MXPA97009662A - Impregn applicator tip - Google Patents

Abstract

An applicator tip (5) for distributing a polymerizable and / or crosslinkable material (3) which is porous, absorbent or adsorbent and includes a polymerization or crosslinking initiator (6). The initiator initiates polymerization or crosslinking when the polymerizable and / or crosslinkable material is distributed through the tip of the applicator. The polymerizable and / or crosslinkable material can be applied to a variety of substrates

Description

APPLICATOR TIP, IMPREGNATED FIELD OF THE INVENTION This invention relates to the polymerization and / or crosslinking of a polymerizable and / or crosslinkable material. This invention also relates to the application of the polymerizable and / or crosslinkable material to various substrates with an application device.

BACKGROUND The terms "polymerized" and "polymerizable", as used in the present application, encompass the terms "crosslinkable / crosslinked and grafted / grafted" as defined in the art. For example, the term polymerization not only includes the combination of monomers and prepolymers to form oligomers and polymers, but also includes the joining of oligomers and polymers by various bridging constituents (crosslinking) and binding to oligomers and chain polymers. laterals that have several atomic constituents (grafts). In some applications, the physical properties of the polymerized and / or crosslinked material are extremely important. For example, surgical action adhesives REF: 26193 rapid, sealants, bioactive agent release matrices and implants used in medicine, surgery and other applications in vi require close control of the polymerized and / or crosslinked material. These materials include, for example, the alpha-cyanoacrylates described in U.S. Patent Nos. 5,328,687 to Leung et al., 3,327,841 to Wic er et al., 3,722,599 to Robertson, 3,995,641 to Kronenthal et al., 3,940,362 to Overhults, and U.S. Patent Application Serial No. 08 / 266,647. The subject matter of the above references is incorporated herein by reference. Typically, when used as adhesives and sealants, the cyanoacrylates are applied in monomeric form to the surfaces to be bonded or sealed, where typically the anionic polymerization occurs in the monomer itself, resulting in the desired adhesive bond with a seal . The implants, such as rods, nets or meshes, screws, and plates, may be formed of cyanoacrylate polymers, typically formed by radical initiated polymerization. Efforts to increase tissue compatibility of alpha-cyanoacrylates have included modifying the alkyl ester group of the cyanoacrylates. For example, by increasing the bond of the alkyl ester chain to form analogs of higher cyanoacrylates, for example, it has been found that butyl-2-cyanoacrylates and octyl-2-cyanoacrylates, improve biocompatibility but that higher analogs degrade at slower speeds than lower alkyl cyanoacrylates. Other examples of modified alpha-cyanoacrylates used in biodicic applications include carbalkoxyalkyl, alpha-cyanoacrylates (see, for example, U.S. Patent No. 3,995,641 to Kronenthal et al.), Fluorocyanoacrylates (see, e.g., U.S. Patent No. 3,722,599 to Robertson et al.), And the alkoxyalkyl 2-cyanoacrylates (see, for example, U.S. Patent No. 3,559,652 to Banitt et al.). Other efforts have included mixing alpha-cyanoacrylates with dimethyl methylene aldeonate and higher esters of 2-cyanoacrylic acid (see, for example, U.S. Patent No. 3,591,676 to Hawkins et al.). In other efforts to increase the usefulness of the alpha-cyanoacrylate adhesive compositions for surgical applications, certain viscosity modifiers have been used in combination with alkyl alpha-cyanoacrylate monomers, such as methyl alpha-cyanoacrylate. See, for example, U.S. Patent Nos. 3,564,078 (wherein the viscosity modifier is poly (ethyl 2-cyanoacrylate)) and 3,527,841 (wherein the viscosity modifier is poly (lactic acid)).

