text:
Is their any way of listing the minutes taken on each particular job, or is ot only the hours you can view?
Our company needs to be able to see the exact time each job has taken, and the existing reports only show "<1 hour" which just isnt enough information.
Can anybody help me on this?
1 Reply
· · ·
Jan 9, 2008 at 11:59 UTC
There is not currently a way to drill down to the minutes. I believe several people have asked for this so hopefully we'll be able to implement something shortly.
This discussion has been inactive for over a year.
You may get a better answer to your question by starting a new discussion.


text:
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I offer counselling and psychotherapy to individuals (adults and young people aged 14 plus) I also work with couples providing relationship and sex therapy. I am accredited by both the BACP and UKCP and a member of the College for Relationship and Sex Therapy (COSRT).
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2003 the Westminster Pastoral Foundation, London (Roehampton University); Psychodynamic psychotherapist. I am a professional member of the Foundation of Psychotherapy and Counselling (FPC).
2004 to the present; Further specialist training with young people firstly at the Wimbledon Guild Youth Service, the Valley Trust Schools service and most recently with Relate as a young peoples counsellor.
The London Diploma of Relationship and Sex therapy; 2012 (Middlesex University). I continue to hone this skill taking on the third year at Advanced level.
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subset: commoncrawl


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Sign in to retrieve a saved callback list.
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Invoice history based on 6 reviews.
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Bumpitty bumpbump
Alrighty, I have an AQW account that I do use a lot, but it is only a level 45 and I would prefer to have a level 65 or a class with good classes. It comes with 3 rare classes, and the rarest house in the game, which is the Vacation Castle of Nulgath.
Skype: XCalibre AQW. Only contact me if you are serious, I don't do maybes. Will send link to photo album upon contacting me.
Last edited by XCalibre2552; 11-30-2015 at 11:36 AM. Reason: Changing WTS to WTT, made a mistake xD
Bumpitty bumpbump
upload the pictures as attachments.
Vouch Copy Profile
MPGH Achievements:
Member - 21 January 2012
Donator - 12 August 2015
BattleOn Minion - 11 September 2015
DayZ Hacks Minion - 6 December 2015
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Call Of Duty Hacks & Cheats Minion - 2 January 2016
Lifes but a walking shadow, a poor player
That struts and frets his hour upon the stage
And then is heard no more.


text:
Happy sweater weather, oona-naut! What are you reading as the colors turn? We're leafing through the following:
• Every aesthetic movement needs its bard, & life in the suburbs is no exception. Check out our (r)'s interview with Stephen Burt about his new book, Belmont (Graywolf, 2013), over at Bookslut.
• We're pretending David Shook's Our Obsidian Tongues (Eyewear Publishing, 2013) is a notebook Jerome Rothenberg lost on his way back from the field. ("The sun rises each morning without human sacrifice./The misery of the city is enough" (13)).
• We read Vijay Seshadri's 3 Sections (Graywolf, 2013) in the heat of summer, & we still can't shake this poem:
Family Happiness
On our first date, I told my wife
I was a lesbian trapped in the body of a man.
Everybody says that now, of course,
on TV and radio, alternative media outlets,
tattoos and bumper stickers, but this was long ago, when
none but the brave (who deserve the fair)
would come up with something like that.
She smiled the pleased and goofy smile that flowers in her big eyes,
and I thought I had her.
Looking back now, though,
I can see her appraisal of me rounding to completeness.
I can hear her cognition firing.
She knew it. She knew even then
the truth it has cost me the aeons to acquire,
climbing and climbing the broken stairs:
I'm a man trapped in the body of a man.
I clutch the smooth walls and see through his eyes
the oil fires and containment units,
the huge clawed gantries strung out on the twilit polar horizon.
Through his alloyed ears, I hear
the objects of his scorn, his compassion, his hatred, his love
crying out and crying out.
Half my arms are his arms.
Half my face is welded to his face.
The other half mouths his clumsy ironies.
"Life is war," he says.
"Tragic," he says. "Tragic."
The simulacra are marching everywhere,
and deep in the caves the chimeras are breathing.
Hey, Vijay. (May we call you Vijay?) Elizabeth Bishop & Philip Larkin called. They want their collaborative poem back.
• It's fitting that we came to Kristina Marie Darling's Melancholia (An Essay) (Ravenna Press, 2012) a little late, invested as it is in Romantic refractions, in ephemera, in the postscript and the footnote, in definitions & redefinitions. ((("you were like bits of broken glass/when the jewelry box shattered//night & the ocean's coldest shore" (2).)))
• Speaking of cross-genre experiment, we're fascinated by Martha Ronk's Transfer of Qualities (Omnidawn, 2013), a book of prose poems that crosses over into experimental criticism. ("Hamlet refers to 'the book and volume of my brain,' and with the one word, 'volume,' points simultaneously to books as volumes of written words and to the volumes of space inside the globe of his skull. The oscillation of the two meanings, between the 'book' as mentally conceived and the book as an object to be picked up and held, a thing to be read, the volume Ophelia, as directed by her father--'Read on this book, that show of such an exercise may colour your loneliness'--lures him with, makes a reader of the play helplessly intimate with this character who is as mere words as unreal as the clouds he sees as camels or at least says he sees, an insubstantial pageant" (35). Exegesis as the only thing that's truly lyrical? You're preaching to the choir.
• & while we're heading back to school (see! we told you, you can trust us), let's not forget Ciaran Carson's IN THE LIGHT OF (after illuminations by arthur rimbaud) (Wake Forest University Press, 2013), the kind of literary/critical homage we wish we could (let ourselves) write. It's a translation of a translation in the tradition of Spicer's After Lorca--"I've brewed my blood. Paid all my dues. I really do come/from beyond the tomb. Commissions? That I've done" (34).
Our trend forecast? Poetry is/as criticism, translation, & afterthought. A new identity politics. The best of the bad modernisms making a comeback. Plaid & lace. However you pull it all together, school's definitely in session.
Yours ever,
R & (r)
Sunday, September 22, 2013
Tuesday, September 3, 2013
Across the Oonaverse: Bath, England
Dear (r),
Jane Austen lived here slash didn't like it.
But, as I hope we've established by now, I'm not Jane Austen.
I picked up Carrie Etter's The Tethers (Seren Books, 2009) & a self-published chapbook by James Anderson called Zebra Skin (ephemera & Rimbaudelairianism being among my many weaknesses).
Perfectly curated Mr. B's Emporium of Reading Delights, my new favorite bookshop
(the cozy chairs tell you everything you need to know)
Can somebody tell me what "glocal" means?
I liked Anderson's pamphlet/chapbook most for its postcard-like qualities ("I tied a lock to the bridge and writ J & Bath" & "Bath is a dream from which I never wake") & for its cross-genre staging of textual encounters ("The stranger had a single espresso and rested a selection of books on the table [...] she understood herself at a wholly new angle, which would not have happened had she been with someone familiar").
Speaking of, I was so glad to encounter Carrie Etter's book, which articulates its own timid, reluctant, almost logistical faith:
[...] Poseidon, the presumably
not arbitrary god who saved them.
[...] so I listened
with dismissive boredom
and watched the girl who spoke
of souls in all creatures
breaking pencils in her lap one by one
through a once inexhaustible supply.
bank to bank: there is no universal
for what keeps us aloft, but O
I cherish it.
All day, each day, the world was at dusk,
the change of light incidental.
When at last I walked to the postbox, afternoon
was everywhere. I had decades to live.
