ES2234014T3 - Polimeros polilacticos acidos. - Google Patents
Polimeros polilacticos acidos.Info
- Publication number
- ES2234014T3 ES2234014T3 ES97917392T ES97917392T ES2234014T3 ES 2234014 T3 ES2234014 T3 ES 2234014T3 ES 97917392 T ES97917392 T ES 97917392T ES 97917392 T ES97917392 T ES 97917392T ES 2234014 T3 ES2234014 T3 ES 2234014T3
- Authority
- ES
- Spain
- Prior art keywords
- acid
- lactide
- tartaric
- units
- lactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 229920000642 polymer Polymers 0.000 title description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 4
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical group OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 5
- LFKLPJRVSHJZPL-UHFFFAOYSA-N 1,2:7,8-diepoxyoctane Chemical compound C1OC1CCCCC1CO1 LFKLPJRVSHJZPL-UHFFFAOYSA-N 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 3
- BOGVTNYNTGOONP-UHFFFAOYSA-N 3,4-dihydroxyoxolane-2,5-dione Chemical compound OC1C(O)C(=O)OC1=O BOGVTNYNTGOONP-UHFFFAOYSA-N 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 abstract description 6
- 235000014655 lactic acid Nutrition 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 5
- -1 CARBOXYL GROUPS Chemical group 0.000 abstract description 2
- 150000001261 hydroxy acids Chemical class 0.000 abstract 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
POLIESTER BIODEGRADABLE PREPARADO A PARTIR DE ACIDO LACTICO Y, OPTATIVAMENTE, OTRO ACIDO O ACIDOS HIDROXI. EL POLIESTER CONTIENE DE 4 A 100 GRUPOS CARBOXILO Y UN PESO MOLECULAR MEDIO DE 1.000 A 200.000 G/MOL. SE EXPONEN IGUALMENTE PROCEDIMIENTOS PARA LA OBTENCION DE TALES POLIESTERES.
Description
Polímeros polilácticos ácidos.
Esta invención se refiere a poliésteres
biodegradables y a métodos para su preparación.
Los polímeros biodegradables se han usado, por
ejemplo, como excipientes en composiciones de fármacos de liberación
sostenida. Véanse, por ejemplo, las patentes U.S. nº 3.773.919 y nº
4.767.628. Son ejemplos de tales polímeros, copolímeros de ácido
láctico y ácido glicólico, que se producen por policondensación de
ácido láctico y ácido glicólico o por polimerización con apertura de
anillo con láctido y glicólido. Véase, por ejemplo, Drug Carriers
in Biology and Medicine, ed. Gregoriadis, G., págs.
241-245 (Academic Press, Londres 1979).
La publicación internacional nº WO 94/15587
describe conjugados iónicos de liberación sostenida de polímeros y
fármacos. Dado que el fármaco básico está iónicamente conjugado al
polímero ácido, es importante aumentar la acidez del polímero para
facilitar la formación del conjugado.
Esta invención proporciona un método para
preparar un poliéster biodegradable o su derivado. El método incluye
hacer reaccionar un ácido
polihidroxi-policarboxílico obtenible por reacción
del ácido tartárico con dianhídrido
1,2,4,5-bencenotetracarboxílico o
1,2,7,8-diepoxioctano con ácido láctico o un láctido
para producir un poliéster, por ejemplo, calentando los reactivos
entre 100ºC y 250ºC. El ácido
polihidroxi-policarboxílico reacciona también
concomitantemente con ácido glicólico o un glicólido.
Tal como se usa aquí, un "ácido
hidroxi-policarboxílico" contiene como mínimo un
grupo hidroxi (por ejemplo, entre 1 y 20 grupos hidroxi) y como
mínimo dos grupos carboxilo (por ejemplo, entre 2 y 40 grupos
carboxilo); un "ácido
polihidroxi-policarboxílico" contiene como mínimo
2 grupos hidroxi (por ejemplo, entre 2 y 20 grupos hidroxi) y como
mínimo 2 grupos carboxilo (por ejemplo, entre 2 y 40 grupos
carboxilo); un "ácido policarboxílico" contiene como mínimo 2
grupos carboxilo; un poliepoxi contiene como mínimo 2 grupos epoxi
(por ejemplo, 2 grupos epoxi); y un "poliol" contiene como
mínimo 2 grupos hidroxi (por ejemplo, entre 2 y 20 grupos
hidroxi).
