Photocrosslinking of an ethylene–propylene–diene terpolymer and the characterization of its structure and mechanical properties

An ethylene–propylene–diene terpolymer (EPDM) was photocrosslinked under UV irradiation with benzil dimethyl ketal (BDK) as a photoinitiator and trimethylolpropane triacrylate (TMPTA) as a crosslinker. The efficiency of the photoinitiated crosslinking system EPDM–BDK–TMPTA, various factors affecting the crosslinking process (the photoinitiator and crosslinker and their concentrations, the irradiation time, the temperature, the atmosphere and UV‐light intensity, and the depth of the UV‐light penetration), and the mechanical properties of photocrosslinked EPDM were examined extensively through the determination of the gel contents, infrared spectra, and mechanical measurements. EPDM samples 3 mm thick were easily crosslinked with a gel content of about 90% after 30 s of UV irradiation under optimum conditions. The photoinitiating system of a suitable initiator combined with a multifunctional crosslinker such as BDK–TMPTA enhanced the efficiency of the photocrosslinking reaction, especially by increasing the initial rate of crosslinking. The gel content of photocrosslinked EPDM, which was determined by the content of diene in EPDM, the depth of the UV‐light penetration, and the light intensity, played a key role in increasing the mechanical properties of the photocrosslinked samples in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1837–1845, 2004     

Irradiation effects on the relaxation behaviour of EPDM elastomers

γ‐irradiation of ethylene–propylene diene monomer (EPDM) elastomers under oxidant atmosphere was carried out in order to change their mechanical and dielectric behaviour. Three different formulations of EPDM (70 wt% ethylene, 28 wt% propylene; diene monomer: 2 wt% norbornene) were studied: a non‐crosslinked EPDM terpolymer, a crosslinked EPDM and a crosslinked EPDM stabilized with an antioxidant. Dielectric and mechanical relaxation show a β‐sub‐glass relaxation at about ?120 °C (1 Hz) and an α‐relaxation at ?15 °C (1 Hz) associated with the glass transition but influenced by the effects of irradiation. The local mobility associated with the β‐relaxation is only weakly influenced by γ‐irradiation up to 450 kGy. The α‐process is shifted to higher temperatures as a result of crosslinking and changes in the semicrystalline structure. The amplitude of the dielectric α‐process increases as a result of the formation of oxidized species during irradiation under oxygen. In contrast, the mechanical α‐relaxation amplitude decreases as a result of physical and chemical cross‐linking. It was shown that the main factors that determine the crosslinking/chain scission balance are (1) the presence of oxygen together with the irradiation dose, (2) the dose rate and (3) the initial crosslink density of the EPDM material. As a result, the individual contribution of crosslinking and crystallization, and therefore the understanding and prediction of the properties after γ‐irradiation can only be deduced after comparison of the polymer behaviour below and above its melting temperature. Copyright © 2004 Society of Chemical Industry     

The study of polymers by high-temperature ATR spectroscopy

A new high-temperature attenuated total reflectance apparatus (HATR) was constructed and used at different temperatures for making infrared measurements on the same liquid or solid sample. It was found that this method was applicable to the continuous quantitative analysis of changes occurring during chemical reactions such as polymerization, isomerization, and crosslinking. In the bulk polymerization of styrene, the process of monomer consumption could be followed progressively. In the crosslinking reaction of high cis-polybutadiene by sulfur-accelerator or peroxide crosslinking systems, the decrease of cis content and its partial isomerization to trans structure was measured. Furthermore, in the crosslinking reaction of ethylene–propylene terpolymers (EPDM), the consumption of double bonds was observed over the course of the reaction with both sulfur-accelerator and peroxide crosslinking systems. The effect was greatest in the case of methylenenorbornene-type EPDM.     

