NZ192138A - Elastomeric surgical suture - Google Patents
Elastomeric surgical sutureInfo
- Publication number
- NZ192138A NZ192138A NZ192138A NZ19213879A NZ192138A NZ 192138 A NZ192138 A NZ 192138A NZ 192138 A NZ192138 A NZ 192138A NZ 19213879 A NZ19213879 A NZ 19213879A NZ 192138 A NZ192138 A NZ 192138A
- Authority
- NZ
- New Zealand
- Prior art keywords
- percent
- suture
- filament
- units
- weight
- Prior art date
Links
- 150000002148 esters Chemical class 0.000 claims description 35
- 229920000642 polymer Polymers 0.000 claims description 27
- 230000000704 physical effect Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- -1 poly(tetramethyleneoxide) Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 229920002959 polymer blend Polymers 0.000 claims 2
- 239000000463 material Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000003356 suture material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- CAWGQUPKYLTTNX-UHFFFAOYSA-N 3,4,5,6-tetrahydro-2,7-benzodioxecine-1,8-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=CC=C12 CAWGQUPKYLTTNX-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 101150093912 claE gene Proteins 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
-
- 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
- A61L17/04—Non-resorbable materials
-
- 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
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Vascular Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Surgery (AREA)
- Textile Engineering (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
Description
» t -r~r: .T" Pnor&y •> ■ ^ ^ Complete Specification Filed: • claEs: W!h!^P°3YMAy39&4 Publication Date: .. .M. I • * iw« •»»'>** /
BACKGROUND OF THE INVENTION The present invention relates to surgical sutures, and more particularly, to soft, elastomeric sutures having unique handling and knot tying characteristics. The sutures may be prepared from segmented copolyether/. 10 esters or other elastomeric polymers.
Many natural and synthetic materials are presently used as surgical sutures. These materials may be used as single filament strands, i.e, monofilament sutures, 15 or as multifilament strands in a braided, twisted or other multifilament construction. Natural materials such as silk, cotton, linen, and the like, of course do not lend themselves to the fabrication of monofilament sutures and are accordingly generally used in one of the 20 multifilament constructions.
Synthetic materials which are extruded in continuous lengths can be used in monofilament form. Common synthetic monofilament sutures include polyethylene 25 terephthalate, polypropylene, polyethylene, and nylon. Such monofilament sutures are preferred by surgeons for many surgical applications due to their inherent smoothness and noncapillarity to body fluids. t 9 2 The presently available synthetic monofilament sutures all suffer to a greater or lesser degree from one particular disadvantage, that is inherent stiffness. Besides making the material more difficult to handle and use, suture stiffness can adversely affect knot tying ability and knot security. It is because of the inherent stiffness of available monofilament sutures that most larger suture sizes are braided or have other multifilament constructions with better handling flexibility.
Monofilament sutures of the prior art are also characterized by a low degree of elasticity, the most elastic of the above-mentioned synthetics being nylon which has a yield elongation of about 1.7 percent and a visco-15 elastic elongation of about 8.5 percent. The inelasticity of these sutures also makes knot tying more difficult and reduces knot security. In addition, the inelasticity prevents the suture from "giving" as a newly sutured wound swells, with the result that the suture may 20 place the wound tissue under greater tension than is desirable, and may even cause some tearing, cutting or necrosis of the tissue.
The problems associated with the use of inelastic sutures 25 in certain applications were recognized in U.S. Patent No. 3,454,011, where it was proposed to fabricate a surgical suture composed of Spandex polyurethane. Such sutures, however, were highly elastic with "rubbery" characteristics and did not find general acceptance in 30 the medical profession. 1 is accordingly an object of the present invention tj provitte^a novel soft, limp, monofilament sutur^-ms£e-rial. It is~^skfurther object of this invention to pro-W.McC 35 vide a monofilamerv&^s^ture wvth^a^controlled degree of elasticity to accommoda£ja>i§Hanging wound conditions. It is another obje^t-^r this invervE^bon to provide a new, nonabsorbable suture having a diameter^oifrom about Q^OiT'to 1.0 mm and possessing unique and desii-able ETH-4 6 7 1 C 'J £3; O 3 ^ M ^ physical propog-fadioci-i Thcoo and-other objects will be appamnf tfre ansuing description and claims.
SUMMARY Monofilament sutures of the present invention are characterized by the following combination of physical properties: Yield elongation - from about 2 to 9 percent Visco-elastic elongation - from about 10 to 30 percent Young's modulus - from about 30,000 to 200,000 psi Tensile strength - at least about 40,000 psi Knot strength - at least about 30,000 psi Sutures possessing the above characteristics may be pre-15 pared by melt extruding certain elastomeric polymers such as copolyether/ester polymers to form a continuous filamentary strand, and thereafter drawing the extruded filament to obtain the desired suture properties. Certain copolyether/ester polymers available commercially 20 from E. I. du Pont de Nemours & Co. under the tradename "HYTREL" have been discovered to be suitable starting materials for the preparation of sutures in accordance with the present invention.
