ULTRA-HIGH-MOLECULAR-WEIGHT POLYETHYLENE PRODUCTS INCLUDING VASCULAR PROSTHESIS DEVICES AND METHODS RELATING THERETO AND EMPLOYING PSEUDO-GEL STATES

Abstract: A pseudo-gel comprising a suitable solvent in an amount of 1 to 10 percent by weight and an ultra-high-molecular-weight polyethylene in an amount of 99 to 90 percent by weight, said polyethylene being a semicrystalline network with adjustable crystalline morphology comprising randomly dispersed and oriented chain-folded single crystals, stacks of single crystals, spherulite crystals, and extended-chain shish-kebab-type of fibrils with lengths up to a few millimeters and widths up to 20 mu m. Also, the semicrystalline ultra-high molecular-weight polyethylene obtained by removal of said solvent from the pseudo-gel. Further, the method for making the pseudo-gel and the ultra-high-molecular-weight polyethylene product.

Description: 1 . ULTRA-HIGH-MOLECULAR-WEIGHT POLYETHYLENE 2 PRODUCTS INCLUDING VASCULAR PROSTHESIS DEVICES AND 3 METHODS RELATING THERETO AND EMPLOYING PSEUDO-GEL STATES 4 5 S P E C .I F _I C A T I. O N 6 7 This invention relates to a novel ultra-high- 8 molecular-weight polyethylene product, useful for vascular g prosthesis devices and for both industrial and biomedical 0 uses calling for high-impact/ low-friction, high wear- 1 resistance, high-porosity, and softness or for one or more 2 of these qualities. The invention also relates to such 3 devices. It further relates to a novel method for processing solution-grown ultra-high molecular weight polyethylene 5 crystalline morphologies which may form pseudo-gel states 6 when the polymer is dissolved in a suitable volatile or 7 non-volatile solvent at an elevated temperature and the 8 solution is cooled to or below the temperature at which the 9 polymer crystals are grown. Additionally it relates to 0 methods involving further processing of the pseudo-gel 1 states and their products after solvent extraction into 2 profiles and shapes with physical and mechanical properties 3 that may be tailored to specific biomedical (e.g., vascular 4 and orthopedic prosthesis and sutures) and industrial applications. 6 7 Background of the Invention 8 Qualities such as softness, porosity, and bio- compatibility have long been sought in the field of vascular prosthesis. The development of vascular prostheses has been a subject of extensive work over the last 25 years. Most synthetic vascular prostheses have been products of the application of textile technology in this field and have been woven or knitted tubular structures designed to resemble the softness and flexibility of the natural blood vessels. The two major synthetic polymers used as vascular prostheses have been Dacron polyester and polytetra- 3 fluoroeth lene (PTFE) . * These woven or knitted tubular structures are porous and have been produced with smooth or veiour surfaces. The c. porosity, which has been claimed to play a determinant role for the healing process of the arterial prostheses, can be controlled to some extent by adjusting the thread size, or q v the interstices size, and by the texturization or knit pattern of the synthetic fabric. High degrees of porosity ^ may lead to excessive blood loss after implantation; the ■ ^ veiour has been claimed to have the advantage that it fills • " the interstices of the underlying fabric, thus reducing • ^ implant bleeding without reducing the porosity of the 5 implant. ■ * ■ " The DeBakey Ultra-light-weight Knitted Prosthesis ■ *-' (USCI, Inc.), the Cooley Graft and the Wesolowski Weavenit *-° (Meadox, Inc.) and the Microknit (Golaski Lab, Inc.) are " "smooth wall" commercial Dacron arterial prostheses of 20 different geometric and compositional configurations; the 2-*- Sauvage Filamentous Veiour Prosthesis (USCI, Inc.) is an 22 example of a veiour Dacron vascular prosthesis material. 23 Woven PTFE prostheses have low porosity and have not 24 been used as much as the Dacron prostheses. Also, it has 25 been suggested that their use should be temporary, their 26 permanent use being "dangerous". More recently, "expanded" 27 PTFE, called "Gore-tex" (W. L. Gore & Assoc, Inc.) has 28 become available. "Gore-tex" is a network of small nodules 29 interconnected by thin fibrils and with an adjustable 30 porosity from 0 to 96%, and it has been used with generally • ■ - encouraging results. Studies with smooth vascular prostheses 32 of expanded PTFE (85% porosity) and . with ultra-light weight 33 woven PTFE showed that the patency (i.e., openness or non- 34 occlusion) of the expanded PTFE prostheses was significantly 35 longer (4.5 - 10 months) in comparison to the woven PTFE 36 37 38 "^ prostheses, which occluded in 101 days. It was also demonstrated that the porosity played a critical role in the 3 healing process. 4 A recent theoretical calculation of the porosity in 5 woven fabrics shows that although their porosity can be 6 designed to vary over a wide range, the existing woven 7 vascular prostheses, e.g. Woven Cooley and Woven DeBakey 8 prostheses have had a low degree of porosity which might not 9 permit complete healing, particularly in small diameter, 10 low-blood-flow locations where the 5 year patency rate is 11 less than 30%. Λ Ultra-high-molecular-weight polyethylene (UHMWPE) is another polymer which has attracted the interest of many 14 workers for the preparation of artificial prostheses, ^ particularly the construction of orthopedic joint devices. 