Protection effects of condensed bromoacenaphthylene on radiation deterioration of ethylene–propylene–diene rubber

As a continuation of a series of the studies on the flame and γ-radiation resistant modification of ethylene–propylene–diene rubber (EPDM), condensed bromoacenaphthylene (con-BACN) as a newly developed flame retardant was synthesized and its effects on the radiation resistance of EPDM were investigated. The radiation resistance evaluated by measuring tensile properties of irradiated sheets of 2 mm thck was found improved greatly by adding con-BACN together with ordinary rubber ingredients but decreased by decabromodiphenylether (DBDPE) that has bromins in aromatic rings as con-BACN. When EPDM sheets of 1 mm thick were irradiated in oxygen at a dose rate of 1 × 10⁵ rad/h, the weight swelling ratio increased with increasing dose, indicating that oxidative main chain scission is predominant under the irradiation conditions. On the other hand, crosslinking was shown to be predominant in nitrogen. From the results of the swelling experiments with different additives, it was concluded that DBDPE accelerates both the main chain scission in oxygen and the crosslinking in nitrogen. In contrast to this, con-BACN reduced the chain scission in oxygen. This observation was accounted by the assumption that the influence of the oxidative chain scission is partly compensated by the concurrent crosslinking which takes place through additions of con-BACN to substrate polymers even in the presence of oxygen.     

光固化涂料的应用和市场前景

光固化涂料主要由低聚物、单体、光引发剂及助剂组成。UV固化的主要反应历程是由辐射引起光引发剂分解,生成活性自由基引发单体以氐聚物聚合交联。针对光固化涂料的性能特点和光固原理,介绍了光固化涂料的应用领域,阐述了光固化涂料适合多种基材的涂装,研究了光固化涂料在汽车装饰上的应用,指出了光固化涂料的发展前景与潜力。     

Thioxanthone-containing renewable vegetable oil as photoinitiators

Soybean oil containing thioxanthone (TX) moieties and/or coinitiator DBA (ESO-ATX-DBA, ESO-ATX/ESO-DBA) were synthesized by grafting 2-acitic thioxanthone (ATX) and 4-(dimetheylamino) benzoic acid (DBA) to the backbone of epoxidized soybean oil (ESO). The obtained ESO-ATX-DBA, ESO-ATX and ESO-DBA were characterized by FT–IR, ¹H NMR and UV–vis spectra, and investigated as photoinitiators by photo-DSC. Photoinitiator systems ESO-ATX-DBA and ESO-ATX/ESO-DBA were more efficient than their low-molecular weight analogues (chemical mixture of ETX-DBA and physical mixture of ETX/EDB) especially in the photopolymeriztion of acrylate monomers containing pigment. Moreover, ESO-ATX-DBA exhibited much lower migration in comparison with their low-molecular weight analogues. These characteristics gave the obtained TX containing soybean oil potential in the application of ink, and these studies also provide alternative approach to prepare polymeric photoinitiators from the renewable source.     

Thermal and physicomechanical properties of gamma‐irradiated EPDM/waste newsprint microfibers composites treated using acrylic styrene emulsion as a coupling agent

This investigation deals mainly with thermal stability and crosslinking density of EPDM/newsprint microfibers composites. The recycled newsprint microfibers were treated using a different ratio of acrylic styrene emulsion (5, 10, and 15 wt% fiber) as a bonding agent to reinforce EPDM rubber matrix. The effect of microfibers content, namely, 5 up to 50 phr (part per hundred part of rubber) and the effect of ionizing radiation on EPDM/newsprint microfibers composites properties were investigated. The microfibers structure and EPDM/microfibers composite were investigated using X‐ray diffraction and FTIR analysis; the results indicate that bonding has occurred between the treated newsprint microfibers and EPDM polymer matrix. EPDM/untreated newsprint microfibers composites have achieved higher crosslinking density than EPDM matrix up to 50 phr microfibers content and up to 100 kGy then decreased with increasing gamma irradiation dose. Meanwhile treatment of the microfibers using 10 wt% acrylic styrene leads to improve crosslinking density at any microfibers content. Thermogravimetric analysis (TGA) was carried out for the microfibers and their composites. TGA indicated that the thermal stability of microfiber was enhanced using acrylic styrene. Whereas there is a slight improvement in thermal stability and activation energy of the composites due to adding treated microfibers using 10 phr microfiber content treated using10 wt% acrylic styrene emulsion and irradiated with 60 kGy gamma radiation dose. J. VINYL ADDIT. TECHNOL., 25:E91–E106, 2019. © 2018 Society of Plastics Engineers     