Monofilament sutures having physical properties in accordance with the present invention are particularly useful in many surgical procedures where the suture is used to close a wound which may be subject to later swelling or change in position. The combination of low 30 Young's modulus and significant yield elongation provides the suture with an appreciable degree of controlled elasticity under low applied force. As a result, the suture is able to "give" to accommodate swelling in the wound area. The relatively high visco-elastic yield 35 elongation and high tensile strength of the suture allows the suture to stretch during knot tie-down so that the knot "snugs down" for improved tying ability and knot security with a more predictable and consistent knot ETH-4 61 1 4 geometry regardless of variations in suture tying technique or tension.
BRIEF DESCRIPTION OF DRAWINGS 5 Figure 1 is a representative stress-strain curve characteristic of the surgical filaments of the present invention .
Figure 2 is a representative stress-strain curve compar-10 ing filaments of the present invention with monofilament sutures of the prior art.
DESCRIPTION OF PREFERRED EMBODIMENTS The sutures of the present invention are characterized by 15 a combination of physical properties which are unique for monofilament sutures, and which provide the sutures of the present invention with unique and desirable functional properties.
The characteristic properties of the inventive sutures are readily determined by conventional test procedures. Figure 1 illustrates a typical stress-strain or load-elongation diagram for the sutures of this invention. In Figure 1, yield elongation (Ey) is the point at which 25 permanent deformation of the suture begins to take place. So long as the filament is not elongated beyond Ey, elastic recovery is essentially complete. The sutures of the present invention have an Ey with the range of 2 to 9 percent.
Young's modulus is a measure of the slope of the stress-strain curve over the initial portion of the curve extending from the origin. In Figure 1, line a is a drawn tangent to the curve at the origin, and Young's modulus 35 is equal to tan 8. The slope of the curve, and Young's modulus, are seen to be a measure of the resistance to elongation in the initial elastic portion of the curve. The sutures of the present invention are designed to have a significant, but relatively low modulus of 30,000 to Jj A ii 1 200,000 psi, and preferably within the range of 50,000 to 150,000 psi. A modulus within the claimed range provides the correct amount of increasing tension on the suture as the suture is extended toward its yield point 5 (Ey). At lower values of Young's modulus, the suture readily elongates under very low tension to its yield point and the advantages of having a significant yield elongation are lost. At higher values of Young's modulus, filament stiffness becomes the controlling consideration, 10 and the softness and good handling properties of the suture diminish.
The portion of the stress-strain curve extending between Ey and Ev on Figure 1 is the visco-elastic region during 15 which there is considerable elongation and permanent deformation of the suture with only slightly increasing tension. The visco-elastic elongation (Ev) of the sutures of the present invention is controlled to be within the range of from about 10 to 3 0 percent. This 20 property of the suture allows the suture to draw down during knotting to assure good knot security.
As the suture is elongated beyond Ev, the load increases rapidly as indicated in Figure 1. This rapid increase 25 in load imparts a positive feel to the suture which, in the hands of a skilled surgeon, signals when Ev and maximum knot security are achieved. Preferably, the value of Ev is at least 2.5 times the value of Ey in order to provide the surgeon with a broad visco-elastic 30 region in which to work during suture tie-down.
As seen in Figure 1, the load from 0 to Ev elongation is relatively low compared to the breaking load (Sb). Preferably, the breaking load or straight tensile strength 35 is at least 40,000 psi, and the load Sv corresponding to visco-elastic elongation is less than one-third of the breaking load, with the result that the suture may be easily knotted under relatively low forces and without 1 9 6 risk of unintentionally breaking the suture. Knot strength of the suture is preferably at least 30,000 psi.
The breaking elongation (Eb) of the sutures of the pres-5 ent invention are generally within the range of 30 to 100 percent. Although this property is not critical to the performance of the suture since suture elongation in use does not generally exceed Ev, it is preferable that Eb be at least 1.5 x Ev in order to reduce the pos-10 sibility of inadvertently over elongating and breaking the suture during tie-down.
The unique mechanical properties of the sutures of the present invention will be more readily appreciated from 15 Figure 2 where such sutures are compared to nylon and polypropylene sutures of the prior art. Representative physical properties of these three suture materials are given in Table I. Each of these prior art sutures has a considerably higher Young's modulus which results in the 20 characteristic stiffness of these materials. In addition, neither suture has a noticeable Ey or an extended visco-elastic region which characterize the sutures of the invention and impart the desirable properties discussed above.
