text:
Econo Lodge Philadelphia Airport
600 S. Governor Printz Blvd
Lester, PA 19029
Phone: (610) 521-3900
Fax: (610) 521-1704
Eden Cemetery
1434 Springfield Road
Collingdale, PA 19023
+1 610 583 8737
Mo to Sa from 09:00 AM to 03:00 PMThe Eden Cemetery is a monumental African-American cemetery and is sited in Collingdale, Delaware County in Pennsylvania. It boasts of being the oldest cemetery in the entire United States that is African-American owned. It was established on June 20, 1902. It comprises of 23 sections and provides for burial practices, foundation and memorials. Occupying great historic importance, the cemetery site is listed on the distinguished National Register of Historic Places since 2010.
Earn valuable points toward free nights.


text:
cost to build fireplace and chimney
We are preparing to build a new house and I'm in the process of figuring the cost. The house includes a single chimney, two flues (one for a fireplace and one for utilities). The fireplace/firebox will be brick (not huge, about 4 feet wide) and the sections of the chimney not exposed will be cinderblock or other block. Where the chimney exits at the roof line will be brick. The chimney will run from the basement and through 2 floors above. I'm trying to get a rough ballpark cost of what this might cost.... any thoughts would be appreciated. We're located on Cape Cod, Massachusetts.
Thanks very much.
I have a very similar situation as you are proposing. The portion of chimney in the garage is cinderblock. The outside is brick. When my house was built in 1995, I paid $8,000. Adjust this for inflation.
I live in the Ohio Valley which is probably less expensive than your area. I know you are trying to get an estimate...but a firplace is nothing to go cheap on. I would go to the nearest masonry supply store and ask them for recommendations for a "good mason." You could end up spending thousands of dollars on your dream fireplace / chimney and if it isn't built correctly...you won't be a ble to get a chemical log to burn in it.
I built a house 3+ years ago with solid masonry fireplace / chimney. My mason came highly recommended and actually did an awesome job; all the way up until he quit showing up! He basically completed everything except my stone face on exterior of chimney. I finally said, "what the hell...I can do this." So I did...and it looks great!
My fireplace is roughly 9' wide and my chimney is 22' high. My mason was going to charge me $5,000 labor and I was to supply all materials. I pulled all the stone out of my own creek.
I ended up paying him roughly $2,500 and another $4,000 for cmu, sand, flues, cement etc, etc. So if he would have completed it...I would have had $9,000 +/- in it.
Good luck...

subset: commoncrawl


text:
Deviant Art
Read Me RealRead Me Real
I am the person to breathe you real
Reawaken perfect in any age
I house every moment you hold dear
Receptacle of your every hope and fear
Witness to your anger when you engage
Returned again to breathe you real
Memories still fresh of how we feel
Locked together on third eye's stage
All the moments that I hold dear
I can hear your voice when I hold you near
Give you my mind, free of your cage
A playground for me to breathe you real
Come with me again on time line's wheel
Do not be afraid to turn the page
Our story has all the moments I hold dear
It's our voices on the wind we hear
All it takes for me to be assuaged
Stories on the wind when I breathe you real
Stories in my mind, moments I hold dear
Close To Something RealClose To Something RealClose To Something Real5 years ago in Traditional Fixed Forms More Like This
Just give me a place to heal
Sanctuary to cease this race
Somewhere dark to find something real
Peace and quiet to break the seal
Around my heart to softly embrace
The pieces of me I need to heal
I want to break down and feel
Let my soul wander out to fill this space
Searching for that shining something real
Engulfed by all that makes me kneel
Until I've lost all trace
Of any piece of me to heal
Then like a bell's muffled peal
Soft and gentle caress my face
The presence of something real
Life moves on along the wheel
Returning to me my grace
What piece have I left to heal
I'm closer now to something real
Reaper In Your DreamsReaper In Your DreamsReaper In Your Dreams5 years ago in Traditional Fixed Forms More Like This
Now you see the blackened reaper in your dreams
Surcease of my hollow heart, with warmth and love to fill
I've come for you by night in the cold moon beams
I've been dark and cold for eons, and eons more it seems
Existing to take souls and spirits, existing dark and still
Now you see the blackened reaper in your dreams
Watching you from afar in your black shirts and jeans
Walking alone, singing to yourself, on that lonely deserted hill
I come for you by night in the cold moon beams
Seeing you, guarding over your sleep breaks me apart at the seams
Your body warm, your heart with passion spills
I'll show you now, the blackened reaper of your dreams
I can't live any longer, staying only in your dream
It's time to make this love real, think of me until
I return for you with the Plutonian moon beams
I'll give you love eternal, the love of ages till it seems
The love you've known on earth, will only be minute and shrill
I am now and will always be the reaper in your dre
Another Way To DieAnother Way To DieAnother Way To Die5 years ago in Traditional Fixed Forms More Like This
The setting sun paints us red
Another last look at the sky
Our battlefield is my bed
A silver moon will see us dead
This time we cannot lie
After the setting sun shades us red
In this room the ghosts have fled
Hating to stand idly by
Watching us battle on the bed
Our weapons, our minds, defenses we shed
Left us with another kind of high
As the dying sun leaves us red
Onto this field our bodies have led
This pull on my hunger I cannot deny
Anticipation marks the field around my bed
Across this waning light you are spread
Love is just another way to die
The sun is gone but we still glow red
Passion makes a battlefield of my bed
Where I Once DiedWhere I once DiedWhere I Once Died6 years ago in Free Verse More Like This
My fears spring to life
In this place where I once died
And no matter how hard I tried
I keep returning to my home of strife
This place holds all of me
All the good guys and bad guys I've been
To work it out I let them in
Looking around my home of sorrow, set me free
All the devils who disturbed me and the angels
Who cried tears of snow white sorrow
Caress the never fading rain on my heart tomorrow
Cut through the black and leave the tangle
All the loves I've had that never lasted
Tied up my heart in strings of joy
Looking up through my past, I was just a boy
For the part I played, I never should have been cast
Life and love moves on along the wheel
This unholy place holds years of me
But even we who got out and survived can see
It was living in this place that taught us to feel
River of RustRiver of RustRiver of Rust5 years ago in Free Verse More Like This
More than ever I fear
That I may fall
Dancing in this Hall
Whispers in my ear
In love with my lust
The missing sliver
Walking this old river
Of slag and rust
Old unused emotions
Grown solid with pain
Come feed the rain
Warm with insinuation
The river shifts
From static bliss
With just a kiss
Rivulets leap and lift
As you breathe my name
Your moment of need
I feel my heart bleed
Nothing's the same
This moment's so new
I only feel your touch
The touch I like too much
This moment is you
You feed the rain
You, my passions author
That moves the water
From where its lain
Don't walk away
Without your love
Your gift from above
My life is but a river of rust
I'm The DreamI'm The DreamI'm The Dream5 years ago in Traditional Fixed Forms More Like This
I'm the night at the end of day
I speak aloud just to you
I'm the dream when your mind's astray
I bring the thoughts you turn away
Exalting the acts you couldn't do
In the night at the end of day
I'm the harbinger to show you a way
The one inside to frighten you
See my dream when your mind's astray
I'm the cold, darkness here to stay
I'm the cloud across the blue
Bringing the night at the end of day
I'm your evil, come what may
Your mental cynic aloof and true
This is the dream, your mind's astray
I feel the hurt from where you lay
Their betrayal isn't something new
A fateful night at the end of day
My dream and your mind no longer stray
Slow Dying FlowerSlow Dying FlowerSlow Dying Flower6 years ago in Free Verse More Like This
I met her years ago
i didn't know her power
Who could foresee that our love
Would be a slow dying flower?
Though years and seasons came and passed
I feel now as strongly as I felt
Trying to build a love that would last
I forgot to check the cards that I'd been dealt
Bright colors now that bloom
We'd sit and stare, to slowly pass the hour
Even with long deadened vine, and dried-up soil
Time still hasn't killed our brightly blooming flower
I'd burn it down to ash
If I would only dare
I woke up today wearing a frown
Last night I found it had made a pair
Let Me Rest In PeaceLet me rest in peaceLet Me Rest In Peace6 years ago in Songs & Lyrics More Like This
All I ever wanted
Was to love a certain someone
That's all i ever chased
It's a race I've never won
I beg and beg and then i plead
It's like whispering in a dead mans ear
I just can't seem to stop this game
I stand and face because I can't hide in fear
Take your claws away from me
Let me rest in peace
Why can't you ever see?
Won't you let me rest in peace!
I'm washed up and through
With all your painful tricks
My soul can't go on like this
It makes me fuckin sick
I'm done with love, leave me be!
I never will again
Take these arrows from my heart
Set me free and then,
Take your claws away from me
Let me rest in peace
Why can't you ever see?
Won't you let me rest in peace!
I danced all through your web
I made it out the other side
I told you once, that's fuckin it
I'm jumpin off this roller coaster ride
Take your claws away from me
Let me rest in peace
Why can't you ever see?
Won't you let me rest in peace!