In U.S. Patent No. 5,328,687 to Leung et al., All of the content of which is incorporated herein by reference, the use of formaldehyde scavengers has been proposed., to improve the biocompatibility of alpha-cyanoacrylate polymers, whose biodegradation produces formaldehyde, for use in in vi vo applications. Additionally, in the US Application Serial No. 08 / 266,647, all of the content of which is incorporated herein by reference, the rate of biodegradation of the alpha-cyanoacrylate polymer is achieved by regulating the pH of an immediate environment in vi vo a biocompatible composition. It is also known that various compounds can affect the polymerization of alpha-cyanoacrylate monomers, including acids to inhibit or slow polymerization (for example, US Patent No. 3,896,077 to Leonard et al.), And bases for accelerating polymerization (for example, U.S. Patent No. 3,759,264 to Coover and U.S. Patent No. 4,042,442 to Dombroski et al.). Also, conventionally, many polymerization and / or crosslinking inhibitors are added to the polymerizable and / or crosslinkable materials to increase their shelf life. However, the amount of polymerization inhibitor that can be added to the polymerizable and / or crosslinkable material is limited due to the negative impact on any subsequent polymerization process. In particular, if a large amount or concentration of polymerization inhibitor is added to stabilize the polymerizable and / or crosslinkable material, the polymerizable and / or crosslinkable material can be stabilized to a degree which could adversely affect the polymerization. Accordingly, the polymerizable and / or crosslinkable materials may contain only a limited amount of polymerization inhibitor. For certain applications of polymerizable and / or crosslinkable material there is a need to control the curing time of the polymerizable and / or crosslinkable material. For example, the surgical adhesives used for some surgical procedures require polymerization materials that harden rapidly or relatively less quickly, depending on the procedure involved (eg, US Patent No. 5,328,687 to Leung et al., And US application Serial No. 08 / 266,647, the descriptions of which are incorporated herein by reference). Other bonding processes, including sealing and bonding or adhesion processes in the construction and automotive industries, molding processes in the plastics industry, and coating processes in the textile and electronics industries, require a variety of times hardening. Many of these applications require control of the hardening time to facilitate the adequate strength, elasticity and hardness of a polymerized material which at the same time provides the necessary amount of working time to apply the polymerized material to a desired substrate. Several distribution devices have been developed for the purpose of applying and mixing multiple components simultaneously. For example, US Patent No. 3,468,548 to Leigh discloses a dispenser for distributing two paste-like materials, such as creams or gels. One of the materials is stored in a tube and a second material is stored in a chamber of a nozzle attached to the tube. When the first material is forced out of the tube, it flows through the nozzle and mixes with the second material. U.S. Patent No. 3,891,125 to Morane et al. describes a device for storing two separate products and mixing the products before application. A product is stored in a nozzle attached to a container containing a second product. The product in the nozzle falls by the force of gravity towards the container that contains the second product and mixing occurs. Subsequently, the mixed products can be forced from the container and applied to a suitable substrate.

U.S. Patent No. 3,770,523 to Biswas relates to the application of a slurry explosive in a perforation or container. A stream of the explosive in suspension is thickened by mixing the stream with a crosslinking agent by means of a plurality of streams of jets which impact on the suspension stream. U.S. Patent No. 4,801,008 to Rich discloses a disposable cartridge that includes a chamber containing a plurality of components of an adhesive system that react with each other. The components are separated from each other by a barrier film. They are expelled through a nozzle where they are mixed with a static mixing element.

BRIEF DESCRIPTION OF THE INVENTION There continues to be a need in the industries for improved process polymers, resins and coatings to control the properties of the polymerized materials by controlling the speed and / or degree of polymerization and / or crosslinking. In addition, there is a need to provide a simplified and economical process for applying polymerizable and / or crosslinkable materials to various substrates. We have invented a cheap device and a method that simplifies the application of a variety of polymerizable and / or crosslinkable materials to substrates that provide control over the properties of the material, especially the materials that cure quickly and the materials for medicinal use . This invention provides a system for distributing a polymerizable and / or crosslinkable material from an applicator, comprising an applicator tip with a polymerization initiator and / or crosslinking for the material. The tip of the applicator according to the present invention provides several advantages, including the ability to: a) control the molecular weight of the polymerized or crosslinked material; b) controlling the hardening time of the polymerized or crosslinked material; c) provide precision and convenience in the application of the material to a substrate; d) extend the shelf life of the material; e) reduce the presence of residual monomer and avoid odors associated with the monomer; and f) control the flow properties of the applied materials. The applicator tip of the present invention can be used to apply to a plurality of substrates a wide variety of monomers and polymers that undergo polymerization and / or crosslinking by the use of a polymerization initiator and / or crosslinking. In addition, the tip of the applicator of the present invention can be used in a wide variety of monomeric and polymeric systems, such as, for example, in the application of a plurality of components of adhesive systems.

