Melt versus solvent coating: Structure and properties of block–copolymer‐based pressure‐sensitive adhesives

Pressure‐sensitive adhesives (PSAs) composed of a styrene–isoprene–styrene triblock copolymer and a midblock‐associating resin were prepared via solvent and hot‐melt coating. The formulations and thermal histories up to the point of coating were identical, yet significant differences in the properties were observed as a function of the coating method. The solvent‐coated PSA showed superior shear holding power, and the hot‐melt‐coated PSA performed better in tack and peel tests. Two factors resulting from the processing conditions were responsible for these property differences. The quick cooling process occurring after hot‐melt coating led to a poorly defined microstructure and, therefore, less physical crosslinking. Rheological data for melt‐pressed and solvent‐cast PSA films confirmed these microstructural differences. The increased solubility of the tackifier in the solvent additionally created a composition gradient in the solvent coating. Annealing improved the long‐range order of both hot‐melt and solvent coatings, producing a body‐centered cubic microstructure identified by small‐angle X‐ray scattering. This microstructure improved the shear strength of both types of adhesive coatings, whereas the peel and tack properties of the solvent coatings remained inferior to those of the hot‐melt coatings because of differences in the surface compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3355–3367, 2002     

Epoxy–imide resins from N‐(4‐ and 3‐carboxyphenyl)trimellitimides. I. Adhesive and thermal properties

Epoxy–imide resins were obtained by curing Araldite GY 250 (diglycidyl ether of bisphenol‐A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac–epoxy resin; polyfunctional) with N‐(4‐ and 3‐carboxyphenyl)trimellitimides derived from 4‐ and 3‐aminobenzoic acids and trimellitic anhydride. The adhesive lap shear strength of epoxy–imide systems at room temperature and at 100, 125, and 150°C was determined on stainless‐steel substrates. Araldite GY 250‐based systems give a room‐temperature adhesive lap shear strength of about 23 MPa and 49–56% of the room‐temperature adhesive strength is retained at 150°C. Araldite EPN 1138‐based systems give a room‐temperature adhesive lap shear strength of 16–19 MPa and 100% retention of room‐temperature adhesive strength is observed at 150°C. Glass transition temperatures of the Araldite GY 250‐based systems are in the range of 132–139°C and those of the Araldite EPN 1138‐based systems are in the range of 158–170°C. All these systems are thermally stable up to 360°C. The char residues of Araldite GY 250‐ and Araldite EPN 1138‐based systems are in the range of 22–26% and 41–42% at 900°C, respectively. Araldite EPN 1138‐based systems show a higher retention of adhesive strength at 150°C and have higher thermal stability and T_g when compared to Araldite GY 250‐based systems. This has been attributed to the high crosslinking possible with Araldite EPN 1138‐based systems arising due to the polyfunctional nature of Araldite EPN 1138. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1729–1736, 2000     

Thermal characterization of three‐component blends for hot‐melt adhesives

Traditional solvent‐based adhesives used in the footwear industry have been demonstrated as harmful to the workers' health and environment. Solvent‐free three‐component adhesives (hot‐melt adhesives or HMAs) for various applications including the leather and footwear industry are becoming more and more attractive. Thus, the formulation of a three‐component HMA was realized in this study. Thermogravimetry, differential scanning calorimetry, and the apparent strength of the adhesive bond were used to investigate the relationship between their properties and the polymer/wax/resin compositions. The thermal stability of HMA formulations was determined and compared with thermal traces based on an additive weight computation of the single components' thermal profiles. All HMA formulations showed a direct relationship between the glass‐transition temperature and the apparent adhesive shear strength at the leather–rubber interface. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2889–2901, 2001     

Synthesis and characterization of high‐performance epoxy resin based on disiloxane and 4,4′‐oxybis(benzoic acid) ester