A no ser que se especifique lo contrario, el
ácido láctico puede ser ácido D-láctico o ácido
L-láctico, y el láctido puede ser
D-láctido, L-láctido o
DL-láctido.
A no ser que se definan de otra manera, todos los
términos técnicos y científicos usados aquí tienen el significado
que comúnmente entiende un experto corriente en la técnica a la que
pertenece la invención.
Se cargó un reactor de vidrio de 500 ml con 203,2
g de L-láctido (Cilag AG, Schaffhausen, Suiza), 81,8
g de glicólido (Cilag) y 15,0 g de ácido L-tartárico
(Riedel de Haen, Seelze, Alemania). El ácido
L-tartárico se había secado adicionalmente sobre
pentóxido de fósforo en un aparato Abderhalden (Aldrich, Milwakee,
WI, U.S.A). Se añadieron 5,3 ml de una solución 0,1 M de hexanoato
de 2-etilo en tolueno (proporción estequiométrica de
200 ppm). Después de secar en vacío a temperatura ambiente durante 1
hora para eliminar el tolueno, el reactor se puso bajo atmósfera de
nitrógeno y se sumergió en un baño de aceite precalentado a 200ºC,
manteniéndose a 200ºC durante 4 horas mientras que se agitaba por
medios mecánicos. Se obtuvo un copolímero amorfo que comprendía
65,13% de unidades de ácido láctico, 32,56% de unidades de ácido
glicólico y 2,31 unidades de tartárico (65/32/2
PLG-TA). El índice de acidez del copolímero se
determinó valorimétricamente que era de 0,630 mequiv/g (por ejemplo,
índice de acidez (miliequivalentes/g) = normalidad del NaOH
multiplicada por el volumen de NaOH requerido para neutralizar 1
gramo del poliéster).
Se cargó un recipiente de reacción con una mezcla
de 22,61 g de ácido L-tartárico y 27,39 g de
dianhídrido
benceno-1,2,4,5-tetracarboxílico y
se sumergió en un baño de aceite a 200ºC. Una vez que fundió la
mezcla, se elevó la temperatura del recipiente a 220ºC en 40 minutos
y se mantuvo esta temperatura durante 30 minutos más mientras que la
mezcla se agitaba vigorosamente. Después de enfriar a temperatura
ambiente, el compuesto se caracterizó por volumetría ácida,
resultando un índice de acidez de 12,96 mequiv/g.
Se calentó a reflujo una solución de 13,50 g de
ácido L-tartárico en 200 ml de acetona (secada
previamente sobre cloruro cálcico). Se añadieron gota a gota 11,50 g
de 1,2, 7,8-diepoxioctano a lo largo de 30 minutos
usando un embudo de adición. La solución se mantuvo luego a reflujo
durante 3 horas. Los oligómeros se recuperaron por evaporación en
acetona y posterior secado en vacío. El índice de acidez medido fue
de 4,03 mequiv/g.
Se cargó un reactor de vidrio de 500 ml con 203,2
g de glicólido, 81,8 g de L-láctido y 14,9 g del
iniciador descrito en el Ejemplo 2. Se siguió el mismo protocolo
descrito en el Ejemplo 1, excepto que el baño de aceite se mantuvo a
220ºC y la polimerización se efectuó en un tiempo total de 8 horas.
El copolímero final tenía sólo 8,5% en peso de
L-láctido residual, tenía un índice de acidez de
0,77 mequiv/g y un peso molecular medio de 12.900 g/mol.
Se cargó un reactor de vidrio de 500 ml con 129,4
g de glicólido, 52,8 g de L-láctido y 18,5 g del
iniciador descrito en el Ejemplo 3. Se siguió el mismo protocolo
descrito en el Ejemplo 1, excepto que el baño de aceite se mantuvo a
200ºC y la polimerización se efectuó en un tiempo total de 5 horas.
El copolímero final tenía sólo 10,6% en peso de
L-láctido residual, tenía un índice de acidez de
0,47 mequiv/g y un peso molecular medio de 30.500 g/mol.
Claims (2)
1. Un poliéster biodegradable que comprende
unidades de ácido láctico, unidades de ácido glicólico y unidades
derivadas de un iniciador a la medida, en el que el mencionado
iniciador a la medida es obtenible haciendo reaccionar ácido
tartárico y el dianhídrido
1,2,4,5-bencenotetracarboxílico.
