WO2008080613A1 - Medical devices comprising a modified polyamide - Google Patents
Medical devices comprising a modified polyamide Download PDFInfo
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- WO2008080613A1 WO2008080613A1 PCT/EP2007/011449 EP2007011449W WO2008080613A1 WO 2008080613 A1 WO2008080613 A1 WO 2008080613A1 EP 2007011449 W EP2007011449 W EP 2007011449W WO 2008080613 A1 WO2008080613 A1 WO 2008080613A1
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- Prior art keywords
- saturated
- natural number
- acid
- optionally substituted
- carboxylic acid
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- 0 BCNC(C)*C(OB)=O Chemical compound BCNC(C)*C(OB)=O 0.000 description 1
Classifications
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- 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
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- 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
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- 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
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
Definitions
- the present invention refers to medical devices comprising a modified polyamide or to modified polyamides or modified polyamide elastomers with the polyamides having high flexibility and high stress resistance, especially tensile strength or tear resistance, in addition to the good physical characteristics of the known polyamide elastomers.
- Polyamides or polyamide elastomers have been used in the polymer industry for a long time and - due to their enormous range of possible applications - are found in many branches of industrial products. Recently in the area of medicinal devices good use has been made of these materials especially in implants.
- One of the most important use of polyamide or polyamide elastomers is related to medical balloons, especially in the field of percutaneous transluminal angioplasty (PTA) or percutaneous transluminal coronary angioplasty (PTCA).
- PTA percutaneous transluminal angioplasty
- PTCA percutaneous transluminal coronary angioplasty
- the most popular polyamides used include different sorts of Nylons or mixed forms such as PEBAXTM.
- the invention thus refers to a medical device or medical devices comprising a polymer producible by contacting/mixing one or more polyamides with an at least mono-substituted ⁇ , ⁇ -di-carboxylic acid or its alkyl ester and heating to a temperature above 150° C.
- the invention further resides in medical devices comprising a polymer according to general formula IV
- the invention further refers to a polymer producible by contacting/mixing one or more polyamides with an at least mono-substituted ⁇ , ⁇ -di-carboxylic acid or its alkyl ester and heating to a temperature above 150° C.
- the invention further also resides in a polymer according to general formula IV
- the invention furthermore resides in the use of a polymer according to the invention in the production of medical devices, medical balloons, balloon material, stents, stent grafts, and catheters.
- the invention is directed to a method of treatment of a disease, like a cardiovascular disease, especially a stenosis, using in a patient, being a mammal, especially a human, in need thereof a medical device according to the invention, desirably in minimal invasive surgery like PTCA.
- the invention is directed to the use of a medical device according to the invention for the treatment of a disease, like a cardiovascular disease, especially a stenosis, especially through minimal invasive surgery like PTCA.
- a disease like a cardiovascular disease, especially a stenosis, especially through minimal invasive surgery like PTCA.
- the invention thus refers to a medical device comprising a polymer producible by contacting/mixing one or more polyamides with an at least mono-substituted ⁇ , ⁇ -di- carboxylic acid or its alkyl ester and heating to a temperature above 150° C.
- the heating is done a) already during the mixing/contacting and/or b) under protective gas atmosphere, preferably under argon and/or c) to a temperature above 200° C, preferably above 220 0 C and/or d) in 2 steps with different temperatures preferably divided by an intermediate step in which the second temperature is reached within a certain time limit and/or e) over a time period of more than 3 h, preferably of more than 4h.
- the mixing is done under protective gas atmosphere - preferably under argon - in a first heating step at more than 200° C - preferably 220 0 C - for more than 1h - preferably 2h.
- the temperature was consequently raised within 10 to 30 min - preferably within 20 min - to more than 220 0 C -preferably to 250 0 C - and the mixture was stirred for another
- Nylon Over Nylon, coming in different sorts, especially Nylon-12, the polymers of the invention show the advantage, that they are more flexible and/or have a lower water absorption. Especially the lack of flexibility is often considered as a drawback in medical devices using Nylon.
- PEBA Over PEBA (e.g. PEBAX ® ) the polymers of the invention show the advantage, that they are slightly more rigid and/or have a lower water absorption, again making them superior for the intended special use and allowing a much needed compromise balancing flexibility and rigidity.