Epoxy‐terminated siloxane‐contained resin (BCDS/OBBA‐ETS) with high tensile strength and lap shear strength as well as good thermal stability was synthesized and characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. Carboxy‐capped disiloxane‐4,4′‐oxybis (benzoic acid) ester oligomer (BCDS/OBBA) was firstly prepared from the reaction between 1,3‐bis(chloromethyl)‐1,1,3,3‐tetramethyl‐disiloxane and 4,4′‐oxybis(benzoic acid) (OBBA) in N,N‐dimethylformamide in the presence of triethylamine. Then, the BCDS/OBBA oligomer was reacted with epichlorohydrin to obtain the title BCDS/OBBA‐ETS resin. Cured with liquid polyamide L‐651, or diethylenetriamine, the mechanical and thermal properties as well as the lap shear strength of the BCDS/OBBA‐ETS resin were evaluated. The results indicated that the BCDS/OBBA‐ETS resin exhibited good thermal stability below 200°C, and the glass transition temperature (T_g) was about 64°C after cured with L‐651. The tensile strength of same cured BCDS/OBBA‐ETS resin was 27.46 MPa with a stain at break of 42.11%, and the lap shear strength for bonding stainless steel was 18.59 MPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Heterocyclic‐based epoxy‐terminated structural adhesive. II. Curing,adhesive strength,and thermal stability

We studied the curing behavior of heterocyclic‐based epoxy‐terminated resins using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylicdianhydride, and the commercial hardener of Ciba‐Geigy's two‐pack Araldite as curing agents. The adhesive strength of the adhesives was measured by various ASTM methods such as lap‐shear, peel, and cohesive tests on metal–metal, wood–wood, and wood–metal interfaces. All of these results were compared with those of an epoxy resin prepared from bisphenol‐A and epichlorohydrin resin with an epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3520–3526, 2002     

Peel and shear strength of pressure‐sensitive adhesives prepared from epoxidized natural rubber

Peel and shear strength of two grades of epoxidized natural rubber (ENR 25 and ENR 50)‐based pressure‐sensitive adhesive was studied. Coumarone‐indene resin was used as the tackifier, whereas toluene was chosen as the solvent throughout the experiment. The tackifier loading was varied from 0 to 80 parts per hundred parts of rubber (phr). A SHEEN hand coater was used to coat the adhesive on substrate to give a coating thickness of 30, 60, 90, and 120 μm. Peel strength and shear strength of the adhesive were determined by using a Lloyd adhesion tester and Texture analyzer, respectively. Results show that maximum peel strength occurs at 40 phr of coumarone‐indene resin for both ENRs studied an observation, which is attributed to the maximum wettability of the substrate. However, the shear strength shows a gradual decrease with increasing tackifier loading because of the decrease in cohesive strength of adhesive. ENR 25 consistently indicates higher peel strength and shear strength than ENR 50. Generally, peel and shear strength increases with coating thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007.     

Influence of aliphatic amine epoxy hardener on the adhesive properties of blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with epoxy resin

The adhesive properties have been investigated in blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with diglycidyl ether of bisphenol A and three different aliphatic amine epoxy hardener. The adhesives properties are evaluated in steel alloy substrate using single‐lap shear test. The copolymers are initially miscible in the stoichiometric blends of epoxy resin and hardener at room temperature. Phase separation is noted in the course of the polymerization reaction. Different morphologies are obtained according to the amine epoxy hardener. The most effective adhesive for steel–steel joints in single‐lap shear test is the blends using 1‐(2‐aminoethyl)piperazine (AEP) as hardener. This system shows the biggest lap shear strength. However, the modified adhesives show a reduction in the mechanical resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and properties of carbon nanotube/styrene–ethylene–butylene–styrene composites via a sequential process of (electrostatic adsorption aided dispersion)‐plus‐(melt mixing)

Carbon nanotube (CNT)/styrene–ethylene–butylene–styrene (SEBS) composites were prepared via a sequential process of (electrostatic adsorption assisted dispersion)‐plus‐(melt mixing). It was found that CNTs were uniformly embedded in SEBS matrix and a low percolation threshold was achieved at the CNT concentration of 0.186 vol %. According to thermal gravimetric analysis, the temperatures of 20% and 50% weight loss were improved from 316°C and 352°C of pure SEBS to 439°C and 463°C of the 3 wt % CNT/SEBS composites, respectively. Meanwhile, the tensile strength and elastic modulus were improved by about 75% and 181.2% from 24 and 1.6 MPa of pure SEBS to 42 and 4.5 MPa of the 3 wt % CNT/SEBS composite based on the tensile tests, respectively. Importantly, this simple and low‐cost method shows the potential for the preparation of CNT/polymer composite materials with enhanced electrical, mechanical properties, and thermal stability for industrial applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40227.     