16 because of its outstanding abrasion resistance and strength. ^"' UHMWPE, in contrast to the conventional high-density poly- 18 ethylenes having average molecular weights up to approxi¬ 19 mately 400,000, has an extremely high molecular weight, 20 typically 2 - 8 million, and is intractable. The polymer is 21 supplied as fine powder and is processed into various 22 profiles using compression molding and ram extrusion 23 processes. The intractability of the polymer can be overcome 24 by varying the degree of material cohesion and its initial 25 morphology, more specifically by the formation of gel states 26 and single-crystal mat morphologies and by heating the 27 polymer melt to high temperature ranges, under inert 28 conditions, in which the viscosity of the melt is reduced 29 significantly for melt processing. The preparation of UHMWPE 30 gel states and single crystal mat morphologies have been ^- L pursued predominantly for the development of ultra-high 32 modulus and strength fibers. Melt processing of UHMWPE at JJ high temperatures under inert conditions has been investi¬ 34 gated for the development of melt-crystallized morphologies with enhanced mechanical properties which may result from •3 Jσ the material cohesion which is achieved by processing under ' such conditions. 38 • Although the prior art covers to a large extent the preparation of superstrong UHMWPE fibrous morphologies by spinning processes which involve a gel intermediate, the focus of the works has been mainly on the development of filamentary products with high modulus and strength in one direction. Also, there has been an expressed desire that ' such filamentary products have reduced porosity, because ° porosity may have an adverse effect on the effective ° transmission of load within the oriented filamentary ■ ^ products. On the contrary, the development of products with ■ * •■ * • bulk properties or enhanced isotropic mechanical properties • *-2 from gel-like precursors has received no attention. " Furthermore, little effort has been devoted to determining -^ the effect of the morphology of the gel-like precursor on 15 the physical properties and the deformability of the 16 products form gel-like precursors. These areas fall within • * • ' the scope of my invent ion and they have a potential impact 18 on the production of biomedical devices such as vascular and • * ■ ' orthopedic prostheses and sutures and also on the 20 fabrication of profiles possessing the outstanding wear 21* properties of UHMWPE. 22 An example of a stretched UHMWPE fiber and a process 23 for making it is U.S. Patent No. 4,413,110. There a slurry 24 of polymer in paraffin oil is heated to between 180° and 25 250 O C, preferably 200°-240°C. and is then cooled to a 26 temperature between -40°C and +40°C. , the paraffin oil being 27 replaced by a more volatile solvent at a temperature below 28 50oc. and the cooling being rapid and done in such a way as 29 to produce a "gel fiber". This "gel fiber" is then treated 30 to evaporate the more volatile solvent and to stretch the 33- "xerogel" fiber, as it is called, at 12QOC + 160°C. 32 preferably above 135°C. The porosity of the resultant fiber 33 is stated to be "no more than about 10% (preferably no. more 34 than about 6% and more preferably no more than about 3%)". 35 36 37 .8 S_ummary of the Invention *" The present invention includes the formation and use J of UHMWPE pseudo-gels. ^ The term gel in the prior art referred to a macro- scopically coherent structure, that (1) is spatially cross- *. linked, (2) comprises a major amount of low molecular-weight 7 liquid, and (3) exhibits elastic properties not unlike those 8 of solids. q On the contrary, in this specification and in the 0 claims the terms "pseudo-gel" and "gel-like" refer to a ■ ^ concentrated solution of organic polymer which contains an entangled three-dimensional semicrystalline network the • ^ morphology of which may vary with the conditions of ■ ^ preparation or crystallization, for example, when the "* pseudo-gel of this invention is prepared under isothermal ** • " and quiescent conditions, the crystals in the pseudo-gel • * • ' have predominantly a lamellar morphology, with single 18 crystals on spherulitic crystals. The number of single 19 crystals decreases, and the crystalline morphology becomes 20 more complex as the solution concentration increases. On the 21 other hand, when the pseudo-gel of this invention is 22 prepared under non-isothermal and quiescent conditions, a 23 large fraction of extended chain crystals (shish-kebab 24 crystals) are also present. However, because the molecular 25 entanglements in this semicrystalline network are not 26 permanent, such solutions undergo flow when a shear stress, 27 no matter how small, is applied. Therefore, such pseudo-gels 28 exhibit time-dependent elastic properties and are not true 29 gels, as the term is properly used, because they do not 30 possess an equilibrium shear modulus. ^ In contrast to the prior art, the present invention 32 provides for the preparation of an UHMWPE crystalline 33 morphology with isotropic mechanical properties from a 34 pseudo-gel precursor. Different crystalline morphologies are 35 obtainable under different processing conditions. This 36 crystalline morphology has an enhanced porosity which cannot 37 8 1 be exhibited by melt-crystallized