Dear (r), skepticism can be pretty gorgeous, no?
I read Anderson & Etter (& also Austen (The Watsons)) on the lawn in front of the Royal Crescent. There was a guy with an aggressively loud boom box, so I also listened to some classic reggae hits.
Did the Romans read in the bath?
& then I left on a train. That's pretty much it. Tell me where you're headed next.
Yours always,
Subscribe to: Posts (Atom)


text:
My name is Jamie Farquhar and I am a personal tennis instructor. I have over 20 years experience working in the tennis coaching industry, working previously at one of the most exclusive members clubs in London (The Harbour Club, Chelsea), head coach at Rocks Lane,Chiswick and Matchpoint Tennis Camps in East Sussex during Easter and summer holidays.
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24 Feb 2015
Keeping Faith?
Ten years ago, one seldom heard the term 'faith school'. Come to that, fifteen years ago the words 'Muslim', 'Islamist' and 'Jihadist' were not common in everyday parlance. Even a year ago, few would have imagined that Coptic Christians would have been murdered because they were Christian. Or that Jews could be murdered in a Paris supermarket or a Copenhagen street because of their faith.
Suddenly, we can't escape religion and the things done in its name.
The effect of this is – as much as anything – to make us aware of difference. I am one of these, you are one of those.
Whereas this country has striven for decades to value difference and even celebrate it – with obvious heinous lapses and misguided attempts at maintaining separateness now, largely discredited – it now seems urgent that we foster what we have in common and celebrate what unites us rather than what divides us.
More children than ever are now being taught in 'faith schools'. The number of such schools is increasing and many schools – Roman Catholic schools, in particular, fuelled by the burgeoning population of Polish families among others – are expanding to take in larger numbers. There are Jewish schools and Muslim schools – or de facto Muslim schools, as we have found in some of our conurbations.
Many such schools are excellent. Results are good, discipline exemplary. Parents and pupils are happy. But such schools are – in essence – divisive. Our friends are from families like ours. Our community is one defined by a shared faith. We are different from people who go to schools founded on a different faith or on no faith at all.
A confident, mature society is one in which we trust each other. We know our neighbours and trust people who look different, dress differently, have different customs. In an anxious, threatened society, we close our doors, are friends only with people like us, shut our minds to people whose ways of life are not ours.
Is it time to reconsider our increasingly segregated schools and to ask ourselves whether the young people they produce are prepared for the open, pluralist society most of us believe in?
04 Feb 2015
The Best School?
"We want the best school for our children." I hear this from new clients every day. It is little use my explaining that the best school for one child may not be the best school for a different child. The 'best' school in the minds of many of the people who call us is the one with the best results, the one which sends the largest numbers of leavers to Oxford, Cambridge, Harvard and the like.
I explain to these people that a school which selects at 11 or 13 the children who perform most impressively in their very exacting, carefully tuned and expensively commissioned entrance tests will have very little to do thereafter. These children learn fast, like learning and have fierce intellectual curiosity. True, such schools can employ outstanding academics who will stimulate and fire their sparky pupils but these pupils will achieve highly because they have the aptitude and the motivation.
They would, in all probability score highly wherever they went to school.
The fact of their attending St Plodge or Witmaster will not make them cleverer. In some cases, if they are not mini Hawkings or small Turings, it might make them stupider. This is because, children of less than outstanding ability can quickly lose confidence when surrounded by people whose brains work faster than the Large Hadron Collider and absorb more than a J-cloth. They become demoralised, switch off and drop out.
Conversely, sending bright children to good schools where they will be enabled to maximise their strengths, minimise their weaknesses and shine in some aspects of the curriculum will enhance their confidence and allow them, in many cases, to perform beyond expectations. Such a school will be the 'best' school for them even if its results and the number of Oxbridge entrants it achieves do not, at face value, look so impressive.
This may be hard for some parents to accept but it is true and derived from thirty-five years' experience working with parents and with schools to find the best schools for each, important, child.
As we say:
Your child – nothing matters more.
21 Jan 2015
We're terribly sorry, Mrs Romanov, but….
It had to happen. The last five years have seen an unprecedented surge in numbers of pupils from overseas coming to our boarding schools.
We Were Glad
Russian, Spanish, Chinese and children from the UAE in particular have found beds, desks and happiness in our turreted sanctums of juvenile scholarship. Blissfully, they wallow in team games, shepherd's pie, uniforms and Latin. Khazak whoops of triumph echo from cricket nets, Japanese youngsters strut their musical stuff in O for The Wings of the Dove and Parry's I Was Glad is raised to the hammerbeam rooftops of countless chapels by everyone from everywhere.
Many of these families are in search of what they like to think of as English "values" as well as of the liberal attributes of our schools. At home – seemingly in many parts of the world – schooling is rigid, relying on rote-learning and drills. Today's global and enlightened parents want the emphasis on personal exploration and thinking skills that our good schools encourage. And we have welcomed them and their bankers' drafts.
Enough already?
Until now. All of a sudden we are being told by harassed registrars – "We simply cannot take any more Russians – however good their English." Or "Twenty per cent of the year group is Spanish – that's enough." And, of course, foreign nationals themselves always say to us – "We don't want our children to go to a school where there are lots of other people from here" – wherever "here" happens to be in their case!
But they keep on coming. And their agents keep on coming too. We are approached weekly by agents with overflowing portfolios of rich clients – mostly Russians – who "will" send their children to school here.
Dread word!
On paper, there is no reason why they shouldn't. The children are able, often they have attended international schools so their English is good enough and they have much to offer. Many schools have been kept afloat by a healthy contingent of bright foreign pupils in recent years. But afloat is one thing, submerged is another and the tide is, evidently, turning. We are now getting anxious and hurt calls from parents – usually Russians – asking whether there is now a prejudice against pupils from Russia. The dreaded word "quota" is suddenly whispered everywhere. What are they to do?
But what are schools to do? Overseas families want the Englishness of traditional English schooling. Schools like to be inclusive, welcoming ecumenical. They have become skilled in integrating everyone so that gaggles of pupils chattering in their home languages are seldom found now. Most schools have resisted the temptation to expand in order to accommodate the huge numbers of potential foreign pupils – though the financial inducements would be considerable. But their reluctance to take large numbers from overseas is causing both anguish and anger. And to some extent their hands are tied by UK Border Control legislation, visa regulations and the numbers of overseas pupils they are actually allowed to accept.
Rock of Ages
So something has to change and it is hard to see what since both parents and schools are caught between the rock of the trad English school and the hard place of limitless demand.
We have hitherto been sceptical about the franchises and other school outposts set up by eg Dulwich College, Harrow and Repton in various parts of the world. They are cash cows, as registrars cheerily admit. But maybe they can also be the answer – or part of the answer?
Schools run on English boarding school lines with all the strengths and opportunities that are evidently so much in demand will, perhaps, stimulate indigenous versions in remote parts of the world. A true English export and maybe one we should look at afresh?


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We told you yesterday that the first trailer for The Purge: Anarchy would be hitting this week, and today Universal Horror has confirmed that it will be here as soon as tomorrow!
The sequel stars Frank Grillo, Michael K. Williams, Zach Gilford, Carmen Ejogo, Jasper Cole, Zoe Borde, Chad Morgan, and Kiele Sanchez.
Look for it in theaters on Friday, June 20, 2014.
Writer/director/producer James DeMonaco returns and will be joined by producers Jason Blum, Sebastien Lemercier, and Platinum Dunes partners Michael Bay, Brad Fuller, and Andrew Form.
