and cure. Then custom IOL fabricate using milling machine. Properties of a Biomedical Device

[0058] We disclose that after curing, the final product (material, device) replicates mechanical properties of living tissue.

[0059] We disclose that mechanical properties of a biomedical device, e.g., IOL and breast implant, are tunable by brush architecture. In various aspects, the Young’s modulus varies between 1 and 5 kPa, preferably between 0.5 and 5 kPa. to 0.1 kPa. In various aspects, polymer networks exhibit intense strain-stiffening characterized by a firmness parameters ^^=0.2, preferably up to ^^=0.4, and even more preferred up to ^^=0.9. The strength (stress-at-break) is up to 1 MPa, elongation at break up to 10x, compressibility up to 5x.

[0060] We disclose that polymer networks behave elastically at a deformation frequency of 1 Hz ascharacterized by a damping factor of tan ^^ < 0.2, preferably tan ^^ < 0.1.

[0061] In various aspects, molded device can be rigid to allow post-molding lathing Lath-able to make customized biomedical devices such as Implantable Collamer® Lens (ICL) or Intraocular Lenses (IOL) with specific features.

[0062] We disclosed a coating method to change the surface of formed network to lubricious and bio fouling resistance Coating can be applied to a surface of custom-made mold or a molded and cured product (device) to enhance lubriciousness, provide anti-fouling, and hinder posterior calcification opacification.

[0063] We disclose that formed networks have a refractive index tunable by composition and fraction of monomers in the block copolymers from about 1.4 to about 1.5, preferably from ~1.42 to ~1.48, and more preferably from ~1.43 to ~1.47 at a body temperature of about 37oC.

[0064] We disclose that refractive index is varied through copolymerization (controlled incorporation) of chemically different side chains (polymer sections in both backbone and side chains) such as poly(n-butyl acrylate) (PBA) and poly(isobutylene) (PIB). Device Modification and Removal

[0065] We disclose a coating method to change the surface of formed network to lubricious and bio fouling resistance. For example FIGs 8B and 8C show how IOL can be coated. Additionally, FIG. 12 shows other schematics for coating of biomedical devices.

[0066] In various aspects, mechanical properties can be changed on demand after molding and / or implantation by altering brush network architecture. Mechanical properties are presented in FIGs 9A to 9K, showing different measurements and kinetics and curing of polymer formation.WSGR Docket No. Accolens-701.601

[0067] If needed, an implanted device can be removed through its degradation by applying external stimuli such as light, heat, and ultrasound. This is shown in the schematics of FIGs.2A and 2B, FIGs.3A to 3C, and to FIG.4.

[0068] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification. Implants

[0069] Soft implants are a type of medical implant that are designed to be more flexible and comfortable than traditional implants. These implants find applications across diverse cosmetic and reconstructive procedures, spanning from (i) breast augmentation (ii) Facial implants (iii) Earlobe repair (iv) Scar revision (v) internal contact lens and (vi) Intraocular lens. Typically crafted from low glass transition temperature (Tg) polymers, such as silicone, these implants contain oligomers, which are not fully integrated into the polymer network. Consequently, these oligomers (e.g., short silicone oils chains), gradually leach out over time. Current silicone breast implants are gels compromising of approximately 70 wt% leachable small silicone polymeric chains necessitating encapsulation within a luminal bag. The implants are then injected into the body through a relatively sizable incision. Recent development can be injection of lumen in the body through the small incision and then fill it with silicone materials that faced with some technical and health issues. Furthermore, injectable polymeric implants crosslinked through external stimulation exhibit low gel fraction, presenting challenges in terms of biocompatibility and susceptibility to leaking.

[0070] Other soft silicone implants are most commonly used in the following areas in face: 1) Cheek to add volume and definition to the cheekbones 2) Chin to improve chin projection and create a more balanced profile.3) Jawline to sharpen the jawline and create a more sculpted appearance and 4) lips to increase lip volume and enhance the shape of the lips. Here are some of the advantages of soft silicone implants: Natural-looking, because they are softer and more flexible, soft silicone implants can move more naturally with facial expressions, resulting in a more natural look than traditional implants. Less noticeable than traditional implants, especially in areas withWSGR Docket No. Accolens-701.601 thin tissue coverage. Minimal discomfort because the softer material may also be more comfortable than traditional implants. However they are not integrated polymer network as a single part and faced with challenges such as: leaching out of diluent from implant to the tissue and not only bring some concern about finding silicon materials of tissue all-around but also this can lead to an uneven or unnatural appearance. The other issue with current facial tissue is visibility and palpability because they are softer and do not mimic mechanical properties of living tissue. As a result, there's a higher chance of the implant outline being highlighted through the skin, especially in areas with thin tissue coverage. Current facial implants don’t’ have enough durability due to their leach-ability and gel fraction and they need to be replaced sooner.

[0071] Developments in intraocular lens (IOL) technology, particularly in accommodating custom lenses, offer intriguing possibilities. These lenses address the need for cataract surgery, which arises from the loss of clarity and mechanical properties in the natural crystalline lens. To replace the crystalline lens effectively, optically transparent, biocompatible, and stable polymeric materials with suitable refractive index and Abbe number are essential. Adaptive IOLs mimic the mechanical properties of the natural lens, allowing for accommodation by the ciliary muscles. Cataract surgery becomes necessary when the natural lens stiffens due to factors like cross-linking from exposure to harsh environmental conditions such as UV light. Stiffening of the lens makes it challenging to focus on near objects, leading to blurry vision. Current IOLs, typically rigid and monofocal / bifocal / multifocal, necessitate patients to choose between near or far sight, often requiring additional glasses. Accommodative IOLs offer a solution, enabling clear vision across a wide range of distances without the need for glasses or contact lenses.

[0072] Different methods and technologies are developing for making accommodative lenses that we will discuss in next paragraphs. Research groups and some companies use air, solvent or gels that contain solvent for making accommodative IOL. Nishi’s attempts at developing an Endo capsular balloon filled with silicone oil failed when severe posterior capsule opacification occurred (Nishi 1997). They designed acrylic lens with hollow optic and hollow haptic that filled with silicone oil to have low bulk modulus that ciliary muscles can contract the IOL and push oil from haptic into the optic and shange the curvature of optical zone. There is other product in the market with silicone materials that have hinge and by contracting the ciliary muscles the optical part can go back and forth and change the focusing point. These developed systems have issues such as slow response and mis-displacement respectively.

[0073] Other efforts are from Jean Marie Parel, MD (Bascom Palmer) and Steven Koopmans (Pharmacia) that attempted to using capsular bag and refilling it with monomers and macromonomers that can go through in situ polymerizing to make a soft polymer (Hao et al, 2010;WSGR Docket No. Accolens-701.601 Koopmans, 2003 and 2006) but unfortunately, they faced inflammation of the eye and posterior capsular opacification (PCO)

[0074] Both scientists ended their efforts after in vivo animal trials presented significant complications including inflammation of the eye and posterior capsular opacification (PCO).

[0075] In our prior work we proved to have solvent free soft polymeric network we can change the structure of polymer chains of network from linear to comb or brush structure and for having nonlinear network we need to have stretched polymer chains in the network same as what A-B-A polymeric system showed and mimic mechanical properties of living tissue.

[0076] What we need to have for breast implant is biostable, non-leachable soft elastomer and for IOL application that polymer system should be clear with appropriate refractive index. In addition, the viscosity of the polymeric system should be low enough without any solvent that can be moldable, injectable ex vivo and in vivo in the tissue cavity, capsular bag, lumen and mold. When we want to form the network in the tissue cavity or capsular bag we need to have system that make network with very high gel fraction to avoid leaching out of anything from network without using external stimuli and catalyst or any other additives.

[0077] These formed polymer networks should have low modulus similar to the young less than 1000 pascal and flexible that can change shape when the ciliary muscles of the eye can contract the lens during accommodation and enough flexible that reshape very quickly enough to refocus near and far in a short time. It means that once the muscles of accommodation relax, the lens will resume its baseline shape, allowing the patient to see at a distance. The surface of molded breast implant and IOL can be treated with polymeric solution to coat the polymer network to make the surface biofouling resistance lubricious and easy to administration. These materials can also be injected to the already coated molds, bags like capsular bag and lumen and cure in them with or without stimuli.

[0078] Changing the chemistry and keeping the structure of these block copolymers to polymers those have Tm higher than room temperature and mouldability and lathe ability of these materials present us with an opportunity to custom design the biomedical device using milling machines. This technique allow us to custom make the IOL for each eye and each patient. In order to calculate the correct power for cataract surgery and IOL, three primary parameters of each eye should be considered. These parameters are axial length of the eye, the depth of anterior chamber and corneal curvature. These parameters only determine the IOL power and custom made IOL can address other issues that each eye has struggling to see images with the best quality. We can address toric IOL needs and any corneal disorder by this new material and processing method.WSGR Docket No. Accolens-701.601

[0079] There is a need in the art for a solvent-free, stimuli free, injectable polymer that is solvent free curable to form tunable super soft and elastic synthetic elastomer that is capable of being injected in to the mold or in vivo / ex vivo bag or capable to lathe to make custom biomedical device for each patient, all owing for the creation of an entirely new class of biomedical devices such as accommodative IOL, Breast implant, internal contact lens, facial implant.

[0080] There are some companies that are working to make artificial accommodative crystalline lens. For example, there are companies working on new micro-optical system filled with air as a refractive medium, and some companies utilize air and silicone. However, there is a chance for pacification of air through silicone. An air-filled human implant may be a very novel territory. Fibrosis of the capsule is also a consideration for some products s – based on laterally shifting optics, driven by the ciliary muscle. Pigmentary diagnosis is another consideration Haptics are very thin. Goes in the sulcus bag, so if people get surgery young (like in their 50s) they could get pigmentary issues as they age. Bag can get more rigid with time. Some current products are not easy to implant; the user must go around one actuator at a time to get the lens in and can still end up with a couple actuators outside of the bag.

[0081] In one or more embodiments, the present invention constructs a multi block polymer or copolymer. The polymer by design is cured in presence or absence of external stimuli such as light, temperature to form solvent free soft elastomers. The elastomers are suitable for biomedical devices including but not limited to breast implants, accommodative IOL, Internal contact lens, facial fillers in the form of molded, capsulated or custom- molded or milled. These multi block copolymers have low Tg enabling fluidity for injection, designed with crystallization point or melting point higher than processing temperature required for milling polishing and lathing. The multi block copolymers can synthesized as a single branch or multi branch with number of branches ranging from 3 to n with n having dendrimer like structure. The block copolymers can be made as homopolymer or random copolymer blocks and can be synthesized using different polymerization techniques such as free radical polymerization, ATRP, RAFT, ROMP, nitroxide mediated. Monomers can be short or long (macromonomer) with single active site such as acrylate, methacrylate, norbornene, and etc. Each block can be linear, comb and brush-like structure. For chemical crosslinking of blocks, functional groups such as hydroxyl, amine, azide, alkene, thiol, furyl, maleimide, aldehyde, and isocyanate, among others, is incorporated into the polymer backbone. Each functional group can be converted to other type of reactive moieties based on crosslinking strategies and application needs. Cross linking of reactivated multi block copolymer can be done in presence or absence of any external stimuli, catalyst, light, or temperature.WSGR Docket No. Accolens-701.601

[0082] Monomers such as any derivative of PDMS-MA and the residues of any silicone monomer methacrylate or acrylate that have hydroxyl or amine moieties or any hydroxyl alkyl with long alkyl those have low Tg lower than room temperature in polymer state. These multi block copolymers can also be synthesized using monomers and macromonomers with melting point higher than room temperature but lower than body temperature (20C<Tm<37C). Examples are as PVL and PCl with appropriate degree of polymerization. These block copolymers undergo typical purification methods (i.e., column chromatography) and / or end group removal and modification process (i.e., thermal treatment) before use. The polymer network can be formed by mixing the similar or different block copolymers with complimentary reactive moieties. The polymer network can be formed by mixing the block copolymers with linear homo polymer or copolymer with the same or different complimentary reactive end groups moieties. The copolymers used for cross linking can be designed as cleavable in which one or more of the internal chains can be cleaved using stimuli such as heat, light or mechanical force. The polymer network or elastomers can be formed in typical molds, custom mold or in the custom capsular bag for ex vivo network formation for implantation in the body. The polymer network can be formed also by injection of the mixture into the cavity or implanted capsulary bag directly. The elastomer curing time can be varied from minutes to hours. Similarly, stiffness of the elastomers prepared in this manner are tunable within the range of 100 Pa to 10 MPa.

[0083] In various embodiments, mold surface can be treated with a layer of polymer coating by spray drying or pad printing. In other embodiments, the biomedical devices molded in a rod shape and the final shape of biomedical devices have been created by milling and lathing then polishing to address some specialty needs for patient’s eyes.

[0084] In the first aspect, the present invention describes synthesis of multi block copolymers with linear, comb and brush blocks, initiated from mono, bi, tri and tetra functional initiator. Typical synthesis such as free radical, ATRP, RAFT and in some cases nitroxide mediated polymerization can be used. Each polymer arm comprise a multi block polymer chain that are homo, or copolymers. Each block may have methacrylate, acrylate and / or norbornene monomers that have polar or active groups such as Thiol, hydroxyl, amine, among others.

[0085] In one or more embodiments, the block copolymers contain macromonomers wherein the acrylate, methacrylate and norbornene macromonomers comprise polydimethylsiloxane, polyisobutylene, poly butylmethacrylate, or any alkyl acrylate with low Tg (not limited to these) or polymers with Tm higher than processing temperature and lower than body temperature such as polyVL or pCL (not limited to these). In one or more embodiments the multi block linear, comb and brush copolymers (mono, bi, tri, tetra and dendrimer) of the present invention includes any oneWSGR Docket No. Accolens-701.601 or more of the above referenced embodiments of the first aspect of the present invention wherein the acrylate, methacrylate, norbornene have the formula:wherein R1 is hydrogen or a alkyl group having 1 carbon and 3 hydrogen atoms such as methyl; each R2 is independently hydrogen, an alkyl radical having 1 to 6 carbon atoms, or a -CO-Y-R’’’ radical wherein Y is -O-, -S- or -NH-, R3 is an alkyl radical having 1 to about 10 carbon atoms; R4 is a linking group (e.g., a divalent alkenyl radical having 1 to about 12 carbon atoms); A denotes - O- or -NH-; B denotes -CO-, -OCO- or –COO-; C denotes an aromatic radical having 6 to about 30 carbon atoms; f is 0 to 6; a is 0 or 1; b is 0 or 1; and c is 0 or 1.