Poly(vinyl alcohol)–lignin blended resin for cellulose‐based composites

Wood has limitations in strength because of its biostructural defects, including vessels. To overcome this limitation, composite materials can be innovated by breaking wood down into cellulose and lignin and reassembling them for bio‐originating strong structural materials. In this study, an ecofriendly resin was developed that was suitable for cellulose‐based composites. To overcome the low dimensional stability of lignin and to increase its interactions with cellulose, it was blended with poly(vinyl alcohol) (PVA). The PVA–lignin resin was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, thermal analysis, mechanical tensile testing, and lap‐shear joint testing. The adhesion properties of the PVA–lignin resin increased with increasing PVA content. PVA played the role of synthetic polymer and that of linker between the cellulose and lignin, like hemicellulose does in wood. The PVA–lignin resin exhibited a high miscibility, mechanical toughness, and good adhesion properties for nanocellulose composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46655.     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002     

Influence of thermoplastic elastomers on adhesion in polyethylene–wood flour composites

The mechanical properties of recycled low-density polyethylene/wood flour (LDPE/WF) composites are improved when a maleated triblock copolymer styrene–ethylene/butylene–styrene (SEBS–MA) is added as a compatibilizer. The composites' tensile strength reached a maximum level with 4 wt % SEBS–MA content. The compatibilizer had a positive effect on the impact strength and elongation at break but decreased the composites' stiffness. Dynamic mechanical thermal analysis (DMTA), a lap shear adhesion test, and a scanning electron microscope (SEM) were used to investigate the nature of the interfacial adhesion between the WF/SEBS and between the WF/SEBS–MA. Tan δ peak temperatures for the various combinations showed interaction between the ethylene/butylene (EB) part of the copolymer and the wood flour in the maleated system. The shear lap test showed that adhesion between the wood and SEBS–MA is better than between the wood and SEBS. The electron microscopy study of the fracture surfaces confirmed good adhesion between the wood particles and the LDPE/SEBS–MA matrix. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1845–1855, 1998     

Shear creep resistance of styrene–isoprene–styrene (SIS)‐based hot‐melt pressure‐sensitive adhesives

The effects of the properties of substrates and tackifier on the shear creep of SIS‐based HMPSAs were investigated. The holding power (t_b) and shear adhesion failure temperature (SAFT) were measured. The relationship between the complex viscosity and the holding power was examined. The holding power and SAFT values of the triblock SIS blends were higher than those of the diblock‐containing SIS blends, perhaps because blends using triblock SIS have higher crossover temperature and complex viscosity than those using diblock‐containing SIS. Higher levels of aromatic resin‐modified aliphatic tackifier and rosin ester were found to decrease the holding power of the HMPSAs. This maybe due to the fact that rosin ester and aromatic‐modified aliphatic resin are compatible with both the ends and midblocks of SIS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 825–831, 2006     

Rubber solution adhesives for wood-to-wood bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1185–1189, 1998     

Effect of N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine antioxidant on the adhesion properties of (zinc oxide)‐filled (epoxidized natural rubber 25)‐based pressure‐sensitive adhesives