Blood Love and LifeLove Is The BloodBlood Love and Life6 years ago in Free Verse More Like This
Love is the blood that runs through my veins
that chills like ice in the freezing cold rain
that ever fights to ease the pain
what we have always sought to regain
Love is the blood that drives my burdened soul
following the flowing red road to find what makes my heart whole
pushing and kicking me towards its goal
often forgetting to stop and pay the toll
Love is the blood that boils and bubbles with passions heat
the invisible current of pleasure no one can beat
it gives us wings on our feet
and lets us fly to the place where true lovers meet
Love is the blood that sleeps in my tears
the essence that scares away all my fears
like a shield wall no one can ever hear
the velvet glove over iron protection, soft and sheer
Blood Is The Life
Blood is the life through storm and flame
the thing that changes just to stay the same
aloof and endearing regardless of fortune or fame
what allows us to keep playing the game
Blood is the life I would freely spill it
give it to those w
Crossroads TriggerCrossroads TriggerCrossroads Trigger3 years ago in Traditional Fixed Forms More Like This
When the summer's over, dark clouds hide the sun
Here are the fruits of field and mine
Wanting use when all is said and done
Learning to walk the spring, the summer run
Read the deeds of those behind
Prepare for when the clouds will hide the sun
Many crossroads trigger we walk, choose your gun
Decide your line of fire, many chosen blind
Only what's behind is seen when all is said and done
Of economists and politicians bleat I've wanted none
Nor will I suffer under piety's shrine
Because no one is to blame when all is said and done
In spring I write my works of one
As the autumn sunset beckons to mind
There's no hurry anymore when all is said and done
The smokes and winds of fools we shun
But the question is always there to remind
What harvest will be had when the clouds hide the sun
Who will I be when all is said and done?
You Can't Stop The RainYou Can't Stop The RainYou Can't Stop The Rain6 years ago in Free Verse More Like This
The rain pours on
Clouds bathed in grey
Is the silver lining kept at bay?
An old man smiling walks on
A little girl, with long dark chocolate locks
Hides sad eyes under her hood
She feels sad when it rains, like all children should
Hand in hand with her mom, through the rain she walks
The rain falls heavy to the earth
Running over rocks, under feet
Dripping from leaves, onto our streets
Two souls destined to meet from their birth
Peeking from under the edge
She sees old blue eyes smiling up
Hands held in front of him like a cup
Sipping the rain he stands before a tall hedge
Why do you smile, sir? The worlds in pain
Her small voice drew his attention
Where is anything good worth mention?
Her green eyes mute in the pouring rain
That we live to love, and experience he wanted to say
A look plays behind his wise eyes
Remembering long gone questions of why
From a daughter who looked at him the exact same way
Don't cry, he said, for this falling water
The earth needs t
...and Kisses...and Kisses...and Kisses6 years ago in Free Verse More Like This
It was a beautiful night for a romance
Two friends, so close, feel the urge to take a chance
The porch under the smooth summer skies
I saw the stars up above shining in her eyes
The first was so delicate, so sweet, so light
Colors of life went neon from dull, made a day of my long night
The second was an attack to my senses, I barely caught
My mind sent reeling down spirals fast, wild, and hot
The fantasy continued on and on, with no room left to move
nowhere existed, nothing mattered, no more to prove
I think I've fallen in love, awakened by our lust
hot as hellfire, burning angel's wings to dust
Your Sympathy is NothingIf the pawn shop would buy backYour Sympathy is Nothing5 years ago in Free Verse More Like This
all these broken promises
you left me holding
I'd take them
and sell them
and buy a pretty diamond ring
and shove it right down your throat.
I'm not running low yet
I've got a ton of disappointment
A metric ton of it
A fleet of trucks full to the brim
A lake of being let down
I'm dragging it behind me
Dragging it to the store
Trying to take it back
But no one will have it.
Since no one will take it
no one wants it
I'm bringing it back
to return it from whence it came
and I am going to give it all back
every last drop
You'll take every let down
every insult
every slight
everything you did to me
you can have it all back
I'm letting go.
irresolute heartsi.irresolute hearts6 years ago in Free Verse More Like This
now you have not broken my heart yet
but you are bending it more than i am
used to; it is creased where you folded
its edges to fit comfortably in your pocket
and you have not stolen my breath yet
but i can feel stardust catch in my
bronchial tubes; we can meet at the lips
and you can breathe deep the butterflies
the words in my mind are not misplaced yet
but you are starting to disorganize them;
i am forgetting that it is politically incorrect
to tell you that i miss you, you are amazing
you have not blinded me yet but i can feel
the corners of my eyes begin to lose focus;
your freckled skin is exotic on its own but
the shadows of your secrets make you beautiful
truthfully speaking i have not gone and
fallen for you yet; lately my stomach
has been twisting and my balance is slowly
beginning to succumb to your gravity
Behind Closed EyesBehind Closed EyesBehind Closed Eyes5 years ago in Traditional Fixed Forms More Like This
Of her there are many things to say
Behind closed eyes
I dream the world far away
Near her I wear no disguise
A siren calls when she sings
That call is stronger behind closed eyes
Touching her can mean many things
Restrain myself so we're on the same page
Yet, I can't help smiling when she sings
Right now this sea is hard to gauge
She has a warm and gentle touch
Desire and temptation on the same page
I've grown to like her so much
Minds flying on the wings of doves
She has a warm and gentle touch
I must hold back from this being love
There's so many things i want to say
My heart pounds like the wings of a dove
Lying next to her I dream the world far away
I'm No Longer RushingI'm No Longer RushingI'm No Longer Rushing6 years ago in Free Verse More Like This
Don't be in a hurry to get things done
We're all rushing, now life's no fun
People just live till they die, then the battles won
But now I'm in a hurry and I don't know why
Times have been real dark of late
Struggling to live, struggling not to hate
I wish I could shove all my problems in a crate
And drop it in the ocean, let it sink, let it die
My heart is chained to four wild beasts
Pulling in every way, North, West, South and East
I'd hoped their plan to have me drawn and quartered would succeed at least
But my heart stays whole, in one piece no matter how hard they try
I merely hang in silent tension
Struggling to remember reasons to give my life mention
Struggling to turn away from that one question
The chains start to slip as I remember our life, just you and I
I Thought I Was DifferentI thought I was different.I Thought I Was Different5 years ago in Limerick More Like This
I thought I knew you.
I thought you'd pick me, out of the two.
How could you pick her,
And play with my heart?
I thought we had something right from the start.
Right at the moment I said yes to you,
My world had changed
But is now ripped in two.
How could you pick her,
And mess with my head?
You made me cry while I sat on my bed.
I was alone
With no one to hold.
I felt uneasy.
I felt cold.
How could you pick her,
And toy with my soul?
Do you know how it feels not to have you anymore?
I don't care what you say.
I don't care what you do.
Because, Mr.Not-My-Guy,
I Hate You.
|Sta.sh Submit


text:
well done
great capture, love the colours, well done
Thank you both, very much.
gorgeous shot well done
Thanks, Maree.
he's beautiful:)
nice details…wow
Thank you both, very much.
Yours are gorgeous! wow.. We only have one kind of hummingbird in my area, the Ruby Throat, its beautiful, but wow what I would do to see some of the ones you have photographs of.
Thanks Danielle. That's what we have, this was the first time I've seen one with these colors.


text:
1965 Buick Skylark GS 2 Door Hardtop. V-8 Wildcat 445, 4 Speed, Bucket Seats, Factory Radio, Power Steering, Power Brakes, Dual Exhaust, American Racing... More
1967 Buick Skylark Convertible. Frame Off Restoration of this Skylark Resto Mod done in 2008. Rebuilt Engine, Power Brakes, Automatic Transmission on... More
18K Mile "UNRESTORED" Gem! Drives and operates in ALL respects just like Brand New! NO DECAY- NO LEAKS - EVERYTHING WORKS FULLY & PROPERLY. 15 Factory Options including PS,... More
1968 Buick Skylark Custom Hardtop, one owner original car, kept in storage in southern Califhtnia for 30 years. Never been out side at night... More
Buick 1963 Riviera, early production model, fully restored, body taken down to bare metal before repaint, 91,000 original miles, previous owner owned 47 years,... More
If you're a car guy, I don't care what you drive, you know better than to mess with the big, bad, blown Buicks. Right... More
JUST IN AND GREAT VALUE! THIS CAR HAS NOT BEEN DETAILED YET READY FOR SALE. LOTS OF PHOTOS COMING SOON. IF YOU WANT US... More
1991 Buick Reatta Convertible, This is a very special one of a kind car. Because only 205 convertibles were delivered to dealerships, it was... More
For sale here is a very clean and sharp 1962 Buick Skylark convertible. Currently on display at the Murphy Automobile Museum in Oxnard, California,... More
GR Auto Gallery is pleased to present this 1968 Buick Riviera Sport Coupe for purchase. The Riviera was designed by GM legend Bill Mitchell... More
Just arrived, this beautiful convertible has been well cared for and garaged since new. All original floor pans attest to its care by its prior... More
This is a fully restored, all numbers matching, FIRST YEAR of the dual quad 360HP Super Wildcat powerplant mated with every conceivable option offered... More
If you're reading this ad, you've probably been looking for just the right Reatta to enjoy and drive. Look no further, this is it! Here is your opportunity to... More
FOR SALE Up for sale is a redone 1985 Buick Regal T-Type. Powered by an upgraded 3.8 liter V6 tuned to 12 lbs... More
~CALL US FOR A DETAILED DESCRIPTION OF THE CAR! WE DO A 150+ POINT CHECK ON EACH VEHICLE AND ARE HAPPY TO SHARE... More


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Movable backrests allow for customization.