- the material of the invention seem to show higher stability, especially if compared to the effects of thermo-oxidation shown by PEBA and/or also an improved dimensional stability.
- contacting/mixing is understood as placing the at least 2 substances (polyamide and acid) in physical contact, e.g. in a common container, optionally mixing them to increase the amount of areas in contact between the substances.
- alkyl ester of the at least mono-substituted ⁇ , ⁇ -di- carboxylic acid is understood as an ester between the acid function on one end of the acid and a C 1-6 -alkyl group.
- At least monsubstituted means either “monosubstituted” or “polysubstituted”.
- aryl is understood as meaning ring systems with at least one aromatic ring but without heteroatoms even in only one of the rings. Examples are phenyl, naphthyl, fluoranthenyl, fluorenyl, tetralinyl or indanyl, in particular 9H- fluorenyl or anthracenyl radicals, which can be unsubstituted or monosubstituted or polysubstituted.
- cycloalkyl radical or group is understood as meaning saturated and unsaturated (but not aromatic) cyclic hydrocarbons (without a heteroatom in the ring), which can be unsubstituted or mono- or polysubstituted.
- C ⁇ -cycloalkyl represents C 3 - or C 4 -cycloalkyl
- Cs-s-cycloalkyl represents C 3 -, C 4 - or C 5 -cycloalkyl
- C ⁇ -cycloalkyl represents C 3 -, C 4 -, C 5 - or C 6 - cycloalkyl
- C 3-7 -CyClOa Iky I represents C 3 -, C 4 -, C 5 -, C 6 - or C 7 -cycloalkyl
- C 3-8 - cycloalkyl represents C 3 -, C 4 -, C 5 -, C 6 -, C 7 - or C 8 -cycloalkyl
- C ⁇ s-cycloalkyl represents C 4 - or C 5 -cycloalkyl
- C ⁇ -cycloalkyl represents C 4 -, C 5 - or C 6 -cycloalkyl, C 4 .
- the cycloalkyl radicals are preferably cyclopropyl, 2-methylcyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cycloheptyl, cyclooctyl, and also adamantly.
- heterocyclyl a “heterocyclyl radical” or group or “heterocyclic ring system” is understood as meaning heterocyclic ring systems which contain one or more heteroatoms from the group consisting of nitrogen, oxygen and/or sulfur in the ring or ringsystem, and can also be mono- or polysubstituted.
- the ringsystem may consist either of only one saturated or unsaturated or even aromatic ring or may consist of 2, 3 or 4 saturated or unsaturated or even aromatic rings, which are condensed in that between two or more of the rings ring members are shared.
- heterocyclyls examples which may be mentioned from the group of heterocyclyls are furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, phthalazine, benzo-1 ,2,5-thiadiazole, imidazo-thiazole, benzothiazole, indole, benzotriazole, benzodioxolane, benzodioxane, carbazole and quinazoline.
- Optionally at least monsubstituted means either “not substituted” if the option is not fulfilled, "monosubstituted” or “polysubstituted”, and “at least monsubstituted” means either “monosubstituted” or "polysubstituted”.
- Aliphatic radicals/groups are optionally mono- or polysubstituted and may be branched or unbranched, saturated or unsaturated.
- Aliphatic radicals as defined in the present invention, include alkyl, alkenyl and alkinyl radicals.
- Unsaturated aliphatic radicals as defined in the present invention, include alkenyl and alkinyl radicals.
- Preferred aliphatic radicals according to the present invention include but are not restricted to methyl, ethyl, vinyl (ethenyl), ethinyl, propyl, n-propyl, isopropyl, allyl (2-propenyl), 1-propinyl, methylethyl, butyl, n-butyl, iso-butyl, sec-butyl, tert-butyl butenyl, butinyl, 1- methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, n-pentyl, 1 ,1-dimethylpropyl,
- alkyl radical or group is understood as meaning saturated and unsaturated, linear or branched hydrocarbons, which can be unsubstituted or mono- or polysubstituted.
- saturated alkyl encompasses e.g. -CH 3 and -CH 2 -CH 3 .
