Styrene-Butadiene Polytelomers for Pressure-Sensitive Applications

Novel styrene-butadiene polymer latex compositions and their utility for pressure-sensitive and other adhesive applications are described. These compositions, termed polytelomers, are based on the concept of synthesising sequentially a low glass transition temperature, high molecular weight (polymeric) fraction, followed by a high glass transition, low molecular weight (telomeric) fraction, in an attempt to simulate the compounding of elastomeric adhesives. Some of the described compositions can exhibit multiphase morphology, having discrete styrene-rich domains surrounded by butadiene rich phase, both of these phases being embedded in a “honeycomb” carboxyl-rich phase. The compositions were characterized by dynamic mechanical spectroscopy and by electron transmission microscopy, as well as by molecular weight distribution and glass transition temperature range data. Examples of adhesive applications are also given.     

The influence of the polymerization on properties of an ethylacrylate/2-ethyl hexylacrylate pressure-sensitive adhesive suspension

In this paper, the batch suspension copolymerization process for production of microsphere acrylic pressure-sensitive adhesives (PSA) is presented. The effects of different process and chemical parameters on adhesion properties are discussed. The reaction was monitored in-line by using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Properties of the adhesive suspension (particle size), adhesive (gel phase, molecular weight, glass transition temperature (T_g)) and adhesion properties (tack, peel strength and shear) were determined. The results have shown that reaction kinetics strongly depends on polymerization temperature and initiator concentration. On the other hand, adhesion properties depend mainly on the T_g of the polymer and on the amount of insoluble gel fraction in the adhesive.     

Processing study of a high temperature adhesive

An adhesive-bonding process cycle study was performed for a polyimidesulphone. The high molecular weight, linear aromatic system possesses properties which make it attractive as a processable, low-cost material for elevated temperature applications. The results of a study to better understand the parameters that affect the adhesive properties of the polymer for titanium alloy adherends are presented. These include the tape preparation, the use of a primer and press and simulated autoclave processing conditions. The polymer was characterized using Fourier transform infrared spectroscopy, glass transition temperature determination, flow measurements, and weight loss measurements. The lap shear strength of the adhesive was used to evaluate the effects of the bonding process variations.     

Adhesive properties of ABA poly(styrene-b-isoprene) block copolymers

ABA poly(styrene-b-isoprene) block copolymers with various molecular weight and elastomeric content were used as heat activated adhesives. The shear strength of glass to glass joints was tested. The influence of activation temperature and ageing on shear strength was also examined. Good adhesive and cohesive behaviour was found for copolymers with low total molecular weight and identical block lengths. These results were explained by the fact that phase separation does not easily occur in such copolymers.     

航空航天用环氧耐高温胶粘剂研究

通过使用聚合诱导相分离技术,研制成功以少量的热塑性塑料为连续相的耐高温高强度环氧树脂复合胶粘剂,分别在聚醚酰亚胺改性环氧树脂的体系中得到了分散相、双连续相以及反转相结构,使得环氧树脂胶粘剂的耐热性能得到大幅度的提高.为了精确控制改性体系的相形态,对聚醚酰亚胺的用量、分子质量等对相形态的影响进行了深入研究,得到了控制相形态的关键因素.     

Dynamic mechanical properties of polystyrene‐block‐poly[ethylene‐co‐(ethylene‐propylene)]‐block‐polystyrene triblock copolymer/hydrocarbon oil blends

Blend systems of polystyrene‐block‐poly(ethylene‐co‐(ethylene‐propylene))‐block‐polystyrene (SEEPS) triblock copolymer with three types of hydrocarbon oil of different molecular weight were prepared. The E″ curves as a function of temperature exhibited two peaks; one peak at low temperature (? ?50°C), arising from the glass transition of the poly[ethylene‐co‐(ethylene‐propylene)] (PEEP) phase and a high temperature peak (? 100°C), arising from the glass transition of the polystyrene (PS) phase. The glass transition temperature (T_g) of the PEEP phase shifted to lower temperature with increasing oil content. The shifted T_g depended on the types of oil and was lower for the low molecular weight oil. The T_g of PS phase of the present blend system, were found to be constant and independent of the oil content, when molecular weight of the oil is high. However, for the lower molecular weight oil, the T_g of the PS phase also shifted to lower temperatures. This fact indicates that the oil of high molecular weight is merely dissolved in the PS phase. The E′ at (75°C, at which temperature both of PEEP and PS phases are in glassy state, was found to be independent of oil content. In contrast, at 25°C, at which temperature the PEEP phase is in rubbery state, the E′ decreased sharply with increasing oil content. This result indicates that the hydrocarbon oil was a selective solvent in the PEEP phase. It mainly dissolved in the PEEP phase, although slightly dissolved into the PS phase as well, when molecular weight of oil is low. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Multiblock copolymers consisting of polyester and polyaliphatic blocks