Porch swings are nostalgic fixture, but Mississippi-based SwingLab versions have a contemporary look. Each bench is handcrafted from heirloom-quality cypress and the backrests are removable, so they can be configured to customize seating options.
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Colby Armstrong receives 2-game suspension
Apr 2, 2010, 3:12 PM EDT
The NHL handed Colby Armstrong a two game suspension for last night's ugly hit on Mathieu Perrault of the Washington Capitals, according to the Atlanta Journal Constitution. Brandon had a great write-up of the hit earlier this morning, so I'll defer to his take.
Despite Perreault turning up ice, Armstrong certainly came at him from a straight-ahead direction. You can see video of the hit here.
That does not change the fact, however, that Armstrong's hit was dangerous and highly illegal. This is not a case of Perreault skating with his head down and then getting rocked, but of Armstrong needlessly leading with his hand and forearm for what should have been a big open-ice hit.
Perreault attempted to dodge the hit at the very last instant, which contributed to the hit looking pretty bad. That doesn't change the fact that Armstrong's hit was illegal and he should face supplemental discipline for the hit.
Look, I don't consider myself a go-to source regarding judgment on these hits. All I can say is that it – along with the hits by Matt Cooke and Mike Richards – seemed unnecessary. It's an irresponsible hit regardless of whether or not it is worthy of a suspension.
If the league has to be ruthless with punishments to get players to stop being foolish, then so be it.
Update: Here's the video of the hit from NHL.com.
- Laura - Apr 2, 2010 at 10:52 PM
It was even *more* unnecessary when you see it takes Army out of position and almost allows a Caps' breakaway. Stupid, selfish play and it takes him out for 2 vital games.
Not a huge Army fan anyway, but stuff like this is why I'd be ok if he walks.
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Pronunciation: sacrificial
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A contact lens possessing a wettable surface in its aqueous environment of use fabricated from a hydrophobic addition polymer incorporating between about 0.5 and about 30% weight oxirane substituted units in the backbone thereof, wherein the outer surfaces of said lens contain an effective hydrophilic inducing amount of a reaction product of said oxirane substituted units of the formula ##STR1## wherein R is hydrogen or methyl;
R1 is ##STR2## or lower alkylene; n is 1 to 4; and
R0 is hydrogen or ##STR3## with a water soluble reactive organic amine, alcohol, thiol, urea or thiourea or a sulfite, bisulfite or thiosulfate, and the use thereof by placement in the eye of a patient in need of the same to correct vision defects of a refractive nature.
1. A contact lens possessing a wettable surface in its aqueous environment of use fabricated from a hydrophobic addition polymer incorporating between about 0.5 and about 30 percent by weight oxirane substituted units in the backbone thereof, wherein the outer surfaces of said lens contain an amount sufficient to increase the contact angle by at least 5�, of a reaction product of said oxirane substituted units of the formula: ##STR12## wherein R is hydrogen or methyl;
R1 is ##STR13## or lower alkylene; n is 1 to 4; and
Ro is hydrogen or ##STR14## with a water soluble amine, alcohol, thiol, urea or thiourea, or a sulfite, bisulfite or thiosulfate.
2. A contact lens according to claim 1, wherein the contact angle is increased by at least 10�.
3. A contact lens according to claim 2, wherein the contact angle is increased by at least 15�.
4. A contact lens according to claim 1, wherein the reaction product is a reaction product between said oxirane and a water soluble aliphatic, cycloaliphatic or aromatic primary or secondary amine having up to 12 carbon atoms.
5. A contact lens according to claim 1, wherein the reaction product is a reaction product between said oxirane and a water soluble pharmaceutically acceptable salt of a sulfite, bisulfite or thiosulfate.
6. A contact lens according to claim 1, wherein the hydrophobic polymer has a contact angle less than about 150�.
7. A contact lens according to claim 6, wherein said contact angle is less than 145�.
8. A contact lens according to claim 1, wherein the contact lens material is a silicone containing copolymer.
9. A contact lens according to claim 1 wherein the reaction product is prepared by conducting the reaction in aqueous medium at a PH between 3 and 10 and a temperature between 0 and 100� C. for a period of time sufficient such that the surface region of the lens, up to 10 percent of the thickness thereof is reacted to form reaction product.
Contact lenses are commonly placed into two categories, soft lenses and hard lenses. Soft lenses are rubbery and pliable, and they are fitted so as to closely match the shape of the cornea. Because of their softness they are more comfortable for the wearer than are hard lenses and because of their tight fit they have to be oxygen permeable in an amount sufficient to meet the needs of the cornea if worn for extended periods.
Hard lenses on the other hand have to possess excellent dimensional stability and are fitted so as to sit on the cornea only with the center of the lens, leaving enough space between their edges and the eye to allow good tear liquid exchange and thereby oxygen supply to the cornea. Although hard lenses are less comfortable to wear, they can be fabricated with greater precision and are preferred to correct, for instance, astigmatism. For both types of lenses excellent wettability by the tear liquid is important. This is especially true for soft lenses; soft lenses which cannot freely rotate on the eye and which are not easily wettable can become stuck to the cornea--which also is hydrophobic--and difficult to remove, sometimes only with injury to the eye, due to the suction-cup effect. For this reason commercially successful soft lenses are primarily of the hydrogel type, most commonly made from poly(2-hydroxyethyl methacrylate, HEMA), from HEMA copolymers, or from vinylpyrrolidone copolymers. These contact lenses generally contain from 38-75% water and thus water content is primarily responsible for their softness, their oxygen permeability (DK) of about 8 to about 30 barrers and their good physiological response.
On the negative side, the high water content makes a rather weak polymer, and oxygen permeability cannot therefore be further increased by raising water content or cutting thinner lenses. Oxygen permeability of 20-50 barrers for hard lenses and up to 100 barrers for soft lenses are desirable and required for extended wear contact lenses. In addition, hydrogel contact lenses have to be regularly sterilized.
These drawbacks could be overcome if silicone rubber could be used as contact lens material; it is strong, comfortably soft and polysiloxane is the polymer with one of the highest known oxygen permeability. Unfortunately polysiloxane is also very hydrophobic and imparts this hydrophobicity to polymers which contain a substantial amount of it. This hydrophobic character also leads to excessive deposition of protein and/or lipids on a contact-lens surface.
A number of methods have been used to make polymethylmethacrylate (PMMA) and polysiloxane based contact lenses more wettable. U.S. Pat. No. 4,131,696 describes the treatment of PMMA contact lenses with aqueous, colloidal suspensions of inorganic hydroxides. Plasma-treatment in a glow discharge chamber using water, hydrazine, ammonia, formamide, ethylene diamine and similar compounds is used to hydrophilize PMMA and silicone rubber and is described in U.S. Pat. No. 3,952,178. A similar process using gases such as oxygen, nitrogen, NO2, N2 O, N2 O3, NO, SO2 and CO is described in FR No. 2,483,310. U.S. Pat. No. 4,139,660 describes the treatment of hydrophobic surfaces with halides of elements from group IV of the Periodic Table, followed by an aqueous rinse. U.S. Pat. No. 4,055,378 describes a treatment by activated oxygen ions of an SiO2 -filled silicone lens, by which the SiO2 filler becomes exposed to the surface and/or organic silicone groups are oxidized to SiO2 to thereby render the surface more wettable. U.S. Pat. No. 4,062,627 and U.S. Pat. No. 4,099,859 describe free-radical initiated grafting reactions of N-vinylpyrrolidone or hydroxyalkyl(meth)acrylates on the surfaces of silicone rubber contact lenses.
Every one of these methods suffers from one or several drawbacks. For example, plasma treatments and oxidizing treatments of PMMA and silicone surfaces produce only very thin modified surface regions and therefore these treatments do not provide sufficiently permanent wettability. If the effect wears off, it can only be restored by a new and expensive repetition of the original treatment. Grafting methods involve the use of a swelling monomer on a precision-cut contact lens, which can easily lead lo permanent distortions of its optical properties. In addition, by the very nature of free-radical initiated grafting reactions quality control is very difficult and the whole process is cumbersome. The grafting polymerization must be conducted at temperature levels and periods of time under which the vinyl monomer is capable of diffusing into and swelling previously grafted polymer chains, thereby producing irregular regions of proliferating grafting by a positive feedback effect. In other words, after the very first grafting to the hydrophilic silicone surface has been accomplished the new surface is much more absorptive to the monomer. The monomer is thermodynamically compelled to swell the grafted hydrophilic polymer and further irradiation will produce additional grafting in regions already reached in the polymer. Thus, the process is one of positive feedback and can lead to gross differences in amount of grafted hydrophilic polymer per unit area to silicone substrate. Upon subsequent immersion in water the more grafted regions swell to the greater degree, thereby potentially distorting the interface and producing undesirable optical dispersion.
