CA1205235A - Poly(glycolic acid)/poly(alkylene glycol)block copolymers and method of manufacturing the same - Google Patents

Poly(glycolic acid)/poly(alkylene glycol)block copolymers and method of manufacturing the same

Info

Publication number
CA1205235A
CA1205235A CA000440921A CA440921A CA1205235A CA 1205235 A CA1205235 A CA 1205235A CA 000440921 A CA000440921 A CA 000440921A CA 440921 A CA440921 A CA 440921A CA 1205235 A CA1205235 A CA 1205235A
Authority
CA
Canada
Prior art keywords
poly
copolymer
surgical
glycolic acid
suture
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
Application number
CA000440921A
Other languages
French (fr)
Inventor
Donald J. Casey
Kenneth R. Huffman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covidien AG
Original Assignee
American Cyanamid Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Application granted granted Critical
Publication of CA1205235A publication Critical patent/CA1205235A/en
Expired legal-status Critical Current

Links

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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06—At least partially resorbable materials
    • A61L17/10—At least partially resorbable materials containing macromolecular materials
    • A61L17/12—Homopolymers or copolymers of glycolic acid or lactic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

POLY(GLYCOLIC ACID)/POLY(ALKYLENE GLYCOL)BLOCK COPOLYMERS
AND METHOD OF MANUFACTURING THE SAME

ABSTRACT OF THE DISCLOSURE
Multiblock copolymers having the following general formula:

Description

~2~S235 -- 1 ~

PO~Y(GLYCOLIC ACID~/POLY(ALKYLENE GLYCOL) BLOCK COPOLYMERS AND METHOD OF
MANUFACTURING THE SAME
This invention provides a copolymer ~rom which can be manufactured an absorbable surgical article, particularly a monofilament suture possessing the desired characteristics of flexibility, resulting in good handling properties, and biodegradability. Such is achieved, according to the invention, through the modifi~ation of polyglycolic acid polymer ~o produce a copolymer, the ex-truded fibers of which e~hibit a lower tensile modulus than monofilaments of polyglycolic acid alone, resulting in increased flexibility. The copolymers are bioabsorb-able.
The copolymers of this invention are multiblock copolymers produced by introducing poly(alkylene glycol) blocks in~o poly(glycolic acid), through the transester-ification of poly~glycolîc acid) with an hydroxyl-ended poly~alkylene glycol) and with the degree of polymeriza-tion of the copolymer being increased by the subsequent addition of an aromatic orthocarbc)nate resulting in chain extension and reduction of brittleness. A preferred poly (alkylene glycol) is poly(oxyethylene) while a preferred orthocarbonate is tetra-~-tolyl orthocarbonate.
The copolymers have the following general formula:

E 2~ OR~n -~ CCH~O ~ 3 where R represents an alkylene group and Ar is an aromatic group and the poly(glycolic acid~ content is abouk 80 to 85 percent and the poly(oxyalkylene) content is about 20 -to 15 percent, 1 and m are the same or a different positive integer and n is 23 to 91.

~ ~ 3LZ~5~5 Thus, an object of this invention is the provision of a poly(gl~colic acid)/poly(oxyalkylene)multiblock co-polymer.
A further object of this invention is the provi-sion of a method of polymerization and aromatic orthocar-honate addition for producing the poly~glycolic acid)/-poly(oxyalkylene) block copolymer.
The copolymers of the invention find ad~a~tageous utility in the manufacture o~ surgical articles and phar-maceutical compositions as is known in the art for polymer -absorbable in living animals. Thus, yet further objects of this invention include the provision of a sterile sur~
gical article, a suture or ligature, particularly in the form of flexible monofilaments, a suture in the form of a needle and a suture co~bination, a surgical clip or staple, a surgical prosthesis, textile structures, coup-lings, tubes or other forms of support or a self-~sup-porting ilm, hollow tube, beads or gel, containing a uniforml~ dispersed drug for controlled continuous admin-istr~tion, manufactured from a copolymer, or by a method described above.
There have been various prior art suggestions for modifying polyglycolic acid, such as by copolymerization o glycoliae monomer with other monomers, to produce a polymer possessing the requisite properties desired in a monoilament suture. Fore exampla, the prior art discloses the sequential addition of a cyclic ester monomer, such as a lactide, lactone, oxalate or carbonate, to glycolide monomer in the copolymerization process. Triblock copolymers with lactic acid units predominantly on both ends of a glycolide polymer chain are disclosed in the prior art, as are copolymers of trimethylene carbonate and glycolide, and monofilament sutures made therefrom.
Other copolymers for use as bioabsorbahle mat-exials have been disclosed. For example, the prior art discloses a normally solid bioabsorbable hydrolyzable poly-meric reaction product of a polyglycolic acid composition and a polyester of diglycolic acid and an unhindered gly-col. Copolymers of l(-) lactide with glycolide have also been used as suture material. Further, polyethylene oxide/polyethylene terephthalate copolymers have been disclosed as biodegradable elastomeric biomaterials.
The production of copolymers based on monomers foxmed from lactic acid or glycolic acid has also been known for nonbiological purposes. For example, the prior artdiscloses the condensation of glycolic acid with a polyethylene glycol mixture to form an ester with an average mol~cular weight of 5105 for treating fabric for imprn~ed tear strength and abrasion resistance.
The addition of aromatic orthocarbonates during the formation of a fiber-forming polyester by the reaction of a dicarboxylic acid or its functional derivative with a glycol is disclosed in thé prior art.
The prior axt also discloses poly(ortho-ester) co- and homopolymers and polytorthocarbonate) co-and homopolymers useful for forming delivery devîces with drug dispersed therein for release by controlled pol~merîc erosion over a prolonged period of time. Gly-colide and ethylene glycol are reacted to form an oligo-mer which is polymerized by condensation with various monomers to yield the desired polymers. The copolymers contain only isolated oxyethylene connecting groups and the orthocaxbonate units contain ring structures.

