text:
Pattaya Park Beach Resort - UPDATED 2017 Prices & Reviews (Thailand) - TripAdvisor
All Pattaya Restaurants Restaurants near Pattaya Park Beach Resort
All things to do in Pattaya Things to do near Pattaya Park Beach Resort
We can't find prices for this accommodation From {rate_price} {rate_periodicity} Return to Map Pattaya Park Beach Resort
#56 of 447 Hotels in Pattaya
345 Jomtien Beach | Pattaya City, Pattaya 20150, Thailand345 Jomtien Beach | Pattaya City, Pattaya 20150, Thailand
Best prices for your stay 7/30/2017 7/31/2017Ages of Children: change Please provide ages Age Update Search $36$33View DealSAVE $3 $35View Deal$36View DealBooking.com$35Hotels.com$35TripAdvisor$35View all 7 dealsPriceline$33Expedia.com$35Ctrip.com$36Booking.com$35Hotels.com$35TripAdvisor$35CancelonPrices are the average nightly price provided by our partners and may not include all taxes and fees. Taxes and fees that are shown are estimates only. Please see our partners for more details. All photos (718) Full view Traveler (372)Pool & Beach (86)Room & Suite (86)
$33Priceline View Deal OverviewRoomsReviewsAboutPhotosNearbyQ&ARoom TipsMore Similar hotelsSee all 447 hotels in PattayaCosy Beach Hotel540 reviews#32 of 447 hotels in Pattaya The Pattaya Park Hotel79 reviews#201 of 447 hotels in Pattaya Tara Court Hotel329 reviews#15 of 447 hotels in Pattaya Green Park Resort607 reviews#54 of 447 hotels in Pattaya Overview 4.0 343 reviewsExcellent24%Very good49%Average18%Poor6%Terrible3%1 week ago“Nice place for activities ”Apr 1, 2017“Legend hotel”Free InternetFree ParkingAir ConditioningBeachfrontPoolRestaurantRoom ServiceFamily RoomsBar/LoungeLaundry ServiceWater ParkStar rating provided by Expedia.3.0 Star HotelAll hotel details
Similar hotelsSee all 447 hotels in PattayaCosy Beach Hotel540 reviews#32 of 447 hotels in Pattaya The Pattaya Park Hotel79 reviews#201 of 447 hotels in Pattaya Tara Court Hotel329 reviews#15 of 447 hotels in Pattaya Green Park Resort607 reviews#54 of 447 hotels in Pattaya Rooms Jul 30Jul 31|1 room, 2 adults, 0 childrenAgeAges of Children Update Search Update Standard Room Getting you more information on this room See More Free Cancellation Select Show Available Rooms Sorry, this partner no longer has rooms available on TripAdvisor. Please visit one of our 6 partner sites to see rooms from $33.We're sorry, there are no rooms available on TripAdvisor. Please change your dates, or view all Pattaya hotels with availabilityStandard Room Getting you more information on this room See More Free Cancellation Select {"BOOKING_FEATURES": ["IB_IRG_RATE_VERIFICATION","IB_STREAMLINED_SELECTED_ROOM","IB_POST_BOOKING_LOGIN_US","IB_NEW_REG_FLOW_INTERRUPTER","IB_SHOW_EMAIL_FOR_INSECURE_LOGIN","RCMS_INLINE_ROOM_GRID_MAX_OCC","IB_POST_BOOKING_LOGIN","IB_IRG_PERFORMANCE_METRICS","IB_IRG_MATCH_META","MOB_BOOKING_EMAIL_AGREE_HIDE","CHILDREN_SEARCH","IB_EXPRESS_BOOK","IB_DW_INLINE_PASSWORD","ATTRACTIONS_REMOVE_PAYMENT_ADDRESS_FIELDS","HR_IB_EXCLUDE_TAXES_AND_FEES","IB_DW_CCNAME_WITH_AUTOCOMPLETE","IB_IRG_PERFORMANCE_METRICS_MOBILE","IB_BOOKNOW_CLEAN_WITH_ICON_SHORT_BTN","STORED_CARDS","IB_POST_BOOK_LOGIN_CTA","IB_PRICE_WINS_COPY","IB_DW_PROMPT_KNOWN_EMAIL","IB_PRICES_OUTSIDE_ROOM_BUTTON","IB_EXIT_INTERRUPTER","IB_SHOW_AMENITIES_AS_ICONS","IB_NEW_REG_FLOW","META_AIR","IB_REVIEW_BOOKING_BUTTON","IB_INLINE_ROOM_GRID","IBEX_HIGH_EQUITY_BRANDING","IB_PRICE_WINS_POST_TX","IB_BOOKING_FORM_FAVICON","IB_KIPLINGER_AWARD","IB_URGENCY_BLOCK","IB_NEW_REG_FLOW_POST_BOOK"] , "IMPRESSION_KEY": "95515103110c497bacd1421d06f9001c", "roomSelectionModel": {"partnerInfos":[],"multiplePartners":false,"polling":{"locationId":1191092,"bookingSessionId":null,"detailedAvailabilityKey":null,"commerceContentIds":[112313572],"additionalContentIds":[],"pollCount":0,"checkin":{"day":30,"month":7,"year":2017},"checkout":{"day":31,"month":7,"year":2017},"adults":2,"child_rm_ages":"","rooms":1,"display_rooms":300,"entryPrice":35,"entryCurrency":"USD","complete":false,"formKey":"","showAllRooms":true,"genNewBookingSessionId":false,"winningProviderAtClick":"","selectedRoomKey":null,"impressionKey":"95515103110c497bacd1421d06f9001c","navArea":null,"referringServlet":"Hotel_Review","highestMetaPrice":36,"lowestMetaPrice":33,"additionalPartner":false,"highestMetaPriceDisplay":36,"roomsToVerify":[],"clazz":null},"summary":null,"unavailable":false,"metaOffers":[],"mismatchCheckModel":null,"totalMediaCount":0,"hotelPhotos":[],"noticeHeaderMessage":null,"moreProviders":null,"lowestPricePartner":null,"showAllRooms":true,"isMetaCheaper":false,"isBookingLessThanOrEqualToMeta":null,"avgHistoricalPrice":0.0,"avgHistoricalDisplayPrice":null,"expressBookState":{"hasFullTravelerInfo":false,"hasReducedBillingInfo":false,"hasFullBillingInfo":false},"highestMetaPrice":36,"lowestMetaPrice":33,"highestMetaPriceDisplay":36,"hotelName":"Pattaya Park Beach Resort","hasSpecialTimeOfStayTaxes":false,"trackingTree":null,"trackingTreeId":null,"showPriceHoverTooltip":false,"trackingContext":"eyJzdGF0ZSI6IkhPVEVMX0FVQ1RJT04iLCJwIjoiSFJfTWFpbkNvbW1lcmNlIiwiaWRzIjp7IkJGSyI6Ijk1NTE1MTAzMTEwYzQ5N2JhY2QxNDIxZDA2ZjkwMDFjIiwiQUlLIjoiZDFjMmNkYmFjOTYzNDM3M2JlMTk0MmVjMmQ0MjRlZTQifSwiZW50cnlTZXJ2bGV0IjoiSG90ZWxfUmV2aWV3In0=","cheaperPricesExist":false,"enableLPF":false,"priceDropPercent":0,"canExpandRooms":false,"expandRoomsToAllPartners":false,"roomSelectionKey":null,"useSupplierDirectTreatment":false,"isSupplierDirect":false,"showProviderSeparator":false,"clazz":null,"seeMoreMessage":null,"seeMoreIFrameMessage":null,"isPricelineCom":false}, "ibAvailability": true, "metaAvailability": true, "topOfferIsIB": false, "numHacTries": -1, "checkIn": "07/30/2017", "checkOut": "07/31/2017", "lowestPrice": "$33", "hasDates": true, "hacComplete": false, "contentIdMappings": {"112286069":"Expedia","112313572":"BookingCom","112299108":"TravelocityEWS","112286878":"OrbitzEWS"}, "pollingEnabled": false, "preventScroll": false, "offerClickToken": null, "conditionalUpdate": false, "mightGetRooms": true, "divClasses": "ppr_rup ppr_priv_hr_inline_room_grid_hsx", "singlePartnerRoomGridWidget": {"containerClass":null,"widget":{"name":"ibex_room_grid_hsx","moduleList":["handlers","tracking"],"template":"ibex_room_grid_hsx__widget","divClasses":"prw_rup prw_ibex_room_grid_hsx","js":{"handlers":"(ta.prwidgets.getjs(this,'handlers'))","tracking":"(ta.prwidgets.getjs(this,'tracking'))"},"dust":{"sub_header":"ibex_room_grid_hsx__sub_header"}},"scriptFlags":null}, "multiPartnerRoomGridWidget": null, "mismatchMessage": {"containerClass":null,"widget":{"name":"ibex_mismatch_message","moduleList":["handler"],"template":"ibex_mismatch_message__widget","divClasses":"prw_rup prw_ibex_mismatch_message","js":{"handler":"(ta.prwidgets.getjs(this,'handler'))"},"dust":{}},"scriptFlags":null}, "maxRoomsToShow": 300, "isTablet": false, "roomGridRowWidget": {"containerClass":null,"widget":{"name":"ibex_room_grid_row_hsx","moduleList":[],"template":"ibex_room_grid_row_hsx__widget","divClasses":"prw_rup prw_ibex_room_grid_row_hsx","js":{},"dust":{"amenities":"ibex_room_grid_row_hsx__amenities","condition_col":"ibex_room_grid_row_hsx__condition_col","price_text":"ibex_room_grid_row_hsx__price_text","reservation_col":"ibex_room_grid_row_hsx__reservation_col"}},"scriptFlags":null}, "mismatchMessageLightbox": null, "deviceInfo": "OtherOS OtherBrowser", "bookOnTripAdvisor": "Book on <img class=\"ibHeaderImg\" alt=\"TripAdvisor\" src=\"https:\/\/static.tacdn.com\/img2\/branding\/rebrand\/TA_logo_primary.png\"\/>"} Write a ReviewReviews (343)Traveler rating Excellent10Very good8Average5Poor7Terrible3Traveler typeFamiliesCouplesSoloBusinessFriendsTime of year Mar-MayJun-AugSep-NovDec-FebLanguage All languages English (33)Russian (285)Thai (28)More languages Language English (33)Russian (285)Thai (28)Chinese (Sim.) (8)French (1)German (1)Japanese (1)Korean (1)See what travelers are saying: 1 - 5 of 33 reviews
Rachel W298Reviewed 1 week ago via mobile Nice place for activities The staff are not friendly. They are curt and seem a little put out at times by questions. They do not speak English well . No towels given out after 3:00 and the amenities are terrible. The rooms are old fashioned but spacious. We had...MoreThank Rachel W PongCCKui Buri, Thailand149Reviewed April 1, 2017 via mobile Legend hotelOne of my fav hotel since i was young. This was my fisrt after at least 20 years.
I agree to every comments that said the hotel is old and tired. However, you need to consider the price you have paid for. They are not...MoreThank PongCC SwarnavzMumbai (Bombay), India6Reviewed December 8, 2016 good lobby but old and smelly rooms...I booked the room online but exited within half hour..good thing is twe got our refund ...the interior is too old and has big open balconies which are not safe with kids around.. very isolated feeling and also its not very centrally located...Thank Swarnavz gianni k42Reviewed June 6, 2016 via mobile Never Will go backOld, dirty and with very bad staff and management.
Staff very rude and can see...More1 Thank gianni k Kriangsak_TeerakBangkok, Thailand6722Reviewed April 13, 2016 via mobile Best budget summer tripWe took friends and their kid to Pattaya Park, instead of more expensive parks. And we loved it. It cost 100 baht per adult. What I like the most is that it had a mix of local and foreign tourists. They also had lax regulation...MoreThank Kriangsak_Teerak PreviousNext1234567Updating list... Similar hotelsSee all 447 hotels in PattayaCosy Beach Hotel540 reviews#32 of 447 hotels in Pattaya The Pattaya Park Hotel79 reviews#201 of 447 hotels in Pattaya Tara Court Hotel329 reviews#15 of 447 hotels in Pattaya Green Park Resort607 reviews#54 of 447 hotels in Pattaya About Amenities Top amenitiesRestaurantPoolBeachfrontFree InternetFree ParkingBar/LoungeRoom ServiceHotel AmenitiesChildren Activities (Kid / Family Friendly)Free ParkingLaundry ServiceRoom ServiceRoom amenitiesAir ConditioningRefrigerator in roomMinibarThings to doRestaurantPoolBar/LoungeDetails Price range$33 - $72 (Based on Average Rates for a Standard Room) Hotel classStar rating provided by Expedia.Hotel Style#8 Top resorts Hotel in Pattaya Room typesFamily Rooms Number of rooms718 Reservation OptionsTripAdvisor is proud to partner with Expedia, Hotels.com, Booking.com, TripOnline SA, Travelocity, Cancelon, Priceline and Ctrip TA so you can book your Pattaya Park Beach Resort reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers. LocationThailand >Chonburi Province >Pattaya Also Known AsPattaya Park Beach Hotel Pattaya Show More Show Less Add Photo Photos All photos (718) Full view Traveler (372)Pool & Beach (86)Room & Suite (86)Dining (41)Hotel & Grounds (280)Bathroom (4)Family and Play Areas (4)
Nearby Sponsored by: Nearby HotelsSee all 447 hotels in PattayaRabbit Resort1,653 reviews .26 miles away Chateau Dale Resort44 reviews .42 miles away Avalon Beach Resort201 reviews .43 miles away Centara Grand Phratamnak Pattaya440 reviews .43 miles away Nearby RestaurantsMarco's48 reviews .42 miles away Indian By Nature860 reviews .43 miles away Fraser's Sports Bar and Pub264 reviews .43 miles away Indian By Nature Restaurant11 reviews .43 miles away Nearby AttractionsMermaids Dive Center Pattaya108 reviews .61 miles away Khao Phra Tamnak (Khao Phra Bat)121 reviews .69 miles away Sabaii Massage17 reviews .73 miles away Dongtan Beach48 reviews .35 miles away Questions & AnswersSee all 11 questions Get quick answers from Pattaya Park Beach Resort staff and past guests.Note: your question will be posted publicly on the Questions & Answers page.Verification: Posting guidelinesSubmitPreviousNext1234
Room Tips "Better not to come"ST20140418over a year agoRead review "Heiger floors have less a/c unit noise"rajeevnawalkhaover a year agoRead review "Sea view room type at Tower Wing will enjoy your trip (So high so good)"CuTeeTHAover a year agoRead review "Avoid if u are not on a tight budget."Ameer Mover a year agoRead review Show More Is This Your TripAdvisor Listing? Own or manage this property? Claim your listing for free to respond to reviews, update your profile and much more. Claim Your Listing Know better. Book better. Go better. © 2017 TripAdvisor LLC All rights reserved. Terms of Use | Privacy Policy | Site MapSome photos provided by VFM Leonardo.* TripAdvisor LLC is not a booking agent and does not charge any service fees to users of our site... (more) TripAdvisor LLC is not responsible for content on external web sites. Taxes, fees not included for deals content. EXPLOREAbout UsHelp CenterCURRENCY/COUNTRY$USDUnited States