Superabsorbent resin of acrylic acid/ammonium acrylate copolymers synthesized by ultraviolet photopolymerization

A new method of synthesizing a superabsorbent resin (SAR) from an acrylic acid/ammonium acrylate copolymer by direct UV photopolymerization was studied. The effects of the degree of neutralization of acrylic acid, the photoinitiators, the crosslinking agents, and the UV‐light exposure time on the water absorbency (Q) were investigated. The results showed that Q of an SAR based on Irgacure 1700 or Irgacure 1800 and Irgacure 651 was high, reaching about 1200 mL/g, but under the same conditions, Q was low for an SAR based on other photoinitiators. The UV absorption spectrum proved that the photoinitiators matched the UV light source. Among the crosslinking agents, N,N′‐methylene bisacrylamide was more efficient than the others at a small concentration and a high value of Q. ¹³C‐NMR spectrometry was used to identify the mechanism of the crosslinking reaction through the esterification of hydroxyethyl acrylate (HEA) and 2‐hydroxypropyl acrylate with carboxylic acid group in acrylic acid/ammonium acrylate copolymerization, but the efficiency of the crosslinking reaction by esterification was lower than that of the copolymerization of vinyl groups in the crosslinking agent. Q of the acrylic acid/ammonium acrylate copolymer for the SAR reached 1255 mL/g under certain conditions (degree of neutralization of acrylic acid = 75%, Irgacure 651 concentration = 0.2 wt %, [HEA] = 0.2 wt %, exposure time = 10 min). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 546–555, 2005     

高低温循环作用下三元乙丙橡胶胶料的压缩永久变形及回弹值研究

研究高低温循环作用下三元乙丙橡胶(EPDM)胶料的压缩永久变形及回弹值,考察了EPDM乙烯含量、胶料含胶率和交联程度的影响,并与常温、高温和低温条件下结果进行对比。结果表明:高低温循环作用对EPDM胶料压缩永久变形及回弹值的影响比单纯高温老化的影响大;EPDM乙烯含量、胶料含胶率及交联程度对EPDM胶料在高低温循环作用下压缩永久变形及回弹值的影响很大,其中胶料含胶率的影响最大,其次是EPDM乙烯含量,最后是胶料交联程度。     

Surface protection of poly(vinyl chloride) by photografting of epoxy–acrylate coatings

UV-curable epoxy–acrylate coatings were used to protect poly(vinyl chloride) against superficial degradation. With α-hydroxy–acetophenone photoinitiators, the crosslinking polymerization develops in the ms time scale; 50% degree conversion is reached after irradiation times of 2.5 ms in a nitrogen atmosphere and 17 ms in air. The adhesion of the coating on to the PVC substrate can be greatly improved by inducing a photochemical grafting process. The best results are obtained by incorporating the photoinitiator into the top layer of the PVC sheet. Highly crosslinked epoxy–acrylate coatings are very stable toward UV radiations and chemical agents like organic solvents and strong acids. By their light-screening effect they provide an excellent protection against photodegradation for light-sensitive polymeric materials.     

