CA2292654C - Cross-linked nylon block copolymers - Google Patents
Cross-linked nylon block copolymers Download PDFInfo
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- CA2292654C CA2292654C CA002292654A CA2292654A CA2292654C CA 2292654 C CA2292654 C CA 2292654C CA 002292654 A CA002292654 A CA 002292654A CA 2292654 A CA2292654 A CA 2292654A CA 2292654 C CA2292654 C CA 2292654C
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- Prior art keywords
- nylon
- block copolymer
- copolymer
- crosslinked
- crosslinking
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M25/00—Catheters; Hollow probes
- A61M25/10—Balloon catheters
- A61M25/1027—Making of balloon catheters
- A61M25/1036—Making parts for balloon catheter systems, e.g. shafts or distal ends
-
- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
Abstract
A cross-linked nylon block copolymer comprising a copolymer containing a polyamide block and an elastomeric block, irradiation cross-linked, including a compound which promotes cross-linking therein. In process form, the present invention comprises supplying a nylon block copolymer, containing a polyamide block and an elastomeric block, along with cross-linking promotor and exposing the block copolymer to irradiation, sufficient to cross-link the copolymer and improve mechanical properties therein. The cross-linked nylon block copolymers here have particular utility in both the medical and wire and cable industries.
Description
WO 98/55171 PCTNS98109~5~
a 1 CROSSL~1NKCD NYLON 13~OCTC COPOLY1V~>GItS
Field of the Invention
a 1 CROSSL~1NKCD NYLON 13~OCTC COPOLY1V~>GItS
Field of the Invention
2 The present invention relates to the preparation of crosslinked nylon block
3 copolymer materials, and to their use in medical applications, particular as a - ' 4 compone:zt for the preparation of a rigidired stem section for a catheter or otllcr sitnilar medical devicc:_ :In addition, the crossli~nked nylon block copolymer materials 6 herein have utility in the wire and cable industry.
Back rg ound of the Invention 7 Generally, nylon block copolymers may be alternating blocks of polyumidc 8 segments and other scgrxicnts such as segments of elastomeric polymers such as 9 polyethcrs, polyesters, hydrocarbons or polysiloxanes, Thcsc xaylon block copolytnerS
aze gexterally prepared b;y copolymcrizing a lactam monomer in the present of the 11 elastomeric polymers component. A more detailed discussion of the structure and I2 method pf preparing particular types of nylon block copolymers can be found in U.S.
13 PectcntNo. X1,031,164.
14 The polyaz~cxid~ segments and elastomeric polymer segments of the nylon block copolymers each contribute to the respective properties of the final polymer. In 16 order to obtain high rnoclulus materials, polyamidc segments of higher molecular I7 weight and/or higher r eight percent can be employed. Alternatively, greater tensile X 8 elongation and impact properties, as well as lower surface hardness, may be obiaincd 19 by using higher percent:; of and/or higher molecular weight elastomeric polymer component, 21 Lf.S. Patent No. 4,617,355 appears to be one of the first disclosures of a 22 crosslink:ed nylon block copolymer, chemically, through the use of polyfunctiot~al 23 amine compounds- 'i"L~a.t is, the crosslinked nylon block copolymers are prepared by a 24 reaction scheme in which polyfunctional amines act as crosslinking agents.' More specifica~,lly, a crossliruk~°d material was reportedly syncthcsiT,cd by reacting an acyl ZG lactarrl facntionalized nuaterial with the polyfunctional amine to prepare crosslinked - 27 acyl lactam materials which were then. concurrently or subsequently r'cacted With 28 lactam nnonoznex in tl~e presence of a lactam polymerization catalyst to form the 29 crosslizz;4ced nylon block copolymer material. h was reported therein that 6y chemically ero5slinkin;~, It was discovered that the overatl properties of the final ..a 1 polymer could be varied even if one maintains the molecular weight and weight 2 percent of the elastomeric polymer component.
3 While the above chemical method of crosslinking a nylon block copolymer
Back rg ound of the Invention 7 Generally, nylon block copolymers may be alternating blocks of polyumidc 8 segments and other scgrxicnts such as segments of elastomeric polymers such as 9 polyethcrs, polyesters, hydrocarbons or polysiloxanes, Thcsc xaylon block copolytnerS
aze gexterally prepared b;y copolymcrizing a lactam monomer in the present of the 11 elastomeric polymers component. A more detailed discussion of the structure and I2 method pf preparing particular types of nylon block copolymers can be found in U.S.