- d- 2 -alkyl represents C 1 - or C 2 -alkyl
- Ci -3 -alkyl represents C 1 -, C 2 - or C 3 -alkyl
- C 1-4 -alkyl represents C 1 -, C 2 -, C 3 - or C 4 -alkyl
- C 1-5 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, or C 5 - alkyl
- C 1-6 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 - or C 6 -alkyl
- C 1-7 -alkyl represents C 1 -
- C 1-8 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 - or C 7 -alkyl
- C 1-8 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 -,
- C 1-10 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 -, C 7 -, C 8 -, C 9 - or C 10 - alkyl and C 1-18 -alkyl represents C 1 -, C 2 -, C 3 -, C 4 -, C 5 -, C 6 -, C 7 -, C 8 -, C 9 -, C 10 -, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - or C 18 -alkyl.
- the alkyl radicals are preferably methyl, ethyl, vinyl (ethenyl), propyl, allyl (2-propenyl), 1-propinyl, methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1 ,1-dimethylpropyl, 1 ,2- dimethylpropyl, 2,2-dimethylpropyl, hexyl, 1-methylpentyl, if substituted also CHF 2 , CF 3 or CH 2 OH etc.
- substituted in the context of this invention is understood as meaning replacement of at least one hydrogen radical by F, Cl, Br, I, NH 2 , SH or OH; within that "monosubstituted” means the substitution of exactly one hydrogen radical, whereas "polysubstituted” means the substitution of more than one hydrogen radical with “polysubstituted” radicals being understood as meaning that the replacement takes effect both on different and on the same atoms several times with the same or different substituents, for example three times on the same C atom, as in the case of CF 3 , or at different places, as in the case of e.g.
- alkylene is understood as meaning a divalent alkyl group like -CH 2 - or -
- the at least mono-substituted di-carboxylic acid is selected from at least mono-substituted oxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, I .Z-heptane-dicarboxylic acid, 1 ,8-octane-di- carboxylic acid, 1 ,9-nonane-di-carboxylic acid, I .IO-decane-di-carboxylic acid, 1 ,11- undecane-di-carboxylic acid, i . ⁇ -dodecane-di-carboxylic acid; preferably from adipic acid or I .IO-decane-di-carboxylic acid.
- the at least mono-substituted di-carboxylic acid is selected from at least mono-substituted oxalic acid, malonic acid, succinic acid, fumaric acid, gluta
- n and n are independently from each other selected from a natural number and 0 and n + m is between 1 and 9, preferably between 3 and 7;
- R 2 is selected from hydrogen or d- 4 -alkyl
- R 1 is any radical, preferably a sterically voluminous group.
- a "sterically voluminous group” is understood as a radical that due to its steric effect, derived from the amount of space occupied by atoms of the molecule, does give a relatively high effect of steric hindrance.
- Steric effects arise from the fact that each atom within a molecule occupies a certain amount of space. If atoms are brought too close together, there is an associated cost in energy, and this may affect the molecule's preferred shape and chemical reaction.
- Steric hindrance occurs when the size of groups within a molecule prevents chemical reactions that are observed in related smaller molecules or may also restrict molecular geometry between adjacent groups.
- n and n are independently from each other selected from 0, 1 , 2 or 3 and n + m is 3;
- n and n are independently from each other selected from 0, 1 , 2, 3, 4, 5, 6 or 7 and n + m is 7;
- n and n are independently from each other selected from 0, 1 , 2 or 3 and n + m is 3.
- R 3 and R 3 is selected from hydrogen, while the other may be either hydrogen or C 1-4 -Alkyl;
- bonds marked by a dotted line “" ** "" may be a double bond, with the proviso, that if there are 2 double bonds they may not touch the same C-atom;
- R 1 is any radical, preferably a sterically voluminous group.
- R 1 is selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted d-e aliphatic radical; an optionally substituted Aryl; a saturated or non-saturated, optionally substituted C 3- io-Cycloalkyl; an optionally substituted heterocyclyl.
- the at least mono-substituted ⁇ - ⁇ -di-carboxylic acid is 3-tert. butyl adipic acid.
