Mai Motomontant Didinti Wa Tuulloin
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MAIMOTOMONTANT US009914786B2 DIDINTI WA TUULLOIN (12 ) United States Patent (10 ) Patent No. : US 9 ,914 , 786 B2 De Wit ( 45 ) Date of Patent : *Mar . 13 , 2018 (54 ) PROCESS TO PREPARE CROSSLINKED 4 ,404 , 371 A 9 / 1983 Bellmann et al . CELLULOSE ETHERS , CROSSLINKED 9 , 115 ,217 B2 * 8 /2015 De Wit .. .. .. C08B 15 /005 CELLULOSE ETHERS OBTAINABLE BY 2002 /0119116 AL 8 / 2002 Sahatjian et al. SUCH PROCESS AND THE USE THEREOF 2008 /0009616 A11 /2008 Frank et al . (71 ) Applicant : AKZO NOBEL N . V ., Arnhem ( NL ) FOREIGN PATENT DOCUMENTS ( 72 ) Inventor: Paulus Pieter De Wit, Westervoort EP 824096 A1 1 / 1998 (NL ) EP 1 260 522 B1 4 / 2006 GB 3955106 A 2 / 1981 GB 215834 A 8 / 1985 (73 ) Assignee : Akzo Nobel Chemicals International JP 51 028185 A 3 / 1976 B . V . , Arnhem (NL ) SU 1549966 3 / 1990 WO WO 80 / 00842 5 / 1980 ( * ) Notice : Subject to any disclaimer , the term of this WO WO 98 / 27117 A 6 / 1998 patent is extended or adjusted under 35 WO WO 2003 /093395 A1 11/ 2003 WO WO 2005 /030279 AL 4 / 2005 U . S . C . 154 (b ) by 79 days. WO WO 2005 / 123781 A 12 / 2005 This patent is subject to a terminal dis claimer . OTHER PUBLICATIONS ( 21 ) Appl. No. : 14 /795 , 314 Barbucci et al. Synthesis , chemical and rheological characterization of new hyaluronic acid -based hydrogels , J. Biomater Sci. Polymer (22 ) Filed : Jul. 9 , 2015 Edn , vol . 11, No. 4 , pp . 383 - 399 ( 2000 ) . Heinze et al. , “ Esterification of Polysaccharides ,” Inorganic Poly (65 ) Prior Publication Data saccharide Esters , Springer Laboratory , p . 136 , 2006 ( 3 Pages) . US 2015 /0307631 A1 Oct . 29, 2015 International Search Report, PCT/ EP2009 /054348 , dated Jun . 19 , 2009 , 15 pages . Related U . S . Application Data European Search Report , EP 08154474 . 4 , dated Sep . 19 , 2008 , 9 pages . (63 ) Continuation of application No. 12 / 937 ,813 , filed as Leone Gemma , et al. , “ New Phosphorylated Derivatives of application No . PCT /EP2009 / 054348 on Apr. 10 , Carboxymethylocellulose With Osteogenic Activity ” , Polymers for 2009 , now Pat . No . 9 , 115 ,217 . Advanced Technologies Jul. 2008 John Wiley and Sons Ltd ., The Atrium GB , vol. 10 , No . Jan . 2008 , pp . 824 - 830 . (60 ) Provisional application No . 61 /046 , 116 , filed on Apr. Dulong V , et al. , “ Hyaluronan -based Hydrogels Particles Prepared 18 , 2008 . by Cross- Linking With Trisodium Trimetaphosphate , Synthesis and Characterization ” , Carbohydrate Polymers , Applied Science Pub ( 30 ) Foreign Application Priority Data lishers , Ltd . Barking , GB , vol . 57 . , No . 1 , Aug. 12 , 2004 , pp . 1 -6 . Apr . 14 , 2008 (EP ) .. .. .. .. .. 08154474 (Continued ) (51 ) Int . Cl. Primary Examiner — Shaojia Anna Jiang C08B 15 / 05 ( 2006 .01 ) Assistant Examiner — Everett White C08B 15 / 10 ( 2006 .01 ) ( 74) Attorney , Agent, or Firm — Sandra B . Weiss C08B 31 / 00 ( 2006 .01 ) C08B 15 / 00 ( 2006 .01 ) (57 ) ABSTRACT C08B 5 / 00 ( 2006 .01 ) The invention relates to a dry or slurry process to prepare (52 ) U . S . CI. phosphate -crosslinked cellulose ethers from a cellulose CPC .. .. .. C08B 15 /005 (2013 .01 ) ; C08B 5 / 00 starting material comprising the steps of adding an alkaliz ( 2013 .01 ) ing agent to the cellulose starting material to achieve mer (58 ) Field of Classification Search cerization , adding an ethehfying agent to the reaction mix CPC .. .. C08B 15 /05 ; C08B 15 / 10 ; C08B 31/ 00 ture to achieve etherification of the cellulose , and adding a USPC .. .. .. .. .. .. 536 / 56 , 62, 106 , 117, 124 crosslinking agent to the reaction mixture to achieve cross See application file for complete search history . linking of the cellulose , wherein at least part of the alkal izing agent is added to the cellulose starting material before ( 56 ) References Cited the etherification and / or crosslinking reactions take place to obtain alkalized cellulose ; the crosslinking agent and the U . S . PATENT DOCUMENTS etherifying agent are added one after the other in random 3 , 106 ,531 A 10 / 1963 Lindenfors order or simultaneously ; the crosslinking agent is an alkali 3 , 374 , 224 A 3 / 1968 Sommers metal thmetaphosphate ; and the crosslinking and etherifica 3 , 574 , 188 A 4 / 1971 Takehara et al . tion steps are performed at an elevated temperature . Addi 3 ,658 , 790 A 4 / 1972 Bernardia tionally , the invention relates to crosslinked cellulose ethers 3 ,661 , 895 A 5 / 1972 Germino et al. obtainable by the above process having a viscosity and /or 4 ,035 , 195 A 7 / 1977 Podlas water absorption capacity higher than their non - crosslinked 4 , 183 ,765 A 1 / 1980 Podlas 4 , 250 , 306 A 2 / 1981 Lask et al . equivalents and the use thereof. 4 , 321, 367 A 3 / 1982 Cheng et al . 