It has now unexpectedly been discovered that if glycidyl groups containing contact lenses are treated under mild aqueous conditions with a variety of primary or secondary amines, thiols, thiourea, sulfite or thiosulfate, a permanently wettable surface is obtained without impairing the clarity or the optical quality of the lens. It is a further advantage of the process of this invention that it is exceedingly simple and very easy to control and, should the effect ever wear off, very safely and easily repeated by the wearer of the lens at home. It is a further objective of this invention to use the described surface-treatment of glycidyl groups containing contact lenses during the routine contact lens cleaning procedures carried out by the contact lens wearer. We speculate that the high quality and distortion-free nature of the final contact lens is a result of the single-step nature of the reaction. Step-reactions, of which polycondensation is a prime example, are much easier to control than are chain-reactions, where a very rapid growth reaction generally leads unpredictably to very high molecular weights. Single-step reactions also assure excellent compatibility of the treated surface with the underlying bulk polymer whereas the high molecular weight of free-radical grafted chains leads to phase separation and thereby optical haziness.
Glycidyl acrylate and glycidyl methacrylate as components of silicone-free hydrogel contact lenses have been specifically described in U.S. Pat. Nos. 3,787,380, 3,758,448, 3,772,235, 3,947,401; in several other patents it is disclosed as a possible component of the monomer mixture. In all instances the purpose of using this monomer is to influence water uptake and crosslinking reactions. U.S. Pat. Nos. 4,182,725, 4,182,723 and 4,169,119 describe silicone rubber lenses made wettable by inclusion of small amounts of glycidyl(meth)acrylate polymers, without additional surface treatment. Although an increase in wettability has been shown in these patents, this increase is insufficient to fulfill the requirements of a silicone-based soft contact lens having a surface of sufficient wettability to provide for adequate patient comfort.
In Canadian Pat. No. 1,099,546 glycidyl methacrylate is used as part of a hydrogel-contact lens formulation to introduce rigidity.
U.S. Pat. No. 4,338,419, in relevant part, discloses the complete removal of residual uncrosslinked oxirane units present as a minor impurity in a crosslinked hydrophilic hydrogel material formed of a polymerized comonomer mixture initially containing not more than 5% oxirane monomer as a crosslinking agent, and exemplifying less than 1% by weight thereof in the initial monomer mixture, by reaction with a thiol. No increase in the hydrophilicity of the surface of the lens materials is reported.
It is an object of the present invention, in clear contradistinction to the prior art, to provide normally hydrophobic oxirane containing contact lenses with a substantially increased hydrophilic surface, i.e. to increase the wettability thereof, by incorporating a hydrophilic inducing amount of a water soluble organic amine, alcohol, thiol, urea or thiourea, or a sulfite, bisulfite or thiosulfate - oxirane reaction product on the surfaces of such lens.
It is a further object of the present invention to provide a method to correcting vision defects of a refractive nature by placing in the eye of a patient in need of the same, a contact lens made of such material containing the aforementioned surface modification.
These and other objects of the instant invention are more fully set forth in the following detailed description.
One embodiment of the present invention relates to a contact lens possessing a wettable surface in its ocular aqueous environment of use fabricated from a hydrophobic addition polymer incorporating between about 0.5 and about 30% by weight oxirane substituted units in the backbone thereof, wherein the outer surfaces of said lens contain an effective hydrophilic inducing amount of a reaction product of said oxirane substituted units of the formula ##STR4## wherein R is hydrogen or methyl;
R1 is ##STR5## or lower alkylene; n is 1 to 4; and
R0 is hydrogen or ##STR6## with a water soluble organic amine, alcohol, thiol, urea or thiourea, or a sulfite, bisulfite or thiosulfate.
By hydrophobic addition polymers is meant that class of addition polymers which exhibits a contact angle by the captive bubble technique of less than about 150�, preferably less than about 145�, most preferably, less than about 140�.
Alternatively, the hydrophobicity of such addition polymers can be characterized in terms of the wettability of the polymer surface, generally expressed as the rate at which a water film on the surface of the polymer retracts or beads up. Thus, in the context of the present invention, useful oxirane containing hydrophobic addition polymers are those wherein a sample, having a vertical length of 40 mm, a width of 20 mm and a thickness of 1 mm is vertically removed from distilled water and the water film retracts, or beads up, at a rate such that about 90% of the surface is visually water free in less than about three seconds, preferably about two seconds or less.
By a hydrophilic inducing amount of the aforementioned reaction product of water soluble organic amine, alcohol, thiol, urea or thiourea, or a sulfite, bisulfite or thiosulfate with the oxirane containing units of formula I is meant an amount sufficient to increase the contact angle, as measured by the captive bubble technique by at least 5�, more preferably at least 10�, most preferably at least 15�.
In terms of wettability, as defined in accordance with the retraction time of a 40-mm by 20-mm by 1-mm sample, a hydrophilic inducing amount can be characterized as an amount sufficient to increase the 90% retraction time of water to greater than about 5 seconds, preferably greater than about 10 seconds.
Hydrophobic addition polymers containing units of formula I are known, per se, or can be manufactured by polymerization techniques well known in the art, by copolymerizing between about 0.5 and about 30 percent by weight of an oxirane containing monomer of the formula ##STR7## with about 99.5 to about 70 percent by weight of one or more conventional mono- or polyvinylic comonomers employed in the contact lens field.
Suitable comonomers include alkyl acrylates and methacrylates, especially C1 -C20 alkyl acrylates and C1 -C20 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like; alkanoic vinyl esters, especially C1 -C6 alkanoic vinyl esters such as vinyl acetate, vinyl butyrate and the like; alkenes, especially C2 -C8 alkenes, including ethylene, 1-butene, 1-hexene, and the like; styrenes, especially styrene and alpha-methyl styrene; vinyl ethers, especially C1 -C6 alkyl vinyl ethers, including methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, and the like; dialkyl maleates, fumarates or itaconates, especially C1 -C6 dialkyl maleates, fumarates or itaconates, including dimethyl maleate, dimethyl fumarate, diethyl maleate, dimethyl itaconate and the like; allyl ethers and esters, especially allyl C1 -C6 alkyl ethers and allyl C2 -C6 alkanoate esters, including allyl methyl ether, allyl ethyl ether, allyl acetate and the like; perfluoro C3 -C6 alkyl acrylates or methacrylates; perfluoroalkoxylated bis-acrylates or -methacrylates; poly- or oligo-alkylsiloxane acrylates or methacrylates, and the like.
Also, minor amounts of a crosslinking agent, to increase hardness, stability and the mechanical characteristics of the polymer are generally employed. Suitable crosslinking agents include, for example, C2 -C6 alkylene ether di-methacrylates and acrylates, e.g. ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerine trimethacrylate; allyl acrylate or methacrylate, divinyl benzene, poly- or oligo-alkylsiloxane di-acrylate or -methacrylate, and the like.
Also, as a minor constituent, there may be present one or more conventional hydrophilic monomers. The amount of such hydrophilic monomers will, for the purposes of this invention, be less than the amount needed to raise the aforementiond contact angle of the polymer to greater than about 150�, preferably less than 145�, most preferably less than about 140�, and in an amount insufficient to retard the 90% retraction time to greater than about three seconds, preferably insufficient to retard the 90% retraction time to greater than about two seconds or less. Suitable hydrophilic monomers include those conventional monomers employed in the contact lens field include hydroxylated C2 -C6 alkyl acrylates and methacrylates, including 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, and 2,3-dihydroxypropyl methacrylate; N-vinyl lactams, including N-vinyl pyrrolidone; acrylamide; C1 -C2 alkyl acrylamides, such as methyl acrylamide or dimethyl acrylamide; and the like.
Preferably, the hydrophobic addition polymer is an addition polymer containing from about 1 to about 20 weight percent of the units of formula I, i.e. formulated from a corresponding amount of the monomer of formula II. Most preferably, the polymer contains from about 5 to about 12 weight percent of the units of formula I.
Preferred comonomers are C1 -C6 acrylates and methacrylates, including methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like; ethylene glycol dimethacrylate; and poly- or oligo-alkylsiloxane mono- or bi-acrylates or methacrylates; or mixtures thereof.
Preferred monomers of formula II include glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. Most preferred is glycidyl methacrylate.
The polymer can be obtained from the monomer mixture by methods known per se. Thus, the monomer mixture can be polymerized at a temperature between about 0� C. to about 100� C., in the optional presence of a free radical catalyst and/or in the presence of actinic radiation, such as UV radiation.
The polymer may be cast in the form of a contact lens by the use of a conventional mold, or by spin casting polymerization techniques or may be cast as a rod, or as buttons which are then machined into the desired shape of a contact lens.
For example, contact lenses suitable for carrying out surface reactions can be made by either molding or casting, or by machining from clear polymers containing about 0.5 to about 30 weight percent of units of formula I in the polymer backbone. They can be hard contact lens materials as exemplified by polymethylmethacrylate (PMMA), such as PMMA copolymers with glycidyl methacrylate; or they can be silicone containing hard lenses, which contain in addition to PMMA or other hard (meth)-acrylic polymers oxygen-permeable poly- or oligosiloxane units, and which are for instance described in U.S. Pat. Nos. 3,808,178; 4,120,570; 4,139,513; 4,152,508; 4,189,546; and 4,157,508. Since glycidyl methacrylate is a monomer which imparts high hardness to an acrylic copolymer, its use as an additional comonomer in the compositions covered in these patents does not negatively influence their properties.