, ,, ` ~ ~ 3LZ~52~S

DESCRIPTXON OF THE PREFERRED EMBODIMENTS
The multiblock copolymers of this inv~ntion are obtaincd by transesterification of poly(glycolic acid) and an hydroxyl ended poly~al~ylene glycol) such as poly-(oxyethylene) in the presence of a catalyst to produce, it is theorized, an intermediate ABA copolymer:
O
~OCH2C ~-ORl + H -~OCH2CH2 ~ OH
PGA POE

O O
Il ~1 ~--~CH2C ~ CH2CH ~n -~CC~2 ~--H
ABA Copolymer ~he deqree of polymerization of the ABA copolymer is in-creased by the addition of an aromatic orthocarbonate, such as tetra-~-tolyl orthocarbonate, to yield an (AB) n type multiblock copolymer:

O O
H----~OCH2C ~ - ~OCH2CH2~--O ~CCH20 ~ -H
;~5 ABA Copolym~r : ~ C~OAr)4 , .
o o O~r --~OC~I2C )~ Cl~2cl~2~-n ~-CC~2o ~ ~ -_ O~r (~B)n Multiblock Copolymcr 3'~ wherein R represents an alkylene group and Ar is an aromatic group, the poly(glycolic acid) content is about 80 to 85 pe:rcentt -the poly(oxyalkylene) content is about 20 to 15 percent, 1 and m are the same or a dlfferent positive integer and n is 23 to 91.

` lZ05;~5 The hydroxyl~ended poly (alkylene glycol) useful in the invention may advantageously comprise hydroxyl-ended poly~thylene oxide, polypropylene oxide and poly-(oxyethylene-co-oxypropylene). Generally the poly(alky-lene) oxides must be water soluble so that they can be excreted by the body once the copolymer suture has de-graded. Examples of poly(alkylene glycols) capable of pro-ducing linear polymers are poly(oxyethylene glycols) and poly(oxypropylene~ poly (oxyethylene)glycols (block copoly-mers). The foregoing are commercially available in a variety of molecular weights. Examples of suitahle aro-matic orthocarbonates are set forth in th~ prior art.
Example 1 Preparation of ~5/15 ABA Copolymer Dried polyglycolic acid (PGA~ pellets, 33g, were melted in a Brabender mixing head at 235C under N2. A
~ixture of 5.~g poly(oxyethylene) (Mol. Wt. 4000) and 35 mg. of Sb2O3 was added and mixiing was continued for 30 minutes. The reactor was disassembled and the molten polymer was solidified in a stream of ~2~ crushed in a press, ground to 10 mesh in a Wiley mill, and dried in ~acuum. A small sample was purified by reprecipita~ion from hexafluoroacetone sesquihydrate (HFAS) into acetone.

Example 2 Prep ation of 80/20 ABA Copolymer The procedure of Example 1 was followed using 32g PGA, 8g poly(oxyethylene~ of Mol. Wt. 4000, and 35 mg Sb2O3.
Example 3 Preparation of 92.5/7.5 ABA Copol~mers The procedure of Example 1 was followed using 37g PGA, 3g poly(oxyethylene) of Mol. Wt. 1000, and 40 mg Sb o .
2 3 S;~3S

Example 4 Preparation of 85/15 Multiblock (AB)n Copolymers A mixture of 32g dried PGA pellets, 5.7g of poly(oxyethylene) (Mol. Wt. 4000), and 35 mg. of Sb2O3 was melted at 235 under N2 in a Brabender mixing head.
Mixing was continued for 30 minutes at which point l.Og of tetra-_-tolylorthocarbonate was added. Mixing was continued or another 2 minutes and the apparatus was dis assemble~ and the polymer quenched in a stream of N2.
Example 5 Preparation of 80/20 Multiblock (AB)n Copolymers .
The procedure of Example 4 was repeated using 32g PGA, 8g poly(oxyethylene) MD1~ Wt. 4000 and 35 mg. of Sb2O3. ~fter 30 minutes mixing at 235, lg of tetra-p-tolylorthocarbonate was added and mixing was continued for 4 minutes. The apparatus was then disassembled and the polymer quenched in a stream of N2.
The properties of the block copolymers produced accordîng to the above examples, compared to those of poly-glycolic acid above, are set forth in Table I.

5~3S

o o o o o ~ o ~ ,~
E~ ,~

oo o o ~ S ~ 1~ o :~ ~ ~~ ~ ~ O ~
~ ~ o o o o o ~ o C~
~, O ~;
~ o ~ ,~
. :~
~: ~ ~ ,q ~ ~ S
P~
o
3 o~
h o~P ) I u ~ o . m o o o ~1 dJ ~ ,_~ c~ l_ ,i C'`J
Q ,C

P~

Q-O O O O O O Q~
o o o O O
~1 q~ O O O ,0 0 Q.
~0 0 ~

o a) a .," ~ ~

~ ~ ~ r - ` ~Z~523S

- 8::-Example 6 Injection molded dumbbells~having dia~eters of 0.060-0.063 inches were prepared from the relatively low molecular weiyht ~inh0.64~ 85/lS PGA/PEG multiblock co-polymer o~ Example 4 and from a control sample of poly-glycolic acid homopolymer. The potential for greater flexibility with the multiblock copolymer was illustrated by three-point bending measurements on the dumbbells which showed a modulus of 4x105 psi (2.75 GPa~ for the copolymer and a modulus of 13x105 psi (8.9 GPa) for the polyglycolic acid.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A multiblock copolymer useful for the manufacture of bioabsorbable surgical articles comprising the formula:

