Photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives containing type-II photoinitiators

UV-crosslinking is an established technology used in many industrial manufacturing processes. New applications and technical specifications of UV technologies stimulate the continuous development of photoinitiators that can efficiently meet specific requirements. A typical class of radical-reactive type-II photoinitiators has been used for the UV-initiated crosslinking of acrylic pressure-sensitive adhesives (PSAs).The activity of type-II photoinitiators such as: benzophenone derivatives, thioxanthone derivative, antraquinone derivative and fluorenone (without tertiary amine as a co-initiator) in the photoreactive UV-crosslinkable acrylic pressure-sensitive adhesives was described. The effect of the type-II photoinitiators on the acrylic PSA properties (tack, peel, and shear strength) was summarized.     

Development in the area of UV-crosslinkable solvent-based pressure-sensitive adhesives with excellent shrinkage resistance

Solvent-based UV-crosslinkable pressure-sensitive adhesives (PSA) present a new class of products that offers the potential to produce a novel generation of ultraviolet cured self-adhesive products with excellent shrinkage resistance. A variety of solvent-based pressure-sensitive adhesives were prepared by synthesis in ethyl acetate with solid content on 50 wt.% with 2-ethylhexyl acrylate, methyl acrylate, acrylic acid, N-vinyl caprolactam and unsaturated photoinitiators: 4-acryloyloxy benzophenone, allyl benzoine and phenyl-(1-acryloyloxy)-cyclohexyl ketone. The main emphasis is given to the influence of viscosity and molecular mass of synthesized adhesive on their shrinkage. Further trials show the effect of the UV-crosslinking process with UV-lamp and comparison with acrylics PSA crosslinked with metal chelates aluminium acetylacetonate and titanium acetylacetonate on shrinkage. Further examinations describe the influence of various factors such as UV exposure time and UV dose on very relevant PSA performance such as shrinkage on coated PVC carrier.     

Development of solvent-free acrylic pressure-sensitive adhesives

The present publication describes a problem to develop solvent-free acrylic pressure-sensitive adhesives (PSA). Solvent-free PSA are established materials for the manufacturing of various self-adhesive products. Only by means of these acrylic PSA was it possible to succeed in drafting the present surprisingly efficient generation of double-sided pressure-sensitive adhesive tapes, medical products, protective masking films, films for the graphics market, and various specialty products. New applications and technical specifications stimulate the continuous development of new methods of polymerization of solvent-free acrylates. New syntheses of solvent-free acrylic PSA include polymerization in the reactor with removal of the solvent and polymerization on the carrier. The polymerization process is connected with UV-crosslinking.     

Synthesis of Silicone Modified Acrylic Resin Paint and It's Properties Studies

An acrylic resin coating by itself, shows resistance to weather and color retention, but has poor high-temperature resistance. The silicone resin exhibits excellent weatherability, good heat resistance and strong hydrophobicity. To improve the exterior durability, dirt-pickup resistance and color retention of acrylic resin, a little amount of silicone functional group was introduced into it, taking advantaging of high dissociation energy and low surface tension, good stability to gloss and heat,ultraviolet light resistance of the Si-O bond of polysilonxane^[1,2].     

Influence of thermal reactive crosslinking agents on the tack,peel adhesion,and shear strength of acrylic pressure-sensitive adhesives

In recent decades, the basic technology of pressure-sensitive adhesive (PSA) acrylics has developed into a sophisticated science. The main properties of acrylic PSAs such as tack, peel adhesion, and shear strength are determined to a large extent by the kind and quantity of crosslinking agents added to the synthesized PSAs. In order to improve their adhesive (tack, peel adhesion) and cohesive (shear strength) properties, a wide range of amino resin thermal crosslinkers are tested. An acrylic PSA based on 2-ethylhexylacrylate, n-butyl acrylate, and acrylic acid was synthesized by performing a radical polymerization in ethyl acetate. After the addition of amino resins to the acrylic PSA and carrying out thermally initiated crosslinking processes to prepare one-sided self-adhesive tapes, their properties were assessed.     