Another class of contact lenses especially useful for this invention are silicone containing lenses, such as hydrophobic, silicone containing lenses, as for instance disclosed in U.S. Pat. Nos. 4,182,725 or 4,245,069.
Inclusion of about 0.5 to about 30 weight percent glycidyl methacrylate into the above disclosed polymer compositions gives lenses which can be modified in the manner described hereinafter.
Most preferred silicone contact lens materials are:
Hydrophobic, silicone containing copolymers of 1-30% glycidyl (meth)acrylate, 50-90% of the reaction product of a diisocyanate capped polydimethylsiloxanylalkyl-polyol of a MW from 800-5000 with 2-hydroxyethyl (meth)acrylate, or N-tertbutylaminoethyl methacrylate, or of said polydimethylsiloxane polyol with 2-isocyanatoethyl methacrylate, and 0-40% of a C1 -C20 alkyl (meth)acrylate.
The reactive compounds may be a water soluble aliphatic, cycloaliphatic or aromatic primary, secondary or tertiary amine or polyamine, especially those having up to 12 carbon atoms, and preferably amines which contain an additional functional group as part of the molecule, such as a conventional hydrophilic moiety, or several such moieties. Primary and secondary amines are the preferred compounds.
Conventional hydrophilic moieties which may be present as substituents include, for example, hydroxy, amido, polyethoxy, lower alkoxy, carboxy, sulfato, sulfonamido, sulfo, phosphato, phosphonato, and the like. Preferred polyethoxy groups include polyethyleneoxy of 2 to 100 units.
Other reactive compounds are water soluble sulfite, bisulfite and thiosulfate salts, water soluble mono- or dithiols, either aliphatic or aromatic in nature, and preferably water soluble thiols of up to 12 carbon atoms optionally containing one or more hydrophilic substituents, e.g. as enumerated in the preceding paragraph.
Exemplary of suitable water soluble compounds are:
methylamine, dimethylamine, ethylamine, isopropylamine, diisopropylamine, poly(ethyleneimine), 2-aminopropylether, polyethylene or polypropylene oxide diamine (Jeffamine) and those in which the amine is contained in a ring such as pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine, ethylenediamine, bis-aminopropylpiperazine, aniline, p-methoxyethoxybenzylamine, aminoethanol, diethanolamine, n-propanolamine, di-n-propanolamine, isopropanolamine, diisopropanolamine and other lower branched alkanols which can be polyhydroxy such as 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, 1,3 bis [tris(hydroxymethyl)methylamino]propane, N-(3-aminopropyl)diethanol, D-glucosamine, N-methyl-D-glucamine, N-(β-hydroxyethyl)piperazine, 2-piperidineethanol, p-aminophenol, aminocresol, aminobenzylalcohol, glycine, serine, aspartic acid, sarcosine, tyrosine, tricine, 3-aminobutyric acid, 6-aminohexanoic acid, 4-amino-3-hydroxybutyric acid, 2-aminoethanesulfonic acid, N-methyltaurine, 2-aminoethyl hydrogen sulfate, N-(2-acetamido)-2-aminoethanesulfonic acid, aminobenzoic acid, p-aminocinnamic acid, 4-amino-3-hydroxy-1-naphthalene sulfonic acid, aminosalicylic acid, 6-amino-m-toluenesulfonic acid, 3-amino-L-tyrosine dihydrochloride, purines, pyrimidines, adenine, 2-aminopurine, cytosine, thymine, uracil, adenosine, cytidine, guanosine, deoxyadenosine, thymidine, adenylic acid, adenosine triphosphate, thymidylic acid, deoxycetidine diphosphate, thymidinediphosphate, aminopyridines, imidazole, 2-aminoimidazole, oxazole, thiazole, (4-aminobutyl)-guanidine, S-(2-aminoethyl)isothiouronium hydrobromide, 3-aminocrotonamide, phosphatidylethanolamines, and the like.
Preferred water soluble thiols include: ##STR8## R1 "=H or R4 " and R2 "=H or R5 " where R4 ", R5 " and R3 " are independently straight or branched chain alkyl, cycloalkyl, aryl, aralkyl, alkaryl up to 12 carbon atoms which may be unsaturations or interrupted by heteroatoms such as oxa, imino or the like, or R1 " and R2 " together is an aliphatic divalent radical of up to 6 carbon atoms, and R4 ", R5 " and R3 " may be unsubstituted or be substituted with one or more of the aforementioned hydrophilic substituents.
Useful preferred compounds include water soluble amines of the general structure: ##STR9## wherein R1 '=H or R3 " where R3 ' and R2 ' may be independently a straight or branched chain alkyl, aralkyl, alkaryl, aryl or cycloalkyl of up to 12 carbon atoms that may include unsaturation or be interrupted by heteroatoms such as oxa, imino and the like, or R1 ' and R2 ' together form a divalent aliphatic radical of up to 6 carbon atoms which is unsubstituted or substituted by one or more hydrophilic groups. R3 ' or R'2 can also together represent a heterocyclic moiety. Suitable hydrophilic groups are those recited above.
Exemplary of suitable water soluble thiols are:
ethanethiol, 1,4-butanedithiol, 2-mercaptoethylether, pentaerythretoltetrathiopropionate and acetate; polyethyleneglycoldimercaptoacetate and methylthioglycolate, allyl mercaptan, 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 1-thioglycerol, thioerythritol, 2,3-dimercaptopropanol, pentaerythretolmono (di; tri)thiopropionate or acetate, thioglycolic acid, thioacetic acids, 3-mercaptopropionic acid, thiolactic acid, thiomalic acid, thiosuccinic acid, thiosalicylic acid, thiobenzoic acid and their respective water soluble salts, glutathione, furfuryl mercaptan, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-3-pyridinol, dimethylaminopropanethiol, 2-mercaptoethylamine, 2-n-butylaminoethanethiol, and the like.
Also, especially preferred are the water soluble salts of sulfite, bisulfite and thiosulfate, especially the pharmaceutically acceptable salts thereof.
Exemplary of suitable water soluble ureas and thiouras are:
urea, methylurea, ethylurea, butylurea, hydantoin, 5-hydantoinacetic acid, 2-amino-3-ureido-propionic acid, diureidoacetic acid,pyrimidinetetrone, 6-amino-1,3-dimethyluracil, 5-aminoorotic acid, 2-amino-5-ureidovaleric acid, 2-imidazolidinone; thiourea, 1-methyl-2-thiourea, 5-methyl-2-thiouraci1,2-imidazolidinethione, and the like.
Exemplary of suitable water soluble alcohols are:
methanol, ethanol, glycol, glycerol, polyvinyl alcohol, polyethylene glycol, dextrose, glucose, mannose, fructose, sorbitol, maltose, dextran, dextrin, agarose, gum arabic, phenol, acetamidophenol, pyrogallol, resorcinol, and the like.
The reaction can be carried out in any liquid medium which is a solvent for the reactant but is preferably an aqueous medium, consisting of water or water-solvent mixtures. The addition of solvent to the reaction medium is sometimes necessary to ensure penetration of the reactant into the substrate, especially if this substrate is hard and hydrophobic. Solvents may also be required to solubilize otherwise insoluble reactants. It is in some applications such as contact lenses desirable to cause as little swelling of the substrate as possible during the reaction in order to avoid later optical distortion.
In many cases it is also advisable to use a buffered aqueous solution to insure reproducibility and avoid unfavorably high or low pH range. Preferably the reaction is carried out at a pH between 3 and 10, more preferably between 7 and 9. Since at the very low pH necessary to effect reaction between glycidyl groups and tertiary amines, hydrolysis of the glycidyl group occurs also, tertiary amines are generally unsuited to prepare the products of this invention. Any of the commonly used buffers can be used as long as they do not interfere with the reaction, for instance phosphates, borate, citrates. Some reactants, such as TRIS (trihydroxymethylaminomethane) are themselves buffers.
The reaction temperature can vary over a wide range, typically it is between 0� and 100� C., preferably between 20� and 60� C., most preferable between 25� and 35� C. The reaction time can also vary as a matter of choice of reaction temperature and reactant concentration. Dependent on substrate and reactant, reaction times from 1 minute to 1 day are useful and most commonly they range from 10 minutes to 5 hours.
Reactant concentrations can vary from 0.1% to 100%, preferably they range from 5% to 50%, most preferable they are between 10 and 30%.
When the reaction is carried out in primarily aqueous or in organic medium with hydrophobic contact lenses, especially silicone containing materials, the reaction and resulting modification can be restricted to a surface region whose depth depends on a variety of parameters such as molecular size of reactant, nature and amount of cosolvent, reaction time and temperature. By determining the rate of diffusion and of reaction of a given reactant the depth of the modified region can accurately be predicted. Generally, a depth of up to about 10 percent of the thickness of the lens can be reacted. Excessive penetration may result in reduced oxygen permeability and should generally be avoided. Also, excessive penetration of the reaction may in some instances, unduly distort the lens parameters, e.g. shape. Preferably a depth of up to about 5 percent of the thickness is reacted.