wherein R represents an alkylene group and Ar is an aromatic group, the poly(glycolic acid) content is about 80 to 85 percent, the poly(oxyalkylene) content is about 20 to 15 percent, 1 and m are the same or a different positive integer and n is 23 to 91.
2. A multiblock copolymer as claimed in claim 1 where is ethylene.
3. A multiblock copolymer as claimed in claim 2 wherein the aromatic group is tetra-p-tolyl.
4. A surgical article manufactured from a copolymer as claimed in claim 1.
5. A flexible monofilament suture or ligature manufac-tured from a copolymer as claimed in claim 1.
6. A surgical article as claimed in claim 4 selected from the group consisting of a suture, ligature, needle and suture combination, surgical clip, surgical staple, surgi-cal prosthesis, textile structure, coupling, tube, and support.
7. A method of making a multiblock copolymer comprising transesterifying poly(glycolic) acid and a hydroxyl-ended poly(alkylene glycol), in the presence of a catalyst, and adding to the copolymer produced thereby, an aromatic orthocarbonate to extend the chain polymerization and reduce brittleness.
8. A method as claimed in claim 7 wherein the poly-(alkylene glycol) is poly(oxyethylene) and the aromatic orthocarbonate is tetra-p-tolyl orthocarbonate.
9. A surgical article manufactured from copolymer made according to a method claimed in claim 7.
10. A bioabsorbable flexible monofilament suture or liga-ture manufactured from copolymer made according to a method claimed in claim 7.
11. A surgical article as claimed in claim 9 selected from the group consisting of a suture, ligature, needle and suture combination, surgical clip, surgical staple, surgi-cal prosthesis, textile structure, coupling, tube, and support.
12. A hydrolyzable monofilament fiber formed from a mul-tiblock copolymer comprising the formula:

wherein R represents an alkylene group and Ar is an aromatic group, the poly(glycolic acid) content is about 80 to 85 percent, the poly(oxyalkylene) content is about 20 to 15 percent, 1 and m are the same or a different positive integer and n is 23 to 91, having a tensile modulus below 1X106 psi.
CA000440921A 1982-11-12 1983-11-10 Poly(glycolic acid)/poly(alkylene glycol)block copolymers and method of manufacturing the same Expired CA1205235A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US441,306 1982-11-12
US06/441,306 US4438253A (en) 1982-11-12 1982-11-12 Poly(glycolic acid)/poly(alkylene glycol) block copolymers and method of manufacturing the same

Publications (1)

Publication Number Publication Date
CA1205235A true CA1205235A (en) 1986-05-27

Family

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Family Applications (1)

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Country Status (5)

Country Link
US (1) US4438253A (en)
EP (1) EP0108912B1 (en)
JP (1) JPS59100131A (en)
CA (1) CA1205235A (en)
DE (1) DE3378371D1 (en)