13 PectcntNo. X1,031,164.
14 The polyaz~cxid~ segments and elastomeric polymer segments of the nylon block copolymers each contribute to the respective properties of the final polymer. In 16 order to obtain high rnoclulus materials, polyamidc segments of higher molecular I7 weight and/or higher r eight percent can be employed. Alternatively, greater tensile X 8 elongation and impact properties, as well as lower surface hardness, may be obiaincd 19 by using higher percent:; of and/or higher molecular weight elastomeric polymer component, 21 Lf.S. Patent No. 4,617,355 appears to be one of the first disclosures of a 22 crosslink:ed nylon block copolymer, chemically, through the use of polyfunctiot~al 23 amine compounds- 'i"L~a.t is, the crosslinked nylon block copolymers are prepared by a 24 reaction scheme in which polyfunctional amines act as crosslinking agents.' More specifica~,lly, a crossliruk~°d material was reportedly syncthcsiT,cd by reacting an acyl ZG lactarrl facntionalized nuaterial with the polyfunctional amine to prepare crosslinked - 27 acyl lactam materials which were then. concurrently or subsequently r'cacted With 28 lactam nnonoznex in tl~e presence of a lactam polymerization catalyst to form the 29 crosslizz;4ced nylon block copolymer material. h was reported therein that 6y chemically ero5slinkin;~, It was discovered that the overatl properties of the final ..a 1 polymer could be varied even if one maintains the molecular weight and weight 2 percent of the elastomeric polymer component.
3 While the above chemical method of crosslinking a nylon block copolymer
4 has been reported, no reports exist concerning the development of a nylon block copolymer by a more convenient method such as irradiation. The closest attempts in 6 this regard can be found, for example, in Plast. Massy, 1993, No. 2, pp 35-37, which 7 contains a paper entitled "Production and Properties of Crosslinked Compositions of 8 Aliphatic Nylons". According to the abstract, a study was conducted on the process 9 of radiation crosslinking of an aliphatic polyamides (i.e., not a nylon block copolymers) and an assessment is made of the properties and network compositions I I obtained. The materials studied were nylon-6, nylon-6,6 and nylon-12. The 12 polyfunctional monomers employed to accelerate crosslinking were triallyl cyanurate 13 and triallyl isocyanurate. Mechanical data is supplied.
14 Similarly, in the Chinese Journal of Polymer Science, Vol. 7, No. 1, there is a 1 ~ paper entitled "Characterization of Irradiated Crystalline Polymer-Isothermal 16 Crystallization Kinetics of Radiation Induced Crosslinked Polyamide 1010".
As 17 disclosed therein, after irradiation, the service temperature of the resin is raised to 18 about 240 °C. In addition, network formation is said to greatly change the 19 crystallization behavior of the otherwise crystalline polyamide material.
Finally, it is worth noting that various other disclosures have been uncovered, 21 which recite thermoset (or crosslinked) polyamide resins, but again, no mention or 22 suggestion of irradiation crosslinking of a nylon block copolymer is described. For 23 example, in U.S. Patent No. 5,198,551 entitled "Polyamide Thermosets" there is 24 disclosed what is termed curable polyamide monomers, curable liquid crystal polyamide monomers and thermoset compositions prepared therefrom. The 26 theremoset polyamides so prepared all contained highly aromatic type structure.
27 Similarly, in U.S. Patent No. 5,3154,011, which is a divisional of the'S51 Patent, 28 there ~is again described curable polyamide monomer systems, which monomers 29 represent highly aromatic type functionality.
1 The fact that there have been no reports concerning the development of a 2 convenient route for the preparation of a crosslinked nylon block copolymer is 3 underscored when reference is made to U.S. Patent No. 5,584,821, which discloses an 4 angiographic catheter which has a relatively stiff though flexible shaft and a soft tip.
The soft tip consists primarily of a tungsten loaded polyether block amide (PEBA) 6 copolymer surrounded by two thin PEBA layers. This three ply radiopaque tip is 7 bonded to a PEBA shaft. The shaft is reinforced either by an inner nylon ply or by 8 metal braiding.
9 In other words, pursuant to the teachings of U.S. Patent 5,584,821 when it comes to the production of a soft tip catheter with a relatively stiffer body, the 11 teachings therein emphasize that the stiffer body portion relies upon the use of a metal 12 braided reinforced PEBA copolymer or a co-extruded two ply wall consisting of nylon 13 and PEBA copolymer. That being the case, it becomes clear that inasmuch as PEBA
14 type copolymers are widely used in catheter type applications, it would serve a long-standing need if one could conveniently produce a more rigid and toughened PEBA
16 catheter, without the need for the structural modifications emphasized in the prior art.
17 Accordingly, it is an object of this invention to prepare a crosslinked nylon 18 block copolymer, wherein said polymer is conveniently crosslinked by the process of 19 irradiation or other high energy source, wherein such crosslinked nylon block copolymer has particular utility as a component of a medical catheter product.
21 More specifically, it is object of the present invention to prepare a crosslinked 22 nylon block copolymer elastomeric formulation, via irradiation techniques, wherein 23 the elastomeric composition, subsequent to crosslinking, exhibits improvement in 24 properties such as mechanical strength, heat resistance, and hardness, and in particular, the crosslinked material so produced demonstrates elongational behavior 26 when exposed to elevated temperatures under conditions of constant stress.
27 Furthermore, it is an object of the present invention to crosslink nylon block 28 copolymer systems, wherein such crosslinking improves the overall elastomeric 29 toughness of the block copolymer, thereby providing what can be termed a much WO 98!55171 1'CT/US98/09257 more durable nylon block copolymer product for a variety of miscellaneous applications in the medical industry.