morphologies, and it is readily deformable in the solid state into products with different properties in one or more directions. ^ This invention .provides a method for the preparation of UHMWPE vascular prostheses by processing the UHMWPE in the pseudo-gel state. The pseudo-gel is prepared by dissolving a suitable concentration of the polymer in a suitable solvent, preferably a non-volatile solvent, at an ° elevated -temperature well above the temperature at which the ■ *"0 pseudo-gel forms and then cooling to or below the ϋ temperature at which the polymer crystals grow and the 1 pseudo-gel forms. The pseudo-gel is subsequently processed 13 under compression or tension into products of different 14 profiles. Extraction of the solvent from the shaped pseudo- ■ " gel products leads to semi-crystalline porous morphologies 16 with geometrical configurations analogous to those of their • *-' pseudo-gel precursors. These morphologies may be processed 18 further, at a temperature below or close to their melting 1 point. 20 This invention provides also a method for the 1 construction of vascular prostheses by (a) compressing the 22 pseudo-gels into thin films between hot plates, e.g., at 23 100-170°C, (b) wrapping the pseudo-gel film around a ^ rotating mandrel into a multilayer tubular structure, and is 4J (c) extracting the non-volatile solvent from the tubular ^° structure on the mandrel, for example extracting first with 2' a more volatile solvent and then drying out the tubular ΛO structure by evaporating the more volatile solvent. 2' This invention also provides for the preparation of 30 anisotropic UHMWPE morphologies with enhanced mechanical 3 properties, obtained by solid-state deforming, i.e., at a 3 temperature near or below the melting point of UHMWPE, the 33 semicrystalline polymer after extraction of the solvent, by 3^ extrusion, drawing, molding, and forging techniques. 35 36 37 8 This invention also provides for the preparation of an UHMWPE semicrystalline material which has adjustable 3 porosity from zero up to more than 90%. This material can be made with sufficient body to maintain its shape and cross- 5 sectional area; it is uniformly expansive and readily deformable to generate products with bulk properties, in ' contrast to filamentary products. 8 Brief Description of the Drawings 0 Fig. 1 is a flow sheet of a process embodying the 2 principles of the invention. 3 1 " Fig. 2 is a flow sheet of another process embodying 1 the principles of the invention. 16 1' Fig. 3 is a flow sheet of a third process embodying 1° the principles of the invention. 19 0 Fig. 4 is an optical photomicrograph at about lOOx 21 of a UHMWPE pseudo-gel morphology prepared under non- 9 ■ ^9 isothermal and quiescent conditions (N Q) . The morphology W s viewed with cross-polarized light. 24 ^ Fig. 5 is a reproduction of a scanning electron 2° micrograph of a UHMWPE semicrystalline morphology obtained 27 from the pseudo-gels after solvent extraction and drying, ώσ according to the invention, the pseudo-gel having been 2° prepared under isothermal and non-quiescent conditions 30 (INQ). 31 3 Fig. 6 is a similar scanning electron micrograph 3 reproduction of a greater enlargement of the same kind of 3 UHMWPE semicrystalline morphology of this invention the 35 pseudo-gel having been prepared under isothermal and non- 36 quiescent conditions .(INQ)-. 37 8 1 Fig . 7 is an optical photomicrograph at about lOOx 2 of a UHMWPE pseudo-gel morphology obtained under i sothermal 3 and non-quiescent condi tions ( INQ) . The morphology was * viewed with cross-polar ized light. 5 ° F ig . 8 is a similar scanning electron micrograph reproduction of a semicrystalline UHMWPE morphology of the invention obtained from the pseudo-gel after solvent ° extracting and drying, the pseudo-gel having been prepared " under isothermal and quiescent conditions ( IQ) . 1 Fig . 9 is an optical photomicrogr aph at about l OOx of a UHMWPE pseudo-gel morphology obtained under isothermal ^" and quiescent cond itions ( IQ) . The morphology was v iewed 5 with cross-polar ized light. 6 ' Fig. 10 is a graph plotting Young's modulus versus ° draw ratio for a UHMWPE of this invention. The solid-line 5 curve represents observed values and the broken-line curve 0 shows estimated maximum values for the UHMWPE of this 1 invention. 2 3 F ig . 11 i s a simi lar g raph for a conventional - polyethylene , but not a UHMWPE. 5 6 Description of Some Preferred Embodiments of the Invention ' As shown in Fig. 1, an UHMWPE pseudo-gel according 8 to this invention may be prepared from a raw UHMWPE powder 9 20 by dissolving the UHMWPE in a solvent at 21, preferably a 0 non-volatile solvent such as paraffin oil, in a temperature 1 range from 140 - 170°C, preferably in the high end of the 2 temperature range in order to disrupt the thermally 3 per s istent ex tended chain morphology of the raw UHMWPE 4 powder and decrease the number of 'nucleation s i tes which 5 allow for the prepar ation , upon cooling , of large lamellar ° single crystals . These are known to have a more regular 7 cha in folded crystalline morphology than melt-crystallized 8 and solution-grown crystal morpholog ies obtained by rapid cooling , and there fore have fewer inter cry stall ine and 3 intracrystalline tie molecule s. Such tie molecules affect the deformation behavior of the semicrystalline morphologies that are obtained after extraction of the solvent from the pseudo-gel. 7 An UHMWPE used in th is wor k was a HiFax 1900 8 (Hercules, Inc.) with an average molecular weight of 2 - 8 x ^ 10 6 . The UHMWPE was added slowly to the paraffin oil (MCB 0 Reagents, EM Science, PX 0045-3) to concentrations from 1 to 11 8% by weight. To avoid degradation of the polymer at high 12 temperatures, the polymer is preferably stabilized with 13 approximately 0.5 wt. % (based on the polymer) of BHT 1^" antioxidant (butyl hydroxy toluene) and heated under inert 15 conditions.The mixtures were stirred slowly under constant 1° conditions at a temperature of 150°C. A solution 22 was I' obtained that appeared clear until it was cooled in step 23 1° to a temperature of approximately 123°C, where it became ' opaque as the pseudo-gel was formed. 