Families Citing this family (226)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60244083A (en) * 1984-05-18 1985-12-03 Pioneer Electronic Corp Chip hall element and manufacture thereof
JPS60244084A (en) * 1984-05-18 1985-12-03 Pioneer Electronic Corp Chip hall element
US4883699A (en) * 1984-09-21 1989-11-28 Menlo Care, Inc. Polymeric article having high tensile energy to break when hydrated
US4911691A (en) * 1984-09-21 1990-03-27 Menlo Care, Inc. Assembly for adminstering IV solution
US4857602A (en) * 1986-09-05 1989-08-15 American Cyanamid Company Bioabsorbable surgical suture coating
EP0258780B1 (en) * 1986-09-05 1993-06-23 American Cyanamid Company Polyesters containing alkylene oxide blocks as drug delivery systems
US4716203A (en) * 1986-09-05 1987-12-29 American Cyanamid Company Diblock and triblock copolymers
IL82834A (en) * 1987-06-09 1990-11-05 Yissum Res Dev Co Biodegradable polymeric materials based on polyether glycols,processes for the preparation thereof and surgical artiicles made therefrom
FI83477C (en) * 1987-07-10 1991-07-25 Biocon Oy Absorbent material for fixing tissues
US5002562A (en) * 1988-06-03 1991-03-26 Oberlander Michael A Surgical clip
CA2004658C (en) * 1988-06-03 1995-10-10 Michael A. Oberlander Arthroscopic clip and insertion tool
DE4005415C2 (en) * 1990-02-21 1996-04-11 Boehringer Ingelheim Kg Process for the preparation of polyesters based on hydroxycarboxylic acids
CA2059245C (en) * 1991-02-08 2004-07-06 Michael P. Chesterfield Method and apparatus for calendering and coating/filling sutures
US5225520A (en) * 1991-04-17 1993-07-06 United States Surgical Corporation Absorbable composition
US5502159A (en) * 1991-04-17 1996-03-26 United States Surgical Corporation Absorbable composition
DE69229261T2 (en) * 1991-09-27 1999-11-04 Terumo Corp FLEXIBLE PART FOR MEDICAL USE
US5352515A (en) * 1992-03-02 1994-10-04 American Cyanamid Company Coating for tissue drag reduction
DE4218510A1 (en) * 1992-06-02 1993-12-09 Pharmatech Gmbh Process for the preparation of biodegradable polyesters
US5522841A (en) * 1993-05-27 1996-06-04 United States Surgical Corporation Absorbable block copolymers and surgical articles fabricated therefrom
US5702717A (en) * 1995-10-25 1997-12-30 Macromed, Inc. Thermosensitive biodegradable polymers based on poly(ether-ester)block copolymers
US5665428A (en) * 1995-10-25 1997-09-09 Macromed, Inc. Preparation of peptide containing biodegradable microspheres by melt process
US5711958A (en) * 1996-07-11 1998-01-27 Life Medical Sciences, Inc. Methods for reducing or eliminating post-surgical adhesion formation
US6696499B1 (en) * 1996-07-11 2004-02-24 Life Medical Sciences, Inc. Methods and compositions for reducing or eliminating post-surgical adhesion formation
DE19636688A1 (en) * 1996-09-10 1998-03-12 Clariant Gmbh Polymeric acetals of hydroxycarboxylic acids and their derivatives and processes for their preparation
US6191236B1 (en) 1996-10-11 2001-02-20 United States Surgical Corporation Bioabsorbable suture and method of its manufacture
US6211249B1 (en) * 1997-07-11 2001-04-03 Life Medical Sciences, Inc. Polyester polyether block copolymers
EP1024790A4 (en) * 1997-08-08 2000-10-25 Univ Utah Res Found Injectable biodegradable block copolymer gels for use in drug delivery
US6316522B1 (en) * 1997-08-18 2001-11-13 Scimed Life Systems, Inc. Bioresorbable hydrogel compositions for implantable prostheses
US5854382A (en) * 1997-08-18 1998-12-29 Meadox Medicals, Inc. Bioresorbable compositions for implantable prostheses
US6201072B1 (en) 1997-10-03 2001-03-13 Macromed, Inc. Biodegradable low molecular weight triblock poly(lactide-co- glycolide) polyethylene glycol copolymers having reverse thermal gelation properties
US6117949A (en) * 1998-10-01 2000-09-12 Macromed, Inc. Biodegradable low molecular weight triblock poly (lactide-co-glycolide) polyethylene glycol copolymers having reverse thermal gelation properties
US6004573A (en) * 1997-10-03 1999-12-21 Macromed, Inc. Biodegradable low molecular weight triblock poly(lactide-co-glycolide) polyethylene glycol copolymers having reverse thermal gelation properties
US8668737B2 (en) 1997-10-10 2014-03-11 Senorx, Inc. Tissue marking implant
US7637948B2 (en) * 1997-10-10 2009-12-29 Senorx, Inc. Tissue marking implant
US20020164374A1 (en) * 1997-10-29 2002-11-07 John Jackson Polymeric systems for drug delivery and uses thereof
US6270464B1 (en) 1998-06-22 2001-08-07 Artemis Medical, Inc. Biopsy localization method and device
US6161034A (en) * 1999-02-02 2000-12-12 Senorx, Inc. Methods and chemical preparations for time-limited marking of biopsy sites
US6841617B2 (en) * 2000-09-28 2005-01-11 Battelle Memorial Institute Thermogelling biodegradable aqueous polymer solution
US7087244B2 (en) * 2000-09-28 2006-08-08 Battelle Memorial Institute Thermogelling oligopeptide polymers
US20040228794A1 (en) * 1998-04-10 2004-11-18 Battelle Memorial Institute Therapeutic agent carrier compositions
US20050147690A1 (en) * 1998-09-25 2005-07-07 Masters David B. Biocompatible protein particles, particle devices and methods thereof
US7662409B2 (en) * 1998-09-25 2010-02-16 Gel-Del Technologies, Inc. Protein matrix materials, devices and methods of making and using thereof
US6287499B1 (en) 1998-10-09 2001-09-11 United States Surgical Corporation Process of making bioabsorbable block copolymer filaments