Multiblock-(AB)_n-copolymers, consisting of hard segments of poly(butylene terephthalate) (PBT) and soft segments of dimerized fatty acid were synthesized and analysed with DSC and DMTA. The polymers were characterized by their limiting viscosity number and melt flow index. The glass transition temperature (T_g) and melting temperature (T_m) increase with decreasing weight fraction of the dimerized fatty acid and with the increase of the crystalline phase content. It was found that the elasticity (?) depends on the content of dimerized fatty acid in the amorphous phase. Tensile properties were described as a function of the degree of polycondensation P_k (molecular weight).     

Blends of polycarbonate and poly(hexamethylene sebacate): II. Effect of molecular weight on compatibility

Blends of polycarbonate (PC) and poly(hexamethylene sebacate) (HMS) with two different molecular weights were prepared and their thermal properties were studied via differential scanning calorimetry. It was found that the high molecular weight PC (HPC) and high molecular weight HMS (HHMS) were partially miscible as evidenced by the decrease in glass transition temperature of HPC in the blends. This partial miscibility is attributed to the interaction of the carbonyl dipole of the ester group and the highly polarizable aromatic carbonate structure. When the low molecular weight PC or HMS was used, the compatibility was enhanced because of the increased entropic contribution to the Gibbs free energy of mixing. In all the blends prepared, the PC crystallized as a result of the plasticizing effect of HMS. Bisphenol-A diphenyl carbonate (dimer) was synthesized and used as the dimeric model of PC. This material was found to be an excellent diluent for HPC. A single glass transition was found in the HPC/dimer system and the temperature was dependent on the composition. The Couchman's equation was found to fit very well the glass transition temperature versus composition relationship for this system. A single glass transition was also found in the HHMS/dimer system. The melting point depression analysis was performed and resulted in a very low heat of fusion for the 100% crystalline HHMS. It may suggest that the dimer and HHMS are not completely miscible in the amorphous region.     

Control of structure and mechanical properties for binary blends of poly(3‐hydroxybutyrate) and cellulose derivative

Structure and mechanical properties for binary blends composed of a poly(3‐hydroxybutyrate) (PHB) and a cellulose derivative, such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), have been studied by means of dynamic mechanical analysis, isothermal crystallization measurements, and tensile testing. It is found that β relaxation temperature due to glass transition of PHB or PHB‐rich phase in the blends, in which the cellulose derivative has lower molecular weight, is almost the same as that of the pure PHB. On the other hand, the peak location is shifted to even lower temperature than that of the pure PHB by blending the cellulose derivative with higher molecular weight, although the cellulose derivative is a glassy polymer with high glass transition temperature. Further, the blend with lower β relaxation temperature exhibits ductile behavior with low modulus in uniaxial deformation. The difference in the structure and mechanical properties for the blends are found to be determined by the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3447–3452, 2007     

Thermophysical and thermomechanical properties of Norland Optical Adhesives and liquid crystal composites

Thermophysical and thermomechanical properties of UV-cured Norland Optical Adhesives (NOA65) and low molecular weight Liquid Crystal E7 systems were investigated. Thin films of Polymer Dispersed Liquid Crystal were prepared by Polymerization Induced Phase Separation and UV-curing. Phase diagrams were established using Polarized Optical Microscopy and DSC to determine the lines of nematic to isotropic phase transition as well as the glass transition temperature changes with the system composition. Mechanical measurements were performed in the static and dynamic modes to determine the moduli in terms of the curing time, the temperature and the amount of low molecular weight liquid crystal molecules. Thermomechanical measurements were found to overestimate the glass transition temperature as compared to calorimetric data. Variations of the Young's modulus and the molecular weight defining the mesh size of the network were analyzed in terms of the curing time and liquid crystal concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚碳酸酯二醇型水性聚氨酯胶粘剂的研究

采用预聚体分散法制备了一系列聚碳酸酯二醇(PCDL)型水性聚氨酯(WPU)胶粘剂,并借助傅里叶变换红外光谱(FT-IR)法来跟踪预聚体的合成过程,同时还考察了该WPU胶粘剂的粘度、热稳定性和初粘强度等性能。实验结果表明,PCDL的结构和相对分子质量对该WPU胶粘剂的性能影响很大;以PCDLT-6002为原料制备的WPU胶粘剂,其粘度最低(175 mPa.s)、热稳定性最好、软链段玻璃化转变温度(Tg)最低(-33.97℃)、有软段结晶熔融峰且初粘强度最高(81N/25 mm,此时活化温度为70℃)。     

