text:
Schneebaum, Alyssa, Rumplmaier, Bernhard, Altzinger, Wilfried. 2015. Gender in Intergenerational Educational Persistence Across Time and Place. Empirica 42 (2), 413-445.
Show publication in ePubWU
@ARTICLE{Schneebaum2015,
title = {Gender in Intergenerational Educational Persistence Across Time and Place},
author = {Alyssa Schneebaum and Bernhard Rumplmaier and Wilfried Altzinger},
doi = {http://dx.doi.org/10.1007/s10663-015-9291-5},
url = {http://link.springer.com/article/10.1007/s10663-015-9291-5},
journal = {Empirica},
abstract = {Primarily using data from the 2010 European Social Survey, we analyze intergenerational educational persistence in 20 European countries, studying cross-country and cross-cluster differences; changes in the degree of intergenerational persistence over time; and the role of gender in determining educational persistence across generations. We find that persistence is highest in the Southern and Eastern European countries, and lowest in the Nordic countries. While persistence in the Nordic and Southern countries has declined over time, it has remained relatively steady in the rest of Europe. Our analysis highlights the importance of a detailed gender analysis in studying intergenerational persistence, finding that mothers education is a stronger determinant of daughters (instead of sons) education and fathers education a stronger determinant of the education of their sons. For most clusters, declines in intergenerational persistence over time are largely driven by increasing mobility for younger women.},
Primarily using data from the 2010 European Social Survey, we analyze intergenerational educational persistence in 20 European countries, studying cross-country and cross-cluster differences; changes in the degree of intergenerational persistence over time; and the role of gender in determining educational persistence across generations. We find that persistence is highest in the Southern and Eastern European countries, and lowest in the Nordic countries. While persistence in the Nordic and Southern countries has declined over time, it has remained relatively steady in the rest of Europe. Our analysis highlights the importance of a detailed gender analysis in studying intergenerational persistence, finding that mothers education is a stronger determinant of daughters (instead of sons) education and fathers education a stronger determinant of the education of their sons. For most clusters, declines in intergenerational persistence over time are largely driven by increasing mobility for younger women.
Empirica
Gender in Intergenerational Educational Persistence Across Time and Place
http://link.springer.com/article/10.1007/s10663-015-9291-5
http://dx.doi.org/10.1007/s10663-015-9291-5
Schneebaum, Alyssa (Details)
Rumplmaier, Bernhard (Former researcher)
Altzinger, Wilfried (Details)
Department of Economics (Crespo Cuaresma) (Details)
Competence Center for Sustainability Transformation and Responsibility WE (Details)
Economics of Inequality FI (Details)


The World Buddhist Youth Conference originally founded in Bangkok, for the first time holds their conference at Fo Guang Shan. Master Hsing Yun presides.
In accordance with Fo Guang Shan regulations, Master Hsing Yun retires, passing the abbotship on to Venerable Hsin Ping. By emphasizing "respectful adherence to Buddhist regulations, the continual transmission of learning from master to disciple, the management of affairs according to the rules, and the establishment of leadership," Master Hsing Yun reaffirms the democratic nature of Fo Guang Shan.
The World Sutric and Tantric Buddhist Conference takes place at Fo Guang Shan. The theme of the conference is "The Integration of Sutric and Tantric Buddhism and the Development of World Culture." More than 300 scholars from around the world participate, as do four Tantric Dharma masters.
Master Hsing Yun and Chao Pu-chu, President of the Chinese Buddhist Association of mainland China, meet one another in Bangkok for the first time.
Master Hsing Yun and 1200 others celebrate their sixtieth birthdays together.
Venerable Yi Hua, who had received a master's degree in comparative religion at the Indian International University, becomes the abbess of the Chinese Buddhist Temple, Sarnath, India.
Master Hsing Yun leads a delegation to spread the Dharma and provide medical care in northern Thailand. While there, he establishes the Fo Guang Shan Association to Aid Northern Thailand.
The Fo Guang Shan Cultural and Educational Foundation holds its first alms-round fund raising event. Under the leadership of Venerable Tzu Hui the foundation actively promotes Buddhist culture and education.
The Fo Guang Shan audio-visual center is established. This center produces movies, videos, and cassettes so that the propagation of the Dharma need not rely entirely on the written word.
Large-scale Dharma functions entitled, "Revival of the Buddha's Time" is held at Chiang Kai Shek Stadium in Kaohsiung. Master Hsing Yun delivers to a total of 120,000 devotees his message on giving people faith, joy, hope, and convenience.
After ten years of diligent work, the Fo Guang Encyclopedia is published.
The 16th World Fellowship of Buddhists is held at Hsi Lai Temple in the United States. This is the first time that the fellowship has held a conference in the Western hemisphere. It also provides the first opportunity for Buddhist organizations from Taiwan and mainland China to participate in the same conference.
Master Hsing-Yun is invited by the California Legislature to perform purifying services to start the session. This is the first time that a Buddhist master has performed such a service in America. The master will eventually conduct such services in New York and Chicago.


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redpajama_set_name: RedPajamaGithub


Where is the update for CS for the FW 1.00.003 ?
WTH is happening to DJI ? IOS people has it and CS (sold by DJI) has no UPdate as of now !!
SO PEOPLE STOP BUYING ACCESSORIES FROM DJI TO AVOID GETTING ... !!
CrystalSky is out. Smart Controller is in.
In say 18-months, Smart Controller will be out. InteliSky will be in.
I would have to agree. Now that the smart RC is out I would be surprised if we see anything further at all for the CS. I'm sure they are just selling off their remaining stock before it disappears from their online store.
So DJI will just drop the FW update for CS like That ? !!!!
Hi there, thank you for reaching out and we're sorry for the inconvenience. With regards to that as per our developer, they will be going to release an update for the Crystalsky soon and they working on it now. I hope you understand. Thank you for your consideration.
I think this is just a Marketing evil ploy to delay CS FW, so people will buy the SmartController (FW had just updated) ..
I dont see any reason why this is purposely delayed..
It's called the Chinese New Year!
WHERE IS IT ...DJI ?


Love your morning picture - beautiful and your amaryllis is gorgeous! I'm sure the new guests will just love your Air BnB - such an inviting space. Good luck with the glasses. I've had nothing but transition lenses since I needed bifocals years ago. I love them and have had no issues.
You'll love the transitional lenses although it will take a day or two to get used to them. They are very '60's acid tripy at first. Once your eyes and brain get together on where to look in order to see the distance you are trying to see, they are wonderful!
I love the idea of transition lenses - but I am having a hard time transitioning to multi-vision lenses. My eyes prefer cheaters like Kym.
Your amaryllis is gorgeous! And, it does look like it has much more to bloom!
Looking forward to seeing your new frames! I love my Transitions, but have had the same frames for years. Maybe I need (want, really) some new ones, too! Artist's Perch seems like the perfect name for your Airbnb. And lastly, your amaryllis is stunning! Lots of flower stalks, loads of blossoms, more to come, and I love that close-up photo!
I always want a "second opinion" when I'm getting new glasses. The longer days are glorious, and I'm trying to not think to hard about the upcoming change in which my morning light goes away again for a few weeks.
I always surprise myself when I see myself in the mirror with my reading glasses - I fear transition ones would make me too alarmed!
AirB&B is getting to be a more favorite way to stay these days, especially with kids. More room to run or wander around, whatever the size is nicer than one room. And a view! Whatever that may be too.
I LOVE my transition lenses! One caveat, the do not darken enough in the car and I bought a pair of sunglasses for car use. But, when out and about the transitions are fantastic. They take a little longer to lighten again, but are still pretty fast as getting back to normal. Your amaryllis is really elegant and delicate. I love looking at its lines.
I hate the transition lenses. As a quilter they had a residual color that skewed colors on fabrics. And they never got dark enough for outside use. I use trifocals for indoor glasses since progressive ones have a narrower field of vision. And I get my sunglasses as dark as possible with only distance and mid vision. hope you like your new glasses. I want the magic stuff that they have at optomitrists that they can dip glasses in and get them spotless.
Can't wait for longer daylight hours! Posting to compliment your morning pic.


10-page flutter book featuring digital prints of original embroidered illustrations from a one-off fabric book created for the 'Redesigning the Medieval Book' competition for the Bodleian Library. Captioned with symptoms relieved by the featured plants – for example, Artemesia leaves repel fever, nausea, worms, insects and dragons (who knew?) – with titles with hand-finished gold frames. Medieval tile patterned endpapers, a wraparound card cover with laser foiled title and a hemp cord fastening.