US9820824B2 (en) 1999-02-02 2017-11-21 Senorx, Inc. Deployment of polysaccharide markers for treating a site within a patent
US20090030309A1 (en) 2007-07-26 2009-01-29 Senorx, Inc. Deployment of polysaccharide markers
US8361082B2 (en) 1999-02-02 2013-01-29 Senorx, Inc. Marker delivery device with releasable plug
US8498693B2 (en) 1999-02-02 2013-07-30 Senorx, Inc. Intracorporeal marker and marker delivery device
US7983734B2 (en) 2003-05-23 2011-07-19 Senorx, Inc. Fibrous marker and intracorporeal delivery thereof
US6725083B1 (en) 1999-02-02 2004-04-20 Senorx, Inc. Tissue site markers for in VIVO imaging
US7651505B2 (en) * 2002-06-17 2010-01-26 Senorx, Inc. Plugged tip delivery for marker placement
US6862470B2 (en) * 1999-02-02 2005-03-01 Senorx, Inc. Cavity-filling biopsy site markers
US6575991B1 (en) 1999-06-17 2003-06-10 Inrad, Inc. Apparatus for the percutaneous marking of a lesion
US7887551B2 (en) 1999-12-02 2011-02-15 Smith & Nephew, Inc. Soft tissue attachment and repair
US7153312B1 (en) 1999-12-02 2006-12-26 Smith & Nephew Inc. Closure device and method for tissue repair
US6589549B2 (en) 2000-04-27 2003-07-08 Macromed, Incorporated Bioactive agent delivering system comprised of microparticles within a biodegradable to improve release profiles
US7018645B1 (en) * 2000-04-27 2006-03-28 Macromed, Inc. Mixtures of various triblock polyester polyethylene glycol copolymers having improved gel properties
EP2319449B1 (en) * 2000-11-20 2016-03-09 Senorx, Inc. Tissue site markers for in vivo imaging
GB0116341D0 (en) * 2001-07-04 2001-08-29 Smith & Nephew Biodegradable polymer systems
EP2298354B1 (en) 2001-10-10 2014-03-19 ratiopharm GmbH Remodelling and glycoconjugation of interferon-beta
US7173003B2 (en) * 2001-10-10 2007-02-06 Neose Technologies, Inc. Granulocyte colony stimulating factor: remodeling and glycoconjugation of G-CSF
US7157277B2 (en) * 2001-11-28 2007-01-02 Neose Technologies, Inc. Factor VIII remodeling and glycoconjugation of Factor VIII
US8008252B2 (en) 2001-10-10 2011-08-30 Novo Nordisk A/S Factor VII: remodeling and glycoconjugation of Factor VII
US7214660B2 (en) 2001-10-10 2007-05-08 Neose Technologies, Inc. Erythropoietin: remodeling and glycoconjugation of erythropoietin
CN101724075B (en) 2001-10-10 2014-04-30 诺和诺德公司 Remodeling and glycoconjugation of peptides
US7795210B2 (en) * 2001-10-10 2010-09-14 Novo Nordisk A/S Protein remodeling methods and proteins/peptides produced by the methods
WO2003059994A1 (en) * 2002-01-10 2003-07-24 Mitsubishi Rayon Co., Ltd. Molded polyester
GB0202233D0 (en) * 2002-01-31 2002-03-20 Smith & Nephew Bioresorbable polymers
WO2003092468A2 (en) * 2002-04-29 2003-11-13 Gel-Del Technologies, Inc. Biomatrix structural containment and fixation systems and methods of use thereof
US20040084805A1 (en) * 2002-05-01 2004-05-06 Jonn Amy T. Continuous process for the preparation of absorbable monofilament fibers of block copolymers and the use thereof
US20030228366A1 (en) * 2002-06-11 2003-12-11 Chung Shih Reconstitutable compositions of biodegradable block copolymers
US7649023B2 (en) * 2002-06-11 2010-01-19 Novartis Ag Biodegradable block copolymeric compositions for drug delivery
MXPA04012496A (en) * 2002-06-21 2005-09-12 Novo Nordisk Healthcare Ag Pegylated factor vii glycoforms.
CA2497792C (en) * 2002-09-06 2014-08-05 Insert Therapeutics, Inc. Cyclodextrin-based polymers for therapeutics delivery
US8262963B2 (en) * 2002-10-04 2012-09-11 Tyco Healthcare Group Lp Process of making bioabsorbable filaments
WO2004032792A2 (en) * 2002-10-04 2004-04-22 Tyco Healthcare Group Lp Process of making bioabsorbable filaments
US20060036158A1 (en) 2003-11-17 2006-02-16 Inrad, Inc. Self-contained, self-piercing, side-expelling marking apparatus
US9314235B2 (en) 2003-02-05 2016-04-19 Smith & Nephew, Inc. Tissue anchor and insertion tool
EP1596765A2 (en) * 2003-02-10 2005-11-23 Smith & Nephew, Inc. Resorbable devices
CA2519092C (en) * 2003-03-14 2014-08-05 Neose Technologies, Inc. Branched water-soluble polymers and their conjugates
US8791070B2 (en) 2003-04-09 2014-07-29 Novo Nordisk A/S Glycopegylated factor IX
US20070026485A1 (en) * 2003-04-09 2007-02-01 Neose Technologies, Inc. Glycopegylation methods and proteins/peptides produced by the methods
BRPI0410164A (en) * 2003-05-09 2006-05-16 Neose Technologies Inc compositions and methods for preparing human growth hormone glycosylation mutants
US7877133B2 (en) 2003-05-23 2011-01-25 Senorx, Inc. Marker or filler forming fluid
US8465537B2 (en) * 2003-06-17 2013-06-18 Gel-Del Technologies, Inc. Encapsulated or coated stent systems
GB0317192D0 (en) * 2003-07-19 2003-08-27 Smith & Nephew High strength bioresorbable co-polymers
US9005625B2 (en) 2003-07-25 2015-04-14 Novo Nordisk A/S Antibody toxin conjugates
EP1660013A4 (en) 2003-08-26 2011-07-20 Gel Del Technologies Inc Protein biomaterials and biocoacervates and methods of making and using thereof
US20050273002A1 (en) * 2004-06-04 2005-12-08 Goosen Ryan L Multi-mode imaging marker
US7842661B2 (en) * 2003-11-24 2010-11-30 Novo Nordisk A/S Glycopegylated erythropoietin formulations
US20070254834A1 (en) * 2003-11-24 2007-11-01 Defrees Shawn Glycopegylated Erythropoietin
US20080305992A1 (en) * 2003-11-24 2008-12-11 Neose Technologies, Inc. Glycopegylated erythropoietin
US8633157B2 (en) * 2003-11-24 2014-01-21 Novo Nordisk A/S Glycopegylated erythropoietin
US7956032B2 (en) 2003-12-03 2011-06-07 Novo Nordisk A/S Glycopegylated granulocyte colony stimulating factor