Effect of Molecular Weight on Processing and Adhesive Properties of the Phenylethynyl-Terminated Polyimide LARC™-PETI-5

Three different molecular weight versions of the phenylethynyl-terminated polyimide LARC™-PETI-5 were synthesized. The materials synthesized had theoretical number average molecular weights of 2500, 5000, and 10000 g mol. Differential Scanning Calorimetry (DSC) was performed on the dry powder form of these materials to establish cure conditions which result in high glass transition temperatures. Lap shear specimens were prepared from adhesive tape made from each material and with the thermal cure conditions determined from the DSC data. The tensile shear data established which processing conditions provided the best adhesive strengths. Titanium tensile shear strengths as high as 52.6 MPa (7630 psi) at RT and 35.2 MPa (5100 psi) at 177°C were determined. Processing temperatures as low as 316°C and pressures as low as 0.17 MPa (25 psi) resulted in good adhesive properties. The tensile shear properties of these materials were unaffected by hydraulic fluid. The molecular weight of LARC™-PETI-5 has an important effect on the bonding pressures required to obtain good tensile shear strengths. The effect of molecular weight on the utility of PETI-5 to be used as a primer to maintain surface quality for bonding was also investigated.     

Effects of the compatibility of a polyacrylic block copolymer/tackifier blend on the phase structure and tack of a pressure‐sensitive adhesive

Adhesion and viscoelastic properties and morphology of a polyacrylic block copolymer/tackifier blend were investigated. Special rosin ester resins with different weight average molecular weights of 650, 710, 890, and 2160 were used as the tackifier and blended with a polyacrylic block copolymer consisting of poly(methyl methacrylate) and poly(n‐butyl acrylate) blocks at tackifier content levels of 10, 30, and 50 wt %. The compatibility decreased with an increase in molecular weight. From TEM observation, the number of formed agglomerates of the tackifier with sizes on the order of several tens of nanometers increased with increasing tackifier content and molecular weight of the tackifier in the range from 650 to 890. For the tackifier with a molecular weight of 2160, micrometer‐sized agglomerates were observed. The storage modulus at low temperature and the glass transition temperature of adhesive measured by a dynamic mechanical analysis increased dependent on the number of formed nanometer sized agglomerates. Tack was measured using a rolling cylinder tack tester over wide temperature and rolling rate ranges, and master curves were prepared in accordance with the time‐temperature superposition law. Tack and peel strength were optimum at a blend combination of intermediate compatibility, i.e., the molecular weight of 890. These optimum properties were correlated to maximal values of the storage modulus at room temperature and the glass transition temperature. Therefore, it was found that these features of blend properties are strongly affected by the nanometer sized agglomerates of tackifier. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dielectric investigation of molecular dynamics of blends: III. Effect of molecular weight in TMPC/PS blends

Dielectric and calorimetric measurements have been carried out for tetramethyl polycarbonate/polystyrene (TMPC/PS) blends with different compositions. The effect of varying the molecular weight of the weakly polar component (PS) on the molecular dynamics of the polar segments of TMPC has been thoroughly studied over wide ranges of frequency (10⁻²−10⁵ Hz), temperature (50–220°C) and number average molecular weight, M̄_n, (6500–560 000 g mol⁻¹). All blends were found to be compatible regardless of the composition ratio and the molecular weight of PS. Some new and interesting experimental findings have been observed concerning the effect of molecular weight on the glass temperature and on the broadness of the glass transition and relaxation. Neither the kinetics nor the distribution of relaxation times of the local process observed in pure TMPC was affected by blending with PS, regardless of the composition ratio or the molecular weight of PS. It has been concluded that the mixing of the polymeric components to form a homogeneous single phase (compatible blend) does not take place on a segmental level but on a structural one. The size of this structural level has been suggested to have the same volume as the cooperative dipoles, which is assumed to be the minimum volume responsible for a uniform glass transition (10–15 nm). The molecular weight dependence of the relaxation characteristics of the glass process and temperature could be attributed to the variation in the size and packing of the structural units.     

Einfluß der struktur auf einige eigenschaften von polyurethan- und polyestermelamin-lacken

A method for calculating the crosslink density of systems originating from low molecular weight compounds is described. It is possible to determine quantitatively the influence of the crosslink density and the chemical composition on the glass transition temperature of network structures. This will be illustrated by crosslinked polyurethanes. On polyester melamine resins it will be shown that both the molecular weight of the polyester and the crosslink density of the network play an important role in the development of high solids coating systems as far as the solids content and the sagging are concerned.     