value: This website is an American online travel company that operates a website and mobile app with user-generated content and a comparison shopping website.


text:
Amazon.co.uk:Customer reviews: Joules Men's Bosworth Wellington Boots
Price:£21.81 - £55.97
Size: 10 UKColour: Black (Black Black)Verified Purchase
Bought these for a concert for my BF. I got a women's pair. We wore both for about 8-9 hours and walked over 11miles that day. They we comfy, held up, looked great, and we both got compliments. Would buy again!
Excellent product - very comfortable for dog walking.
A little larger than expected, however that makes it easier to get them on and off. They are very comfortable, even when used for long dog walks. I would highly recommend them.
4.0 out of 5 starsFor my husband these wellies were great except the size 9 were too small and the ...
For my husband these wellies were great except the size 9 were too small and the 10 were a little big but we still kept them!
£27.29-£65.15
£40.73-£63.95
£41.35-£65.15
£25.54-£41.95
‹ See all details for Joules Men's Bosworth Wellington Boots

type: global

value: This website is an American multinational technology company which focuses on e-commerce, cloud computing, digital streaming, and artificial intelligence.


text:
Nashville Predators goalie Pekka Rinne (35), of Finland, blocks a shot by Vancouver Canucks left wing Daniel Sedin (22), of Sweden, during the third period of an NHL hockey game Tuesday, Jan. 10, 2017, in Nashville, Tenn. The Predators won in overtime 2-1. (AP Photo/Mark Zaleski) (The Associated Press)
Vancouver Canucks goalie Ryan Miller (30) stops a shot by Nashville Predators center Ryan Johansen, bottom, during the third period of an NHL hockey game Tuesday, Jan. 10, 2017, in Nashville, Tenn. The Predators won in overtime 2-1. (AP Photo/Mark Zaleski) (The Associated Press)
Vancouver Canucks defenseman Luca Sbisa (5), of Italy, knocks the puck away from Nashville Predators center Calle Jarnkrok (19), of Sweden, as goalie Ryan Miller (30) defends in net during the third period of an NHL hockey game Tuesday, Jan. 10, 2017, in Nashville, Tenn. The Predators won in overtime 2-1. (AP Photo/Mark Zaleski) (The Associated Press)
NASHVILLE, Tenn. – Calle Jarnkrok scored a short-handed goal with 1.5 seconds remaining in overtime to lift the Nashville Predators to a 2-1 win over the Vancouver Canucks on Tuesday night.
With under a minute left in the third and Miller pulled in favor of an extra attacker, Nashville's Colton Sissons carried the puck up ice, but Vancouver's Sven Baertschi knocked it loose, sending Sutter the other way. At the right faceoff dot, Sutter snapped a wrist shot between Rinne's pads.
Watson scored the game's first goal 35 seconds into the second period. From the left point, Mike Fisher's shot ricocheted off of the end boards and came to Watson in the lower part of the right faceoff circle. With Miller on the other side as a result of Fisher's chance, Watson corralled the puck and put it into the vacated net for his third goal of the season.
The loss snapped Miller's five-game winning streak.
Rinne was tested early in the first period when Jack Skille had an open look at the Nashville net from the low slot. The Finn, normally known for his spectacular glove saves, denied Skille's chance with the crown of his goalie mask to keep the game scoreless.
NOTES: Nashville LW Viktor Arvidisson returned to the lineup after missing two games with an upper-body injury. ... Tuesday's game was the 100th of Watson's NHL career. ... Vancouver is 6-2-2 against the Central Division this season. ... Canucks C Bo Horvat saw his seven-game point scoring streak end.

value: This website is an American multinational conservative cable news television channel based in New York City. It is owned by Fox News Media, which itself is owned by the Fox Corporation.


text:
Now run by Jos with help from husband Tim LGF has... - Review of Le Grand Fougueyrat - TripAdvisor
“We met for drinks around the pool and then in for...”
“Adults Only Hotel in South West Rural France”
Now run by Jos with help from husband Tim LGF has... - Review of Le Grand Fougueyrat
“Perfect food, wine, location and host”
Review of Le Grand Fougueyrat
Our online travel partners don't provide prices for this hotel, but we can search other options in Saint Julien d'Eymet
Ranked #1 of 1 Hotels in Saint Julien d'Eymet
Perfect food, wine, location and host
Now run by Jos with help from husband Tim LGF has been spruced up and is as wonderful as ever. With much more flexibility of dates and board i.e. b & b, half or full board available this lovely guest house should attract a wider variety of guests. Jos' cooking and welcoming personality make your stay so relaxing and enjoyable. The facilities for table tennis, badminton, snooker, boules, golf, fishing, and of course swimming along with free bikes make for a holiday where you can choose to do as much or little as you like. The locale is also wonderful to explore with lovely french markets and stunning architecture in abundance.
Room Tip: All rooms are ensuite and open on to the pool. There are also rooms which are wheelchair friendly...
Ask Chrissie B about Le Grand Fougueyrat
All reviews badminton skittles tony host france
Lovely stay, good food, good wine, beautiful countryside.
After reading some of the previous comments on Trip Advisor we didn't know quite what to expect when we arrived at Le Grand Fougueyrat knowing that it's no longer just a house party venue with lots of organised activities. Jocelyne now runs Le Grand Fougueyrat and she is the most charming host, nothing is too much trouble and her cooking is wonderful also accompanied by complimentary wine which comes from their own grapes. We enjoyed delicious meals outside surrounded by vineyards and fields of sunflowers. We stayed on a half board basis but B&B is also available. The rooms are basic and would benefit from a makeover but they are clean with en suite shower rooms. All rooms open onto the lovely pool area. There are bicycles to ride, which we did, even venturing into Eymet .
Le Grand Fougueyrat is an excellent base to explore the Perigord region. Jocelyne met us at Bergerac Airport as we hadn't arranged car hire but it is advisable to pre book particularly during the summer season as we found it difficult to organise a car for a few days at short notice. We really enjoyed our week's stay, it was nice to eat with the other guests, English and French with the English practising French and the French practising their English. Many thanks to Jocelyne for making our stay so enjoyable.
Ask Lynn and David S about Le Grand Fougueyrat
1 Thank Lynn and David S
Brilliant fun, great for the family.....forgotten what holidays could be like!
Kids loved playing in the pool with the other kids who were there (even if it was a little cold for my liking!) and certainly enjoyed engaging in some banter with Tony.
Highlight of the holiday is most certainly the canoeing trip on the Dordogne. This is a full days trip, extremely good value as you take in a full days gentle canoeing with a lunch on the banks of the river.
Yes it is a little tired in places at Le Grand Fougeyrat, but if you want good wholesome fun, food and wine, prepared to join in, you will have a wonderful time.Tony, Sharon and Jocely are wonderful hosts and work their socks off to make sure you have a great time.
Ask TallBlerk about Le Grand Fougueyrat
2 Thank TallBlerk
Just returned from a week and a half at Le Grand Fougueyrat. Can't think of any negatives at all. Food was excellent quality, varied and delicious. Wine was plentiful and just as fine and delicious as the food. Company and hospitality was second to none. Activities were fun, and just enough. Weather was good too which made it one of the best holidays we've had!!! We were treated not like holiday guests but friends and we loved it all. Many thanks to Tony, Sharon and Jocelyn - we'll be back.
Ask BarbaraMaryW about Le Grand Fougueyrat
We stayed in the house for a week and had a good time. The place really need getting up to today's standard but the food was good and luckily the weather was nice so we could use the pool and sit outside. Sharon and Joyelyn really run the place now and keep it going but it could do with a good clean up. If the place was brought up to date it could be a great place again and hopefully someone will do that soon.
Ask GretaEssex about Le Grand Fougueyrat
We have just (15 mins ago!) come back from a short stay with Tony and Sharon. Our first. And, from what I gather from the other reviews on this site, it was uncharacteristically quiet, there being just the four of us. But that did not detract one little bit from the sheer joy of the experience. Tony is a great host and (I hope you'll forgive me, Tony) he is also a bit of a "character" - in a good way, of course. And Sharon is such a lovely and hard-working hostess. They make a good team.
We ate well, drank well and spent the rest of the time chatting, playing games (I won't forget the "smells" game for a long time!) and generally having a very pleasant time. They are lovely people, it's a gorgeous part of the world. Everyone ought to go there - but only if you are prepared to enter into the spirit of the place. Old farts need not apply, even though I myself am 50 something. Age is a state of mind!
Ask barrieluck about Le Grand Fougueyrat
Shhhhh..... keep it to yourself.
Don't go to this place if you want a fancy room and food. Don't go there if you haven't got a sense of humour. And certainly don't go there if you're boring.
If however you like a laugh, are light-hearted and don't take yourself too seriously, if you like the idea of a sort of summer Christmas run by a manic hippie-like character, if you like good hearty food with no frills and aren't too fussy about your wine, then this is the place for you.
Race you there .....
Ask essexcoastmum about Le Grand Fougueyrat
3 Thank essexcoastmum
Also consider these accommodations in or near Saint Julien d'Eymet
Been to Le Grand Fougueyrat? Share your experiences!
Additional Information about Le Grand Fougueyrat
Address: Saint Julien d'Eymet, Saint Julien d'Eymet, France
Location: France > Nouvelle-Aquitaine > Dordogne > Saint Julien d'Eymet
Unique Hotel in South West Rural France. Half & Full Board 7 day deals available.All Drinks included English and French spoken by all members of staff.19 metre Swimming Pool, Indoor Badminton Court, Tennis Court, Snooker RoomFREE access to our own Carp Fishing LakeTable Tennis, Golf Practice, Boules Area, Skittle Alley, FREE Cycles Hire, FREE Wi-Fi ... more less