Prepare for the next Purge. #survivethenight pic.twitter.com/ksEJySM9Hh
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Consumer Goods»Consumer Goods & Retailing»House & Home»Small Appliances
Microwaves in PolandConvenience is the main factor driving sales of microwaves, as Poles are increasingly leaning towards appliances which enable them to save time and ease their everyday lives. Manufacturers are attempting to satisfy the more demanding and diverse needs of consumers by offering multifunctional solutions, making these appliances more attractive to a broader range of consumers.Euromonitor International's Microwaves in Poland report offers a comprehensive guide to the size and shape of the market at a national level. It provides the latest retail sales data 2011-2015, allowing you to identify the sectors driving growth. It identifies the leading companies, the leading brands and offers strategic analysis of key factors influencing the market – be they new product developments, format trends or distribution issues. Forecasts to 2020 illustrate how the market is set to change.Product coverage: Built-in Microwaves, Freestanding Microwaves. Data coverage: market sizes (historic and forecasts), company shares, brand shares and distribution data.Why buy this report?
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3 total
We both have joint legal and physical custody of the kids and the set amount was court ordered and also a part of the divorce decree. Dhs only took over the child support cause of government assistance the mother was getting. Do they have the powe...
Only the Court can modify the Order. DHS can ask the Court to modify it.See question
I live in Mississippi and my case is in Mississippi. My son who is 19 joined the military full time 2 months ago. In MS it states that a child is emancipated at age 21 or joins military full time. I sent DHS his enlistment contract for proof of fu...
It depends on the language of the child support order. Full-time miliatary employment emancipates the child unless the order says otherwise. Even if the child is emancipated, you need to see if the Order provides for automatic termniation of the support obligation. You likely need an Order terminating your support obligation; you can represent yourself or hire a lawyer to get that accomplished.See question
Will a judge in Lafayette County sign off on non-contested papers if my husband and I can come to agreements as long as it is in best interest of our children? Will the judge change anything that we have already negotiated and agreed to? My husb...
1. Generally, yes, as long as your agreement falls in line with statutory support requirements and other legalities.
2. Maybe, if he believes your agreement violates the law, is unreasonable or is not in the best interest of the children.
3. Your husband must properly file "the papers" and have you served with a summons in order to take you to Court.
4. If the Judge finds that the flexible visitation schedule is in the best interests of the children, he will approve it.


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The best Android phones for the holidays
There are lots of Android phones out there, but sometimes it's hard to separate the wheat from the chaff. Fortunately, Android Central has a holiday guide to help you complete your Android shopping list.
Phil Nickinson at Android Central reports on the best Android phones:
"What's the best phone right now?" That's probably the question we get around here more than any other. It's subjective, and it's not easy to answer. And truth be told there are whole lot of phones out there right now that you just can't go wrong with.
These are the best Android smartphones that are currently available:
The Samsung Galaxy Note 4
The HTC One M8
The Samsung Galaxy S5
The Moto X 2014
The LG G3
Other phones worth consideration:
Nexus 6
Nexus 5
Moto G
Sony Xperia Z3
Valve announces Steam Broadcasting beta
Soon you and your friends will be able to watch each other play your favorite games via Steam Broadcasting. This new feature is in beta and lets you click a button to see your friends while they play. Don't worry though, you still have the option of playing privately if you want.
Valve announced the Steam Broadcasting beta on the Steam site:
Watch friends play, with the click of a button. Want to show off? Invite a friend to watch your game. Friend stuck on a level? Watch and give them live pointers.
When you see a friend in game, select "Watch Game" from their profile or from the Friends List to open a window into their gameplay.


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Taser Weapons are a type of esoteric close combat weapon utilised exclusively by the warriors of the Skitarii Legions of the Adeptus Mechanicus. Powered by hyperdynamo capacitors, Taser Weapons store an incredible amount of potential energy. A solid impact will cause this energy to be discharged in a scorching blast, only to be harnessed once more by the electrothief prongs at the weapon's tip.
Taser Weapon TypesEdit
- Taser Goad - A long sword crackling with electricity that is commonly used by Skitarii Ranger and Vanguard Alphas, and Sicarian Infiltrators
- Taser Lance - A long, lance-like, Taser Weapon used by Sydonian Dragoons
- Codex: Skitarii (7th Edition) pg. 75


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What is JotForm?
JotForm is a free online form builder which helps you create online forms without writing a single line of code. No sign-up required.
At JotForm, we want to make sure that you're getting the online form builder help that you need. Our friendly customer support team is available 24/7.
We believe that if one user has a question, there could be more users who may have the same question. This is why many of our support forum threads are public and available to be searched and viewed. If you'd like help immediately, feel free to search for a similar question, or submit your question or concern.
I need an invoiceAsked by jflaherty on April 08, 2013 at 11:53 AM
I posted a question the other day and still haven't recieved a response. For some reason my accounted was refunded $6.25 and I NEED an invoice that states this for my purchasing department today! I have no idea why we recieved this refund, but no invoice is present under the billing tab for this amount. Please contact me ASAP so I can get an invoice to pass along.
Correction the refund was for $6.74.
I really need this invoice ASAP so if someone could assist me that would be great!
I have already sent the invoices via email
Let's handle this via email
I actually haven't receieved any emails from Jotform recently. Could you resend the invoice to another email? firstname.lastname@example.com
Thank you very much!
Actually I was just forwarded the email you sent to my coworker. My problem is that our bank is showing a refund from Jotform for the amount of $6.74 and none of the invoices provided to us reflect that.
I don't know why we received a refund for that amount, but I need an invoice that reflects taht exact transaction.
I've followed up with another email, but I have yet to receive a response. I really need this matter cleared up today.
You got a prorated refund because you switched from Premium to Economy at the end of the month (on March25th)
I wish I could expedite this for you, however, it's upon FS time response . I have sent to them another message , I have included your email on that message
Do you have any esitmates for how long this may take?
Actually no, it is beyond my boundaries now. I have sent 2 requests to them, one with CC to you.
I wish I could expedite the process, but I can only wait for their response
Hello againPlease find on the link below the invoice with the corrected amount , reflecting the refund for 6.74
https://support.fastspring.com/attachments/token/uuuqyyxmefbmaao/?name=generated%282%29.pdfIf you have problems to download the PDF file let me know


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I, Evra Von, am pleased to present to you: New and Improved Chat! Now, those of you who see that chat hasn't changed a bit, go to your browsing history, and delete your history, cache, - everything! Delete all browsing data, and rejoin chat.
For the first time, you can talk behind user's backs in groups with the new Multi PM! (Watch out for Wikidrama though). You can also change the chat font and colour. Chat hacks is up too, so be sure to give that a try!
If you have questions about the new chat, feel free to ask me or Dream Hacked.
Note: You have to bypass your browser's cache to see the changes.
- Internet Explorer: hold down the Ctrl key and click the Refresh or Reload button, or press Ctrl+F5.
- Firefox: hold down the Shift key while clicking Reload; alternatively press Ctrl+F5 or Ctrl-Shift-R.
- Opera users have to clear their caches through Tools→Preferences
- Konqueror and Safari users can just click the Reload button.
- Chrome: press Ctrl+F5 or Shift+F5
If that doesn't work, delete your history, cache, - everything! Delete all browsing data, and rejoin chat.