[0086] In an illustrative embodiment, the multi block multi arm copolymers first includes monomeric units derived from either a short, long, bulky siloxane monomer containing an ethylenically unsaturated reactive end group. In a non-limiting illustrative embodiment, suitable silicone-containing monomers including but not limited to a short and long polydimethylsiloxane, bulky polysiloxanylalkyl (meth)acrylic monomer, a bulky polysiloxanylalkyl carbamate monomer and mixtures thereof. A representative example of a silicone-containing monomer includes a short, long and bulky polysiloxanylalkyl(meth)acrylic monomer represented by a structure of Formula I:wherein X denotes -O-, -NR6- where each R6 is hydrogen or a C1-C10 alkyl group; R1 independently denotes hydrogen or methyl; each R2 independently denotes a lower alkyl radical such as a C1-C10 group, a phenyl radical, each R3, R3 independently denotes a lower alkyl radical such as a C1-C4 group, or phenyl radical. R4 is a linking group (e.g., a divalent alkenyl radicalWSGR Docket No. Accolens-701.601 having 1 to about 12 carbon atoms), R5 is hydroxyl, azide, SH, or amine groups; a,a1 is 0 to 10; b, b1 is 0 to 4; and c, c1 is 0 or 1, d, d1 is 0 to 4, e, e1 is 0 to 9, f, f1 is 0 to 4 and g is 0 to 50.

[0087] Representative examples of silicone-containing monomers include monomethacryoxypropyl terminated polydimethylsiloxane, asymmetric 3-methacryloyloxypropyltris(trimethylsiloxy)silane or tris(trimethylsiloxy)silylpropyl methacrylate, sometimes referred to as TRIS, tris(trimethylsiloxy)silylpropyl vinyl carbamate, sometimes referred to as TRIS-VC, pentamethyldisiloxanyl methylmethacrylate, phenyltetramethyl-disiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane, (3-METHACRYLOXY-2- HYDROXYPROPOXYPROPYL)METHYL BIS(TRIMETHYLSILOXY)SILANE (3- methacryloxy-2-hydroxy propoxy)propyl bis(trimethyl siloxy)methyl silane, sometimes referred to as Sigma and the like and mixtures thereof.

[0088] In one embodiment, the silicone-containing monomer is a tris(trialkylsiloxy)silylalkyl methacrylate-containing monomer such as a tris(trimethylsiloxy)silylpropyl methacrylate- containing monomer.

[0089] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the multi arm multi block copolymer further each block and arm includes monomeric units derived from a hydrophilic and hydrophobic monomer having one or more reactive functionalities and an ethylenically unsaturated reactive end group. In an illustrative embodiment, suitable hydrophobic / hydrophilic monomers including but not limited to those containing an active hydrogen atom such as, for example, hydrophilic monomers having hydroxyl, amino or carboxylic acid reactive functionalities and an ethylenically unsaturated reactive end group as discussed above. Suitable hydroxy-substituted hydrophilic monomers includes but not limited to hydroxy (meth)acrylates and (meth)acrylamides, such as any hydroxy or amino alkyl (meth)acrylate such as 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), glycerol methacrylate, glycerol acrylate, polyethylene glycol methacrylate, polyethylene glycol acrylate, N-2-hydroxyethyl methacrylamide, hydroxy butyl or hexyl acrylate and methacrylate and the like and mixtures thereof. Amino-substituted monomers include allyl amine.

[0090] In non-limiting illustrative embodiments, as may be combined with one or more of the preceding paragraphs, the multi arm multi block copolymer further each block and arm includes monomeric units derived from another silicon or any monomer with low Tg that monomer having one or more reactive functionalities and an ethylenically unsaturated reactive end group. In an illustrative embodiment, suitable low Tg monomers include, for example, those containing an active hydrogen atom from amine or hydroxyl group and epoxy group such as, for example, (3-WSGR Docket No. Accolens-701.601 methacryloxy-2-hydroxypropoxypropyl)methyl bis(trimethylsiloxy)silane or any silicon monomer has NH, OH, NCO, DBCO, Aldehyde, and epoxy among others.

[0091] In one or more embodiments, the multi arm multi block linear, comb, brush polymer and copolymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invitation having formula:

[0092] Suchwhere x and y are an integer from about 1 to 6; n1, n2,m1,m2 are integer from 0 to 5000; p and q is an integer from about 2 to about 16 and 3 to 50 respectively and Z can be O, NH, NR and R can be any alkyl group from c1 to c10 and R 1 is H or any alkyl c1-c3.WSGR Docket No. Accolens-701.601

[0093] or Such asz can be O, NH and NR and R can be any alkyl from c1-c3; n1, n2,m1,m2 and o2 are integer from 0 to 5000; p is an integer from about 2 to about 10 and a to g and a1 to f1 are an integer from 0 to 10, R1 can be H or alkyl from c1-c3 and R2, R3 R4 can be alkyl from C1-C10, r and r1 can be1 to 6 independently and A can be 1 to 4 presenting number of arms or functionality of initiators or CTA.

[0094] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention in each block having the formula:WSGR Docket No. Accolens-701.601

[0095] Figure of A-r-C partand n and m are is an integer from about 1 to about 5000. where x and z can be O, NH and NR and R can be any alkyl from c1-c3; n, m and o are integer from 1 to 5000; p is an integer from about 2 to about 10 and a to g and a1 to f1 are an integer from 0 to 10, R1 can be H or alkyl from c1-c3 andWSGR Docket No. Accolens-701.601 R2, R3 R4 can be alkyl from C1-C10, R5 and R6 are OH, NH2, epoxy, azide, aldehyde, NCO, methacrylate, acrylate, thiol not limited to these functions independently.

[0096] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention in each block having the formula:

[0097] Full figure of copolymer:

[0098] where x, Y, Z are O, NH, NR4 and R4 can be c1-c3, R can be H or C1-C3, a is an integer from about 3 to about 50; m, n, o is a 0 to 5000 and at least one of them more than 10 and R1 and R2 are independently OH, NH2, epoxy, azide, aldehyde, acrylate, methacrylate, vinyl, allyl, thiol, NCO, furan, maleimide but not limited to. B is an integer between 1 to 10 and r is between 1 to 4 that show the arms of block copolymer. R3 is the residue of multi functional initiator or CTA.WSGR Docket No. Accolens-701.601

[0099] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention wherein x, Y, Z are O, NH, NR4 and R can be H or C1-C3, a is an integer from about 3 to about 50; m, n, o is a 0 to 5000 and at least one of them more than 10; b is an integer between 1 to 10 and r is between 1 to 4 that show the arms of block copolymer. R3 is the residue of multi functional initiator or CTA.

[0100] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention further comprising a plurality of alkene functional groups covalently bonded to the acrylate, methacrylate, norbornene polymer chains in one or all blocks of arms through terminal hydroxyl, amine, thiol, (not limited) groups partially or fully converted. In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention further comprising a plurality of alkene functional groups covalently bonded to the three methacrylate polymer chains through terminal hydroxyl groups on the (3-methyharyloxy- 2-hydroxypropyl)methyl bis (trimethyl-siloxy)silane or (3-methyharyloxy-2- hydroxypropyl)methylpolydimethylsiloxane.WSGR Docket No. Accolens-701.601

[0101] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention wherein x, Y, Z are O, NH, NR4 and R can be H or C1-C3, R4 are independently OH, NH2, epoxy, azide, aldehyde, acrylate, methacrylate, vinyl, allyl, thiol, NCO, furan, maleimide but not limited to, a is an integer from about 3 to about 50; m, n, o is a 0 to 5000 and at least one of them more than 10; f and f1 are integer between 0 to 500: b is an integer between 1 to 10 and r is between 1 to 4 that show the arms of block copolymer. R3 is the residue of multi-functional initiator or CTA.

[0102] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention having a formula selected from:WSGR Docket No. Accolens-701.601

[0103] Figure final copolymers (different formats)Y, Z are O, NH, NR4 and R can be H or C1-C3, R4 are independently OH, NH2, epoxy, azide, aldehyde, acrylate, methacrylate, vinyl, allyl, thiol, NCO, furan, maleimide but not limited to, a is an integer from about 3 to about 50; m, n, o is a 0 to 5000 and at least one of them more than 10; f, f1 h and j are integer between 0 to 500; b and b1are an integer between 1 to 10 and r is between 1 to 4 that show the arms of block copolymer. R3 is the residue of multi-functional initiator or CTA.

[0104] Crosslinker can share similar composition to multi block copolymer with same R4 or complimentary to R4 such as acrylate, methacrylate, amine, aldehyde, azide, alkene, furan, maleimide, thiol vinyl, allyl among others.

[0105] Crosslinker can be synthesize as linear or branched polymer and copolymers with end groups same R4 or complimentary to R4 such as acrylate, methacrylate, amine, aldehyde, azide, alkene, furan, maleimide, thiol vinyl, allyl among others.

[0106] Mixture of amine terminated crosslinker and acrylate functionalized multi block multi arm copolymer results in network formation without external stimuli and in the absence of solvent and catalyst. Similarly, mixture of acrylate terminated crosslinker and amine functionalized multi block multi arm copolymer, results in network formation without external stimuli and in the absence of solvent.

[0107] Mixture of furan terminated crosslinker and maleimide functionalized multi block multi arm copolymer results in network formation without external stimuli and in the absence of solvent and catalyst. Similarly, mixture of maleimide terminated crosslinker and furan functionalized multiWSGR Docket No. Accolens-701.601 block multi arm copolymer, results in network formation without external stimuli and in the absence of solvent. and catalyst if R4 in block copolymer is acrylate and amine end group on the x linker or verse versa, and furan in block copolymer and maleimide on end groups of x-linker or verse versa.

[0108] Multi block multi arm copolymer in presence of crosslinker forms a network with external stimuli and in the absence of solvent, if R4 in block copolymer is such as acrylate, methacrylate, amine, aldehyde, azide, alkene, furan, maleimide, thiol vinyl, allyl among others. limited to and on the x linker there are functional groups such as acrylate, methacrylate, amine, aldehyde, azide, alkene, furan, maleimide, thiol vinyl, allyl but not limited to

[0109] In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention wherein the multi arm multi block linear, comb and brush co polymer is optically clear. In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention wherein the multi arm multi block linear, comb and brush co polymer has a refractive index of from about 1.40 to about 1.49, preferably from about 1.42 to about 1.48, and more preferably from about 1.43 to about 1.46 at 37 °C. In one or more embodiments, the multi arm multi block linear, comb and brush co polymer of the present invention includes any one or more of the above referenced embodiments of the first aspect of the present invention having a degree of polymerization for each arm between about 100 and about 3000,

[0110] This polymer could be used to create a soft, flexible breast implant and facial filler. The breast implant and facial filler would remain soft and flexible like the natural tissue and mimic mechanical properties.

[0111] This polymer could also be used to create a soft, flexible accommodating intraocular lens (IOL). Such an IOL would mimic the properties of a young, healthy human lens, maintaining its softness and flexibility. During accommodation, when the ciliary muscles of the eye contract, the flexible lens would reshape to increase its optical power, enabling the patient to focus on near objects. When the ciliary muscles relax, the lens would return to its baseline shape, allowing the patient to see clearly at a distance. Additionally, this novel material could be employed as the optic for a presbyopia-correcting intraocular lens (IOL).

[0112] While lower order aberrations of the cornea (such as sphere and cylinder) can be corrected with glasses or contact lenses, many higher order aberrations (HOA) of the cornea (such as coma and trefoil) cannot be corrected. More than 60 different HOAs have been identified, and manyWSGR Docket No. Accolens-701.601 cannot be corrected with glasses or contact lenses. With a custom-made IOL, preoperative measurements of the eye can be used to determine an ideal IOL to correct for a specific eye’s needs. Using corneal topography, aberrometry (wavefront technology), and other imaging and diagnostic tools, one could create a computer model of the ideal shape of an IOL or an accommodating IOL for each patient. Using the computer model, a mold could be made, and the Generation 2 material could be molded inside of it to create a custom-made IOL to correct for each specific eye’s needs. Network

[0113] There is a need in the art for solvent-free, polymeric systems capable of forming synthetic elastomer with or without external stimuli and with and without catalyst. Additionally, it is advantageous that polymers are capable of being molded / casted, injected and milled in an ordinary or custom mold for making biomedical devices personalized for individual patients. Such capabilities present new administration routs for custom shapes with minimal incision to address some challenges of current biomedical devices such as breast implant, facial implants and fillers and IOL and internal contact lenses. FIGs 6A and 6B and FIGs 7A and 7B show how the polymer network described in one or more embodiments herein can be used in such biomedical devices.

[0114] In a second aspect, the present invention is directed to fluidity and injectability of one to multi block and one to multi arms linear, comb and brush copolymer that have Tg lower than room temperature or processing temperature or Tm lower body temperature, Adjusting the viscosity to an appropriate level enables the polymer melt to pass through narrow needles without the need for a solvent.

[0115] In a third aspect, the present invention is directed to a stimuli free, catalyst free, and curable (one to multi) block (one to multi) arms linear, comb and brush copolymer comprising the block copolymer described above, and second part same block copolymer with complimentary reactive moieties or block copolymer with different composition with the complimentary active moieties or linear homo and copolymer with low Tg with active moieties as side groups or end groups.

[0116] In some embodiments, the first part of composition ((one to multi) block (one to multi) arms linear, comb and brush copolymer) comprise from about 1 wt% to about 99 wt% second part (block copolymer with complimentary reactive moieties or block copolymer with different composition with the complimentary active moieties or linear homo and copolymer with low Tg with active moieties as side groups or end groups). In some embodiments the second part of curable composition has one or more cleavable bonds such and bond that can cleave thermally, mechanically or by light.WSGR Docket No. Accolens-701.601

[0117] In a forth aspect, the present invention is directed to curable (one to multi) block (one to multi) arms linear, comb and brush copolymer comprising the block copolymer described above, and second part same block copolymer with complimentary reactive moieties or block copolymer with different composition with the complimentary active moieties or linear homo and copolymer with low Tg with active moieties as side groups or end groups using external stimuli such as light or temperature and / or catalyst such as photoinitiator or thermal initiator.

[0118] In some embodiments, the first part of composition ((one to multi) block (one to multi) arms linear, comb and brush copolymer) comprise of about 1 wt% to about 99 wt% second part (block copolymer with complimentary reactive moieties or block copolymer with different composition with the complimentary active moieties or linear homo and copolymer with low Tg with active moieties as side groups or end groups). In some embodiments the second part of curable composition has one or more cleavable bonds such and bond that can cleave thermally, mechanically or by light.

[0119] In one or more embodiments, the above cured polymeric systems of the present invention contains one or more of the above referenced embodiments of the second / third and fourth aspect of the present invention wherein the resin is colorless and clear.

[0120] In one or more embodiments, the above block copolymer in the present invention contains one or more of the above referenced embodiments of the second / third and fourth aspect of the present invention wherein the copolymers comprising UV or blue light blocker in their structure from about 0.1 to 2.0 mole%.

[0121] In fifth aspect, the present invention is directed to a soft and flexible one to multi block and one to multi arms linear, comb and brush copolymer network for use in breast implant, facial filler, intraocular lenses and internal contact lens comprising the curable co polymer resin described above.

[0122] In one or more embodiments, the soft and flexible cured above mentioned copolymeric network of the present invention includes any one or more of the above referenced embodiments of the fourth aspect of the present invention having Young’s modulus of from about 0.1 KPa to about 5 MPa.