In the following examples, wettability is determined by contact-angle measurements on the underside of samples immersed in distilled water, floating either an air bubble or a drop of n-octane to the lower surface. In these measurements a high contact angle corresponds to high wettability. In some cases wettability is denoted in terms of retraction time. We define the retraction time as follows: if a sample (40-�20-�1-mm) is vertically removed from water, the water film on the surface retracts (or beads up). The number of seconds elapsing until 90% of the surface is free of water is defined as the retraction time (=tR). Low wettability would correspond to a tR of less than three seconds, preferably two seconds or less.
The polymers listed in Table A are prepared by UV-initiated free-radical polymerization of vinylic monomers with a suitable dimethacrylate as crosslinking agent. The short-chain crosslinking agent is ethylene glycol dimethacrylate (EGDA); Polymeric crosslinking agents are either the trimethylacrylate (PSM) obtained by reacting 1 mol of a polydimethylsiloxane-triol of �6000 MW (fluid 7248' from DOW CORNING) with 3 moles isophorone diisocyanate followed by capping with 2-hydroxyethyl methacrylate (≡PSM) or the dimethacrylate (PEM) obtained by reacting 1 mol of poly-n-butyleneoxide diol of �2000 MW (Polymeg 2000, Wyandotte Chem. Corp.) with 2 moles isophorone diisocyanate followed by capping with 2-hydroxyethyl methacrylate.
60 g PSM, 30 g methyl methacrylate (MMA) and 10 g glycidyl methacrylate (GMA) are mixed in a bottle together with 0.2% 1-hydroxycyclohexyl phenyl ketone (IRGACURE-184), a UV-initiator. The sample is degassed under nitrogen and filled into MYLAR lined glass molds (10-cm�10-cm) using 1-mm rubber cord or cut-out 0.1-mm MYLAR sheet spacers. The molds are irradiated by Black-Light Blue Sylvania lamps for 3 hours, after which time the sample is removed and extracted in absolute ethanol for two days. After drying the polymer can be used for surface modification.
The following examples show the effect of solvent on the yield of reaction and the results are summarized in Table 1.
Three sections (19-�7-�1-mm) of polymer 1 of combined weight of 0.3787 g (5.33�10-4 moles GMA) are stirred for 19 hours in a solution of 1.72 g: (0.016 moles) diethanolamine in 4.4 g absolute ethanol (final volume of 6 ml). Then the samples are washed by stirring in absolute ethanol (25 ml, 3�1 hr.). The samples are then dried in a vacuum oven at 70� C. for 21/2 hours. From the weight of modified polymer (0.4108 g), the yield based on GMA is calculated to be 57%.
This example is performed in a similar fashion to that of example 1 except the solvent used is 70% ethanol/30% water (w/w). The final washing step (total of 4 washings) is followed by an additional wash in absolute ethanol before vacuum drying. The calculated yield based on GMA content is 24%.
The following table lists the compositions synthesized in the manner described above.
TABLE A__________________________________________________________________________PolymerComposition %NumberPEM PSM HEMA DMA MMA EHA BA GMA EGDA__________________________________________________________________________1 50 10 20 202 50 10 20 203 60 20 204 19 -- 60 20 15 15 -- 60 256 39.5 39.5 20 17 40 40 208 39.5 39.5 20 19 40 40 2010 79 20 111 79 20 112 50 30 2013 50 30 20__________________________________________________________________________ HEMA: 2hydroxyethyl methacrylate MMA: methyl methacrylate DMA: dimethyl acrylamide EHA: 2ethylhexyl acrylate BA: butyl acrylate GMA: glycidyl methacrylate EGDA: ethylene glycol dimethacrylate
This example is performed in a similar fashion to that of Example 2 except the solvent used is 60% ethanol/40% aqueous buffer (pH 9). Since the concentration of buffer is 1% (potassium phosphate and sodium borate) and that of reactant approximately 3.4 Molar, the solvent behaves as 60% ethanol/40% water. The calculated yield based on GMA content is 10%.
This example is performed in a similar fashion to that of example 2 except the solvent used is deionized water. The washing step is 2�1 h water, 2�1 h 60% ethanol/40% water and then absolute ethanol. The calculated yield based on GMA content is 0%.
The results in Table 1 show that the yield of the reaction decreases as the percent of water in the reaction solvent increases. Since the samples swell to a greater extent in ethanol than in water (length of sample in ethanol, water and dry state is 2.1, 2.0 and 1.9 cm respectively) more epoxy groups would be exposed in ethanol and available for reaction with the amine. Also we note that as the reaction proceeds the modified samples swell to an even greater extent. For example, a dry sample 1.9 cm in length increases to 2.1 cm after swelling in absolute ethanol then after a reaction with diethanol amine in ethanol the length increases further to 2.5 cm. This can account for the yield dropping from �60% when the reaction takes place in absolute ethanol to a negligible value when the reaction takes place in deionized water (or buffer, pH 9). Note that by stating the yield is zero means that the weight gained after the drying step is not detectable. A 0.1% yield, which would not be detected by our weighing procedure, can result in a depth of several thousand Angstoms having been modified. We also note from Table 1 that the introduction of the alcohol groups from diethanolamine increases the hydrophilicity of the material.
TABLE 1______________________________________Reaction of Polymer 1 withDiethanolamine1 in Ethanol and Aqueous Ethanol Yield H2 OEx. Solvent (%) (%)______________________________________1 Absolute 57 11.2 Ethanol22 70% Ethanol 24 8.1 30% Water33 60% Ethanol 10 6.1 40% Buffer (pH 9)44 Deionized 0 3.2 Water5______________________________________ 1 30 molar excess of amine to epoxy groups. 2 19 hours at room temperature in a volume of 6 ml. 3 161/2 hours at room temperature in a volume of 6 ml. 4 161/2 hours at room temperature in a volume of 5 ml. 5 161/2 hours at room temperature in a volume of 5 ml.
The following examples show the dramatically improved wettability of polymer 2 after treatment with amine and sulfite reactants in 15% ethanol/85% water. The reaction procedure used is essentially that mentioned earlier except the last washing step is not with ethanol but with deionized water. The contact angles are measured after approximately 7 days equilibration in water.
The monomer EHA is included in the polymer 2 composition to give the final product a soft, draping quality. In addition to rendering the final polymerized samples soft, the addition of EHA also leads to a material that is more hydrophobic. Thus in reaction solvents that contain a high proportion of water the polymerized sample swells to an even lower degree resulting in an even more surface specific reaction (i.e. less dept).
______________________________________ Contact AngleEx. Reactant Air/H2 O Octane/Water______________________________________5 TRIS1 168 1676 D-glucosamine2 (pH 8) 167 1687 Na2 SO3 3 156 1608 --, control4 146 142______________________________________ 1 1.53 g TRIS in 10 g solvent (TRIS = Tris (hydroxymethyl)aminomethane). 2 2.73 g DGlucosamine.HCl in 10 g solvent, halfneutralized. 3 1.6 g Na2 SO3 in 18 g solvent. 4 Polymer 2 in 10 g solvent without reactant.
The results in the above table indicate, in most cases, more than a 20� increase in contact angle. This wettability change can be observed more dramatically by eye. Water on the control sample beads up within seconds, but clings for several minutes on the reacted samples.
The following examples show an improved wettability of polymer 1 after treatment with amine and sulfite reactants in 15% ethanol/85% water. The reaction procedure is similar to that for example 5-8. In this case the replacement of EHA with MMA leads to a polymer that is a harder and stiffer material than polymer 2.
______________________________________ Contact AngleEx. Reactant Air/H2 O Octane/Water______________________________________ 9 TRIS 152 14610 D-Glucosamine (pH 8) 148 13911 Na2 SO3 -- 14712 --, Control -- 138______________________________________
For this polymer the contact angle increase is significant but much less than that for the more flexible polymer 2.
The following example with polymer 3 shows the high wettability of the siloxane macromer compositions after a posttreatment. reaction in 15% ethanol/85% water.
______________________________________ Contact AngleEx. Reactant Air/H2 O Octane/Water______________________________________13 TRIS 161 15614 --, Control 144 141______________________________________
The following example shows the wettability change as a function of reation time for polymer 3 reacted with TRIS in 15% ethanol/85% water. After the designated time, the sample is subjected to the washing procedure as stated in example 5.
______________________________________ Contact AngleReaction Time Air/H2 O Octane/H2 O______________________________________No Tris, Control 146 14210 min 155 1431.5 h 159 15917 h 168 167______________________________________
The results show that although at 10 minutes a 9� air/water contact angle change occurred, only a 1� change occurred in the octane/water angle. However a significant change is observed in both angles after 1.5 hours although still not of the same magnitude as that of an overnight reaction.
The following examples demonstrate the universality of the post-treatment reaction on non-silicone copolymers containing 20% GMA in 15% ethanol/85% water. In these materials the rigidity is increased with MMA and the flexibility increased with EHA. Also shown is that the presence of crosslinking agent does not disturb the effect of the reaction. The reaction procedure is similar to that of examples 5-8.
______________________________________ Contact AngleEx. Polymer Number Reactant Air/H2 O Octane/H2 O______________________________________16 6 TRIS 143 13017 Na2 SO3 136 13218 CONTROL 121 10219 7 TRIS 119 8320 Na2 SO3 140 13621 CONTROL 119 9722 8 TRIS 128 11823 Na2 SO3 137 13624 CONTROL 113 9725 9 TRIS 122 10526 Na2 SO3 115 10627 CONTROL 114 9328 10 TRIS 120 11129 Na2 SO3 134 12330 CONTROL 111 9531 11 Na2 SO3 142 13932 CONTROL 109 89______________________________________
If one averages the contact angle increases on different copolymers one finds, for sodium silfite, a 17� air/water and 30� octane/water angle increase and for TRIS a 9� air/water and 7� octane/water angle increase over that of the unreacted control.
