Poly(β-pinene) as an efficient biobased tackifier for metallocene poly(ethylene) based hotmelt adhesives

Gaspar, André S.; Cordeiro, Joel; Simões, Patrícia Alexandra Carvalho; Gameiro, D.; Rocha, Fernando; Serra, Arménio C.; Coelho, Jorge F. J.; Fonseca, A. C.

doi:10.1016/j.ijadhadh.2022.103111

Cited by 9 publications

(5 citation statements)

References 25 publications

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“…On the other hand, boron-based catalysts like BCl 3 and B(C 6 F 5 ) 3 are known to yield low molecular weight poly(β-pinene) because of frequent β-proton elimination [9][10][11]. For the low-molecularweight poly(β-pinene), the adhesive properties of blend polymers with the styrene-isoprene block copolymer or polyethylene are investigated [10,15].…”

Section: Introductionmentioning

confidence: 99%

A Bio-Based Tackifier Synthesized by Room-Temperature Cationic Copolymerization of Isobutene and β-Pinene

Ajala,

Nakayama,

Shiono

et al. 2024

Catalysts

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Whereas the cationic homopolymerization of β-pinene and isobutene (IB) have been extensively studied, their copolymerization is still very scarce, and the conditions under which copolymerization can occur are limited to extremely low temperatures. Moreover, the application of the copolymer has not been reported. Here, a series of room-temperature copolymerizations of β-pinene and IB, using group 13 compounds as catalysts, were conducted. The copolymerizations yielded a low molecular weight (Mn ~ 103) and a narrow molecular weight distribution (Mw/Mn < 2.0) copolymer, with a satisfactory yield at various comonomer feeds, and their glass transition temperature was predictable from the comonomer composition. Furthermore, the tackifying property of the obtained copolymer was investigated using a 180° peel adhesion test. A blend polymer of the copolymer and a styrene-isoprene triblock copolymer showed a high peeling force (0.58 ± 0.14 N/10 mm) and a glass transition temperature low enough for its application as a pressure-sensitive adhesive.

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Section: Introductionmentioning

confidence: 99%

A Bio-Based Tackifier Synthesized by Room-Temperature Cationic Copolymerization of Isobutene and β-Pinene

Ajala,

Nakayama,

Shiono

et al. 2024

Catalysts

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“…Hot melt adhesive film is a plastic adhesive, for its easy transport, non-polluting, and fast curing widely use. [1][2][3][4][5][6] Ethylene-vinyl acetate (EVA) hot melt adhesive film is a mainstream hot melt adhesive, which is an ethylene and vinyl acetate (VA) copolymer. 1,[7][8][9][10][11][12][13] Vinyl acetate properties and applications depend on the vinyl acetate content in EVA.…”

Section: Introductionmentioning

confidence: 99%

The curing kinetics and properties of self-healing and thermally conductive polymeric composites based on ethylene vinyl acetate copolymer filled with nano alumina

Lin,

Zhang,

Gao

et al. 2024

Journal of Plastic Film & Sheeting

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We have investigated a self-healing thermally conductive Ethylene-vinyl acetate (EVA) hot melt adhesive (NAEDS, which denotes the addition of nano-alumina and disulfide bonded EVA hot melt adhesives) that can be used to effectively solve adhesive layer separation problem in photovoltaic (PV) modules and the difficulty of recycling. More specifically, we used diallyl disulfide as a cross-linking agent for EVA and alumina nanofillers as a reinforcing phase. The nano alumina filler gave the EVA better thermal conductivity. We used FTIR, SEM, and DSC to characterize and analyze NAEDS properties. The disulfide bonds in NAEDS underwent a rearrangement reaction under ultraviolet light, resulting in the self-healing of the resin (self-healing efficiency of 78.8%). The added nano alumina not only reduced the resin curing activation energy, improving its curing performance but also enhanced its thermal conductivity, achieving a 2.61 W/(m*k) thermal conductivity coefficient. The overall NAEDS performance is improved.

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“…The Lewis acid catalyzed carbocationic isomerization polymerization of β-pinene has been explored since the 1950s [ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 ]. A number of Lewis acids, such as AlCl 3 , AlBr 3 , EtAlCl 2 , Et 2 AlCl, BiCl 3 , SbCl 3 , ZrCl 4 , BF 3 , TiCl 4 , TiCl 3 (O i Pr), SnCl 4 , and ZnCl 2 , and different reaction conditions were used in attempts to carry out the polymerization of β-pinene.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Cationic Polymerization of β-Pinene, a Bio-Based, Renewable Olefin, with TiCl4 Catalyst from Cryogenic to Energy-Saving Room Temperature Conditions

Verebélyi

Szabó

Réti

et al. 2023

IJMS

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Polymers based on renewable monomers are projected to have a significant role in the sustainable economy, even in the near future. Undoubtedly, the cationically polymerizable β-pinene, available in considerable quantities, is one of the most promising bio-based monomers for such purposes. In the course of our systematic investigations related to the catalytic activity of TiCl4 on the cationic polymerization of this natural olefin, it was found that the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4/N,N,N′,N′-tetramethylethylenediamine (TMEDA) initiating system induced efficient polymerization in dichloromethane (DCM)/hexane (Hx) mixture at both −78 °C and room temperature. At −78 °C, 100% monomer conversion was observed within 40 min, resulting in poly(β-pinene) with relatively high Mn (5500 g/mol). The molecular weight distributions (MWD) were uniformly shifted towards higher molecular weights (MW) in these polymerizations as long as monomer was present in the reaction mixture. However, chain–chain coupling took place after reaching 100% conversion, i.e., under monomer-starved conditions, resulting in considerable molecular weight increase and MWD broadening at −78 °C. At room temperature, the polymerization rate was lower, but chain coupling did not occur. The addition of a second feed of monomer in the polymerization system led to increasing conversion and polymers with higher MWs at both temperatures. 1H NMR spectra of the formed polymers indicated high in-chain double-bond contents. To overcome the polarity decrease by raising the temperature, polymerizations were also carried out in pure DCM at room temperature and at −20 °C. In both cases, rapid polymerization occurred with nearly quantitative yields, leading to poly(β-pinene)s with Mns in the range of 2000 g/mol. Strikingly, polymerization by TiCl4 alone, i.e., without any additive, also occurred with near complete conversion at room temperature within a few minutes, attributed to initiation by adventitious protic impurities. These results convincingly prove that highly efficient carbocationic polymerization of the renewable β-pinene can be accomplished with TiCl4 as catalyst under both cryogenic conditions, applied widely for carbocationic polymerizations, and the environmentally benign, energy-saving room temperature, i.e., without any additive and cooling or heating. These findings enable TiCl4-catalyzed eco-friendly manufacturing of poly(β-pinene)s, which can be utilized in various applications, and in addition, subsequent derivatizations could result in a range of high-added-value products.

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Poly(β-pinene) as an efficient biobased tackifier for metallocene poly(ethylene) based hotmelt adhesives

Cited by 9 publications

References 25 publications

A Bio-Based Tackifier Synthesized by Room-Temperature Cationic Copolymerization of Isobutene and β-Pinene

A Bio-Based Tackifier Synthesized by Room-Temperature Cationic Copolymerization of Isobutene and β-Pinene

The curing kinetics and properties of self-healing and thermally conductive polymeric composites based on ethylene vinyl acetate copolymer filled with nano alumina

Highly Efficient Cationic Polymerization of β-Pinene, a Bio-Based, Renewable Olefin, with TiCl4 Catalyst from Cryogenic to Energy-Saving Room Temperature Conditions

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