BRIEF DESCRIPTION OF THE DRAWINGS FIGURE 1 is a side elevational view of an applicator device according to this invention for the application of a polymerizable and / or crosslinkable material. FIGURE 2 is a side elevational view of an alternative applicator device according to the invention. FIGURE 3 is a side elevational view of an alternative applicator device according to the invention.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The applicator tip of the present invention can be employed in a variety of processes for the application of a variety of polymerizable and / or crosslinkable materials. In particular, the polymerizable and / or crosslinkable materials include inorganic and organic materials and combinations thereof. Suitable inorganic materials include but are not limited to siloxanes, silicones, polysulfides and polyphosphazenes. Suitable organic polymerizable and / or crosslinkable materials include but are not limited to natural, synthetic, and semi-synthetic materials. Suitable natural polymerizable and / or crosslinkable materials include but are not limited to polysaccharides, such as starch, cellulose, pectin, algal gums or vegetable gums; polypeptides or proteins, such as casein, albumin, globulin, or carotene; or hydrocarbons, such as rubber or polyisoprene. Suitable organic synthetic materials include but are not limited to thermoplastics and thermoplastic elastomers, such as nylon and other polyamides, polyvinyl chloride, polycarbonates, polyethylene, polystyrene, polypropylene, fluorocarbon resins, polyurethane, and acrylate resins; or thermosetting elastomers, such as phenolic, urethane, epoxide, alkyd or polyester elastomers. Suitable organic semisynthetic materials include but are not limited to celluloses, such as rayon, methylcellulose, or cellulose acetate; or modified starches, such as starch acetate and the like. Examples of suitable polymerizable and / or crosslinkable materials include but are not limited to those set forth in U.S. Patent Nos. 5,328,687 to Leung et al., 3,728,375 to Coover, Jr., et al., 3,970,505 to Hauser et al., 4,297,160. from Kusayama et al., 4,340,708 from Gruber, 4,777,230 from Kamath, 5,130,369 from Hughes et al. and US Application Serial No. 08 / 226,647, the entire description of which is incorporated herein by reference. The polymerizable and / or crosslinkable material may include one of the materials mentioned above or may contain one or more of the materials in a mixture. The material can also be composed of monomers, polymers or oligomers of the polymerizable and / or crosslinkable materials mentioned above. For example, suitable polymerizable and / or crosslinkable materials include the 1, 1-disubstituted ethylene monomers. The 1, 1-disubstituted ethylenic monomers include, but are not limited to, the monomers of the formula: (I) CHR = -CXY wherein X and Y are each groups that extract electrons, strong, and R is H, -CH-CH. or, provided that X and Y are both cyano groups, an alkyl group of d-Ca. Examples of monomers within the scope of formula (I) include alpha-cyanoacrylates, vinylidene cyanides, vinylidene cyanide homologs of Ci-C alkyl, 2-methylene dialkyl malonates, acrylonitriles, vinyl sulphinates and sulfonates. of vinyl of the formula CH2 = CX'Y 'wherein X' is -S02R 'or -S03R' and Y 'is -CN, -COOR', -COCHi, -SO'R 'or -S03R', and R ' is H or hydrocarbyl. The preferred monomers of formula (I) for use in this invention are the alpha-cyanoacrylates. These monomers are known in the art and have the formula CN (II> CHR'-C \ COORJ wherein R2 is hydrogen and R3 is a hydrocarbyl or substituted hydrocarbyl group; a group having the formula -R-0-Rb-0-Rfi, wherein R4 is a 1,2-alkylene group having 2-4 carbon atoms, R: is an alkylene group having 2-4 carbon atoms; carbon, and Rc is an alkyl group having 1-6 -R7- C -O-R »I carbon atoms; or a group that has the formula, OR wherein RJ is -CHa-, -H- '° "C (Hj) a *, and R8 is an organic radical Examples of suitable hydrocarbyl and substituted hydrocarbyl groups include straight chain or branched chain alkyl groups having 1 -16 carbon atoms, straight chain or branched chain CI-CR alkyl groups