Identification and quantification of odorous compounds from adhesives used in food packaging materials by headspace solid phase extraction and headspace solid phase microextraction coupled to gas chromatography–olfactometry–mass spectrometry

Adhesives are often responsible for off-flavors in food in contact with packaging. The aim of this investigation was to identify by GC–O–MS the odorous compounds in five different types of adhesive (hotmelt, vinyl acetate ethylene, starch, polyvinyl acetate and acrylic) used in food packaging. In order to obtain a substantial number of compounds, they were extracted by two complementary extraction methods: HS-SPE and HS-SPME. Fifteen minutes extraction time using PDMS fiber for hotmelt adhesive and DVD/CAR/PDMS fiber for the other adhesives were the best conditions for defining a representative solvent-free adhesive extract using a rapid and simple D-GC–O technique. Thirty-three compounds were identified by GC–O–MS. These include butyric acid, acetic acid, methyl butyrate, 1-butanol and nonanal, which were present in most of the adhesives under study producing cheesy, rancid, sour, medicinal and green aromas, respectively. The concentrations were determined, the most abundant compound being acetic acid with concentrations from 22.9 to 8930 μg g⁻¹ of adhesive.     

UV-curing behavior and adhesion performance of polymeric photoinitiators blended with hydrogenated rosin epoxy methacrylate for UV-crosslinkable acrylic pressure sensitive adhesives

UV-crosslinkable polyacrylates were synthesized for use as pressure sensitive adhesives (PSAs). These polyacrylates acted as polymeric photoinitiators due to the benzophenone incorporated into their backbones. Hydrogenated rosin epoxy methacrylate (HREM; based on hydrogenated rosin and glycidyl methacrylate) was also synthesized as a tackifier, and blended at different levels with the synthesized, UV-crosslinkable polyacrylates for use as PSAs. The effect of the new tackifier, HREM, on the properties of the UV-crosslinkable PSAs was examined in comparison with the properties exhibited by PSA/hydrogenated rosin blends. The characteristics of these PSA/tackifier blends were examined by Fourier-transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and an advanced rheometric expansion system (ARES). In addition, the adhesion performance of the PSA blends was investigated using probe tack tests. DSC and ARES revealed all the PSA blends with HREM or hydrogenated rosin to be miscible at the molecular level. The glass transition temperature (T_g) of HREM was −25.6 °C, which is lower than that of other commercially available rosin tackifiers. FTIR revealed changes in the relative concentration of benzophenone groups in the PSAs at 1580 cm⁻¹, which demonstrated that the crosslinking efficiency is proportional to the benzophenone content and UV dose, but decreases with increasing hydrogenated rosin content. However, the reduced crosslinking reaction efficiency was improved in the PSA/HREM blends due to the low T_g of HREM which only slightly increased the T_g of the PSA blends. Moreover, the relative initial decrease in the probe tack of the PSA/HREM blends was lower than that of the PSA/hydrogenated rosin blends after UV irradiation.     

Synthesis and characterization of an acrylate pressure sensitive adhesive for transdermal drug delivery

The present investigation was directed towards the synthesis of a copolymer of 2‐ethylhexyl acrylate and acrylic acid to be exploited as a pressure sensitive adhesive (PSA) matrix in transdermal drug delivery systems. The polymer synthesis involved free radical solution polymerization using 2, 2′‐azobisisobutyronitrile as the free radical initiator. The experimental methodology involved the optimization of reaction conditions for the polymer synthesis. The optimized copolymer was then characterized by IR, ¹H‐NMR, DSC, GPC and XRD. The PSA was also evaluated for percent free monomer content, intrinsic viscosity, refractive index, moisture uptake potential and film forming properties. To assess it suitability in the development of transdermal systems, peel strength values with respect to release liner as well as human skin and skin irritation potential were also determined. In addition, wear performance test was conducted to evaluate adhesion and adhesive transfer. The synthesized adhesive was found to have good peel strength; exhibited excellent adhesion and adhesive transfer on removal. It was found suitable for use in transdermals and could be further exploited either as an adhesive matrix or as a system component in the area of transdermal drug delivery. Copyright © 2002 John Wiley & Sons, Ltd.     