[0123] In one or more embodiments, the soft and flexible cured above mentioned copolymeric network of the present invention includes any one or more of the above referenced embodiments. In one or more embodiments, the soft and flexible cured above mentioned copolymeric network of the present invention includes any one or more of the above referenced embodiments of the third aspect of the present invention having an ultimate compressive strength (UCS) of from about 10 Pa to about 10 MPa.WSGR Docket No. Accolens-701.601

[0124] In one or more embodiments, the soft and flexible cured above mentioned copolymeric network of the present invention includes any one or more of the above referenced embodiments of the third aspect of the present invention wherein the above mentioned cured copolymeric network is transparent and clear and can filter a specific range of wavelengths.

[0125] In a sixth aspect, the present invention is directed to a breast implant comprising of the above mentioned cured copolymeric system described herein. In some of these embodiments, breast implant has a Young’s modulus of from about 10 Pa to about 5 MPa. In some of these embodiments, artificial intraocular lens has an ultimate compressive strength (UCS) of from about 10 Pa to about 5 MPa after curing with or without external stimuli and catalyst. In these embodiments, the artificial intraocular lens is optically clear.

[0126] In a seventh aspect, the present invention is directed to a method for preparation of the above mentioned cured copolymeric network comprising: combining a block copolymer described herein with a second part block copolymer with complimentary active moieties with the same structure and / or linear homo and copolymer with low Tg with active moieties as side groups or end groups crosslinker, with or without using external stimuli with or without thermal or photo-initiator to form an uncured copolymeric system; and exposing the uncured one in case it needs external stimuli to high temperature or ultraviolet light to produce a cured block copolymeric network. In one or more embodiments, the method for making a cured block copolymer network of the present invention includes any one or more of the above referenced embodiments of the fifth aspect of the present invention wherein the uncured above block copolymeric resin comprises from about 2% to about 98% by volume cross linker. In one or more embodiments, the method for making a cured block copolymeric network of the present invention includes any one or more of the above referenced embodiments of the fifth aspect of the present invention wherein the thermal initiator or photo-initiator is AIBN, Benzyl peroxide, 2,2-dimethoxy- 1, 2-diphenyl ethenone in case need to have external stimuli. • Molding and form shape (mold, lathe) • Surface treatment

[0127] The surface of molded, casted, milled can be treated using plasma treatment or coated with the layer of polymer Compositions

[0128] Provided herein are compositions comprising polymer network comprising a reaction product of copolymer A and reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, andWSGR Docket No. Accolens-701.601 wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, -N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

[0129] Provided herein are compositions comprising polymer network comprising a reaction product of copolymer A and reactant B, wherein: copolymer A is a siloxane containing block copolymer that comprises a reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a branched, multi-arm, structure, or a combination thereof, and wherein the reactive moiety A comprise a -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO group; and reactant B can be a polymer, copolymer, or small molecule, wherein reactant B comprises one or more reactive moiety B, wherein reactive moiety B comprises one or more -SH, -NH2, epoxy group, or alkenyl group or a combination thereof.

[0130] In some embodiments, copolymer A comprises siloxane, polyfluorosiloxane, or polybutyl acrylate. In some embodiments, copolymer A comprises siloxane. In some embodiments, copolymer A is a reaction product of one or more macromonomers. In some embodiments, wherein copolymer A is polymerized via a controlled radical polymerization process. In some embodiments, copolymer A is a random copolymer, a block copolymer, or a combination of random and block copolymers. In some embodiments, copolymer A is a block copolymer or random copolymer. In some embodiments, each block of the copolymer can be a homopolymer or a random copolymer. A random copolymer can have the formula of (M1-r-M2-r-…Mn), wherein the M values are monomer units or blocks and -r- represents that the monomers are arranged randomly along the polymer backbone. A block copolymer can have the formula of (M1-b-M2-b-…Mn) wherein the M values are monomer units or blocks and -b- represents that the different monomer units are connected in a block-like fashion, with long stretches of each monomer type before another type is encountered. A combination of random and block copolymers can have the formula of (M1-r-M2-r-..Mn-b-M'1-b- M'2-b-M'3-b-..M'n-b-M''1-r-M''2-r-..M''n).

[0131] In some embodiments, copolymer A can be a bottlebrush, polymer, comb polymer, or linear polymer with a multi-arm structure. In some embodiments, copolymer A can have the monomeric structure as shown in FIGs.1A to 1C, FIGs.2A and 2B, FIGs.3A and 3B, FIG.4 and FIG.5. In some embodiments, copolymer A can have the monomeric structure as shown in FIGs. 1A to 1C. In some embodiments, copolymer A has a multi-arm structure from 2 to 10 arms. In some embodiments, copolymer A has a multi-arm structure from 3 to 8 arms. In someWSGR Docket No. Accolens-701.601 embodiments, copolymer A has a multi-arm structure of 3 arms. In some embodiments, copolymer A has a multi-arm structure of 4 arms. In some embodiments, copolymer A has a multi-arm structure of 5 arms. In some embodiments, copolymer A has a multi-arm structure of 6 arms. In some embodiments, copolymer A has a multi-arm structure of 7 arms. In some embodiments, copolymer A has a multi-arm structure of 8 arms.

[0132] In some embodiments, copolymer A comprises reactive moiety A. In some embodiments, copolymer A comprises one or more -OH, -SH, -NH2, -N3, or furan groups. In some embodiments, copolymer A comprises -OH, -SH, -NH2, or -N3 groups. In some embodiments, copolymer A comprises -OH, -SH, or -NH2 groups. In some embodiments, copolymer A comprises N3groups. In some embodiments, copolymer A comprises -NH2groups. In some embodiments, In some embodiments, copolymer A comprises -SH groups. In some embodiments, copolymer A comprises one or more -OH groups. In some embodients, the -OH group is converted to an acrylate, methacrylate, allyl, vinyl, amine, thiol, azide furan, maleimide, or DBCO group. In some embodiments, the -OH group is converted to an acrylate, methacrylate, allyl, vinyl, amine, or thiol group. In some embodiments, the -OH group is converted to an acrylate group.

[0133] In some embodiments, reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises one or more reactive moiety B, wherein reactive moiety B comprises one or more -SH, -NH2, epoxy group, or alkenyl group or a combination thereof. In some embodiments, reactant B is a polymer. In some embodiments, reactant B is a copolymer. In some embodiments, reactant B is a copolymer, wherein the copolymer is a bottlebrush polymer, comb polymer, linear polymer with a branched, multi-arm, structure, or a combination thereof. In some embodiments, reactant B is a copolymer that can have the monomeric structures shown in FIGs.2A and 2B, FIGs. 3A and 3B, FIG.4 and FIG.5. In some embodiments, reactant B is a small molecule. In some embodiments, reactant B can be a small molecule crosslinker or a polymer crosslinker shown in FIG.4 and FIG.5.

[0134] In some embodiments, reactant B comprises more than one reactive moiety B. In some embodiments, each reactive moiety B independently comprises -SH, -NH2, -N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof. In some embodiments, each reactive moiety B is independently -SH, -NH2, -N3, furan, maleimide, DBCO, acrylate, methylacrylate, allyl, or vinyl. In some embodiments, each reactive moiety B independently comprises, -NH2, epoxy group, or alkenyl group or a combination thereof. In some embodiments, reactive moiety B comprises one or more -SH, -NH2, or alkenyl group or a combination thereof. In some embodiments, reactive moiety B comprises one or more -SH, -NH2, or a combination thereof.WSGR Docket No. Accolens-701.601 In some embodiments, reactant B comprises more than one reactive moiety B, wherein the reactive moiety B is -NH2.

[0135] In some embodiments, reactant B comprises a degradable site. In some embodiments, the degradable site is degrading using light or local high temperature. In some embodiments, the degradable site comprises nitro benzyl, diene, dienophile, peroxide, azo, or a combination thereof. In some embodiments, the degradable site comprises nitro benzyl. In some embodiments, the degradable site comprises diene, dienophile, peroxide, or azo.

[0136] In some embodiments, reactant B is a siloxane-containing polymer or copolymer. In some embodiments, reactant B is (20-25% aminopropylmethylsiloxane)-dimethylsiloxane copolymer, (2-3% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (6-7% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, aminopropyl terminated polydimethylsiloxane, mercaptopropyl terminated polydimethylsiloxane, (30-35% dodecylmethylsiloxane)-[7-10% hydroxy(polyethyleneoxy(6-9)propyl)methylsiloxane]- (55-65% dimethylsiloxane) terpolymer, (aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, acryloxy terminated ethyleneoxide dimethylsiloxane-ethyleneoxide aba block copolymer, or aminopropyl terminated polydimethylsiloxane. In some embodiments, reactant B has a CAS No.117440-21-8. In some embodiments, reactant B has a CAS No.67923-07-3. In some embodiments, reactant B has a CAS No.99363-37-8.

[0137] In some embodiments, reactant B is a copolymer that include any amine alkyl methacrylate or acrylate, e.g., aminoethyl methacrylate. In some embodiments, reactant B has a CAS No.106214-84-0.

[0138] In some embodiments, reactant B is a small molecule with more than one amine group like ethylene diamine.

[0139] In some embodiments, reactant B is the reactant B illustrated in Example 22.

[0140] In some embodiments, the copolymer A is a reaction product of monomers that comprise a structure of Formula (Ia), Formula (Ib), and / or Formula (Ic):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl; each R1’is independently hydrogen or C1-C3 alkyl; each R2is independently C1-C10 alkyl group or phenyl; each R3is independently C1-C4 alkyl group or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl group; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each a is independently 0 to 10; each b is independently 0 to 10; each c is independently 0 to 10; each d is independently 0 to 10; each e is independently 0 to 10; each f is independently 0 to 10; each g is independently 0 to 50; each a1 is independently 0 to 10; each b1 is independently 0 to 10; each c1 is independently 0 to 10; each d1 is independently 0 to 10; each e1 is independently 0 to 10; each f1 is independently 0 to 10; and each p is independently 0 to 10.

[0141] In some embodiments, wherein the copolymer A comprises a structure of Formula (II):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl; each R1’is independently hydrogen or C1-C3 alkyl; each R2is independently C1-C10 alkyl group or phenyl; each R3is independently C1-C4 alkyl group or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl group; each a is independently 0 to 10; each b is independently 0 to 4; each c is independently 0 or 1; each d is independently 0 to 4; each e is independently 0 to 9; each f is independently 0 to 4; each g is independently 0 to 50; each a1 is independently 0 to 10; each b1 is independently 0 to 4; each c1 is independently 0 or 1; each d1 is independently 0 to 4; each e1 is independently 0 to 9; each f1 is independently 0 to 4; each m is independently1 to 5000; each n is independently 1 to 5000; each o is independently 0 to 5000; and each p is independently 0 to 10.

[0142] In some embodiments, the copolymer A comprises a structure of Formula (III):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3alkyl group; each R6is independently H or C1-C10alkyl group; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each R8is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each g is independently 0 to 50; each m is independently1 to 5000; each n is independently 1 to 5000; each o is independently 0 to 5000; each q is independently 1 to 10; and each r is independently 1 to 10.

[0143] In some embodiments, the copolymer A comprises a structure of Formula (IV):wherein: each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl group; each R6is independently H or C1-C10 alkyl group; each m1 is independently 0 to 5000; each m2 is independently 0 to 5000; each n1 is independently 0 to 5000; each n2 is independently 0 to 5000; each q is independently 1 to 10; each p is independently 0 to 10; each s is independent 2 to 10; x is 1 to 6; and y is 1 to 6.

[0144] In some embodiments, each X is independently -O- or -NR6-. In some embodiments, each X is independently -O-. In some embodiments, each X is independently -NR6-. In someWSGR Docket No. Accolens-701.601 embodiments, each X is independently -NH-. In some embodiments, each X is independently - NCH3-.

[0145] In some embodiments, each Z is independently -O- or -NR6-. In some embodiments, each Z is independently -O-. In some embodiments, each Z is independently -NR6-. In some embodiments, each Z is independently -NH-. In some embodiments, each Z is independently - NCH3-.

[0146] In some embodiments, each R1is independently hydrogen or C1-C3alkyl. In some embodiments, each R1is independently hydrogen. In some embodiments, each R1is independently C1-C3 alkyl. In some embodiments, each R1is independently methyl. In some embodiments, each R1is independently ethyl. In some embodiments, each R1is independently propyl.

[0147] In some embodiments, each R1’is independently hydrogen or C1-C3alkyl. In some embodiments, each R1’is independently hydrogen. In some embodiments, each R1’is independently C1-C3 alkyl. In some embodiments, each R1’is independently methyl. In some embodiments, each R1’is independently ethyl. In some embodiments, each R1’is independently propyl.

[0148] In some embodiments, each R2is independently C1-C10 alkyl or phenyl. In some embodiments, each R2is independently C1-C10 alkyl. In some embodiments, each R2is independently phenyl. In some embodiments, each R2is independently C1-C5alkyl. In some embodiments, each R2is independently C1-C3alkyl. In some embodiments, each R2is independently methyl. In some embodiments, each R2is independently ethyl. In some embodiments, each R2is independently propyl.

[0149] In some embodiments, each R3is independently C1-C4alkyl or phenyl. In some embodiments, each R3is independently phenyl. In some embodiments, each R3is independently C1-C4 alkyl. In some embodiments, each R3is independently C1-C3 alkyl. In some embodiments, each R3is independently methyl. In some embodiments, each R3is independently ethyl. In some embodiments, each R3is independently propyl.

[0150] In some embodiments, each R4is independently C1-C10 alkyl. In some embodiments, each R4is independently C1-C10alkyl. In some embodiments, each R4is independently phenyl. In some embodiments, each R4is independently C1-C5alkyl. In some embodiments, each R4is independently C4 alkyl. In some embodiments, each R4is independently C1-C3 alkyl. In some embodiments, each R4is independently methyl. In some embodiments, each R4is independently ethyl. In some embodiments, each R4is independently propyl. In some embodiments, each R4is independently butyl.

[0151] In some embodiments, each R5is independently -OH, -N3, -SH, or -NH2. In some embodiments, each R5is independently -OH or -NH2. In some embodiments, each R5isWSGR Docket No. Accolens-701.601 independently -OH. In some embodiments, each R5is independently -N3In some embodiments, each R5is independently -SH2. In some embodiments, each R5is independently NH2.

[0152] In some embodiments, each R6is independently H or C1-C10 alkyl. In some embodiments, each R6is independently H or C1-C5alkyl. In some embodiments, each R6is independently H. In some embodiments, each R6is independently C1-C10 alkyl. In some embodiments, each R6is independently C1-C5 alkyl. In some embodiments, each R6is independently C1-C3alkyl. In some embodiments, each R6is independently methyl. In some embodiments, each R6is independently ethyl. In some embodiments, each R6is independently propyl.

[0153] In some embodiments, each independently R7is -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide. In some embodiments, each independently R7is -OH, -NH2, -N3, -SH, acrylate, methylate, vinyl, allyl, furan, or maleimide. In some embodiments, each independently R7is -OH, -NH2, -SH, acrylate, methylate, furan, or maleimide. In some embodiments, each independently R7is -OH, -NH2, -SH, acrylate, or methylate. In some embodiments, each independently R7is -OH, -NH2, or -SH. In some embodiments, each independently R7is -NH2. In some embodiments, each independently R7is -SH. In some embodiments, each independently R7is acrylate. In some embodiments, each independently R7is methylate.