substituted with an acyloxy group, a haloalkyl group, an alkoxy group, a halogen atom / a cyano group, or a haloalkyl group; linear or branched chain having from 2 to 16 carbon atoms, straight chain or branched chain alkynyl groups having from 2 to 12 carbon atoms, cycloalkyl groups, aralkyl groups, alkylaryl groups, and aryl groups In the cyanoacrylate monomer of formula (II), RJ is preferably an alkyl group having 1-10 carbon atoms or a group having the formula -AOR9, wherein A is a divalent straight or branched chain alkylene or oxyalkylene radical having 2-8 carbon atoms, and R ' 'is a linear or branched alkyl radical having 1-8 carbon atoms. Examples of groups represented by the formula -AOR1 include l-methoxy-2-propyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-methoxyethyl, 3-ethoxyethyl and 3-methoxybutyl. Especially advantageous alpha-cyanoacrylate monomers for use in this invention are methyl alpha-cyanoacrylate, butyl alpha-cyanoacrylate, 2-octyl alpha-cyanoacrylate, 2-methoxy-2-propyl cyanoacrylate, cyanoacrylate 2- butoxyethyl, 2-isopropoxyethyl cyanoacrylate and 3-methoxybutyl cyanoacrylate. Equally advantageous are 2-methylene malonates, such as dimethyl 2-methylenemalonate.

The alpha-cyanoacrylates of formula (II) wherein R 3 is a hydrocarbyl or substituted hydrocarbyl group that can be prepared according to methods known in the art. Reference is made, for example, to U.S. Patent Nos. 2,721,858 and 3,254,111, each of which is incorporated herein by reference. For example, alpha-cyanoacrylates can be prepared by reacting an alkyl cyanoacetate with formaldehyde in a non-aqueous organic solvent and in the presence of a basic catalyst, followed by pyrolysis of the anhydrous intermediate polymer in the presence of a polymerization inhibitor. Alpha-cyanoacrylate monomers prepared with low moisture content and essentially free of impurities are preferred for biomedical use. The alpha-cyanoacrylates of the formula (II) wherein R3 is a group having the formula -R4-0-R1 > -0-R6 can be prepared according to the method described in U.S. Patent No. 4,364,876 (Kimura et al.), Which is incorporated herein by reference. In the method of Kimura et al., Alpha-cyanoacrylates were prepared by producing a cyanoacetate by esterification of acetic acid with an alcohol by transesterification of an alkyl cyanoacetate and an alcohol; the condensation of the cyanoacetate and formaldehyde or paraformaldehyde in the presence of a catalyst at a molar ratio of 0.5-1.5: 1, preferably 0.8-1.2: 1, to obtain a condensate; depolymerizing the condensation reaction mixture either directly or after removal of the condensation catalyst to produce crude cyanoacrylate; and distilling the crude cyanoacrylate to form a high purity cyanoacrylate. The alpha-cyanoacrylates of formula (II) wherein R3 is a group having the formula -R'-C-O-R.1 can be prepared OR be prepared according to the procedure described in U.S. Patent No. 3,995,641 to Kronenthal et al., which is incorporated here as a reference. In the method of Kronenthal et al., Such alpha-cyanoacrylate monomers are prepared by reacting an alkyl ester of an alpha-cyanoacrylic acid with a cyclic 1,3-diene to form a Diels-Alder adduct, which is subjected to then to alkaline hydrolysis followed by acidification to form the corresponding alpha-cyanoacrylic acid adduct. The adduct of alpha-cyanoacrylic acid is preferably esterified by means of an alkyl bromoacetate to produce the corresponding carbalkoxy ethyl alpha-cyanoacrylate adduct. Alternatively, the adduct of alpha-cyanoacrylic acid can be converted to the adduct of alpha-cyanoacryloyl halide by reaction with a thionyl chloride. The alpha-cyanoacryloyl halide adduct is then reacted with alkyl hydroxyacetate or an alkyl hydroxyacetate substituted with methyl to produce the corresponding carbalkoxymethyl alpha-cyanoacrylate adduct or corresponding carbalkoxyalkyl alpha-cyanoacrylate adduct, respectively. The cyclic 1,3-diene blocking group is finally removed and the carbalkoxymethyl alpha-cyanoacrylate adduct or carbalkoxyalkyl alpha-cyanoacrylate adduct is converted to the corresponding carbalkoxyalkyl alpha-cyanoacrylate