NZ547554A (en) * 2003-12-03 2009-09-25 Biogenerix Ag Glycopegylated granulocyte colony stimulating factor
US20060040856A1 (en) * 2003-12-03 2006-02-23 Neose Technologies, Inc. Glycopegylated factor IX
CA2548822C (en) * 2003-12-08 2015-08-11 Gel-Del Technologies, Inc. Mucoadhesive drug delivery devices and methods of making and using thereof
GB0329654D0 (en) 2003-12-23 2004-01-28 Smith & Nephew Tunable segmented polyacetal
CA2552892C (en) * 2004-01-08 2014-08-05 Neose Technologies, Inc. O-linked glycosylation of peptides
US7608092B1 (en) 2004-02-20 2009-10-27 Biomet Sports Medicince, LLC Method and apparatus for performing meniscus repair
SI1718258T1 (en) 2004-02-23 2009-08-31 Euro Celtique Sa Abuse resistance opioid transdermal delivery device
US20080300173A1 (en) 2004-07-13 2008-12-04 Defrees Shawn Branched Peg Remodeling and Glycosylation of Glucagon-Like Peptides-1 [Glp-1]
US20090292110A1 (en) * 2004-07-23 2009-11-26 Defrees Shawn Enzymatic modification of glycopeptides
EP1781305A2 (en) * 2004-08-13 2007-05-09 Angiotech International Ag Compositions and methods using hyaluronic acid and hyaluronidase inhibitors
EP1799249A2 (en) * 2004-09-10 2007-06-27 Neose Technologies, Inc. Glycopegylated interferon alpha
US20060115455A1 (en) * 2004-10-22 2006-06-01 Reed Kenneth C Therapeutic RNAi agents for treating psoriasis
US20080176790A1 (en) 2004-10-29 2008-07-24 Defrees Shawn Remodeling and Glycopegylation of Fibroblast Growth Factor (Fgf)
US7909851B2 (en) 2006-02-03 2011-03-22 Biomet Sports Medicine, Llc Soft tissue repair device and associated methods
US9017381B2 (en) 2007-04-10 2015-04-28 Biomet Sports Medicine, Llc Adjustable knotless loops
US20060189993A1 (en) 2004-11-09 2006-08-24 Arthrotek, Inc. Soft tissue conduit device
US7601165B2 (en) 2006-09-29 2009-10-13 Biomet Sports Medicine, Llc Method and apparatus for forming a self-locking adjustable suture loop
US8088130B2 (en) 2006-02-03 2012-01-03 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
US7905904B2 (en) 2006-02-03 2011-03-15 Biomet Sports Medicine, Llc Soft tissue repair device and associated methods
US8840645B2 (en) 2004-11-05 2014-09-23 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
US8128658B2 (en) 2004-11-05 2012-03-06 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to bone
US7749250B2 (en) 2006-02-03 2010-07-06 Biomet Sports Medicine, Llc Soft tissue repair assembly and associated method
US8303604B2 (en) 2004-11-05 2012-11-06 Biomet Sports Medicine, Llc Soft tissue repair device and method
US8137382B2 (en) 2004-11-05 2012-03-20 Biomet Sports Medicine, Llc Method and apparatus for coupling anatomical features
US9801708B2 (en) 2004-11-05 2017-10-31 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
US8298262B2 (en) 2006-02-03 2012-10-30 Biomet Sports Medicine, Llc Method for tissue fixation
US7905903B2 (en) 2006-02-03 2011-03-15 Biomet Sports Medicine, Llc Method for tissue fixation
US8118836B2 (en) 2004-11-05 2012-02-21 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
US8361113B2 (en) 2006-02-03 2013-01-29 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
US7857830B2 (en) 2006-02-03 2010-12-28 Biomet Sports Medicine, Llc Soft tissue repair and conduit device
US7914539B2 (en) 2004-11-09 2011-03-29 Biomet Sports Medicine, Llc Tissue fixation device
US8998949B2 (en) 2004-11-09 2015-04-07 Biomet Sports Medicine, Llc Soft tissue conduit device
US8034090B2 (en) 2004-11-09 2011-10-11 Biomet Sports Medicine, Llc Tissue fixation device
US20100009902A1 (en) * 2005-01-06 2010-01-14 Neose Technologies, Inc. Glycoconjugation Using Saccharyl Fragments
EP1858543B1 (en) 2005-01-10 2013-11-27 BioGeneriX AG Glycopegylated granulocyte colony stimulating factor
US9187546B2 (en) * 2005-04-08 2015-11-17 Novo Nordisk A/S Compositions and methods for the preparation of protease resistant human growth hormone glycosylation mutants
US10357328B2 (en) 2005-04-20 2019-07-23 Bard Peripheral Vascular, Inc. and Bard Shannon Limited Marking device with retractable cannula
US20110003744A1 (en) * 2005-05-25 2011-01-06 Novo Nordisk A/S Glycopegylated Erythropoietin Formulations
US20080255026A1 (en) * 2005-05-25 2008-10-16 Glycopegylated Factor 1X Glycopegylated Factor Ix
US20060293709A1 (en) 2005-06-24 2006-12-28 Bojarski Raymond A Tissue repair device
CA2619571A1 (en) * 2005-08-18 2007-02-22 Smith & Nephew, Plc High strength devices and composites
US20070105755A1 (en) 2005-10-26 2007-05-10 Neose Technologies, Inc. One pot desialylation and glycopegylation of therapeutic peptides
CN102719508A (en) * 2005-08-19 2012-10-10 诺和诺德公司 Glycopegylated factor VII and factor VIIA
US8039462B2 (en) * 2005-09-19 2011-10-18 Neuronascent, Inc. Methods and compositons for stimulating neurogenesis and inhibiting neuronal degeneration
US8052658B2 (en) 2005-10-07 2011-11-08 Bard Peripheral Vascular, Inc. Drug-eluting tissue marker
WO2007044017A1 (en) * 2005-10-14 2007-04-19 Doney Grant W Polymer manufacturing process
US20090048440A1 (en) * 2005-11-03 2009-02-19 Neose Technologies, Inc. Nucleotide Sugar Purification Using Membranes
US8574235B2 (en) 2006-02-03 2013-11-05 Biomet Sports Medicine, Llc Method for trochanteric reattachment
US8771352B2 (en) 2011-05-17 2014-07-08 Biomet Sports Medicine, Llc Method and apparatus for tibial fixation of an ACL graft