The mechanical properties of the sutures of the present invention reflected in the relative values of Ev and Ey in combination with the low Young's modulus and high tensile strength are unique in the field of surgical su-30 tures and distinguish the monofilament sutures of the present invention from all prior art materials.
TABLE I Suture property Suture material Polypropylene Nylon This invention Diameter, mils (mm) 12.5 (0.32) 12.8 (0.33) 12.9 (0.33; Tensile strength, psi (Kg/cm2) 58,900 (4,100) 75,200 (5,300) 64,700 (4,500) Elongation to break, % 32.2 40.1 39. 5 Visco-elastic elongation (Ev), % 9.0 8.5 14.8 Yield elongation (Ey), % 1.1 1.7 2.2 Stress at Ey (Sy), psi (Kg/cm2) ,100 (360) 3,600 (250) 2,500 (180) Stress at Ev (Sv), psi (Kg/cm2) ,700 (1,800) 13,200 (930) 9,200 (650) Young's modulus, psi (Kg/cm2) 425,000 (29,900) 221,000 (15,500) 112,000 (7,900) 1 9 8 Sutures having mechanical properties in accordance with the present invention may be prepared from the segmented copolyether/ester compositions disclosed in U.S. Patent No. 3,023,192, incorporated herein by reference, which states in part at Column 2, line 20 et seg.: "The copolyetheresters of this invention are prepared by reacting one or more dicar-boxylic acids or their ester-forming derivatives, one or more difunctional polyethers with the formula: (in which R is one or more divalent organic radicals and £ is an integer of a value to provide a glycol with a molecular weight of between about 350 and about 6,000), and one or more dihydroxy-compounds selected from the class consisting of bis-phenols and lower aliphatic glycols with the formula: (in which £ is 2-10), with the proviso that the reactants be selected so that substantially all of the repeating units of the polyester contain at least one aromatic ring. The resulting ester is then polymerized." The preparation of other related segmented thermoplastic copolymers are described in the following additional references which are also incorporated herein by reference for their teachings in this regard: U.S. Patents Nos. 3,651,014; 3,763,109; 3,766,146; and 3,784,520.
According to the above references, the disclosed segmented thermoplastic copolymers may be cast as films, injection molded to form objects, or melt extruded to form filaments. The products obtained in accordance with these references, however, are characterized by physical properties which are not desirable for surgical sutures.
HO(RO) H P HO(CH0) OH Z Q q £TH-4 6 7 ' ~ 19213 9 In particular, the filaments of the references are rubbery with a very high degree of elasticity as indicated by break elongations in excess of 500 percent. Tensile strengths, on the other hand, are very low, generally less than 8,000 psi. The filaments prepared from co-polyether/esters in accordance with the teachings of these references therefore do not possess the mechanical properties' of the sutures of the invention, and, in fact, are obviously not at all suitable for use as surgical sutures.
The disadvantages of the prior art references are overcome by means of the present invention wherein filaments extruded from certain copolyether/esters are quenched and drawn with the result that the mechanical properties of the filaments are controlled to be within the specific limits discovered to be particularly desirable for surgical sutures.
The segmented copolyether/esters useful in the present invention comprise a multiplicity of recurring long chain ether/ester units and short chain ester units joined head to tail through ester linkages according to the following general formula: 0 0 0 0 II II II II t(O-D-O-C-R-C) (O-G-O-C-R-C - 0), ] (I) a d n The long chain ether/ester units of the polymer are represented by the general formula: O 0 II II ■ -O-G-O-C-R-C (II; wherein G is a divalent radical remaining after the removal of terminal hydroxyl groups from a poly(C2_^g alkylene oxide)glycol having a molecular weight within the range of about 350 to 6,000, and R is a divalent radical remaining after the removal of carboxyl groups from an aromatic dicarboxylic acid having a molecular weight of less than about 300. u i h - 4 ti 7 1 921 The short chain ester units are represented by the general formula: 0 O ii ii -O-D-O-C-R-C- (III) wherein D is a divalent radical remaining after removal 5 of hydroxyl groups from an alkyldiol having a molecular weight of less than about 250, and R is as defined above.
In the above Formula I, a is an integer such that the short chain copolymer segments represented by a comprise 10 from 50 to 90 percent by weight of the total copolymer composition; b is an integer such that the long chain copolymer segments represented by b comprise from 10 to 50 percent of the total copolymer composition; and n is the degree of polymerization resulting in a fiber-15 forming copolymer.
The copolyether/esters represented by Formula I may be melt extruded, quenched and drawn to obtain filaments having physical properties desirable for surgical su-20 tures as above defined. Polymer to be extruded is dried at about 200-220°F in a circulating hot air oven and/or under vacuum in order to remove all traces of moisture and other volatile materials. The polymer is then melt extruded and water quenched in accordance with the con-25 ventional melt spinning techniques for synthetic fibers. The fiber is finally drawn at least about 5X, and usually from about 7X to 9X to achieve molecular orientation .