Many years ago I and my class made a Push-Pull Meters with dowel rod and a cotton reels and had great fun with them, measuring all sorts of pushes and pulls.OK we could have used conventional force meters, the school had enough of them for class use, however making one yourself and then using it seems to make a big difference in understanding.
A recent question made me look for my plans – no chance. Search the internet – no luck. My team were of no help so I therefore decided to do the obvious thing, make one myself.
These are the drawings of my endeavours. The equipment list is cotton reel (wooden would be nice but if it's plastic ok), a length of dowel rod with a diameter which will allow it to pass through the central hole of the cotton reel, an elastic band (probably 4 cm long but have a set of them for experimentation), a paperclip which is opened up to make a hook, some drawing pins or sellotape …….and I think thats it.
Once constructed the next task it to calibrate it. If you have access to a set of weights, great. you can create a little bag which will hold them, hang it on the hook and away you go. A 1kg mass will apply a 1 Newton force on the elastic band. This is where the choice of the elastic band is important – a thin band is obviously much more sensitive than a thick band. On the other hand, why not make up your own scale of push a pulls – a five marble/ 3 marble/1 marble push or pull. Below are the images that I created for my answer to the 10 yr olds question.
Thanks team and thanks Mariah for the question. My team are quite correct there are lots of pushes and pulls. Can you think of more? What about gravity? That pulls things to the ground. What about the wind, that pushes things.
In science and in our daily life we put things into groups. The things in the group all have something in common. All fish are grouped together, they can all breathe underwater. Can you see anything else they have in all fish have which is the same?
All bicycles are grouped together, they all have two wheels. They also have some other things in common (the same).
If all forces are grouped together , they all involve pushes and pulls. The group that pushes and pulls is called forces.
Aiden, great question,a difficult answer. I hope that you have investigated which things float and which things sink. You should be able to look around you and say 'That floats' and 'That sinks". Think about this – when something sinks it seems to be breaking the surface of the water. What is it breaking? I pass this back to my team.
The attractive forces between water molecules are called intermolecular forces. Look at this post to find out more. When the much bigger metal boat hits the water, because of it's design (spread out) there are lots more water particles that push on the boat and keep it floating. Squash the boat up into a small lump of metal and drop it into the water. What do you think will happen? Let me know what you think by leaving a comment in the 'Leave a Reply' box below.
Vinay. These are the initial thoughts of my friends. I will reply later.
I'm back ….. So the siphon it is. For animations on siphons go to this great animation where you will see a true siphon in action.
The amazing thing is that initially the siphon was thought to be delivered by air pressure. Then somebody created a siphon in a vacuum. So ideas have changed. Not everything in science is 'absolute truth' . One of the driving forces in science development is attempting to disprove accepted laws.
Imran. A great question. I would like to answer it in a slightly different way (you can sometimes do that with questions). After you push a ball it starts moving but does it stay moving?
When you push the ball you transferring your push (force) to the ball and it moves. Newton (a great scientist and questioner) thought "Why does it stop moving? I have transferred my force to the ball and it should keep moving until it transfers that force to something else" But it does stops moving. I put this question to my friends and they came up with the following thoughts.
Why not investigate moving balls over different surfaces. You could use wood, paper, carpet, or the floor as surfaces and see how far the ball rolls BUT you have to make it a fair test. How do you create the same force? How do you transfer the same force to the ball?
What an excellent question. How do I answer this? Firstly I think we need to know what we mean by science. Here is what my friends said when I asked them the question.
My favourite definition of science is that it is 'applied curiosity'. People who enjoy science have a curiosity about the physical and natural world that surrounds them. This leads them to investigate it.
Look at the see-saw in the picture above. Why does a small mass seem to balance a larger mass? Lets move the masses around and see if we can get other positions where they balance? This is curiosity in action.
So what about forces, are they part of the natural world or the physical world? What is a force?
The forces we meet every day are pushes and pulls. Pushes and pulls make things move.
Gravity is another force … jump off a chair and you are pulled to the ground, you moved because of the pull of gravity. Another force is friction – how does that affect movement? Force and movement are therefore intertwined. Investigate movement and you are investigating forces. And that leads to lots of questions. Do things always move at the same speed when a force is applied? Curiosity, curiosity, curiosity.
So please show your curiosity by asking more questions and I leave you with a question of your own. Are forces part of the natural world or the physical one, or both, or neither?
I hope this gives you some answers to your excellent question. Any more questions?