The effect of antioxidant, namely, N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine (IPPD), on the adhesion properties of epoxidized natural rubber (ENR 25)‐based pressure‐sensitive adhesive was investigated. The concentration of the IPPD was varied from 0 to 5 parts by weight per hundred parts of rubber (phr). Coumarone‐indene resin, zinc oxide, toluene, and polyethylene terephthalate were used as the tackifier, filler, solvent, and substrate, respectively. A Lloyd Adhesion Tester operating at different testing rates (10–60 cm/min) was used to determine the loop tack, peel strength, and shear strength at 60‐µm and 120‐µm coating thicknesses. Results indicate that adhesion properties increase with IPPD up to 2 phr of content, after which it decreases with further addition of the antioxidant. This observation is attributed to the culmination of wettability and compatibility at the optimum IPPD concentration. The 60‐µm coated sample consistently shows higher adhesion strength than that of 120‐µm coated sample. Loop tack and peel strength increase with testing rate up to 30 cm/min. However, shear strength increases with increasing testing rate in the testing rate investigated in this study. J. VINYL ADDIT. TECHNOL., 21:111–115, 2015. © 2014 Society of Plastics Engineers     

Effect of zinc oxide on the viscosity and adhesion property of epoxidized natural rubber/acrylonitrile‐butadiene rubber‐based pressure‐sensitive adhesives

Viscosity, loop tack, peel strength, and shear strength of epoxidized natural rubber (ENR 50)/acrylonitrile‐butadiene rubber (NBR)–based pressure‐sensitive adhesive were studied in the presence of zinc oxide. The zinc oxide concentration was varied from 10 to 50 parts by weight per hundred parts of rubber (phr). Coumarone–indene resin with loading of 40 phr was chosen as the tackifier resin. Toluene and polyethylene terephthalate were used as the solvent and coating substrate, respectively, throughout the experiment. The adhesive was coated on the substrate by using a SHEEN hand coater. Viscosity of the adhesive was determined by a Brookfield Viscometer, whereas the loop tack, peel strength, and shear strength were measured by a Lloyd Adhesion Tester operating at 30 cm/min. Results indicate that viscosity increases with zinc oxide concentration owing to the concentration effect. Loop tack and peel strength pass through a maximum value at 20 phr of zinc oxide concentration. This observation is associated with the effect of varying degrees of wettability of the adhesive on the substrate. Shear strength, however, increases steadily with increasing zinc oxide loading owing to the steady increase in cohesive strength. In all cases, the adhesion properties of adhesives increase with increasing coating thicknesses. J. VINYL ADDIT. TECHNOL., 22:410–414, 2016. © 2015 Society of Plastics Engineers     

Thermoplastic elastomeric nanocomposites from poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer and clay: Preparation and characterization

Thermoplastic elastomer (TPE)–clay nanocomposites based on poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer (SEBS) were prepared. Natural sodium montmorillonite (MMT) clay was organically modified by octadecyl amine to produce an amine‐modified hydrophobic nanoclay (OC). Commercially available Cloisite 20A (CL20) and Cloisite 10A, tallow ammine modified nanoclays, were also used. The intergallery spacing of MMT increased on amine modification as suggested by the shifting of the X‐ray diffraction (XRD) peak from 7.6 to 4.5 and 3.8° in the cases of OC and CL20, respectively. The latter demonstrated no XRD peak when it was used at 2 and 4 parts phr in the SEBS system. Transmission electron microscopy studies showed the intercalation–exfoliation morphology in SEBS containing 4 parts of CL20₄–SEBS, agglomeration in SEBS having 4 parts of MMT, and mixed morphology in SEBS with 4 parts of OC systems. Locations of the clay particles were indicated by the atomic force micrographs. Mechanical and dynamic mechanical thermal analysis studies confirmed the best properties with the CL20₄–SEBS nanocomposites. Significant improvements in mechanical properties such as tensile strength, modulus, work to break, and elongation at break were achieved with the CL20₄–SEBS in polymer‐layered silicate nanocomposites. Dynamic mechanical studies further showed the affinity of the organoclays toward both segments of the TPE and a compatibilization effect with CL20 at a 4‐phr loading. Atomic force microscopy showed distinctly different morphologies in nanocomposites prepared through solution and melt processing. Comparisons of the mechanical, dynamic mechanical, and morphological properties of the nanocomposites prepared by melt and solution intercalation processes were done. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2040–2052, 2006     