The preparation of fibers useful as surgical sutures from copolyether/esters in accordance with the present invention is demonstrated by the following examples which are presented by way of illustration and are not limiting of the present invention. The polymers utilized in 35 these examples are copolyether/esters prepared from 1,4-butanediol, dimethyl phthalate, and polytetra-methylene ether glycol (M.W. of about 1,000), and are 11 commercially available from E. I. du Pont de Nemours & Co. under the tradename "HYTREL". The polymer contains intrapolymerized butylenephthalate hard segments (short chain ester units) and polytetramethylene ether terephthalate soft segments (long chain ester units) and has the following general structure as reported in the Journal of Elastomers and Plastics 9_, 416-38 (Oct. , 1977) : oo oo [ 0 - (CH2)4 - 0 - C - - C]al0(CH2CH2CH2CH20)x - C " C]fa (TO (hard segment) (soft segment) wherein a and b are as defined above and x is an integer reflecting the molecular weight of the ether glycol re-actant (x = 14 for M.W. of about 1,000).
In the following examples, physical properties of individual monofilaments were determined on an Instron tensile tester under the following conditions: Crosshead speed (XH) Chart speed (CS) Sample length (GL) Scale load (SL) in/min 10 in/min 5 in 2 lbs/in With reference to Figure 1, Young's modulus is calculated from the slope a of the stress-strain curve in the initial linear, elastic region as follows: • .. , , , . . tan 8 x GL x CS x SL Young's modulus (psi) = XH x XS wherein 8 = the angle indicated in Figure 1 . 2 XS = the cross-sectional area of the fiber, m SL, XH, CS, and GL are as identified above.
Yield stress (Sy) is the load at the point of intersection of lines a and b drawn tangent to the initial elastic region and the visco-elastic region, respectively, of the curve as illustrated in Figure 1. Yield elongation (Ey) is the elongation corresponding to Sy and is read directly off the stress-strain curve. ^21 3 12 Visco-elastic stress (Sv) is the load at the point of intersection of line b with line c drawn tangent to the curve as illustrated in Figure 1. Visco-elastic elongation (Ev) is the elongation corresponding to Sv and is read directly off the curve.
Break elongation (Eb) and breaking tensile strength (Sb) are read directly off the stress-strain curve as illustrated in Figure 1.
EXAMPLE I A sample of copolyether/ester of Formula IV having approximately 40 wt percent soft segments and comprising approximately 51 percent terephthaloyl units, 16 percent 15 units derived from polytetramethylene ether glycol, and 33 percent units derived from 1,4-butanediol was dried four hours at 200°F in a circulating hot air oven and then further dried under vacuum at 100 microns (no heat) for 16 hours. The dry polymer was placed in a one-inch 20 horizontal extruder and extruded through a J/50/1 die at an extrusion temperature of 380°F.
The extrudate was quenched in water at ambient temperature and drawn to a size 2-0 monofilament suture using a 8.8X 25 draw ratio at a temperature of 530°F and with a take-up speed of 485 ft/min. Physical properties of the resulting filaments are given in Table II.
EXAMPLE II A sample of copolyether/ester of Formula IV having approximately 23 wt percent soft segments and comprising approximately 45 percent terephthaloyl units, 4 percent orthophthaloyl units, 20 percent units derived from polytetramethylene ether glycol and 31 percent units derived 35 from 1,4-butanediol was dried and extruded at 400°F as described in Example I. The extrudate was quenched and drawn into a size 2-0 monofilament using a 7.5X draw ratio at a temperature of 450°F and with a take-up speed of - 4 0 V 1 9 13 412 ft/min. Physical properties of the resulting filaments are given in Table II.
EXAMPLE III A sample of copolyether/ester of Formula IV having approximately 18 wt percent soft segments and comprising approximately 41 percent terephthaloyl units, 35 percent units derived from polytetramethylene ether glycol and 24 percent units derived from 1,4-butanediol was 10 dried and extruded at 405°F as described in Example I. The extrudate was quenched and drawn into a size 2-0 monofilament suture using a 6.5 draw ratio at a temperature of 560°F. The take-up speed was 75 ft/min. Physical properties of the resulting filaments are given in 15 Table II. It is noted that the Young's modulus of these filaments exceeded the maximum desirable limit for sutures of the present invention.
EXAMPLE IV Three parts of a copolyether/ester of Example I and two parts of a copolyether/ester of Example III were dry blended to provide a polymer having a total of 30.2 percent soft segments. The blended material was dried in a vacuum oven for two hours at 1-2 mm Hg (no heat), and 25 then heated at 50°C for three hours at 1-2 mm Hg.
