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Influence of Phase Separation on Performance of Graft Acrylic Pressure-Sensitive Adhesives with Various Copolyester Side Chains.

ABSTRACT: Acrylic pressure-sensitive adhesives with various polyester side-chain lengths were synthesized to investigate the effect of branching on phase separation and polymer mechanical performance. The polyester macromonomers (MMs) were produced through ring-opening co-polymerizations of l-lactide (l-LA) and ?-caprolactone (?-CL) initiated with 2-hydroxyethyl methacrylate (HEMA), which provides the polyester chains with terminal vinyl groups. By varying the HEMA content, a range of MM chain lengths constructed from L₁₀C₄ (five l-LA and four ?-CL units) to L₁₀₀C₄₀ were obtained at a constant monomer mole ratio. Copolymerization of 2-ethylhexyl acrylate and acrylic acid with these MMs at constant mass composition provided a series of comb copolymers consisting of acrylic backbones with polyester branches of various chain lengths. Characterization of thin films cast from the polymers using thermal analysis and scanning probe microscopy showed a transition from a homogeneous phase to the formation of distinct microphases with increasing branching chain lengths. Rheological analysis of the linear viscoelastic responses was also used through small-amplitude oscillatory shear, and dynamic master curves were constructed by time-temperature superposition. The rheological data were also consistent with phase separation for the longer side-chain lengths of L₅₀C₂₀ and L₁₀₀C₄₀. The extra elastic contribution at low frequency and the temperature dependence of a _T both show obviously effect of separated phases. Performance testing of polymer films showed that the chain extension resulted in a significant increase in both peel strength and shear resistance, which was accompanied by a modest decrease in film tackiness. The results demonstrate that tailoring branch chain structures provide a promising means for controlling the properties of the high-biomass content adhesive polymers.

SUBMITTER: Wang Y

PROVIDER: S-EPMC6644624 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Influence of Phase Separation on Performance of Graft Acrylic Pressure-Sensitive Adhesives with Various Copolyester Side Chains.

Wang Yanjiao Y Weng Feiyin F Li Jiaxu J Lai Lei L Yu Wei W Severtson Steven John SJ Wang Wen-Jun WJ

ACS omega 20180626 6

Acrylic pressure-sensitive adhesives with various polyester side-chain lengths were synthesized to investigate the effect of branching on phase separation and polymer mechanical performance. The polyester macromonomers (MMs) were produced through ring-opening co-polymerizations of l-lactide (l-LA) and ε-caprolactone (ε-CL) initiated with 2-hydroxyethyl methacrylate (HEMA), which provides the polyester chains with terminal vinyl groups. By varying the HEMA content, a range of MM chain lengths con ...[more]

PMID: 31458860

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Project description:Pressure-sensitive adhesives (PSAs) are usually made from viscoelastic, high-molecular-weight copolymers, which are fine-tuned by adjusting the comonomer ratios, molecular weights, and cross-link densities to optimize the adhesion properties for the desired end-use. To create a lightly cross-linked network, an ultraviolet (UV) photoinitiator can be incorporated. Here, we present the first use of perfluorophenylazide chemistry to control precisely a polyacrylate network for application as a PSA. Upon UV irradiation, the highly reactive nitrene from the azide moiety reacts with nearby molecules through a C-H insertion reaction, resulting in cross-linking via covalent bonding. This approach offers three benefits: (1) a means to optimize adhesive properties without the addition of an external photoinitiator; (2) the ability to switch off the tack adhesion on demand via a high cross-linking density; and (3) a platform for additional chemical modification. A series of poly(n-butyl acrylate-co-2,3,4,5,6-pentafluorobenzyl acrylate) or poly(PFBA-co-BA) copolymers were synthesized and modified post-polymerization into the photo-reactive poly(n-butyl acrylate-co-4-azido-2,3,5,6-tetrafluorobenzyl acrylate) [azide-modified poly(PFBA-co-BA)] with various molar contents. When cast into films, the azide-modified copolymers with a high azide content achieved a very high shear resistance after UV irradiation, whereas the tack and peel adhesion decreased strongly with the increase in azide content, indicating that excessive cross-linking occurred. These materials are thus photo-switchable. However, in the low range of azide content, an optimum probe tack adhesion energy was obtained in films with a 0.3 mol % azide content, where a long stress plateau (indicating good fibrillation) with a high plateau stress was observed. An optimum peel adhesion strength was achieved with 0.5 mol % azide. Thus, the adhesion was finely controlled by the degree of cross-linking of the PSA, as determined by the azide content of the copolymer chain. Finally, as a demonstration of the versatility and advantages of the material platform, we show an azide-aldehyde-amine multicomponent modification of the azide copolymer to make a dye-functionalized film that retains its adhesive properties. This first demonstration of using azide functionality has enormous potential for functional PSA design.

Project description:Pressure sensitive adhesives made with blends of thermoplastic polyurethanes (TPUs PSAs) with satisfactory tack, cohesion, and adhesion have been developed. A simple procedure consisting of the physical blending of methyl ethyl ketone (MEK) solutions of two thermoplastic polyurethanes (TPUs) with very different properties-TPU1 and TPU2-was used, and two different blending procedures have been employed. The TPUs were characterized by infra-red spectroscopy in attenuated total reflectance mode (ATR-IR spectroscopy), differential scanning calorimetry, thermal gravimetric analysis, and plate-plate rheology (temperature and frequency sweeps). The TPUs PSAs were characterized by tack measurement, creep test, and the 180° peel test at 25 °C. The procedure for preparing the blends of the TPUs determined differently their viscoelastic properties, and the properties of the TPUs PSAs as well, the blending of separate MEK solutions of the two TPUs imparted higher tack and 180° peel strength than the blending of the two TPUs in MEK. TPU1 + TPU2 blends showed somewhat similar contributions of the free and hydrogen-bonded urethane groups and they had an almost similar degree of phase separation, irrespective of the composition of the blend. Two main thermal decompositions at 308-317 °C due to the urethane hard domains and another at 363-373 °C due to the soft domains could be distinguished in the TPU1 + TPU2 blends, the weight loss of the hard domains increased and the one of the soft domains decreased by increasing the amount of TPU2 in the blends. The storage moduli of the TPU1 + TPU2 blends were similar for temperatures lower than 20 °C and the moduli at the cross over of the moduli were lower than in the parent TPUs. The improved properties of the TPU1 + TPU2 blends derived from the creation of a higher number of hydrogen bonds upon removal of the MEK solvent, which lead to a lower degree of phase separation between the soft and the hard domains than in the parent TPUs. As a consequence, the properties of the TPU1 + TPU2 PSAs were improved because good tack, high 180° peel strength, and sufficient cohesion were obtained, particularly in 70 wt% TPU1 + 30 wt% TPU2 PSA.

Dataset Information

Influence of Phase Separation on Performance of Graft Acrylic Pressure-Sensitive Adhesives with Various Copolyester Side Chains.

Publications

Influence of Phase Separation on Performance of Graft Acrylic Pressure-Sensitive Adhesives with Various Copolyester Side Chains.

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