text:
PARA GENTE TRANQUILA - Review of Son Corb Boutique Hotel, Son Servera, Spain - TripAdvisor
Things to do near Son Corb Boutique Hotel
PARA GENTE TRANQUILA - Son Corb Boutique Hotel
Review of Son Corb Boutique Hotel
Camino de Sa Punta Pn s/n | Predio Son Corb, 07559 Son Servera, Majorca, Spain |
Ranked #4 of 4 Hotels in Son Servera
Ask miguelafuente about Son Corb Boutique Hotel
Thank miguelafuente
There are newer reviews for Son Corb Boutique Hotel
All reviews snack menu cala bona recharge the batteries a wonderful stay cooked breakfast minute stroll a great week rooms are spacious at lunchtime pool bar lovely hotel restaurants and bars short break the air conditioning every morning recommend this hotel yogurt
Ask Rinocero about Son Corb Boutique Hotel
1 Thank Rinocero
Ask MlmAfg about Son Corb Boutique Hotel
1 Thank MlmAfg
bcastanyer
Ask bcastanyer about Son Corb Boutique Hotel
Thank bcastanyer
Kiliman73
Buen primer impacto, fallan los detalles
Ask Kiliman73 about Son Corb Boutique Hotel
1 Thank Kiliman73
Ask carloshhh about Son Corb Boutique Hotel
1 Thank carloshhh
Ask Miss_Opiniones about Son Corb Boutique Hotel
1 Thank Miss_Opiniones
Also consider these accommodations in or near Son Servera
Been to Son Corb Boutique Hotel? Share your experiences!
Additional Information about Son Corb Boutique Hotel
Address: Camino de Sa Punta Pn s/n | Predio Son Corb, 07559 Son Servera, Majorca, Spain
Location: Spain > Balearic Islands > Majorca > Son Servera
Peace, relaxation, tranquility, amplitude, personal touch, grace are the words most used by those who have already hosted with us to describe their stay at Son Corb when they promise to return to spend their holidays in this old possessio of the most seaworthy Majorca. At barely 500m from the beach and the marina of Cala Bona, Son Corb offers its inhabitants the possibility of enjoying its large swimming pool, sauna, freely available bicycles and all the spaces conceived for their comfort. And if you wish to have something while sunbathing in the swimming pool, our snack is at your disposal. Small caprices to eat and the most refreshing drinks. The golf clubs of Son Severa y Pula are less than 2 km from this establishment that is at barely one hour from the airport of Palma by car. Son Corb is the ideal place for hiking lovers that will have their special tune-up in the paths that cross this property of 30 hectares and in its 11.000 square meters garden. ... more less
TripAdvisor is proud to partner with Hotels.com, Travelocity, Expedia, Orbitz, Priceline, TripOnline SA, Cancelon, Hotwire, Cheap Tickets, Evoline ltd and HotelQuickly so you can book your Son Corb Boutique Hotel reservations with confidence. We help millions of travelers each month to find the perfect hotel for both vacation and business trips, always with the best discounts and special offers.