- A is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- A' is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- B and B' independently from one another are selected from H or C 1-4 - Alkyl
- x is a natural number between 1 and 24;
- x' is a natural number between 1 and 24;
- y is a natural number ⁇ 1.
- A is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -;
- A' is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -;
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11 or 5; x' is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11 or 5;
- polyamide is a structure according to general formula III,
- A is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -;
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11.
- the polyamide is selected from Nylon 6; Nylon 6,6; Nylon 11 ; or Nylon 12; preferably is Nylon 12.
- the polyamide is selected from Nylon 6; Nylon 6,6; Nylon 11 ; or Nylon 12; preferably is Nylon 12
- the at least mono-substituted ⁇ , ⁇ -di-carboxyloc acid is 3-tert. butyl adipic acid.
- the at least mono-substituted ⁇ , ⁇ -di-carboxylic acid is added in an amount resulting in a molar ratio between the acid and the polyamide (wherein the molarity of the polyamide is calculated relatively based on the equivalent number of theoretical lactam units in the polyamide) of between 0.05 and 0.0005, preferably between 0.025 and 0.001.
- the at least mono-substituted ⁇ , ⁇ -di-carboxylic acid is added in an amount resulting in a molar ratio between the acid and the polyamide calculated (wherein the molarity of the polyamide is calculated relatively based on the number and molecular weight of the polymerized amide building block
- the molar ratio results in between 0.05 and 0.0005, preferably between 0.025 and 0.001.
- reaction is executed using reactive extrusion.
- Another aspect of the invention refers to a medical device B comprising a polymer (named polymer B hereafter) according to general formula IV or IVa
- A is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- A' is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N 1 O or S;
- B and B' independently from one another are selected from H or C 1 ⁇ - Alkyl
- x is a natural number between 1 and 24;
- x' is a natural number between 1 and 24;
- y is a natural number ⁇ 1.
- z is a natural number ⁇ 1 or 0;
- n and n are independently from each other selected from 0 and a natural number between 1 and 9 and n + m is a natural number between 1 and 9;
- R i 1 is any radical, preferably a sterically voluminous group.
- B and B' independently from one another are selected from H or C 1-4 - Alkyl
- x is a natural number between 1 and 24;
- y is a natural number ⁇ 1.
- z is a natural number ⁇ 1 or 0;
- R >1 : i.s selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted C 1 - S aliphatic radical; an optionally substituted Aryl; a saturated or non-saturated, optionally substituted C 3- io-Cycloalkyl; an optionally substituted heterocyclyl.
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; preferably is 5, 10 or 11 , more preferably is 5 or 11 , most preferably is 11 ;
- z + y is between 20 and 2000, preferably 40 and 1000;
- R 1 is selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted alkyl-radical, preferably is iso-propyl or tert. butyl, more preferably is tert. butyl.
- R 1 is tert. butyl.
- the polymer or the polymer B is modified in at least one of the end groups with liquid crystalline oligomers (LCOs/LC-oligomers).
- the medical device or the medical device B according to the invention is selected from implanted or implantable medical devices, more preferably is selected from (medical) balloons or balloon material, stents, stent grafts, grafts, graft connectors or catheters.
- Balloon in the context of this invention especially means a balloon like those used in (coronary) balloon angioplasty (PTA/PTCA) and the material used for these balloons, especially balloon catheters.
- PTA/PTCA coronary balloon angioplasty
- a balloon catheter is inserted into an artery or other lumen and advanced to e.g. a narrowing in a coronary artery. The balloon is then inflated by gas or fluids to enlarge the lumen and/or - often - to place a medical device.
- Stenor means an elongate implant with a hollow interior and at least two orifices and usually a circular or elliptical, but also any other, cross section, preferably with a perforated, lattice-like structure that is implanted into vessels, in particular blood vessels, to restore and maintain the vessels patent and functional.
- “Graft” means an elongate implant with a hollow interior and with at least two orifices and usually circular or elliptical, but also any other, a cross section and with at least one closed polymer surface which is homogeneous or, optionally, woven from various strands.
- the surface preferably is impermeable to corpuscular constituents of blood and/or for water, so that the implant serves as a vascular prosthesis and is usually employed for damaged vessels or in place of vessels.