20 The uniformity of a so-produced UHMWPE pseudo-gel 24 21 depends on the conditions of preparation. When the crystals 22 are grown in the concentrated solution under non-isothermal 23 and quiescent conditions, herein called NIQ, the UHMWPE ^ pseudo-gel is non-uniform and is comprised of a mixture of S *" J single crystals and a fibπllar network in which the fibrils 2° have a shish-kebab crystalline morphology; the shish kebab 27 fibrils in the UHMWPE pseudo-gel can be up to 2 - 3 mm. long 2° and 20 μm. wide. This non-uniform structure is shown in Fig. 9 4 . 0 The semicrystalline morphologies in Figs. 5 and 6 31 were obtained from the pseudo-gel shown in Fig. 7 which was 32 prepared under isothermal and non-quiescent conditions, 3 herein called INQ. These semicrystalline morphologies were 3 prepared by solvent extraction of the pseudo-gel followed by JJ drying. Fig. 5 is a scanning electron micrograph of such a 3 « semicrystalline morphology; the degree of magnification is shown by the white bar which corresponds to 0.1 mm. in the 38 1 actual semicrystalline morphology. A further magnification 2 is shown in Fig. 6, when the white bar corresponds to 10 μm. Fig. 7 is taken from an optical photomicrograph of the ^ pseudo-gel at about lOOx and shows a typical shish-kebab 5 fibrillar structure surrounded by randomly oriented single ° crystals and stacks of single crystals, as viewed with cross-polarized light. ° Thus, UHMWPE pseudo-gels prepared under either non- 9 isothermal or non-quiescent conditions exhibit remarkable 0 continuity and resistance to shear deformation. 1 The pseudo-gel shown in Fig. 9 was prepared under 2 isothermal and quiescent conditions, herein called IQ. hen 3 the pseudo-gelation process occurs under isothermal and 4 quiescent conditions, the pseudo-gel is more uniform, has a 5 more turbid texture, and consists mainly of stacks of single 6 crystals and large spherulitic crystals (up to 200 μm in 7 diameter) with a significantly diminished fraction of shish 8 kebab fibrils, and resistance to shear deformation. Fig. 8 9 is a scanning electron micrograph of the semicrystalline 0 morphology obtained by solvent extraction and drying of a 1 pseudo-gel like that of Fig. 9. ^ The different crystalline morphologies of the UHMWPE 3 pseudo-gels obtained under different conditions of 4 preparation can be ascertained also by the thermal behavior 5 of the semicrystalline UHMWPE products which are obtained by 6 extracting, in step 25, the paraffin oil from the pseudo-gel 7 precursor with a more volatile solvent such as hexane, and 8 subsequently evaporating out, step 26, the volatile solvent 9 off in a drying process, leaving a semicrystalline UHMWPE 0 morphology 27. The results of the thermal analysis are 1 summarized in Table I. 2 3 4 5 6 7 8 1 TABLE I 2 Thermal analysis data of semicrystalline ^ UHMWPE morphologies from gel-like precursors 5 of different concentrations and different 6 processing histories. 7 8 Gel concentration Tm Crystallinity 9 (%W/W) (°C.) (%) 10 11 2 137 72 12 3 136.5 76 13 4 136.4 72 14 5 137 75 15 5* 129.8 73 16 17 18 * Pseudo-gel preparation under isothermal and quiescent 19 conditions. 20 21 The first column of Table I indicates the percent 22 concentration of the gel-like precursor, the second column n "" the melting temperature of the semicrystalline morphologies 24 after the evaporation of the volatile solvent, and the third 25 column the percent crystallinity of these semicrystalline 26 morphologies. The melting endotherms were obtained at 27 5°C./min. under N2 and the degree of crystallinity was 28 calculated, assuming that the heat of crystallization of a 29 perfect polyethylene crystal is 293 J/g. 30 The thermal analysis results indicate that the melting temperature of the semicrystalline structures is independent 32 of the concentration of the gel-like precursors which were 33 obtained under non-isothermal non-quiescent conditions; 34 however, it is lower when the gel-like precursor was 35 prepared under isothermal and quiescent conditions. The 36 higher melting endotherm of the crystalline structures at 37 approximately 137 Q C. from pseudo-gels which were prepared 38 under non-isothermal or non-quiescent conditions indicates that the crystals should have an extended chain configuration and is in agreement with the optical observations (e.g.. Fig. 4) that so-produced pseudo-gels are comprised to a large extent of a shish kebab fibrillar network. The lower melting endotherm of the crystalline ° structure at 129.9°C. from a gel-like precursor which was 5 prepared under isothermal and quiescent conditions (see 10 Figs. 8 and 9) indicates that the crystals in this case have 11 a chain-folded configuration, and, again, this is in 1 agreement with the observation that the isother ally 1 produced pseudo-gels under quiescent conditions are 1^" comprised of chain-folded crystals, like the stacks of 15 single crystals and spherulites shown in Figs. 8 and 9. 