The following examples show that the effectiveness of the post-treatment on GMA containing SIMAC compositions extends to levels of GMA much less than 20%. The polymers 3a-3g are synthesized according to the procedure given in Ex. A by replacing GMA with MMA in polymer No. 3. The reaction procedure is similar to that in examples 5-8 using TRIS in 15% ethanol.
__________________________________________________________________________ Contact AnglePol. Treated Untreated ControlEx. # MMA % GMA (%) Air/H2 O Octane/H2 O Air/H2 O Octane/H2 O__________________________________________________________________________33 3 -- 20 158 154 147 14234 3a 5 15 158 154 143 13135 3b 10 10 157 154 147 13936 3c 15 5 154 152 144 13637 3d 17.5 2.5 160 152 -- --38 3e 19 1 153 151 -- --39 3f 19.5 0.5 151 147 -- --40 3g 20 -- 147 141 144 141__________________________________________________________________________
The following examples show that the effectiveness of the Posttreatment on GMA containing non-silicone copolymers covers a wide range of GMA content. Polymers 6a and 6b are synthesized according to the procedure given in Ex. A by replacing GMA with MMA. Also synthesized is a homopolymer of GMA, crosslinked with 1% EGDA (Pol.6c). In these cases a lowering of GMA content is balanced by an increase in MMA content. The reaction procedure is similar to that noted in examples 5-8 this time using TRIS in 15% ethanol.
__________________________________________________________________________ Contact AngleMMA GMA Treated UntreatedEx. Pol. (%) (%) Air/H2 O Octane/H2 O Air/H2 O Octane/H2 O__________________________________________________________________________41 6a 54.5 5 151 134 134 11742 6b 49.5 10 160 143 135 12743 6c -- 99 + 1% EGDA 143 131 127 112__________________________________________________________________________
The results show an approximately 17� octane/H2 O contact angle increase after reaction with TRIS over that of the unreacted control.
The following examples show the effectiveness of the posttreatment in 15% ethanol, on polymer 3 with a variety of primary amines. The reaction procedure is similar to that noted in examples 5-8.
______________________________________ Contact AngleEx. Reactant tR a Air/H2 O Octane/H2 O______________________________________44 H2 NCH2 CH2 OH 64 157 15245 H2 NC(CH3)2 CH2 OH >120 154 15146 H2 NC(CH2 OH)3 >120 155 15247 Polymer 3 Control 1 141 134______________________________________ a tR = retraction time in seconds evaluated 4 days after reaction with amine.
The results show a dramatic improvement in wettability using primary amines containing the hydrophilic hydroxyl function.
The following examples show the effectiveness of the posttreatment in 15% ethanol on polymer 3 with a variety of secondary amines. The reaction procedure is similar to that noted in examples 5-8.
__________________________________________________________________________ Contact AngleEx. Reactant tR, s Air/H2 O Octane/H2 O__________________________________________________________________________48 HN[CH(CH3)2 ]2 5 154 15049 HN[CH2 CH(OH)CH3 ]2 4 155 15250 (HOCH2)3 CNH(CH2)3 NHC(CH2 OH)3 3 154 15051 HN(CH3)CH2 [CH(OH)]4 CH2 OH 30 155 14452 HN(CH3)CH2 CH2 SO3 Na �100 148 146 53 ##STR10## 10 157 15354 HN(CH3)CH2 COOH �100 153 15055 (HOCH2)3 CNHCH2 COOH 3 150 14747 --, Control 1 141 134__________________________________________________________________________ tR = retraction time
The results show that even a hydrophobic amine (Ex. 48) can lead to a wettability increase presumably because the hydroxyl group produced on opening the epoxy ring counteracts the hydrophobic methyl groups. Examples 52 and 54 point out that ionic groups strongly affect the retraction time.
The following examples show the effectiveness of the posttreatment in 15% ethanol on polymer 3 with a variety of mercaptans. The reacton procedure is similar to that noted in examples 5-8 except that the solutions are 10% in mercaptan and 1 M in NaOH. The final pH of the resultant solution is indicated in the Table below.
______________________________________ Contact Angle Air/ Octane/Ex. Reactant pH tR,s H2 O H2 O______________________________________56 HSCH2 CH2 OH 10 28 158 15457 HSCH2 CH(OH)CH2 OH 10 58 156 15358 HSCH2 COOH 5.5 31 156 15259 --O--HSC 6 H4 COOH 7.6 >100 157 15347 --, Control -- 1 141 134______________________________________ tR = retraction time
The results are similar to the secondary amine examples in that ionic groups (Ex. 59) lead to especially long retraction times.
We use two methods to more fully characterize the reaction of GMA containing polymers with various reactants in 15% ethanol i.e. (A) infrared absorption changes and (B) tinting.
(A) In this method we find it necessary to use thin (0.1-mm) films of a polymer that swell in this solvent and then monitor the decrease of the infrared absorption bands, corresponding to the epoxy group, signaling its reaction. The bands monitored using polymer 5 are 850 and 910 cm-1.
(B) A novel way of providing evidence for the posttreatment reaction is by dyeing thick (1-mm) films with fluoresceinamine. The amino group of this dye reacts with epoxy groups and therefore films still containing epoxy groups are tintable. The posttreated films are placed in a 0.04% solution of fluoresceinamine, pH≈12. The films are then extracted overnight in methanol and then further extracted by soxhlet extraction (25 hours in absolute ethanol).
The following examples show the effectiveness of the posttreatment in 15% ethanol on polymer 3 with thiourea, a hydrazide and thiosulfate. The reaction procedure is similar to that noted in Examples 5-8 except that the solutions are 1.5 g of reactant in 15 g solvent.
______________________________________ Contact AngleEx. Reactant Air/H2 O Octane/H2 O______________________________________60 ##STR11## 147 14361 H2 NNHCO+N(CH3)3 Cl- 149 14462 Na2 S2 O3 151 14463 Control, no reactant 142 139______________________________________
The results show an improvement in wettability over that of the untreated control.
The following examples show reactions on polymer 4 using a hydrophilic primary amine and secondary amine. Where a reaction occurs (by disappearance of epoxy bands) tinting fails and where a reaction fails (by non-disappearance of epoxy bands) tinting occurs. Included is a control polymer (Polymer 5) that does not contain epoxy groups (Ex. 68).
______________________________________ Intensity of FluoresceinamineExample Reactant I.R. Emissiona______________________________________64 H2 NCH2 CH2 OH + 165 N--methyl-D-glucamine + 166 Tricine - 667 no reactant - 668 Control, no epoxy 1______________________________________ + = reacted, - = unreacted 1 = colorless, 8 = deep colored a Intensity determined while sample illuminated with lamp of 360nm emission maximum.
The results show that simple primary and secondary amines react but a hindered amine such as tricine fails to react. The control example (No. 68) shows that the amino dye is not absorbed strongly by non-covalent action and that non-epoxy sites in the polymer are not reactive to the amine.
The following examples demonstrate the tintability by reactive dyes of posttreated polymers.
A sample of polymer 3 and of polymer 3 treated with 1-thioglycerol according to the procedure described in example 57 (�1-mm thick) are soaked for one half hour in 4 ml of 10% Na2 CO3 pH 11.6 and then 0.1 ml of dyestuff stock solution (0.1 g Royal Blue in 10 ml of 1 mM HCl) is added. The samples are kept overnight in the dyestuff solution, rinsed in buffer pH 7.4 (50 mM potassium phosphate) and extracted for 24 h in 20 ml of methanol. The blue color of the thioglycerol treated sample does not change on subjecting the sample to soxhlet extraction (66 hours, distilled water), whereas the control becomes completely colorless.
The following example describes the tinting with Royal Blue of Polymer 4 which has been treated with diisopropanolamine in a procedure described in example 49.
The tinting procedure is the same as that described in Example 69.
The resultant blue color is of deeper intensity than that described in example 69.
The following example describes the tinting with Brilliant Yellow G of polymer 4 which has been treated with TRIS in aqueous solution in a procedure described in example 5.
The dyestuff stock solution contains 0.1 g of dye in 10 ml of 1 mM HCl. The tinting procedure (using a 0.1-mm film) is similar to that described in example 69 except the wash procedure is completed with the methanol extraction.
The resultant tint is a deep yellow color.
The following examples show the depth of modification as a function of reactant, solvent, temperature or time.
This example shows a time course of reaction of an Rf thiol (i.e. C8 F17 C2 H4 SH) with the epoxy groups of a dry sample of polymer 15.
The solution, composed of 94 g Rf SH, 12 g triethylamine and 114 g absolute ethanol is maintained at 48� C. Dry samples with dimensions 15�15�1 mm are placed in the solution and at specified times removed and immediately extracted in 300 g of absolute ethanol (maintained at 50� C.) for at least 4 hours with a minimum of one change of fresh ethanol. The samples are dried overnight in vacuo at 80�. From the weight gained the yield of reaction is calculated. An SEM-electron microprobe scan for sulfur reveals the depth of the modification as well as the reaction yield. The following table compares the yield calculated from the weight gain and the line scan.