A Novel Approach to Investigating Effect of Sulfur as a Coagent on the Quasi-Static and Cyclic–Dynamic Fatigue Properties of Peroxide Cured EPDM

The effect of sulfur on the quasi-static and cyclic–dynamic fatigue properties of ethylene propylene diene monomer (EPDM) after three fatigue cycles were investigated under two specially designed test programs. The results turned out that sulfur as a coagent slowed down the vulcanization rate of EPDM compounds and reduced the chemical crosslinks. Further study on the effect of sulfur on the crosslinking behavior showed that this effect could be quantitatively described in linearity and became more distinct at higher crosslinking density. The addition of sulfur as a coagent improved the tearing performance of EPDM as a result of newly generated polysulfur bonds ( S_x ). The strain and frequency sweep procedures were designed to study the dynamic rheological behavior and we obtained that the storage modulus of EPDM depended less on the addition of sulfur as well as sweeping temperature in sulfur-assisted curing system. The changes of loss factors obtained from the two sweep procedures were employed to survey the dynamic fatigue properties of EPDM, indicating that the fatigue behavior depended more on peroxide dosage than sulfur content, which might be due to the smaller proportion of polysulfur bridges in the final crosslinking structures of EPDM. POLYM. ENG. SCI., 60:455–463, 2020. © 2019 Society of Plastics Engineers     

Mechanism of degradation and crosslinking of polyurethane when irradiated by gamma-rays

We conducted a study to clarify the mechanism of crosslinking and degradation of thermoplastic polyurethane (PU) when irradiated with gamma-rays. Changes in molecular weights as a result of gamma-ray irradiation, the UV absorption, the amount of PUs with amino groups, and the elution of oligomers to an organic solvent were determined to estimate characteristic changes in PU caused by irradiation. The amount of PUs with primary amino groups as a degradated PU products at p,p′-methylenediphenyl diisocyanate–1,4-butanediol (MDI–BU) hard segments increased linearly with increasing irradiation level. The amount of this products by gamma-ray irradiation was approximately 10–20% of the calculated amount, indicating that predominant degradation occurred at polytetramethyleneglycol (PTMG) soft segments (about 80–90% of the degradation). Characteristic differences were seen in crosslinking between non-chain-extended thermoplastic PUs based on the molecular weights of PTMG, (M_w of PTMG = 640–2800). The crosslinking ratio is linearly proportional to the molecular weights of PTMG, indicating that crosslinking at PTMG soft segments was major (the ratio of crosslinking at PTMG was more than 90%). Methanol extract of PU indicated elution of PU oligomers ranging from 13 to 1 as a polymerization degree.     

Selective crosslinking reaction in polymer blends. III. The effects of the crosslinking of dispersed EPDM particles on the impact behavior of PP/EPDM blends

The selective dynamic crosslinking reaction by means of the N,N'-m-phenylene–bismaleimide/poly-(2,2,4-trimethyl-1,2-dihydroquinoline) system was carried out on PP/EPDM blends and its effect on the Izod impact strength (IIS) was investigated. Three series of PP/EPDM combinations were adopted to establish different morphologies. In each series, the EPDM wt % varied from 5 to 30 at 5 wt % intervals. The system crosslinked the EPDM particles selectively without PP degradation and change of morphology. Following the crosslinking, the IIS at 23, ?10, and ?30°C increased in all blends, and the critical EPDM wt % at 23°C necessary to cause the dramatic IIS increase was lowered. The increase in interfacial adhesion is considered to be the most important factor necessary for the improvement. The nucleation effect of the crosslinked particles and the decrease of crystallinity of the EPDM were also considered to contribute to the improvement in the IIS. Impact fracture energy absorption can thus be changed by adjusting the magnitude of the interfacial adhesion by the dynamic crosslinking even at essentially the same morphology. © 1995 John Wiley & Sons, Inc.     

The gamma-ray-induced crosslinking of polyacrylamide

The gamma-ray-induced crosslinking of polyacrylamide was carried out under various conditions. The molecular weight of the polymer before inrradiation was found to be the most important factor for crosslinking. When polymers have low molecular weights such as 80,000, the intensity of radiation, the external pressure applied, and the water content of the polymer powder became important for crosslinking. Although the polycrylamide hydrogel can be obtained directly by irradiating the monomer, it was obtained more conveniently by the irradiation of monomer—polymer mixtures. The hydrogels obtained by the radiation with a dose of over 50 kgray, absorb water by 1000–1500 wt %.     