- “Stent graft” means a connection between a stent and a graft.
- a stent graft preferably comprises a vascular prosthesis reinforced with a stent (both as defined above), wherein a polymer layer is homogeneous or, optionally, woven, knitted plaited etc. from various strands and is either impermeable for corpuscular constituents of blood and/or for water or can also be permeable. More preferably, the stent has on at least 20% of its surface a perforated (lattice-like), preferably metallic, outer layer and at least one closed polymer layer that is located inside or outside the stent outer layer.
- the closed polymer layer may be homogeneous or, optionally, woven from various strands, and is impermeable for corpuscular constituents of blood and/or for water.
- a further perforated (lattice-like), preferably metallic, inner layer may be located inside the polymer layer.
- “Graft connector” means an implant that connects at least two hollow organs, vessels or grafts, consists of the materials defined for grafts or stent grafts and/or has the structure defined for the latter.
- a graft connector has at least two, three or four, orifices, arranged, for example, as an asymmetric "T" shape.
- Catheter means a tubular instrument intended for introduction into hollow organs. More preferably, a catheter may be designed for use in guiding other catheters, or for angiography, ultrasound imaging, or - especially - balloon catheters for dilatation or stent delivery. This includes also a “Catheter pump” meaning a catheter provided on its tip with a propeller able to assist the pumping of the myocardium.
- the invention resides in a polymer producible by contacting/mixing one or more polyamides with an at least mono-substituted ⁇ , ⁇ -di- carboxylic acid or its alkyl ester and heating to a temperature above 150° C.
- the proviso applies that the at least mono- substituted ⁇ , ⁇ -di-carboxylic acid may not be methyl adipic acid, preferably may not be 3-methyl adipic acid.
- the heating is done a) already during the mixing/contacting and/or b) under protective gas atmosphere, preferably under argon and/or c) to a temperature above 200° C, preferably above 220 0 C and/or d) in 2 steps with different temperatures preferably divided by an intermediate step in which the second temperature is reached within a certain time limit and/or e) over a time period of more than 3 h, preferably of more than 4h.
- the mixing is done under protective gas atmosphere - preferably under argon - in a first heating step at more than 200° C - preferably 220 0 C - for more than 1h - preferably 2h.
- the temperature was consequently raised within 10 to 30 min - preferably within 20 min - to more than 220 0 C -preferably to 250 0 C - and the mixture was stirred for another 2h.
- the at least mono-substituted di-carboxylic acid is selected from at least mono-substituted oxalic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, 1 ,7- heptane-dicarboxylic acid, 1 ,8-octane-di-carboxylic acid, 1 ,9-nonane-di-carboxylic acid, 1 ,10-decane-di-carboxylic acid, 1 ,11-undecane-di-carboxylic acid, 1 ,12- dodecane-di-carboxylic acid; preferably from adipic acid or 1 ,10-decane-di- carboxylic acid.
- n and n are independently from each other selected from a natural number and 0 and n + m is between 1 and 9, preferably between 3 and 7; ,2
- R is selected from hydrogen or C ⁇ -alkyl
- R i1 is any radical, preferably a sterically voluminous group.
- n and n are independently from each other selected from 0, 1 , 2 or 3 and n + m is 3;
- n and n are independently from each other selected from 0, 1 , 2, 3, 4, 5, 6 or 7 and n + m is 7;
- n and n are independently from each other selected from 0, 1 , 2 or 3 and n + m is 3.
- R 3 and R 3 are selected from hydrogen, while the other may be either hydrogen or C 1-4 -Alkyl;
- bonds marked by a dotted line may be a double bond, with the proviso, that if there are 2 double bonds they may not touch the same C-atom;
- R is any radical, preferably a sterically voluminous group.
- R 1 is selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted C 1-6 aliphatic radical; an optionally substituted Aryl; a saturated or non-saturated, optionally substituted C 3 . 1 0 -Cycloalkyl; an optionally substituted heterocyclyl.
- the at least mono-substituted ⁇ - ⁇ -di-carboxylic acid is 3-tert. butyl adipic acid.