by heating the adduct in the presence of a slight deficiency of maleic anhydride. Examples of monomers of formula (II) include the cyanopentadienoates and alpha-cyanoacrylates of the formula: / CN (III) CHZ-C wherein Z is -CH * CH1 and R3 is as defined above. The monomers of formula (III) wherein R3 is an alkyl group of 1-10 carbon atoms, ie the esters of 2-cyano? Enta-2,4-dienoic acid, can be prepared by reacting an appropriate 2-cyanoacetate with acrolein in the presence of a catalyst such as zinc chloride. This method of preparing 2-cyano-penta-2,4-dienoic acid esters is described, for example, in U.S. Patent No. 3,554,990, which is incorporated herein by reference. The polymerizable and / or crosslinkable materials may include additives, such as polymerization inhibitors or stabilizers, viscosity modifiers, free radical scavengers, pH modifiers (e.g., U.S. Patent Application Serial No. 08 / 266,647, subject matter of which is incorporated herein by reference), other monomers, formaldehyde scavengers (e.g., U.S. Patent No. 5,328,687 to Leung et al., the subject matter of which is incorporated herein by reference), colorants, lubricants , release or transfer agents, surfactants, defoamers, plasticizers, mixtures thereof and other additives. The polymerizable and / or crosslinkable material can be pure (without additional added compounds) or be in a solvent, emulsion or suspension. Suitable solvents according to the present invention include alcohol, ether alcohol, hydrocarbons, halogenated hydrocarbons, ethers, acetals, ketones, esters, organic acid acids containing sulfur or nitrogen, mixtures thereof and the like. Other suitable solvents are described in U.S. Patent No. 5,130,369 to Hughes et al., And U.S. Patent No. 5,216,096 to Hattori et al., All of the disclosures of which are incorporated herein by reference. These solvents can be used either independently or in combination of two or more. They may also be used in conjunction with water to the extent that the polymerizable and / or crosslinkable material is dissolved or suspended in such a mixture. The total amount of solvent that can be incorporated into the polymerizable and / or crosslinkable material can be from 0 to 99, preferably 1 to 50, and more preferably from 3 to 25 percent by weight. The selection of the amount, of course, will depend on the desired monomer and process conditions, and amounts outside those ranges may be acceptable. The polymerizable and / or crosslinkable material may also contain polymerization initiators or inhibitors, chain transfer agents, stabilizers or mixtures thereof. Suitable inhibitors and stabilizers of polymerization are described in U.S. Patent Nos. 5,322,912 to Georges et al., 4,581,429 to Solomon et al., 4,340,708 to Gruber, 4,364,876 to Kimura et al., And 4,297,160 to Kuyasama et al. All descriptions of those patents are incorporated herein by reference. The stabilizer or inhibitor may be added to the polymerizable and / or crosslinkable material in an amount of 0 to 50, preferably 0.001 to 25, and more preferably 0.0002 to 10 weight percent. The selection of the amount, of course, will depend on the desired monomer and the process conditions, and quantities outside those ranges may be acceptable. Suitable chain transfer agents that can be incorporated into the polymerizable and / or crosslinkable material of the present invention include those described in U.S. Patent No. 5,130,369 to Hugues et al., The entire disclosure of which is incorporated herein by reference. reference. The amount of chain transfer agent included in the polymerizable and / or crosslinkable material may be from 0 to 25, preferably from 1 to 15, and more preferably from 2 to 10 weight percent. The selection of the quantity, of course, will depend on the desired monomer and process conditions, and quantities outside those ranges may be acceptable. Suitable viscosity modifiers, plasticizers and lubricants, which may or may not themselves be polymerizable and / or crosslinkable, which may be added to the polymerizable and / or crosslinkable material of the present invention include those set forth in U.S. Patent No. 4,297,160. from