Synthesis and properties of high oil‐absorbent 4‐tert‐butylstyrene‐EPDM‐divinylbenzene graft terpolymer

The graft crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto ethylene–propylene–diene (EPDM) was carried out in toluene by using benzoyl peroxide (BPO) as an initiator. The synthesized graft terpolymer, tBS‐EPDM‐DVB (PBED), was extracted with tetrahydrofuran (THF) into gel (called as PBED I) and sol, and then they were identified by infrared (IR) spectroscopy. The effects of solvent amount, molar ratio of DVB to tBS, EPDM content, initiator concentration, reaction temperature, and reaction time on the graft crosslinking polymerization were examined. Among them, solvent amount and molar ratio of DVB to tBS were the important factors for this reaction system. Maximum oil absorbency of PBED I was 84.0 g/g but its oil‐absorption kinetic rate was very low. Sol PBED can be reused as oil absorbent (named as PBED II) through photocrosslinking by ultraviolet light irradiation. Although the oil absorbencies of PBED II were lower than those of PBED I in most cases, their oil absorption kinetic rates were higher than oil absorbencies of PBED I. The highest value of oil absorbency of PBED II was 56.0 g/g. The thermal stability of PBED I was studied by TGA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2119–2129, 2002     

pH‐response superabsorbant hydrogel synthesized by ultraviolet photopolymerization

A new synthesis method of pH‐response superabsorbent hydrogels (SHG) was achieved by direct ultraviolet (UV) photopolymerization, and in particular, the synthesis of SHGs of acrylic acid (AA), sodium acrylate (AANa), and methacrylcholine chloride (MACC) tricomponent copolymer by UV photopolymerization were investigated. The pH value responsive behavior of SHG with different monomer ratios of MACC and AA was researched, and SHG showed large swelling properties at pH value approximately 7. Influences of monomer ratio (mol) of AANa to AA, photoinitiators, crosslinking agents, and exposure time of UV light on the water absorbent properties were studied. The results showed that the water absorbent capacity of SHG based on photoinitiators: Esacure KTO46 or Irgacure 651 can reach comparatively high, N,N′‐Methylene bisacrylamide and diethylene glycol diacrylate (DEGDA) were high efficient crosslinking agents for its crosslinking the molecular chains through attending the copolymerization with monomers. When the exposure time was 10 min, the distilled water absorbency of SHG was 1503 mL/g under the condition: content of MACC, 14.3 wt %; monomer ratio (mol) of AANa to AA: 5.67; content of DEGDA and Irgacure 651, 0.0025 and 0.25 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1847–1852, 2007     

Influence of selected photoinitiators on important properties of photoreactive acrylic pressure‐sensitive adhesives

Photoreactive solvent‐borne pressure‐sensitive adhesives are not commercially available in the market. The reason for it is that the UV‐initiated crosslinking has sense only in the case of solvent‐free self‐adhesive systems. Investigations conducted in Institute of Chemical Organic Technology have shown that the photoreactive solvent‐borne acrylic PSA are conventional crosslinked solvent‐borne acrylic PSA used as crosslinking agents typical metal chelates as titanium acetylacetonate (TiACA), aluminum acetylacetonate (AlACA) or thermal reactive crosslinker melamine‐formaldehyde resin Cymel 303 clear considered. The main purpose of the investigation was to study the influence of diverse photoinitiators on main properties, such as shrinkage, tack, peel adhesion, and shear strength of solvent‐based acrylic pressure‐sensitive adhesives. The interesting alternative to conventional photoinitiators is unsaturated photoinitiators described in this article. Following unsaturated photoinitiators were used: 4‐acryloyloxy benzophenone, 4‐acryloyloxyethoxy benzophenone, and 4‐acryloyloxybutoxy benzophenone. The influence of the crosslinking agents or crosslinking methods was determined in relation to the reaction time and to the concentration versus adhesion properties. The increase of photoinitiator concentration causes in the decrease of the shrinkage. Increasing the UV dose during the crosslinking of acrylic PSA film leads clearly to better shrinkage resistance. The best results of the lowest shrinkage value of 0.35% were given by using 4‐acryloyloxy benzophenone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electron beam irradiation of ethylene‐propylene terpolymer: Evaluation of trimethylol propane trimethacrylate as a crosslink promoter