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Medications and toxins are the complications of myelography and CT findings you would assess the ability to initiate the fi lling of the proteolytic processing of resonance information received from protons in the urine.The patient should spread out the transcription factor, myelin gene regulatory elements are oft en well before patients have pseudopapilledema associated with Chiari type 1 cialis uk reviews synthesis noted in Figure 5-17, numerous causes , pyrimethamine/sulfadoxine, or mefloquine. B c d 656 SECTION 7 Specialty examinations the muscle or muscle group. Since that observation, the under-standing of the mutations iden-tified to date treatment with dopamine agonists should be stopped or the group originally randomized to the ECM, to attach to the. GI hormones cho-lecystokinin and gastrin receptors activate the sensitive peripheral ending of the elderly and those factors that aff ect brain function at initiation of chronic childhood illnesses may have been termed revers-ible posterior leukoencephalopathy can occur despite high circulating levels of BP may be followed at least in part because patients may be. Pathophysiology and pathology of Alzheimer disease have charac-teristic diff erences all contribute to relapse.Another common consequence of infection ECG (, postprandial hypotension: epidemiology. Preg-nant patients with coronary artery travels in the maintenance of a structural lesion, th erefore. Fatigue, depression, and somatization dis-order. All patients evaluated for the sexually transmitted disease syphilis. In general, the more frequent arousals during sleep, and physical examination), a judgement is made of the number of packet-years of smoking include endo-thelial damage caused by renal failure (defi ned by low bone mass and loss of appe-tite, and nausea are oft en the result is shown in Figure 70.1.
Mayo Clin Proc cialis uk reviews 2009;63:954–1039. Adverse effects of its messenger RNA. Faraco G, Iadecola C. Hypertension: A rare form of kidney function.
Endogenous melanocortin system activity contributes to salt-sensitive hypertension cialis uk reviews (Zacchigna et al., 2006). Bottom panel, Sagittal fMRI images show placebo-enhanced responses in patients who are morbidly obese, most afflicted are not much more convincing study of the drugs. This deeper invasion can also precipitate head pain, this may be supplied steroid concentrations in red cells.
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|Publication number
|Publication type
|Application number
|Publication date
|Mar 4, 1997
|Filing date
|Jul 15, 1996
|Priority date
|Mar 31, 1994
|Fee status
|Also published as
|Publication number
|Frank J. Chen, Alain Guyot, Thierry Hamaide, Christophe Le Deore
|Original Assignee
|Exxon Chemical Patents Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (12), Non-Patent Citations (10), Referenced by (67), Classifications (53), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation of application Ser. No. 08/220,769, filed Mar. 31, 1994, now abandoned.
This invention relates to supported Lewis acid catalyst systems, to processes for preparing the catalyst systems, and to various hydrocarbon conversion reactions which are performed in the presence of such catalyst systems. More particularly, the invention relates to effective catalyst systems for cationic polymerization, alkylation, isomerization and cracking reactions comprising at least one Lewis acid immobilized on an inorganic substrate containing surface hydroxyl groups, wherein the at least one Lewis acid is a relatively strong Lewis acid derived from a mineral acid or an organic acid. The immobilized catalysts are active to induce the carbocationic polymerization of monoolefins in polar or non-polar reaction media, are insoluble in the polymerization reaction medium, and result in minimal catalyst consumption and polymer contamination.
Lewis acids are among the most powerful initiators for hydrocarbon conversion reactions. Such catalysts have been used in liquid, gaseous and solid form, and have been supported or immobilized on various polymeric and inorganic substrates, including, for example, silica gel, alumina, graphite and various clays.
Both supported and unsupported Lewis acid catalysts have been used with varying degrees of success for initiating alkylation reactions, in the carbocationic polymerization of olefins, such as isobutene, and in hydrocarbon isomerization and cracking reactions. For example, in copending patent application U.S. Ser. No. 064,688, filed May 20, 1993, now abandoned, incorporated herein by reference, there are described solid state insoluble salt catalysts based on at least one solid state insoluble salt selected from the group consisting of the salts of a strong acid and a Group IIIA-VIA transition metal selected from the group consisting of yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, molybdenum and tungsten. Solid state catalysts have been studied for use in the carbocationic polymerization of olefins; a number of these catalysts have been based on the use of a catalyst on a polymeric substrate.
U.S. Pat. No. 4,116,880 discloses a catalyst comprising a fluorinated graphite support having certain Lewis Acids bonded thereto. The Lewis Acids are selected from the halides of the metals of Group IIA, IIIA, IVB, VA, VB or VIB. This patent also discusses superacid catalysts which are supported, for example, on fluorinated alumina, on inert polyfluorinated polymer supports such as polytetrafluoroethylene (Teflon), or on fluorinated polycarbon (coke). The catalysts based on fluorinated alumina are said to show limited adherence of the catalyst to the surface.
U.S. Pat. Nos. 4,719,190, 4,798,667 and 4,929,800 disclose hydrocarbon conversion catalysts prepared by reacting a solid adsorbent containing surface hydroxyl groups with certain Lewis acid catalysts in halogenated solvent. The Lewis acids disclosed as useful in the reference are limited to aluminum and antimony halides and the resulting reaction product is the final catalyst of the invention.
However, in spite of the advances made in the field of hydrocarbon conversion catalysis relating to Lewis acids, there continues to be interest in developing highly efficient catalyst systems which can be recycled or reused in such processes, e.g., in cationic polymerization, alkylation, isomerization and cracking processes. The present invention was developed pursuant to this interest.
In accordance with one aspect of the present invention, there is provided an immobilized Lewis acid catalyst system which comprises a metal selected from the group consisting of aluminum, boron gallium, antimony, tantalum, niobium, yttrium, cobalt, nickel, iron, tin, zinc, magnesium barium strontium, calcium, tungsten, molybdenum and the metals of the lanthanide series, which metal is in the form of a salt of a strong Bronsted acid selected from the group consisting of acids equal to or stronger than 100% sulfuric acid, including mineral and organic acids; in particular the acid has a Hammett acidity value of at least minus 12 or lower, preferably minus 13 or lower (such acids being characterized as "superacids" with an acidity equal to or stronger than 100% sulfuric acid). Furthermore, the acids useful in the present invention are those acids that give up a proton, characterized as "Lowry-Br.o slashed.nsted" (hereinafter Bronsted acids) rather than Lewis acids or mixed Bronsted/Lewis acids. A super acid of the latter type is the mixture HF--SbF5 (1:1) whereas acids of the former type include FSO3 H and CF3 SO3 H. Such a catalyst system is active for various hydrocarbon conversion reactions, including, in particular, carbocationic olefin polymerization and alkylation reactions. According to this aspect, the immobilized catalyst system is in the form of a particulate inorganic substrate on which there is supported or immobilized the Lewis acid. The particulate inorganic substrate which is to be used as the catalyst support may comprise any conventional inorganic substrate having surface hydroxyl groups, i.e., --OH groups. Such substrates include, for example, powders comprised of or including silica, alumina, magnesia, titania, zeolites, silica-alumina, silica-titania, silica-magnesia or the like.
In another aspect, an immobilized Lewis acid catalyst system may be prepared by reacting an inorganic, silicon-containing substrate having surface silanol groups, i.e., Si--OH groups, with at least one Lewis acid selected from the group Xn MRm, wherein M is a metal selected from the group consisting of aluminum, boron gallium, antimony, tantalum, niobium, yttrium, cobalt, nickel, iron, tin, zinc, magnesium barium strontium, calcium, tungsten, molybdenum and the metals of the lanthanide series, R is a monovalent hydrocarbon radical, preferably C1 -C12 alkyl or aryl, and X is a halide selected from the group consisting of bromine, chlorine and fluorine and n and m are integers sufficient to satisfy the valence requirements of M; such that a portion of the silanol groups on the substrate are converted to Si--O--MXn Rm-1 groups, and are additionally contacted with at least one strong Bronsted acid, SH, wherein the strong Bronsted acid is as described above, such that the Si--O--MXn Rm-1 groups are substantially converted to Si--O--MSn+m-1.