- A is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- A' is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- B and B' independently from one another are selected from H or C 1-4 - Alkyl
- x is a natural number between 1 and 24;
- x' is a natural number between 1 and 24;
- y is a natural number ⁇ 1.
- A is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -;
- A' is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -; and/or
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11 or 5;
- x' is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11 or 5;
- polyamide is a structure according to general formula III,
- A is a branched or linear, saturated or non-saturated, optionally substituted divalent aliphatic group; preferably is optionally substituted alkylene; more preferably is - CH 2 -;
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; more preferably is 5, 10 or 11 , most preferably is 11.
- the polyamide is selected from Nylon 6; Nylon 6,6; Nylon 11 ; or Nylon 12; preferably is Nylon 12.
- the polyamide is selected from Nylon 6; Nylon 6,6; Nylon 11 ; or Nylon 12; preferably is Nylon 12
- the at least mono-substituted ⁇ , ⁇ -di-carboxyloc acid is 3-tert. butyl adipic acid.
- the at least mono-substituted ⁇ , ⁇ -di-carboxylic acid is added in an amount resulting in a molar ratio between the acid and the polyamide (wherein the molarity of the polyamide is calculated relatively based on the equivalent number of theoretical lactam units in the polyamide) of between 0.05 and 0.0005, preferably between 0.025 and 0.001.
- the at least mono-substituted ⁇ , ⁇ -di-carboxylic acid is added in an amount resulting in a molar ratio between the acid and the polyamide calculated (wherein the molarity of the polyamide is calculated relatively based on the number and molecular weight of the polymerized amide building block
- the molar ratio results in between 0.05 and 0.0005, preferably between 0.025 and 0.001.
- reaction is executed using reactive extrusion.
- polymer B named polymer B hereafter
- IVa general formula IV or IVa
- A is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- A' is a divalent, branched or linear, saturated or non-saturated, optionally substituted hydrocarbon chain, with optionally at least one carbonatom being replaced by a heteroatom selected from N, O or S;
- B and B' independently from one another are selected from H or Ci -4 - Alkyl
- x is a natural number between 1 and 24;
- x' is a natural number between 1 and 24; y is a natural number ⁇ 1.
- z is a natural number ⁇ 1 or 0;
- n and n are independently from each other selected from 0 and a natural number between 1 and 9 and n + m is a natural number between 1 and 9;
- R 1 is any radical, preferably a sterically voluminous group. In an embodiment of the polymer B according to formula IV or IVa the proviso applies that R 1 may not be methyl.
- B and B' independently from one another are selected from H or C 1-4 - Alkyl
- x is a natural number between 1 and 24;
- y is a natural number ⁇ 1.
- z is a natural number ⁇ 1 or 0;
- R 1 is selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted C 1-6 aliphatic radical; an optionally substituted Aryl; a saturated or non-saturated, optionally substituted C 3- 10 -Cycloalkyl; an optionally substituted heterocyclyl.
- R 1 may not be methyl.
- x is a natural number between 3 and 13, preferably is a natural number between 5 and 11 ; preferably is 5, 10 or 11 , more preferably is 5 or 11 , most preferably is 11 ;
- z + y is between 20 and 2000, preferably 40 and 1000;
- R 1 is selected from halogen; a branched or linear, saturated or non- saturated, optionally substituted Ci -4 alkyl-radical, preferably is iso-propyl or tert. butyl, more preferably is tert. butyl.
- IVa and/or V x is 11 ;
- R 1 is tert. butyl.
- the polymer B or the polymer according to the invention is modified in at least one of the end groups with liquid crystalline oligomers (LCOs/LC-oligomers).
- LCOs/LC-oligomers liquid crystalline oligomers
- Another aspect of the invention provides a process for the production of a polymer
- polyamide/s is contacted/mixed with an at least mono-substituted ⁇ , ⁇ -di-carboylic acid, preferably at least mono- substituted adipic acid, and then the mixture is heated to a temperature above 150° C.
- the at least mono-substituted ⁇ ,co-di-carboylic acid preferably the at least mono- substituted adipic acid is added in an amount resulting in a molar ratio between the acid and the polyamide calculated relatively based on the equivalent number of lactam Units in the polyamide between 0.05 and 0.0005, preferably between 0.025 and 0.001 ;
- reaction is executed using reactive extrusion.