US8652171B2 (en) 2006-02-03 2014-02-18 Biomet Sports Medicine, Llc Method and apparatus for soft tissue fixation
US7959650B2 (en) 2006-09-29 2011-06-14 Biomet Sports Medicine, Llc Adjustable knotless loops
US9538998B2 (en) 2006-02-03 2017-01-10 Biomet Sports Medicine, Llc Method and apparatus for fracture fixation
US8251998B2 (en) 2006-08-16 2012-08-28 Biomet Sports Medicine, Llc Chondral defect repair
US11259792B2 (en) 2006-02-03 2022-03-01 Biomet Sports Medicine, Llc Method and apparatus for coupling anatomical features
US8968364B2 (en) 2006-02-03 2015-03-03 Biomet Sports Medicine, Llc Method and apparatus for fixation of an ACL graft
US8597327B2 (en) 2006-02-03 2013-12-03 Biomet Manufacturing, Llc Method and apparatus for sternal closure
US8652172B2 (en) 2006-02-03 2014-02-18 Biomet Sports Medicine, Llc Flexible anchors for tissue fixation
US8936621B2 (en) 2006-02-03 2015-01-20 Biomet Sports Medicine, Llc Method and apparatus for forming a self-locking adjustable loop
US8562645B2 (en) 2006-09-29 2013-10-22 Biomet Sports Medicine, Llc Method and apparatus for forming a self-locking adjustable loop
US11311287B2 (en) 2006-02-03 2022-04-26 Biomet Sports Medicine, Llc Method for tissue fixation
US9271713B2 (en) 2006-02-03 2016-03-01 Biomet Sports Medicine, Llc Method and apparatus for tensioning a suture
US8562647B2 (en) 2006-09-29 2013-10-22 Biomet Sports Medicine, Llc Method and apparatus for securing soft tissue to bone
US9078644B2 (en) 2006-09-29 2015-07-14 Biomet Sports Medicine, Llc Fracture fixation device
US8801783B2 (en) 2006-09-29 2014-08-12 Biomet Sports Medicine, Llc Prosthetic ligament system for knee joint
US8506597B2 (en) 2011-10-25 2013-08-13 Biomet Sports Medicine, Llc Method and apparatus for interosseous membrane reconstruction
US10517587B2 (en) 2006-02-03 2019-12-31 Biomet Sports Medicine, Llc Method and apparatus for forming a self-locking adjustable loop
US9149267B2 (en) 2006-02-03 2015-10-06 Biomet Sports Medicine, Llc Method and apparatus for coupling soft tissue to a bone
WO2007103276A2 (en) 2006-03-03 2007-09-13 Smith & Nephew, Inc. Systems and methods for delivering a medicament
CN101516388B (en) * 2006-07-21 2012-10-31 诺和诺德公司 Glycosylation of peptides via O-linked glycosylation sequences
US20080294039A1 (en) * 2006-08-04 2008-11-27 Senorx, Inc. Assembly with hemostatic and radiographically detectable pellets
US20090171198A1 (en) * 2006-08-04 2009-07-02 Jones Michael L Powdered marker
US7945307B2 (en) * 2006-08-04 2011-05-17 Senorx, Inc. Marker delivery system with obturator
US8500818B2 (en) 2006-09-29 2013-08-06 Biomet Manufacturing, Llc Knee prosthesis assembly with ligament link
US9918826B2 (en) 2006-09-29 2018-03-20 Biomet Sports Medicine, Llc Scaffold for spring ligament repair
US11259794B2 (en) 2006-09-29 2022-03-01 Biomet Sports Medicine, Llc Method for implanting soft tissue
US8672969B2 (en) 2006-09-29 2014-03-18 Biomet Sports Medicine, Llc Fracture fixation device
US8969532B2 (en) 2006-10-03 2015-03-03 Novo Nordisk A/S Methods for the purification of polypeptide conjugates comprising polyalkylene oxide using hydrophobic interaction chromatography
CA2665480C (en) * 2006-10-04 2019-11-12 Shawn Defrees Glycerol linked pegylated sugars and glycopeptides
EP2079385B1 (en) 2006-10-23 2013-11-20 C.R.Bard, Inc. Breast marker
WO2008059975A1 (en) * 2006-11-17 2008-05-22 Japan As Represented By President Of National Cardiovascular Center Blood-coagulation inhibiting material, coating material and in vivo indwelling members made by using the material, and method of treatment
CN101594831B (en) * 2006-11-30 2011-09-14 史密夫和内修有限公司 Fiber reinforced composite material
EP2109409B1 (en) 2006-12-12 2018-09-05 C.R.Bard, Inc. Multiple imaging mode tissue marker
US8401622B2 (en) 2006-12-18 2013-03-19 C. R. Bard, Inc. Biopsy marker with in situ-generated imaging properties
US20080176958A1 (en) 2007-01-24 2008-07-24 Insert Therapeutics, Inc. Cyclodextrin-based polymers for therapeutics delivery
DK2144923T3 (en) * 2007-04-03 2013-05-13 Biogenerix Ag METHODS OF TREATMENT WITH USING GLYCOPEGYLATED G-CSF
JP5416090B2 (en) * 2007-04-18 2014-02-12 スミス アンド ネフュー ピーエルシー Expansion molding of shape memory polymer
EP2142227B1 (en) 2007-04-19 2012-02-29 Smith & Nephew, Inc. Multi-modal shape memory polymers
DE602008006181D1 (en) * 2007-04-19 2011-05-26 Smith & Nephew Inc GRAFT FIXATION
JP2010531135A (en) * 2007-06-04 2010-09-24 ノボ ノルディスク アクティーゼルスカブ O-linked glycosylation using N-acetylglucosaminyltransferase
AU2008261691A1 (en) * 2007-06-11 2008-12-18 Nanovasc, Inc. Stents
ES2551123T3 (en) * 2007-06-12 2015-11-16 Ratiopharm Gmbh Improved process for the production of nucleotide sugars
ES2564826T3 (en) * 2007-06-21 2016-03-29 Neuronascent, Inc. Methods and compositions to stimulate neurogenesis and inhibit neuronal degeneration using isothiazolopyrimidinones
US7968811B2 (en) * 2007-06-29 2011-06-28 Harley-Davidson Motor Company Group, Inc. Integrated ignition and key switch
US8207112B2 (en) * 2007-08-29 2012-06-26 Biogenerix Ag Liquid formulation of G-CSF conjugate
US8357767B2 (en) * 2007-10-03 2013-01-22 Polynovo Biomaterials Limited High modulus polyurethane and polyurethane/urea compositions
AU2008345047A1 (en) * 2007-12-26 2009-07-09 Gel-Del Technologies, Inc. Biocompatible protein particles, particle devices and methods thereof
JP5647899B2 (en) * 2008-01-08 2015-01-07 ラツィオファルム ゲーエムベーハーｒａｔｉｏｐｈａｒｍ ＧｍｂＨ Glycoconjugation of polypeptides using oligosaccharyltransferase