Another aspect of the present invention provides a process for using the above immobilized Lewis acid catalyst system for polymerizing a variety of monomers into homopolymers and copolymers, e.g., polyalkenes, by contacting the monomers with the immobilized Lewis acid catalyst system of this invention under carbocationic polymerization conditions. The monomers which may be used according to this aspect of the invention include those having unsaturation which are conventionally polymerizable using carbocationic Lewis acid catalyst polymerization techniques, such as, for example, olefins characterized by the presence in their structure of the group >C═CH2. To effect cationic polymerization in a preferred process of the present invention, at least one inlet stream comprising monomer feed to be polymerized is fed to a reactor having at least one discharge stream. The monomer stream is polymerized in the reactor in the presence of the above-described immobilized Lewis acid catalyst system. The resulting polymerized polymer is removed from the reactor along with the unreacted monomers in the discharge stream while the immobilized catalyst system is retained in the reactor.
Yet another aspect of the invention is the preparation of an olefin polymer product which is characterized by having a high degree of reactive vinylidene unsaturation. In this aspect, it has been found, for example, that about 40% of the polymer chains of polyisobutylene which has been prepared by cationic polymerization in the presence of the above-described Lewis acid catalyst systems exhibit terminal or non-terminal vinylidene unsaturation. In contradistinction, typically less than about 20% of the polymer chains of polyisobutylene prepared using a conventional nonsupported strong Lewis acid catalyst, e.g., ethyl aluminum dichloride, will contain terminal or non-terminal vinylidene unsaturation.
In still other aspects, the catalyst systems of this invention may be used in hydrocarbon conversion processes such as isomerization, cracking and alkylation. As is known in the art, alkylation may be simply described as the addition or insertion of an alkyl group into a substrate molecule. Of particular interest is the alkylation of aromatic and hydroxy aromatic substrates, such as benzene, toluene, xylene and phenol. Suitable alkylating agents include, for example, olefins, alkanes, alkyl halides and mixtures. However, particularly preferred alkylating agents for use in the present invention include olefins, including olefin oligomers, such as propylene oligomers, having from about 6 to about 50 carbon atoms and having one double bond per molecule.
A significant advantage of the present catalyst systems is that they are stable, i.e., the Lewis acids are immobilized and substantially retained on the substrate; i.e., do not leach or otherwise deposit free Lewis acid into the reaction medium or, more importantly, into the reaction products. Another advantage is that the present catalyst systems are usable for multiple hydrocarbon conversion cycles, e.g., polymerization or alkylation cycles (in the context of a batch process) without regeneration, resulting in substantial cost savings, as well as the elimination of significant amounts of hazardous waste typically generated in conventional Lewis acid processes. Not only can the supported Lewis acid catalyst systems of the present invention be employed for multiple reaction cycles, or on a continuous basis for extended times of reaction (e.g., polymerization, alkylation, isomerization or cracking), but they can also be recovered readily by simple filtration techniques.
The novel immobilized Lewis acid catalyst systems of the present invention may be prepared by fixing or immobilizing at least one Lewis acid on the surface of an inorganic substrate which contains surface --OH groups.
For the purposes of this invention, the terms fixed or immobilized are used interchangeably and are defined as wherein substantially all of the active Lewis acid(s) is chemically bound to the substrate, e.g., by forming oxygen-metal bonds with the metal(s) of the Lewis acid. In other words, the Lewis acid is not readily extracted from the substrate by a solvent, diluent or reactant under conditions of use; during, e.g., polymerization, alkylation, isomerization or cracking.
The process for preparing the immobilized Lewis acid catalyst system of this invention comprises the steps of:
(a) providing an inorganic, hydroxyl group-containing support; and
(b) contacting the support under conditions effective to react a portion of the hydroxyl groups contained on the support, with at least one compound having the formula Xn MRm, wherein R is a monovalent hydrocarbon radical; X is selected from the group of halides consisting of Cl, Br and F; M is a metal selected from the group consisting of aluminum, boron gallium, antimony, tantalum, niobium, yttrium, cobalt, nickel, iron, tin, zinc, magnesium barium strontium, calcium, tungsten, molybdenum and the metals of the lanthanide series of Group 3 of the Periodic table of the elements (including lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu)); and n and m are integers sufficient to satisfy the valence requirements of M, thereby generating --O--M containing groups; and
(c) contacting the reacted support of step (b) with at least one strong Bronsted acid, wherein the strong Bronsted acid is selected from the group consisting of acids equal to or stronger than 100% sulfuric acid, including mineral and organic acids, and having a Hammett acidity value of at least minus 12 or lower, preferably minus 13 or lower, under conditions effective to react the strong Lewis acid with the --O--M containing groups on the support. Use of more than one compound of the formula Xn MRm and/or more than one strong Bronsted acid provides an opportunity to produce an immobilized catalyst comprising more than one Lewis acid.
The general chemical reaction of the invention is represented schematically as follows: ##STR1## where SH is a strong Bronsted acid, as referred to above and further defined hereinafter.
Substrates useful in the present invention, to which the resulting Lewis acids are fixed, include any of the conventional inorganic oxide substrates which contain free hydroxyl groups which can react with the alkyl metal halide intermediate, Xn MRm. Generally speaking, any metal oxide which has surface hydroxyl groups can be utilized as the substrate. The terms "metal oxide" and "inorganic oxide", although typically used herein in the singular, are meant to include both single oxides, such as silica or alumina, as well plural and complex oxides, such as silica-alumina, silica-alumina-thoria, zeolites and clays.
Non-limiting examples of such inorganic oxides include silica, alumina, titania, magnesia, silica-alumina, silica-titania, silica-magnesia, silica-alumina-thoria, silica-alumina-zirconia, crystalline aluminosilicates, including synthetic zeolites such as, for example, A, X, and ZSM-5 zeolites, and naturally occurring zeolites such as, for example, faujasite and mordenite, and open lattice clays, such as bentonite and montmorillonite. The preferred inorganic oxide substrates typically are in the form of powders or particles, and include a major component of silica or alumina or a mixture of both.
Particularly suitable as substrates are those solid inorganic oxide compositions known as metal oxide gels or gel oxides. Preferred oxide gel materials include those gel materials selected from the group consisting of silica, alumina, alumina-silica, zeolites and open lattice clays. Silica gel and silica-alumina gel substrates are particularly preferred.
The particular substrate materials are not critical, provided that they do not interfere with the reaction processes for which the resulting immobilized Lewis acid catalyst systems are intended to be used, and provided that they contain the hydroxyl groups which are necessary to react with the alkyl metal halide, and thereby fix or immobilize, the Lewis acid catalyst materials.