16 Also, it is clear from the data in Table I that the percent 17 crystallinity of the semicrystalline structure is indepen- 18 dent of the studied concentration range of its gel-like 19 precursors as well as its processing history. 20 A semicrystalline UHMWPE structure which is prepared AJ* from a pseudo-gel intermediate combines morphological 22 features which cannot be exhibited by the morphologies 23 obtained either by compacting the as-received fine powder 24 stock or by melt crystallization. These morphological 25 features arise from (a) the controlled material cohesion 26 which is incomplete in the compacted powders and the melt- 27 crystallized morphologies prepared by partial fusion. 28 (b) the d iminished , vis at vis the excess ive , "amount of 29 physical entanglements" in the melt-crystallized morpholo¬ 30 gies prepared by complete melting , and (c) the great 3 variation of the crystalline morphology, from a chain-folded JA to an extended chain crystalline morphology, depending on 33 the processing cond itions dur ing the preparation of the 34 pseudo-gel precursor . The importance of the first two 35 factors relates to the balanced enhancement of the de form- , 36 ability of the semicrystalline structures from gel-like 37 precursors and their mechanical properties. The role of the 38 third factor, and particularly the generation of a fibrillar network, comprised of extended-chain shish-kebab crystals, 3 is important because such structure has a larger amount of free volume and consequently a high degree of porosity. In comparison to the knitted and woven textures whose porosity can be adjusted to some extent by the thread size, interstices size, and the texturization of the synthetic fabric, the intrinsic fibrillar networks of this invention Q . . . . 7 have the advantage that their porosity can be adjusted by 0 thermal and mechanical means. 1 Thermal treatment may be brought about by heating the 2 semicrystalline structure from a gel-like precursor to a temperature close to or above the melting point of the * polymer and then cooling to ambient under modest compression 5 m <_ approximately 50 Atm) . This treatment resulted in a 6 significant porosity reduction. 17 Similarly, when a semicrystalline- structure from a 18 gel-like precursor was compressed at ambient temperature 19 under 500 Atm, its porosity was reduced as a result of the 20 densification process that takes place during the 21 compression process. 2 The porosity of the semicrystalline structure from a 2 gel-like precursor may be controlled also by the evapora- 2 " tion rate of the volatile solvent during the drying process s well as by solid-state deformation. The effects of " •σ pressure, temperature, and solid-state deformation on the Δ 27 / percent porosity of UHMWPE semicrystalline morphologies from 28 gel-like precursors of different concentrations are 29 summarized in Table II. 30 31 32 33 34 35 36 37 38 1 TABLE II 2 The effect of temperature, pressure and solid 4 state deformation on the percent porosity of UHMWPE semicrystalline morphologies from gel- 6 like precursors of different concentrations. 7 8 UHMWPE Sample Porosity (%) 9 ° NIQ - pseudo-gel, 1% 90.5 1 NIQ - pseudo-gel, 2% 51 2 NIQ - pseudo-gel, 4% 63 3 SSD - pseudo-gel, 4%/DR = 4 . 49 NIQ - pseudo-gel, 5% 49 SSD - pseudo-gel, 5%/DR = 8 40 6 INQ - pseudo-gel, 5% 78 7 IQ - pseudo-gel, 5% 79.5 ° NIQ - pseudo-gel, 5%/compressed under 500 Atm 0.2 9 NIQ - pseudo-gel, 5%/heated to 140°C./50 Atm 8.7 0 NIQ - pseudo-gel, 8% 49 1 melt crystallized 7.3 2 3 NIQ = non-isothermal and quiescent conditions ^ INQ = isothermal and non-quiescent conditions iQ = isothermal and quiescent conditions. SSD = solid state deformed DR = draw ratio 8 9 The porosity was calculated from density 0 determination, assuming that the density of polyethylene is 1 960 kgm" 3 . The symbol NIQ indicates that the gel-like 2 precursor was prepared under non-isothermal and quiescent 3 conditions; INQ indicates that the gel-like precursor was prepared under isothermal and non-quiescent conditions; and iQ indicates that the gel-like precursor was prepared under 6 isothermal and quiescent conditions. SSD indicates a 7 semicrystalline morphology from an NIQ-pseudo-gel which was 8 de formed in the sol id state by tens i le drawing at ambient temperature and at the indicated Draw Ratio (DR) de termined by the cross-sectional areas before and after drawing . The data in Table II ind icates clearly that the poros i ty of the semi crystalli ne UHMWPE morpho log ies from gel-like precursors depends on the cond itions of prepara¬ tion and can be adjusted over a wide range from 0 to 90% by o a suitable choice of temperature and pressure , and solid- Q state deformation. 