According to one aspect of the invention, a crosslinked nylon block copolymer is provided The rriethod comprises a copolymer containing a polyamide block and an elastomeric block, irradiation crosslinked, including a compound which promotes crosslinking therein, wherein the compound which promotes crosslinking comprises one of triallylisocyanurate and triallylcyanurate.
According to another aspect of the invention, in an intravascular flexible cathetc;r having a tnbukar shaft is provided. This method comprises a.
nylon block copolymer, and a~ soft flexible tuhular tip distal of and bonded to the shaft, the improvement comprising irradiation crosslinking the nylon block copolymer of the tubular shaft, wherein the crosslinking increases the rigidity of the shaft relative to the sots: flexible distal tip.
According to another .aspect of the invention in a balloon type catheter having a tubular shaft is provided. The method comprises a nylon block copolymer and an integrally formed balloon section, the improvement comprising irradiation crosslinking the nylon block copolymer of the balloon section, wherein the crosslinkirrg lowers the percent elongation of the balloon section as compared to the elongation prior to crosslinking.
According to another aspect of the invention a process for preparing a crosslinked nylon block eopalymer is provided. This method comprises supplying a copolymer containing a polyamide block and an elastomeric block, mixing a crosslinking promoter into the copolymer, and exposing the copolymer with promoter to irradiation crosslinking.
WO 9x/55171 PCTNS98l09257 2 Brief Description of Preferred Embodiments 3 A, crosslinked nylon block copolymer comprising a copolymer containing a 4 polydmicte block and an clastomexiC block, irradiation crosslirthed, including a compound which proaxiotes crosslinking therein. Ira process form, the present 6 invention comprises supplying a nylon block copolymer, containing a polyamidc 7 block and an clastomcric block, along with crosslinking promotor and exposing said 8 block copolymer to irradiation, sufFicienz to crosslink said block copolyzncr axed 9 improve tnechanical prt~perties therein, particularly the ability of said block copolymer to elongate upon cxposttre to a constant load of about 29 psi (2039 11 gtn/cm2) at an elevated temperature of about 200 °C for 15 min.
12 As noted above, the present invention in composition form relates to a an 13 imadiati~on.crosslinkrd nylon block e.opolytxtcr . Preferably. tile nylon block 1 ~ copolyamr is a nylon block copolymer sold by A'fOCHEM under the tradename PEBAX~~ which is a elastomeric type nylon block copolymer. The commercial 16 PEBAx: polymers consist of polyether blocks separated by polyAmide blocks.
The 17 polyeth~3r blocks may be based upon polyethylene glycol, polypropylene glycol, or 18 polytetrarxtethylene ether glycol. 'f he polyamides are usually based upon nylon-11 but 19 may be based upon nylons G of nylon-6,G or even a copolymer such as nylon-6/nyton-11. A wide range of block polyamid~s ha"ve been offered and vary in the type of 21 polyether, the natuze of the polyamide block and the ratio of poiyether to polyazxE,itde 22 blocks. The polymers range in hardness from Shore A 60 to Shore L772 which is 23 broader than for the thermoplastic polyester and thermoplastic polyurethane rubbers.
24 Meltin~~ range is also clependeni on the particular composition, and varies between 1 ~0 - 215 °C.
26 The above nylon block copolymers have been found to undergo crosslitlking 27 upon exposure tv irradiation. Listed below in Table I arc the, results of various ~~
28 exposure levels as applied to a rEBA~ Shore 72~ material, containing 2.0%
'T~.'IC
29 (triallylisocyonurate) and the corresponding changes in mechanical properties ', 3p observed: 4A
';
0 MR 5 MR l OMR 15MR 20MR
T.S. (psi) 8,632 10,531 7,751 (g/cmz) 606,890 740,403 544,959 Yield (psi) 4,026 4,979 5,186 (g/cm') 283,056 350,059 346,612 100% Mod (psi)3,498 4,035 4,216 (g/cm'') 245,934 283,689 296,414 Elong (%) *404.2 *358.3 *283.3 ** **
Creep (%) * * * 54.3 61.4 S 8.3 63.0 Set (%) -- 1.5 4.1 3.6 4.6 3 * = Necked 4 * * = NOTE: The 1 Smr and 20mr samples necked and there was very little elongation (less than 0.635 cm).).
6 * * * At 200 °C, the unexposed material melted. At 1 SO °C the unexposed 7 material elongated 0.0794 cm. (3.1 %). At 175 °C it broke in the clamp, but did not 8 melt. The sample elongated 1.5875 cm. (62.5%) before it broke.
9 One of the more relevant properties reported on in Table I, is the % Creep which was measured at 200 °C, 29 psi (2,039 gm/cmz) , over a 15 minute period. This 1 I is formally known as the "Test Method for Measurement of Hot Creep of Polymeric 12 Insulations", Publication T-28-562, published by the Insulated Cable Engineers 13 Association, Inc, of South Yarmouth, Massachusetts. In accordance with the present 14 invention, elongations of less than 100% are preferred, and most preferred is an I S elongation of about 10-65%.