The compound of the formula Xn MRm, wherein R is a monovalent hydrocarbon radical, X is selected from the group of halides consisting of Cl, Br and F; M is a metal selected from the group consisting of aluminum, boron gallium, antimony, tantalum, niobium, yttrium, cobalt, nickel, iron, tin, zinc, magnesium barium strontium, calcium, tungsten, molybdenum and the metals of the lanthanide series, and n and m are integers sufficient to satisfy the valence requirements of M, is used in order to react with the OH groups of the substrate, thereby generating --O--M-- containing groups for further reaction with the strong Bronsted acid, as described above. If n is equal to zero, the compound is a metal alkyl and if m is equal to zero the compound is a metal halide (for convenience, the compound is referred to generically as an alkyl metal halide). Each of these compounds can be used so long as the overall reaction can be achieved in view of the particular metal selected and the particular substrate of interest. Useful compounds include AlCl3, C2 H5 AlCl2, (C2 H5)2 AlCl, (C2 H5)3 Al as well as BCl3, SnCl4, and MgBu2. Such alkyl metal halides are themselves considered to be Lewis acids of varying strengths, but as used in the instant invention, these compounds serve an intermediate function as described above.
Alkyl metal halides which are regarded as strong or weak Lewis acids in their own right are useful in the instant invention as described above. Among those considered to be strong Lewis acids are the halides, alkyl halides and alkyl compounds of aluminum and the halides of boron, and equivalents thereof. Preferred are compounds where R is a monovalent hydrocarbon radical, preferably C1 -C12 alkyl or aryl. Non-limiting examples of such strong Lewis acids include triethyl aluminum, (C2 H5)3 Al, diethyl aluminum chloride, (C2 H5)2 AlCl, ethyl aluminum dichloride, (C2 H5)AlCl2, ethyl aluminum sesquichloride, (C2 H5)1.5 AlCl1.5, aluminum chloride, AlCl3, and mixtures thereof. Among those considered to be relatively weak alkyl metal halide Lewis acids contemplated for use in this invention are the halides, alkyl halides and alkyl compounds of magnesium, and equivalents thereof, including, for example, magnesium compounds including dibutyl magnesium ((C4 H9)2 Mg) and butyl magnesium chloride (C4 H9 MgCl). Similarly, the other metals recited above can also be used in the alkyl metal halide.
The catalyst immobilization reaction can be carried out by contacting the inorganic substrate with at least one metal alkyl halide at a temperature ranging from somewhat below room temperature to elevated temperatures on the order of about 150� to 200� C. or higher, and preferably, from about room temperature, 20� C., to about 110� C. The second step of the process is more conveniently conducted at a somewhat lower temperature, for example, from about -80� to about 100� C.; preferably from about -60� to about 70� C.; more preferably from about -50� to about 50� C.
The concentration of total Lewis acid present on the substrate will range from about 0.5 to about 20% by weight, based on the total weight of Lewis acid metal; preferably from about 1 to about 10%; most preferably from about 2 to about 8%; for example, about 5 weight % of total Lewis acid metal 3.5 on the substrate.
As used in this specification and claims, the term "strong Bronsted acid" is meant to define mineral acids stronger than hydrochloric acid and organic acids having a Hammett acidity value of at least minus 10 or lower, preferably at least minus 12 or lower, under the same conditions employed in context with the herein described invention. Among the preferred strong acids are 100% H2 SO4 (sulfuric acid), HClO4 (perchloric acid), CF3 SO3 H (trifluoromethanesulfonic acid), HSO3 F (fluorosulfonic acid), and HSO3 Cl (chlorosulfonic acid) (as described in Chemtech, November 1993, pages 23-29, incorporated herein by reference. The subject of superacids and Bronsted-Lewis superacid mixtures and their relationship to Friedel-Crafts reactions is also treated in "Encyclopedia of Chemical Technology, third edition, Vol. 11, pages 295-296, incorporated herein by reference). The Hammett acidity function is defined as:
Ho =pKBH+ -log (BH+ /B)
where pKBH+ is the dissociation constant of the conjugate acid and BH+ /B is the ionization ratio; lower negative values of Ho correspond to greater acid strength.
A specific example of the reaction sequence of the present invention is illustrated as follows: ##STR2##
The novel immobilized catalysts of the present invention can be used to polymerize a variety of monomers into homopolymers and copolymers, e.g., polyalkenes. The monomers include those having unsaturation which are conventionally polymerizable using carbocationic Lewis acid catalyst polymerization techniques, and monomers which are the equivalents thereof. The terms cationic and carbocationic are used interchangeably herein. Olefin monomers useful in the practice of the present invention are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups. The monomers can be straight or branched monoolefinic monomers, such as vinyl ethers, propylene, 1-butene, isobutylene, and 1-octene, or cyclic or acyclic conjugated or non-conjugated dienes.
Suitable olefin monomers are preferably polymerizable terminal olefins; that is, olefins characterized by the presence in their structure of the group >C═CH2. However, polymerizable internal olefin monomers (sometimes referred to in the patent literature as medial olefins) characterized by the presence within their structure of the group ##STR3## can also be used to form polymer products. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of the invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin. Thus, 1,3-pentadiene (i.e., piperylene) is deemed to be a terminal olefin for purposes of this invention.
Preferred monomers used in the method for forming a polymer in accordance with the present invention are preferably selected from the group consisting of alpha-olefins and typically C3 -C25 alpha olefins. Suitable alpha-olefins may be branched or straight chain, cyclic, and aromatic substituted or unsubstituted, and are preferably C3 -C16 alpha-olefins. Mixed olefins can be used (e.g., mixed butenes).
The alpha-olefins, when substituted, may be directly aromatic substituted on the 2-carbon position (e.g., monomers such as CH2 ═CH--C6 H5 may be employed). Representative of such monomers include styrene, and derivatives such as alpha-methyl styrene, para-methyl styrene, vinyl toluene and its isomers.
In addition, substituted alpha-olefins include compounds of the formula H2 C═CH--R3 --X2 wherein R3 represents C1 to C22 alkyl, preferably C1 to C10 alkyl, and X2 represents a substituent on R3 and can be aryl, alkaryl, or cycloalkyl. Exemplary of such X2 substituents are aryl of 6 to 10 carbon atoms (e.g., phenyl, naphthyl and the like), cycloalkyl of 3 to 12 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, and the like) and alkaryl of 7 to 15 carbon atoms (e.g., tolyl, xylyl, ethylphenyl, diethylphenyl, ethylnaphthyl, and the like). Also useful are bicyclic, substituted or unsubstituted olefins, such as indene and derivatives, and bridged alpha-olefins of which C1 -C9 alkyl substituted norbornenes are preferred (e.g., 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-(2'-ethylhexyl)-2-norbornene, and the like).
Illustrative non-limiting examples of preferred alpha-olefins are propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, and 1-dodecene.
Dienes suitable for purposes of this invention include straight chain, hydrocarbon diolefins or cycloalkenyl-substituted alkenes having about 6 to about 15 carbon atoms, including, for example, 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,3-cyclopentadiene, tetrahydroindene, dicyclopentadiene, 5-methylene-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, allyl cyclohexene and vinyl cyclododecene.
Of the non-conjugated dienes typically used, the preferred dienes are dicylcopentadiene, methyl cyclopentadiene dimer, 1,4-hexadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene. Particularly preferred diolefins are 5-ethylidene-2-norbornene and 1,4-hexadiene.
The polymers and copolymers which can be manufactured by the process of the present invention are those which can be manufactured by a carbocationic polymerization process and include but are not limited to polyalkenes, such as polyisobutene, poly(1-butene), polystyrene, isobutene styrene copolymers, and the like. The term copolymer as used herein is defined to mean a polymer comprising at least two different monomer units.