text:
Patent US6559089 - Metallocene catalyst component for use in producing isotactic polyolefins - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsProvided is a metallocene catalyst component for use if preparing isotactic polyolefins, which component has the general formula (I): R″ (CpR1R2R3)(Cp′R′n) MQ2 wherein Cp is a substituted cyclopentadienyl ring; Cp′ is substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting...http://www.google.com/patents/US6559089?utm_source=gb-gplus-sharePatent US6559089 - Metallocene catalyst component for use in producing isotactic polyolefinsAdvanced Patent SearchPublication numberUS6559089 B1Publication typeGrantApplication numberUS 09/424,416PCT numberPCT/EP1998/003099Publication dateMay 6, 2003Filing dateMay 26, 1998Priority dateMay 26, 1997Fee statusPaidAlso published asDE69815846D1, DE69815846T2, DE69839354D1, DE69839354T2, EP0881236A1, EP0984989A1, EP0984989B1, EP1283223A2, EP1283223A3, EP1283223B1, WO1998054230A1Publication number09424416, 424416, PCT/1998/3099, PCT/EP/1998/003099, PCT/EP/1998/03099, PCT/EP/98/003099, PCT/EP/98/03099, PCT/EP1998/003099, PCT/EP1998/03099, PCT/EP1998003099, PCT/EP199803099, PCT/EP98/003099, PCT/EP98/03099, PCT/EP98003099, PCT/EP9803099, US 6559089 B1, US 6559089B1, US-B1-6559089, US6559089 B1, US6559089B1InventorsAbbas Razavi, Vincenzo BelliaOriginal AssigneeFina Technology, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (5), Referenced by (11), Classifications (22), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetMetallocene catalyst component for use in producing isotactic polyolefins
US 6559089 B1Abstract
Provided is a metallocene catalyst component for use if preparing isotactic polyolefins, which component has the general formula (I): R″ (CpR1R2R3)(Cp′R′n) MQ2 wherein Cp is a substituted cyclopentadienyl ring; Cp′ is substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR* 3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vincinal to the distal substituent, and is of the formula YR# 3, in which Y is chosen from Group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$ 3, in which Z is chosen from Group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, each R′ is the same or different and is hydrocarbyl having 1 to 20 carbon atoms in which 0≦n≦8; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.
What is claimed is: 1. A metallocene catalyst component for use in preparing isotactic polyolefins, which comprises (i) a catalyst component of the general formula:
R″CpR1R2R3)(Cp′R′n)MQ2 wherein Cp is a substituted cyclopentadienyl ring; Cp′ is a substituted or unsubstituted fluorcarbonyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a group of the formula XR′3, in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent, and is of the formula YR# 3, in which Y is chosen from Group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and is hydrogen atom or is of the formula ZR$ 3, in which Z is chosen from the Group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, each R′ is the same or different and is hydrocarbyl of 1 to 20 carbon atoms in which 0≦n≦8; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen; and (ii) a regioisomer thereof in which R2 is proximal to the bridge and positioned vicinal to the distal substituent.
2. A metallocene catalyst component according to claim 1, wherein R1 is C(CH3)3, C(CH3)2Ph, CPh3 or Si(CH3)3.
3. A metallocene catalyst component according to claim 2, wherein R1 is C(CH3)3.
4. A metallocene catalyst component according to claim 1, wherein R* is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl.
5. A metallocene catalyst component according to claim 4, wherein R* is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
6. A metallocene catalyst component according to claim 1, wherein is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl and may be the same or different.
7. A metallocene catalyst component according to claim 6, wherein R′ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
8. A metallocene catalyst component according to claim 1, wherein X is carbon or silicon.
9. A metallocene catalyst component according to claim 1, wherein Y is carbon.
10. A metallocene catalyst component according to claim 1, wherein Z is carbon.
11. A metallocene catalyst component according to claim 1, wherein R2 is CH3.
12. A metallocene catalyst component according to claim 1, wherein R3 is CH3.
13. A metallocene catalyst component according to claim 1, wherein R″ is alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphene or amine.
14. A metallocene catalyst component according to claim 13, wherein R″ is isopropylidene or dimethylsilanediyl.
15. A metallocene catalyst component according to claim 1, wherein M is zirconium or titanium.
16. A metallocene catalyst component according to claim 1, wherein Q is halogen.
17. A metallocene catalyst component according to claim 1, wherein Q is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl.
18. A metallocene catalyst component according to claim 17, wherein Q is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
19. A metallocene component according to claim 1, wherein the fluorenyl ring is unsubstituted at both positions 4 and 5.
20. A metallocene catalyst component, according to claim 1, which further comprises an aluminum co-catalyst or boron containing co-catalyst capable of activating the catalyst component.
21. A metallocene catalyst component according to claim 20 wherein the aluminum containing co-catalyst is an alumoxane, an alkyl aluminum, a Lewis acid or combinations thereof.
22. A metallocene catalyst component according to claim 21 wherein the aluminum containing co-catalyst is an oligomeric linear alumoxane of the formula: or an oligomeric cylic alumoxane of the formula: wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C8 alkyl group.
23. A metallocene catalyst component according to claim 22 wherein R is methyl.
24. A metallocene catalyst component according to claim 20 wherein the boron containing co-catalyst is a triphenylcarbenium boronate.
25. A metallocene catalyst component according to claim 24 wherein the boron containing co-catalyst is a tetrakis-pentafluorophenyl-borato-triphenylcarbenium.
26. A metallocene catalyst component according to claim 1, which further comprises an inert support.
27. A metallocene catalyst component according to claim 26 where the support is a porous solid.
28. A metallocene catalyst component according to claim 27 where the support is talc, inorganic oxide or polyolefin resin.
29. A metallocene catalyst component according to claim 28 wherein the support is a finely divided inorganic oxide.
30. A metallocene catalyst component according to claim 29 wherein the support is a Group 2a, 3a, 4a or 4b metal oxide.
31. A metallocene catalyst component according to claim 30 wherein the support is a silica, alumina and mixtures thereof.
32. A metallocene catalyst component according to claim 30 wherein the support is magnesia, titania, zirconia, alone or in mixtures with silica or alumina.
33. A metallocene catalyst component according to claim 31 wherein support is silica having a surface area between 200 and 700 m2/g and a pore volume between 0.5 and 3 m2/g.
34. A metallocene catalyst component according to claim 28 wherein the support is finely divided polyethylene.
35. A metallocene catalyst component according to claim 20 wherein the aluminum to transition metal mole ratio is between 1:1 and 100:1.
36. A metallocene catalyst component according to claim 35 wherein the aluminum to transition metal mole ratio is between 5:1 and 50:1.
37. A metallocone catalyst component according to claim 26, which further comprises a hydrocarbon solvent of 4 to 7 carbon atoms.
38. A metallocene catalyst component according to claim 37 wherein the hydrocarbon solvent is heptane, toluene or cyclohexane.
39. A metallocene catalyst component for use in preparing isotactic polyolefins, which comprises isopropylidene-(3-t-butyl-5-methyl-cyclopentadienyl fluorenyl) ZrCl2 and isopropylidene-(3-t-butyl-2-methylcyclopentadienyl fluorenyl) ZrCl2.
40. A process of making a catalyst comprising:
a) contacting (i) a catalyst component of the general formula: R″(CpR1R2R3)(Cp′R′n)MQ2 wherein Cp is a substituted cyclopcntadicnyl ring; Cp′ is a substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadicnyl ring which is distal to the bridge, which distal substituent comprises a group of the formula XR* 3, in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent, and is of the formula YR# 3, in which Y is chosen from Group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is a substituent on the cyclopentadicnyl ring which is proximal to the bridge and is hydrogen atom or is of the formula ZRS 3, in which Z is chosen from the Group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, each R′ is the same or different and is hydrocarbyl of 1 to 20 carbon atoms in which 0≦n≦8; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen; and (ii) a regioisomer thereof in which R2 is proximal to the bridge and positioned vicinal to the distal substituent; and
b) activating the catalyst components with a co-catalyst. 41. The process of making a metallocene catalyst, according to claim 40, wherein R1 is C(CH3)3, C(CH3)2Ph, CPh3 or Si(CH3)3.
42. The process of making a metallocene catalyst according to claim 40, wherein R1 is C(CH3)3.
43. The process of making a metallocene catalyst according to claim 40, wherein R* is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl.
44. The process of making a metallocene catalyst according to claim 43, wherein R* is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
45. The process of making a metallocene catalyst according to claim 40, wherein R′ is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl and may be the same or different.
46. The process of making a metallocene catalyst according to claim 45, wherein R′ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
47. The process of making a metallocene catalyst according to claim 40, wherein X is carbon or silicon.
48. The process of making a metallocene catalyst according to claim 40, wherein Y is carbon.
49. The process of making a metallocene catalyst according to claim 40, wherein Z is carbon.
50. The process of making a metallocene catalyst according to claim 40, wherein R2 is CH3.
51. The process of making a metallocene catalyst according to claim 40, wherein R3 is CH3.
52. The process of making a metallocene catalyst according to claim 40, wherein R″ is alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphene or amine.
53. The process of making a metallocene catalyst according to claim 52, wherein R″ is isopropylidene or dimethylsilanediyl.
54. The process of making a metallocene catalyst according to claim 40, wherein M is zirconium or titanium.
55. The process of making a metallocene catalyst according to claim 40, wherein Q is halogen.
56. The process of making a metallocene catalyst according to claim 40, wherein Q is alkyl, aryl, alkenyl, alkylaryl or aryl alkyl.
57. The process of making a metallocene catalyst according to claim 56, wherein Q is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
58. The process of making a metallocene catalyst according to claim 40, wherein the fluorenyl ring is unsubstituted at both positions 4 and 5.
59. The process of making a metallocene catalyst according to claim 40, wherein the co-catalyst is an aluminum containing co-catalyst or a boron containing co-catalyst capable of activating the catalyst component.
60. The process of making a metallocene catalyst according to claim 59 wherein the aluminum containing co-catalyst is an alumoxane, an alkyl aluminum, a Lewis acid or combination thereof.
61. The process of making a metallocene catalyst according to claim 60 wherein the aluminum containing co-catalyst is an oligomeric linear alumoxane of the formula: or an oligomeric cylic alumoxane of the formula: wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C8 alkyl group.
62. The process for making a metallocene catalyst according to claim 61 wherein R is methyl.
63. The process making a metallocene catalyst according to claim 59 wherein the boron containing co-catalyst is a triphenylcarbenium boronate.
64. The process for making a metallocene catalyst according to claim 63 wherein the boron containing co-catalyst is a tetrakis-pentafluorophenyl-borato-triphenylcarbenium.
65. The process for making a metallocene catalyst according to claim 40, which further comprises supporting the catalyst on an inert support.
66. The process for making a metallocene catalyst according to claim 65 where the support is a porous solid.
67. The process for making a metallocene catalyst according to claim 66 where the support is talc, inorganic oxide or polyolefin resin.
68. The process for making a metallocene catalyst according to claim 67 wherein the support is a finely divided inorganic oxide.
69. The process for making a metallocene catalyst according to claim 68 wherein the support is a Group 2a, 3a, 4a or 4b metal oxide.
70. The process for making a metallocene catalyst according to claim 69 wherein the support is a silica, alumina and mixtures thereof.
71. The process for making a metallocene catalyst according to claim 69 wherein the support is magnesia, titania, zirconia, alone or in mixtures with silica or alumina.
72. The process for making a metallocene catalyst according to claim 70 wherein the support is silica having a surface area between 200 and 700 m2/g and a pore volume between 0.5 and 3 m2/g.
73. The process for making a metallocene catalyst according to claim 66 wherein support is finely divided polyethylene.
74. The process for making a metallocene catalyst according to claim 59 wherein the aluminum to transition metal mole ratio is between 1:1 and 100:1.
75. The process for making a metallocene catalyst according to claim 74 wherein the aluminum to transition metal mole ratio is between 5:1 and 50:1.
76. The process for making a metallocene catalyst according to claim 65 which further comprises a hydrocarbon solvent of 4 to 7 carbon atoms.
77. The process for making a metallocene catalyst according to claim 74 wherein hydrocarbon solvent is heptane, toluene or cyclohexane.
78. The process for making a metallocene catalyst according to claim 40 wherein an alumoxane is dissolved in a hydrocarbon solvent; an inert support is slurried in a hydrocarbon solvent; the alumoxane dissolved in the hydrocarbon solvent is added to the inert support slurried in the hydrocarbon solvent; and the metallocene catalyst component is added to the slurry.
79. process for making a metallocene catalyst according to claim 78 wherein the solvent is mineral oil, alkane, cycloalkane or aromatic.
80. The process for making a metallocene catalyst according to claim 79 wherein the solvent is pentane, isopesentane, hexane, heptane, octane, nonane, cyclopentane, cyclohexane, benzene, toluene, ethylbenzene and diethylbenzene.
81. The process for making a metallocene catalyst according to claim 80 wherein the solvent is toluene.
Olefins having 3 or more carbon atoms can be polymerised to produce a polymer with an isotactic stereochemical configuration. For example, in the polymerisation of propylene to form polypropylene, the isotactic structure is typically described as having methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer. This can be described using the Fischer projection formula as follows: Another way of describing the structure is through the use of NMR spectroscopy. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm with each “m” representing a “meso” diad or successive methyl groups on the same side in the plane.
In contrast to the isotactic structure, syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Using the Fischer projection formula, the structure of a syndiotactic polymer is described as follows: In NMR nomenclature, a syndiotactic pentad is described as . . . rrr . . . in which “r” represents a “racemic” diad with successive methyl groups on alternate sides of the plane.
EP-A-0537130 discloses the use of a C1 symmetric metallocene catalysts for the production of isotactic polypropylene. A preferred catalyst is isopropylidene (3-t-butyl-cyclopentadienyl fluorenyl)ZrCl2. This catalyst has a bulky t-butyl group positioned on the cyclopentadienyl ring distal to the isopropylidene bridge. This catalyst has the advantage that it consists of only one stereoisomer and so no isomeric metallocene separation is required at the final stage of its synthesis. Whilst polypropylene preparation using this catalyst produces isotactic polypropylene, the polymer product has poor mechanical properties because of the presence of regiodefects and relatively low molecular weight.
Regiodefects occur in the polymer chain when, instead of producing a perfect isotactic polyolefin in which each monomeric unit is positioned head-to-tail in relation to the next, mis-insertions of the monomers occur so as to give either a head-to-head or tail-to-tail mis-match. In the polymerisation process according to EP-A-0619325, there is a typical mis-insertion frequency of around 0.4%. These so called (2-1) regiodefects are partially transferred to the so called (1-3) insertion through an isomerisation process leaving units of four CH2 groups in the backbone of the polypropylene chain. This has a deleterious effect on the physical and mechanical properties of the polymer and results in low molecular weight isotactic polypropylene with a low melting point.
In a first aspect, the present invention provides a metallocene catalyst component for use in preparing isotactic polyolefins, which component has the general formula:
R″(CpR1R2R3)(Cp′R′n)MQ2 (I)
wherein Cp is a substituted cyclopentadienyl ring; C′p is a substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent, and is of the formula YR#3, in which Y is chosen from group IVA, and each R@ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, preferably carbon, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, each R′n is the same or different and is hydrocarbyl having 1 to 20 carbon atoms in which 0≦n≦8; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen. In one embodiment, the metallocene catalyst component of the present invention has the general formula:
wherein Cp is a substituted cyclopentadienyl ring; Cp′ is a substituted or unsubstituted fluorenyl ring; R″ is a structural bridge imparting stereorigidity to the component; R1 is a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a group of the formula XR*3; in which X is chosen from Group IVA, preferably carbon or silicon, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, preferably carbon, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon each R′n, is the same or different and is hydrocarbyl having 1 to 20 carbon atoms in which hydrocarbyl having 1 to 20 carbon atoms in which 0≦n≦8; is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.
Polyolefins produced using metallocene catalyst component of the present invention are not only found to be isotactic but are also found to be substantially free of regiodefects. Accordingly, the polyolefins produced thereby have improved mechanical properties including a high weight average molecular weight typically of the order of 150,000-600,000 and elevated melting point. Without wishing to be bound by any theory, it is postulated that the bulky group on the cyclopentadienyl ring contributes to the stereospecificity of the polymerisation reaction whereas the proximal substituent(s) on the cyclopentadienyl ring contribute to the regiospecificity of monomer insertion and the increase of molecular weight.
In the bulky distal substituent group R1, X is preferably C or Si. R* may be a hydrocarbyl such as alkyl, aryl, alkenyl, alkylaryl or aryl alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl. RI may comprise a hydrocarbyl which is attached to a single carbon atom in the cyclopentadienyl ring or may be bonded to two carbon atoms in that ring. Preferably, R1 is C(CH3)3, C(CH3)2Ph, CPh3 or Si(CH3)3, most preferably C(CH3)3.
The proximal substituents R2 and R3 are preferably CH3.
The structural bridge R″ is preferably alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphene or amine bridging the two Cp rings. R″ is preferably dimethylsilanediyl in which the two Cp rings are bridged by the silicon atom, or isopropylidene in which the two Cp rings are bridged by position 2 of the isopropylidene.
The fluorenyl ring Cp′ can have up to 8 substituent groups R′n, each of which is the same or different and may be a hydrocarbyl selected from alkyl, aryl, alkenyl, alkyl aryl or aryl alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl. These substituents must be selected so that they do not interfere with coordination of the monomer to the metal. Preferably, therefore, the fluorenyl ring is unsubstituted at both positions 4 and 5, these positions being distal to the bridge.
In a further aspect, the present invention provides a metallocene catalyst component for use in preparing isotactic polyolefins, which comprises (i) a catalyst component as defined above; and (ii) a regioisomer thereof in which R2 is proximal to the bridge and positioned vicinal to the distal substituent.
Such regioisomers are frequently relatively easy to prepare because they are formed as a “by-product” during the synthetic route by which the catalyst component (i) may be made.
Surprisingly, it has been found that catalyst components including both regioisomers can be used in the preparation of isotactic polyolefins which have a multimodal, especially a bimodal, molecular weight distribution.
In a further aspect, the present invention provides a catalyst system for use in preparing isotactic polyolefins, which comprises (a) a catalyst component as defined above; and (b) an aluminium- or boron-containing co-catalyst capable of activating the catalyst component. Suitable aluminium-containing co-catalysts comprise an alumoxane, an alkyl aluminium and/or a Lewis acid.
Suitable boron-containing co-catalysts may comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L′—H]+[B Ar1 Ar2 X3 X4]— as described in EP-A-0277004 (page 6, line 30 to page 7, line 7)
In a further aspect, the present invention provides use of a catalyst component as defined above and a co-catalyst which activates the catalyst component, for the preparation of isotactic polyolefins, preferably polypropylenes. In a still further aspect, the present invention provides use of a metallocene catalyst component comprising (i) the catalytic component and (ii) a regioisomer thereof, in which R2 is proximal to the bridge and positioned vicinal to the distal substituent, for the preparation of isotactic polyolefins, especially polypropylenes, having a multimodal molecular weight distribution, preferably a bimodal molecular weight distribution.