The dried mixture was melt blended in a 3/4-inch Brabender extruder with a 25-inch barrel with a 20/1 screw and extruded at 430°F through a 5/32-inch die in a vertical 30 monofilament assembly. The extrudate was water quenched at ambient temperature, pelletized, and again dried as described above for the dry-blended material before extruding into monofilament sutures. A size 2-0 monofilament suture of this material was extruded at 400°F using 35 a 7.9X draw ratio at a temperature of 460°F and a take-up speed of 435 ft/min. Physical properties of the resulting filaments are given in Table II.
LTll-s 6 7 i Q 9 1 7 0 I 1L I J o 14 EXAMPLE V 3.5 Parts of a copolyether/ester of Example I and 1.5 parts of a copolyether/ester of Example III were dry-blended for a total of 33.4 percent soft segments and 5 extruded following the general procedure of Example IV, and using a final draw ratio of 7.5X with a draw temperature of 485°F and a take-up speed of 412 ft/min to obtain a size 2-0 monofilament suture. The physical properties of the resulting filaments are given in 10 Table II.
EXAMPLE VI The procedure of Example IV was repeated using various blends of copolyether/ester polymers of Examples I, II 15 and III having the compositions and blended in ratios as shown in Table III. The physical properties of the resulting filaments are also given in Table III.
EXAMPLE VII A copolyether/ester of Example I with 40 wt percent soft segments was dried and extruded in accordance with the general procedure of Example I using a 20 mil spinnerette to obtain a size 5-0 suture, and a 50 mil spinnerette to obtain a size 0 suture. Drawing conditions and physical 25 properties of the resulting suture are compared in Table IV with a size 2-0 suture of the same composition prepared according to Example I.
J! 'if riJJEtfy* 1 i SEP 1980 TABLE II Examples I II III IV V Suture size 2-0 o i cn o i cn o i cn 2-0 Diameter, mils (mm) 11.1 (0.28) 13.1 (0.33) 12.2 (0.31) 13.2 (0.34) 13. 2 (0.34) Knot strength, psi (Kg/cm2) 37,200 (2,600) 39,700 (2,780) 44,900 (3,140) 40,100 (2,800) 41,000 (2,870) Tensile strength, psi (Kg/cm2) 64,100 (4,490) 71,300 (4,990) 72 ,300 (5,060) 65,500 (4,580) 60,500 (4,200) Break elongation, % 31. 8 27.8 18. 3 .2 31.4 Visco-elastic elongation, % 18.6 13.3 7.25 .35 11.6 Yield elongation, % 3.2 2.9 2.6 4.2 4.7' Young's modulus, psi (Kg/cm2) 50,000 (3,500) 172,000 (12,000) 320,000 (22,400) 140,000 (9,800) 120,000 (8,400) >6 N) M t-3 />* r~ "VT! ""I-T3 r*- ■) Tf5!\? r'i TABLE III Polymer compositions Wt % soft Wt ratio segments of of components components Wt % soft segments in blend Young's modulus psi (Kg/cm ) Break elongation Eb, % Visco-elastic elongation Ev, % Yield elongation Ey, % 40/23 65/35 34.05 84,000 ( 5,850) 34.8 14.3 9.2 40/18 75/25 34 .50 107,000 ( 7,470) 33.4 13.3 3.2 40/23 50/50 31.50 105,000 ( 7,320) 33.7 14.7 1.9 40/18 70/30 33.40 120,000 ( 8,390) 31.4 11.6 4.7 40/18 65/35 32 . 30 134,000 ( 9,400) 27.5 12.1 4.6 40/18 60/40 31.20 140,000 ( 9,790) 26. 5 .2 4.8 40/18 55/45 .10 170,000 (11,920) 24.5 .8 2.6 40/18/23 /30/40 26.60 173,000 (12,080) 18.9 .3 3.5 40/23/18 /30/40 26 .10 201,000 (14,060) 22.4 .3 2.8 17 TABLE IV Suture size -0 2-0 0 Draw ratio '7.5 co • 00 7.3* Draw temperature, °F 340 530 370 Take-up, ft/min 205 485 110 Diameter, mils 7.08 11.10 14.03 Knot strength, psi (Kg/cm2) 48,600 (3,400) 37,200 (2,600) 34,200 (2,400) Tensile strength, psi (Kg/cm2) 67,500 (4,700) 64,100 (4,400) 68,600 (4,800) Break elongation, % 43.5 31.8 36.7 Visco-elastic elongation, % . 8 18. 6 17.6 Yield elongation, % 3.0 3.2 6.3 Young's modulus, psi (Kg/cm2) 49,000 (3,400) 50,000 (3,500) 51,000 (3,600) "•Two stage draw EXAMPLE VIII Monofilament sutures prepared from a copolyether/ester of Example II with 23 wt percent soft segments were sterilized by cobalt-60 irradiation and with ethylene oxide in accordance with conventional procedures for sterilizing surgical sutures. The physical properties of the sutures were affected only slightly by ethylene oxide sterilization, and even less by cobalt-60, as shown by the data in Table V. hi'H-4u7 1 921 38 18 TABLE V 1 921 3 Suture Nonsterile Sterilized control o 60 Co E.O.