16 As can be seen, unexposed PEBAX actually melted under these conditions of 17 testing, and no elongation was observed. By contrast, after a 5 megarad total 18 exposure, the percent creep is about 54.6%. In other words, irradiation clearly 19 promotes crosslinking and network formation within the nylon block copolymer
14 Similarly, in the Chinese Journal of Polymer Science, Vol. 7, No. 1, there is a 1 ~ paper entitled "Characterization of Irradiated Crystalline Polymer-Isothermal 16 Crystallization Kinetics of Radiation Induced Crosslinked Polyamide 1010".
As 17 disclosed therein, after irradiation, the service temperature of the resin is raised to 18 about 240 °C. In addition, network formation is said to greatly change the 19 crystallization behavior of the otherwise crystalline polyamide material.
Finally, it is worth noting that various other disclosures have been uncovered, 21 which recite thermoset (or crosslinked) polyamide resins, but again, no mention or 22 suggestion of irradiation crosslinking of a nylon block copolymer is described. For 23 example, in U.S. Patent No. 5,198,551 entitled "Polyamide Thermosets" there is 24 disclosed what is termed curable polyamide monomers, curable liquid crystal polyamide monomers and thermoset compositions prepared therefrom. The 26 theremoset polyamides so prepared all contained highly aromatic type structure.
27 Similarly, in U.S. Patent No. 5,3154,011, which is a divisional of the'S51 Patent, 28 there ~is again described curable polyamide monomer systems, which monomers 29 represent highly aromatic type functionality.
1 The fact that there have been no reports concerning the development of a 2 convenient route for the preparation of a crosslinked nylon block copolymer is 3 underscored when reference is made to U.S. Patent No. 5,584,821, which discloses an 4 angiographic catheter which has a relatively stiff though flexible shaft and a soft tip.
The soft tip consists primarily of a tungsten loaded polyether block amide (PEBA) 6 copolymer surrounded by two thin PEBA layers. This three ply radiopaque tip is 7 bonded to a PEBA shaft. The shaft is reinforced either by an inner nylon ply or by 8 metal braiding.
9 In other words, pursuant to the teachings of U.S. Patent 5,584,821 when it comes to the production of a soft tip catheter with a relatively stiffer body, the 11 teachings therein emphasize that the stiffer body portion relies upon the use of a metal 12 braided reinforced PEBA copolymer or a co-extruded two ply wall consisting of nylon 13 and PEBA copolymer. That being the case, it becomes clear that inasmuch as PEBA
14 type copolymers are widely used in catheter type applications, it would serve a long-standing need if one could conveniently produce a more rigid and toughened PEBA
16 catheter, without the need for the structural modifications emphasized in the prior art.
17 Accordingly, it is an object of this invention to prepare a crosslinked nylon 18 block copolymer, wherein said polymer is conveniently crosslinked by the process of 19 irradiation or other high energy source, wherein such crosslinked nylon block copolymer has particular utility as a component of a medical catheter product.
21 More specifically, it is object of the present invention to prepare a crosslinked 22 nylon block copolymer elastomeric formulation, via irradiation techniques, wherein 23 the elastomeric composition, subsequent to crosslinking, exhibits improvement in 24 properties such as mechanical strength, heat resistance, and hardness, and in particular, the crosslinked material so produced demonstrates elongational behavior 26 when exposed to elevated temperatures under conditions of constant stress.
27 Furthermore, it is an object of the present invention to crosslink nylon block 28 copolymer systems, wherein such crosslinking improves the overall elastomeric 29 toughness of the block copolymer, thereby providing what can be termed a much WO 98!55171 1'CT/US98/09257 more durable nylon block copolymer product for a variety of miscellaneous applications in the medical industry.
According to one aspect of the invention, a crosslinked nylon block copolymer is provided The rriethod comprises a copolymer containing a polyamide block and an elastomeric block, irradiation crosslinked, including a compound which promotes crosslinking therein, wherein the compound which promotes crosslinking comprises one of triallylisocyanurate and triallylcyanurate.
According to another aspect of the invention, in an intravascular flexible cathetc;r having a tnbukar shaft is provided. This method comprises a.
nylon block copolymer, and a~ soft flexible tuhular tip distal of and bonded to the shaft, the improvement comprising irradiation crosslinking the nylon block copolymer of the tubular shaft, wherein the crosslinking increases the rigidity of the shaft relative to the sots: flexible distal tip.
According to another .aspect of the invention in a balloon type catheter having a tubular shaft is provided. The method comprises a nylon block copolymer and an integrally formed balloon section, the improvement comprising irradiation crosslinking the nylon block copolymer of the balloon section, wherein the crosslinkirrg lowers the percent elongation of the balloon section as compared to the elongation prior to crosslinking.
