JPS58132017A - Extrudable polyurethane for prosthesis - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION In recent years, significant progress has been made in the development of vascular replacement It techniques. For example, U.S. patent f for "polyurethane elastomer for cardiac assist devices" related to Zeicher.
l14. IS'L 604til! 111I! ! ,
A family of polyurethanes is disclosed that has excellent properties for use in forming moldable prosthetics. However, one drawback of the polyurethanes disclosed in this patent is that they are not extrudable. There are many prosthetics and other devices that must be blood compatible that can be efficiently manufactured solely by extrusion or blow molding.

For example, base manufacturer leads, blood bags, catheters and 1. It is clear that devices such as V, tubes must be made of materials that meet a number of criteria. The most important criterion is that the materials from which these devices are made must be blood compatible. That is, the formation of a thrombus that could cause a defect in the peripheral blood flow must not occur. Of course, this material must be non-toxic.

In addition to the above, the device materials used to fabricate the vascular prosthesis have a high degree of elasticity, strength, and non-destructive properties.
#L It is desirable to have the ability to learn.

As mentioned above, for the fabrication of certain types of rims, it is desirable that the material be extrudable.

The present invention relates to a family of extrudable polyurethane polymers specifically designed for use in devices requiring a high degree of hemocompatibility. These polymers are characterized by consisting primarily of linear segmented aliphatic polyurethane efstomers. This group of polymers is aliphatic and polyether based with 10-row urethane bonds in the molecular backbone and exhibits excellent bending life, favorable hydrolytic stability, and high blood compatibility. show.

In addition to the above, these polymers can be pelletized,
and by extrusion such as 6-edge pacemaker leads, blood batts, catheters and I,V.

You can make various coloring devices such as tubes.

This combination of superior properties makes this group of polymers useful in devices requiring blood contacting surfaces.

Accordingly, it is an object of the present invention to provide an extrudable material suitable for use in forming devices requiring a high degree of hemocompatibility.

First of all, the invention will be described in detail in its broadest aspects. The polyurethane elastomer of the present invention comprises an aliphatic organic diisocyanate, a high molecular weight polyether polyol, and a specific low molecular weight glycol (chain extender).
It is a rubber-like reactive product with The low molecular weight glycol is t4-butanediol.

In addition to the above-mentioned required components, the reaction components preferably include a catalyst and optionally an antioxidant and an extrusion layer temperature lubricant.

Generally, polyurethane polymers are the product of a reaction between a diisocyanate and a compound having an active water bulk moiety, such as a hydroxyl group.

Diisocyanates are isocyanoxylic compounds that have two functional groups. Polymerization is performed using divalent human gastric sil compounds (
An example of an aliphatic diisocyanate useful in the present invention is hexamethylene diisocyanate) (poly6-urethane), which can be a simple glycol or a polymeric glycol. HDI) C0 0CN (CH,), NCO Isoron diisocyanate) (IPDI) Trimethylhexamethylene diisocyanate (MHDI) (i:H″ Diciterhexylmethane diisocyanate (HMDI) CM, (C・Hl・NC0) .

and dimer acid diisocyanate)t (DDI).

A preferred diisocyanate for producing φ polymers according to the present invention is dicyclohexylmethane diisocyanate (group H).

Although many aliphatic diisocyanates can be used to prepare the polymers according to the invention, numerous tests have shown that one choice for high molecular weight preols is britetramethylene ether glycol (PTMIG) H (OCH* CH
s CHm CHl ) m OH.

This molecular polyol was found to be the only polyol for producing urethane, which is chromatically compatible and has the other properties listed above. Generally, the glycol should have an average molecular weight of about 500-5.000, preferably to00-4000.

In a preferred JIli1 embodiment of the present invention, the molecular weight is 2.00.
0 PTMEG is used.

As mentioned above, the lengthening agent for the polymers of the present invention is t4-but4kale (HO-CH-CH5-CH, -
CH, -OH).

A preferred polyurethane has the following structural formula: TMEG, where 1 ml is an integer chosen to give a molecular weight between 500 and 0,000, X is a Jll number between 1 and 5, and 1 ml is 12Q. , number average molecular weight in Goo units and 51 翫00
is an integer chosen to give a weight average molecular weight of 0 molecular weight units.

As can be seen from the above formula, the polymer of the present invention has three types of repeating units, namely diol and diisocyanate! It is made from cloglycol. The relationship of these repeating units to each other is determined by the desired properties. for example,
For tubes requiring soft and elastomeric properties (70 siam), two diisocyanate repeat units and one ! for each diol. There is cloglycol. For harder materials, diols vs. diisocyanates) and! The ratio of Dalicol to alcohol can be increased to produce a harder material. for example,
For catheters (50 cylinders D), repeat 2 butanediol units for each incyanate and each matarodalichol.

These reactants are supplied in approximately the amount of liters required to form the polymer.

In order to obtain a sufficiently cured polyurethane casing in a short time comparable to gold salts, a suitable catalyst for accelerating the polymerization reaction is usually incorporated into the mixture. The catalysts include N-methylphosphorus, trimethylamine, triethylamine, lead octoate, diptyltin dilaurate, and dioctyltin ditheurate. Dioctyl dilaurate
is a suitable catalyst.

