Use of Acrylic Functionalized (Meth)acrylic Cross‐Linked Polymer Microparticles in Photopolymerized Acrylic Films

Abstract

The effect of reactive (meth)acrylic cross‐linked polymer microparticles (reactive CPM, also called reactive microgels) used as cross‐linking agents has been studied on the thermo‐mechanical properties of different photopolymerized thin films. The matrix was based on the copolymerization of isobornyl acrylate and ethoxy ethoxy ethyl acrylate or butyl acrylate. Various concentrations of CPM were initially blended with the monomers. These solutions were photopolymerized under UV radiation to obtain hard and transparent films. Since CPM were reactive respect to monomers, they acted as multifunctional cross‐linkers, resulting in networks after polymerization. The well distributed and highly functional CPM which connected acrylate linear chains worked as well defined chemical clusters and gave to the networks a very unique structure. By varying the reactive CPM concentration, the relationship between the number of double bonds introduced into the network by the CPM acting like cross‐linkers and the rubbery modulus of the films was determined from viscoelastic measurements. The structure of CPM, the average functionality and also crystallinity were modified to change networks properties. In addition, reactive groups have been preferentially introduced at the surface vicinity by using a new functional stabilizing agent. CPM were also compared to linear polymers with the same composition. From viscoelastic properties, it is concluded that CPM are very efficient cross‐linkers. However, very high CPM incorporation led to high extent of intramolecular reaction, reducing the cross‐linking efficiency. During thermal aging, CPM and linear copolymer seemed to rearrange leading the film structure to an equilibrium state.TEM micrograph of a photopolymerized film (30 wt.‐% of CPM‐0% ODA + 70 wt.‐% of IBOA/EEEA) after thermal aging.magnified imageTEM micrograph of a photopolymerized film (30 wt.‐% of CPM‐0% ODA + 70 wt.‐% of IBOA/EEEA) after thermal aging.

Chemical modification and synthesizing conditions of nanocomposite hydrogels with high mechanical strength crosslinked by hydrophilic reactive microgels

“…9). Rapid polymerization would lead to low mechanical strength, similar to the literature described 8. The number of grafting chains with short‐chain length or free polymer chains (not grafting any HRM microsphere) increased under fast polymerization rate, and so the short‐terminated chains cannot entangle two vicinal HRM nanoparticles.…”

“…It is of interest to gain the possibility for a mild chemical modification of the nanoparticles to design their structure and properties. The nanoparticles with double bonds can be useful as toughening agents for photopolymerized thin films or thermosets 8, 9. The hyaluronic acid (HA)‐based hydrogel materials with HA hydrogel particles embedded in and covalently crosslinked to a secondary network exhibit unique structural and mechanical characteristics 10.…”

Chemical modification and synthesizing conditions of nanocomposite hydrogels with high mechanical strength crosslinked by hydrophilic reactive microgels

“…9). Rapid polymerization would lead to low mechanical strength, similar to the literature described 8. The number of grafting chains with short‐chain length or free polymer chains (not grafting any HRM microsphere) increased under fast polymerization rate, and so the short‐terminated chains cannot entangle two vicinal HRM nanoparticles.…”

“…It is of interest to gain the possibility for a mild chemical modification of the nanoparticles to design their structure and properties. The nanoparticles with double bonds can be useful as toughening agents for photopolymerized thin films or thermosets 8, 9. The hyaluronic acid (HA)‐based hydrogel materials with HA hydrogel particles embedded in and covalently crosslinked to a secondary network exhibit unique structural and mechanical characteristics 10.…”

Preparation of microgel composite hydrogels by polymer post-crosslinking method

“…Reactive microgels have also been used as multifunctional crosslinkers for photopolymerized thin films or thermosets to improve their mechanical properties [16,17]. In addition to the direct polymerization method by adding the reactive microgels containing C=C double bonds, the crosslinked structure can also be obtained by postcrosslinking of the polymers through irradiation, peroxide, drying, heating, and so on [18][19][20][21].…”

Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization

“…Recent advances in living polymerization techniques have made possible the synthesis of a wide variety of synthetic polymers with well‐defined and complex architectures, such as star polymers, branched macromolecules, or nano‐/microgels 1–3. In the last decade, those small‐size polymeric gels have found increasing interest for numerous potential applications, for instance in the health care, coating, or the pharmaceutical industry 4–6. Because of their small dimension and their compact structure, they are ideal carriers for dyes, biomedical, or pharmaceutical compounds.…”

Chemical modification and synthesizing conditions of nanocomposite hydrogels with high mechanical strength crosslinked by hydrophilic reactive microgels

“…9). Rapid polymerization would lead to low mechanical strength, similar to the literature described 8. The number of grafting chains with short‐chain length or free polymer chains (not grafting any HRM microsphere) increased under fast polymerization rate, and so the short‐terminated chains cannot entangle two vicinal HRM nanoparticles.…”

“…It is of interest to gain the possibility for a mild chemical modification of the nanoparticles to design their structure and properties. The nanoparticles with double bonds can be useful as toughening agents for photopolymerized thin films or thermosets 8, 9. The hyaluronic acid (HA)‐based hydrogel materials with HA hydrogel particles embedded in and covalently crosslinked to a secondary network exhibit unique structural and mechanical characteristics 10.…”

Preparation of microgel composite hydrogels by polymer post-crosslinking method

“…Reactive microgels have also been used as multifunctional crosslinkers for photopolymerized thin films or thermosets to improve their mechanical properties [16,17]. In addition to the direct polymerization method by adding the reactive microgels containing C=C double bonds, the crosslinked structure can also be obtained by postcrosslinking of the polymers through irradiation, peroxide, drying, heating, and so on [18][19][20][21].…”

Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization

“…Recent advances in living polymerization techniques have made possible the synthesis of a wide variety of synthetic polymers with well‐defined and complex architectures, such as star polymers, branched macromolecules, or nano‐/microgels 1–3. In the last decade, those small‐size polymeric gels have found increasing interest for numerous potential applications, for instance in the health care, coating, or the pharmaceutical industry 4–6. Because of their small dimension and their compact structure, they are ideal carriers for dyes, biomedical, or pharmaceutical compounds.…”

Chemical modification and synthesizing conditions of nanocomposite hydrogels with high mechanical strength crosslinked by hydrophilic reactive microgels

“…9). Rapid polymerization would lead to low mechanical strength, similar to the literature described 8. The number of grafting chains with short‐chain length or free polymer chains (not grafting any HRM microsphere) increased under fast polymerization rate, and so the short‐terminated chains cannot entangle two vicinal HRM nanoparticles.…”

“…It is of interest to gain the possibility for a mild chemical modification of the nanoparticles to design their structure and properties. The nanoparticles with double bonds can be useful as toughening agents for photopolymerized thin films or thermosets 8, 9. The hyaluronic acid (HA)‐based hydrogel materials with HA hydrogel particles embedded in and covalently crosslinked to a secondary network exhibit unique structural and mechanical characteristics 10.…”

Preparation of microgel composite hydrogels by polymer post-crosslinking method

“…Reactive microgels have also been used as multifunctional crosslinkers for photopolymerized thin films or thermosets to improve their mechanical properties [16,17]. In addition to the direct polymerization method by adding the reactive microgels containing C=C double bonds, the crosslinked structure can also be obtained by postcrosslinking of the polymers through irradiation, peroxide, drying, heating, and so on [18][19][20][21].…”

Pegylated thermally responsive block copolymer micelles and nanogels via in situ RAFT aqueous dispersion polymerization

“…Recent advances in living polymerization techniques have made possible the synthesis of a wide variety of synthetic polymers with well‐defined and complex architectures, such as star polymers, branched macromolecules, or nano‐/microgels 1–3. In the last decade, those small‐size polymeric gels have found increasing interest for numerous potential applications, for instance in the health care, coating, or the pharmaceutical industry 4–6. Because of their small dimension and their compact structure, they are ideal carriers for dyes, biomedical, or pharmaceutical compounds.…”