[0154] In some embodiments, each R8is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide. In some embodiments, each independently R8is -OH, -NH2, -N3, -SH, acrylate, methylate, vinyl, allyl, furan, or maleimide. In some embodiments, each independently R8is -OH, -NH2, -SH, acrylate, methylate, furan, or maleimide. In some embodiments, each independently R8is -OH, -NH2, -SH, acrylate, or methylate. In some embodiments, each independently R8is -OH, -NH2, or -SH. In some embodiments, each independently R8is -NH2. In some embodiments, each independently R8is -SH. In some embodiments, each independently R8is acrylate. In some embodiments, each independently R8is methylate.

[0155] In some embodiments, each a is independently 0 to 10. In some embodiments, each a is independently 0 to 5. In some embodiments, each a is independently 0. In some embodiments, each a is independently 1. In some embodiments, each a is independently 2. In some embodiments, each a is independently 3. In some embodiments, each a is independently 4. In some embodiments, each a is independently 5. In some embodiments, each a is independently 6. In some embodiments, each a is independently 7. In some embodiments, each a is independently 8. In some embodiments, each a is independently 9. In some embodiments, each a is independently 10.WSGR Docket No. Accolens-701.601

[0156] In some embodiments, each b is independently 0 to 10. In some embodiments, each b is independently 0 to 5. In some embodiments, each b is independently 0. In some embodiments, each b is independently 1. In some embodiments, each b is independently 2. In some embodiments, each b is independently 3. In some embodiments, each b is independently 4. In some embodiments, each b is independently 5. In some embodiments, each b is independently 6. In some embodiments, each b is independently 7. In some embodiments, each b is independently 8. In some embodiments, each b is independently 9. In some embodiments, each b is independently 10.

[0157] In some embodiments, each c is independently 0 to 10. In some embodiments, each c is independently 0 to 5. In some embodiments, each c is independently 0. In some embodiments, each c is independently 1. In some embodiments, each c is independently 2. In some embodiments, each c is independently 3. In some embodiments, each c is independently 4. In some embodiments, each c is independently 5. In some embodiments, each c is independently 6. In some embodiments, each c is independently 7. In some embodiments, each c is independently 8. In some embodiments, each c is independently 9. In some embodiments, each c is independently 10.

[0158] In some embodiments, each d is independently 0 to 10. In some embodiments, each d is independently 0 to 5. In some embodiments, each d is independently 0. In some embodiments, each d is independently 1. In some embodiments, each d is independently 2. In some embodiments, each d is independently 3. In some embodiments, each d is independently 4. In some embodiments, each d is independently 5. In some embodiments, each d is independently 6. In some embodiments, each d is independently 7. In some embodiments, each d is independently 8. In some embodiments, each d is independently 9. In some embodiments, each d is independently 10.

[0159] In some embodiments, each e is independently 0 to 10. In some embodiments, each e is independently 0 to 5. In some embodiments, each e is independently 0. In some embodiments, each e is independently 1. In some embodiments, each e is independently 2. In some embodiments, each e is independently 3. In some embodiments, each e is independently 4. In some embodiments, each e is independently 5. In some embodiments, each e is independently 6. In some embodiments, each e is independently 7. In some embodiments, each e is independently 8. In some embodiments, each e is independently 9. In some embodiments, each e is independently 10.

[0160] In some embodiments, each f is independently 0 to 10. In some embodiments, each f is independently 0 to 5. In some embodiments, each f is independently 0. In some embodiments, each f is independently 1. In some embodiments, each f is independently 2. In some embodiments, each f is independently 3. In some embodiments, each f is independently 4. In some embodiments, each f is independently 5. In some embodiments, each f is independently 6. In some embodiments, each fWSGR Docket No. Accolens-701.601 is independently 7. In some embodiments, each f is independently 8. In some embodiments, each f is independently 9. In some embodiments, each f is independently 10.

[0161] In some embodiments, each g is independently 0 to 50. In some embodiments, each g is independently 0 to 40. In some embodiments, each g is independently 0 to 30. In some embodiments, each g is independently 0 to 20. In some embodiments, each g is independently 0 to 5. In some embodiments, each g is independently 0. In some embodiments, each g is independently 1. In some embodiments, each g is independently 2. In some embodiments, each g is independently 3. In some embodiments, each g is independently 4. In some embodiments, each g is independently 5. In some embodiments, each g is independently 6. In some embodiments, each g is independently 7. In some embodiments, each g is independently 8. In some embodiments, each g is independently 9. In some embodiments, each g is independently 10.

[0162] In some embodiments, each a1 is independently 0 to 10. In some embodiments, each a1 is independently 0 to 5. In some embodiments, each a1 is independently 0. In some embodiments, each a1 is independently 1. In some embodiments, each a1 is independently 2. In some embodiments, each a1 is independently 3. In some embodiments, each a1 is independently 4. In some embodiments, each a1 is independently 5. In some embodiments, each a1 is independently 6. In some embodiments, each a1 is independently 7. In some embodiments, each a1 is independently 8. In some embodiments, each a1 is independently 9. In some embodiments, each a1 is independently 10.

[0163] In some embodiments, each b1 is independently 0 to 10. In some embodiments, each b1 is independently 0 to 5. In some embodiments, each b1 is independently 0. In some embodiments, each b1 is independently 1. In some embodiments, each b1 is independently 2. In some embodiments, each b1 is independently 3. In some embodiments, each b1 is independently 4. In some embodiments, each b1 is independently 5. In some embodiments, each b1 is independently 6. In some embodiments, each b1 is independently 7. In some embodiments, each b1 is independently 8. In some embodiments, each b1 is independently 9. In some embodiments, each b1 is independently 10.

[0164] In some embodiments, each c1 is independently 0 to 10. In some embodiments, each c is independently 0 to 5. In some embodiments, each c is independently 0. In some embodiments, each c1 is independently 1. In some embodiments, each c1 is independently 2. In some embodiments, each c1 is independently 3. In some embodiments, each c1 is independently 4. In some embodiments, each c1 is independently 5. In some embodiments, each c1 is independently 6. In some embodiments, each c1 is independently 7. In some embodiments, each c1 is independently 8.WSGR Docket No. Accolens-701.601 In some embodiments, each c1 is independently 9. In some embodiments, each c1 is independently 10.

[0165] In some embodiments, each d1 is independently 0 to 10. In some embodiments, each d1 is independently 0 to 5. In some embodiments, each d1 is independently 0. In some embodiments, each d1 is independently 1. In some embodiments, each d1 is independently 2. In some embodiments, each d1 is independently 3. In some embodiments, each d1 is independently 4. In some embodiments, each d1 is independently 5. In some embodiments, each d1 is independently 6. In some embodiments, each d1 is independently 7. In some embodiments, each d1 is independently 8. In some embodiments, each d1 is independently 9. In some embodiments, each d1 is independently 10.

[0166] In some embodiments, each e1 is independently 0 to 10. In some embodiments, each e1 is independently 0 to 5. In some embodiments, each e1 is independently 0. In some embodiments, each e1 is independently 1. In some embodiments, each e1 is independently 2. In some embodiments, each e1 is independently 3. In some embodiments, each e1 is independently 4. In some embodiments, each e1 is independently 5. In some embodiments, each e1 is independently 6. In some embodiments, each e1 is independently 7. In some embodiments, each e1 is independently 8. In some embodiments, each e1 is independently 9. In some embodiments, each e1 is independently 10.

[0167] In some embodiments, each f1 is independently 0 to 10. In some embodiments, each f1 is independently 0 to 5. In some embodiments, each f1 is independently 0. In some embodiments, each f1 is independently 1. In some embodiments, each f1 is independently 2. In some embodiments, each f1 is independently 3. In some embodiments, each f1 is independently 4. In some embodiments, each f1 is independently 5. In some embodiments, each f1 is independently 6. In some embodiments, each f1 is independently 7. In some embodiments, each f1 is independently 8. In some embodiments, each f1 is independently 9. In some embodiments, each f1 is independently 10.

[0168] In some embodiments, each m is independently 1 to 5000. In some embodiments, each m is independently 1 to 2500. In some embodiments, each m is independently 1 to 2000. In some embodiments, each m is independently 1 to 1000. In some embodiments, each m is independently 1 to 800. In some embodiments, each m is independently 1 to 600. In some embodiments, each m is independently 1 to 400. In some embodiments, each m is independently 1 to 200. In some embodiments, each m is independently 1 to 100.

[0169] In some embodiments, each m1 independently is 1 to 5000. In some embodiments, each m1 is independently 1 to 2500. In some embodiments, each m1 is independently 1 to 2000. In someWSGR Docket No. Accolens-701.601 embodiments, each m1 is independently 1 to 1000. In some embodiments, each m1 is independently 1 to 800. In some embodiments, each m1 is independently 1 to 600. In some embodiments, each m1 is independently 1 to 400. In some embodiments, each m1 is independently 1 to 200. In some embodiments, each m1 is independently 1 to 100.

[0170] In some embodiments, each m2 is independently 1 to 5000. In some embodiments, each m2 is independently 1 to 2500. In some embodiments, each m2 is independently 1 to 2000. In some embodiments, each m2 is independently 1 to 1000. In some embodiments, each m2 is independently 1 to 800. In some embodiments, each m2 is independently 1 to 600. In some embodiments, each m2 is independently 1 to 400. In some embodiments, each m2 is independently 1 to 200. In some embodiments, each m2 is independently 1 to 100.

[0171] In some embodiments, each n is independently 1 to 5000. In some embodiments, each n is independently 1 to 2500. In some embodiments, each n is independently 1 to 2000. In some embodiments, each n is independently 1 to 1000. In some embodiments, each n is independently 1 to 800. In some embodiments, each n is independently 1 to 600. In some embodiments, each n is independently 1 to 400. In some embodiments, each n is independently 1 to 200. In some embodiments, each n is independently 1 to 100.

[0172] In some embodiments, each n1 is independently 1 to 5000. In some embodiments, each n1 is independently 1 to 2500. In some embodiments, each n1 is independently 1 to 2000. In some embodiments, each n1 is independently 1 to 1000. In some embodiments, each n1 is independently 1 to 800. In some embodiments, each n1 is independently 1 to 600. In some embodiments, each n1 is independently 1 to 400. In some embodiments, each n1 is independently 1 to 200. In some embodiments, each n1 is independently 1 to 100.

[0173] In some embodiments, each n2 is independently 1 to 5000. In some embodiments, each n2 is independently 1 to 2500. In some embodiments, each n2 is independently 1 to 2000. In some embodiments, each n2 is independently 1 to 1000. In some embodiments, each n2 is independently 1 to 800. In some embodiments, each n2 is independently 1 to 600. In some embodiments, each n2 is independently 1 to 400. In some embodiments, each n2 is independently 1 to 200. In some embodiments, each n2 is independently 1 to 100.

[0174] In some embodiments, each o is independently 0 to 5000. In some embodiments, each o is independently 0 to 2500. In some embodiments, each o is independently 0 to 5000. In some embodiments, each o is independently 0 to 2000. In some embodiments, each o is independently 0 to 1000. In some embodiments, each o is independently 0 to 800. In some embodiments, each o is independently 0 to 600. In some embodiments, each o is independently 0 to 400. In someWSGR Docket No. Accolens-701.601 embodiments, each o is independently 0 to 200. In some embodiments, each o is independently 0 to 100.

[0175] In some embodiments, each p is independently 0 to 10. In some embodiments, each p is independently 2 to 8. In some embodiments, each p is independently 2 to 5. In some embodiments, each p is independently 2. In some embodiments, each p is independently 3. In some embodiments, each p is independently 4. In some embodiments, each p is independently 5.

[0176] In some embodiments, each q is independently 1 to 10. In some embodiments, each q is independently 1 to 8. In some embodiments, each q is independently 1 to 5. In some embodiments, each q is independently 1. In some embodiments, each q is independently 2. In some embodiments, each q is independently 3. In some embodiments, each q is independently 4. In some embodiments, each q is independently 5.

[0177] In some embodiments, each r is independently 1 to 10. In some embodiments, each r is independently 1 to 8. In some embodiments, each r is independently 1 to 5. In some embodiments, each r is independently 1. In some embodiments, each r is independently 2. In some embodiments, each r is independently 3. In some embodiments, each r is independently 4. In some embodiments, each r is independently 5.

[0178] In some embodiments, each s is independently 2 to 10. In some embodiments, each s is independently 2 to 8. In some embodiments, each s is independently 2 to 5. In some embodiments, each s is independently 2. In some embodiments, each s is independently 3. In some embodiments, each s is independently 4. In some embodiments, each s is independently 5.

[0179] In some embodiments, each a is independently 0 to 5; each b is independently 0 to 5; each c is independently 0 to 5; each d is independently 0 to 5; each e is independently 0 to 5; each f is independently 0 to 5; each g is independently 0 to 5; each a1 is independently 0 to 5; each b1 is independently 0 to 5; each c1 is independently 0 to 5; each d1 is independently 0 to 5; each e1 is independently 0 to 5; and each f1 is independently 0 to 5. In some embodiments, each a is independently 0 to 3; each b is independently 0 to 3; each c is independently 0 to 3; each d is independently 0 to 3; each e is independently 0 to 3; each f is independently 0 to 3; each g is independently 0 to 3; each a1 is independently 0 to 3; each b1 is independently 0 to 3; each c1 is independently 0 to 3; each d1 is independently 0 to 3; each e1 is independently 0 to 3; and each f1 is independently 0 to 3.

[0180] In some embodiments, each m is independently1 to 2000; each n is independently 1 to 2000; each o is independently 0 to 2000; and each p is independently an integer from 2 to 5. In some embodiments, each m is independently 1 to 1000; each n is independently 1 to 1000; each o is independently 0 to 1000; and each p is independently an integer from 2 to 5. In some embodiments,WSGR Docket No. Accolens-701.601 each m is independently 1 to 500; each n is independently 1 to 500; each o is independently 0 to 500; and each p is independently an integer from 2 to 5. In some embodiments, each m is independently 1 to 200; each n is independently 1 to 200; each o is independently 0 to 200; and each p is independently an integer from 2 to 5. In some embodiments, each m is independently 1 to 100; each n is independently 1 to 100; each o is independently 0 to 100; and each p is independently an integer from 2 to 5.

[0181] In some embodiments, n+m is at least 500. In some embodiments, n+m is 500 to 1000. In some embodiments, n+m is 500 to 750. In some embodiments, n+m is 750 to 1000. In some embodiments, n+m is 100 to 500. In some embodiments, n+m is 100 to 250. In some embodiments, n+m is 250 to 500.

[0182] In some embodiments, the ratio of n to m is 1:5 to 1:50. In some embodiments, the ratio of n to m is 1:5 to 1:25. In some embodiments, the ratio of n to m is 1:10 to 1:20. In some embodiments, the ratio of n to m is 1:10 to 1:15. In some embodiments, the ratio of n to m is 1:10. In some embodiments, the ratio of n to m is 1: 15. In some embodiments, the ratio of n to m is 1:20.