In a further aspect, the present invention provides a process for preparing isotactic polyolefins, especially polypropylenes, which comprises contacting a catalyst system as defined above with at least one olefin, preferably propylene, in a reaction zone under polymerisation conditions.
In one embodiment, the process for preparing the bridged metallocene catalyst components comprises contacting a substituted cyclopentadiene having bulky and non bulky substituents on the cyclopentadienyl ring with a fluorene under reaction conditions sufficient to produce a bridged substituted dicyclopentadiene. The process further comprises contacting the bridged substituted dicyclopentadiene with a metal compound of the formula MQk as defined above under reaction conditions sufficient to complex the bridged dicyclopentadiene to produce a bridged metallocene wherein M and Q are each defined as above and 0≦k≦4. The process step of contacting the bridged substituted dicyclopentadiene with a metal compound can be performed in a chlorinated solvent.
In a further embodiment, the process comprises contacting a substituted cyclopentadiene having bulky and non bulky substituents on the cyclopentadienyl ring with an alkyl silyl chloride of the formula R{tilde over ( )}2SiHal2 wherein R{tilde over ( )} is a hydrocarbyl having 1 to 20 carbon atoms and Hal is a halogen. A second equivalent of an optionally substituted fluorene is added to produce a silicon bridged substituted cyclopentadienyl fluorenyl ligand. The subs={tilde over ( )}quent steps are similar to those above for producing a bridge disubstituted cyclopentadienyl-fluorenyl ligand coordinated to metals such as Zr, Hf and Ti.
In a further embodiment, the process comprises contacting a substituted cyclopentadiene with a fulvene producing agent such as acetone to produce a substituted fulvene. Subsequently, in a second step, the fulvene is reacted with fluorene to produce a carbon bridged substituted cyclopentadienyl-fluorenyl ligand that will produce the desired metallocene catalysts after reacting with MCl4, in which M is Zr, Hf or Ti.
FIG. 1 shows an illustration of the three-dimensional structure of a preferred catalyst component of the present invention as obtained by X-ray diffraction analysis of isopropylidene (3-tert.butyl-5-methyl cyclopentadienyl-fluorenyl) ZrCl2;
FIG. 2 shows an illustration of the three-dimensional structure of a preferred catalyst component of the present invention as obtained by X-ray diffraction analysis of isopropylidene (3-tert.butyl-2-methyl cyclopentadienyl-fluorenyl) ZrC2;
FIG. 3 shows the results of gel permeation chromatography on isotactic polypropylene produced at 40� C. using a mixture of the isomers shown in FIGS. 1 and 2 as a catalyst component; and
FIG. 4 shows the results of gel permeation chromatography on isotactic polypropylene produced at 60� C. using a mixture of the isomers shown in FIGS. 1 and 2 as a catalyst component.
Synthesis of isopropylidene(3-t-butyl-5-methylcyclopentadienyl fluorenyl)ZrCl2 A) Synthesis of the trimethyl fulvene
In a round bottom flask equipped with magnetic stirring bar and nitrogen inlet is placed 350 ml of methanol (at −78� C.) containing freshly prepared methylcyclopentadiene under nitrogen. To this solution is added a solution of 28.6 g of acetone in 50 ml of methanol drop wise. Subsequently 52.5 g of pyrrolidine is added. The reaction mixture is stirred at ambient temperature for 24 hours. After neutralization with acetic acid and separation of the organic phase the solvent is evaporated and the remaining yellow oil is subjected to distillation. A mixture of 6,6,3-tritethyl fulvene and 6,6,5,-trimethyl fulvene is obtained in 65% yield.
B) Synthesis of methyl-t-butyl-cyclopentadiene
The product obtained in step A is placed in 21 flask and dissolved in 350 ml of diethyl ether and cooled down to 0� C. To the solution is added drop wise 140.6 ml of methyl lithium in ether (1.6 mol). The reaction is completed after a few hours. After adding 40 ml of saturated solution of NH4Cl in water the organic phase is separated and dried with MgSO4. The evaporation of the solvent leads to the isolation of a yellow oil as two stereo isomers quantitatively.
C) Synthesis of t-butyl-trimethyl-fulvene
In a 500 ml flask is placed 12.60 g of the product obtained in step B and dissolved in 40 ml of methanol. The mixture is cooled down to −78� C. 2.15 g acetone in 10 ml of ethanol is added slowly. In the next step 4 g of pyrrolidine in 10 ml of methanol is added. After six hours the reaction is terminated by addition of 10 ml of acetic acid. After separation of organic phase, drying, evaporation of solvents and distillation an orange oil is obtained (8.95 g).
D) Synthesis of 2,2-[(3-t-butyl-methyl-cyclopentadienyl)fluorenyl]propane
In round bottom flask is placed 3.8 g fluorene in 100 ml of THF under nitrogen. 14.2 ml of methyl lithium in ether (1.6 mol) is added. The reaction mixture is stirred for 3 hours and then reacted with 4.70 g of the product obtained in step C dissolved in 10 ml of THF. The reaction is terminated after 8 hours by the addition of a saturated solution of NH4Cl in water. The organic phase is separated, the solvents evaporated and 8.5 g of the title compound is obtained as an oily mixture of two principal isomonomers, 2,2-[(3-t-butyl-5-methyl-cyclopentadienyl)fluorenyl]propane and 2,2-[(3-t-butyl-2-methyl-cyclopentadienyl)fluorenyl]propane.
E) Synthesis of the mixture of isopropylidene(3-t-Bu-5-methyl-cyclopentadienyl fluorenyl)ZrCl2 (1) and isopropylidene (3-t-Bu-2-methyl-cyclopentadienyl fluorenyl)ZrCl2 (2)
2 g of the ligand obtained in step D is dissolved in 250 ml THF under nitrogen and reacted with 7.3 ml methyl lithium in ether (1.6 mol). The reaction mixture is stirred over night. The solvent is evaporated next day and the dianion of the ligand is isolated which is reacted with 3.8 g of ZrCl4 in 200 ml ether at −78� C. The mixture is stirred for 6 hours at room temperature. The two isomers can be separated by solvent separation since (1) is less soluble in dichloromethane than (2).
Isopropylidene(3-t-butyl-5-methyl-cyclopentadienyl fluorenyl)ZrCl2 is recovered, the structure of which is shown in FIG. 1.
Synthesis of isopropylidene(3-t-butyl-2-methyl-cyclopentadienyl fluorenyl)ZrCl2 The synthetic procedure according to Example 1 is followed except that, after solvent separation at the end of step E, isopropylidene(3-t-butyl-2-methyl-cyclopentadienyl fluorenyl)ZrCl2 is recovered. The structure of this isomer is shown in FIG. 2.
Synthesis of mixture of isopropylidene(3-t-butyl-5-methylcyclopentadienyl fluorenyl)ZrCl2 and isopropylidene(3-t-butyl-2-methylcyclopentadienyl fluorenyl)ZrCl2 The synthetic procedure according to Example 1 is followed except that the step of solvent separation of the two isomers is omitted.
Polymerisation Procedures I
Each polymerisation was performed in a 4 liter bench reactor with pure propylene or with diluent such as cyclohexane or isobutane with the quantities reported in the following Tables. Polymerisation was initiated by introducing metallocene (0.5 to 5 mg) pre-contacted with 1 ml of MAO (methylaluminoxane) (30% solution in toluene obtained from WITCO) three minutes prior to its introduction into the reactor.
Tables 1 and 2 show the results of polypropylene production using the catalyst system of Example 1. Entries 1 to 4 compare polymerisation of pure propylene (bulk-entry 1) with those using the diluents cyclohexane (entry 2) and isobutane at two different partial pressures of hydrogen (entries 3 and 4). The polymerisation temperature for each of these entries was 60� C. Entries 5 and 6 compare bulk propylene polymerisation at the higher temperatures of 70� C. and 80� C. respectively. It is apparent that a molecular weight of about 200,000 to about 450,000 was obtainable. Polypropylene having a melt temperature of at least 139� C. was obtained, in this case around 140� C. The polymers obtained exhibited monomodality on gel permeation chromatography (results not shown).
Polymerization with iPr (5-Me-3-tBu-Cp Flu) ZrCl2 Pol.
MI2 Mn
(gPP/gCat/h)
Key: MI2 = Melt index; Mn = number average molecular weight; Mw = weight average molecular weight; D = Mw/Mn; D′ = Mz/Mw 1. Bulk Propylene; 2. Slurry in Cyclohexane; 3. Slurry in isobutane *0.25 NI H2; **1 NI H2 Table 2 shows the microtacticity of the polymer obtained using the catalyst according to Example 1 under polymerisation conditions as defined by the corresponding entries in Table 1. The results were obtained using 13C NMR spectroscopy. It will be apparent that the polypropylene contained more than 80% of pentads in the purely isotactic form (mmmm) and a virtually undetectable frequency of misinsertions.
Tables 3 and 4 show corresponding data in relation to the bulk polymerisation of propylene using the catalyst system of Example 2. The weight average molecular weight of the polypropylene in this case is much lower than for the polypropylene produced using the catalyst of Example 1. The melt temperatures reported in Table 3 are also lower than those in Table 1. Table 4 shows the microtacticity of the polymers of the two entries in Table 1 from which it will be apparent that the percentage of purely isotactic pentads is reduced as compared with those reported in Table 2. Importantly, a misinsertion frequency of up to 0.4% is found in Table 4 as compared with the virtually undetectable frequency of misinsertions reported in Table 2.
Microtacticity with iPr (5-Me-3-tBu-Cp Flu) ZrCl2 NMR
mmmr %
mmrr %
mrrm %
(1) inversions observed but too low to be quantified. TABLE 3
Bulk polymerization with iPr (2-Me-3-tBu-Cp Flu) ZrCl2 Pol.
Key: MI2 = Melt index; Mn = number average molecular weight; Mw = weight average molecular weight; D = Mw/Mn; D′ = Mz/Mw TABLE 4
Microtacticity with iPr (2-Me-3-tBu-Cp Flu) ZrCl2 Pol.
Bulk polymerization with the mixture of isomers
iPr (2-Me-3-tBu-Cp Flu) ZrCl2 + iPr (5-Me-3-tBu-Cp Flu) ZrCl2 Hourly
Key: MI2 = Melt index; Mn = number average molecular weight; Mw = weight average molecular weight; D = Mw/Mn; D′ = Mz/Mw Tables 5 and 6 show the results of corresponding bulk propylene polymerisation with a mixture of the two isomers from Examples 1 and 2. These polymers have relatively high melt temperatures. However, unlike the polymers reported in Table 1 using the single isomer isopropylidene (3-t-butyl-5-methylcyclopentadienyl fluorenyl)ZrCl2 which exhibits monomodality on gel permeation chromatography, polymers produced using the mixture of isomers exhibit bimodality. This is apparent from FIGS. 3 and 4 which show respectively the results of gel permeation chromatography on the polymers of entries 1 and 2 of Table 5.
Table 6 shows steric pentad concentrations and regiodefects concentrations.
iPr (2-Me-3-tBu-Cp Flu) ZrCl2 + iPr (5-Me-3-tBu-Cp Flu) ZrCl2 Pol. Temp
Synthesis of dimethylsilyl(2,5-dimethyl-3-t-butyl-cyclopentadienyl fluorenyl)zirconium dichloride
Formula: Me2Si(2,5-Me2-3-tBu-Cp flu)ZrCl2 C26H30SiZrCl2 Mw: 532.68
A. Preparation of 1,3-dimethylcyclopentadiene
Reaction: 3  -  Me  -  2  -  cyclopentenone + Me—MgBr    Ether ,  0  �   C .     1 , 3  -  Me 2  -  3  -  OMgBr  -  2  -  cyclopentene 1 ,  3  -  Me 2  -  3  -  OMgBr  -  2  -  cyclopentene + H 2  O      1 , 3  -  Me 2  -  2  -  cyclopenten  -  3  -  ol 1 , 3  -  Me 2  -  2  -  cyclopenten  -  3  -  ol    84  –86�   C .   1 , 3  -  Me 2  -  cyclopentadiene Procedure
In a flask under nitrogen, were placed 200 ml (0.6 mol.) of methylmagnesium bromide (3.0 molar in ether) and 200 ml of dry ether at 0� C. Then a solution of 49.19 g (0.5117 mol.) of 3-methyl-2-cyclopentenone in 50 ml of dry ether was added dropwise to this solution. After a stirring period (one hour), the reaction mixture was yellow-red. The reaction was further continued at room temperature for 24 hours. The reaction mixture was treated with 500 ml of water cooled to 0� C. After separation and drying over anhydrous MgSO4, the solvent of the organic phase was removed in vacuo (500-550 mbars) to room temperature. The viscous red oil was distilled and collected at −78� C. Fractional distillation at 84-86� C. yielded 24.10 g (50.14%) of a clear colorless liquid, containing a small quantity (ca. 5%) of 1-methylcyclopentadiene.
Reaction 1 , 3  -  Me 2  -  cyclopentadiene + acetone    methanol ,  pyrrolidine     1 , 3 , 6 , 6  -  Me 4  -  fulvene Procedure
In a 250 ml flask, under nitrogen, were placed 50 ml of methanol at −78� C. Then 24.10 g (0.256 mol.) of 1,3-dimethylcyclopentadiene was added to the methanol. After that, a solution of 7.5 ml (0.102 mol.) of acetone in 25 ml of methanol was added dropwise to this solution. Finally, a solution of 12.8 ml (0.154 mol.) of pyrrolidine in 25 ml of methanol was added dropwise to the reaction mixture. After an hour, the reaction mixture was red and the reaction was further continued for 2 days. After neutralization with 10 ml of acetic acid and 50 ml of water, the reaction mixture was separated and dried over anhydrous MgSO4. The solvent of the organic phase was removed in vacuo (10-2 mbar) and yielded 15.62 g (45.45%) of a clear red liquid.
C. Preparation of 1-t-butyl-2,4-dimethyl cyclopentadiene
Reaction 1 , 3 , 6 , 6  -  Me 4  -  fulvene + Me—Li    Ether ,  0  �   C .   ( 1  -  t  -  Bu  -  2 , 4  -  Me 2  -  Cp )  —Li +  ( 1  -  t  -  Bu  -  2 , 4  -  Me 2  -  Cp )  —Li + + H 2  O    1  -  t  -  Bu  -  2 , 4  -  Me 2  -  cyclopentadiene Procedure
In a 1 liter flask, under nitrogen, were placed 200 ml of dry ether and 15.20 g (0.113 mol.) of 1,3,6,6-tetramethylfulvene. The yellow solution was cooled to 0� C. Then, a solution of 70.8 ml (0.113 mol.) of methyllithium (1.6 molar in ether) was added dropwise to this solution. The reaction was further continued at room temperature for 24 hours. The reaction mixture was treated with 50 ml of solution of NH4Cl (saturated) After separation and drying over anhydrous MgSO4, the solvent of the organic phase was removed in vacuo (10-2 mbar) and yielded 13.21 g (77.63%) of a clear yellow oil.
D. Preparation of chlorodimethyl-(9-fluorenyl)silane
Reaction fluorene + Me—Li    0  �   C . Ether   fluorenyllithium fluorenyllithium + Me 2  SiCl 2    Hexane     chlorodimethyl  -  ( 9  -  fluorenyl )  silane Procedure
Into a 3000 ml flask, under nitrogen, was placed a solution of dichlorodimethyl silane (80.2 ml, 0.64 mol.) in 1000 ml of dry hexane, and the solution was Dre-cooled to −78� C. A suspension of fluorenyllithium (53.13 g, 0.32 mol.) in 2000 ml of hexane was slowly added via a cannula and the reaction mixture was stirred for an additional one hour at this temperature. The resulting mixture was gradually allowed to warm to room temperature and stirred for another 16 hours. The reaction mixture was then filtered under nitrogen, through a Celite plug (250 ml). The filtrate was concentrated and kept at −20� C. overnight. The resulting light-green crystals were recrystallised from hexane at −20� C. to afford 75.09 g (90.68 % yield) of chlorodimethyl-(9-fluorenyl)silane.
E. Preparation of (2,5-dimethyl-3-t-butyl)-dimethyl-(9-fluorenyl)silane
Reaction 1  -  t  -  Bu  -  2 , 4  -  Me 2  -  Cp + Me—Li    THF ,  0  �   C .   ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  —Li +  ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  —Li + + Me 2  Si  ( flu )  Cl    THF     Me 2  Si ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  ( flu ) Procedure
Into a 1000 ml flask, under nitrogen, was placed 10 g of 1-t-Bu-2,4-Me2-Cp in 250 ml of dry tetrahydrofuran, and the solution was pre-cooled to 0� C. Then, a solution of 41.6 ml (0.0666 mol.) of methyllithium was added dropwise to the solution. After a stirring period, the reaction mixture was white. The reaction was further continued at room temperature for 4 hours. After that, a solution of 17.22 g (0.0666 mol.) of chlorodimethyl-(9-fluorenyl)silane in 80 ml of dry tetrahydrofuran was added dropwise to this solution. The reaction was further continued for 24 hours. The solvent of the organic phase was removed in vacuo (10-2 mbar) at 40� C. for 3 hours. The ligand was extracted with 2�300 ml of n-pentane. After filtration, the n-pentane was removed in vacuo at 40� C. and yielded 23.75 g (95.72%) of a clear brown oil.
F. Preparation of dimetchylsilyl(2,5-dimethyl-3-t-butyl-cyclopentadienyl)(flyorenyl)zirconium dichchloride
Reaction Me 2  Si ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  ( flu ) + 2  Me—Li    Ether ,  0  �   C .     Me 2  Si ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  —Li +  ( Flu )  —Li + Me 2  Si ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  —Li +  ( Flu )  —Li +   ZrCl 4     Me 2  Si ( 2 , 5  -  Me 2  -  3  -  t  -  Bu  -  Cp )  ( Flu )  ZrCl 2 + 2  LiCl Procedure
In a 500 ml flask, under nitrogen, was placed 10 g of ligand in 100 ml of dry diethylether. The solution was pre-cooled to 0 �C. A solution of 33.5 ml (0.0537 mol.) of methyllithium (1.6 molar/diethylether) was added dropwise to this solution. After a stirring period (24 hours), the solvent was removed in vacuo. The red powder was washed with 200 ml of pentane and yielded 12.4 g of a red power. Into a 500 ml flask, was placed the red dianion ligand, in 200 ml of pentane. 6.5 g (0.027 mol.) of zirconium tetrachloride was added to this suspension. The mixture was red-brown and the reaction was further continued for 24 hours in a glove box. After washing and filtration, the red powder was solubilised in 100 ml of dichloromethane. The solution was filtered and the filtrate was removed in vacuo and yielded 13.2 g (92.3%) of orange powder.
Polymerisation Procedures II
Each polymerisation was performed in a 4 liter bench reactor with pure propylene or with diluent such as cyclohexane or isobutane with the quantities reported in the following Tables. Polymerisation was initiated by introducing metallocene (0.5 to 5 mg) precontacted with 1 ml of MAO (methylaluminoxane) (30% solution in toluene obtained from WITCO) three minutes prior to its introduction into the reactor.
Tables 7 and 8 show the results of polypropylene production using the catalyst of Example 5. Entries 1 to 4 compare polymerisation of pure polypropylene (bulk-entry 1) with those using the diluents cyclohexane (entry 2) and isobutane at two different partial pressures of hydrogen (entries 3 and 4). The polymerisation temperature for each of these entries was 600C. It is apparent that a molecular weight of about 50,000 to about 150,000 was obtainable. Polypropylene having a melt temperature of at least 141� C. was obtained. The polymers obtained exhibited monomodality on gel permeation chromatography (results not shown).
Table 8 shows the microtacticity of the polymer obtained using the catalyst according to Example 5 under polymerisation conditions as defined by the corresponding entries in Table 7. The results were obtained using 13C NMR spectroscopy. It will be apparent that the polypropylene contained more than 84% of pentads in the purely isotactic form (mmmm) and a virtually undetectable frequency of misinsertions.
Bulk Polymerization with 1-dimethylsilyl-(3-t-butyl 2, 5-dimethylcylopentadienylp
fluorenyl) zirconium dichloride
Pol Temp
51.6 22.7
Key: MFI—Melt Flow Index, Mn = number average molecular weight, Mw = weight average molecular weight D = Mw/Mn; D′ = Mz/Mw TABLE 8
Microtacticity with Me2Si (3-tBu-2,5-dimethylene) FluZrCl2 Pol
(1) Inversions observed but too low to be quantified (2) Not observed Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS5459117Aug 27, 1993Oct 17, 1995Ewen; John A.Doubly-conformationally locked, stereorigid catalysts for the preparation of tactiospecific polymersUS5631202 *Sep 24, 1993May 20, 1997Montell Technology Company B.V.Stereospecific metallocene catalysts with stereolocking α-CP substituentsEP0537130A1Sep 23, 1992Apr 14, 1993Fina Technology, Inc.Process and catalyst for producing isotactic polyolefinsEP0693497A2Jul 12, 1995Jan 24, 1996PCD-Polymere Gesellschaft m.b.H.Process for the preparation of silicon-bridged asymmetric cyclopentadienyl-, indenyl- and fluorenyl-containing ligand systemsEP0747406A1Jun 6, 1996Dec 11, 1996Fina Technology, Inc.Process for producing syndiotactic/isotactic block polyolefins* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS7475098 *Mar 19, 2002Jan 6, 2009Network Appliance, Inc.System and method for managing a plurality of snapshotsUS7488789Dec 26, 2003Feb 10, 2009Mitsui Chemicals, Inc.Propylene copolymer, polypropylene composition, and uses thereof, transition metal compounds and catalyst for olefin polymerizationUS7678934Aug 4, 2008Mar 16, 2010Mitsui Chemicals, Inc.Propylene copolymer, polypropylene composition and uses thereof, transition metal compound and olefin polymerization catalystUS7728078Aug 4, 2008Jun 1, 2010Mitsui Chemicals, Inc.Propylene copolymer, polypropylene composition and uses thereof, transition metal compound and olefin polymerization catalystUS7737239Aug 4, 2008Jun 15, 2010Mitsui Chemicals, Inc.Propylene copolymer, polypropylene composition and uses thereof, transition metal compound and olefin polymerization catalystUS7767313Aug 4, 2008Aug 3, 2010Mitsui Chemicals, Inc.Polypropylene composite film comprising a metallocene-catalyzed propylene/1-butene random copolymerUS7834204May 24, 2006Nov 16, 2010Mitsui Chemicals, Inc.Fluorene derivative, transition metal compound, catalyst for olefin polymerization, and process for producing olefin polymerUS7879960Aug 29, 2005Feb 1, 2011Mitsui Chemicals, Inc.Process for producing propylene polymerUS8426534 *Aug 25, 2006Apr 23, 2013Total Research & Technology FeluyImpact copolymer in single reactorUS8716418Dec 16, 2010May 6, 2014Mitsui Chemicals, Inc.Process for producing syndiotactic α-olefin polymerCN101010350BAug 29, 2005Jan 2, 2013三井化学株式会社Process for producing propylene polymer* Cited by examinerClassifications U.S. Classification502/152, 556/53, 526/159, 526/943, 526/160, 556/43, 526/158, 502/103, 526/169.2, 556/11, 526/351International ClassificationC08F4/642, C08F10/00, C08F4/64, C08F110/06, C08F4/659Cooperative ClassificationY10S526/943, C08F10/00, C08F4/65904, C08F4/65912, C08F110/06European ClassificationC08F10/00Legal EventsDateCodeEventDescriptionAug 8, 2000ASAssignmentOwner name: FINA RESEARCH, S.A., BELGIUMFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RAZAVI, ABBAS;BELLIA, VINCENZO;REEL/FRAME:011121/0432Effective date: 20000420Owner name: FINA RESEARCH, S.A. ZONE INDUSTRIELLE C 7181 SENEFOwner name: FINA RESEARCH, S.A. ZONE INDUSTRIELLE C 7181 SENEFFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RAZAVI, ABBAS;BELLIA, VINCENZO;REEL/FRAME:011121/0432Effective date: 20000420Nov 2, 2006FPAYFee paymentYear of fee payment: 4Oct 29, 2010FPAYFee paymentYear of fee payment: 8Oct 30, 2014FPAYFee paymentYear of fee payment: 12RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services