0 As shown in Fig. 2, UHMWPE pseudo-gel states contain- 1 ing preferably a non-volatile solvent can be processed by 1 molding or rolling under compression in step 31 to obtain 1 thin gel-like film 32, preferably in a temperature range close to or above the temperature at which the pseudo-gel is formed (approximately 123°C.). Subsequently, the thin 1" pseudo-gel film 32 can be wrapped in step 33 with or without tension on a mandrel to give a multilayer tubular structure", I8 a process which allows also for the build up of the tubular wall thickness. Cohesion of the successive pseudo-gel layers on w is achieved by a molecular reptation process which may occur * ■ * ■ between adjacent layers and result in a tubular wall with II fraying resi.stance. 23 The volatile solvent such as n-hexane replaced the 24 non-volatile solvent in step 25 and is removed by evapora¬ 25 tion in step 34, to give a moderately shrunk, hoop stressed 26 structure 35, in a drying step. Typically, the evaporation 9 *"7' of the volatile solvent from the pseudo-gel is accompanied 28 by considerable shrinkage, which when constrained has the 29 advantage of resulting in the development of hoop stresses 30 which enhance (a) the molecular chain orientation in the 31 circumferential direction and consequently the lateral 32 strength of the tubular structures and (b) the molecular ^^ chain interpenetration in the overlapping pseudo-gel layers, 3 thus resulting in a coherent tubular wall. ^5 Further enhancement of the mechanical performance of 36 the tubular structures can be achieved by solid-state J/ drawing in step 36 of the hoop-stressed dried tube 35. The 8 . - 16 - . ' • ■ 1 process may result in tubular products 37 having a biaxially oriented fibrillar network structure with mechanical 3 integrity along and across the draw direction. This 4 integrity results from the superposition of the circu feren- 5 tial orientation, which is obtained by the constrained shrinkage during the evaporation of the volatile solvent, and the axial orientation during the solid-state deformation process on the mandrel. The solid-state deformation 'was performed at ambient temperature, and the draw ratio (DR) was calculated from the displacement of markers on the 1 tubular wall after drawing. 12 Fig. 10 shows in a solid line curve average experi¬ 13 mental modulus values at different draw ratios. The 1 variation of experimentally determined initial modulus with 15 the draw ratio is non-linear for the solid-state-drawn 1 UHMWPE semicrystalline morphologies of this invention to a 17 draw ratio of 8, in contrast to the previously established 1° linear relation for melt-crystallized, high-density (not 1 ultra-high molecular weight) polyethylene resins shown in 20 Fig. 11; the difference is presumably due to the high 21 porosity of the UHMWPE semicrystalline morphologies, in 22 comparison to the low-porosity, melt-crystallized, high- 23 density polyethylenes, which diminishes and allows for 24 effective load transmission at significantly higher draw- 25 ratios. Fig. 10 shows in a broken-line curve a graph of 26 experimentally determined maximum initial modulus values 27 ' from my new material at different draw ratios. no ° Fig. 3 shows a process much like that of Fig. 2. 29 7 Pieces of pseudo-gel 40 are compressed at step 41 to make a 30 gel-like sheet 42. The sheet 42 is wrapped around a mandrel 3 43 to produce a gel-like tube 44, which is then extracted 32 t 45 to give a dry tube 46. This may be further processed, 33 as at 47, as by drawing, or may be received from the mandrel 34 43 o give a vascular product 48. c JJ Alternative methods for the preparation of tubular 36 products with a biaxially oriented fibrillar ne-twork 37 structure include processes such as solid-state extrusion .8 1 through inverted conical dies and blowing air through the 2 tubes. Both processes are also suitable for the preparation 3 of biaxially oriented UHMWPE films which can be obtained by 4 splitting the biaxially oriented tubes along their length. Also, some or most of the conventional thermoplastic processes, such as rolling, extrusion, drawing, compression molding, forging, and extrudo-rolling are amenable to Q processing UHMWPE semicrystalline morphologies from gel-like 9 precursors into products with different profiles and geometric configurations and with adjustable mechanical 1 properties over a wide range. 12 Tests .in vivo indicate that artificial vascular 13 prostheses made by this process can be handled conveniently 14 and sutured to the natural vascular system readily. The 15 vascular prostheses, isotropic UHMWPE semicrystalline tubes 16 approximately 5 - 6 cm. long were implanted in the iliac 17 aorta of mature dogs for an observation period of up to four 1° months and exhibited very satisfactory anastomosis. Bleeding 19 through the wall of the prosthesis was not observed during 20 the implantation process. The prostheses are uniformly 21 expansive under the pulsatile blood pressure and are 22 flexible so that they bend without sharp corners. They do 3 n ot show aneurysms at and beyond the anastomatic interfaces 24" or along their body. (Aneurysms are local and progressive 25 enlargements of vessel because of loss of vascular 26 elasticity.) The vascular prostheses of this invention can be 98 ° fabricated in different geometric configurations, straight, 9 crimped, smooth, or rough wall surfaces with adjustable porosities and mechanical properties over a wide range. 31 Furthermore, this invention includes within its scope the 2 use of isotropic and anisotropic UHMWPE morphologies from 33 gel-like precursors in other biomedical application, such " as orthopedic prostheses, sutures, and ligatures, in which 35 a suitable combination of porosity and mechanical properties is necessary. 