Kusayama et al., the entire description of which is incorporated herein by reference. The polymerizable and / or crosslinkable material according to the present invention may also contain formaldehyde scavengers and pH modifiers as described in U.S. Patent No. 5,328,687 to Leung et al., And U.S. Patent Application Serial No. 08 / 266,647, respectively, the descriptions of which are fully incorporated herein by reference. Referring now more in detail to the figures of the drawings, an applicator device incorporating an aspect of the present invention is shown generally at 1 in Figure 1. The device comprises a cylindrical applicator container 2 containing a polymerizable material and / or crosslinkable 3, a piston 4 for forcing the material 3 of the container 2 and an applicator tip 5 having a portion 6 thereof comprising a polymerization initiator and / or crosslinking. Figure 2 illustrates another embodiment of the invention and includes an applicator device 10. The device comprises a cylindrical applicator container 20 containing a polymerizable and / or crosslinkable material 30 enclosed in a fragile bottle 40, and an applicator tip 50 having a portion 60 thereof comprising an initiator of the polymerization and / or crosslinking. Figure 3 illustrates another embodiment, and includes an applicator device 100. The device comprises a cylindrical applicator container 200 containing polymerizable and / or crosslinkable material enclosed in a fragile flask 400, and an applicator tip 500 containing a polymerization initiator. and / or crosslinking. The tip of the applicator according to the present invention can have a variety of suitable shapes, including but not limited to conical, cylindrical, chisel or polygonal shapes. For example, the tip may be a tube, cannula, catheter, single or multiple lumen form, or comprise a rolling sphere, brush, cotton swab or similar tip. Preferably the tip of the applicator is conical. The end having a lowered circumference is preferable the end from which the tip material of the applicator leaves and is shaped in such a way as to facilitate application of the material to any suitable substrate. The length of the tip of the applicator can also be varied depending on various application parameters, such as the proximity of the applicator container containing the polymerizable and / or crosslinkable material to the substrate to which the material is to be applied. The size of the end of the tip in which the material leaves the tip can be varied depending on the application. The container of the applicator according to the present invention can also be of a variety of shapes and sizes depending on the intended use. For example, for the application of limited amounts of polymerizable and / or crosslinkable material, the container of the applicator can be a syringe, a tube, a bottle, a bulb or a pipette. For example, a fragile closed tube 400 of polymerizable and / or crosslinkable material 300 in a flexible container 200 as shown in Figure 3 is a preferred type of applicator. For applications of polymerizable and / or crosslinkable material in larger amounts, applicator containers such as, for example, tanks or reactor vessels may be used. The tip of the applicator according to the present invention can be detachable from the applicator container containing polymerizable and / or crosslinkable material. Such an applicator tip could be attached to the applicator container before being used and detached from the applicator container after being used to prevent premature polymerization or crosslinking of the non-applied material in the applicator container. At this point the tip of the applicator may be discarded and a new applicator tip may be placed on the applicator container for subsequent use or the tip of the applicator may be reused. Additionally, the applicator tip according to the present invention may comprise multiple parts, with at least one part comprising the initiator. For example, the component comprising the initiator can be fabricated separately from the other components of the tip of the applicator and assembled before being attached to the applicator container.