Diameter, mils 12. 5 12.6 13.2 Knot strength, psi (Kg/cm2) ,300 (2,500) 33,400 (2,300) 29 ,900 (2,100) Tensile strength, psi (Kg/cm2) 70,300 . (4,900) 70,000 (4,900) 67 ,700 (4,800) Break elongation, % 28.2 31. 6 45.2 Visco-elastic elongation, % 13.2 . 0 23. 5 Yield elongation, % 2.9 2.3 2.2 Young's modulus, psi (Kg/cm2) 185,000 (13,000) 165,000 (11,600) 138,000 (9 ,600) The important physical properties of the sutures prepared from copolyether/esters are responsive to changes 15 in polymer composition and processing conditions. For example, visco-elastic elongation and yield elongation increase as the proportion of soft segments in polymer are increased, and conversely, Young's modulus decreases with an increasing proportion of soft segments. The 2-0 break elongation may be decreased and tensile strength increased by employing higher draw ratios during the manufacture of the suture. By regulation of the composition and processing variables therefor, it is possible to obtain specific mechanical properties for in-25 dividual sutures with a great degree of latitude.
While the preceding examples have been directed to the preparation of monofilament sutures of copolyether/esters, this was for the sake of convenience in describing one 3 0 polymer system and the effect of various polymer compositions and spinning conditions on fiber properties. The copolyether/ester polymers may also be used in the 1 921 38 19 manufacture of braided or other multifilament suture constructions, and single filaments and braids may be used in the preparation of surgical fabrics and knitted or woven prosthetic devices such as vein and arterial grafts.
In addition, elastomeric filaments having a combination of physical properties in accordance with the present invention may be prepared from other polymer systems such as polyurethane or silicone elastomers or polyether copolymers of urethane or silicone elastomers. Furthermore, 10 elastomeric filaments of the present invention may be blended with each other, with other elastomeric or non-elastomeric filaments, and with either absorbable or nonabsorbable filaments in order to provide yarns and fabrics with special properties, all of which is deemed to be in-15 eluded within the scope of the present invention.
L Q 'M7 0 L I JO
Claims (27)
1. An elastomeric surgical suture being a monofilament having the following combination of mechanical properties: Yield elongation - from 2 to 9 percent Visco-elastic elongation - from 10 to 30 percent Young's modulus - from 30,000 to 200,000 psi Tensile strength - at least 40,000 psi Knot strength - at least 30,000 psi
2. A suture of Claim 1 having a diameter of from 0.01 to 1.0 mm.
3. A suture of Claim 1 wherein the Young's modulus is 50,000 to 150,000.
4. A suture of Claim 1 wherein the tensile stress at the visco-elastic elongation yield point is less than one-third the suture tensile strength.
5. A suture of Claim 1 having an elongation to break of 30 to 10 0 percent.
6. A suture of Claim 5 wherein the elongation to break is at least 1.5 times the visco-elastic elongation.
7. A suture of Claim 1 wherein the visco-elastic elongation is at least 2.5 times the yield elongation.
8. A suture of Claim 1 in a sterile condition.
9. A suture of Claim 8 with a needle attached to at least e end thereof.
10. A suture of Claim 1 comprising a drawn and oriented monofilament of a segmented copolyether/ester polymer.
11. A drawn and oriented elastomeric surgical filament being a segmented copolyether/ester consisting essentially 2i 192 133 of a multiplicity of recurring long chain ether/ester units and short chain ester units joined head to tail through ester linkages and having the following general formula: 0 0 0 0 >1 II u II _ A(0 - D- O- C- R- C) (O-G-O-C-R-C - 0)v7 a. it n wherein G is a divalent radical remaining after the removal of terminal hydroxyl groups from a poly(C2_^Q alkylene oxide) glycol having a molecular weight of 350 to 6,000; R is a divalent radical remaining after removal of carboxyl groups from an aromatic dicarboxylic acid having a molecular weight less than 300; and D is a divalent radical remaining after removal of hydroxyl groups from an alkyldiol having a molecular weight less than 250; a and b are integers such that the short chain units represented by a comprise from 50 to 90 percent by weight of the composition; b is an integer such that the long chain copolymer segments represented by b comprise from 10 to 50 percent of the total copolymer composition; and n is the degree of polymerization resulting in a fiber-forming polymer, said drawn filaments being characterized by the following physical properties: Tensile strength - at least 40,000 psi Knot strength - at least 30,000 psi Yield elongation - from 2 to 9 percent Visco-elastic elongation - from 10 to 30 percent Young's modulus - from 30,000 to 200,000 psi
12. A filament of Claim 11 having a surgical needle attached to at least one end and useful as a surgical suture.
13. A filament of Claim 12 in a sterile condition. 22 192138
14. A filament of Claim 11 wherein G is derived from poly(tetramethyleneoxide)glycol, D is derived from 1,4-butanediol and R is derived from a phthalic acid.