PSA performances and viscoelastic properties of SIS‐based PSA blends with H‐DCPD tackifiers

Hotmelt pressure sensitive adhesives (PSAs) usually contain styrenic block copolymers like styrene–isoprene–styrene (SIS), SBS, SEBS, tackifier, oil, and additives. These block copolymers individually reveal no tack. Therefore, a tackifier is a low molecular weight material with high glass transition temperature (T_g), and imparts the tacky property to PSA. The SIS block copolymer with different diblocks was blended with hydrogenated dicyclopentadiene (H‐DCPD tackifier), which has three kinds of T_g. PSA performance was evaluated by probe tack, peel strength, and shear adhesion failure temperature. PSA is a viscoelastic material, so that its performance is significantly related to the viscoelastic properties of PSAs. We tested the viscoelastic properties by dynamic mechanical analysis and the thermal properties by differential scanning calorimeter to investigate the relation between viscoelastic properties and PSA performance. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2839–2846, 2006     

In situ thermal reduction of graphene oxide in a styrene–ethylene/butylene–styrene triblock copolymer via melt blending

We report an in situ thermal reduction of graphene oxide (GO) in a styrene–ethylene/butylene–styrene (SEBS) triblock copolymer matrix during a melt‐blending process. A relatively high degree of reduction was achieved by melt‐blending premixed GO/SEBS nanocomposites in a Haake mixer for 25 min at 225 °C. Infrared spectral results revealed the successful thermal reduction of, and the strong adsorption of SEBS on, the graphene sheets. The glass transition temperature of polystyrene (PS) segments in SEBS was enhanced by the incorporation of thermally reduced graphene oxide (TRGO). The resultant TRGO/SEBS nanocomposites were used as a masterbatch to improve the mechanical properties of PS. Both the elongation at break and the flexural strength of PS/SEBS blends were enhanced with the addition of the TRGO. Our demonstration of the in situ thermal reduction of GO via melt blending is a simple, efficient strategy for preparing nanocomposites with well‐dispersed TRGO in the polymer matrix, which could be an important route for large‐scale fabrication of high‐performance graphene/polymer nanocomposites. © 2013 Society of Chemical Industry     

Epoxy–imide resins based on bis (carboxyphthalimide)s

Epoxy–imide resins have been obtained through the reaction of Araldite GY 250 (diglycidylether of bisphenol-A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac-epoxy resin; polyfunctional) with bis(carboxyphthalimide)s derived from 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylmethane and trimellitic anhydride. For each epoxy-imide resin system, epoxy equivalent to carboxy equivalent ratio has been optimised to obtain the maximum tensile lap shear adhesive strength on stainless steel substrates at room temperature. The lap shear strength at 100, 150, and 175°C has been determined for the optimum ratio. Araldite EPN-1138-based systems give the lap shear strength of 141–182 kg/cm² at room temperature for the optimum compositions and retain about 84–100% of the lap shear strength at 150°C. Araldite GY-250-based systems have lap shear strength of 183–193 kg/cm² and retain 76–84% of the lap shear strength at 150°C except for the one cured with bis (carboxyphthalimide) prepared from 4,4′-diaminodiphenylmethane, which retains only 17% of the lap shear strength. Among the systems studied, Araldite GY 250 cured with bis (carboxyphalimide) synthesized from 3,3′-diaminodiphenylsulfone appears to be the best, retaining 75% (138 kg/cm²) of the lap shear strength at 175°C.     

PP-R铝塑复合管用热熔胶的研制

将PP／HDPE用马来酸酐(MAH)进行熔融接枝改性制得PP—R铝塑复合管用热熔胶树脂，红外光谱分析证实MAH确已接枝到树脂上。当HDPE比例占40％，MAH接枝率0．7％时，树脂与铝箔和PP—R有最大的剥离强度。在该树脂中添加10％的增粘树脂、40％的粘度调节剂后，获得了剥离强度达135N／cm的热熔胶。