value: This website is a search engine provided by Google. Handling over 3.5 billion searches per day, it has a 92% share of the global search engine market.


text:
Amazon.co.uk: Hardcover - AmazonGlobal Eligible / Martial Arts / Combat Sports & Self-Defence: Books
£6.64 new (48 offers) £7.97 used (11 offers) (41)
£5.83 new (43 offers) £6.95 used (9 offers) (15)
Bruce Lee's Fighting Method by Bruce Lee (1 Sep 2008)
£20.62 £20.51
£13.30 new (31 offers) £16.34 used (10 offers) (18)
18 Buddha Hands: Southern Praying Mantis Kung Fu by Roger D. Hagood, Charles Alan Clemens and Jack Man Louie (1 Aug 2012)
£20.62 new (13 offers) £20.62 used (5 offers) FREE Delivery on orders over £10
Karate-Do Kyohan: The Master Text by Gichin Funakoshi (27 Mar 2013)
£15.22 new (30 offers) £18.92 used (8 offers) (20)
The Complete Ninja: The Secret World Revealed by Masaaki Hatsumi (1 Sep 2014)
FREE Delivery on orders over £10 and 1 more promotion When Buddhists Attack: The Curious Relationship Between Zen and the Martial Arts by Jeffrey K. Mann (10 Sep 2012)
£5.85 new (30 offers) £7.57 used (8 offers) (3)
The Wing Chun Compendium by Wayne Belonoha (31 Dec 2005)
£15.39 new (25 offers) £20.53 used (10 offers) (9)
Bushido: The Soul of Japan by Inazo Nitobe (15 Oct 2012)
£5.78 new (32 offers) £5.00 used (9 offers) (1)
The Twenty Guiding Principles of Karate: The Spiritual Legacy of the Master by Gichin Funakoshi and Jotaro Takagi (29 Mar 2013)
£5.46 new (24 offers) £6.57 used (9 offers) (2)
Encyclopedia of Japanese Martial Arts by David A. Hall (7 Jan 2013)
£22.00 new (26 offers) £25.61 used (9 offers) (3)
Shoninki, The Secret Teachings of the Ninja: The 17th Century manual on the Art of Concealment by Master Natori Masazumi (1 Sep 2010)
£5.05 new (34 offers) £3.50 used (16 offers) (9)
£4.29 new (23 offers) £6.12 used (7 offers) (35)
The Art of Peace (Shambhala Library) by Morihei Ueshiba and John Stevens (28 Apr 2005)
£5.11 new (21 offers) £5.11 used (10 offers) (26)
Meditation and the Martial Arts (Studies in Religion and Culture) by Michael L. Raposa (30 Nov 2003)
£11.75 new (14 offers) £6.57 used (8 offers) FREE Delivery on orders over £10
The Comprehensive Illustrated Manual of Martial Arts of Ancient Korea by Sang H. Kim (Jan 2001)
£14.99 new (4 offers) £75.08 used (4 offers) (3)