[0183] In some embodiments, n is less than 10% of the polymer network. In some embodiments, n is about 1% to less than 10% of the polymer network. In some embodiments, n is less than 5% of the polymer network. In some embodiments, n is about 1% to less than 5% of the polymer network. In some embodiments, n is about 1% of the polymer network. In some embodiments, n is about 2% of the polymer network. In some embodiments, n is about 3% of the polymer network. In some embodiments, n is about 4% of the polymer network. In some embodiments, n is about 5% of the polymer network.

[0184] In some embodiments, n is about 5% to about 30% of the polymer network. In some embodiments, n is about 10% of the polymer network. In some embodiments, n is about 20% of the polymer network. In some embodiments, n is about 30% of the polymer network.

[0185] In some embodiments, each q is independently 1 to 10; and each r is independently 1 to 5. In some embodiments, each q is independently 1 to 5; and each r is independently 1 to 4. In some embodiments, each q is independently 1 to 3; and each r is independently 1 to 3. In some embodiments, each q is independently 1 to 2; and each r is independently 1 to 2.

[0186] In some embodiments, copolymer A is a reaction product of monomers that comprise Formula (Ia). In some embodiments, X is -O-, R1is methyl, each R3is methyl, R4is C4 alkyl, a is 0, b is 3, c is 0, d is 0, e is 0, and f is 0.

[0187] In some embodiments, copolymer A is a reaction product of monomers that comprise Formula (Ib). In some embodiments, X is -O-, R1is methyl, R5is -OH, a1 is 0, b1 is 1, c1 is 1, d1 is 1, e1 is 1, f1 is 1, and R2is methyl.WSGR Docket No. Accolens-701.601

[0188] In some embodiments, copolymer A is a reaction product of monomers that comprise Formula (Ic).

[0189] In some embodiments, copolymer A is a reaction product of monomers that comprise a siloxane-containing monomer of Formula (Ib-1),TFormula (Ib-1) wherein: R1 is hydrogen or C1-C3 alkyl; each R2is independently C1-C4alkyl; Y is -O-, -S- or -NH-; X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-, n is an integer number selected from 0 to 100; and m is an integer number selected from 0 to 100.

[0190] In some embodiments, copolymer A is a reaction product of monomers that comprise a siloxane-containing monomer of Formula (Ib-2),Formula (Ib-2) wherein R1is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl; Y is -O-, -S- or -NH-; X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH-, n is an integer number selected from 0 to 100; and m is an integer number selected from 0 to 100.WSGR Docket No. Accolens-701.601

[0191] In some embodiments, copolymer A is a reaction product of monomers that comprise a siloxane-containing monomer of Formula (V),Formula (V) wherein: n is an integer number selected from 0 to 100; and each R3is independently C1-C4alkyl.

[0192] In some embodiments, described herein is a siloxane-containing monomer of Formula (V-1),Formula (II) wherein n is an integer number selected from 0 to 100.

[0193] In some embodiments, copolymer A is a reaction product of monomers that comprise a siloxane-containing monomer of Formula (Ia-1),Formula (Ia-1) wherein R1is hydrogen or C1-C3alkyl; Y is -O-, -S- or -NH-; X is -O-, -S-, -NH-C=O-O- or -NH-C=O=NH- or -NH- ; each R4is independently C1-C4alkyl;WSGR Docket No. Accolens-701.601 n is an integer number selected from 0 to 100; I is an integer number selected from 0 to 100; and m is an integer number selected from 0 to 100.

[0194] In some embodiments, copolymer A is a reaction product of monomers that comprise a siloxane-containing monomer of Formula (Ia-2),Formula (Ia-2) wherein R1 is hydrogen or an alkyl group having 1 carbon and 3 hydrogen atoms such as methyl; Y is -O-, -S- or -NH-; X is -O-, -S- , -NH-C=O-O- or -NH-C=O=NH- or -NH- ; n is an integer number selected from 0 to 100; I is an integer number selected from 0 to 100; and m is an integer number selected from 0 to 100.

[0195] In some embodiments, the copolymer A comprises a copolymer selected from Examples 1-20. In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes (Bbb). In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes (Bbb). In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) combs (B-r-D). In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) combs (B-r-D). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate) Bottlebrushes (Bbb). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate) Bottlebrushes (Bbb). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate) combs (B-r-D). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate) combs (B-r-D). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate)-b-Poly(dimethylsiloxane) combs (B-r-D)-b-(B’-r-D’). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate)-b-Poly(dimethylsiloxane) combs (B-r-D)-b-(B’-r-D’). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate)-b-(Poly(dimethylsiloxane)2 combs (B-r-D)-b- (B’-r-D’). In some embodiments, the copolymer A comprises Poly(poly-n butyl acrylate)-b- (Poly(dimethylsiloxane))2 combs (B-r-D)-b-(B’-r-D’)2. In some embodiments, the copolymer A comprises Poly(Poly(dimethylsiloxane))-b-( poly-n butyl acrylate)2 combs (B-r-D)-b-(B’-r-D’)2. In some embodiments, the copolymer A comprises Poly(Poly(dimethylsiloxane))-b-( poly (poly-n butyl acrylate))2 combs (B-r-D)-b-(B’-r-D’)2. In some embodiments, the copolymer A comprisesWSGR Docket No. Accolens-701.601 Poly(dimethylsiloxane) Bottlebrushes-b( poly(dimethylsiloxan copolymer) (Bbb)-b-(A-C)2(in this case A=B). In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes-b( poly(dimethylsiloxan copolymer) (Bbb)-b-(A-C)2(in this case A=B). In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes-b-( (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane) (Bbb)-b-(C)2. In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes-b-( -( (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane) (Bbb)-b-(C)2. In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrush-b- (Hydroxylhexylmethacrylate) (Bbb)-b-(C)2. In some embodiments, the copolymer A comprises Poly(dimethylsiloxane) Bottlebrushes-b-(Hydroxylhexylmethacrylate (1-5 mole% respect to EX2) (Bbb)-b-( C)2.

[0196] In some embodiments, the copolymer A comprises one or more block copolymer segments and one or more random copolymer segments. In some embodiments, the copolymer A is represented by A-b-B-b-A, wherein A represents a polymer with acrylate functional group and B represents a siloxane-containing polymer (e.g, Poly(dimethylsiloxane)), and “A-b-B” represents a block copolymer segment of polymer A and polymer B. In some embodiments, the copolymer A is represented by A-r-B-b-B-b-A-r-B, wherein A represents a polymer with acrylate functional group and B represents a siloxane-containing polymer (e.g, Poly(dimethylsiloxane)), “A-b-B” represents a block copolymer segment of polymer A and polymer B, and “A-r-B” represents a random copolymer segment comprising A and B. In some embodiments, A is polymer with acrylate functional group with DP 10-100. In some embodiments, A is polymer with acrylate functional group with DP 30. In some embodiments, A is polymer with acrylate functional group with DP 42. In some embodiments, A is polymer with acrylate functional group with DP 20-30. In some embodiments, B part is PDMS MCR-M11 brush with DP 900. In some embodiments, B part is PDMS MCR-M11 brush with DP 600. In some embodiments, B part is PDMS MCR-M11 brush with DP 300-1500. In some embodiments, “A-r-B” is a random copolymer segment comprising monomers A and B, wherein A being a monomer with acrylate functional group and B being a siloxane-containing monomer. In some embodiments, “A-r-B” has a DP of 10-100. In some embodiments, “A-r-B” has a DP of 20-60. In some embodiments, A is a polymer with DP 10-100. In some embodiments, A is a polymer with DP 20-50. In some embodiments, B is a polymer with DP 10-100. In some embodiments, B is a polymer with DP 20-50. In some embodiments, the copolymer A is a di-block copolymer. In some embodiments, the copolymer A is a tri-block copolymer. In some embodiments, the copolymer A has 4, 5, or more blocks. In some embodiments, each of the block segments of copolymer A is a homopolymer. In someWSGR Docket No. Accolens-701.601 embodiments, each of the block segments of Copolymer A is a copolymer (e.g., a random copolymer of 2 or more monomers). In some embodiments, copolymer A comprises two or more block segments, which comprise one or more segments of homopolymer and one or more segments of random copolymer. In some embodiments, the copolymer A is a tri-block copolymer, comprising 3 blocks of homopolymer. In some embodiments, the copolymer A is a tri-block copolymer, comprising (i) a first segment that is a random copolymer (e.g., of 2 or more monomers), (ii) a second segment that is a block of homopolymer, and (iii) a third segment that is a random copolymer.

[0197] In some embodiments, the polymer network is formed via cross-linking between the reactive moiety A of copolymer A and the reactive moiety B of reactant B. In some embodiments, the cross-linking is formed spontaneously. In some embodiments, the cross-linking is formed without catalyst or stimuli. In some embodiments, the stimuli can be temperature or light.

[0198] In some embodiments, reactive moiety A and reactive moiety B is randomly distributed. In some embodiments, wherein reactant B is a copolymer, and reactive moiety A and reactive moiety B is randomly distributed or block distributed at the end of the copolymers.

[0199] In some embodiments, wherein the polymer network is formed spontaneously upon injection into or casting on a mold or a cavity. In some embodiments, the polymer network can be formed ex vivo. In some embodiments, the polymer network can be formed in vivo. In some embodiments, the polymer network is formed after injection into the body.

[0200] In some embodiments, copolymer A has one or more low glass transition temperature (Tg) monomers. In some embodiments, the one or more low Tgmonomers have a Tgof at most 100 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most 80 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most 50 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof at most 40 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most 30 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most 35 ºC. In some embodiments, the one or more low Tg monomers have a Tgof at most 25 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof at most 20 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof at most 10 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most 0 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most -50 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof at most -100 ºC. In some embodiments, the one or more low Tg monomers have a Tg of at most -120 ºC.

[0201] In some embodiments, the one or more low Tg monomers have a Tg of about 30-50 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof about 30-40 ºC. In someWSGR Docket No. Accolens-701.601 embodiments, the one or more low Tgmonomers have a Tgof about 0-50 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about 0-30 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about -10 to 20 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof about -10 to 50 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about -150 to -10 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about -150 to -50 ºC. In some embodiments, the one or more low Tgmonomers have a Tgof about -150 to -100 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about -140 to -110 ºC. In some embodiments, the one or more low Tg monomers have a Tg of about -120 ºC.

[0202] In some embodiments, the Tgis less than 35 ºC. In some embodiments, the Tgis less than 25 ºC. In some embodiments, the Tgis less than 20 ºC. In some embodiments, the Tgis about 0 ºC to about 25 ºC. In some embodiments, the Tg is about 10 ºC to about 25 ºC. In some embodiments, the Tg is about 15 ºC to about 25 ºC.

[0203] In some embodiments, the molecular weight of copolymer A is about 5000 g / mol to about 10,000,000 g / mol. In some embodiments, the molecular weight of copolymer A is about 5000 g / mol to about 10,000 g / mol. In some embodiments, the molecular weight of copolymer A is about 5000 g / mol to about 8,000 g / mol. In some embodiments, the molecular weight of copolymer A is about 5000 g / mol to about 6,000 g / mol.

[0204] In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 10,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 9,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 8,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 7,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 6,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 5,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 4,000 g / mol. the molecular weight of reactant B is about 500 g / mol to about 3,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 2,000 g / mol. In some embodiments, the molecular weight of reactant B is about 500 g / mol to about 1,000 g / mol.

[0205] In some embodiments, the ratio of copolymer A to reactant B is about 1000 to about 0.01. In some embodiments, the ratio of copolymer A to reactant B is about 1000 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 900 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 800 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 700 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 600 to about 0.1. In someWSGR Docket No. Accolens-701.601 embodiments, the ratio of copolymer A to reactant B is about 500 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 400 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 300 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 200 to about 0.1. In some embodiments, the ratio of copolymer A to reactant B is about 100 to about 0.5. In some embodiments, the ratio of copolymer A to reactant B is about 50 to about 0.5. In some embodiments, the ratio of copolymer A to reactant B is about 25 to about 0.5. In some embodiments, the ratio of copolymer A to reactant B is about 10 to about 0.5. In some embodiments, the ratio of copolymer A to reactant B is about 10 to about 1.

[0206] In some embodiments, the polymer network is cured from about 1 minute to about 100 hours. In some embodiments, the polymer network is cured from about 5 minute to about 48 hours. In some embodiments, the polymer network is cured from about 5 minute to about 36 hours. In some embodiments, the polymer network is cured from about 5 minute to about 24 hours. In some embodiments, the polymer network is cured from about 30 minute to about 12 hours. In some embodiments, the polymer network is cured from about 1 hour to about 6 hours.

[0207] In some embodiments, the polymer network has a Young’s modulus of about 50 Pa to about 10 MPa. In some embodiments, the polymer network has a Young’s modulus of about 100 Pa to about 10 MPa. In some embodiments, the polymer network has a Young’s modulus of about 200 Pa to about 10 MPa. In some embodiments, the polymer network has a Young’s modulus of about 0.5 kPa to about 1 MPa. In some embodiments, the polymer network has a Young’s modulus of about 0.5 kPa to about 100 kPa. In some embodiments, the polymer network has a Young’s modulus of about 0.5 kPa to about 10 kPa. In some embodiments, the polymer network has a Young’s modulus of about 1.0 kPa to about 10 kPa.

[0208] In some embodiments, the polymer network has a viscosity below about 105cP. In some embodiments, the polymer network has a viscosity below about 104cP. In some embodiments, the polymer network has a viscosity below about 103cP. In some embodiments, the polymer network has a viscosity between about 10 cP to about 103cP. In some embodiments, the polymer network has a viscosity between about 102cP to about 103cP. In some embodiments, the polymer network has a viscosity between about 10 cP to about 102cP.

[0209] In some embodiments, the polymer network has strain-stiffening parameter from about 0.1 to about 1.0. In some embodiments, the polymer network has strain-stiffening parameter from about 0.1 to about 0.4. In some embodiments, the polymer network has strain-stiffening parameter from about 0.1 to about 0.3. In some embodiments, the polymer network has strain-stiffening parameter from about 0.1 to about 0.2.WSGR Docket No. Accolens-701.601

[0210] In some embodiments, the polymer network has elongation-at-break from about 0.5% to about 25%. In some embodiments, the polymer network has elongation-at-break from about 1.0% to about 20%. In some embodiments, the polymer network has elongation-at-break from about 1.5% to about 15%. In some embodiments, the polymer network has elongation-at-break from about 1.5% to about 10%. In some embodiments, the polymer network has elongation-at-break from about 1.5% to about 5%.

[0211] In some embodiments, the polymer network has stress-at-break from about 0.05 MPa to about 10 MPa upon uniaxial extension and from about 0.05 MPa to about 10 MPa upon uniaxial compression. In some embodiments, the polymer network has stress-at-break from about 0.05 MPa to about 5 MPa upon uniaxial extension and from about 0.05 MPa to about 5 MPa upon uniaxial compression. In some embodiments, the polymer network has stress-at-break from about 0.05 MPa to about 2.5 MPa upon uniaxial extension and from about 0.05 MPa to about 2.5 MPa upon uniaxial compression. In some embodiments, the polymer network has stress-at-break from about 0.05 MPa to about 1 MPa upon uniaxial extension and from about 0.05 MPa to about 1 MPa upon uniaxial compression.