37 38 1 Other polymers which fall in the same category and 2 can be obtained from gel-like precursors are ultra-high- 3 molecular-weight polypropylene, polyvinyl alcohol, and 4 nylons (polyamides) . 5 To those skilled in the art to which this invention 6 relates, many changes in construction and widely differing 7 embodiments and applications of the invention will suggest Q ° themselves without departing from the spir it and scope of the invention. Such embodiments may include the fabrication 0 of UHMWPE knitted and woven vascular prostheses , sutures , 1 and composite structures of UHMWPE filamentary an non- 2 filamentary semicrystalline morphologies. The disclosures 3 and the descriptions herein are purely illustrative and are 4 not intended to be in any sense limiting. What is claimed is : 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8

Claims: 1 1. A pseudo-gel comprising a suitable solvent in an 2 amount of 1 to 10 percent by weight and an ultra-high- 3 molecular-weight polyethylene in an amount of 99 to 90 percent by weight, said polyethylene being a semicrystalline network with adjustable crystalline morphology comprising randomly dispersed and oriented chain-folded single crystals, stacks of single crystals, spherulite crystals,' ° and extended-chain shish-kebab-type of fibrils with lengths q up to a few millimeters and widths up to 20 μm. 10 1 2. The semicrystalline ultra-h igh molecular-we ight 1 polyethylene obtained by removal of said solvent from the pseudo-gel of claim 1. 14 15 3. A semi crystalli ne morphology of ultra-high- 1 molecular-weight polyethylene compr ising randomly disper sed 1 and or iented sing le crystals , stacks of single crystals , ° spherulitic crystals, and shish-kebab-type of fibr ils wi th 19 lengths up to a few millimeters and widths up to 20 μm. , a 20 melting point of 125 - 140°C. , measured at a heating rate of 21 5θC./min., a crystallinity of about 70%, measured on the 22 basis that the heat of fusion of a perfect polyethylene no ^ J crystal is 293 J/g. , and a porosity from about 50 to 90%, 24 measured on the basis that the density of polyethylene is 27 ' 4. A method for making an ultra-high-molecular-weight 28 polyethylene product for use in vascular prostheses and the 29 like, comprising, 30 dissolving ultra-high-molecular-weight polyethylene in a solvent at an elevated temperature, 32 cooling the solution to temperature at which polymer crystals grow into an intercrystalline network that produces 34 a pseudo-gel state, and 35 extracting the solvent to produce a semi-crystalline 36 porous morphology. 37 8 5. The method of claim 4 wherein the cooling step is done under non-isothermal, quiescent conditions. 3 6. The method of claim 5 followed by drawing the semicrystalline morphology resulting from the extracting step, at a draw ratio of at least 5 and at a temperature in the range from ambient temperature to a temperature not o exceeding the melting point of said semicrystalline q morphology. 10 11 7. The method of claim 5, comprising, between the 12 cooling and extracting steps, the step of compressing the 13 gel. 14 15 8. The method of claim 4 wherein the cooling step is 1 done under isothermal, noή-quiescent conditions. 17 1° 9. The method of claim 4 wherein the cooling step is 5 done under isothermal, quiescent conditions. 20 4 9 1 1 10. A method for making an ultra-high-molecular-weight 99 polyethylene product for use in vascular prostheses and the 23 like, comprising, 24 ^ dissolving ultra-high-molecular-weight polyethylene in 25 a non-volatile solvent at an elevated temperature, ° cooling the solution to temperature at which polymer 27 . crystals grow i.nto an mtercrystallme network that produces 28 a pseudo-gel state, and 29 ^ extracting the non-volatile solvent to produce a semi- ° crystalline porous morphology. 31 r\ *y """ 11. The method of claim 10 wherein the cooling step is O JJ done under non-isothermal, quiescent conditions. 34 35 36 37 38 12 . The method of cla im 11 followed by dr aw ing the resulting product at a temperature no lower than amb ient and no higher than the melting point of the semicrystalline porous morphology and at a draw ratio of at least 5. 5 ° 13. The method of claim 11, comprising, between the cooling and extracting steps, compressing the gel between 8 plates at 100° to 160°C. 9. 14. The method of claim 10 wherein the cooling step is 1 done under isothermal, non-quiescent conditions. 12 13 15. The method of claim 10 wherein the cooling step is 1 done under isothermal, quiescent conditions. 15 1 16. A method for making a tubular profile of ultra- 1 high-molecular-weight polyethylene with adjustable wall 18 thickness, comprising the successive steps of 19 wrapping an ultra-high-molecular-weight polyethylene ΛU pseudo-gel containing nonvolatile solvent on a mandrel, 21 extracting the solvent from the pseudo-gel with a more 9 ώΛ 9 volatile solvent , and 23 evapo ra t ing the vo lati le so lvent f rom the tubu lar 24 profile . 25 2° 17. The method of claim 16, comprising making an 27 anisotropic ultra-high-molecular-weight polyethylene tubular 2° structure by following the evaporating steps with the step 29 of stretching the tube on the mandrel. 