2. Un poliéster biodegradable que comprende
unidades de ácido láctico, unidades de ácido glicólico y unidades
derivadas de un iniciador a la medida, en el que el mencionado
iniciador a la medida es obtenible haciendo reaccionar ácido
tartárico y 1,2,7,8-diepoxioctano.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IE960307 | 1996-04-23 | ||
| IE960307A IE960307A1 (en) | 1996-04-23 | 1998-10-07 | Acidic polylactic polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2234014T3 true ES2234014T3 (es) | 2005-06-16 |
Family
ID=11041149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES97917392T Expired - Lifetime ES2234014T3 (es) | 1996-04-23 | 1997-04-22 | Polimeros polilacticos acidos. |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US6111033A (es) |
| EP (3) | EP1479707A3 (es) |
| JP (2) | JP3155013B2 (es) |
| AT (1) | ATE282653T1 (es) |
| AU (1) | AU727340C (es) |
| CA (1) | CA2250981C (es) |
| CZ (1) | CZ299398A3 (es) |
| DE (2) | DE69731623T4 (es) |
| DK (1) | DK0895517T3 (es) |
| ES (1) | ES2234014T3 (es) |
| HU (1) | HUP0000732A3 (es) |
| IE (1) | IE960307A1 (es) |
| IL (1) | IL126422A (es) |
| NO (1) | NO984923L (es) |
| NZ (1) | NZ332018A (es) |
| PL (1) | PL329598A1 (es) |
| RU (1) | RU2165942C2 (es) |
| WO (1) | WO1997040085A2 (es) |
Families Citing this family (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6221958B1 (en) * | 1993-01-06 | 2001-04-24 | Societe De Conseils De Recherches Et D'applications Scientifiques, Sas | Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides |
| IE960308A1 (en) | 1996-04-23 | 1997-11-05 | Kinerton Ltd | Sustained release ionic conjugate |
| DE19640269A1 (de) * | 1996-09-30 | 1998-04-02 | Basf Ag | Verwendung einer wäßrigen Dispersion eines biologisch abbaubaren Polyesters zur Umhüllung von Düngemittelgranulaten |
| US6126919A (en) | 1997-02-07 | 2000-10-03 | 3M Innovative Properties Company | Biocompatible compounds for pharmaceutical drug delivery systems |
| UA54505C2 (uk) | 1997-04-03 | 2003-03-17 | Гілфорд Фармасьютікалз Інк. | Полімери, що біологічно розкладаються, зшиті фосфатами, композиції, вироби і способи для їх виготовлення і використання |
| BR9809064A (pt) | 1997-04-03 | 2002-01-02 | Guilford Pharm Inc | Polìmeros biodegradáveis de poliéster de tereftalato-polifosfato, composições, artigos e métodos para fazer e usar os mesmos |
| US6867181B1 (en) | 1997-06-02 | 2005-03-15 | Societe De Conseils De Recherches Et D'applications Scientifiques, S.A.S. | Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides |
| EP1035158A4 (en) * | 1997-10-29 | 2002-01-30 | Kanebo Ltd | RESIN COUPLING WITH BIODEGRADABILITY AND FOAMABILITY |
| US6548302B1 (en) | 1998-06-18 | 2003-04-15 | Johns Hopkins University School Of Medicine | Polymers for delivery of nucleic acids |
| US6419709B1 (en) | 1998-10-02 | 2002-07-16 | Guilford Pharmaceuticals, Inc. | Biodegradable terephthalate polyester-poly(Phosphite) compositions, articles, and methods of using the same |
| US6153212A (en) * | 1998-10-02 | 2000-11-28 | Guilford Pharmaceuticals Inc. | Biodegradable terephthalate polyester-poly (phosphonate) compositions, articles, and methods of using the same |
| US6350464B1 (en) | 1999-01-11 | 2002-02-26 | Guilford Pharmaceuticals, Inc. | Methods for treating ovarian cancer, poly (phosphoester) compositions, and biodegradable articles for same |