[0212] In some embodiments, the polymer network has a refractive index from about 1.0 to about 2.0 at a body temperature of about 37 ºC. In some embodiments, the polymer network has a refractive index from about 1.2 to about 1.8 at a body temperature of about 37 ºC. In some embodiments, the polymer network has a refractive index from about 1.4 to about 1.5 at a body temperature of about 37 ºC.

[0213] In some embodiments, the polymer network is for use in drug delivery, implantation, external and implantable contact lenses, or intraocular lenses. In some embodiments, the polymer network is for use in drug delivery. In some embodiments, the polymer network is for use in implantation. In some embodiments, the implantation is for breast implantation. In some embodiments, the polymer network is injected into a lumen. In some embodiments, the lumen is already implanted in the breast. In some embodiments, the polymer network is for use in intraocular lenses. In some embodiments, the polymer network is injected directly into a bag of crystalline lens implanted in an eye after extraction of cataract. In some embodiments, the polymer network is casted to a custom mold before implanting in an eye.

[0214] In some embodiments, the polymer network is formed as a medical device. In some embodiments, the medical device is an implant, a microneedle array, a wound dressing pad, a tissue adhesive, a tissue sealant, a tissue filler, a dermal filler, a vascular graft, a catheter, an implantable contact lens, or an intraocular lens. In some embodiments, the medical device is an implant. In some embodiments, the implant is a breast implant. In some embodiments, the medical device is aWSGR Docket No. Accolens-701.601 microneedle array. In some embodiments, the medical device is a wound dressing pad. In some embodiments, the medical device is a tissue adhesive. In some embodiments, the medical device is a tissue sealant. In some embodiments, the medical device is a tissue filler. In some embodiments, the medical device is a dermal filler. In some embodiments, the medical device is a vascular graft. In some embodiments, the medical device is an implantable contact lens. In some embodiments, the medical device is an intraocular lens. Methods

[0215] Provided herein are methods of making a polymer network, the method comprising reacting copolymer A with reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, and wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, -N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

[0216] Provided herein are methods of making a polymer network, the method comprising reacting copolymer A with reactant B, wherein: copolymer A is a siloxane containing block copolymer that comprises a reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a branched, multi-arm, structure, or a combination thereof, and wherein the reactive moiety A comprise a -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO group; and reactant B can be a polymer, copolymer, or small molecule, wherein reactant B comprises one or more reactive moiety B, wherein reactive moiety B comprises one or more -SH, -NH2, epoxy group, or alkenyl group or a combination thereof.

[0217] In some embodiments, copolymer A is polymerized via a controlled radical polymerization process. In some embodiments, the controlled radicalization polymerization process is free radical polymerization (FRP), atom transfer radical polymerization (ATRP), SARA ATRP, anionic polymerization, or reversible addition-fragmentation chain-transfer polymerization (RAFT). In some embodiments, the controlled radicalization polymerization process is ATRP or RAFT. In some embodiments, the controlled radicalization polymerization process is ATRP. In some embodiments, the controlled radicalization polymerization process is RAFT. In some embodiments, the controlled radicalization polymerization process is SARA ATRP. In some embodiments, the controlled radicalization polymerization process is free radical polymerization (FRP). In some embodiments, the controlled radicalization polymerization process is anionicWSGR Docket No. Accolens-701.601 polymerization. In some embodiments, the controlled radicalization polymerization process is anionic polymerization.

[0218] In some embodiments, copolymer A and reactant B form the polymer network without a catalyst or a stimuli. In some embodiments, copolymer A and reactant B form the polymer network without a catalyst. In some embodiments, copolymer A and reactant B form the polymer network without a stimuli. In some embodiments, the stimuli is an initiator. In some embodiments the stimuli is a radical initiator. In some embodiments, the stimuli is a thermal initiator. In some embodiments, the stimuli is AIBN, Benzyl peroxide, or 2,2-dimethoxy- 1, 2-diphenyl ethenone.

[0219] Exemplary features of the presently disclosed polymer networks include: • -Multi block and not limited to any number and each block can be homo or copolymer and copolymer can be random or block • -Each block can have active moieties • -Each block can be linear, comb or brush and combination • -Low Tg for all blocks • -High gel fraction more than 98%, non leachable • -All blocks can have very low Tg and structure and DP of each block don’t have any effect of flow-ability and injectability • -Chemistry with Tm lower than and body temperature and higher than room temperature (processing temp) • Biocompatibility • Side chains of each block can have extended chain

[0220] Exemplary polymerization techniques used for the presently disclosed polymer networks include: • -All polymerization techniques • ATRP • RAFT • ROMP • Nitroxide mediated • Can be One-pot • Not limited to any initiator CTA, ATRP and how many arms(1 to 4 arms) for viscisty control • Not limited to the type of ligand (ATRP) or co catalyst (RAFT)

[0221] Exemplary crosslinking techniques used for the presently disclosed polymer networks include:WSGR Docket No. Accolens-701.601 • NO water sensitive • Long shelf life • W or w / o external stimuli can be cured • Single unit or multi unit, with same active • No or slow xlinking at RT • On demand at 37C • Curing time: min-hrs @ 37C tunable • Permanent or degradable X-linker • External stimuli degradable (light, mechanically)

[0222] Exemplary properties for the presently disclosed polymer networks include: • Low Tg: solvent-free fluid • Appropriate Tm and Tc for machinability and flowability • Brush / arm: low viscosity melt • Low ^^-parameter: no phase separation • 3-5 years shelf lifetime • One part and two parts • No catalyst • Injectable, castable, lathe-able • Rouse time • Elasticity at 1 Hz • Removable implant • Cleavable / reversible xlink • Natural IOL G=1-10 kPa Strain-stiffening (^^) • Applicable to all soft tissues

[0223] Exemplary methods of use of the presently disclosed polymer networks include: • Injection / filling a capsule (lumen): in-vivo and ex-vivo • Milling (hard-to-soft) • 3D, 4D, pad, additive manufacturing • Lathe-able • Casting in capsular bag then implanted • Implanted bag then injection of polymer

[0224] Exemplary surface treatment of the presently disclosed polymer networks include: • compatibility (bio, cyto, microbe, protein, calcification)WSGR Docket No. Accolens-701.601 • comfort (lubricity) • Insertion, administration • Method of surface treatment (Spray, drop coating and pad printing)

[0225] Exemplary methods of removal of the presently disclosed polymer networks include: • Light: UV may cause degradation or hardening of synthetic IOL • Heat (HIFU) • Mechanical • Mechanochemical chain scission Definitions

[0226] Unless defined otherwise, all terms of art, notations and other technical and scientific terms or terminology used herein are intended to have the same meaning as is commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and / or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art.

[0227] Throughout this application, various embodiments may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0228] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an agent” includes a plurality of such agents, reference to “a stabilizer” includes a plurality of such stabilizers, and reference to “the cell” includes reference to one or more cells (or to a plurality of cells) and equivalents thereof known to those skilled in the art, and so forth. When ranges are used herein for physical properties, such as molecular weight, or chemical properties, such as chemical formulae, all combinations and subcombinations of ranges and specific embodiments therein are intended to be included.

[0229] The term “about” or “approximately” can mean within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on howWSGR Docket No. Accolens-701.601 the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, “about” can mean a range of up to 20%, up to 15%, up to 10%, up to 5%, or up to 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, within 5-fold, or within 2-fold, of a value.

[0230] The term “comprising” (and related terms such as “comprise” or “comprises” or “having” or “including”) is not intended to exclude that in other certain embodiments, for example, an embodiment of any composition of matter, composition, method, or process, or the like, described herein, “consist of” or “consist essentially of” the described features.

[0231] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances in which it does not.

[0232] Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 50 is understood to include any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, “nested sub-ranges” that extend from either end point of the range are specifically contemplated. For example, a nested sub-range of an exemplary range of 1 to 50 may comprise 1 to 10, 1 to 20, 1 to 30, and 1 to 40 in one direction, or 50 to 40, 50 to 30, 50 to 20, and 50 to 10 in the other direction.

[0233] As used here, the term “polymerization” or “polymer” encompasses all kind of polymerization and polymers, including e.g., homopolymer and copolymers. Accordingly, polymerization also encompasses homo-polymerization and copolymerization.

[0234] As used herein, a “low Tg” monomer or a “low Tg” cross linker refers to the monomer, or cross linker, when homo-polymerized, lead to a polymer that has a low Tg as described herein. For example, the phrase “one or more low Tgmonomers have a Tgof at most 30oC” refers to one or more monomers, when they are homo-polymerized, lead to a polymer(s) that has / have a Tg of at most 30oC.

[0235] The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.WSGR Docket No. Accolens-701.601 EXAMPLES

[0236] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, devices and / or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C. or is at ambient temperature, and pressure is at or near atmospheric. Materials

[0237] Monomethacryloxypropyl-terminated poly(dimethylsiloxane) (MCR-M11, average molar mass 1000 g / mol, PDI=1.15),poly n-Butyl acrylate (pnBA, MW= 1000, 2000 g / mol) and Hydroxyl alkyl acrylate and methacrylate (propyl, butyl, pentyl, hexyl, 98%) were purified using a basic alumina column to remove inhibitor. monoaminopropyl-terminated poly(dimethylsiloxane) (MCR- A11,12, average molar mass 1000 and 2000 g / mol, PDI=1.15), and α,ω-Amino-terminated poly(dimethylsiloxane) (DMS-A, with average molar masses 5000 and 10000 g / mol, PDI=1.15) were obtained from Gelest and purified using basic alumina columns to remove inhibitor. (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane (96%), Methacryloyl chloride (MMAC1, >97%), phenylbis(2,4,6-trimethyl-benzoyl)phosphine oxide (BAPOs), triethylamine (TEA), copper(I) chloride (CuCl, ≥99.995%), copper(I) bromide (CuBr, 99.999%), IEA and IEM isocyanoethylmetacrylate and acrylate, tris[2-(dimethylamino)ethyl]amine (Me6TREN), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA, 99%), ethyl α- bromoisobutyrate (EBiB), α-bromoisobutyryl bromide (BIBB, 98%), ethylene bis(2- bromoisobutyrate) (2-BiB, 97%), AIBN, Bi functional CTA, Tri functional CTA, Tetra functional CTA, Bifunctional ATRP Initiator, Tri functional ATRP initiator, Tetra functional ATRP initiator dimethyl formaldehyde (DMF), dimethyl acetamide (DMA), tetrahydrofuran (THF), p-xylene (PX), and acrylic acid (AA, 99%) were purchased from Aldrich and used as received, as were all other reagents and solvents. Example 1: Synthesis of Poly(dimethylsiloxane) Bottlebrushes (Bbb)

[0238] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with EBiB, (bi functional, tri functional and tetra functional) (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), Me6TREN (2.9 mg, 3.3 μL), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and thenWSGR Docket No. Accolens-701.601 immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. The AFM images, molecular weight, and PDI measurements of the product are shown in Table 1. TABLE 1 Sample Nbb NMRaMn NMRb# ARM PDMS 300 295 295000 g / mole - PDMS 600 572 572000 - PDMS 900 710 710000 - PDMS 1200 1020 1020000 - PDMS 2000 1700 1700000 - PDMS 2000 450 each arm 1800000 4 PDMS 3000 2500 2500000 - PDMS 3000 620 each arm 2480000 4 a Number average degree of polymerization of bottlebrush backbone (nbb) determined by 1H NMR; b Mn of bottlebrush backbone (nbb) determined by 1H NMR; Example 2: Synthesis of Poly(dimethylsiloxane) Bottlebrushes (Bbb)

[0239] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with CTA, (bi functional, tri functional and tetra functional) (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), AIBN (ratio AIBN / CTA=1 / 10), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. The AFM images, molecular weight, and PDI measurements of the product are shown in Table 1. TABLE 2 Sample Nbb NMRaMn NMRb# ARM PDMS 300 282 282000 g / mole - PDMS 600 540 540000 - PDMS 900 730 730000 - PDMS 1200 980 980000 -WSGR Docket No. Accolens-701.601 PDMS 2000 1600 1600000 - PDMS 2000 420 each arm 1680000 4 PDMS 3000 2300 2300000 - PDMS 3000 590 each arm 2360000 4 a Number average degree of polymerization of bottlebrush backbone (nbb) determined by 1H NMR; b Mn of bottlebrush backbone (nbb) determined by 1H NMR; Example 3: Synthesis of Poly(dimethylsiloxane) combs (B-r-D)

[0240] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with EBiB, (bi functional, tri functional and tetra functional) (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), Me6TREN (2.9 mg, 3.3 μL), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back- filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 4: Synthesis of Poly(dimethylsiloxane) combs (B-r-D)

[0241] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with CTA, (bi functional, tri functional and tetra functional) (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), AIBN (ratio AIBN / CTA=1 / 10), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back- filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 5: Synthesis of Poly(poly-n butyl acrylate) Bottlebrushes (Bbb)

[0242] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with EBiB, (bi functional, tri functional and tetra functional) (12.5 μmol), Poly-n butyl acrylate monomethacrylate terminated (15.0 mmol), Me6TREN (2.9 mg, 3.3 μL), and Toluene (12.0 mL). The solution wasWSGR Docket No. Accolens-701.601 bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PpBA polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. PBA macromonomer synthesis is shown in FIG.11. Example 6: Synthesis of Poly(poly-n butyl acrylate) Bottlebrushes, (Bbb)

[0243] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with CTA, (bi functional, tri functional and tetra functional) (12.5 μmol), Poly-n butyl acrylate monomethacrylate terminated (15.0 mmol), AIBN (ratio AIBN / CTA=1 / 10), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PpBA polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 7: Synthesis of Poly(poly-n butyl acrylate) combs (B-r-D)

[0244] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with EBiB, (bi functional, tri functional and tetra functional) (12.5 μmol), Poly-n butyl acrylate monomethacrylate terminated (15.0 mmol), Me6TREN (2.9 mg, 3.3 μL), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PpBA polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 8: Synthesis of Poly(poly-n butyl acrylate) combs (B-r-D)

[0245] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with CTA, (bi functional, tri functional and tetra functional) (12.5 μmol), Poly-n butyl acrylate monomethacrylate terminated (15.0 mmol), AIBN (ratio AIBN / CTA=1 / 10), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, thenWSGR Docket No. Accolens-701.601 The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PpBA polymer with degree of polymerization (DP) of the backbone (nbb)˜900. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 9: Synthesis of Poly(poly-n butyl acrylate)-b-Poly(dimethylsiloxane) combs (B-r-D)- b-(B’-r-D’)

[0246] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 8 (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) AIBN (ratio AIBN / CTA=1 / 10), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bi block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 10: Synthesis of Poly(poly-n butyl acrylate)-b-Poly(dimethylsiloxane) combs (B-r- D)-b-(B’-r-D’)

[0247] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer from example7, MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11, Me6TREN (2.9 mg, 3.3 μL), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back- filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bi block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached.WSGR Docket No. Accolens-701.601 Example 11: Synthesis of Poly(poly-n butyl acrylate)-b-(Poly(dimethylsiloxane)2 combs (B-r- D)-b-(B’-r-D’)

[0248] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer from example7 prepared using bifunctional initiator, MCR-M11 (15.0 g, 15.0 mmol), (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11, Me6TREN (2.9 mg, 3.3 μL), (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a tri block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 12: Synthesis of Poly(poly-n butyl acrylate)-b-(Poly(dimethylsiloxane))2 combs (B-r- D)-b-(B’-r-D’)2

[0249] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 8 (12.5 μmol) prepared using bifunctional CTA, MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy-2- hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) AIBN (ratio AIBN / CTA=1 / 10), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bi block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 13: Synthesis of Poly(Poly(dimethylsiloxane))-b-( poly-n butyl acrylate)2 combs (B- r-D)-b-(B’-r-D’)2

[0250] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer from example7 prepared using bifunctional initiator, MCR-M11 (15.0 g, 15.0 mmol), (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11, Me6TREN (2.9 mg, 3.3 μL), (3- Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane orWSGR Docket No. Accolens-701.601 Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a tri block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 14: Synthesis of Poly(Poly(dimethylsiloxane))-b-( poly (poly-n butyl acrylate))2 combs (B-r-D)-b-(B’-r-D’)2

[0251] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 8 (12.5 μmol) prepared using bifunctional CTA, MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy-2- hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) AIBN (ratio AIBN / CTA=1 / 10), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11) and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bi block brush / comb-like polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 15: Synthesis of Poly(dimethylsiloxane) Bottlebrushes-b( poly(dimethylsiloxan copolymer) (Bbb)-b-(A-C)2(in this case A=B)

[0252] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 1 using bifunctional ATRP initiator (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy- 2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11), Me6TREN (2.9 mg, 3.3 μL), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached.WSGR Docket No. Accolens-701.601 Example 16: Synthesis of Poly(dimethylsiloxane) Bottlebrushes-b( poly(dimethylsiloxan copolymer) (Bbb)-b-(A-C)2(in this case A=B)

[0253] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer example 2 using bifunctional CTA (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), (3-Methacryloxy- 2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-5 mole% respect to M11), AIBN (ratio AIBN / CTA=1 / 10), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached.

