Degradable shape-memory polymer networks from oligo[(l-lactide)-ran-glycolide]dimethacrylates

Choi, N.-Y.; Lendlein, Andreas

doi:10.1039/b702515g

Cited by 101 publications

(67 citation statements)

References 40 publications

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“…The shape-memory behavior is obtained after deforming SMPs at temperatures higher than T fix , followed by a cooling process to a temperature below T fix under a constant stress to maintain the temporary shape. [3,12,13] Once the polymer is reheated above T fix , the permanent shape is recovered due to the entropic relaxation of constrained chains. [14] This process is a so-called one-way shape-memory effect, whereby only the recovery step (e.g., length contraction) is spontaneous.…”

Section: Introductionmentioning

confidence: 99%

Design of Cross‐Linked Semicrystalline Poly(ε‐caprolactone)‐Based Networks with One‐Way and Two‐Way Shape‐Memory Properties through Diels–Alder Reactions

Raquez

Vanderstappen

Meyer

et al. 2011

Chemistry A European J

119

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Cross-linked poly(ε-caprolactone) (PCL)-based polyesterurethane (PUR) systems have been synthesized through Diels-Alder reactions by reactive extrusion. The Diels-Alder and retro-Diels-Alder reactions proved to be useful for enhancing the molecular motion of PCL-based systems, and therefore their crystallization ability, in the design of cross-linked semicrystalline polymers with one-way and two-way shape-memory properties. Successive reactions between α,ω-diol PCL (PCL(2) ), furfuryl alcohol, and methylene diphenyl 4,4'-diisocyanate straightforwardly afforded the α,ω-furfuryl PCL-based PUR systems, and subsequent Diels-Alder reactions with N,N-phenylenedimaleimide afforded the thermoreversible cycloadducts. The cross-linking density could be modulated by partially replacing PCL-diol with PCL-tetraol. Interestingly, the resulting PUR systems proved to be semicrystalline cross-linked polymers, the melting temperature of which (close to 45 °C) represented the switching temperature for their shape-memory properties. Qualitative and quantitative measurements demonstrated that these PUR systems exhibited one-way and two-way shape-memory properties depending on their cross-linking density.

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Section: Introductionmentioning

confidence: 99%

Design of Cross‐Linked Semicrystalline Poly(ε‐caprolactone)‐Based Networks with One‐Way and Two‐Way Shape‐Memory Properties through Diels–Alder Reactions

Raquez

Vanderstappen

Meyer

et al. 2011

Chemistry A European J

119

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“…While in AB polymer networks both segments contribute to the overall elasticity of the polymer network, [5] the elasticity in grafted polymer networks is mainly determined by the crosslinking segments. [6,7,10] A versatile synthesis route for SMP networks is based on macrodimethacrylates [11][12][13] obtained from (co)polyesterdiols [14] as starting materials. For the present study a poly(e-caprolactone) network with grafted poly(ethylene glycol) side chains (CLEG) that exhibits two distinct melting transitions T m,PEG (T m,A ) and T m,PCL (T m,B ) was investigated.…”

Section: Introductionmentioning

confidence: 99%

In Situ X‐Ray Scattering Studies of Poly(ε‐caprolactone) Networks with Grafted Poly(ethylene glycol) Chains to Investigate Structural Changes during Dual‐ and Triple‐Shape Effect

Wagermaier¹,

Zander²,

Hofmann³

et al. 2010

Macromol. Rapid Commun.

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The dual- and triple-shape effects of multiphase polymer networks that contain two crystallizable chain segments have been assessed in situ by combining X-ray measurements with thermomechanical investigations. The studied polymer, named CLEG, is a multiphase polymer network of crystallizable poly(ε-caprolactone) (PCL) with grafted poly(ethylene glycol) (PEG) side chains. Wide-angle (WAXS) and small-angle X-ray scattering (SAXS) measurements were combined with temperature-controlled in situ tensile testing experiments. This integrated approach enables systematic investigation and interpretation of relevant structural features during the programming procedures and the thermally-induced recovery process. Main results concern the combined effect of PCL and PEG crystals on shape fixation, the specific role of low-melting PCL crystallites in the fixation of the low temperature temporary shape, and the different orientation behavior of PCL and PEG crystals during certain stages of the programming procedure. These results demonstrate that crystal orientation effects are dominant for the PCL crystals. The effects of the low temperature PCL crystals could only be investigated when synchrotron radiation was applied. These findings indicate the great potential of in situ X-ray investigations for the creation of design-relevant knowledge about the microscopic foundations of dual- and triple-shape effects in appropriate polymer systems.