According to another aspect of the invention a process for preparing a crosslinked nylon block eopalymer is provided. This method comprises supplying a copolymer containing a polyamide block and an elastomeric block, mixing a crosslinking promoter into the copolymer, and exposing the copolymer with promoter to irradiation crosslinking.
WO 9x/55171 PCTNS98l09257 2 Brief Description of Preferred Embodiments 3 A, crosslinked nylon block copolymer comprising a copolymer containing a 4 polydmicte block and an clastomexiC block, irradiation crosslirthed, including a compound which proaxiotes crosslinking therein. Ira process form, the present 6 invention comprises supplying a nylon block copolymer, containing a polyamidc 7 block and an clastomcric block, along with crosslinking promotor and exposing said 8 block copolymer to irradiation, sufFicienz to crosslink said block copolyzncr axed 9 improve tnechanical prt~perties therein, particularly the ability of said block copolymer to elongate upon cxposttre to a constant load of about 29 psi (2039 11 gtn/cm2) at an elevated temperature of about 200 °C for 15 min.
12 As noted above, the present invention in composition form relates to a an 13 imadiati~on.crosslinkrd nylon block e.opolytxtcr . Preferably. tile nylon block 1 ~ copolyamr is a nylon block copolymer sold by A'fOCHEM under the tradename PEBAX~~ which is a elastomeric type nylon block copolymer. The commercial 16 PEBAx: polymers consist of polyether blocks separated by polyAmide blocks.
The 17 polyeth~3r blocks may be based upon polyethylene glycol, polypropylene glycol, or 18 polytetrarxtethylene ether glycol. 'f he polyamides are usually based upon nylon-11 but 19 may be based upon nylons G of nylon-6,G or even a copolymer such as nylon-6/nyton-11. A wide range of block polyamid~s ha"ve been offered and vary in the type of 21 polyether, the natuze of the polyamide block and the ratio of poiyether to polyazxE,itde 22 blocks. The polymers range in hardness from Shore A 60 to Shore L772 which is 23 broader than for the thermoplastic polyester and thermoplastic polyurethane rubbers.
24 Meltin~~ range is also clependeni on the particular composition, and varies between 1 ~0 - 215 °C.
26 The above nylon block copolymers have been found to undergo crosslitlking 27 upon exposure tv irradiation. Listed below in Table I arc the, results of various ~~
28 exposure levels as applied to a rEBA~ Shore 72~ material, containing 2.0%
'T~.'IC
29 (triallylisocyonurate) and the corresponding changes in mechanical properties ', 3p observed: 4A
';
0 MR 5 MR l OMR 15MR 20MR
T.S. (psi) 8,632 10,531 7,751 (g/cmz) 606,890 740,403 544,959 Yield (psi) 4,026 4,979 5,186 (g/cm') 283,056 350,059 346,612 100% Mod (psi)3,498 4,035 4,216 (g/cm'') 245,934 283,689 296,414 Elong (%) *404.2 *358.3 *283.3 ** **
Creep (%) * * * 54.3 61.4 S 8.3 63.0 Set (%) -- 1.5 4.1 3.6 4.6 3 * = Necked 4 * * = NOTE: The 1 Smr and 20mr samples necked and there was very little elongation (less than 0.635 cm).).
6 * * * At 200 °C, the unexposed material melted. At 1 SO °C the unexposed 7 material elongated 0.0794 cm. (3.1 %). At 175 °C it broke in the clamp, but did not 8 melt. The sample elongated 1.5875 cm. (62.5%) before it broke.
9 One of the more relevant properties reported on in Table I, is the % Creep which was measured at 200 °C, 29 psi (2,039 gm/cmz) , over a 15 minute period. This 1 I is formally known as the "Test Method for Measurement of Hot Creep of Polymeric 12 Insulations", Publication T-28-562, published by the Insulated Cable Engineers 13 Association, Inc, of South Yarmouth, Massachusetts. In accordance with the present 14 invention, elongations of less than 100% are preferred, and most preferred is an I S elongation of about 10-65%.
16 As can be seen, unexposed PEBAX actually melted under these conditions of 17 testing, and no elongation was observed. By contrast, after a 5 megarad total 18 exposure, the percent creep is about 54.6%. In other words, irradiation clearly 19 promotes crosslinking and network formation within the nylon block copolymer
5 WO 98!55171 PCT/US98/09257 1 material, and as a thenmoset, it no longer melts and flow, and elastomeric behavior is 2 observed.
3 Also, as can be seen from Table I, exposure to 5 megarads results in an 4 associated drop in the percent of elongation from about 404 % to about 358 %, which is a characteristic expected due to crosslinking. In addition, exposure at 5 megarads
3 Also, as can be seen from Table I, exposure to 5 megarads results in an 4 associated drop in the percent of elongation from about 404 % to about 358 %, which is a characteristic expected due to crosslinking. In addition, exposure at 5 megarads
6 increases the tensile strength from about 8600 psi (604,640 gm/cm2) to about 10,500
7 psi {738,224 gm/cmz) , which is again a result of network crosslink formation.