15. A filament of Claim 14 wherein R is selected from the group consisting of terephthaloyl, isophthaloyl, orthophthaloyl, and mixtures thereof.
16. A filament of Claim 14 wherein said poly(tetramethyleneoxide) glycol has a molecular weight of about 1,000.
17. A filament of Claim 14 wherein the long chain units represented by b comprise about 4 0 wt percent of the copolyether/ ester.
18. A filament of Claim 17 comprising approximately 51 percent terephthaloyl units, 16 percent units derived from polytetramethylene ether glycol, and 33 percent units derived from 1,4-butanediol.
19. A filament of Claim 18 characterized by a visco-elastic elongation of about 19 percent and a Young's modulus of about 50,000 psi.
20. A filament of Claim 14 wherein the long chain units represented by b comprise about 2 3 wt percent of the copolyether/ ester.
21. A filament of Claim 20 comprising approximately 45 percent terephthaloyl units, 4 percent orthophthaloyl units, 2 0 percent units derived from polytetramethylene ether glycol and 31 percent units derived from 1,4-butanediol.
22. A filament of Claim 21 characterized by a visco-elastic elongation of about 13 percent and a Young's modulus of about 170,000 psi. — * "^rroFFfCS 23 t8
23.3. A filament of Claim 16 being a mixture of individual segmented copolyether/ester polymers having from 18 to 40 percent by weight long chain ester units wherein said filament contains an average of from 26 to 35 percent by weight long chain ester units.
24. A filament of Claim 2 3 wherein said polymer mixture comprises from 55 to 75 percent by weight of polymer having 40 percent by weight long chain ester units, and from 25 to 45 percent by weight of polymer having 18 percent by weight long chain ester units.
25. A filament of Claim 23 wherein said polymer mixture comprises approximately 30 percent by weight of a polymer having 40 percent by weight long chain ester units, from 30 to 4 0 percent by weight of a polymer having 2 3 percent by weight long chain ester units, and from 30 to 40 percent by weight of a polymer having 18 percent by weight long chain ester units.
26. A woven or knitted surgical fabric comprised of filaments of Claim 11.
27. A fabric of Claim 26 in a seamless tubular construction . WEST-WALKER, McCABE per: ATTORNEYS FOR THE APPLICANT
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US96765678A | 1978-12-08 | 1978-12-08 | |
US7705579A | 1979-09-26 | 1979-09-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
NZ192138A true NZ192138A (en) | 1984-05-31 |
Family
ID=26758834
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NZ192138A NZ192138A (en) | 1978-12-08 | 1979-11-15 | Elastomeric surgical suture |
Country Status (23)
Country | Link |
---|---|
AR (1) | AR222361A1 (en) |
AT (1) | AT370999B (en) |
AU (1) | AU530057B2 (en) |
BR (1) | BR7907998A (en) |
CA (2) | CA1141915A (en) |
CH (1) | CH643460A5 (en) |
DE (1) | DE2949181A1 (en) |
ES (1) | ES486698A0 (en) |
FR (1) | FR2473316B1 (en) |
GB (1) | GB2038704B (en) |
HK (1) | HK30083A (en) |
IL (1) | IL58897A (en) |
IN (1) | IN151798B (en) |
IT (1) | IT1164078B (en) |
MX (1) | MX152227A (en) |
MY (1) | MY8400142A (en) |
NL (1) | NL7908845A (en) |
NZ (1) | NZ192138A (en) |
PH (1) | PH22728A (en) |
PL (1) | PL141223B1 (en) |
PT (1) | PT70564A (en) |
SE (1) | SE7910106L (en) |
SG (1) | SG10283G (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4388926A (en) * | 1980-12-22 | 1983-06-21 | Ethicon, Inc. | High compliance monofilament surgical sutures comprising poly[alkylene terephthalate-co-(2-alkenyl or alkyl)succinate] |
US4689424A (en) * | 1981-08-06 | 1987-08-25 | Ethicon, Inc. | Radiation sterilizable absorbable polymeric materials and methods for manufacturing the same |