Novel surface fixation technology of hydrogel based on photochemical method: Heparin-immobilized hydrogelated surface

This article reports a novel photoinduced surface process technology enabling simultaneous hydrogel formation and its surface fixation on polymeric substrates. The process consists of layering two different types of photoreactive coatings on a polymeric surface, an azidophenyl-bearing polymer as an adhesive layer and cinnamoylated copolymer as a hydrogel layer, and subsequent UV irradiation. The photoreactive adhesive polymer coated on a substrate is poly(m-azidostyrene), in which photoreaction of phenyl azido groups is responsible for the chemical bonding between the substrate and hydrogel. N,N-dimethylacrylamide copolymer containing cinnamate moieties in their side chains, which undergo photocrosslinking via intermolecular dimerization, was applied as an overcoat on the adhesive layer. UV irradiation resulted in the formation of hydrogel chemically bonded onto the substrate. This was confirmed by ESCA measurements. A heparin-immobilized hydrogelated surface with controlled release characteristics was demonstrated. © 1993 John Wiley & Sons, Inc.     

Preparation and application of photosensitive copolymers for PDP barrier ribs formed by photolithography

In this work, the photosensitive paste was prepared. It was comprised of inorganic particles and a photosensitive organic component. The inorganic particles included glass, ceramics, and metals. The organic component should contain at least the following photosensitive materials: photosensitive monomers, photoreactive copolymer and photopolymerization initiators. The photoreactive copolymer played a role of an adhesive in the photosensitive paste. Meanwhile in the development stage, the carboxyl groups of the copolymer reacted with the alkalescent developer. Following this, the unexposed part must be removed and an excellent pattern can be formed. A series of three-component acrylic copolymers (MAA/St/MMA) were designed, and then synthesized via free radical polymerization. Subsequently glycidyl methacrylate (GMA) was employed to modify the prepared copolymers through ring-opening reactions between the carboxyl groups and the epoxide groups. Eventually the photosensitive copolymers were obtained and used to form the barrier ribs of PDPs. The chemical structure, glass transition temperature, acid value and molecular weight of photosensitive copolymers had different effects on the structure and pattern of PDP barrier ribs. Through analyzing effects of different polymer performance parameters on the patterns of barrier ribs, the optimal photosensitive copolymer was acquired.     

Electrospinning of a functional perfluorinated block copolymer as a powerful route for imparting superhydrophobicity and corrosion resistance to aluminum substrates

Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.     

Molecular and nanoscale factors governing pressure‐sensitive adhesion strength of viscoelastic polymers

Pressure‐sensitive adhesives (PSAs) are finding increasing applications in various areas of industry and medicine. PSAs are a special class of viscoelastic polymers that form strong adhesive joints with substrates of varying chemical nature under application of light external bonding pressures (1–10 Pa) over short periods of time (1–5 s). To be a PSA, a polymer should possess both high fluidity under applied bonding pressure, to form good adhesive contact, and high cohesive strength and elasticity, which are necessary for resistance to debonding stresses and for dissipation of mechanical energy at the stage of adhesive bond failure under detaching force. For rational design of novel PSAs, molecular insight into mechanisms of their adhesive behavior is necessary. As shown in this review, strength of PSA adhesive joints is controlled by a combination of diffusion, viscoelastic, and relaxation mechanisms. At the molecular level, strong adhesion is the result of a narrow balance between two generally conflicting properties: high cohesive strength and large free volume. These conflicting properties are difficult to combine in a single polymer material. Individually, high cohesive interaction energy and large free volume are necessary but insufficient prerequisites for PSA strength. Evident correlations are observed between the adhesive bond strengths of different PSAs, and their relaxation behaviors are described by longer relaxation times. Innovative PSAs with tailored properties can be produced by physical mixing of nonadhesive long‐ and short‐chain linear parent polymers, with groups at the two ends of the short chains complementary to the functional groups in the recurring units of the long chains. Although chemical composition and molecular structure of such innovative adhesives are unrelated to those of conventional PSAs, their mechanical properties and adhesive behaviors obey the same general laws, such as the Dahlquist's criterion of tack. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

Comparison between thermal crosslinkers based on melamine-formaldehyde and benzoguanamine resin and their influence on main performance of acrylic pressure-sensitive adhesives as tack,peel adhesion,shear strength and pot-life

An acrylic pressure-sensitive adhesive (PSA) was synthesized in ethyl acetate at about 80 °C by the use of 2-ethylhexyl acrylate, ethyl acrylate, methyl acrylate and acrylic acid at presence of thermal radical initiator AIBN. The synthesized acrylic PSA was crosslinked at relatively low temperatures at about 110–125 °C using thermal crosslinkers selected from melamine-formaldehyde resins and benzoguanamine resins. The crosslinking process runs between carboxylic groups of acrylic PSA and reactive groups from investigated amine resins. The choice of suitable thermal reactive crosslinkers has significant and relevant influence at presence of organic acid catalysts on main performance of crosslinked PSA such as tack, peel adhesion and shear strength.     