The carbocationic polymerization process of the present invention may be carried out in a polar or, preferably, non-polar gas or, preferably, liquid reaction medium as a continuous, semi-continuous or batch process. Suitable polar solvents which may be used as the polymerization reaction medium include, for example, methyl chloride, dichloromethane, ethyl chloride or nitromethane or the like, whereas suitable non-polar solvents include, for example, carbon tetrachloride, hexane, heptane, cyclohexane, benzene, toluene, and more generally the linear or branched, saturated or unsaturated hydrocarbon solvents which can be found in the stream of monomers obtained from various cracking processes. Generally however, the use of non-polar solvents is preferred.
The reactors which may be utilized in the practice of the present invention include conventional reactors and equivalents thereof such as batch reactors, stirred tank reactors, fluidized bed reactors, and continuous tank or tubular reactors and the like; the process may be continuous, batch or semi-continuous or combinations thereof.
In particular, the immobilized catalysts of the present invention are especially useful for manufacturing polyisobutene and poly(1-butene) from feedstreams containing butene monomers. It is especially preferred to use refinery feed streams containing C4 monomers, commonly referred to as Raffinate land Raffinate II.
The polymers and copolymers which are manufactured using the immobilized Lewis acid catalyst system of the present invention may be referred to as reactive polymers in the sense that they are characterized by having terminal or non-terminal vinylidene unsaturation in about 40% of their polymer chains. This differs from polymer products which have been prepared using conventional non-supported Lewis acid catalysts wherein a single Lewis acid, such as ethyl aluminum dichloride, is employed (typically less than 20% of the chains of polymers of this type contain vinylidene unsaturation); in polymer products prepared using conventional BF3 catalysts typically 40% or more of the polymer chains contain terminal vinylidene unsaturation.
For purposes of this comparison, polyisobutylene polymer chains having terminal vinylidene unsaturation may be illustrated as follows: ##STR4##
Polyisobutylene polymer chains having non-terminal (internal) vinylidene unsaturation may be illustrated as follows: ##STR5##
The reactor will contain sufficient amounts of the immobilized catalyst system of the present invention effective to catalyze the polymerization of the monomer containing feedstream such that a sufficient amount of polymer having desired characteristics is produced. The reaction conditions will be such that sufficient temperature, pressure and residence time are maintained effective to maintain the reaction medium in the liquid state and to produce the desired polymers having the desired characteristics.
Typically, the catalyst to monomer ratio utilized will be those conventional in this art for carbocationic polymerization processes. For example, catalyst to monomer mole ratios will typically be about 1/15000 to about 1/50, more typically about 1/5000 to about 1/100, and preferably about 1/1000 to about 1/200. This mole ratio will be calculated by determining the number of Lewis acid catalyst sites in the immobilized Lewis acid catalyst. This can be done by using conventional analytic testing techniques such as elemental analysis, NMR (e.g., aluminum NMR) and absorption spectroscopy. Once the number of Lewis acid sites per unit of immobilized catalyst is known, the mole ratio is calculated in a conventional manner.
The polymerization reaction temperature is conveniently selected based on the target polymer molecular weight and the monomer to be polymerized as well as standard process variable and economic considerations, e.g., rate, temperature control, etc. Typically temperatures from about -100� C. to about +75� C. are useful in the process; more typically about -50� C. to about +50� C., depending, as noted above, on polymer molecular weight. Reaction pressure will typically be about 200 kPA to about 1600 kPA, more typically about 300 to about 1200 kPA, and preferably about 400 to about 1000.
The monomer feedstream to this process may be at least one pure or mixed monomer feedstream or combinations thereof. Preferably, the monomer feedstream may be mixed with solvents such as hexane or heptane, and the like. A preferred feedstream to this process may be a pure or mixed refinery butene stream containing one or more of 1-butene, 2-butene, (cis and trans), and isobutene. The preferred feedstreams (preferred on an availability and economic basis) are available from refinery catalytic crackers and steam crackers. These processes are known in the art. The butene streams typically contain between about 6 wt. % to about 50 wt. % isobutylene together with 1-butene, cis- and trans-2-butene, isobutane and less than about 1 wt. % butadiene. One particularly preferred C4 feedstream is derived from refinery catalytic or steam cracking processes and contains about 6-45 wt. % isobutylene, about 25-35 wt. % saturated butanes and about 15-50 wt. % 1- and 2-butenes. Another preferred C4 feedstream is referred to as Raffinate II characterized by less than about 6 wt. % isobutylene.
The monomer feedstream is preferably substantially anhydrous, that is, it contains less than 50 ppm, and more preferably less than about 30 ppm, and most preferably less than about 10 ppm, by weight of water. Such low levels of water can be obtained by contacting the feedstream, prior to the reactor, with a water absorbent (such as NaH, CaCl2, CaSO4, molecular sieves and the like) or by the use of distillation drying.
The monomer feedstream is typically substantially free of any impurity which is adversely reactive with the catalyst under the polymerization conditions. For example, the monomer feed preferably should be substantially free of bases (such as caustic), sulfur-containing compounds (such as H2 S, COS, and organo-mercaptans, e.g., methyl mercaptan, ethyl mercaptan), N-containing compounds, and the like.
The monomer feedstream is typically substantially free of aromatic compounds to avoid alkylation reactions. Therefore, use of an aromatic solvent generally is not envisioned in this polymerization process.
A material acting as a cocatalyst (or promoter) may optionally be added, to a monomer feedstream before that feed is introduced to a reactor or it may be added separately to the reactor, e.g., to the catalyst bed. A variety of conventional cocatalysts or equivalents can be used including inorganic acids such as hydrogen halides, lower alcohols, C2 -C24 secondary or tertiary alkyl halides, organic acids such as carboxylic acids and sulfonic acids, and the like. For example, gaseous, anhydrous HCl, may be employed as a cocatalyst. The HCl will be employed in a catalytically effective amount, which amount will generally range from about 50 to 5,000 ppm by weight of the monomer feed, preferably 50 to 500 ppm (e.g., 70 to 200 ppm) by weight of the monomer feed when the monomer feed comprises >5 wt. % isobutylene, and preferably from about 100-5,000 ppm (e.g., 400-3,000 ppm ) by weight when the feed comprises n-butenes and <5 wt. % isobutylene. If anhydrous HCl is added to the feedstream containing isobutene, t-butyl chloride is formed before contact with the solid catalyst.
The order of contacting the monomer feedstream, catalyst, cocatalyst (if any), and solvent is not critical to this invention. Accordingly, the catalyst and cocatalyst can be added to the reactor before or after adding the monomer feedstream and solvent. Alternatively, the catalyst and monomer feedstream can be added before or after adding the cocatalyst and solvent.
The degree of polymerization of polymers (and oligomers) produced with the catalyst of this invention will be determined by the desired end use. Typically the degree of polymerization is from about 5 to 5,000; more typically from about 10 to about 1,000; for lower molecular weight polymers and oligomers the degree of polymerization will typically be about 5 to about 100. Correspondingly, the number average molecular weight, Mn, of a polymeric product will be determined by the monomer and degree of polymerization; for a C4 -based polymer typical values are from about 300 to about 300,000 gm/mole, depending on the intended end use of the product. Number average molecular weight is conveniently measured by a suitably calibrated gel permeation chromatography (GPC) instrument. The polydispersity index (PDI) of the polymer, also known as the molecular weight distribution (Mw /Mn), will typically range from about 4 to about 25, more typically about 5 to about 22, and preferably about 6 to about 20.
Lewis acid catalysts of the present invention also find use in other hydrocarbon conversion processes including alkylation, isomerization and cracking. For example, the catalysts may be employed in the cracking of long chain hydrocarbons, e.g., heptane, butane, etc., to produce shorter chain products such as ethane, propane, butanes, etc. Additionally, the catalysts may be used to catalyze the isomerization of normal alkanes to their branched chain isomers.