______________________________________ ModificationReaction Time % of cross-section % by(h) by SEM - Line Scan Weight______________________________________1 27 222 53 423 69 626 100 100191/2 100 100______________________________________
The results show that the weight gain is restricted to a small penetration depth and that even after prolonged reaction time no other functional group (i.e. non-epoxy) on the polymer react. The scans are rectangular in shape suggesting that the modification is diffusion controlled.
This example shows the yield of reaction of an 18 hour post-treatment treatment on polymer 12 with 1-thioglycerol under varying solvent and temperature conditions.
The solutions used are 0.3 M thioglycerol in aqueous ethanol containing sodium hydroxide to ensure all thiols existed as the thiolate anion. For example to make a solution in 45% ethanol, 0.5 g 1-thioglycerol is dissolved in 4.16 g 1N NaOH, 3.74 ml water and 8.1 g absolute ethanol. Dry samples (15-x15-x1-mm)are placed in the solutions overnight. They are then extracted in �20 ml of the same solvent composition for �5 hours with three changes of fresh solvent and dried overnight in vacuo at 80�. From the weight gain and SEM line scan the yield of reaction is determined and presented in the Table shown below.
______________________________________ Modification % of cross-section % byTemperature, �C. % EtOH by SEM - Line Scan Weight______________________________________25 15 0 025 45 10 1525 70 32 3350 15 0 050 45 32 2950 70 69 57______________________________________
The results shoe that the yield increases as the temperature is raised and the solvent swelling power (i.e. increased ethanol content) is increased. The modification proceeds as a sharply moving boundary from the surface into the interior of the polymer.
The following examples demonstrate the effect of posttreatment on protein adsorption.
The protein of choice is albumin because of its abundance in body fluids. A 20-x15-x1-mm sample of polymer 12 or 13 is immersed in 1.8 ml of a 14 C-albumin cocktail (10 mM potassium phosphate buffer pH 7.4, 144 mM NaCl, 0.48 mg/ml `cold` bovine serum albumin, 0.02 mg/ml 14 C-bovine serum albumin) for 2 hours at room temperature. The sample is then removed from the cocktail and then subjected to four sequential rinses of 15 ml of water to remove adhering droplets of cocktail. The sample is then stirred in 10 ml 0.1 M Tris-Cl pH 7 containing 1% octylphenoxy polyethoxy ethanol (Triton X-100) for 2 hours at room temperature to elute uncrosslinked but adsorbed protein and then rinsed in 15 ml water. Protein bound to the polymer (after Triton wash) is determined by scintillation counting (15 ml Packard Instagel). The amount of protein eluted by Triton is determined from a 1-ml (10%) sample of the Triton wash counted in 15 ml of Instagel. The total protein bound to the polymer (i.e. after the original 4 water rinses) is the sum of the counts on the polymer after the Triton wash and the counts removed in the Triton wash.
______________________________________ Counts Above Background (cpm) On Polymer AfterEx. Polymer Reactant Total Triton Wash______________________________________74 12 1-thioglycerol 378 7875 12 sarcosine 569 16076 12 Na2 SO3 487 17777 12 TRIS 1150 63078 12 --, Control 1314 97479 13 mercapto- 1220 530 ethanol80 13 --, Control 1556 956______________________________________
The examples shown above indicate dramatic changes in albumin adsorption and desortion (using Triton X-100) of treated samples compared to untreated control samples. The treatments on the above polymers inhibit protein adsorption and facilitate its removal with a nonionic surfactant.
The example shows an improvement in wettability of a polymer sheet (PSM=25%, GMA=15%, neopentyl glycol dimethacrylate=16%, isobornyl methacrylate=44%, prepared as in Example A) after room temperature treatment with an alcohol, polyvinyl alcohol (PVA), and a further improvement in this wettability with the crosslinking of this surface-bound PVA with 1,4-butanediol diglycidyl ether (BUDGE). Where indicated in the reaction sequence below, 2 g of aqueous 10% (w/w) PVA (Elvanol 71-30, DuPont), 3.17 g 10% (w/w) aqueous NaOH or 0.51 g BUDGE is added to the reaction bottle that contains the polymer sheet. The duration of the PVA, NaOH and BUDGE steps are 1 day, 21/4 hours and 2 hours respectively. Exhaustive water washes follow the treatments. The H2 O only (control) bottle is filled with H2 O at the beginning of the experiment.
Retraction times are measured one week after the reaction.
______________________________________ Retraction Time, tRReaction Sequence s______________________________________(a) PVA → NaOH → BUDGE 42(b) PVA → NaOH 23(c) H2 O only (control) <1______________________________________
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(August 20, 2011: Austin, TX 78746) The Westlake Chaparrals topped the visiting Reagan Rattlers volleyball team by a score of 2-0 in Saturday's non-league test.
The Chaparrals now have a 6-0 record. They put it on the line next when they travel to Round Rock for a non-league test on Tuesday, August 23. Westlake will confront a Dragons team coming off a 2-1 non-league loss to Reagan (San Antonio, TX). The Dragons record now stands at 2-3.
The Rattlers (16-5) will now prepare for their test against Round Rock Westwood (Austin, TX). The Warriors enter the non-league test with a 4-2 record. In their last test, Round Rock Westwood was knocked off by Reagan (San Antonio, TX), 2-1, in a non-league test.
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Publishers Ubisoft have issued a press release saying that "Gangnam Style", a recent phenomenon by Korean rapper Psy, will be made available for Just Dance 4 as downloadable content.
"We're dedicated to bringing Just Dance fans access to the music and musicians they love. Our fans were really vocal about wanting Gangnam Style in Just Dance 4 and we listened. This marks the first of many hot upcoming DLC tracks for Just Dance 4" - Carrie Feigel, Ubisoft
Gangnam Style has topped charts across most of Europe and managed to reach #2 on the US Billboard Hot 100.
Just Dance fans will be able to horse-ride along sometime in November.
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No they're making it from the movie ... Speed Racer: The Video Game
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Thanks Rob. I had no idea this one was published. I'm very happy about it! Yes, Jonathan, it is hard as all get-out, ... Street Fighter 2010: The Final Fight review
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This was a very well-written review. Apparently Super Hexagon was developed by Terry Cavanagh (who made vvvvvv), so ... Cosmophony review
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:p p ... TMNT: Smash Up
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text: What a shame. Chicago is such a beautiful city. I've been there twice in the last few years, and were I 23 instead of 33, I'd probably move there. Anyhow, taxes, taxes, taxes... When will people wake up and learn that bigger government only means more wasteful government? It's funny how people criticize me for pointing out when a city has 400 employee's making well over $100k, while so few criticize hikes in taxes and fees on the working man. Cook County sales tax increase proposedHike from 9 to 11 percent By Leah Hope September 18, 2007 - One Cook County commissioner wants to increase the county's portion of the sales tax, and if approved, the sales tax in Cook County would go up to 11 percent. That tax increase would also apply to restaurant and hotel bills. Cook County Commissioner Joan Patricia Murphy said the additional tax revenue would be used to avoid another crisis when it is time to come up with next year's budget. It appears everything is on the table as Cook County commissioners prepare for next year's budget. The last time they called for a sales tax increase was 1992. Some commissioners say it is time to get help. But retailers are saying, look elsewhere. It looks like the board of county commissioners has had enough job cuts throughout the county, including their own staff. They're looking at a gap in the 2008 budget. "We just need to do something other than cut jobs if we want to maintain services to our residents," Commissioner Murphy said. The proposal asks for increases in service and sales taxes. To retailers in Chicago, that means a sales tax would go from nine percent to 11 percent. Some are concerned that an even greater tax will send tourists and shoppers elsewhere. http://abclocal.go.com/wls/story?section=local&id=5664018


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A modern dictionary of Catholic terms, both common and obscure. Find accurate definitions of words and phrases.
The forms of musical worship, as revised and established by Pope Gregory I. It is without definite rhythm and was probably accumulated from Jewish sources. It is accepted as the oldest chant in present day use. Its revised present form is due largely to the energy and inspiration of the monks at the Benedictine Abbey at Solesmes in northwestern France.
All items in this dictionary are from Fr. John Hardon's Modern Catholic Dictionary, © Eternal Life. Used with permission.
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Learn more about Sterling Silver Trillion Cut Ruby Pendant Earrings and 18 inch Necklace Set:
Manufacturer: peora
Mfg Part#: SS2982
Sku: 220973034
See more in Jewelry Sets
|Earrings = Lab Created Ruby, 2 pieces, Trillion cut, 5mm. Earring Dimensions: 1 1/8 x 1/4 inches. Pendant = Lab Created Ruby, 1 piece, Trillion cut, 6mm. Pendant Dimensions: 3/4 x 3/8 inches. Earrings and Pendant have a total weight of 3.10 grams and are set in pure Sterling Silver with .925 stamp. Gemstones have a vibrant rich color and eye clean clarity. The Pendant and Earrings feature top quality workmanship and a beautiful finish. Includes Free 18 inch Sterling Silver Box Style Chain, Free Ribbon Gift Box and .