text:
Skip to main contenteBayShop by categoryShop by categoryEnter your search keywordBedside Tables└Furniture└Home & GardenAll CategoriesAlcohol & FoodAntiquesArtBabyBooks, MagazinesBusinessCamerasCars, Bikes BoatsClothing, Shoes AccessoriesCoinsCollectablesComputers/Tablets & NetworkingCraftsDolls, BearsElectronicsGift CardsHealth & BeautyHome AppliancesHome EntertainmentHome & GardenIndustrialJewellery & WatchesMoviesMusicMusical InstrumentsPet SuppliesPhones & AccessoriesPottery, GlassServicesSporting GoodsStampsTickets, TravelToys, HobbiesVehicle Parts & AccessoriesVideo Games & ConsolesLots More...AdvancedG'day (Sign in to bid or buy) eBay Deals Sell Help & Contact My eBayExpand My eBay My eBay Summary Bids/Offers Watch List Wish List All Lists Purchase History Selling/sold My Collections Followed searches My messagesNotification There seems to be a problem serving the request at this timeYou're hereeBayHome & GardenHome & Garden FurnitureBedside TablesDark Wood Tone Bedside TablesDark Wood Tone Bedside TablesRefineResults in Dark Wood Tone Bedside Tables1-25 of 292 x Walnut Bedside tables Mid Century Modern 1960s style drawers side lamp standWalnut mid century bedside tables. Would be a great addition to the mid-century modern space. large storage space, decent size. We endeavour to mention anything that we consider to be beyond the reasonable result of those years of use.AU $590.00Local pickupor Best Offer9 watchingSet Of 2 Timber Bedside Tables, 2 Drawers, Dark Timber Tone, Balwyn Pick upSET OF 2 TIMBER BEDSIDE TABLES. - Dark Timber Tone. - 2 Drawers. - Collection required from Balwyn, Vic.AU $49.000 bidsEnding 26 Mar at 20:09 AEDST1d 23hLocal pickupScandinavian Danish Retro Modern Timber Wood Bedside Table 2 Drawer StorageOur Selena Bedroom Range with its Scandinavian styling and retro-inspired look will be sure to impress anyone. Constructed with a combination of quality Solid Acacia Wood & Solid Rubber Wood Timber.AU $165.00eBay Premium ServiceFree postage34 sold2 x Modern Rustic Bedside Table -Mango wood nightstand 2 drawers cast iron frameThe Modern Rustic Bedside Table is made from antique, re-purposed mango wood with a black-stained finish to add a unique charm and character. A sturdy black metal frame strapping surrounds its edges and completes its rustic-modern look.AU $283.50eBay Premium ServiceWas: Previous priceAU $378.00or Best OfferFree postage22 watchingNew Solid Acacia Timber Wood Rustic Bed Side Table with 2 DrawersThe Phillipe Bed Side Table is gorgeous design piece. With it's industrial retro theme, the beautiful Solid Acacia Wood is at the forefront with its Java rustic colours. This range features a hand wire brush effect finish to create a wonderful contemporary industrial look for your home.AU $165.00eBay Premium ServiceFree postage10 soldIndustrial Bedside Table - Mango wood nightstand with black metal legsMid-century modern that wonderfully mixes purpose and style, this Industrial Side Table Storage Unit is a must-have in your bedroom. It is compact enough to fit a small bedroom as a night stand, yet it can still hold up on its own as an accent piece in a more spacious bedroom or even in the living room.AU $161.10eBay Premium ServiceWas: Previous priceAU $179.00or Best OfferFree postage26 watchingSolid Timber Wood glass plate Bed Side Table with 1 Drawer & 1 shelfSOLD AS A PAIR
heavy, solid, well made by ijf australia.
56cm to glass top plate x 40cm wide x 50cm deep
very nice. very solid, strong.
glass chipped on edges see last pic.
very minor marks etc.
notable small chip front draw, see pic.
AU $51.00Local pickuppair solid Tasmanian oak rustic bedside tables with single drawerThese bedside tables are solid Tasmanian oak with a beautiful grain pattern that has been sanded back to show its detail. They have been subtly highlighted with turquoise around the drawers, and very soft touches of orange.AU $165.00Local pickup15 watchingRound Moroccan Brown Burnt lamp table side table beside Indian table Round Brown Burnt carved table. 45 cm round x 45 cm high. Its made from Indian Sheesham(Teak). sorry but they do not service P.O boxes. best and cheapest way we can.AU $120.0038 watchingdark brown bedside table with chrome handles and 2 drawers bedroom furnitureDark brown wood tone in colour. the bedside table is in very good condition. You can only see it in the light. there is a faint pattern on the top of the table due to placing grip mat.AU $85.00Local pickupor Best OfferONE OFF solid wood carved french Indian 45cm bedside bed side lamp table CHOC1 x Hand carved solid wood Bedside table B (45 x 40 x 65cm). CARVED COLLECTION - 1 door 1 drawer bedside. - This item is made by quality craftsmen with good quality seasoned old wood. - The product is hand made so will have the character.AU $225.00Free postage3 watchingCountry Lane Rustic Stressed Timber One Drawer, One Cupboard Side TableRustic stressed timber bedside table, side table with one drawer and cupboard. Clean and in very good condition. A few scuffs and scratches in the varnish from use, great classic country rustic look. Excellent size for storage. Useful next to lounge or as bedside table, or spare cupboard in entry or kitchen.
W: 455mm, D: 450mm, H: 690mm
AU $60.00Local pickupVintage Wrought Iron Antique Timber Bedside Cabinet Lamp Table Size 61CM Wide 77CM High 42CM Deep. Beautiful Character Solid timber built Excellent Quality Indian Furniture. We deal directly with artisans in developing countries, providing them with employment opportunities which lead to a better standard of life for them and their wider community.AU $350.00or Best OfferVintage Queen Anne Bedside Tables (2) w. Glass tops, SydneyIn their original condition which are very good for their age. Some ink has been spilt on the inside of one of the drawers throughout its life and there are slight marks to the tops. Collection fromRoseville near Chatswood on North Shore of Sydney.AU $240.000 bidsEnding 30 Mar at 21:30 AEDST6dLocal pickupOak Timber Bedside Table With DrawerUnit is solid timber . Could use some tlc but ok as is. Measures 51cm wide, 38cm deep and 60cm high. Inside of drawer measures 33cm wide , 25cm front to back and 11cm deep Pickup from varroville 2566AU $12.800 bidsEnding 3 Apr at 11:05 AEST9d 15hLocal pickupTwo Matching Solid Wood Bedside TablesBeautiful, Solid wood, American made side tables. Does not disassemble.AU $150.00Local pickupor Best OfferBedside Drawers Lamp Side Table Indian Moroccan Vintage Antique MetalSize 45CM Wide 76CM High 45 CM Deep. Beautiful Character Solid timber built Excellent Quality Indian Furniture. We deal directly with artisans in developing countries, providing them with employment opportunities which lead to a better standard of life for them and their wider community.AU $280.00or Best Offer4 watchingPair of Mango Wood dark wenge Timber bedsides bed side tablesBedside tables-price for the pair. 39 cm Deep. ring first to make sure we still have it. 1 louver door ,drawer on metal runners. OUR FURNITURE IS HANDMADE WITH RUSTIC APPEAL.AU $479.00Pair of Rustic Mango Wood dark wenge Timber Oriental bedsides bed side tablesRustic Bedside tables-price for the pair. 35 cm Deep. OUR FURNITURE IS HANDMADE WITH RUSTIC APPEAL. ring first to make sure we still have it. 66 cm High.AU $449.0014 watchingTimber bedside tableSolid wood timber bedside table, can be bought with matching queen bed and chest of drawers. Please contact the seller if you wish to buy the set. AU $80.000 bidsEnding 26 Mar at 22:29 AEDST2d 1hLocal pickupBallarat Bedside Drawer (Brand New) #2157Ballarat bedside drawers consisting of 2 drawers which are both on runners for a smoother open and close. This range is solid quality furniture. The dark coloured wood with the silver handles make this furniture really stand out.AU $195.00Local pickupor Best OfferMetro Bedside Drawer (Brand New) #2256Metro bedside drawers consisting of two drawers in a beautiful rich finish. Both the drawers are on runners but this piece has no handles giving it a sleek and modern look. This piece would suit almost any home decor.AU $185.00Local pickupor Best OfferRustic bedside chest of drawersRustic small chest of drawers 40cm long x 35cm deep x 65cm high Pick up enmoreAU $40.00Local pickupMadrid Bedside Drawer (Brand New) #2179Both drawers are on casters and have a black squared handle. There is more than one available. No misleading information is intentionally provided. Make Supersized Seem Small. We are located at 1A Myer Court, Beverley.AU $135.00Local pickupor Best OfferModern Rustic Bedside TableThe Modern Rustic Bedside Table is made from antique, re-purposed mango wood with a black-stained finish to add a unique charm and character. A sturdy black metal frame strapping surrounds its edges and completes its rustic-modern look.AU $179.10eBay Premium ServiceWas: Previous priceAU $199.00or Best OfferFree postageView all resultsSponsored ListingsShowing slide {CURRENT_SLIDE} of {TOTAL_SLIDES} - Sponsored ListingsGo to previous slide - Sponsored ListingsModern Rustic Bedside TableAU $179.10Was: AU $199.00Free postageGo to next slide - Sponsored ListingsGot one to sell?Get it in front of 160+ million buyers.You may also likeWhite Bedside TablesBlack Bedside TablesBrown Bedside TablesMedium Wood Tone Bedside TablesGrey Bedside TablesSide Refine PanelShop by CategoryHome & Garden FurnitureBedside TablesArmoires & WardrobesBar StoolsBean BagsBeds & MattressesBedroom Furniture Sets & SuitesBenches & StoolsBookshelvesCabinets & ChestsCD & Video RacksChairsChildren's FurnitureDesks & Home Office FurnitureDining Furniture SetsDressers & Chests of DrawersDressing TablesDrinks Trolleys & Tea TrolleysEntertainment Units & TV StandsFutonsKitchen Islands & Kitchen CartsOttomans, Footstools & PoufsScreens & Room DividersSideboards & BuffetsFurniture SlipcoversSofas & CouchesTablesTrunks & ChestsFurniture Parts & AccessoriesOther Home FurnitureMoreLessBuying formatsee allAll ListingsAuctionBuy It NowColoursee allDark Wood ToneBrandsee allHandmadeUnbrandedNot SpecifiedMaterialsee allOakSolid WoodTimberWoodWood & MetalStylesee allBritish ColonialColonialModernQueen Anne StyleVintage/RetroFeaturessee allConditionsee allBrand NewNew: Never UsedSeller refurbishedUsedPricePlease provide a valid price range$-$Item locationsee allDefaultWithin2 km5 km10 km15 km20 km50 km75 km100 km150 km200 km500 km750 km1000 km1500 km2000 kmofGoAustralia OnlyWorldwideDelivery optionssee allFree postageShow onlysee allReturns acceptedCompleted itemsSold itemsMore refinements...