- Another aspect of the current invention provides the use of a polymer, including polymer B, according to the invention in the production of implants or medical devices, preferably implanted or implantable medical devices, more preferably for the production of balloon/balloon material, of stents, stent grafts, grafts graft connectors or catheters.
- the invention is directed to a method of treatment of a disease, like a cardiovascular disease, especially a stenosis, using in a patient, being a mammal, especially a human, in need thereof a medical device or medical device B according to the invention, desirably in minimal invasive surgery like PTA or PTCA.
- the invention is directed to the use of a medical device or medical device B according to the invention for the treatment of a disease, like a cardiovascular disease, especially a stenosis, especially through minimal invasive surgery like PTA or PTCA.
- a disease like a cardiovascular disease, especially a stenosis, especially through minimal invasive surgery like PTA or PTCA.
- reaction of example 1 is carried out in an extruder by way of the so-called (reactive extrusion) as described in DD 276 290 A1 and Eichhorn et al. (Journal of Applied Polymer Science, Vol. 62, 2053-2060 (1996). Reaction time in each of the 2 steps is reduced to below 30 min.
- 1651 g dried Nylon 12 (with a molecular weight of approx. 26000 g/mol) is mixed with 8.25 g (0.040 mol) 3-tert. butyl adipic acid under argon for 2h at 220° C. The temperature is raised within 20 min to 250 ° C and the mixture is stirred for another 2h.
- the relative molar ratio (see above) is 0.0048, being calculated as 0.040 mol (acid) : 8.368 rel. mol (Polyamid: MW (building block) 197.3).
- Example 4 (0.25%; normal reaction) 1753 g dried Nylon 12 (with a molecular weight of approx. 26000 g/mol) is mixed with
- the relative molar ratio (see above) is 0.0025, being calculated as 0.022 mol (acid) :
- the material according to example 1 was compared to the unmodified Nylon 12 and showed better flexibility than the Nylon and seems to show - calculated based on comparison to literature standards - a higher rigidity than PEBAX®
- Example 6 yielded a brittle polymer with very poor mechanical properties, which was due to that fact not testable by the methods shown above.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Vascular Medicine (AREA)
- Surgery (AREA)
- Heart & Thoracic Surgery (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2007341621A AU2007341621B2 (en) | 2006-12-29 | 2007-12-28 | Medical devices comprising a modified polyamide |
US12/521,552 US8304498B2 (en) | 2006-12-29 | 2007-12-28 | Medical devices comprising a modified polyamide |
CN200780048655.4A CN101611075B (en) | 2006-12-29 | 2007-12-28 | Medical devices comprising a modified polyamide |
EP07857142A EP2118171A1 (en) | 2006-12-29 | 2007-12-28 | Medical devices comprising a modified polyamide |
JP2009543397A JP5337706B2 (en) | 2006-12-29 | 2007-12-28 | Medical devices containing modified polyamide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06027100.4A EP1942128B1 (en) | 2006-12-29 | 2006-12-29 | Modified polyamides |
EP06027100.4 | 2006-12-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008080613A1 true WO2008080613A1 (en) | 2008-07-10 |
Family
ID=37852350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/011449 WO2008080613A1 (en) | 2006-12-29 | 2007-12-28 | Medical devices comprising a modified polyamide |
Country Status (6)
Country | Link |
---|---|
US (1) | US8304498B2 (en) |
EP (2) | EP1942128B1 (en) |
JP (1) | JP5337706B2 (en) |
CN (1) | CN101611075B (en) |
AU (1) | AU2007341621B2 (en) |
WO (1) | WO2008080613A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8304498B2 (en) | 2006-12-29 | 2012-11-06 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a modified polyamide |
US8389646B2 (en) | 2007-05-10 | 2013-03-05 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a co-polymer of a modified polyamide and a polycarbonate |