[0254] Example 15 and 16 can be synthesized by injection of second part of composition that already purged by nitrogen such as(3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane directly to the reaction after 75 mole% of first reaction conversion. These block copolymers also can be prepared. These blocks can be repeated in any number is desire, Example 17: Synthesis of Poly(dimethylsiloxane) Bottlebrushes-b-( (3-Methacryloxy-2- hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane) (Bbb)-b-(C)2

[0255] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 1 using bifunctional ATRP initiator (12.5 μmol), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane or Hydroxylalkylmethacrylate (1-10 mole% respect to EX1), Me6TREN (2.9 mg, 3.3 μL), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 18: Synthesis of Poly(dimethylsiloxane) Bottlebrushes-b-( -( (3-Methacryloxy-2- hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane) (Bbb)-b-(C)2

[0256] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer example 2 using bifunctional CTA (12.5 μmol), (3-Methacryloxy-2-hydroxy propyoxypropyl)methyl bis (trimethylsiloxy)silane (1-10 mole% respect to EX2), AIBN (ratio AIBN / EX2=1 / 10), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomerWSGR Docket No. Accolens-701.601 conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 19: Synthesis of Poly(dimethylsiloxane) Bottlebrush-b-(Hydroxylhexylmethacrylate) (Bbb)-b-(C)2

[0257] ATRP method: A 25 mL Schlenk flask equipped with a stir bar was charged with example 1 using bifunctional ATRP initiator (12.5 μmol), Hydroxylhexylmethacrylate (1-10 mole% respect to ex1), Me6TREN (2.9 mg, 3.3 μL), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then CuCl (1.2 mg, 0.012 mmol) was quickly added to the reaction mixture under nitrogen atmosphere. The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 45° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 20: Synthesis of Poly(dimethylsiloxane) Bottlebrushes-b- (Hydroxylhexylmethacrylate (1-5 mole% respect to EX2) (Bbb)-b-( C)2

[0258] RAFT method: A 25 mL Schlenk flask equipped with a stir bar was charged with polymer example 2 using bifunctional CTA (12.5 μmol), MCR-M11 (15.0 g, 15.0 mmol), Hydroxylhexylmethacrylate (1-5 mole% respect to ex2), AIBN (ratio AIBN / CTA=1 / 10), and Toluene (12.0 mL). The solution was bubbled with dry nitrogen for 1 hr, then The flask was sealed, back-filled with nitrogen, purged for 5 minutes, and then immersed in an oil bath thermostated at 65° C. The polymerization was stopped after 12 hrs at 75% monomer conversion, resulting in a bottlebrush PDMS polymer with degree of polymerization (DP) of the backbone (nbb)˜1200. The polymer was precipitated three times from DMF to purify, and dried under vacuum at room temperature until a constant mass was reached. Example 21. Activation of polymers and synthesis of cross-linkers Activation of block brush / comb like copolymers: A)

[0259] All above examples can be dissolved in toluene (50 grams of polymer part in 200 ml anhydrous toluene and adding triethyl amin or hydrogen bicarbonate (functional group / Base =1 / 1.2) placed in the ice bath and stirred. The acryloyl chloride (Methacryloyl chloride) (10 mole % excess added to the solution drop-wise. After overnight reaction the polymer precipitated in DMF or ACN and purified by dissolving and precipitating then dried under vacuum at room temperature.WSGR Docket No. Accolens-701.601 B)

[0260] All above examples can be dissolved in toluene (50 grams of polymer part in 200 ml anhydrous toluene and adding Dibutyl tin dilaurate (functional group / tin catalyst=10 / 1) placed on the rolled to mixed it well. The isocyano ethyl acrylate or methacrylate (10 mole % excess added to the solution and placed on the roller for overnight. The polymer precipitated in DMF or ACN and purified by dissolving and precipitating then dried under vacuum at room temperature. Synthesis of cleavable cross linker:

[0261] Photo cleavable cross linker: The photo cleavable cross linker synthesized based on below reactions schematics.0.1 mole ONB added to a 150 ml dry flask, and then 100 ml DCM added to dissolve it completely.0.24 mole TEA (triethylamine) added to the solution and the temperature of solution decreased to 0 C and alpha bromo isobutylyl bromide 2.05 times vs ONB added drop-wise while the temperature of the solution kept at 0 c. after completion of adding, the temperature of the solution increased to room temperature and reaction continued for overnight. The solution washed with brine two times and the solvent evaporate and the bifunctional cleavable initiator purified using column. This cleavable initiator has been used to synthesize linear butyl acrylate and above mentioned brush like copolymers. Additionally, ONB-PBA crosslinker synthesis can be seen in FIG.11.

[0262] Thermal or ultrasonic cleavable cross linker: The mechanically or thermally cleavable initiator synthesized using the reactions below. Linear and brush like copolymers has been synthesized using this cleavable initiator.

[0263] Biomedical device preparation stimuli free: Activated brush like copolymers with acrylate moieties added to the different wt percentage of amine terminated polymers (linear orWSGR Docket No. Accolens-701.601 brush like) or different ratio of acrylate to amine group to tune modulus of final elastomer and mix then ready for cast, mold and injection.

[0264] Biomedical device preparation using photo and thermal stimuli: Activated brush like copolymers with any active moieties added to the different wt percentage of same (if acrylate or methacrylate) or complimentary active moieties(such as aldehyde / amine, DBCO / azide, Furan / maleimide, NCO / amine or hydroxyl) terminated polymers or activated brush like copolymers to tune modulus of final elastomer and mix and ready for cast, mold and injection and cure using light, heat with or without catalyst to make elastomer with the medical device shape.

[0265] Breast implant in lumen: Above mentioned mixture can be injected to the lumen in vivo or ex vivo to make breast implant.

[0266] IOL in mold: Above mentioned mixture can be injected to the custom mold (with or without coating) or directly injected to the capsular bag of natural eye or ex vivo injected to the custom bag and then implanted to the eye.

[0267] IOL using milling: Above mentioned mixture can be injected to the rod shape mold and cut to the buttons and then milled to the custom design IOL.

[0268] Coating of biomedical devices: All above mentioned medical devices can be molded in the molds that already coated using spray coating, dip coating and spin coating or coated after molding or milling to make the surface of devices lubricious and biocompatible based on the applications. Uniaxial Tensile Stress Strain Measurements

[0269] Dog bone-shaped samples with bridge dimensions of 12 mm×2 mm×1 mm were loaded into an RSA-G2 DMA (TA Instruments) and subjected to uniaxial extension at a constant strain rate of 0.003 s−1 and temperature of 20° C. To measure elongation-at-break (FIG.20A-F), the samples were stretched until rupture occurred. To verify elasticity, the samples were subjected to repeated loading-unloading cycles. In each case, tests were conducted in triplicate to ensure accuracy of the data. Measurement errors are calculated by taking the standard deviation of the mean of values from three separate experiments. All figures in the main text show dependence of the true stress on the elongation (deformation) ratio λ. The elongation ratio λ for uniaxial network deformation is defined as the ratio of the sample's instantaneous size L to its initial size L0, λ=L / L0. Example 22: Copolymer A and Reactant B TABLE 3 Examples Copolymer Copolymer A Reactant B Reactant B curing Modulus A wt% (within wt% (within time (Pa) at polymer polymer (hr) 0.01Hz network network) 1 A-b-B-b-A198 Amine terminated 2 wt% 7.4 120 at linear PDMS with 0.01Hz 5000 g / moleWSGR Docket No. Accolens-701.601 molecular weight DMS-A21 Gelest 1-1 A-b-B-b-A198 Amine terminated 2 wt% 10 160 at linear PDMS 3000 0.01Hz g / mole molecular weight 1-2 A-b-B-b-A198 (20-25% 2 wt% 10.5 220 at AMINOPROPYLME 0.01 Hz THYLSILOXANE) - DIMETHYLSILOXA NE COPOLYMER,AMS- 1203 GELEST 2 A-b-B-b-A198 wt% Amine terminated 2 wt% 18 744 at linear PDMS with 1Hz 5000 g / mole molecular weight 2-1 A-b-B-b-A198 wt% (0.5-1.5% 2 wt% 18 1058 at AMINOETHYLAMI 1Hz NOPROPYLMETHO XYSILOXANE) - DIMETHYLSILOXA NE COPOLYMER WITH BRANCH STRUCTURE ATM- 1112 3 A-b-B-b-A196 Amine terminated 4 wt% 2.75 218 at linear PDMS with 0.01Hz 5000 g / mole molecular weight 4 A-b-B-b-A195.9 wt% Amine terminated 4.1 wt% 7.5 802 at linear PDMS with 1Hz 5000 g / mole molecular weight 5 A-b-B-b-A297.99 Amine terminated 2.01 wt% 4.7 1315 at linear PDMS with 1Hz 5000 g / mole molecular weight 6 A-b-B-b-A299 wt% Amine terminated 1 wt% 13.4 973 at linear PDMS with 1Hz 5000 g / mole molecular weight 7 A-b-B-b-A298.8 Amine terminated 1.2 wt% 11.7 1084 at linear PDMS with 1Hz 5000 g / mole molecular weight 8 A-b-B-b-A295.9 wt% Amine terminated 4.1 wt% 3.5 2730 at linear PDMS with 1Hz 5000 g / mole molecular weight 9 A-r-B-b-B- 98 Amine terminated 2 wt% 12 110 at b-A-r-B3linear PDMS with 0.01Hz 5000 g / mole molecular weight 10 A-r-B-b-B- 98 wt% Amine terminated 2 wt% 24 450 at b-A-r-B3linear PDMS with 0.01Hz 5000 g / mole molecular weight 11 A-r-B-b-B- 96 Amine terminated 4 wt% 10 230 at b-A-r-B3linear PDMS with 0.01Hz 5000 g / moleWSGR Docket No. Accolens-701.601 molecular weight 12 A-r-B-b-B- 96 wt% Amine terminated 4 wt% 24 580 at b-A-r-B3linear PDMS with 1Hz 5000 g / mole molecular weight 13 A-r-B-b-B- 98.0 wt% Amine terminated 2.0 wt% 12 180 at b-A-r-B4linear PDMS with 0.01Hz 5000 g / mole molecular weight 14 A-r-B-b-B- 98.0wt% Amine terminated 2.0 wt% 24 450 at b-A-r-B4linear PDMS with 0.01Hz 5000 g / mole molecular weight 15 A-r-B-b-B- 96.0 WT% Amine terminated 4.0 wt% 10 350 at b-A-r-B4linear PDMS with 1Hz 5000 g / mole molecular weight 16 A-r-B-b-B- 96.0 wt% Amine terminated 4.0 wt% 22 650 at b-A-r-B4linear PDMS with 1Hz 5000 g / mole molecular weight1Triblock copolymer that the first and third block in the copolymer is block of monomers with acrylate functional group with DP 30, and B part is PDMS MCR-M11 brush with DP 9002Triblock copolymer that the first and third block in the copolymer part in the copolymer A is block of monomers with acrylate functional group with DP 42, and B part is PDMS MCR-M11 brush with DP 6003Triblock copolymer that the first and third block in the copolymer is random copolymer A-r-B of monomers with acrylate functional group and inert macromonomers such as MCR-M11 or 07 with DP 34 and 28 respectively, and B part is PDMS MCR-M11 brush with DP 9004Triblock copolymer that the first and third block in the copolymer is random copolymer A-r-B of monomers with acrylate functional group and inert macromonomers such as MCR-M11 or 07 with DP 25 and 20 respectively, and B part is PDMS MCR-M11 brush with DP 600 DP: degree of polymerization

[0270] Procedure: Adding polymer A in the speed mixer cup and add polymer A part to it without adding any solvent. The cup placed in the machine and adjust the speed of mixer to 200 and 10 mmHg vacuum pressure for 5 minutes. The mixture placed in the syringe for injection to the mold or rheological properties measurement.

[0271] While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.

Claims

WSGR Docket No. Accolens-701.601 CLAIMS What is claimed is:

1. A composition comprising a polymer network comprising a reaction product of copolymer A and reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, and wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, - N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

2. The composition of claim 1, wherein copolymer A comprises siloxane, polyfluorosiloxane, or polybutyl acrylate.

3. The composition of claim 1 or 2, wherein copolymer A is a reaction product of one or more macromonomers.

4. The composition of any one of claims 1 to 3, wherein copolymer A is a block copolymer or random copolymer.

5. The composition of claim 4, wherein each block of the copolymer can be a homopolymer or a random copolymer.

6. The composition of any one of claims 1 to 5, wherein copolymer A is polymerized via a controlled radical polymerization process.

7. The composition of any one of claims 1 to 6, wherein copolymer A comprises a random copolymer, a block copolymer, or a combination of random and block copolymers.

8. The composition of any one of claims 1 to 7, wherein copolymer A has a multi-arm structure from 3 to 8 arms.

9. The composition of any one of claims 1 to 8, wherein copolymer A comprises one or more -OH, -SH, -NH2, -N3, or furan groups.