m is a number of from about 5 to about 1000.
This invention relates to poly(arylamines), methods for the preparation of poly(arylamines) and films thereof. The films of the poly(arylamines) are useful as charge transport layers in light-emitting diodes.
Triarylamines, as evidenced by their low oxidation potentials, are easily oxidized to the corresponding radical cations. The cations are equally easily reduced to the neutral starting amines. This oxidation/reduction process is reversible and can be repeated many times. For this reason, triarylamines are widely used as charge transport materials, specifically for the transport of holes (positive charges).
Charge transport materials are essential to the efficient operation of electrophotographic devices (copying machines and printers) and electroluminescent devices such as light-emitting diodes. In both applications, the triarylamines are used in film form. For electrophotographic applications, a triarylamine and a polymeric binder are dissolved in a suitable solvent and the resulting solution used for coating, see U.S. Pat. Nos. 5,352,554 and 5,352,834. To obtain a film of useful charge transport properties, the loading of triarylamine in the final formulation must be as high as possible. In low concentrations, the triarylamine will act to trap charge carriers instead of transporting them, D. M. Pai, J. F. Yanus, M. Stolka., J. Phys. Chem., Vol. 88, p. 4714 (1984). If the triarylamine compound separates out from the polymer binder or crystallizes into a fine dispersion of crystals in the polymer binder, the film can no longer serve its intended purpose.
Organic electroluminescent devices are typically constructed by sandwiching an organic film or a stack of organic films between an anode and a cathode such that when voltage is applied, holes and electrons are injected and transported into the device. The combination of holes and electrons within the organic layer leads to excitons which can undergo radiative decay to the ground state, emitting the excitation energy in the form of light. For the light to be seen, it is necessary that one of the electrodes be transparent. A major improvement in device efficiency was achieved when a film of a triarylamine was deposited by conventional vapor-phase deposition between the emitting film and the anode, see C. W. Tang, S. A. Van Slyke, Appl. Phys. Lett., Vol. 51, p. 913 (1987), and U.S. Pat. No. 4,539,507. One of the problems associated with devices of this type is the tendency of the organic films to crystallize due to the heat evolved during operation, see C. Adachi, T. Tsutsui, S. Saito, Appl. Phys. Lett., Vol. 56, p. 799 (1990). Contacts between organic layers and electrodes may be destroyed by crystallization, leading to device failure, see J. Kido, M. Kohda, Appl. Phys. Lett., Vol. 61, p. 761 (1992).
Copolymers consisting of aromatic amide and triarylamine groups have been taught as hole-transporting layers in electroluminescent devices, see Japanese Patent 0531163-A. These copolymers are less desirable for use in electroluminescent devices as the concentration of the active triarylamine groups are depressed by the presence of the amide comonomer.
What is needed are relatively high molecular weight charge transport compounds which are capable of forming films. What is needed are films which can be prepared using relatively small amounts of polymer while still maintaining the desirable properties of transporting positive charges. What is also needed are polymeric light-emitting diode devices prepared from such films. What is also needed are processes for the preparation of such compounds.
The invention further relates to films prepared from such poly(arylamines), as well as electrophotographic devices and electroluminescent devices containing such films, such as polymeric light-emitting diodes.
The invention also relates to processes for the preparation of poly(arylamines). One such process comprises contacting one or more monomers such as a dihalogenated tetraaryl-1,2-phenylenediamine with a catalytic amount of a divalent nickel salt, at least a stoichiometric amount of a material capable of reducing the divalent nickel ion to the zero valent state, a material capable of acting as a ligand and an amount of a compound capable of accelerating the reaction in a polar solvent, and an optional co-solvent comprising an aromatic hydrocarbon or ether, under conditions such that one or more poly(arylamines) are prepared.
The polymers of the invention form films which are relatively high molecular weight charge transport compounds which are capable of forming films. The films can be prepared using relatively small amounts of polymer while still maintaining the desirable properties of transporting positive charges. The processes disclosed herein provide efficient means of preparing the disclosed compounds. These and other advantages of the invention will be apparent from the description which follows.
Preferably, Ar1 and Ar2 are independently in each occurrence a C6-18 aromatic radical optionally substituted with C1-12 hydrocarbyl, C1-12 alkoxy, C1-12 thioalkoxy, C1-12 aryloxy, and C1-12 thioaryloxy moieties. More preferably, Ar1 and Ar2 are independently in each occurrence a phenyl, naphthyl or biphenyl group, optionally substituted with C1-5 alkoxyl or C1-6 alkyl. Even more preferably, Ar1 and Ar2 are independently in each occurrence derived from anisole, methoxynapthalene, methoxybiphenyl, phenyl or toluene. Most preferably, Ar1 is phenyl and Ar2 is independently in each occurrence 4-methoxyphenyl or phenyl.
Preferably, A is independently in each occurrence hydrogen, chlorine, or bromine.
Preferably, n is a number of 0 or 1. More preferably, n is 0.
Preferably, m is a number of from about 5 to about 500. More preferably, m is a number of from about 5 to about 100.
The poly(arylamines) of the invention demonstrate strong photo-luminescence in dilute solutions or in the solid state. When such materials are exposed to light of a wavelength of about 300 to about 700 nanometers, the materials emit light of wavelengths in the region of about 400 to about 800 nanometers. More preferably, such materials absorb light of wavelengths of from about 300 to about 400 nanometers and emit light of wavelengths in the region of about 400 to about 650 nanometers. The poly(arylamines) of the invention are readily soluble in common organic solvents. They are processable into thin films or coatings by conventional techniques. The poly(arylamines) of the invention preferably have oxidation potentials of about +0.1 volt or greater, more preferably +0.4 volt or greater and preferably +1.0 volt or less, more preferably +0.7 volt or less.
The poly(arylamines) of this invention preferably have a weight average molecular weight of about 250 Daltons or greater, more preferably about 500 Daltons or greater, even more preferably about 1,000 Daltons or greater; preferably about 1,000,000 Daltons or less, more preferably about 500,000 Daltons or less and most preferably about 50,000 Daltons or less. Molecular weights are determined according to gel permeation chromatography using polystyrene standards.
Preferably, the poly(arylamines) demonstrate a polydispersity (Mw /Mn) of 5 or less, more preferably 4 or less, even more preferably 3 or less and most preferably 2.5 or less.
The monomers useful in the preparation of the poly(arylamines) preferably comprise two amino moieties wherein each amino moiety is bound to three aryl moieties wherein two halo moieties are optionally bound to the monomers. Preferably, the poly(arylamines) comprise from about 5 to about 1000 of the monomers. Preferably, the monomers useful in the preparation of the poly(arylamines) of this invention are illustrated in Formulas (II) and (III): ##STR3## wherein A, Ar1, Ar2 R and n are as previously defined. A preferred monomer is dihalogenated N,N,N',N'-tetraaryl-1,4-phenylenediamine. Such halogenated monomers may be prepared, for example, by contacting one or more diaryldiamines with a haloaromatic compound under reaction conditions sufficient to form the corresponding monomer of Formula (II) or (III). Diaryldiamines useful for this purpose are shown in Formulas (IV) and (V): ##STR4## wherein A, Ar1, Ar2, R and n are as previously defined. Such diaryldiamines may be compounds such as N,N'-diaryl-1,4-phenylenediamine or N,N-diaryl-1,4-phenylenediamine.
The diaryldiamines are contacted with a haloaromatic compound under conditions such that one or more monomers are prepared. Preferably, the contacting of the diaryldiamines with a haloaromatic compound is performed according to the procedures of Gauthier and Frechet in Synthesis, p. 383 (1987), incorporated herein by reference, or according to the procedures of Guram, Rennels and Buchwald, Angewandte Chemie International Edition in English, Vol. 34, p. 1348 (1995), incorporated herein by reference. The diaryldiamines and haloaromatic compounds are contacted and heated in the presence of copper powder and potassium carbonate or the contacting is performed in the presence of sodium t-butoxide and a catalyst comprising a palladium compound and tri-o-tolylphosphine. Preferably, if copper powder and potassium carbonate are used as starting materials, an iodoaromatic compound may be used. Preferably, if sodium t-butoxide and a catalyst comprising a palladium compound and tri-o-tolylphosphine are used as starting materials, a bromoaromatic compound may be used.
wherein A and B are independently in each occurrence hydrogen or a halogen and Ar1 is as previously defined. Preferably, A is individually in each occurrence hydrogen, chlorine or bromine and B is individually in each occurrence bromine or iodine. The amount of haloaromatic compound used is enough to fully substitute the amine nitrogen atoms of the diaryldiamine present in the reactant mixture. Preferably, the diaryldiamines are contacted with a haloaromatic compound in a mole ratio of about 1:10 or less, more preferably in a ratio of about 1:5 or less and even more preferably in a ratio of about 1:3 or less.
The reactants to prepare the monomers are heated to a temperature at which the reaction proceeds at a rate sufficient to form the monomers. Preferably, the reaction temperature is about 100° C. or greater, more preferably about 120° C. or greater and even more preferably about 150° C. or greater. Preferably, the reaction temperature is about 300° C. or less, more preferably about 250° C. or less and even more preferably about 200° C. or less. The reaction time is dependent upon the reaction temperature, the amount of catalyst and the concentration of the reactants. Reaction times are preferably about 5 hours or greater, more preferably about 10 hours or greater and even more preferably about 20 hours or greater. Reaction times are about 50 hours or less, more preferably about 40 hours or less and most preferably about 30 hours or less.
The amount of solvent used in this process can vary over a wide range. Generally, it is desirable to use as little solvent as possible. Preferably, about 1 liter of solvent per mole of diaryldiamines or less is used, more preferably about 0.5 liter or less is used, and most preferably about 0.1 liter or less is used. The lower limit on amount of solvent used is determined by practicality, that is, handleability of the solution and solubility of the reactants and products in the solvent.
The poly(arylamines) of the invention may be prepared by a halide coupling reaction (hereinafter "polymerization reaction") carried out in the presence of a catalytic amount of a divalent nickel salt, at least a stoichiometric amount of zinc powder, a trisubstitued phosphine and an amount of a compound capable of accelerating the coupling reaction in a polar solvent and an optional co-solvent comprising an aromatic hydrocarbon or ether. The nickel (zero valent) catalyst is prepared in situ by contacting a divalent nickel salt with a reducing agent in the presence of a material capable of acting as a ligand and, optionally, a material capable of accelerating the reactions.
In a preferred embodiment, the poly(arylamines) of the invention are prepared by contacting the monomers in the presence of a nickel catalyst according to the procedures of Colon et al., described in Journal of Polymer Science, Part A, Polymer Chemistry Edition, Vol. 28, p. 367 (1990), incorporated herein by reference, and Colon et al., Journal of Organic Chemistry, Vol. 51, p. 2627 (1986), the relevant parts of which are incorporated herein by reference.
The polymerization reaction is preferably carried out in a polar solvent, preferably dimethylformamide, N,N-dimethylacetamide, N-cyclohexylpyrrolidinone or N-methylpyrrolidinone. Up to about 50 volume percent of a non-amide co-solvent can be used. Preferable co-solvents are aromatic hydrocarbons and ethers, for instance, tetrahydrofuran. The process is preferably conducted in the absence of oxygen and moisture, as the presence of oxygen is detrimental to the catalyst and the presence of a significant amount of water leads to premature termination of the process. More preferably, the reaction is performed under an inert atmosphere such as nitrogen or argon.
The catalyst is preferably formed from a divalent nickel salt. The nickel salt may be any nickel salt which can be converted to the zero valent state under reaction conditions. Preferable nickel salts are the nickel halides, with nickel chloride and nickel bromide most preferred. The divalent nickel salt is present in an amount of about 0.01 mole percent or greater, more preferably about 0.1 mole percent or greater and most preferably about 1.0 mole percent or greater, based on the amount of monomer present. The amount of divalent nickel salt present is preferably about 30 mole percent or less, more preferably about 15 mole percent or less, based on the amount of monomer present.
The nickel-catalyzed polymerization reaction is performed in the presence of a material capable of reducing the divalent nickel ion to the zero valent state. Suitable material includes any metal which is more easily oxidized than nickel. Preferable metals include zinc, magnesium, calcium and lithium. The preferred reducing agent is zinc in the powder form. At least stoichiometric amounts of reducing agent based on the amount of nickel is required to maintain the nickel species in the zero valent state throughout the reaction. Preferably, the reducing agent is present in an amount of about 150 mole percent or greater, more preferably about 200 mole percent or greater, and most preferably about 250 mole percent or greater, based on the amount of monomer is used. Preferably, the reducing agent is present in an amount of about 500 mole percent or less, more preferably about 400 mole percent or less and most preferably about 300 mole percent or less, based on the amount of monomer.