30 31 18. The method of claim 17 in which the temperature of 32 stretching is from ambient temperature to the melting point 3 of the semi-crystalline porous morphology obtained after the evaporating step. 35 19. The method of claim 17 in which the draw ratio is 7 at least 5x. 38 1 20. A method for making a tubular profile of ultra- 2 high-molecular-weight polyethylene with adjustable wall 3 thickness, comprising the steps of: 4 dissolving said ultra-high-molecular-weight poly- 5 ethylene in non-volatile solvent at an elevated temperature, cooling the solution to temperature at which polymer ' crystals grow into an intercrystalline network that provides ° a pseudo-gel, wrapping the gel around a mandrel, 0 extracting the non-volatile solvent from the gel with a volatile solvent, and 2 evaporating the volatile solvent from the tubular 3 profile. 4 5 21. The method of claim 20 followed by stretching the tube on the mandrel at a temperature from ambient to 135°C. 7 and at a draw ratio of at least 5x. 8 9 22. A tube of ultra-high-molecular-weight polyethylene 0 semicrystalline morphology useful for vascular prostheses 1 and having a Young's modulus of at least 3 GPa obtained by 2 wrapping an ultra-high-molecular-weight polyethylene pseudo- 3 gel on a mandrel, extracting the solvent with more volatile 4 solvent and evaporating volatile solvent. 5 6 23. The tube of claim 22 in which the porosity is 7 adjustable over the range of 0.2% to 90%. 8 9 24. A pseudo-gel comprising a suitable solvent in an 0 amount of 1 to 10 percent by weight and an ultra-high- molecular-weight polymer in an amount of 99 to 90 percent by 2 weight, said polymer being a semicrystalline network with adjustable crystalline morphology comprising randomly 4 dispersed and oriented chain-folded single crystals, stacks 5 of single crystals, spherulite crystals, and extended-chain 6 shish-kebab-type of fibrils with lengths up to a few 7 millimeters and widths up to 20 μm. 8 1 25 . The semi crystalli ne ultra-high molecular-weight o polymer obtained by removal of said solvent from the pseudo- o J gel of claim 24. 4 26. A semicrystalline morphology of ultra-high- molecular-weight polymer comprising randomly dispersed and oriented single crystals, stacks of single crystals, spherulitic crystals, and shish-kebab-type of fibrils with g lengths up to a few millimeters and widths up to 20 μm. , a 10 melting point of 125 - 140°C, measured at a heating rate of 11 5°C./min., a crystallinity of about 70%, and a porosity from about 50 to 90%. 13 14 27. A method for making an ultra-high-molecular-weight 15 polymer product for use in vascular prostheses and the like, 1 ■L 6 σ compri•si•ng, 17 dissolving ultra-high-molecular-weight polymer in a 18 solvent at an elevated temperature, 19 cooling the solution to temperature at which polymer 20 crystals grow into an intercrystalline network that produces 2 a pseudo-gel state, and " 2"2* extracti.ng • the solvent to produce a semi-crystalline n o porous morphology. 24 25 28. The method of claim 27 wherein the cooling step is 26 done under non-isothermal, quiescent conditions. 27 28 29. The method of claim 28 followed by drawing the 29 semicrystalline morphology resulting from the extracting 30 step, at a draw ratio of at least 5 and at a temperature in 31 the range from ambient temperature to a temperature not 2 exceeding the melting point of said semicrystalline morphology. 34 35 30. The method of claim 28, comprising-, between the' 36 cooling and extracting steps, the step of compressing the" 37 gel. 38 1 31. The method of claim 27 wherein the cooling step is 2 done under isothermal, non-quiescent conditions. 3 4 32. The method of claim 27 wherein the cooling step is done under isothermal, quiescent conditions. 6 ' 33. A method for making a tubular profile of ultra- ° high-molecular-weight polymer with adjustable wall 9 thickness, comprising the successive steps of 0 wrapping an ultra-high-molecular-weight polymer pseudo-gel containing nonvolatile solvent on a mandrel, 2 extracting the solvent from the pseudo-gel with a more 3 volatile solvent, and 4 evaporating the volatile solvent from the tubular profile. 6 7 34. The method of claim 33, comprising making an 8 anisotropic ultra-high-molecular-weight polyethylene tubular 9 structure by following the evaporating steps with the step 0 of stretching the tube on the mandrel. 1 2 35. The method of claim 34 in which the temperature of 3 stretching is from ambient temperature to the melting point 4 of the semi-crystalline porous morphology obtained after the 5 evaporating step. 6 7 36. The method of claim 34 in which the draw ratio is 8 at least 5x. 9 0 37. A method for making a tubular profile of ultra- 1 highrmolecular-weight polyethylene with adjustable wall 2 thickness, comprising the steps of: 3 dissolving said ultra-high-molecular-weight poly¬ 4 ethylene in non-volatile solvent at an elevated temperature, 5 cooling the solution to temperature at which polymer 6 crystals grow into an interσrystalline network that provides 7 a pseudo-gel, 8 1 wrapping the gel around a mandrel, 2 extracting the non-volatile solvent from the gel with J a volatile solvent, and evaporating the volatile solvent from the tubular profile. 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8

Inventors: ZACHARIADES ANAGNOSTIS E, ZACHARIADES, ANAGNOSTIS, E.
Applicants: ZACHARIADES ANAGNOSTIS E, ZACHARIADES, ANAGNOSTIS, E.
Application year: 1985
Main classification: C08J9
IPC codes: A61F2, A61L26, A61L27, B29C43, B29C53, B29C55, B29L23, C08J9