8 As can also be seen in Table I, while an exposure of 5 megarads along with
9 about 2.0 % of a promotor ("TAIC" or "TAC", triallylcyanurate) provides optimum composition and conditions, higher exposure levels are still acceptable. For example, 11 a total exposure of 10 megarads similarly provides a sample that elongates about 61 12 after exposure to 29 psi (2,039 gm/cm2) , at 200 °C for 15 minutes.
However, with 13 respect to this particular sample, it is worth pointing out that the tensile strength drops 14 to about 7750 psi (544,879 gm/cmz) , which may be the onset of some degradation.
I 5 Upon exposure to even higher total levels of irradiation ( 15 and 20 megarads) the 16 sample still demonstrates elongational values of about 58 and 63 %, respectively, 17 however, at such total exposure levels, the samples necked and their was very little 18 elongation at room temperature. Again, this is believed to be the result of the 19 degradation that may take place when total irradiation becomes too high.
With regards to the specific utility of the invention disclosed herein, it is noted 21 that the crossiinked nylon block copolymer disclosed herein has utility in both the 22 medical products field, as well as in the wire and cable industry.
23 More specifically, when it comes to the production of an intravascular flexible 24 catheter having a tubular shaft comprising a nylon block copolymer, and a soft flexible tubular tip distal of and bonded to said shaft, the improvement recited herein 26 comprises irradiation crosslinking said nylon block copolymer of said shaft, wherein 27 said crosslinking increases the rigidity of said shaft relative to said soft flexible distal 28 tip. In addition, in the balloon catheter field, in the case of such catheters 29 manufactured from a nylon block copolymer, the invention herein provides for the preparation of a balloon type catheter, wherein the balloon section relative to the shaft can be converted into a thermoset or crosslinked type structure, thereby increasing its 2 overall mechanical strength, performance, and durability.
3 Accordingly, the compositions and method disclosed herein provide a much 4 more convenient route for the preparation of a novel rigid-flex nylon block copolymer resin, particularly suited for the production of novel type catheter products, without 6 the need for structural modification of the catheter type systems as disclosed and 7 emphasized by the prior art. In addition, the compositions herein are well-suited as an electrical insulating material for the wire and cable industry.
However, with 13 respect to this particular sample, it is worth pointing out that the tensile strength drops 14 to about 7750 psi (544,879 gm/cmz) , which may be the onset of some degradation.
I 5 Upon exposure to even higher total levels of irradiation ( 15 and 20 megarads) the 16 sample still demonstrates elongational values of about 58 and 63 %, respectively, 17 however, at such total exposure levels, the samples necked and their was very little 18 elongation at room temperature. Again, this is believed to be the result of the 19 degradation that may take place when total irradiation becomes too high.
With regards to the specific utility of the invention disclosed herein, it is noted 21 that the crossiinked nylon block copolymer disclosed herein has utility in both the 22 medical products field, as well as in the wire and cable industry.
23 More specifically, when it comes to the production of an intravascular flexible 24 catheter having a tubular shaft comprising a nylon block copolymer, and a soft flexible tubular tip distal of and bonded to said shaft, the improvement recited herein 26 comprises irradiation crosslinking said nylon block copolymer of said shaft, wherein 27 said crosslinking increases the rigidity of said shaft relative to said soft flexible distal 28 tip. In addition, in the balloon catheter field, in the case of such catheters 29 manufactured from a nylon block copolymer, the invention herein provides for the preparation of a balloon type catheter, wherein the balloon section relative to the shaft can be converted into a thermoset or crosslinked type structure, thereby increasing its 2 overall mechanical strength, performance, and durability.
3 Accordingly, the compositions and method disclosed herein provide a much 4 more convenient route for the preparation of a novel rigid-flex nylon block copolymer resin, particularly suited for the production of novel type catheter products, without 6 the need for structural modification of the catheter type systems as disclosed and 7 emphasized by the prior art. In addition, the compositions herein are well-suited as an electrical insulating material for the wire and cable industry.
Claims (12)
1. A crosslinked nylon block copolymer comprising a copolymer containing a polyamide block and an elastomeric block, irradiation crosslinked, including a compound which promotes crosslinking therein, wherein said compound which promotes crosslinking comprises one of triallylisocyanurate and triallylcyanurate.
2. A crosslinked nylon block copolymer of claim 1 wherein the triallylisocyanurate or triallylcyanurate is present at level of about 20% by weight.
3. The crosslinked nylon block copolymer of claim 1, wherein said crosslinked nylon block copolymer elongates after about 15 minutes at about 200 C ° and about 29 psi.
4. The crosslinked nylon block copolymer of claim 3, wherein said elongation is less than about 100%.
5. The crosslinked nylon block copolymer of claim 3, wherein said elongation is about 10-65%.
6. The crosslinked nylon block copolymer of claim 1, wherein said elastomeric block is selected from a group consisting of polyether, polyester, hydrocarbon, polysiloxane, or mixtures thereof.