The process according to the present invention will be explained with reference to the drawings.

Polyurethanes are manufactured from two components, which can be referred to as partial membranes and partial layers.

The partial system is an aliphatic diisocyanate. Part B consists of other ingredients: mataro dalicol (polyether paste), a low molecular weight Ream #IA extender, a catalyst, an antioxidant, and a lubricant. Of course, the -1' catalyst, antioxidant and lubricant are not chemically bonded as part of the polymer.

In order to form a polyurethane member, the necessary chemical amount of cocoon is required.
The combined part and part B are emulsified at room temperature using a mixture to form a moderately reactive thixotropic mixture having a viscosity of about 500 ep* or less.

Emulsification introduces air into the reaction mixture, which must be removed. The air is removed by placing a container containing the molten carbonate under the persalt jar and evacuating the air from the bell-shaped jar with a suction device. The bell jar is evacuated to a pressure of about hspm and the mixture is placed under the bell jar for about 8 minutes to bring the mixture to a boil.

Engineering! After removing the Luzi bottle from the Permoat jar, it is allowed to stand until the exothermic reaction that is occurring brings it to a temperature of about 400°C.

At this point, the mulch is preferably poured into a pan where it is allowed to flow to form an uncured sheet. Then # place the pan containing the sheet in the open,
Heat at a temperature of at least 110° C. for 4 hours or more until the elaszimer is cured. The sheet is then cut or pelletized with a standard belt tie to produce pellets about -inch in length. These pellets are then used in suitable equipment for extrusion of the desired product.

If desired, the pellets can be dissolved in a solvent such as dimethyl aptamide, tetrahydrofuran, 1.4 dioxane and m-virol, if desired. Next, this solution can also be used to create articles by a solvent pouring method.

The invention will now be illustrated by means of non-limiting examples.

67, 75 F dicyta p hexylmethane diiso
292, a mixture of polytetofumethylene ether glycol with a molecular weight of 2,000 and 12.35f of 14-butanediol. The reaction mixture further contained 50 f of antioxidant. The antioxidant used is sold by Ciba-Geigy under the trade name Irganox 1010. The chemical name of the antioxidant is tetotex-[methylene-(45-di-t-butyl-4-hydro-dihydrocinnamic acid)]-methane. Furthermore, in this reaction mixture there is a
It also contained a dropper agent [L5f] sold under the trade name Dalicolupe VL. In addition, a tin-based catalyst α006t, sold under the trade name Kosan 430 by Kosan+noCal2 114912, Karlstad, New Jersey, was also included.

The above components were mixed with HMDI and degassed until all entrained gases were removed. The mixture was then heated under nitrogen atmosphere for 1
Cured to sheet form for 5 hours at 1 QC. The sheet was then cut with a standard pelletizer to form pellets suitable for extrusion.

The physical properties of the cured elaszimer are as follows: tensile strength 4500 psl (minimum), elongation 650, hardness (SiC) 70-75°.The pellets were then processed in an Ikkentomi extruder.

The processing conditions were determined using a 24/1 general-purpose starch with a diameter of 1 inch. 320 Die 550 Throat A tube of suitable dimensions was extruded for use in the water cooling base manufacturer lead. This tube exhibited all the desirable physical properties required for these applications.

The invention may be embodied in other forms without departing from its spirit or essential characteristics.

Accordingly, the above examples are merely for illustrative purposes; the invention is capable of many variations based on the above description, and all such variations are intended to be encompassed within the scope of the invention.

[Brief explanation of the drawing]

The drawings are explanatory views showing the process of extruding articles from the elastomer of the present invention. Procedural amendment (method) Indication of patent counterfeiter Kazuo Wakasugi case of March 18, 1980 Patent application No. 188273 invention,
) Name Relationship to case involving extrudable polyurethane correction for prosthetics Name of patent applicant
Thermo Electron Corporation Agent 〒103 Date of notice of amendment order February 22, 1981〒〒葡正π7 女 11 KE 1 1 冑ze 1r Supplementary IE subject application I7) Inventor → 1 column example bowl The scope of the claims, the detailed description of the invention, the power of attorney and its translation.
1 copy each of drawings 1 copy Contents of amendments Engraving of the drawings as shown in the attached sheet (no changes in content)

Claims (1)

[Scope of Claims] (a) A polymer for use in molding equipment requiring a high degree of liquid compatibility, comprising (a) a polyurethane elastomer, and (a) a polyurethane elastomer that is capable of containing diisocyanate and trimethyl. a diiso-cyanate selected from the group consisting of methylene diisocyanate, dicitalohexylmethane diisocyanate, and Daiiken diisocyanate; (b) ramethylene ether having a molecular weight in the range of soo to 5,000; A polymer characterized by being a reaction product of a polyol and (@)$4-butanediol. (2) A polymer according to claim 11111, wherein the diisocyanate is dicyclosilmethane diisocyanate. (5) The polymer according to claim 2, wherein the polymer is dissolved in a solvent. (4) The polymer according to claim 2, wherein the polymer is in the form of pellets. (5) Producing a polyurethane F-s dimer characterized by consisting of (a) exclusively dicyclomethane diisocyanate and (b) stoichiometric amounts of polytetramethylene ether polyol and t4-butanediol. A two-component system for