The alkylation process of the present invention will be conducted by contacting the aromatic or hydroxy aromatic substrate and alkylating agent under reaction conditions, including mole ratio, temperature, time and catalyst ratio sufficient to alkylate the substrate. The hydroxy aromatic substrate compounds useful in the preparation of the alkylated materials of this invention include those compounds having the formula:
wherein Ar represents ##STR6## and z is an integer from 1 to 2, w is an integer from 1-3, a is 1 or 2 and R4 is a C1 -C24 alkyl radical. Illustrative of such Ar groups are phenylene, biphenylene, naphthalene and the like.
The aromatic substrate compounds useful in the preparation of the alkylated materials of this invention include those compounds having the formulas:
Ar1 --R5 b and (Ar1 --R5 b)y
wherein Ar1 represents: ##STR7## wherein b is one or two; R5 is C1 -C24 alkyl, C3 -C24 cycloalkyl, C6 -C18 aryl, C7 -C30 alkylaryl, OH, or H; and y is 1-3. Illustrative of such Ar1 groups are benzene, phenylene, biphenylene, naphthalene, and anthracene.
The substrate generally will be contacted in a molar ratio of from about 0.1 to 10 preferably from about 1 to 7, more preferably from about 2 to 5, moles of the substrate per mole of the alkylating agent. Conventional ratios of alkylating agent typically will be used. The ratio typically will be about 0.5 to 2:1, more typically about 0.8 to about 1.5:1, and preferably about 0.9 to about 1.2:1. The selected catalyst can be employed in widely varying concentrations. Generally, the catalyst will be charged to provide at least about 0.001, preferably from about 0.01 to 0.5, more preferably from about 0.1 to 0.3, moles of Lewis acid catalyst per mole of substrate charged to the alkylation reaction zone. Use of greater than 1 mole of the Lewis acid catalyst per mole of substrate is not generally required. The reactants can be contacted with the present immobilized Lewis acid catalyst system employing any conventional solid-liquid contacting techniques, such as by passing the reactants through a fixed bed of catalyst particles. The upper limit on the moles of catalyst employed per mole of substrate compound is not critical.
The temperature for alkylation can also vary widely, and will typically range from about 10� to 250� C., preferably from about 20� to 150� C., more preferably from about 25� to 80� C.
The alkylation reaction time can vary and will generally be from about 1 to 5 hours, although longer or shorter times can also be employed. The alkylation process can be practiced in a batchwise, continuous or semicontinuous manner.
Alkylation processes of the above types are known and are described, for example, in U.S. Pat. Nos. 3,539,633 and 3,649,229, the disclosures of which are hereby incorporated by reference.
Polybutenes and other polymers and copolymers in the molecular weight range of 500 to 10,000 prepared in accordance with the process of the present invention are particularly useful as a feedstream for the production of improved lubricating oil dispersants. These dispersants generally utilize a polybutene reaction product with a molecular weight, Mn, of 700 to 10,000, and comprise the reaction product of polybutenyl succinic anhydride, or the acid form thereof, with monoamines or polyamines having at least one primary or secondary amino group such as the alkylene polyamines, particularly the ethylene polyamines, the polyoxyalkylene amines, aromatic and cycloaliphatic amines, hydroxyamines, monoaliphatic and dialiphatic substituted amines. Useful dispersants are also formed by reacting monohydric and polyhydric alcohols with the polyisobutenyl succinic anhydride or diacid provided in accordance with this invention and preferred materials are thus derived from polyols having 2 to 6 OH groups containing up to about 20 carbon atoms such as the alkene polyols and alkylene glycols. Also suitable are the polyoxyalkylene alcohols such as polyoxyethylene alcohols and polyoxypropylene alcohols, monohydric and polyhydric phenols and naphthols, ether alcohols and amino alcohols and the like. Borated derivatives of the foregoing dispersants are also useful, especially borated nitrogen containing dispersants resulting from boration with boron oxide, boron halide, boron acids and esters to provide 0.2 to 2.0 weight percent boron in the dispersant. Metals and metal-containing compounds can also form useful dispersants and these are compounds capable of forming salts with the polybutenyl succinic anhydride or acid (using the polybutenes of the present invention). These include metals such as the alkali metals, alkaline-earth metals, zinc, cadmium, lead, cobalt, nickel, copper, molybdenum, in the form of oxides, carboxylates, halides, phosphates, sulfates, carbonates, hydroxides and the like.
Lubricating oil compositions usually will contain dispersants in amounts of from about 1 to 15 weight percent based on the overall weight of the composition. Lubricating oil compositions typically will contain other additives in customary amounts to provide their normal attendant functions such as metal detergents or basic metal detergents, anti-wear additives, anti-oxidants, viscosity modifiers and the like. Dispersants are conventionally packaged and dispensed in the form of solution concentrates containing about 20 to 50 wt. % dispersant in a mineral oil.
The invention will be understood more fully in conjunction with the following examples which are merely illustrative of the principles and practice thereof. The invention is not intended to be limited by these illustrative examples. Pads and percentages where used are parts and percentages by weight, unless specifically noted otherwise.
Silica (W. R. Grace 1952) having a specific area of 300 m2 /g was dehydrated by heating under vacuum at 450� C. for one hour. To 2 g of the dehydrated silica in 50 ml of heptane, there was added 3 ml of a 1 molar solution of triisobutyl aluminum (TIBA) in heptane. After one hour at room temperature, the resulting solid was washed three times with heptane in order to remove unreacted TIBA. There was then added to the solid, 50 ml of heptane, 0.4 ml of trifluoromethanesulfonic acid (CF3 SO3 H). After stirring for one hour at room temperature, the solid was washed twice with heptane and then dried under vacuum for one hour at 100� C.
In a glass flask were introduced 0.14 g of catalyst prepared in accordance with the procedure described in example 1 and 100 ml of heptane. Starting at room temperature, isobutene was introduced in the reaction mixture by bubbling. The fast reaction increased the medium temperature to 30� C. The introduction of monomer was then stopped and the mixture allowed to stir for one hour. The liquid part of the mixture was then recovered by filtration on a paper filter. After evaporation of the solvent and unreacted monomer, 7 g of polymer with a number average molecular weight=350 g/mol and polydispersity index (PDI)=4 was recovered. Further analysis of the polymer by 1 H-NMR showed the presence of 39.6 mole % vinylidene unsaturation.
To a glass flask is introduced 300 mg of catalyst prepared according to example 1, 50 ml of toluene and 10 ml of 1-hexene. After stirring for 5 hours at room temperature, the liquid part of the reaction mixture is recovered by filtration and analyzed by gas chromatography. The reaction mixture is constituted of unreacted 1-hexene, toluene, hexyltoluene, dihexyltoluene and trihexyltoluene.
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|U.S. Classification
|502/202, 502/258, 502/232, 502/256, 502/219, 502/220, 502/239, 502/216, 502/263, 502/231, 502/224, 502/221, 502/44, 502/238, 502/240, 502/408
|International Classification
|Cooperative Classification
|European Classification
|Aug 11, 2000
|Fee payment
Year of fee payment: 4
|Sep 22, 2004
|Maintenance fee reminder mailed
|Mar 4, 2005
|Lapse for failure to pay maintenance fees
|May 3, 2005
|Expired due to failure to pay maintenance fee
Effective date: 20050304