7. The crosslinked nylon copolymer of claim 1, wherein said polyamide block is selected from a group consisting of nylon-6, nylon-6,6, nylon- 11, copolymer of nylon-6/nylon-11, or mixtures thereof:
8. The nylon block copolymer of claim 1, wherein said irradiation is less than about 20 megarads.
9. The nylon block copolymer of claim 1, wherein said irradiation is 5, 10, 15, or 20 megarads.
10. In an intravascular flexible catheter having a tubular shaft comprising a nylon block copolymer, and a soft flexible tubular tip distal of and bonded to said shaft, the improvement comprising irradiation crosslinking said nylon block copolymer of said tubular shaft, wherein said crosslinking increases the rigidity of said shaft relative to said soft flexible distal tip.
11. In a balloon type catheter having a tubular shaft comprising a nylon block copolymer and an integrally farmed balloon section, the improvement comprising irradiation crosslinking said nylon block copolymer of said balloon section, wherein said crosslinking lowers the percent elongation of said balloon section as compared to the elongation prior to crosslinking.
12. A process for preparing a crosslinked nylon block copolymer comprising supplying a copolymer containing a polyamide block and an elastomeric block, mixing a crosslinking promoter into said copolymer, and exposing said copolymer with promoter to irradiation crosslinking.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/867,362 US5998551A (en) | 1997-06-02 | 1997-06-02 | Crosslinked nylon block copolymers |
| US08/867,362 | 1997-06-02 | ||
| PCT/US1998/009257 WO1998055171A1 (en) | 1997-06-02 | 1998-05-06 | Cross-linked nylon block copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2292654A1 CA2292654A1 (en) | 1998-12-10 |
| CA2292654C true CA2292654C (en) | 2004-07-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002292654A Expired - Fee Related CA2292654C (en) | 1997-06-02 | 1998-05-06 | Cross-linked nylon block copolymers |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US5998551A (en) |
| EP (1) | EP0986414B1 (en) |
| JP (1) | JP2000516992A (en) |
| AT (1) | ATE380566T1 (en) |
| CA (1) | CA2292654C (en) |
| DE (1) | DE69838837T2 (en) |
| WO (1) | WO1998055171A1 (en) |
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| US6325790B1 (en) * | 1995-04-11 | 2001-12-04 | Cordis Corporation | Soft tip catheter |
| US7728049B2 (en) * | 1996-10-08 | 2010-06-01 | Zamore Alan M | Irradiation conversion of thermoplastic to thermoset polymers |
| US6656550B1 (en) | 1996-10-08 | 2003-12-02 | Alan M. Zamore | Dilatation device of uniform outer diameter |
| DE69732121T2 (en) | 1996-10-08 | 2005-12-01 | Alan Zamore | CONVERSION OF THERMOPLASTIC TO DUROPLASTIC POLYMERS BY IRRADIATION |
| US7749585B2 (en) | 1996-10-08 | 2010-07-06 | Alan Zamore | Reduced profile medical balloon element |
| US6245053B1 (en) * | 1998-11-09 | 2001-06-12 | Medtronic, Inc. | Soft tip guiding catheter and method of fabrication |
| WO2001019425A1 (en) | 1999-09-17 | 2001-03-22 | Cook Incorporated | Medical device including expandable balloon |
| US6592550B1 (en) | 1999-09-17 | 2003-07-15 | Cook Incorporated | Medical device including improved expandable balloon |
| US7279521B2 (en) * | 1999-11-10 | 2007-10-09 | Foster Corporation | Nylon nanocomposites |
| WO2001034685A1 (en) * | 1999-11-10 | 2001-05-17 | Neil Charles O | Optimizing nano-filler performance in polymers |
| US6291543B1 (en) * | 2000-05-24 | 2001-09-18 | Polyzen, Inc. | Surfacially cross-linked elastoplastic articles, and method of making the same |
| US6881209B2 (en) * | 2000-05-25 | 2005-04-19 | Cook Incorporated | Medical device including unitary, continuous portion of varying durometer |
| US6946174B1 (en) * | 2000-10-12 | 2005-09-20 | Boston Scientific Scimed, Inc. | Moisture curable balloon materials |
| DE10131729A1 (en) * | 2001-06-21 | 2003-01-09 | Albany Int Corp | Monofilament made of polyamide, textile fabric and method for producing such |
| JP5024694B2 (en) * | 2001-06-21 | 2012-09-12 | 株式会社ビーエムジー | Radiation sterilizable medical material and its use |
| US20030091646A1 (en) * | 2001-06-21 | 2003-05-15 | Shokyu Gen | Medical materials sterilized by radiation and their ways in use |
| US7001663B2 (en) * | 2001-06-21 | 2006-02-21 | Albany International Corp. | Monofilament of polyamide, flat textile product and method for producing same |