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“…[15][16][17][18][19] Amorphous polymer networks were developed based on poly[(L-lactide)-ran-glycolide)] chain segments. [20,21] This material is transparent and has a shape-memory capability, but its mechanical properties have to be further improved. Polymer networks from poly[(L-lactide)-ran-glycolide)]dimethacrylates (DM) tend to be brittle below the glass transition temperature T g of 55°C and are difficult to handle in the course of the network synthesis and extraction without destroying the samples.…”

mentioning

confidence: 99%

Amorphous, Elastic AB Copolymer Networks from Acrylates and Poly[(L‐lactide)‐ran‐glycolide]dimethacrylates

et al. 2008

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Shape-memory polymers (SMP) are dual shape materials, which can fix a temporary shape besides their original shape. The process of deformation under application of an external stress above a transition temperature (T trans ) and fixation by cooling below T trans is called programming. The original, permanent shape can be recovered by application of heat. [1][2][3][4][5] Heating could be realized directly by an increase in environmental temperature or indirectly by exposing to alternating magnetic fields [6,7] or illuminating with IR-light. [8] Shapememory polymers have a high innovation potential as biomaterial, especially for minimally invasive surgery. One basic concept in the development of biodegradable polymer systems with shape-memory properties is based on covalently crosslinked polymer networks, [9][10][11][12] containing switching segments from semi-crystalline poly(e-caprolactone) [10,11,13] or poly[(e-caprolactone)-co-glycolide]. [12] The latter ones enable an accelerated hydrolytic degradation because of the presence of easily hydrolizable ester bonds in the form of glycolate ester bonds. [12,14] Another approach is the development of AB copolymer photoset networks, which are obtained from poly(e-caprolactone)dimethacrylate with n-butylacrylate or cyclohexylmethacrylate by UV-crosslinking. [10,11] These polymer networks showed excellent shape-memory properties and as tested so far good tissue-compatibility, in cell culture and in vivo tests. [15][16][17][18][19] Amorphous polymer networks were developed based on poly[(L-lactide)-ran-glycolide)] chain segments. [20,21] This material is transparent and has a shape-memory capability, but its mechanical properties have to be further improved. Polymer networks from poly[(L-lactide)-ran-glycolide)]dimethacrylates (DM) tend to be brittle below the glass transition temperature T g of 55°C and are difficult to handle in the course of the network synthesis and extraction without destroying the samples. The incorporation of a second amorphous phase with a low glass transition temperature (T g,l ) into these materials, which keeps the material elastic, is a potential strategy to effectively improve the elastic properties of poly[(L-lactide)-ran-glycolide]-segment based networks. Formation of an amorphous mixed phase is supposed to allow an adjustment of the switching temperature for the shape-memory effect to a temperature range between roomand body temperature.In a first approach, to obtain dilactide-based amorphous polymer networks with increased toughness and elasticity at room temperature, multi-phase polymer networks were synthesized from amorphous and degradable ABA triblock macrodimethacrylates based on poly(rac-lactide)-b-poly(propylene oxide)-b-poly(rac-lactide). Atactic poly(propylene oxide) (PPG) with a number average molecular weight M n of 4000 g mol -1 and a low T g of -73°C formed the B-block while the molecular weight of A-blocks from poly(rac-lactide) was varied. Variation in this block length resulted in networks with a T g varying between 11°C ...

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Degradable shape-memory polymer networks from oligo[(l-lactide)-ran-glycolide]dimethacrylates

Cited by 101 publications

References 40 publications

Design of Cross‐Linked Semicrystalline Poly(ε‐caprolactone)‐Based Networks with One‐Way and Two‐Way Shape‐Memory Properties through Diels–Alder Reactions

Design of Cross‐Linked Semicrystalline Poly(ε‐caprolactone)‐Based Networks with One‐Way and Two‐Way Shape‐Memory Properties through Diels–Alder Reactions

In Situ X‐Ray Scattering Studies of Poly(ε‐caprolactone) Networks with Grafted Poly(ethylene glycol) Chains to Investigate Structural Changes during Dual‐ and Triple‐Shape Effect

Amorphous, Elastic AB Copolymer Networks from Acrylates and Poly[(L‐lactide)‐ran‐glycolide]dimethacrylates

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