12 Claims, No Drawings US 9 ,914 ,786 B2 Page 2 ( 56 ) References Cited OTHER PUBLICATIONS Gliko -Kabir , I , et al. , “ Phosphated Crosslinked Guar for Colon Specific Drug Delivery — I. Preparation and Physicochemical Char acterization ” , Journal of Controlled Release, Elsevier , Amsterdam , NL ., vol . 63 , No . 1 - 2 , Jan . 1 , 2000 , pp . 121 - 127 . Chatterjee , P . K . , Gupta , B . S . , eds. , Textile Science and Technology , vol . 13 , Absorbent Technology ( Elesevier 2002 ) , Chapter VII entitled “ Crosslinked Cellulose and Cellulose Derivatives” . Luneva et al ., Vetsi Akademii Navak BSSR , Seryya Khimichnykh navuk ( 1989 ) , (6 ), 92 -95 , English abstract provided . * cited by examiner US 9 , 914 , 786 B2 PROCESS TO PREPARE CROSSLINKED mentioned , including phosphorous oxychloride, which is an CELLULOSE ETHERS , CROSSLINKED undesired chemical from a health and safety point of view . CELLULOSE ETHERS OBTAINABLE BY The purpose of the present invention is to provide a SUCH PROCESS AND THE USE THEREOF process to prepare phosphate -crosslinked cellulose ethers that can be operated at a relatively low temperature while REFERENCE TO RELATED APPLICATION ( S ) reducing the number of steps, and as a consequence is more ( energy ) efficient . Additionally , a purpose of the invention is This application is a continuation of U . S . patent applica to provide a process in which a non - hazardous ( green ) tion Ser. No . 12 / 937 ,813 , filed on Oct. 14 , 2010 , which is a national stage filing under 35 U . S . C . $ 371 of PCT/ EP2009 / 10 crosslinking agent can be used . Another purpose of the 054348 , filed Apr. 10 , 2009 , which claims priority to Euro invention is to provide crosslinked cellulose ethers that have pean Patent Application No . 08154474 . 4 , filed Apr. 14 , a higher viscosity than their non -crosslinked equivalents and 2008 , and U . S . Provisional Patent Application No . 61/ 046 , are soluble in an aqueous solution . 116 , filed on Apr . 18 , 2008 , the contents of which are each It has now been found that the drawbacks of the state of incorporated herein by reference in their entirety . 16 the art can be removed and the above purpose achieved by The present invention relates to a process to prepare a dry or slurry process to prepare phosphate- crosslinked phosphate -crosslinked cellulose ethers , to phosphate - cross - cellulose ethers from a cellulose starting material compris linked cellulose ethers obtainable by such a process, and the ing the steps of adding an alkalizing agent to the cellulose use thereof. starting material to achieve mercerization , adding an etheri JP 51028185 discloses a process to prepare a phosphate - 20 fying agent to the reaction mixture to achieve etherification crosslinked carboxymethyl cellulose (CMC ) by adding to of the cellulose , and adding a crosslinking agent to the CMC 5 - 30 % of sodium hexametaphosphate ( SHMP ) , blend reaction mixture to achieve crosslinking of the cellulose , ing the mixture , and heating to a temperature between 100 wherein and 160° C . In all examples the crude ( or intermediate ) at least part of the alkalizing agent is added to the CMCs were purified in one way or another to obtain 25 cellulose starting material before the etherification and / materials with a neutral or acidic pH before crosslinking . or crosslinking reactions take place to obtain alkalized The products made are said to be ion exchange materials cellulose ; with low swelling power , which materials are generally not the crosslinking agent and the etherifying agent are added soluble in aqueous systems and consequently do not con one after the other in random order or simultaneously ; tribute to any viscosity enhancement. Besides , clearly such 30 the crosslinking agent is an alkali metal trimetaphosphate ; products do not have a high water absorption capacity when and they have low swelling capacity . the crosslinking and etherification steps are performed at As the preparation of cellulose ethers takes place at an an elevated temperature . alkaline pH , it would be much less laborious to start the It is understood that in the above process more alkaliza crosslinking step with a non -purified alkaline cellulose ether, 35 tion and etherification steps can be performed . In one omitting the intermediate step of adjusting the pH as embodiment, etherification steps may be performed with required by the process disclosed in JP 51028185 . It might different etherifying agents , or with a mixture containing also be advantageous to carry out the crosslinking step under more than one etherifying agent, resulting in a cellulose alkaline conditions prior to or simultaneously with the ether containing different substituents . etherification step . 40 In a preferred embodiment the crosslinking agent and the WO 2005/ 123781 discloses a process