The polymerization reaction is performed in the presence of a material capable of acting as a ligand. Preferred ligands include trihydrocarbylphosphines. More preferred ligands are triaryl or trialkylphosphines, with triphenylphosphines being the most preferred. The compound capable of acting as a ligand is present in an amount of from about 10 mole percent or greater, more preferably about 20 mole percent or greater, based on the amount of monomer. The compound capable of acting as a ligand is preferably present in an amount of about 100 mole percent or less, more preferably about 50 mole percent or less, and most preferably about 40 mole percent or less, based on the amount of monomer.
The polymerization reaction can be performed at any temperature at which the reaction proceeds at a reasonable rate. Preferably, the reaction is performed at a temperature of about 25° C. or greater, more preferably about 50° C. or greater, and most preferably about 70° C. or greater. Below about 25° C., the rate of reaction is unacceptably low. Preferably, the reaction is performed at a temperature of about 200° C. or less, more preferably about 150° C. or less, and most preferably about 125° C. or less. Temperatures substantially higher than about 200° C. can lead to degradation of the catalyst. The reaction time is dependent upon the reaction temperature, the amount of catalyst and the concentration of the reactants. Reaction times are preferably about 1 hour or greater and more preferably about 10 hours or greater. Reaction times are about 100 hours or less, more preferably about 72 hours or less and most preferably about 48 hours or less. The amount of solvent used in this process can vary over a wide range. Generally, it is desirable to use as little solvent as possible. Preferably, about 10 liters of solvent per mole of monomer or less are used, more preferably about 5 liters or less are used, and most preferably about 2 liters or less are used. The lower limit on amount of solvent used is determined by practicality, that is, handleability of the solution and solubility of the reactants and products in the solvent.
In another embodiment, the poly(arylamines) of the invention may be prepared by a process disclosed in Ioyda et al., Bulletin of the Chemical Society of Japan, Vol. 63, p. 80 (1990), relevant parts incorporated herein by reference. Such method is similar to the method described hereinbefore. In particular, the catalyst is a divalent nickel salt introduced as a nickel halide bis-triphenylphosphine complex. The reaction may be performed in a variety of polar solvents. These solvents can include acetone, dimethylformamide, tetrahydrofuran and acetonitrile. The reaction is accelerated by the addition of about 10 mole percent of an organo-soluble iodide such as tetraethylammonium iodide. Such a reaction is performed at a temperature of from about 20° C. to about 100° C. for about 1 to about 24 hours.
In another embodiment, the poly(arylamines) of the invention may be prepared via the process disclosed by Yamamoto, Progress in Polymer Science, Vol. 17, p. 1153 (1992), relevant parts incorporated herein by reference. Such method is similar to the method described hereinbefore. In such process, the monomers are contacted with at least a stoichiometric amount of nickel catalyst in the form of nickel (1,5-cyclooctadiene) complex and at least a stoichiometric amount of 1,5-cyclooctadiene as a ligand in an inert solvent, such as tetrahydrofuran. The reaction is preferably conducted at about 70° C. or higher for about two or more days.
In another embodiment, the poly(arylamines) of the invention may be prepared by the process disclosed in Miyaura et al., Synthetic Communication, Vol. 11, p. 513 (1981 ), and Wallow et al., American Chemical Society Polymer Preprint, Vol. 34 (1), p. 1009 (1993), relevant parts of both references incorporated herein by reference. In such process, the halogens on the monomers are converted to the corresponding lithio- or Grignard moieties. Such processes are well known in the art, see for example March, Advanced Organic Chemistry, 2d Ed., pp. 408-414 (McGraw-Hill, 1977). The resulting lithio- or Grignard derivatives are reacted with a trialkyl borate to form the corresponding boronic acid: M. Rehalin et al., as disclosed in Makromoleculaire Chemie, Vol. 191, pp. 1991-2003 (1990), relevant parts incorporated herein by reference. The resulting boronic acid derivatives are contacted in the presence of a catalytic amount of tetrakis(triphenylphosphine)-palladium(0) and an aqueous base under conditions such that the poly(arylamines) of the invention are prepared.
The tetrakis(triphenylphosphine)-palladium(0) may be generated in situ by the addition of a soluble palladium salt (for instance palladium acetate or palladium chloride) and at least four molar equivalents of triphenylphosphine. The catalyst is present in a sufficient amount to promote the desired reaction and to facilitate a reasonable rate of reaction. Preferably, the catalyst is present in an amount of about 0.01 mole percent or greater, more preferably about 0. 1 mole percent or greater, and most preferably about 1.0 mole percent or greater, based on the amount of monomer present. The tetrakis(triphenylphosphine)-palladium(0) is preferably present in an amount of about 20 mole percent or less, more preferably about 10 mole percent or less, and most preferably about 5 mole percent or less, based on the amount of monomer.
The above reactants are contacted in a solvent which does not react with the reactants or deactivate the catalysts. Preferable solvents include aromatic hydrocarbons, lower alkanols, aliphatic ethers and N,N-dialkylamides, with toluene and ethanol being more preferred.
The process as disclosed in Miyaura et al. is preferably conducted in the absence of oxygen, as the presence of oxygen is detrimental to the catalyst. More preferably, the reaction is performed under an inert atmosphere such as nitrogen or argon.
The above reaction can be performed at any temperature at which the reaction proceeds at a reasonable rate. Preferably, the reaction is performed at a temperature of about 50° C. or greater, more preferably about 70° C. or greater, and most preferably about 80° C. or greater. Below about 50° C., the rate of reaction is unacceptably low. Preferably, the reaction is performed at a temperature of about 150° C. or less, more preferably about 130° C. or less, and most preferably about 100° C. or less. Temperatures substantially higher than about 150° C. can lead to degradation of the catalyst. The reaction time is dependent upon the reaction temperature, the amount of catalyst and the concentration of the reactants. Reaction times are preferably about 10 hours or greater and more preferably about 20 hours or greater. Reaction times are about 100 hours or less, more preferably about 50 hours or less, and most preferably about 20 hours or less. The amount of solvent used in this process can vary over a wide range. Generally, it is desirable to use as little solvent as possible. Preferably, about 100 liters of solvent per mole of diaryldiamine or less is used, more preferably about 75 liters or less, and most preferably about 50 liters or less. The lower limits on amount of solvent used is determined by practicality, that is, handleability of the solution and solubility of the reactants and products in the solvent.
The poly(arylamines) resulting from all of the above methods of preparation are recovered according to conventional techniques; preferred techniques include filtration and precipitation using a nonsolvent. The poly(arylamines) are useful in preparing coatings and films.
Such coatings and films can be useful as charge transport layers in polymeric light-emitting diodes, in protective coatings for electronic devices and as fluorescent coatings. Polymeric light emitting diode devices contain an electroluminescent substance placed between a pair of electrodes. When electric potential is applied across the electrodes, the electroluminescent substance emits visible light. Typically, one of the electrodes is transparent, permitting the light to shine through. The device contains an anode and a cathode with a hole transport layer and an electron transport layer as the electroluminescent substance between the anode and cathode. For examples of such devices, see U.S. Pat. Nos. 4,356,429, 4,539,507, 4,885,211, 5,047,687, 5,059,862 and 5,061,561, all of which are incorporated herein by reference. The thickness of the coating or film is dependent upon the ultimate use. Generally, such thickness can be from about 0.01 to about 200 microns. In that embodiment wherein the coating is used as a fluorescent coating, the coating or film thickness is from about 50 to about 200 microns. In that embodiment where the coatings are used as electronic protective layers, the thickness of the coating can be from about 5 to about 20 microns. In that embodiment where the coatings are used in a polymeric light-emitting diode, the thickness of the layer formed is about 0.05 to about 2 microns. The poly(arylamines) form good pinhole- and defect-free films. Such films can be prepared by means well known in the art, including spin-coating, spray-coating, dip-coating and roller-coating. Such coatings are prepared by a process comprising applying a composition to a substrate and exposing the applied composition to conditions such that a film is formed.
In a preferred embodiment, the composition applied to the substrate comprises the poly(arylamines) dissolved in a common organic solvent. Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and the like. It is preferable that such solvents have relatively low polarity. Preferably, the solution contains from about 0.5 to about 10 weight percent of the poly(arylamine). For thin coatings, it is preferred that the composition contains from about 0.5 to about 5.0 percent by weight of the poly(di(triarylamine). This composition is then applied to the appropriate substrate by the desired method. The films are preferably substantially uniform in thickness and substantially free of pinholes.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
Glass transition temperatures of polymers were determined by differential scanning calorimetry. Inherent viscosity measurements were conducted at 25° C., 0.5 dL/g. Molecular weights were determined by gel permeation chromatography against polystyrene standards. Cyclic voltammetric analyses were performed with Ag/AgCl as reference; oxidation potentials were determined either with dichloromethane solutions or with polymer films deposited on platinum electrodes.
N,N'-diphenyl-1,4-phenylenediamine (46.3 g, 0.18 mol), 4-iodophenylmethylether (100.0 g, 0.43 mol), copper bronze powder (28 g, 0.44 mol), potassium carbonate (166 g, 1.2 mol), 18-crown-6 ether (7.9 g, 0.03 mol), and 1,2-dichlorobenzene (400 mL) were added to a reactor equipped with a mechanical stirrer, a nitrogen inlet and a condenser was added. The mixture was heated at 180° C. for 90 hours while the water produced by the reaction was removed with a slow flow of nitrogen. After 24 hours, the hot reaction mixture was filtered through a bed and concentrated under reduced pressure to afford dark brown viscous liquid which was percolated through a bed of silica gel with hexane to remove some of the color. Recrystallization twice from acetone afforded 55.7 g (66%) of tan-colored crystals of the monomer.
A solution of N-bromosuccimide (19.0 g, 0.11 mol) and dimethyl formamide (DMF) (150 mL) was added to a stirred solution of N,N'-diphenyl-N,N'-di(4-methoxyphenyl)-1,4-phenylenediamine (25.0 g, 0.053 mol) in DMF (150 mL). The reaction mixture was added to 1 L of toluene and heated to 60° C. The warm solution was washed with water (4×1000 mL) at 60° C. The toluene solution was dried over anhydrous MgSO4, filtered through a bed of silica gel, then concentrated under reduced pressure. Two recrystallizations of the crude product from toluene/hexane gave tan-colored crystals of the monomer (21.6 g, 65%) after drying.
A polymerization reactor was charged with N,N'-di-(4-bromophenyl)-N,N'-di-(4-methoxyphenyl)-1,4-phenylenediamine (6.3 g, 10 mmol), triphenylphosphine (1.35 g, 5 mmol), zinc powder (2.0 g, 30 mmol) and nickel chloride-2,2'-bipyridine complex (NiCl2 -Bipy) (0.1 g, 0.45 mmol). The reactor was evacuated to ˜0.2 mmHg then purged with nitrogen; this cycle was repeated 7 times. To the reactor was added (via syringe) 20 mL of anhydrous dimethyl acetamide (DMAc). The reaction mixture was heated to 80° C. with a stirring rate of 250 rpm. After a few minutes the reaction mixture turned from gray to a brownish-red color which became darker with time. After 1 hour, a solid green cake was formed and mixing was difficult. To the reactor was added 25 mL of DMAc and 40 mL of toluene to dissolve the solid cake. The reaction was stirred at 80° C. for 18 hours. The reaction mixture was added to 500 mL of acetone, precipitating out the product. The precipitate was collected and washed with acetone (3×150 mL). The precipitate was dissolved in 300 mL of chlorobenzene then filtered through a bed of filter aid. The chlorobenzene solution was washed with 300 mL of aqueous 3N HCl and water (2×300 mL). The chlorobenzene mixture was then added to a flask containing 100 mL of water and 50 mL of ethylenediamine. The mixture was stirred at 60° C. for 2 hours. The aqueous layer of the chlorobenzene mixture was removed and the toluene layer of the chlorobenzene mixture was washed with water (3×200 mL). The chlorobenzene mixture was concentrated to a volume of ˜50 mL then slowly added to 300 mL of acetone. The polymer was formed as a yellow precipitate. The yellow precipitate was collected, washed with acetone (2×200 mL) then dried to afford 4.4 g (94%) of a yellow powder. The properties of the polymer are listed in Table I. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
The above example was repeated with N,N'-di-(4-bromophenyl)-N,N'-di-(4-methoxyphenyl)-1,4-phenylenediamine (6.3 g, 10 mmol), triphenylphosphine (1.31 g, 50 mmol), zinc powder (2.0 g, 30 mmol), NiCl2 -Bipy (0.086 g, 0.3 mmol), and N-methylpyrrolidinone (20 mL). The polymerization was terminated after about 6 hours. The polymer cake was dissolved in toluene (200 mL) and the resulting mixture filtered through a bed to remove the inorganic salts. The filtered toluene solution was reduced to about 50 mL volume and was then poured into about 800 mL of acetone to precipitate the desired polymer. The solid was collected by filtration and dried in a vacuum oven overnight at 60° C. to give 3.47 g of yellow polymer whose inherent viscosity in toluene was 0.08 dL/g. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
The above example was repeated with N,N'-di-(4-bromophenyl)-N,N'-di-(4-methoxyphenyl)-1,4-phenylenediamine (3.15 g, 5 mmol), triphenylphosphine (0.66 g, 25 mmol), zinc powder (1.00 g, 15 mmol), NiCl2 -Bipy (0.05 g, 0.17 mmol), and N-cyclohexylpyrrolidinone (11 mL). The polymerization was carried out for 25 hours at 90° C. and the polymer product (2.0 g, inherent viscosity 0.09 dL/g) was isolated by the same procedure described above. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