value: This website is an American multinational e-commerce corporation based in San Jose, California, that facilitates consumer-to-consumer and business-to-consumer sales through its website.


text:
[RSW] Announcing The Rise of Skywalker Set : swtg
limit my search to r/swtg
joinleave722 readers
It's MtG with a Star Wars twist!
Website: www.starwarsthegathering.com
Card Gallery: http://imgur.com/gallery/vA4Ue
Digital clients: Link <--- ONLINE PLAY
Discord: https://discord.gg/dcURQ25
created by nstephenha community for 3 years
WhinyTortoiseOriginal Design
SoulofZendikarDesign & Development
TangentThought300dpi of awesome
discussions in r/swtg
[SWC] This winter prepare for Commander
Does anyone play on Xmage?
Looking for cockatrice expansions
Any alternative printing services for Germany/Europe?
[RSW] Announcing The Rise of Skywalker Set
[RBN] All the other sets online on our website :)
[SWG] Fullart Basic Plains With SW Frame
[SWG] Star Wars The Gathering Wastes Fullarts
[RSW] Announcing The Rise of Skywalker Set (self.swtg)
submitted 15 days ago by Rebornspoilers
Here the symbol, we're pround to announce one more chapter of this amazing game, this time made by us :)
we hope you enjoy this new set with lots of brand new cards and mechanics!
Ready near may 29 :) [or much near if ready] Stay tuned!
https://preview.redd.it/vzz01syjabf41.png?width=916&format=png&auto=webp&s=dbd507343d1b492a43c60269bb5c5640b450d9f4
[–]WhinyTortoiseOriginal Design 2 points3 points4 points 15 days ago (1 child)
Love the set symbol, excited to see what you come up with.
[–]Rebornspoilers[S] 1 point2 points3 points 15 days ago (0 children)
We try to create something in the perfect style of magic and star wars 😊
[–]mothkin 1 point2 points3 points 15 days ago (0 children)
Can't wait! Symbol looks great
[–]SoulofZendikarDesign & Development 0 points1 point2 points 13 days ago (2 children)
How many cards are you planning to have in it?
[–]Rebornspoilers[S] 0 points1 point2 points 13 days ago (1 child)
280 (promo, extended art and special frame included)
[–]SoulofZendikarDesign & Development 2 points3 points4 points 13 days ago (0 children)
Wow! That's a serious expansion!
[–]Jversluy 0 points1 point2 points 12 days ago (1 child)
This is ambitious and I'm looking forward to what you contribute, but can we still expect an "official" Rise of Skywalker set from SoulofZendikar to fit in with the current designs? Really excited to print the complete series in a few months whenever it's all done.
[–]Rebornspoilers[S] 1 point2 points3 points 12 days ago (0 children)
Mmh, we can ask to him, for us is an experiment, so you can compare our work with the one made by SoulofZendikar, there's not a war between us :) When it comes out if the set of SoulofZendikar is better and he want to change or not pubblish it we do what he want. We don't want to take his place for develop more sets of sw. we only want to test ourselves. We don't want to destroy the good work made by SoulofZendikar, we respect them :)
π Rendered by PID 12570 on r2-app-0d287fb0f47e023d8 at 2020-02-21 22:49:53.169519+00:00 running edb4f2a country code: US.

value: This website is an American social news aggregation, web content rating, and discussion website. Registered members submit content to the site such as links, text posts, images, and videos, which are then voted up or down by other members.


text:
The Troll. Written by Julia Donaldson by Julia Donaldson, David Roberts (Illustrator) - New, Rare & Used Books Online at Alibris Marketplace
The Troll. Written by Julia Donaldson	by
Julia Donaldson, David Roberts (Illustrator)
The troll longs for a goat - but has to make do with fish for supper instead. Meanwhile, Hank Chief and his pirate crew are digging for treasure - ...
The troll longs for a goat - but has to make do with fish for supper instead. Meanwhile, Hank Chief and his pirate crew are digging for treasure - but it seems they've sailed to the wrong island. Again. Watch the fun unfold as these two worlds collide.
Collectible from $28.96
The Troll. Written by Julia Donaldson – Hardcover
ISBN: 0230017932
ISBN-13: 9780230017931
Happy Birthday Winnie
Paul Bright, Jane Chapman (Illustrator)
Dinosaurs' day out
Too Hot to Hug!
Steve Smallman, Cee Biscoe (Illustrator)
from $161.22
Title: The Troll
9780230017931
Title: The Troll. Written by Julia Donaldson
Description: Roberts, David. New. Sewn binding. Cloth over boards. 32 p.
Roberts, David. New. Sewn binding. Cloth over boards. 32 p.
Description: New. 2010. Illustrated edition. Hardcover......We ship daily...
New. 2010. Illustrated edition. Hardcover......We ship daily from our warehouse. Over 350, 000 customers served online! Our feedback reflects our service....'Quick delivery and book was exactly as described', 'Great service-thank you! '
Description: New. Book New and in stock. 7/3/2009.
New. Book New and in stock. 7/3/2009.
Reviews of The Troll. Written by Julia Donaldson
Discussions about The Troll. Written by Julia Donaldson

value: This website is is an online store that sells new books, used books, out-of-print books, rare books, and other media through an online network of independent booksellers.


text:
Words that start with felono | Words starting with felono
Words that start with felono | Words starting with felono http://www.thefreedictionary.com/words-that-start-with-felonoPrinter Friendly
9,670,436,956 visitors served
Found 1 words that start with felono. Browse our Scrabble Word Finder, Words With Friends cheat dictionary, and WordHub word solver to find words starting with felono. Or use our Unscramble word solver to find your best possible play! Related: Words containing felono
8-letter words that start with felonoSee also8-letter words that start with felonofelonousSee also:2-letter words with UWords that start with qWords that end in zWords that start with hWords that start with fWords that start with sWords that start with felonWords that start with felonou

value: This website is an American online dictionary and encyclopedia that aggregates information from various sources.


text: MENU Homepage Markets Stocks Currencies Commodities Rates + Bonds Economics Magazine Benchmark Watchlist Economic Calendar Tech Silicon Valley Global Tech Venture Capital Hacking Digital Media Bloomberg West Pursuits Cars & Bikes Style & Grooming Spend Watches & Gadgets Food & Drinks Travel Real Estate Art & Design Politics With All Due Respect Delegate Tracker Culture Caucus Podcast Masters In Politics Podcast What The Voters Are Streaming Editors' Picks Opinion View Gadfly Businessweek Subscribe Cover Stories Opening Remarks Etc Features 85th Anniversary Issue Behind The Cover More Science + Energy Graphics Game Plan Small Business Personal Finance Inspire GO Board Directors Forum Sponsored Content Bloomberg About The Company Sign In Sign In Subscribe August 25, 2016 11:05 PM ET

value: This website is an international news agency headquartered in New York City and a division of Bloomberg L.P. Content produced by Bloomberg News is disseminated through Bloomberg Terminals, Bloomberg Television, Bloomberg Radio, Bloomberg Businessweek, Bloomberg Markets, Bloomberg.com, and Bloomberg's mobile platforms. Since 2015, John Micklethwait has served as editor-in-chief.


text: HomeEpisodesClips BBC Newsline Episodes By date All By date Available now (3) Next on (27) 2000s 2006 October 2010s 2000s 1990s 2009 2008 2007 2006 2005 2004 2003 2002 2001 2000 January February March April May June July August September October November December October 2006 18:302 Oct 2006 02/10/2006 Local news worth watching from across Northern Ireland. BBC One Northern Ireland View Programme information You may also like View all Similar programmes By genre: News Weather By format: Bulletins Magazines & Reviews HomeScheduleTV Guide Explore the BBC Home Home News News Sport Weather Shop Earth Travel Capital iPlayer Culture Autos Future TV Radio CBBC CBeebies Food iWonder Bitesize Travel Music Earth Arts Make It Digital Taster Nature Local Terms of Use About the BBC Privacy Policy Cookies Accessibility Help Parental Guidance Contact the BBC Advertise with us Ad choices Copyright © 2017 BBC. The BBC is not responsible for the content of external sites. Read about our approach to external linking.

value: This website is the BBC's online service. It is a large network of websites including such high-profile sites as BBC News and Sport, the on-demand video and radio services co-branded BBC iPlayer, the children's sites CBBC and CBeebies, and learning services such as Bitesize.


text:
We thought it was sad that most women only get to wear their wedding dress once, so we invited all the women coming to our non-traditional wedding to wear their old wedding dresses again! : pics
u/JGrce
We thought it was sad that most women only get to wear their wedding dress once, so we invited all the women coming to our non-traditional wedding to wear their old wedding dresses again!
i.imgur.com/uqzGXY...
JGrce
Original Poster125 points · 16 days ago · edited 13 days ago
OP WIFE here! Truth be told my main goal was to make the top page of Reddit because marriage is nice but internet points last a life time.
Also, they were all VERY concerned about upstaging me. I knew I was wearing blue but kept it a secret from everyone except my dressmaker, and my hair and makeup artist. I’d been to almost all their weddings and knew they’d be in white. Plus I’m 5’10. In heels I was 6’1. I told them, “I DARE you to upstage me.”
Edit: needed to heal my spelling
Ricenaros
heal : my wounds heal over time
heel: i have bone spurs in my heels
14,612,569 subscribers
19,559,127 subscribers
17,817,808 subscribers
99,503 subscribers
17,020,271 subscribers
851,863 subscribers
625,298 subscribers
3,383,060 subscribers
3,486,302 subscribers