Behaviour of environmentally degraded epoxy adhesives as a function of temperature

ABSTRACT

Structural adhesives are increasingly being used in the aerospace and automotive industries. They allow for light weight vehicles, fuel savings, and reduced emissions. However, the environmental degradation of adhesive joints is a major setback in its wide implementation. Moisture degradation of adhesive joints includes plasticization, attacking of the interface, swelling of the adhesive and consequent creation of residual stresses. This may lead to reversible and irreversible damage. The main factors affecting the strength of adhesive joints under high and low temperatures are the degradation of the adhesive mechanical properties and the creation of residual stresses induced by different coefficients of thermal expansion (between the adhesive and the adherends). The effect of the combined effect of moisture and temperature is not yet fully understood. The aim of this study is to shed light on this subject.

In this work bulk water absorption tests were conducted at different moisture conditions in order to assess the diffusion coefficient, maximum water uptake, and glass transition temperature. Aged and unaged small dogbone tensile specimens were tested under different temperature conditions. The glass transition temperature of the adhesives as a function of the water uptake was assessed. The aim is to determine the evolution of the properties of two epoxy adhesives as a function of two variables (environmental temperature and moisture).     

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     

Morphology and Viscoelastic Behavior of Styrene-Diene Block Copolymers in Pressure Sensitive Adhesives

Linear (SDS) and radial (SD)_x block copolymers of styrene (S) and dienes (D=butadiene or isoprene), varying in composition and molecular weight, were formulated as pressure sensitive adhesives. The morphology of these compositions was determined by electron microscopy of ultra-thin sections and dynamic viscoelastic measurements were made at 35 Hz between -90° and + 140°C or higher. Pressure sensitive tack and holding power were determined and interpreted in terms of morphological and rheological properties.

A high degree of tack resulted only when the tackifying resin was compatible with the polydiene segments of the block polymer and incompatible with the polystyrene segments, provided also that the polydiene-tackifier phase was the continuum with the polystyrene phase forming spherical domains. All effective tackifying resins raised the glass transition temperature (T_g) of the rubbery phase, but plasticized the polymer at temperatures well above T_g Polystyrene domain connectivity was found to lead to diminished tack in block polymers containing more than 30% styrene, a result of decreased creep compliance on the time scale of the bonding process and failure to achieve full contact with the substrate. For adhesives not limited by contact, tack increased with the loss modulus of the adhesive on the time scale of the debonding process. Holding power (shear resistance) increased with polymer styrene content and molecular weight, the polystyrene domain structure effectively inhibiting viscous flow at temperatures sufficiently below T_g of the styrene blocks.     

Compatibility studies of polystyrene–polybutadiene blends by thermal analysis

In order to examine the behavior of incompatible blends of polystyrene and polybutadiene, the glass transition temperature, the melting point, and the specific heat increment at the glass transition temperature for atactic polystyrene (a-PS), isotactic polystyrene (i-PS), polybutadiene (PBD), and blends of a-PS/PBD and i-PS/PBD were determined by use of a differential scanning calorimeter. Blends were prepared by solution casting, freeze-drying, and milling. Weight fractions of polystyrene in the blends ranged from 0.95 to 0.05. The glass transition temperature of polystyrene changed with weight fraction in the blends, and with blending preparation methods; the glass transition temperature of polybutadiene remained essentially unchanged. The specific heat increment at the glass transition temperature of PBD decreases linearly with increasing proportions of PS in the PS/PBD blend for the broad and narrow molecular weight distribution polybutadience polymers, whereas the specific heat increment for PS did not decrease with increasing proportions of PBD in the PS/PBD blend. These results suggest that the polybutadiene dissolves more in the polystyrene phase than does the polystyrene in the polybutadiene phase.     

Thermal and dynamic mechanical properties of polyurethaneureas

Measurements were made of the thermal and dynamic mechanical properties of 22 polyurethaneureas of varying diol molecular weight, type of aromatic chain extender, diol molecular weight distribution, and chain extender stoichiometry. The dynamic mechanical data, obtained as a function of temperature and frequency (in the kHz region), were used to construct master curves of shear modulus and loss factor over a wide range of reduced frequencies. Based on these master curves, interpreted in conjunction with the thermal analysis results, it was found that: Soft segment crystallization occurs at the higher diol molecular weights, dynamic mechanical properties are well correlated with the soft segment glass transition, diol molecular weight influences dynamic mechanical properties by affecting the degree of phase separation and hence glass transition temperature, and neither diol molecular weight distribution nor chain extender stoichiometry have a significant effect, in the ranges studied, on transition temperatures or dynamic mechanical properties.