| US6537585B1 (en) | 1999-03-26 | 2003-03-25 | Guilford Pharmaceuticals, Inc. | Methods and compositions for treating solid tumors |
| AU767837B2 (en) * | 1999-08-18 | 2003-11-27 | Ipsen Pharma S.A.S. | Sustained release formulation of a peptide |
| EP1348444B1 (en) * | 1999-08-18 | 2006-04-12 | Societe De Conseils De Recherches Et D'applications Scientifiques S.A.S. | Sustained release formulation of a peptide complexed with a polymer |
| US7109166B1 (en) | 1999-08-18 | 2006-09-19 | Societe De Conseils De Recherches Et D'applications Scientifiques, Sas | Sustained release formulation of a peptide |
| JP4565290B2 (ja) * | 1999-12-01 | 2010-10-20 | 東洋紡績株式会社 | 高水酸基濃度を有するオキシ酸系脂肪族ポリエステルおよびオキシ酸系脂肪族ポリエステル組成物 |
| JP3450810B2 (ja) | 2000-01-31 | 2003-09-29 | キヤノン株式会社 | 脂肪族ポリエステル、脂肪族ポリエステルの製造方法およびセルロースの再資源化方法 |
| FR2821360B1 (fr) * | 2001-02-27 | 2003-05-30 | Sod Conseils Rech Applic | Procede de preparation de polyesters avec des fonctions acides libres intracatenaires |
| US20030045798A1 (en) * | 2001-09-04 | 2003-03-06 | Richard Hular | Multisensor probe for tissue identification |
| WO2003080629A2 (en) | 2002-02-25 | 2003-10-02 | Guilford Pharmaceuticals, Inc. | Phosphorus-containing compounds with polymeric chains, and methods of making and using the same |
| EP1911763B1 (en) | 2003-01-28 | 2010-08-11 | Ironwood Pharmaceuticals, Inc. | Compositions for the treatment of gastrointestinal disorders |
| US7772188B2 (en) | 2003-01-28 | 2010-08-10 | Ironwood Pharmaceuticals, Inc. | Methods and compositions for the treatment of gastrointestinal disorders |
| CA2544678C (en) | 2003-11-05 | 2013-12-31 | Sunesis Pharmaceuticals, Inc. | Modulators of cellular adhesion |
| KR20050054129A (ko) * | 2003-12-04 | 2005-06-10 | 주식회사 삼양사 | 고분자 미셀을 형성하는 생분해성 분지형 폴리락트산유도체, 및 그의 제조방법 및 용도 |
| DE602004032265D1 (de) * | 2003-12-30 | 2011-05-26 | 3M Innovative Properties Co | Herstellungsverfahren von medizinischen zusammensetzungen |
| DK2444079T3 (en) | 2005-05-17 | 2017-01-30 | Sarcode Bioscience Inc | Compositions and Methods for the Treatment of Eye Diseases |
| MX354786B (es) | 2007-06-04 | 2018-03-21 | Synergy Pharmaceuticals Inc | Agonistas de guanilato ciclasa utiles para el tratamiento de trastornos gastrointestinales, inflamacion, cancer y otros trastornos. |
| US8969514B2 (en) | 2007-06-04 | 2015-03-03 | Synergy Pharmaceuticals, Inc. | Agonists of guanylate cyclase useful for the treatment of hypercholesterolemia, atherosclerosis, coronary heart disease, gallstone, obesity and other cardiovascular diseases |
| ES2830024T3 (es) | 2007-10-19 | 2021-06-02 | Novartis Ag | Composiciones y métodos para el tratamiento del edema macular |
| WO2009139817A2 (en) | 2008-04-15 | 2009-11-19 | Sarcode Corporation | Crystalline pharmaceutical and methods of preparation and use thereof |
| ES2522968T3 (es) | 2008-06-04 | 2014-11-19 | Synergy Pharmaceuticals Inc. | Agonistas de guanilato ciclasa útiles para el tratamiento de trastornos gastrointestinales, inflamación, cáncer y otros trastornos |
| AU2009270833B2 (en) | 2008-07-16 | 2015-02-19 | Bausch Health Ireland Limited | Agonists of guanylate cyclase useful for the treatment of gastrointestinal, inflammation, cancer and other disorders |
| WO2011050175A1 (en) | 2009-10-21 | 2011-04-28 | Sarcode Corporation | Crystalline pharmaceutical and methods of preparation and use thereof |