Following the procedure of Example 1, a mixture of N,N'-diphenyl-1,4-phenylenediamine (13.0 g, 0.05 mol), 3-iodochlorobenzene (31.0 g, 0.13 mol), copper bronze powder (7.5 g, 0.13 mol), 18-crown-6 (2.40 g 0.09 mol), powdered potassium carbonate (50.14 g, 0.36 mol) and 1,2-dichlorobenzene (120 mL) was heated for 20 hours at 190° C. The hot reaction mixture was filtered through a bed, which was washed with toluene (50 mL). Toluene was removed under vacuum from the combined filtrate and the resulting dark brown oil chromatographed on a silica gel column (5×25 cm, 5% CH2 Cl2 in hexane as eluant) to give 7.4 g (31%) of a light yellow viscous oil which solidified upon standing. Recrystallization from methanol-acetone afforded 4.6 g (19%) of monomer product as white flakes (m.p. 124°-127° C.).
A mixture of palladium acetate (180 mg, 0.8 mmol) and tri-o-tolylphosphine (536 mg, 1.7 mmol) and toluene (40 mL) was stirred at ambient temperature for 30 minutes until a homogenous yellow solution was formed. N,N'-diphenyl-1,4-phenylenediamine (5.2 g, 20 mmol), 3-bromochlorobenzene (9.6 g, 50 mmol), sodium tert-butoxide (5.4 g, 56 mmol) and more toluene (120 mL) is added to the above mixture in a reactor vessel. With a slow purge of nitrogen, the reaction vessel was placed into an oil-bath and the stirred reaction was heated to reflux for 14 hours. The reaction mixture was cooled to ambient temperature, treated with hydrochloric acid (6 mL), and filtered through a bed. Removal of the solvent on a rotavapor under reduced pressure afforded a dark brown viscous oil. Flash chromatography on a silica gel column (5×25 cm, 10% toluene in hexane as eluent) provided a light-yellow oil, which solidified on standing at ambient temperature. Recrystallization from methanol/acetone afforded 7.3 g (76%) of product as white flakes (m.p 125°-127° C.).
N,N'-diphenyl-N,N'-di-(3-chlorophenyl)-1,4-phenylenediamine (1.2 g, 2.5 mmol), triphenylphosphine (327.5 mg, 1.25 mmol), zinc powder (490 mg, 7.5 mmol) and NiCl2 -Bipy (21.5 mg, 0.075 mmol) were added to a dry reactor. The reactor was evacuated to ˜3 mm/Hg and was then filled with nitrogen. This cycle was repeated 5 times. 3.5 mL of N-methylpyrrolidinone was added to the reactor and the reactor was evacuated and filled with nitrogen 3 times. The reaction mixture was stirred and heated in an oil bath at 70° C. for 20 hours. The polymer cake thus formed was dissolved in hot chlorobenzene (40 mL). The solution was filtered and concentrated to about 10 mL. Acetone (100 mL) was added to the solution to precipitate the polymer as a white powder. Washing with acetone and drying in a vacuum oven at 60° C. overnight gave 0.78 g (76%) of polymer product. The properties of the polymer are listed in Table I. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
The above Example was repeated at ten times the amounts of all solid reagents. N-Cyclohexyl-pyrrolidinone (13 mL) and N-methylpyrrolidinone (23 mL) were used as the solvent. Polymerization was conducted at 70° C. for 8 hours and 90° C. for 10 hours. The yield of polymer was 8.7 g (85 %). The properties of the polymer are listed in Table I. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
Example 8 was repeated with the exception that the solvent was a 1:1 mixture of N-cyclohexyl-pyrrolidinone and N-methylpyrrolidinone (total 4 mL). Polymerization was allowed to proceed for 10 hours at 70° C. The product (910 mg, 88%) isolated had an inherent viscosity of 0.13 dL/g in CH2 Cl2. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
A mixture of palladium acetate (270 mg, 1.2 mmol) and tri-o-tolylphosphine (804 mg, 2.6 mmol) and toluene (20 mL) was stirred at ambient temperature for 30 minutes until a homogenous yellow solution was formed. To this solution were added N,N'-diphenyl-1,4-phenylenediamine (7.8 g, 30 mmol), 4-bromochlorobenzene (18.9 g, 99 mmol), sodium tert-butoxide (8.1 g, 84 mmol) and more toluene (250 mL). With a slow purge of nitrogen, the reaction vessel was placed into an oil-bath and the stirred reaction was heated to reflux for 12 hours. The reaction mixture was cooled to ambient temperature, treated with hydrochloric acid (9 mL), and filtered through a bed of filtering aid. Removal of the solvent on a rotavapor under reduced pressure afforded a dark brown viscous oil. Flash chromatography on a silica gel column (5×25 cm, 50% benzene/hexane as eluent) provided a light-yellow solid. Recrystallization of the benzene/hexane afforded 11.9 g (82%) of product as white flacks. HPLC analysis indicated the product was in >99% purity.
A 1 L, three-necked, round-bottomed flask, equipped with an overhead stirrer, a nitrogen inlet and a reflux condenser, was charged with N,N'-diphenyl-1,4-phenylenediamine (13.0 g, 0.05 mol), 4-iodochlorobenzene (31.0 g, 0.13 mol), copper bronze powder (12.7 g, 0.20 mol), 18-crown-6 ether (2.6 g, 0.10 mol), powdered potassium carbonate (50.1 g. 0.36 mol) and 1,2-dichlorobenzene (120 mL). With a slow purge of nitrogen through the condenser, the reaction vessel was placed in an oil bath and the stirred reaction was heated at 200° C. for 20 hours. The hot reaction mixture was filtered through a bed of filtering aid, which was washed with toluene (50 mL), and the filtrate was concentrated on a rotavapor under reduced pressure. The solvent residue was further removed with a Kugelrohr apparatus to afford a dark brown viscous oil. Flash chromatography on a silica gel column (5×25 cm, 5% CH2 Cl2 in hexane as eluent) afforded 9.6 g of grey-white solid. The crude product was further washed with toluene and acetone to provide 6.1 g (25%) of off-white powdered material. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
To a dry reactor equipped with a mechanical stirrer, nitrogen/vacuum inlet, and a rubber septum was added N,N'-diphenyl-N,N'-di-(4-chlorophenyl)-1,4-phenylenediamine (12.0 g, 25.0 mmol), triphenylphosphine (3.3 g, 12.6 mmol), zinc powder (4.9 g, 75 mmol), and NiCl2 -Bipy (0.22 g, 0.75 mmol). The reactor was evacuated to ˜3 mmHg and then purged with nitrogen This cycle was repeated five times. To the reactor was added via syringe 45 mL of N-cyclohexylpyrrolidinone and 27 mL of N-methylpyrrolidinone. The reactor was evacuated and purged with nitrogen another three times. The reaction was heated to 70° C. in an oil bath with a stirring rate of 300 rpm. The grey heterogeneous mixture turned gradually to a red-brown liquid which became more and more viscous with time. The stirring was continued at 70° C. for 10 hours and at 90° C. for 10 hours. At the end of the reaction a dark green-brown viscous material was observed. The crude product was dissolved in hot chlorobenzene (300 mL), filtered through a short alumina column to remove the zinc dust. The filtrate was concentrated on a rotavapor to ˜100 mL and the solution was once again passed through an alumina column eluted with THF. The volume of the solution was reduced to ˜100 mL and the polymer was precipitated with acetone (500 mL). The product was collected by filtration, washed with acetone and dried in a vacuum oven at 60° C. overnight to give 9.53 g (93%) of light-yellow powders. The properties of the polymer are listed in Table I. The polymer of this example is useful for hole transport materials in light-emitting diode devices.
An electroluminescent device was fabricated by forming a film (about 80 nm thick) of the polymer of Example 13 by spin coating from a 3% solution in chlorobenzene on ITO-glass (20 ohm/square sheet resistance). This film serves as the hole transport layer. A 2% toluene solution of an emitting polymer, poly(9,9-disubstituted fluorine-2,7-diyl), was applied on top of the hole transport layer by spin coating giving a film of about 100 nm in thickness. Calcium metal was then deposited on top of the emitting polymer by thermal evaporation, serving as the cathode. Upon applying forward bias to the device, blue light was observed at about 9 volt. Light output of 130 cd/m2 was observed at 16 volt, current density of 10 mA/cm2. A similar device without the hole transport layer had a turn-on voltage of about 11 volt, and light output of about 3 cd/m2 at 14 volt, current density of 10 mA/cm2. This illustrates the improvement attainable with the hole transport polymer of this invention.
m is a number of from about 5 to about 500.
m is a number of from about 5 to about 100.
and m is a number of from about 5 to about 100.
6. A process for the preparation of a composition according to claim 1 which comprises contacting one or more monomers corresponding to one or more of Formulas (II) and (III): ##STR6## with a catalytic amount of a divalent nickel salt, at least a stoichiometric amount of a material capable of reducing the divalent nickel ion to the zero valent state and a material capable of acting as a ligand and an amount of a compound capable of accelerating the reaction in a polar solvent and an optional co-solvent comprising an aromatic hydrocarbon or ether under conditions sufficient to form said composition.
7. The process of claim 6 wherein the monomers are prepared by contacting a haloaromatic compound with one or more diaryldiamines corresponding to one or more of Formulas (IV) and (V): ##STR7## under conditions such that compounds of Formula (II) or Formula (III) are formed.
wherein A and B are independently in each occurrence a hydrogen or halogen and Ar1 is independently in each occurrence a C6-18 aryl moiety optionally substituted with a moiety that does not interfere in the polymerization reaction.
9. The process of claim 8 wherein A is hydrogen, chlorine or bromine and B is bromine or iodine and Ar1 is independently in each occurrence derived from napthalene, biphenyl, anisole, methoxynapthalene, methoxybiphenyl, benzene or toluene.
10. The process of claim 9 wherein one or more compounds of Formula (IV) and (V) are reacted with compounds of Formula (VI): A--Ar1 --B in the presence of a catalyst.
11. The process of claim 10 wherein the catalyst is copper powder or palladium and tri-o-tolylphosphine.
12. The process of claim 11 wherein the amount of catalyst is about 0.1 mole percent to about 1000 mole percent relative to the amount of the haloaromatic compound.
13. The process of claim 6 wherein the divalent nickel salt is present in am amount of from about 0.1 to about 10 mole percent based on the amount of monomer, the material capable of reducing the divalent nickel ion to the zero valent state is zinc powder and is present in an amount of about 10 to about 500 mole percent based on the amount of monomer, the material capable of acting as a ligand is triarylphosphine and is present in an amount of about 10 to about 100 mole percent based on the amount of monomer and the amount of compound capable of accelerating the reaction is present from about 10 to about 100 mole percent based on the divalent nickel salt.
14. The process of claim 6 wherein the temperature of the reaction is about 50° C. to about 150° C.
15. A film comprising the composition of claim 1.
16. A process for the preparation of a film comprising applying a composition according to claim 1 to a substrate and exposing the applied composition to conditions such that a film is formed.
17. The film of claim 15 which has a thickness of from about 0.01 to about 200 microns.
Adachi, Chihaya et al., "Confinement of Charge Carriers and Molecular Excitons with in 5-nm-thick Emitter Layer in Organic Electroluminescent Devices with a Double Heterostructure", APPL. PHYS. LETT., vol. 57, No. 6 (Aug. 6, 1990).
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Kuwabara, Yoshiyuki et al., "Thermally Stable Multilayered Organic Electroluminescent Devices Using Novel Starburst Molecules, 4,4', 4"-Tri(N-carbazolyl)triphenylamine (TCTA) and 4,4', 4"-Tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), as Hole-Transport Materials", Advance Materials, vol. 6, No. 9, pp. 677-679 (1994).
loyda et al., Bulletin of the Chemical Society of Japan,vol. 63, pp. 80-87 (1990).
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Everyone handed in their notecards. I'll hand them back tomorrow.
Then we did a journal entry: In any of the books you've read so far, identify a "plot hole" or "convenient plot thread"; that is, something that seems to happen for no other reason than to move the story along.
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Within the eve in the NHL trade deadline, a couple Canadian groups that figure being sellers are scratching pending UFAs who're likely to be moved.In the event the puck drops on Sunday night's Vancouver-Arizona video game, we'll be described as a tiny over fifteen several hours away from the deadline. And since of that, the Canucks will scratch Thomas Vanek. All right, it is verified. #canucks will never dre s Vanek tonight vs . #Yotes Dan Murphy (@sportsnetmurph) February 26, 2018Vanek, 34, is on https://www.stylepanthers.com/florida-panthers-jersey/roberto-luongo-jersey an expiring deal and established to be an unrestricted free of charge agent in the summer. He's scored seventeen plans and 41 details in 61 video games this year which is considered to become out there to the trade market. Wherever Rick Nash (dealt to Boston) and Evander Kane were being recognized as being the top readily available scoring wingers, Vanek firmly matches in like a secondary alternative. The Canucks chose to maintain him out in order to avoid injury and never nece sarily due to the fact a trade is imminent.Source thinks it is a precautionary go and never because they may be near a trade. https://t.co/KCW2ge7gFp Rick Dhaliwal (@DhaliwalSports) February 26, 2018Source : Quite silent on the Vanek entrance, some bigger name forwards need to go right before Vanek market receives extra set up. #Canucks really should obtain a 3rd or 4th spherical pick. Rick Dhaliwal (@DhaliwalSports) February twenty five, 2018Vanek was dealt finally year's trade deadline, way too, relocating from Detroit to Florida for Dylan McIlrath as well as a third- is viagra right for me, is viagra right for me, is viagra right for me, is viagra right for me, is viagra right for me, is viagra right for me, is viagra right for me, is viagra right for me. James Reimer Jersey round choose. He scored just two goals in 20 games together with the Panthers, and afterwards signed a one-year, $2 million agreement with Vancouver in the summer.In the meantime, the Edmonton Oilers are in Anaheim to encounter the Ducks and declared they're going to scratch Pat Maroon. The 29-year-old winger experienced now skipped the prior two Oiler video games having a lower-body harm, though the group noted tonight's go was a nutritious scratch. Patrick Maroon (balanced scratch) & Kris Ru sell (hand) will likely not play for the #Oilers tonight in Anaheim. Edmonton Oilers (@EdmontonOilers) February 26, 2018Maroon has 14 plans in 57 online games this period, 1 year after posting a career-high 27. He is also set to become a UFA at the end in the time and is particularly expected to go in advance of the deadline. Micheal Haley Jersey india pharmacy paypal, india pharmacy paypal, india pharmacy paypal, india pharmacy paypal, india pharmacy paypal, india pharmacy paypal, india pharmacy paypal, india pharmacy paypal. I packed heavy, Maroon said before the weekend since the Oilers headed out on a road trip.