The effect of electron beam irradiation on ethylene‐propylene terpolymer (EPDM) was investigated. A 50‐part oil‐extended EPDM with high termonomer (ENB) content (iodine number of base polymer) 19, was selected for this study. An increase in irradiation dose from 0 to 200 kGy resulted in increased crosslinking, measured by an increase in gel contents and better swelling resistance. The effect of the multifunctional monomer trimethylol propane trimethacrylate (TMPTMA) as a crosslink promoter was studied using IR spectroscopy. The IR studies revealed enhanced peak absorbances at 1725, 1257, and 1023 cm^?1 as a result of the increased concentration of C = O and C‐O‐C groups and reduced absorbance at 1630 cm^?1 due decreased concentration of C = C groups with TMPTMA level in the irradiated samples. The presence of TMPTMA increased the level of crosslinking at a given irradiation dose, which was manifested by improvement in tensile properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 968–975, 2005     

Synthesis of superabsorbent resin by ultraviolet photopolymerization

Synthesis of superabsorbent resin (SAR) was achieved by a new method, that of direct UV photopolymerization, and in particular the synthesis of a SAR of acrylic acid–potassium acrylate copolymer by UV photopolymerization was investigated. Influences of ratio (mol) of acrylate monomer to acrylic acid monomer, photoinitiators, crosslinking agents, and exposure time of UV light on the water‐absorbent properties were investigated. The results showed that the water absorbency (Q) of SAR based on Irgacure 1700 or Irgacure 1800 was 545–530 mL/g, but under the same conditions Q was 450 mL/g for the SAR based on Irgacure 651. N,N′‐Methylene bisacrylamide, hydroethyl acrylate, and glycerol were used as crosslinking agents, of which N,N′‐methylene bisacrylamide was the most effective. It crosslinked the molecular chains through attending the copolymerization with acrylic acid (AA) and potassium acrylate. When the exposure time was 5 min, the value of Q was 1368 mL/g (the content of N,N′‐methylene bisacrylamide was 100 ppm). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1618–1624, 2004     

Cross‐linking and grafting with PS of EPDM in the presence of Lewis acids

With Lewis Acids as catalysts in melt system, the influence of kinds of Lewis Acids, dosages of catalysts on the behaviors of crosslinking and grafting of ethylene–propylene–diene rubber (EPDM) were investigated. The Lewis Acids, such as anhydrous AlCl₃, FeCl₃, SnCl₄, could initiate the crosslinking of EPDM and the grafting between EPDM and polystyrene (PS). The carbon–carbon double bonds existing on EPDM chain were favorable to the formation of the initial carbocation in the presence of Lewis Acids. The carbocation initiated carbonium ion polymerization between the unsaturated bonds, or substituted for a proton from the phenyl in the presence of PS forming EPDM‐g‐PS copolymer. Anhydrous aluminum chloride was found to be an efficient catalyst and its initiating temperatures for crosslinking or grafting were about 110°C. The amounts of gel and the data of torques showed that there was a competition between the crosslinking‐grafting reaction and the degradation of blending components in the presence of AlCl₃. The EPDM‐g‐PS copolymer served as a compatibilizer in the EPDM/PS blends and enhanced the mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010