| WO2011096968A1 (en) * | 2010-02-08 | 2011-08-11 | Danimer Scientific, Llc | Degradable polymers for hydrocarbon extraction |
| US9616097B2 (en) | 2010-09-15 | 2017-04-11 | Synergy Pharmaceuticals, Inc. | Formulations of guanylate cyclase C agonists and methods of use |
| WO2012151343A1 (en) | 2011-05-04 | 2012-11-08 | Balance Therapeutics, Inc. | Pentylenetetrazole derivatives |
| WO2013042677A1 (ja) * | 2011-09-20 | 2013-03-28 | 東洋紡株式会社 | ポリ乳酸系ポリエステル樹脂、ポリ乳酸系ポリエステル樹脂水分散体、水性接着剤、及びポリ乳酸系ポリエステル樹脂水分散体の製造方法 |
| RU2467029C1 (ru) * | 2011-10-25 | 2012-11-20 | Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации | Способ получения биоразлагаемых полиэфиров |
| US9670311B2 (en) * | 2012-02-17 | 2017-06-06 | Toyobo Co., Ltd | Polylactic polyester resin, aqueous polylactic polyester resin dispersion, and production method for aqueous polylactic polyester resin dispersion |
| JP6133847B2 (ja) | 2012-04-27 | 2017-05-24 | 株式会社クレハ | ポリエステル樹脂組成物およびその成形体 |
| US10675376B2 (en) * | 2012-05-24 | 2020-06-09 | Ethicon Llc | Mechanically strong absorbable polymeric blend compositions of precisely controllable absorption rates, processing methods, and products therefrom |
| KR20200108932A (ko) | 2012-07-25 | 2020-09-21 | 에스에이알코드 바이오사이언스 인코포레이티드 | Lfa-1 저해제 및 그의 다형체 |
| KR101548314B1 (ko) * | 2012-12-17 | 2015-08-28 | 주식회사 엘지화학 | 폴리락타이드 수지의 제조방법 |
| WO2014131024A2 (en) | 2013-02-25 | 2014-08-28 | Synergy Pharmaceuticals Inc. | Agonists of guanylate cyclase and their uses |
| AU2014235209B2 (en) | 2013-03-15 | 2018-06-14 | Bausch Health Ireland Limited | Guanylate cyclase receptor agonists combined with other drugs |
| AU2014235215A1 (en) | 2013-03-15 | 2015-10-01 | Synergy Pharmaceuticals Inc. | Agonists of guanylate cyclase and their uses |
| US20140274820A1 (en) * | 2013-03-15 | 2014-09-18 | Danimer Scientific, Llc | Degradable polymers and method for fracking applications |
| JP6661531B2 (ja) | 2013-10-10 | 2020-03-11 | シナジー ファーマシューティカルズ インコーポレイテッド | オピオイド誘発性機能障害の治療に有用なグアニル酸シクラーゼのアゴニスト |
| US10653744B2 (en) | 2016-01-11 | 2020-05-19 | Bausch Health Ireland Limited | Formulations and methods for treating ulcerative colitis |
| RU2715383C1 (ru) * | 2019-06-20 | 2020-02-27 | Общество с ограниченной ответственностью "ТВС" | Способ получения (со)полимера гликолида и/или лактида для изготовления рассасывающихся хирургических изделий |
| CN114940746B (zh) * | 2022-06-17 | 2024-04-26 | 山东采采医疗科技有限公司 | 星型丙交酯乙交酯共聚物及作为药物缓释载体的用途 |
| WO2026050206A1 (en) | 2024-08-27 | 2026-03-05 | Ironwood Pharmaceuticals, Inc. | Combinations of glp-1 and guanylate cyclase c (gc-c) receptor agonists |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3773919A (en) * | 1969-10-23 | 1973-11-20 | Du Pont | Polylactide-drug mixtures |
| IE52535B1 (en) * | 1981-02-16 | 1987-12-09 | Ici Plc | Continuous release pharmaceutical compositions |
| US4523591A (en) * | 1982-10-22 | 1985-06-18 | Kaplan Donald S | Polymers for injection molding of absorbable surgical devices |
| DE3936191C2 (de) * | 1989-10-31 | 1996-10-17 | Boehringer Ingelheim Kg | Neue Copolymere aus Milchsäure und Weinsäure, ihre Herstellung sowie ihre Verwendung |
| JPH0665230A (ja) * | 1992-08-19 | 1994-03-08 | Showa Denko Kk | ラクチドの製造方法 |
| DK0678018T3 (da) * | 1993-01-06 | 2003-04-28 | Kinerton Ltd | Ion molekylærkonjugater af bionedbrydelige polyestere og bioaktive polypeptider |