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L'abadia de Sant Tomàs és un monestir de l'Orde de Sant Agustí, situat a Brno, a la República Txeca. Va ser la llar del genetista i abat Gregor Mendel, que entre 1856 i 1863 va dur a terme, a l'hort de l'abadia, els seus famosos experiments amb pèsols que el van portar a proposar el que després es va conèixer com a lleis de l'herència de Mendel. És l'única abadia agustiniana al món. Allotja un museu dedicat a Mendel. L'església està dedicada a l'Assumpció de la Mare de Déu.

Els agustins van arribar a Brno el 1346, i van aconseguir el patrocini de Jan Jindřich Lucemburský, marcgravi de Moràvia, per a la construcció del claustre primitiu el 1352. El 1653 la comunitat es va traslladar a la ubicació actual. La noble local Sybil Polyxen Františka va fundar en aquesta època una escola musical en el monestir, tradició que es manté en l'actualitat. El compositor txec Pavel Křížkovský va ser agustí al monestir i professor de música litúrgica entre 1848 i 1872. El compositor Leoš Janáček va començar la seva formació musical en el cor del monestir.

Galeria

Referències

Edificis de Brno
Monestirs catòlics
Convents agustins
Leoš Janáček

redpajama_set_name: RedPajamaWikipedia


A few weeks back, I was talking to someone who knows a fair bit about pain. They shared with me the fact that they were experiencing quite significant back pain; had been for a few days after a relatively minor incident. They explained that the pain was pretty severe at times, had interrupted sleep and most movements were reduced and painful. They weren't too concerned, thought it likely that there was a bit of inflammation going on but the whole thing would settle down and eventually go away with a bit of time and some carefully graded movement and activity.
What a powerful and privileged position we are in as clinicians and therapists when people in trouble come to see us- those precious minutes spent on education that can lead to new understanding, the reduction of fear and the abatement of suffering.
"It's exactly what should be happening" – What a powerful and graceful move to make in the dance that is therapy! How do people usually respond? I'm guessing a bit of shock, a bit of surprise and then some curiosity?
A few grey hairs helps with the delivery but the response is usually one of relief…….." Really, it's normal" …." Wow that's a relief" …….