10. The composition of claim 9, wherein copolymer A comprises one or more -OH groups.

11. The composition of claim 10, wherein the -OH group is converted to an acrylate, methacrylate, allyl, vinyl, amine, thiol, azide furan, maleimide, or DBCO group.WSGR Docket No. Accolens-701.601 12. The composition of any one of claims 1 to 11, wherein reactant B is a copolymer, wherein the copolymer is a bottlebrush polymer, comb polymer, linear polymer with a branched, multi-arm, structure, or a combination thereof.

13. The composition of any one of claims 1 to 12, wherein reactant B comprises more than one reactive moiety B, wherein reactive moiety B is -SH, -NH2, -N3, furan, maleimide, DBCO, acrylate, methylacrylate, allyl, or vinyl.

14. The composition of claim 13, wherein reactant B comprises more than one reactive moiety B, wherein the reactive moiety B is -NH2.

15. The composition of any one of claims 1 to 14, wherein reactant B comprises a degradable site.

16. The composition of claim 15, wherein the degradable site is degraded using light or local high temperature.

17. The composition of claim 16, wherein the degradable site comprises nitro benzyl, diene, dienophile, peroxide, azo, or a combination thereof.

18. The composition of claim 1, wherein the copolymer A is a reaction product of monomers that comprise a structure of Formula (Ia), Formula (Ib), and / or Formula (Ic):wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl;WSGR Docket No. Accolens-701.601 each R1’is independently hydrogen or C1-C3alkyl; each R2is independently C1-C10 alkyl or phenyl; each R3is independently C1-C4 alkyl or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each a is independently 0 to 10; each b is independently 0 to 10; each c is independently 0 to 10; each d is independently 0 to 10; each e is independently 0 to 10; each f is independently 0 to 10; each g is independently 0 to 50; each a1 is independently 0 to 10; each b1 is independently 0 to 10; each c1 is independently 0 to 10; each d1 is independently 0 to 10; each e1 is independently 0 to 10; each f1 is independently 0 to 10; and each p is independently 0 to 10.

19. The composition of any one of claims 1 to 18, wherein the copolymer A comprises a structure of Formula (II):WSGR Docket No. Accolens-701.601wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3alkyl; each R1’is independently hydrogen or C1-C3alkyl; each R2is independently C1-C10 alkyl or phenyl; each R3is independently C1-C4 alkyl or phenyl; each R4is independently C1-C10alkyl; each R5is independently -OH, -N3, -SH, or -NH2; each R6is independently H or C1-C10 alkyl group; each a is independently 0 to 10; each b is independently 0 to 4; each c is independently 0 or 1; each d is independently 0 to 4; each e is independently 0 to 9; each f is independently 0 to 4; each g is independently 0 to 50;WSGR Docket No. Accolens-701.601 each a1 is independently 0 to 10; each b1 is independently 0 to 4; each c1 is independently 0 or 1; each d1 is independently 0 to 4; each e1 is independently 0 to 9; each f1 is independently 0 to 4; each m is independently 1 to 5000; each n is independently 1 to 5000; each o is independently 0 to 5000; and each p is independently 0 to 10.

20. The composition of any one of claims 1 to 19, wherein the copolymer A comprises a structure of Formula (III):wherein: each X is independently -O- or -NR6-; each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3 alkyl; each R6is independently H or C1-C10 alkyl; each R7is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each R8is independently -OH, -NH2, -N3, -SH, NCO, epoxy, aldehyde, acrylate, methylate, vinyl, allyl, furan, or maleimide; each g is independently 0 to 50; each m is independently1 to 5000; each n is independently 1 to 5000;WSGR Docket No. Accolens-701.601 each o is independently 0 to 5000; each q is independently 1 to 10; and each r is independently 1 to 10.

21. The composition of claim 20, wherein R7is -OH.

22. The composition of claim 20, wherein R8is -OH.

23. The composition of claim 1, wherein the copolymer A comprises a structure of Formula (IV):wherein: each Z is independently -O- or -NR6-; each R1is independently hydrogen or C1-C3alkyl; each R6is independently H or C1-C10 alkyl; each m1 is independently 0 to 5000; each m2 is independently 0 to 5000; each n1 is independently 0 to 5000; each n2 is independently 0 to 5000; each q is independently 1 to 10; each p is independently 0 to 10; each s is independent 2 to 10; x is 1 to 6; and y is 1 to 6.

24. The composition of any one of claims 18 to 23, wherein each Z is -O-.

25. The composition of any one of claims 18 to 23, wherein each Z is -NH-.

26. The composition of any one of claims 18 to 25, wherein each R1is independently hydrogen or methyl.

27. The composition of any one of claims 18 to 26, wherein each R1’is independently hydrogen or methyl.WSGR Docket No. Accolens-701.601 28. The composition of any one of claims 18 to 27, wherein each R2is independently C1-C10 alkyl group.

29. The composition of claim 28, wherein each R2is independently C1-C3 alkyl.

30. The composition of any one of claims 18 to 29, wherein each R3is independently C1-C4 alkyl.

31. The composition of any one of claims 18 to 30, wherein each R4is independently C1-C5alkyl.

32. The composition of any one of claims 18 to 31, wherein each R5is independently - OH.

33. The composition of any one of claims 18 to 32, wherein each R6is independently H or methyl.

34. The composition of claim 33, wherein each R6is independently H.

35. The composition of any one of claims 20 to 34, wherein each R7is independently - OH.

36. The composition of any one of claims 20 to 35, wherein each R8is independently - OH.

37. The composition of any one of claims 18 to 36, wherein each g is independently 0 to 10.

38. The composition of claim 37, wherein each a is independently 0 to 5; each b is independently 0 to 5; each c is independently 0 to 5; each d is independently 0 to 5; each e is independently 0 to 5; each f is independently 0 to 5; each g is independently 0 to 5; each a1 is independently 0 to 5; each b1 is independently 0 to 5; each c1 is independently 0 to 5; each d1 is independently 0 to 5; each e1 is independently 0 to 5; and each f1 is independently 0 to 5.

39. The composition of any one of claims 19 to 38, wherein each m is independently 1 to 2000; each n is independently 1 to 2000; each o is independently 0 to 2000; and each p is independently 2 to 5.

40. The composition of claim 39, wherein each m is independently 1 to 1000; each n is independently 1 to 1000; each o is independently 0 to 1000; and each p is independently 2 to 5.

41. The composition of any one of claims 20 to 40, wherein each q is independently 1 to 10; and each r is independently 1 to 5.

42. The composition of claim 41, wherein each q is independently 1 to 5; and each r is independently 1 to 4.

43. The composition of claim 18, wherein copolymer A is a reaction product of monomers that comprise Formula (Ia).WSGR Docket No. Accolens-701.601 44. The composition of claim 43, wherein X is -O-, R1is methyl, each R3is methyl, R4is C4 alkyl, a is 0, b is 3, c is 0, d is 0, e is 0, and f is 0.

45. The composition of claim 18, wherein copolymer A is a reaction product of monomers that comprise Formula (Ib).

46. The composition of claim 45, wherein X is -O-, R1is methyl, R5is -OH, a1 is 0, b1 is 1, c1 is 1, d1 is 1, e1 is 1, f1 is 1, and R2is methyl.

47. The composition of claim 1, wherein copolymer A is selected from Examples 1-20.

48. The composition of any one of claims 1 to 47, wherein reactant B is (20-25% aminopropylmethylsiloxane)-dimethylsiloxane copolymer, (2-3% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (6-7% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, aminopropyl terminated polydimethylsiloxane, mercaptopropyl terminated polydimethylsiloxane, (30-35% dodecylmethylsiloxane)-[7-10% hydroxy(polyethyleneoxy(6- 9 propyl)methylsiloxane]-(55-65% dimethylsiloxane) terpolymer, (aminopropylmethylsiloxane) - dimethylsiloxane copolymer, (0.5-1.5% aminoethylaminopropylmethoxysiloxane) - dimethylsiloxane copolymer with branch structure, acryloxy terminated ethyleneoxide dimethylsiloxane-ethyleneoxide aba block copolymer, or aminopropyl terminated polydimethylsiloxane.

49. The composition of any one of claims 1 to 47, wherein reactive moiety B comprises -SH, -NH2or a combination thereof.

50. The composition of claim 49, wherein reactive moiety B comprises -NH2.

51. The composition of any one of claims 1 to 50, wherein the polymer network is formed via cross-linking between one or more reactive moiety A of copolymer A and one or more reactive moiety B of reactant B.

52. The composition of any one of claims 1 to 51, wherein one or more reactive moiety A and one or more reactive moiety B is randomly distributed.

53. The composition of any one of claims 1 to 52, wherein reactant B is a copolymer, and one or more reactive moiety A and one or more reactive moiety B are randomly distributed or block distributed at the end of the copolymers.

54. The composition of any one of claims 1 to 53, wherein the polymer network is formed spontaneously upon injection into or casting on a mold or a cavity.

55. The composition of any one of claims 1 to 54, wherein the polymer network can be formed ex vivo.WSGR Docket No. Accolens-701.601 56. The composition of any one of claims 1 to 54, wherein the polymer network can be formed in vivo.

57. The composition of claim 56, wherein the polymer network is formed after injection into the body.

58. The composition of any one of claims 1 to 57, wherein copolymer A has a glass transition temperature (Tg) of less than 20 ºC.

59. The composition of claim 58, wherein the Tgis less than -50 ºC.

60. The composition of claim 59, wherein the Tg is less than -100 ºC.

61. The composition of claim 58, wherein the Tg is about -150 ºC to about 0 ºC.

62. The composition of claim 61, wherein the Tgis about -150 ºC to about -100 ºC.

63. The composition of claim 62, wherein the Tgis about -130 ºC to about -110 ºC.

64. The composition of any one of claims 1 to 63, wherein the molecular weight of copolymer A is about 5000 g / mol to about 10,000,000 g / mol.

65. The composition of any one of claims 1 to 64, wherein the molecular weight of reactant B is about 500 g / mol to about 10,000 g / mol.

66. The composition of anyone of claims 1 to 65, wherein the ratio of copolymer A to reactant B is about 1000 to about 0.

01.

67. The composition of any one of claims 19 to 66, wherein n+m is at least 500.

68. The composition of any one of claims 19 to 66, wherein n+m is 100 to 500.

69. The composition of any one of claims 19 to 68, wherein the ratio of n to m is 1:10 to 1:

20.

70. The composition of any one of claims 19 to 69, wherein n is less than 5% of the polymer network.

71. The composition of claim 70, wherein n is about 1% to less than 5% of the polymer network.

72. The composition of claim 70, wherein n is about 1% of the polymer network.

73. The composition of claim 70, wherein n is about 2% of the polymer network.

74. The composition of claim 70, wherein n is about 3% of the polymer network.

75. The composition of claim 70, wherein n is about 4% of the polymer network.

76. The composition of any one of claims 19 to 69, wherein n is about 5% to about 30% of the polymer network.

77. The composition of claim 76, wherein n is about 10% of the polymer network.

78. The composition of claim 76, wherein n is about 20% of the polymer network.

79. The composition of claim 76, wherein n is about 30% of the polymer network.WSGR Docket No. Accolens-701.601 80. The composition of any one of claims 1 to 79, wherein the polymer network is cured from about 1 minute to about 100 hours.

81. The composition of claim 80, wherein the polymer network is cured from about 5 minutes to about 24 hours.

82. The composition of claim 81, wherein the polymer network is cured from about 30 minutes to about 12 hours.

83. The composition of claim 82, wherein the polymer network is cured from about 1 hour to about 6 hours.

84. The composition of any one of claims 1 to 83, wherein the polymer network has a Young’s modulus of about 100 Pa to about 10 MPa.

85. The composition of claim 84, wherein the polymer network has a Young’s modulus of about 0.5 kPa to about 10 kPa.

86. The composition of any one of claims 1 to 85, wherein the polymer network has a viscosity below about 105cP.

87. The composition of any one of claims 1 to 86, wherein the polymer network has strain-stiffening parameter from about 0.1 to about 0.

4.

88. The composition of any one of claims 1 to 87, wherein the polymer network has elongation-at-break from about 1.5% to about 10%.

89. The composition of any one of claims 1 to 88, wherein the polymer network has stress-at-break from about 0.05 MPa to about 1 MPa upon uniaxial extension and from about 0.05 MPa to about 1 MPa upon uniaxial compression.

90. The composition of any one of claims 1 to 89, wherein the polymer network has a refractive index from about 1.4 to about 1.5 at a body temperature of about 37 ºC.

91. The composition of any one of claims 1 to 90, for use in drug delivery, implantation, external and implantable contact lenses, or intraocular lenses.

92. The composition of claim 91, wherein the implantation is for breast implantation.

93. The composition of claim 92, wherein the polymer network is injected into a lumen.

94. The composition of claim 93, wherein the lumen is already implanted into the breast.

95. The composition of claim 91, for use in intraocular lenses.

96. The composition of claim 95, wherein the polymer network is injected directly into a bag of crystalline lens implanted in an eye after extraction of cataract.

97. The composition of claim 95, wherein the polymer network is casted to a custom mold before implanting in an eye.WSGR Docket No. Accolens-701.601 98. The composition of any one of claims 1 to 97, wherein the polymer network is formed as a medical device.

99. The composition of claim 98, wherein the medical device is coated with a polymer.

100. The composition of claim 98 or 99, wherein the medical device is an implant, a microneedle array, a wound dressing pad, a tissue adhesive, a tissue sealant, a tissue filler, a dermal filler, a vascular graft, a catheter, an implantable contact lens, or an intraocular lens.

101. The composition of claim 100, wherein the implant is a breast implant.

102. The composition of claim 101, wherein the medical device is an intraocular lens.

103. A method of making a polymer network, the method comprising reacting copolymer A with reactant B, wherein: copolymer A is a copolymer that comprises one or more reactive moiety A, wherein the copolymer A is a bottlebrush polymer, comb polymer, linear polymer with a linear or branched or multi-arm, structure, or a combination thereof, and wherein each reactive moiety A independently comprise -OH, -SH, -NH2, -N3, furan, maleimide, or DBCO groups, wherein copolymer A has one or more low glass transition temperature (Tg) monomers; and reactant B is a polymer, copolymer, or small molecule, wherein reactant B comprises more than one reactive moiety B, wherein each reactive moiety B independently comprises -SH, -NH2, - N3, epoxy group, furan, maleimide, DBCO, or alkenyl group or a combination thereof.

104. The method of claim 103, wherein copolymer A is polymerized via a controlled radical polymerization process.

105. The method of claim 104, wherein the controlled radicalization polymerization process is free radical polymerization (FRP), atom transfer radical polymerization (ATRP), SARA ATRP, anionic polymerization, or reversible addition-fragmentation chain-transfer polymerization (RAFT).

106. The method of claim 105, wherein the controlled radicalization polymerization process is ATRP.

107. The method of claim 105, wherein the controlled radicalization polymerization process is RAFT.

108. The method of any one of claims 103 to 107, wherein copolymer A and reactant B form the polymer network without a catalyst.

109. The method of any one of claims 103 to 107, wherein copolymer A and reactant B form the polymer network without a stimuli.

110. The method of claim 109, wherein the stimuli is heat or light.

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