WO2009099767A2 (en) * 2008-01-31 2009-08-13 C.R. Bard, Inc. Biopsy tissue marker
US20090202642A1 (en) * 2008-02-08 2009-08-13 Xiao Huang Drug Delivery System Comprising Microparticles and Gelation System
CN101965200B (en) 2008-02-27 2013-06-19 诺沃-诺迪斯克有限公司 Conjugated factor VIII molecules
US9327061B2 (en) 2008-09-23 2016-05-03 Senorx, Inc. Porous bioabsorbable implant
WO2010057177A2 (en) 2008-11-17 2010-05-20 Gel-Del Technologies, Inc. Protein biomaterial and biocoacervate vessel graft systems and methods of making and using thereof
US8670818B2 (en) 2008-12-30 2014-03-11 C. R. Bard, Inc. Marker delivery device for tissue marker placement
US20100204570A1 (en) * 2009-02-06 2010-08-12 Paul Lubock Anchor markers
US8343227B2 (en) 2009-05-28 2013-01-01 Biomet Manufacturing Corp. Knee prosthesis assembly with ligament link
US9200112B2 (en) 2009-08-10 2015-12-01 Ethicon, Inc. Semi-crystalline, fast absorbing polymer formulation
AU2010295646B2 (en) 2009-09-15 2016-02-11 Ellipses Pharma Limited Treatment of cancer
US9044524B2 (en) * 2009-10-30 2015-06-02 Ethicon, Inc. Absorbable polyethylene diglycolate copolymers to reduce microbial adhesion to medical devices and implants
AU2010321533A1 (en) * 2009-11-23 2012-05-31 Cerulean Pharma Inc. Cyclodextrin-based polymers for therapeutic delivery
WO2011119607A2 (en) 2010-03-24 2011-09-29 The Board Of Trustees Of The University Of Illinois Viscoelastic ink for direct writing of hydrogel structures
EP2571525A4 (en) 2010-05-18 2016-04-27 Cerulean Pharma Inc Compositions and methods for treatment of autoimmune and other diseases
CN103179959A (en) 2010-10-20 2013-06-26 帝斯曼知识产权资产管理有限公司 Pendant hydrophile bearing biodegradable compositions and related devices
US9357991B2 (en) 2011-11-03 2016-06-07 Biomet Sports Medicine, Llc Method and apparatus for stitching tendons
US9381013B2 (en) 2011-11-10 2016-07-05 Biomet Sports Medicine, Llc Method for coupling soft tissue to a bone
US9370350B2 (en) 2011-11-10 2016-06-21 Biomet Sports Medicine, Llc Apparatus for coupling soft tissue to a bone
US9357992B2 (en) 2011-11-10 2016-06-07 Biomet Sports Medicine, Llc Method for coupling soft tissue to a bone
US9259217B2 (en) 2012-01-03 2016-02-16 Biomet Manufacturing, Llc Suture Button
US20140094432A1 (en) 2012-10-02 2014-04-03 Cerulean Pharma Inc. Methods and systems for polymer precipitation and generation of particles
US9757119B2 (en) 2013-03-08 2017-09-12 Biomet Sports Medicine, Llc Visual aid for identifying suture limbs arthroscopically
US9918827B2 (en) 2013-03-14 2018-03-20 Biomet Sports Medicine, Llc Scaffold for spring ligament repair
USD715442S1 (en) 2013-09-24 2014-10-14 C. R. Bard, Inc. Tissue marker for intracorporeal site identification
USD715942S1 (en) 2013-09-24 2014-10-21 C. R. Bard, Inc. Tissue marker for intracorporeal site identification
USD716451S1 (en) 2013-09-24 2014-10-28 C. R. Bard, Inc. Tissue marker for intracorporeal site identification
USD716450S1 (en) 2013-09-24 2014-10-28 C. R. Bard, Inc. Tissue marker for intracorporeal site identification
CA2926950C (en) 2013-10-10 2022-10-11 Eastern Virginia Medical School 4-((2-hydroxy-3-methoxybenzyl)amino) benzenesulfonamide derivatives as potent and selective inhibitors of 12-lipoxygenase
US10136886B2 (en) 2013-12-20 2018-11-27 Biomet Sports Medicine, Llc Knotless soft tissue devices and techniques
US9615822B2 (en) 2014-05-30 2017-04-11 Biomet Sports Medicine, Llc Insertion tools and method for soft anchor
US9700291B2 (en) 2014-06-03 2017-07-11 Biomet Sports Medicine, Llc Capsule retractor
US10039543B2 (en) 2014-08-22 2018-08-07 Biomet Sports Medicine, Llc Non-sliding soft anchor
US9955980B2 (en) 2015-02-24 2018-05-01 Biomet Sports Medicine, Llc Anatomic soft tissue repair
US9974534B2 (en) 2015-03-31 2018-05-22 Biomet Sports Medicine, Llc Suture anchor with soft anchor of electrospun fibers
EP4192509A1 (en) 2020-08-05 2023-06-14 Ellipses Pharma Ltd Treatment of cancer using a cyclodextrin-containing polymer-topoisomerase inhibitor conjugate and a parp inhibitor
WO2023056368A1 (en) 2021-09-30 2023-04-06 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Cyclic peptides as non-hormonal male contraceptive agents and methods of use thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917410A (en) 1955-06-20 1959-12-15 American Cyanamid Co Polyglycol-polyacid ester treatment of textiles
JPS495630B1 (en) * 1970-03-19 1974-02-08
BE758156R (en) 1970-05-13 1971-04-28 Ethicon Inc ABSORBABLE SUTURE ELEMENT AND ITS
US3784585A (en) 1971-10-21 1974-01-08 American Cyanamid Co Water-degradable resins containing recurring,contiguous,polymerized glycolide units and process for preparing same
US4048256A (en) 1976-06-01 1977-09-13 American Cyanamid Company Normally-solid, bioabsorbable, hydrolyzable, polymeric reaction product
US4070347A (en) 1976-08-16 1978-01-24 Alza Corporation Poly(orthoester) co- and homopolymers and poly(orthocarbonate) co- and homopolymers having carbonyloxy functionality
US4047533A (en) * 1976-09-20 1977-09-13 American Cyanamid Company Absorbable surgical sutures coated with polyoxyethylene-polyoxypropylene copolymer lubricant
US4243775A (en) 1978-11-13 1981-01-06 American Cyanamid Company Synthetic polyester surgical articles
GB2002400B (en) * 1977-07-12 1982-01-20 Ici Ltd Block or graft copolymers and their use as surfactants

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