When I spotted this recipe in the latest issue of Food & Wine, there was little doubt I would try it. Melted ice cream in hot chocolate? Um yes, I must. And while it's a little bit naughty, it's perfect for those special holiday moments, when you can sit down, exhale and indulge a little.
True, this melted ice cream hot chocolate recipe with toasted marshmallows is a little bit naughty, but oh so nice!
For the marshmallows, I used homemade marshmallows that I toasted with my kitchen torch. If you need a great homemade marshmallow recipe, try the one on my site from Butter Bakery (less the coconut). Of course, big store-bought marshmallows will work well, too. If you don't have a torch, simply place the marshmallows on a foil-lined baking sheet under the broiler and without taking your eyes off them for even a second, cook until golden brown and puffy.
A special hot chocolate that's just a bit different. You can use vanilla ice cream or experiment with other flavours like coffee ice cream. For the marshmallows, use either homemade or store-bought. I like to start with 2/3 cup of cocoa and add from there, as cocoa powders vary in their intensity.
Ladle in to mugs and top with large marshmallows. Using a kitchen torch, heat marshmallows until golden. (If you don't have a torch, line a baking sheet with foil and place marshmallows under the oven broiler. DON'T TAKE YOUR EYES OFF THEM! Cook until golden and puffy, then use a spoon to place on top of hot chocolate.
This is unbelievable!! Love it!
Holy cow. What have you done here! This is off the charts!
I was dying to see this recipe and your photos – and it was well worth the wait! I've never added ice cream to hot chocolate and I drink a lot of hot chocolate! That will change the next time I have hot chocolate!
Thanks so much, Jessica. It was one lovely cup of hot chocolate!
This sounds absolutely heavenly. I could just climb into one of those cups!!
Thanks so much, Christie. It was luscious!
Can I melt a little of my whiskey ice cream in there? That would be really nice :) And I love your spoon!
Whiskey ice cream?! That would be very nice :) Thanks Sue.
This looks like the best hot chocolate, I adore the toasted marshmallows!
Goodness, this is the picture of winter indulgence… I love it! The pictures for this recipe are really striking, love the antique spoon!


text:
Steinbecke ist der Name von:

 Steinbecke (Möhne) (GKZ: 2762152), Nebenfluss der Möhne in Nordrhein-Westfalen, Deutschland
 Steinbecke (Valme) (GKZ: 2761212), Nebenfluss der Valme in Nordrhein-Westfalen, Deutschland
 Naturschutzgebiet Steinbecke in Brilon, Nordrhein-Westfalen

Siehe auch:
 Steinbeck


To take full advantage of this new finding, Cuba is developing seven ostrich farms around the island. Some already have been built in the provinces of Holguín, Santiago de Cuba, Guantánamo, Granma and Havana, and another will soon open in the Isle of Youth, the comandante said. The first ostriches, of the blue, red and black-necked families, were imported from Mexico in 1997 and were later cross-bred.
His announcement of the ostrich farms was quickly met with sarcasm, jokes and memes on social media.
Orta, from Cienfuegos in central Cuba, added that her family had spent weeks looking to buy a "carton of eggs" without luck.
The shortages of basic products, chronic because of the perennial crisis in the Cuban economy, have sharpened recently because of the ongoing political crisis in Venezuela and cooling relations with Brazil, where Cuba bought most of the chicken consumed on the island.
Mayra Ocampo, also from Cienfuegos, recalled the crisis known as the "Special Period," when Cuba lost its subsidies following the collapse of the former Soviet Union in the early 1990s. Like many Cubans, she fears that the long power blackouts and "ground beef of soy" will return if the Nicolás Maduro regime in Caracas collapses.
"In those years, people got sick because they didn't eat. We had nothing. Fidel distributed chicks on the ration card to raise them at home. Those who got hens were supposed to have eggs. Mine died because I had nothing to feed them. I lived on a fifth floor and they made a mess all over," Ocampo said.
Also famous on the island were the miniature cows, the size of goats, which could be raised in urban areas and produce milk that the government could no longer provide.
Claria was introduced to Cuba in the 1990s because of their quick reproduction and to fill the growing demand for fresh fish. It is raised in freshwater ponds but can crawl on land, is considered one of the world's 100 most invasive species and has left the island without trout, biajaca and other endemic freshwater species.


text:
Michael David Rapaport (* 20. März 1970 in New York City) ist ein US-amerikanischer Schauspieler und Komiker.

Leben
Nach der Highschool ging Rapaport nach Los Angeles, um dort als Stand-Up-Komiker sein Geld zu verdienen. Seine erste große Filmrolle hatte er 1992 in Zebrahead. Für diesen Film war Rapaport 1993 für einen Independent Spirit Award als bester Hauptdarsteller nominiert. In den folgenden Jahren spielte er in Filmen wie True Romance, Geliebte Aphrodite und Deep Blue Sea.

Von 2001 bis 2004 spielte Rapaport eine Hauptrolle in der Fernsehserie Boston Public. Hiernach war er in der Sitcom Familienstreit de Luxe zu sehen, die auch unter dem Namen Hinterm Sofa an der Front auf RTL II ausgestrahlt wird. In der vierten Staffel der Serie Prison Break spielte Rapaport einen Agenten des Ministeriums für Innere Sicherheit.

Des Weiteren spricht Rapaport im Intro des Musikvideos What Happened? der Hardcoreband H2O. Zudem spielte er im Musikvideo von Jay-Z feat. BLACKstreet – The City Is Mine und im Video Wanna (But I Won't) der Gruppe The High and Mighty vom Album The Highlight Zone mit.

Im Jahr 2011 übernahm Rapaport erstmals die Regie eines Dokumentarfilms. Beats Rhymes & Life – The Travels of A Tribe Called Quest zeichnet den Werdegang der Hip-Hop-Gruppe A Tribe Called Quest von ihrer Gründung bis zur Reunion-Tour im Jahr 2008 nach.

Filmografie (Auswahl)
 1992: Zebrahead
 1993: Codename: Nina (Point of No Return)
 1993: Poetic Justice
 1993: True Romance
 1993: Der Prinz von Bel-Air (The Fresh Prince of Bel-Air, Fernsehserie, Episode 4x01)
 1994: The Foot Shooting Party (Kurzfilm)
 1994: Der Scout (The Scout)
 1995: Higher Learning – Die Rebellen (Higher Learning)
 1995: Kiss of Death
 1995: Geliebte Aphrodite (Mighty Aphrodite)
 1996: Beautiful Girls
 1996: Der Zufallslover (The Pallbearer)
 1997: Metro – Verhandeln ist reine Nervensache (Metro)
 1997: Emergency Room – Die Notaufnahme (ER, Fernsehserie, Episode 4x20)
 1997: Cop Land
 1998: Palmetto – Dumme sterben nicht aus (Palmetto)
 1998: Der Organ-Mann (The Naked Man)
 1999: Deep Blue Sea
 1999: Friends (Fernsehserie, 4 Episoden)
 2000: Schmalspurganoven (Small Time Crooks)
 2000: King of the Jungle
 2000: Men of Honor
 2000: Chain of Fools
 2000: Lucky Numbers
 2000: The 6th Day
 2000: Next Friday
 2000: It's Showtime (Bamboozled)
 2001–2004: Boston Public (Fernsehserie, 57 Episoden)
 2002: Triggermen
 2002: 29 Palms
 2003: Eine gute Nacht zum Sterben (A Good Night to Die)
 2003: Chappelle's Show
 2003: This Girl's Life – Mein Leben als Pornostar (This Girl's Life)
 2005: Hitch – Der Date Doktor (Hitch)
 2005–2007: Familienstreit de Luxe (The War at Home, Fernsehserie, 44 Episoden)
 2006: Verbraten und Verkauft (Grilled)
 2006: Special
 2007–2008: My Name Is Earl (Fernsehserie, 6 Episoden)
 2008: Lange Beine, kurze Lügen und ein Fünkchen Wahrheit … (Assassination of a High School President)
 2008–2009: Prison Break (Fernsehserie, 22 Episoden)
 2010: Royal Pains (Fernsehserie, Episode 2x11)
 2010–2013: Pound Puppies – Der Pfotenclub (Pound Puppies, Fernsehserie, 64 Episoden, Stimme)
 2011: Inside Out
 2011: Beats Rhymes & Life – The Travels of A Tribe Called Quest (Dokumentarfilm, Regie)
 2012: Kiss of the Damned
 2012: The Baytown Outlaws
 2012–2013: The Mob Doctor (Fernsehserie, 7 Episoden)
 2013: My Man Is a Loser
 2013: Taffe Mädels (The Heat)
 2014: Justified (Fernsehserie, 13 Episoden)
 2015: Louie (Fernsehserie, Episode 5x03)
 2015: The Big Bang Theory (Fernsehserie, Episode 9x06)
 2015: Public Morals (Fernsehserie, 10 Episoden)
 2015: Little Boy
 2016: Sully
 2016: Law & Order: Special Victims Unit (Fernsehserie, Episode 17x19 – Obdachlos)
 2016: Chuck – Der wahre Rocky (Chuck)
 2017–2021: Atypical (Fernsehserie)
 2022: Only Murders in the Building