| US5672659A (en) * | 1993-01-06 | 1997-09-30 | Kinerton Limited | Ionic molecular conjugates of biodegradable polyesters and bioactive polypeptides |
| AU706434B2 (en) * | 1994-10-18 | 1999-06-17 | Ethicon Inc. | Injectable liquid copolymers for soft tissue repair and augmentation |
-
1997
- 1997-04-22 WO PCT/IE1997/000031 patent/WO1997040085A2/en not_active Ceased
- 1997-04-22 CA CA002250981A patent/CA2250981C/en not_active Expired - Fee Related
- 1997-04-22 DE DE69731623T patent/DE69731623T4/de not_active Expired - Lifetime
- 1997-04-22 AU AU25752/97A patent/AU727340C/en not_active Ceased
- 1997-04-22 HU HU0000732A patent/HUP0000732A3/hu unknown
- 1997-04-22 DE DE69731623A patent/DE69731623D1/de not_active Expired - Fee Related
- 1997-04-22 CZ CZ982993A patent/CZ299398A3/cs unknown
- 1997-04-22 ES ES97917392T patent/ES2234014T3/es not_active Expired - Lifetime
- 1997-04-22 US US09/171,739 patent/US6111033A/en not_active Expired - Fee Related
- 1997-04-22 DK DK97917392T patent/DK0895517T3/da active
- 1997-04-22 IL IL12642297A patent/IL126422A/en not_active IP Right Cessation
- 1997-04-22 EP EP04020490A patent/EP1479707A3/en not_active Withdrawn
- 1997-04-22 EP EP04020491A patent/EP1479708A3/en not_active Withdrawn
- 1997-04-22 PL PL97329598A patent/PL329598A1/xx not_active IP Right Cessation
- 1997-04-22 RU RU98121127/04A patent/RU2165942C2/ru not_active IP Right Cessation
- 1997-04-22 EP EP97917392A patent/EP0895517B1/en not_active Expired - Lifetime
- 1997-04-22 JP JP53789797A patent/JP3155013B2/ja not_active Expired - Fee Related
- 1997-04-22 AT AT97917392T patent/ATE282653T1/de not_active IP Right Cessation
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1998
- 1998-10-07 NZ NZ332018A patent/NZ332018A/en unknown
- 1998-10-07 IE IE960307A patent/IE960307A1/en not_active IP Right Cessation
- 1998-10-22 NO NO984923A patent/NO984923L/no not_active Application Discontinuation
-
2000
- 2000-11-30 JP JP2000365647A patent/JP3335995B2/ja not_active Expired - Fee Related
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| EP1479708A3 (en) | 2005-05-25 |
| NO984923D0 (no) | 1998-10-22 |
| HUP0000732A3 (en) | 2000-11-28 |
| NO984923L (no) | 1998-10-22 |
| HUP0000732A2 (en) | 2000-07-28 |
| DK0895517T3 (da) | 2005-01-17 |
| AU727340C (en) | 2001-11-08 |
| WO1997040085A2 (en) | 1997-10-30 |
| DE69731623T4 (de) | 2006-08-31 |
| WO1997040085A3 (en) | 1998-01-22 |
| IL126422A (en) | 2004-02-19 |
| CZ299398A3 (cs) | 1999-01-13 |
| EP1479707A2 (en) | 2004-11-24 |
| PL329598A1 (en) | 1999-03-29 |
| AU727340B2 (en) | 2000-12-07 |
| AU2575297A (en) | 1997-11-12 |
| JP2001181378A (ja) | 2001-07-03 |
| US6111033A (en) | 2000-08-29 |
| JP3335995B2 (ja) | 2002-10-21 |
| DE69731623T2 (de) | 2005-10-06 |
| IL126422A0 (en) | 1999-05-09 |
| EP1479708A2 (en) | 2004-11-24 |
| CA2250981C (en) | 2002-07-02 |
| DE69731623D1 (de) | 2004-12-23 |
| JP3155013B2 (ja) | 2001-04-09 |
| EP1479707A3 (en) | 2005-05-18 |
| IE960307A1 (en) | 1997-11-05 |
| NZ332018A (en) | 2000-06-23 |
| EP0895517A2 (en) | 1999-02-10 |
| RU2165942C2 (ru) | 2001-04-27 |
| ATE282653T1 (de) | 2004-12-15 |
| EP0895517B1 (en) | 2004-11-17 |
| JPH11508640A (ja) | 1999-07-27 |
| CA2250981A1 (en) | 1997-10-30 |
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