聚硼硅氧烷的制备及应用研究进展

聚硼硅氧烷作为元素改性聚硅氧烷中的一类新型有机高分子材料,它是将硼元素引入聚硅氧烷的硅氧骨架中而得到聚合物,较普通的有机聚硅氧烷有更优异的耐高温性和粘接性能,因而具有更为广阔的应用前景。本文就近几十年来聚硼硅氧烷的合成方法进行了综述,并简单介绍了聚硼硅氧烷的性能及其作为耐高温胶粘剂、耐热阻燃剂、耐热涂料、硅硼碳氧陶瓷前驱体等材料方面的应用状况。     

阻燃聚丙烯酸酯胶的合成

通过溶液聚合法制得了阻燃性丙烯酸酯胶。研究了甲基丙烯酸2,4,6-三溴苯酯及引发剂用量,交联单体及反应温度、反应时间等对剥离强度的影响。研究了多元共聚丙烯酸酯胶的单体组成、合成工艺及其产品性能。结果表明,制得的胶粘剂在室温下剥离强度为19．5N／cm。     

Multifunctional chemical vapor sensors of aligned carbon nanotube and polymer composites

Partially coating perpendicularly aligned carbon nanotube arrays with an appropriate polymer thin film along their tube length provides a novel concept for developing new sensors of high sensitivity, good selectivity, and excellent environmental stability for the detection of a broad class of chemical vapors with low power consumption. The absorption and desorption of chemical vapors by the polymer matrix cause changes in the inter-tube distance and, hence, the surface resistance across the nanotube film. Simple measurements of the resistance change, therefore, constitute the nanotube-polymer chemical vapor sensors. These rationally designed, aligned carbon nanotube-polymer composite films are flexible and can be effectively integrated into many systems for a wide range of potential applications, including their use as multifunctional sensors for sensing chemical vapors, mechanical deformations, thermal and optical exposures.     

水性纸品上光涂料的研究进展

水性纸品上光涂料是用于印刷品的精加工及包装材料的表面整饬的一种涂料,具有成本低、无污染、无毒无害、性能优良,运输方便等优点,是当前印刷上光涂料的主要发展方向。目前,国内的水性纸品上光涂料生产技术多样化,质量参差不齐,且成本高,耐水、耐磨、光泽度性能都达不到高档印刷品的上光要求,70%的高档水性纸品上光涂料需要依靠进口。本文系统地介绍了目前国内外水性纸品上光涂料的研究进展,总结了水性纸品上光涂料的各自特点与应用,并提出一种水性纸品上光涂料制备的新方法。     

Nanometer Polymer Latex and Its Application in Waterborne Coating

The nanometer materials have been attracting an increasing attention due to the wide applications of this kind of materials in the information technology, national defense, biotechnology, etc. The applications of nanotechnology have also injected impetus into the conventional industries such as coatings, plastics, rubber, adhesive, ceramics, cosmetics. As to coating industry, the nanotechnology has been providing the resulting coating with high performances as well as novel characteristics. The progress in this research field is raising the technology content and even promote the prosperity of this sector.     

Novel Carbazole (Cbz)-Based Carboxylated Functional Monomers: Design,Synthesis, and Characterization

A series of novel functional carbazole (Cbz)-based carboxylated monomers were synthesized and characterized. A Clauson-Kaas procedure, a deprotection step, amide coupling, and hydrolysis were utilized as key chemical reactions towards the multistep synthesis of monomers in good to excellent isolated yields. The design strategy was further extended to complex carbazole-COOH monomers incorporated arylazo groups as photoreactive moieties. In addition, photoreactive hybrid carbazole (Cbz)-pyrrole (Pyr)-based carboxylated monomers, comprising a pyrrole core linking a carbazole and a photoreactive phenylazide or benzophenone moiety through an amide spacer in the molecular structure, were also synthesized. The latter can be utilized for surface modification of polymeric films in their monomeric form or as polymeric microparticles (MPs).