Weblinks

Einzelnachweise

Filmschauspieler
Komiker
US-Amerikaner
Geboren 1970
Mann


Thank you for purchasing your tickets to PWA: Black Label - Lock, Stock and TOO SWEET Barrels on Friday, January 19, 2018 at 8 PM - 11 PM. Your seats have now been reserved to make sure you're as close to the action as possible.
We look forward to providing you with a fun night filled with cheers, laughs and high-intensity pro wrestling action.
You should receive your e-tickets via the email. Please retain and bring your e-ticket receipt on the night as proof of purchase, either printed or on a smart device.
Can't wait to get your fix of Pro Wrestling Australia? You can watch full PWA events including Call to Arms featuring Will Ospreay via our PWA On Demand service.
Please note: If you have purchased a ticket(s) and are unable to attend, you have the choice of changing your ticket(s) to a future event or being issued a refund. No changes or refunds are permitted within 24 hours of the event. If you have not received your digital e-ticket please Contact PWA via the contact from linked or through our social media linked below.


Josh will face Dennis Tubieron in an official eliminator for the WBC World Featherweight title at the First Direct Arena in Leeds on April 11, live on Sky Sports.
Josh is aiming to continue his meteoric rise over the last year inside his intimidating fortress and pick up the vacant WBC International crown in the process, but faces a tough task in the shape of 'The Scorpion' from the Philippines, who boxed for that title in December with his clash against Carlo Magali ending in a controversial draw.
The Leeds star has seen off Samir Mouniemne, Rendall Munroe, Martin Lindsay and Davide Dieli in a dazzling run of displays, and with a raucous hometown army behind him, he'll be aiming to crash into the rankings in style on April 11, with a trip to Berlin on the undercard of Paul Smith's World title rematch against Arthur Abraham to come first on February 21.
Welsh star Nathan Cleverly will return to action in the Light Heavyweight division as he targets German WBA champ Jurgen Braehmer while Martin J Ward will rematch Maxi Hughes in a British title eliminator following their exciting draw in London at the end of 2014. Leeds man and British Light Heavyweight champ Bob Ajisafe features as part of a big line up to be announced over the coming weeks.
Tickets are on sale from 10am on January 7th to Matchroom Fight Pass members from www.matchroomboxing.com priced at £30, £40, £60 and £120 for VIP tickets.
Tickets go on general sale at 10am on January 8th from the First Direct Arena on 0844 248 1585 and at www.firstdirectarena.com. VIP tickets priced at £120 are available exclusively from Matchroom Boxing on 01277 359900 and at www.matchroomboxing.com.


2011: The year of playfulness?
Home/Book review/2011: The year of playfulness?
"Before we get to the fun, don't be misled. This book has a serious message and one that everyone in business in the current climate should pay heed to. The authors – one half of the Eurythmics plus a brandman who's worked with everyone from Coca-Cola to Al Gore's Alliance for Climate Protection – are on a mission to reignite creativity in the workplace. Kids, they say, are instinctively creative. But not only do we lose this skill as we grow up, organisations often obstruct creative behaviour. So, over twelve chapters, they share enough examples, tools, inspiration and insights to enable even the most process-driven employee to get creative.
Now to the games. From the contents list laid out like a board game ("try rolling a dice to tell you which chapter to read next") to the brightly coloured pages that look like someone has read the book before you and highlighted all the useful bits, this is a joy to read. Unlike other cringeworthy attempts at humour in business books, the playful computer-game-like characters and deadpan jokes work. But the real value in all this 'fun' is in the board games at the end of each chapter. Want to come up with as many ideas a possible? Throw some prompter topics into a bowl, connect them each to a fork with a piece of string, mix them up and play idea spaghetti: pick a fork, follow the tangle to the prompter and see how many ideas you come up with in the next five minutes. The player with the most ideas after four rounds wins. Stuck for inspiration on a big problem? Spin a pencil round the wheel of distraction and follow the instructions. You might be told to go for a walk, do a crossword puzzle or have a vodka martini. As the authors say, even if the distracting activity doesn't send you straight to the lightbulb moment, at least you'll have had a good time.
So, if you're desperate for an effective new year business resolution, why not make 2011 the year of playfulness?


text:
Former oilman Parker wakes the sleeping Kerkorian
By David Migoya
Delta Petroleum, oil and gas, roger parker
Somewhere along the line, bankrupt oil exec Roger Parker ticked off the folks at Tracinda Corp, awakening a sleeping dog that is now gnawing on the bones and sucking at the marrow of the skeletal remains.
Parker, 51, is the former CEO at Delta Petroleum and later Recovery Energy who the Securities and Exchange Commission says is the guy responsible for fueling insider trading deals that netted nearly $800,000 for its participants who sold Delta stock in 2008.
[media-credit name="Denver Post file photo" align="alignright" width="270″][/media-credit] Back in the day, Roger Parker was chairman and CEO of Delta Petroleum.
That happened, the SEC says, when Parker let buddy Michael Van Gilder and an as-yet-named individual know that billionaire investor Kirk Kerkorian and his Tracinda outfit were looking to make a major buy-in to Delta. On that info, the insiders bought, then sold Delta stock when Tracinda's $684 million purchase became public.
That's not the sleeping dog part.
Along the way of their partnership, Tracinda ended up loaning Parker $7.5 million to cover a shortfall of Delta stock Parker had margined, having pledged his shares as collateral. The call happened in November 2008 when Delta stock fell below $4.
In court papers, Tracinda said it made the loan because it wanted Parker to pay attention to keeping Delta afloat — and to saving Kerkorian's investment. That patience lasted until May 2009 when Parker was asked to resign as CEO and chairman of the board.
Kerkorian, through his people, had spoken.
What was left unfinished was the business of the loan, even though Delta awarded Parker with a very nice $7 million severance payday.
Tracinda sued to collect. Parker sued back. Tracinda won.
When Tracinda went to collect, they found only a few thousand dollars in a retirement account for a man who's annual income easily topped $1 million.
There was one thing of value — sort of. Parker had joined a new venture called Recovery Energy, which had many of Parker's buddies involved in some manner. That included disgraced insurance man Michael Van Gilder, who's the only one yet charged in the SEC case of insider trading.
On joining the firm in November 2009, Recovery gave Parker 1 million shares of stock, adding another 4.5 million shares in May 2010 when he was named is CEO. The shares were all set to vest in January 2011, but that didn't happen.
By October 2011, the 5.5 million shares shriveled to 1.375 million shares because of a 4:1 reverse stock split.
Tracinda has been chasing those stocks around in an effort to collect on the loan ever since, but Recovery kept rewriting its deal with Parker — 13 different times — and vesting of the stock kept being put off.
Here's the angry dog part.
When Parker filed for personal bankruptcy last month, he listed Tracinda as his largest single creditor at more than $7.6 million.
Last week, a bankruptcy judge approved Tracinda's request for a Rule 2004 exam — legal-speak for a chance to root around through Parker's and Recovery's books.
Why? "The propriety of the repeated extension of the vesting date of the Granted Shares and whether that transaction constituted a fraudulent conveyance under the Bankruptcy Code and/or state law," is how Tracinda says it in court records.
Put simply, Tracinda wants to know if Parker colluded with Recovery in putting off the vesting in order to avoid Tracida's collection efforts.
So now, not unlike the bankruptcy case of radio pitchman Tom Martino, who upset a bank enough for them to try and prove he intentionally hid assets in order to avoid collection — a no-no they were never able to prove — Tracinda has a change to lift up Parker's skirt, per se, and have a looksie at what was going on at Recovery.
There might be something; there might not. But Tracinda seems to be pleased enough to know it's making things uncomfortable for the oilman.
Comments Off on Former oilman Parker wakes the sleeping Kerkorian
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Alicia Wallace is a general assignment business reporter at The Post whose coverage spans tech to bioscience to beer. She's also a data geek who actually enjoys delving through SEC filings.
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text:
Агбалян () — имя собственное; распространено в виде армянской фамилий.
 Агбалян, Гор (род. 1997) — армянский футболист, играющий на позиции полузащитника.
 Агбалян, Никол (1875—1947) — армянский политический и общественный деятель.