NL8202893A (en) * | 1982-07-16 | 1984-02-16 | Rijksuniversiteit | ORGANIC Tolerant, ANTHITHROMBOGENIC MATERIAL, SUITABLE FOR RECOVERY SURGERY. |
US4906729A (en) * | 1988-08-05 | 1990-03-06 | E. I. Du Pont De Nemours And Company | Thermoplastic copolyetherester elastomers |
US5009955A (en) * | 1989-03-06 | 1991-04-23 | General Motors Corporation | Dual modulus oriented elastomeric filaments |
AU694983B2 (en) * | 1994-06-06 | 1998-08-06 | Johnson & Johnson Consumer Companies, Inc. | Novel compositions for dental floss |
AU2007201213A1 (en) * | 2006-04-06 | 2007-10-25 | Tyco Healthcare Group Lp | Yarns containing thermoplastic elastomer copolymer and polyolefin filaments |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3454011A (en) * | 1966-12-28 | 1969-07-08 | Marvin Wagner | Sutures and prosthetic patches |
CA933319A (en) * | 1968-12-04 | 1973-09-11 | Sumoto Misao | Melt spinning elastic polyester polyether block copolymer |
US4127127A (en) * | 1977-05-23 | 1978-11-28 | Alza Corporation | Therapeutic systems made from certain segmented copolyesters |
US4224946A (en) * | 1978-08-14 | 1980-09-30 | American Cyanamid Company | Surgical sutures derived from segmented polyether-ester block copolymers |
-
1979
- 1979-10-30 IN IN1132/CAL/79A patent/IN151798B/en unknown
- 1979-11-15 NZ NZ192138A patent/NZ192138A/en unknown
- 1979-11-27 AU AU53197/79A patent/AU530057B2/en not_active Ceased
- 1979-12-05 IT IT50997/79A patent/IT1164078B/en active
- 1979-12-06 PL PL1979220182A patent/PL141223B1/en unknown
- 1979-12-06 CA CA000341398A patent/CA1141915A/en not_active Expired
- 1979-12-06 FR FR7929946A patent/FR2473316B1/en not_active Expired
- 1979-12-06 DE DE19792949181 patent/DE2949181A1/en active Granted
- 1979-12-07 ES ES486698A patent/ES486698A0/en active Granted
- 1979-12-07 PH PH23379A patent/PH22728A/en unknown
- 1979-12-07 MX MX180381A patent/MX152227A/en unknown
- 1979-12-07 AT AT0776179A patent/AT370999B/en not_active IP Right Cessation
- 1979-12-07 SE SE7910106A patent/SE7910106L/en unknown
- 1979-12-07 GB GB7942325A patent/GB2038704B/en not_active Expired
- 1979-12-07 IL IL58897A patent/IL58897A/en unknown
- 1979-12-07 AR AR279206A patent/AR222361A1/en active
- 1979-12-07 CH CH1089979A patent/CH643460A5/en not_active IP Right Cessation
- 1979-12-07 PT PT70564A patent/PT70564A/en unknown
- 1979-12-07 BR BR7907998A patent/BR7907998A/en unknown
- 1979-12-07 NL NL7908845A patent/NL7908845A/en not_active Application Discontinuation
-
1983
- 1983-03-11 SG SG102/83A patent/SG10283G/en unknown
- 1983-08-18 HK HK300/83A patent/HK30083A/en unknown
-
1984
- 1984-12-30 MY MY142/84A patent/MY8400142A/en unknown
-
1985
- 1985-06-25 CA CA000485231A patent/CA1203137B/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
ES8101387A1 (en) | 1980-12-16 |
CA1141915A (en) | 1983-03-01 |
PL141223B1 (en) | 1987-07-31 |
AU5319779A (en) | 1980-06-19 |
SG10283G (en) | 1983-12-16 |
SE7910106L (en) | 1980-06-09 |
AR222361A1 (en) | 1981-05-15 |
DE2949181A1 (en) | 1980-06-26 |
IT1164078B (en) | 1987-04-08 |
GB2038704B (en) | 1983-01-12 |
IT7950997A0 (en) | 1979-12-05 |
ES486698A0 (en) | 1980-12-16 |
GB2038704A (en) | 1980-07-30 |
FR2473316B1 (en) | 1986-05-23 |
ATA776179A (en) | 1982-10-15 |
DE2949181C2 (en) | 1990-01-18 |
CA1203137B (en) | 1986-04-15 |
AT370999B (en) | 1983-05-25 |
BR7907998A (en) | 1980-07-22 |
FR2473316A1 (en) | 1981-07-17 |
AU530057B2 (en) | 1983-06-30 |
IL58897A (en) | 1982-09-30 |
IL58897A0 (en) | 1980-03-31 |
PH22728A (en) | 1988-11-28 |
PT70564A (en) | 1980-01-01 |
HK30083A (en) | 1983-08-26 |
CH643460A5 (en) | 1984-06-15 |
MX152227A (en) | 1985-06-12 |
NL7908845A (en) | 1980-06-10 |
PL220182A1 (en) | 1980-12-01 |
IN151798B (en) | 1983-07-30 |
MY8400142A (en) | 1984-12-31 |
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