| US7993285B2 (en) | 2002-11-05 | 2011-08-09 | Boston Scientific Scimed, Inc. | Medical device having flexible distal tip |
| DE10311500A1 (en) * | 2003-03-15 | 2004-09-30 | Cooper-Standard Automotive (Deutschland) Gmbh | Pipe, especially flexible cooling water pipe |
| US20050159728A1 (en) * | 2004-01-15 | 2005-07-21 | Thomas Medical Products, Inc. | Steerable sheath |
| US20050234426A1 (en) * | 2004-04-14 | 2005-10-20 | Scimed Life Systems, Inc. | Catheter distal tip design and method of making |
| WO2007054365A1 (en) * | 2005-11-14 | 2007-05-18 | Abbott Laboratories Vascular Enterprises Limited | Method of thermal treatment of a thermally responsive material of medical devices |
| EP2072066A1 (en) * | 2007-12-21 | 2009-06-24 | Abbott Laboratories Vascular Enterprises Limited | Cross-linked polymers in medical devices |
| US9371426B2 (en) * | 2008-12-08 | 2016-06-21 | Sabic Global Technologies B.V. | Compositions having improved tribological properties, methods of manufacture thereof and articles comprising the same |
| US11760847B2 (en) | 2022-01-25 | 2023-09-19 | Green Theme Technologies, Inc. | Solid-state method for treating polyamide and polyester articles |
| CN114539484B (en) * | 2022-02-11 | 2024-03-19 | 浙江脉通智造科技(集团)有限公司 | Crosslinked nylon medical device, preparation method thereof, nylon composition and application |
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|---|---|---|---|---|
| US4031164A (en) * | 1974-06-06 | 1977-06-21 | Monsanto Company | Lactam-polyol-polyacyl lactam terpolymers |
| US4444816A (en) * | 1980-12-03 | 1984-04-24 | Raychem Corporation | Radiation cross-linking of polyamides |
| US4460445A (en) * | 1983-02-28 | 1984-07-17 | Milliken Research Corporation | Radiation-stable polyolefin compositions containing benzaldehyde acetals |
| US4451641A (en) * | 1983-06-13 | 1984-05-29 | Eastman Kodak Company | Radiation-resistant container material of poly(tetramethylene terephthalate) |
| US4617355A (en) * | 1984-06-21 | 1986-10-14 | Dsm Rim Nylon Vof | Cross-linked nylon block copolymers |
| CA1225179A (en) * | 1983-12-12 | 1987-08-04 | James D. Gabbert | Cross-linked nylon block copolymers |
| US4546152A (en) * | 1984-03-07 | 1985-10-08 | Ethicon, Inc. | Poly(p-dioxanone) polymers having improved radiation resistance |
| US4686245A (en) * | 1985-01-02 | 1987-08-11 | General Electric Company | High energy irradiated polycarbonates containing organic borates |
| US4624972A (en) * | 1985-11-25 | 1986-11-25 | The Dow Chemical Company | Gamma radiation resistant carbonate polymer compositions |
| GB8616135D0 (en) * | 1986-07-02 | 1986-08-06 | Bicc Plc | Elastomeric compositions |
| DE58900397D1 (en) * | 1988-06-07 | 1991-11-28 | Inventa Ag | METHOD FOR PRODUCING CROSSLINKED POLYAMIDE MOLDED BODIES. |
| US5198551A (en) * | 1990-04-10 | 1993-03-30 | The United States Of America As Represented By The United States Department Of Energy | Polyamide thermosets |
| US5296556A (en) * | 1990-10-30 | 1994-03-22 | Union Camp Corporation | Three-component curable resin compositions |
| US5584821A (en) * | 1992-06-02 | 1996-12-17 | E-Z-Em, Inc. | Soft tip catheter |
| US5900444A (en) * | 1996-10-08 | 1999-05-04 | Zamore; Alan | Irradiation conversion of thermoplastic to thermoset polyurethane |
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1997
- 1997-06-02 US US08/867,362 patent/US5998551A/en not_active Expired - Lifetime
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1998
- 1998-05-06 CA CA002292654A patent/CA2292654C/en not_active Expired - Fee Related
- 1998-05-06 EP EP98920304A patent/EP0986414B1/en not_active Expired - Lifetime
- 1998-05-06 WO PCT/US1998/009257 patent/WO1998055171A1/en active IP Right Grant
- 1998-05-06 JP JP11502428A patent/JP2000516992A/en active Pending
- 1998-05-06 DE DE69838837T patent/DE69838837T2/en not_active Expired - Lifetime
- 1998-05-06 AT AT98920304T patent/ATE380566T1/en not_active IP Right Cessation
- 1998-07-01 US US09/108,915 patent/US5993415A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000516992A (en) | 2000-12-19 |
| DE69838837T2 (en) | 2009-01-22 |
| DE69838837D1 (en) | 2008-01-24 |
| EP0986414B1 (en) | 2007-12-12 |
| EP0986414A1 (en) | 2000-03-22 |
| WO1998055171A1 (en) | 1998-12-10 |
| EP0986414A4 (en) | 2003-05-14 |
| CA2292654A1 (en) | 1998-12-10 |
| US5998551A (en) | 1999-12-07 |
| ATE380566T1 (en) | 2007-12-15 |
| US5993415A (en) | 1999-11-30 |
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