US8492484B2 (en) | 2007-05-10 | 2013-07-23 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a co-polymer of a polyamide and a polycarbonate diamine |
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CN104710776B (en) * | 2013-12-13 | 2018-10-12 | 上海微创医疗器械(集团)有限公司 | Medical nylon composite pipe material and preparation method thereof |
AU2018280236B2 (en) | 2017-06-07 | 2024-06-06 | Shifamed Holdings, Llc | Intravascular fluid movement devices, systems, and methods of use |
US11511103B2 (en) | 2017-11-13 | 2022-11-29 | Shifamed Holdings, Llc | Intravascular fluid movement devices, systems, and methods of use |
CN112004563A (en) | 2018-02-01 | 2020-11-27 | 施菲姆德控股有限责任公司 | Intravascular blood pump and methods of use and manufacture |
US11964145B2 (en) | 2019-07-12 | 2024-04-23 | Shifamed Holdings, Llc | Intravascular blood pumps and methods of manufacture and use |
WO2021016372A1 (en) | 2019-07-22 | 2021-01-28 | Shifamed Holdings, Llc | Intravascular blood pumps with struts and methods of use and manufacture |
US11724089B2 (en) | 2019-09-25 | 2023-08-15 | Shifamed Holdings, Llc | Intravascular blood pump systems and methods of use and control thereof |
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WO2004069780A1 (en) * | 2003-02-10 | 2004-08-19 | Kyowa Hakko Chemical Co., Ltd. | Process for production of adipic acids having side chains |
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EP1942128B1 (en) | 2006-12-29 | 2016-09-14 | Abbott Laboratories Vascular Enterprises Limited | Modified polyamides |
EP1990356A1 (en) | 2007-05-10 | 2008-11-12 | Abbott Laboratories Vascular Enterprises Limited | Co-polymer of a modifed polyamide and a polycarbonate |
EP1990358B1 (en) * | 2007-05-10 | 2018-06-13 | Abbott Laboratories Vascular Enterprises Limited | Co-polymer of a modifed polyamide and a polyether |
EP1990357A1 (en) | 2007-05-10 | 2008-11-12 | Abbott Laboratories Vascular Enterprises Limited | Co-polymer of a polyamide and a polycarbonate diamine |
-
2006
- 2006-12-29 EP EP06027100.4A patent/EP1942128B1/en not_active Not-in-force
-
2007
- 2007-12-28 EP EP07857142A patent/EP2118171A1/en not_active Withdrawn
- 2007-12-28 CN CN200780048655.4A patent/CN101611075B/en not_active Expired - Fee Related
- 2007-12-28 AU AU2007341621A patent/AU2007341621B2/en not_active Ceased
- 2007-12-28 WO PCT/EP2007/011449 patent/WO2008080613A1/en active Application Filing
- 2007-12-28 JP JP2009543397A patent/JP5337706B2/en not_active Expired - Fee Related
- 2007-12-28 US US12/521,552 patent/US8304498B2/en active Active
Patent Citations (2)
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DE4301097A1 (en) * | 1993-01-18 | 1994-07-21 | Thueringisches Inst Textil | Polyamide hot-melt adhesives prodn., esp. from polyamide re-granulate |
WO2004069780A1 (en) * | 2003-02-10 | 2004-08-19 | Kyowa Hakko Chemical Co., Ltd. | Process for production of adipic acids having side chains |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US8304498B2 (en) | 2006-12-29 | 2012-11-06 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a modified polyamide |
US8389646B2 (en) | 2007-05-10 | 2013-03-05 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a co-polymer of a modified polyamide and a polycarbonate |
US8492484B2 (en) | 2007-05-10 | 2013-07-23 | Abbott Laboratories Vascular Enterprises Limited | Medical devices comprising a co-polymer of a polyamide and a polycarbonate diamine |
Also Published As
Publication number | Publication date |
---|---|
US20110082263A1 (en) | 2011-04-07 |
AU2007341621B2 (en) | 2013-06-27 |
EP2118171A1 (en) | 2009-11-18 |
US8304498B2 (en) | 2012-11-06 |
JP2010514483A (en) | 2010-05-06 |
CN101611075B (en) | 2014-06-25 |
EP1942128A1 (en) | 2008-07-09 |
EP1942128B1 (en) | 2016-09-14 |
JP5337706B2 (en) | 2013-11-06 |
AU2007341621A1 (en) | 2008-07-10 |
CN101611075A (en) | 2009-12-23 |
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