The tip of the applicator may also be in the form of a nozzle for atomizing liquid polymerizable and / or crosslinkable materials. Flat spray or conical, conical, spray nozzles are suitable. The applicator tip according to the present invention can be used in manual or automated applications. For example, manual methods of application may include the use of manual devices such as syringes, adhesive guns, pipettes, eye droppers and the like. Automated application processes include injection molding and painted / sealed / robotized adhesion. The tip of the applicator and the applicator container can also be an integrated unit. The unit can be preformed as a single piece and loaded with polymerizable and / or crosslinkable material. After application of the applicator container material, the unit can be discarded. Additionally such an applicator tip / integral applicator vessel unit can be formed to provide the ability to reload the unit with new material as a multipurpose device. The tip of the applicator may be composed of a variety of materials including polymerized materials such as plastics, foams, rubber, thermosetting, films or membranes. Additionally, the tip of the applicator may be composed of materials such as metal, glass, paper, ceramics, cardboard and the like. The tip material of the applicator may be porous, absorbent or adsorbent in nature to increase and facilitate loading of the initiator on or into the tip of the applicator. For example, the applicator tip may be composed of a material having random pores, a honeycomb material, a material having a woven pattern, etc. The degree of porosity will depend on the materials that are used. The tip of the applicator according to the present invention, where it is connected to the applicator container, may have an elongated tubular portion, out of which the mixed polymerizing and / or crosslinking material is expelled. A portion of the tip of the applicator that is immediately downstream of the applicator container is advantageously porous to avoid a sharp pressure drop and ensure a constant mixing ratio profile. The structure may preferably trap any barriers or materials used to separate multiple components within the applicator container. In this way, none of these barriers will obstruct the device. The initiators that initiate the polymerization and / or crosslinking of the material can be applied to a portion of the surface or to the entire surface of the tip of the applicator, including the inside and outside of the tip. Alternatively, the initiator can be coated only on an inner surface of the tip of the applicator. Preferably, only an inner portion of the tip of the applicator is coated with the initiator. The initiator on the tip of the applicator may be in the form of a solid, such as a powder or a solid film, or in the form of a liquid, such as a viscous or paste-like material. The initiator may also include a variety of additives, such as surfactants or emulsifiers. Preferably, the initiator is soluble in the polymerizable and / or crosslinkable material, and / or comprises or is accompanied by at least one surfactant, which, in the embodiments, assists the initiator to coelute with the polymerizable and / or crosslinkable material. . In the embodiments, the surfactant can help solubilize the initiator in the polymerizable and / or crosslinkable material. The particular primers for the particular systems can be easily selected by one skilled in the art without undue experimentation. Suitable initiators include, but are not limited to, detergent compositions; surfactants: for example, nonionic surfactants such as polysorbate 20 (e.g., Tween 20MR), polysorbate 80 (e.g., Tween 80MR) and poloxamers, cationic surfactants such as tetrabutylammonium bromide, anionic surfactants such as tetradecyl sulfate sodium, and amphoteric or zwitterionic surfactants such as dodecyldimethyl (3-sulfopropyl) ammonium hydroxide, inert salts; amines, imines and amides, such as imidazole, tryptamine, urea, arginine and povidone; phosphines, phosphites and phosphonium salts, such as triphenylphosphine and triethyl phosphite; alcohols such as ethylene glycol, methyl gallate, ascorbic acid, tannins and tannic acid; bases and inorganic salts, such as sodium bisulfite, magnesium hydroxide, calcium sulfate and sodium silicate; sulfur compounds such as thiourea and polysulfides; polymeric cyclic ethers such as monensin, nonactin, capped ethers, calixarenes and polymeric epoxides; cyclic and acyclic carbonates, such as diethyl carbonate; phase transfer catalysts such as Aliauat 336; organometallic compounds such as cobalt naphthenate and manganese acetylacetonate; and initiators of radicals and radicals, such as di-t-butyl peroxide and azobisisobutyronitrile. The polymerizable and / or crosslinkable material may also contain an initiator which is inactive until activated by a catalyst or accelerator (included within the scope of the term "initiator" as used herein) at the tip of the applicator. For example, a monomer containing benzoyl peroxide can be used as the polymerizable material in association with a tip containing an amine accelerator, or a monomer containing methyl ethyl ketone peroxide can be used as the polymerizable material in association with a tip containing naphthenate. of cobalt. Initiators activated by stimulation such as heat and / or light (e.g., ultraviolet or visible light) are also suitable if the tip and / or applicator are appropriately subjected to such stimulation. The initiator can be applied to the surface of the tip of the applicator or it can be impregnated or incorporated in the matrix or in the internal portions of the tip of the applicator. For example, the initiator can be applied to the tip of the applicator by spraying, immersing or brushing the tip of the applicator with a liquid medium containing the initiator. The aqueous medium may include non-aqueous solvents, such as ether, acetone, ethanol, pentane or mixtures thereof; or it can include aqueous solutions. Preferably, the liquid medium is a low boiling temperature solvent. Additionally, the initiator on the tip of the applicator may be present in a variety of concentrations in the medium ranging from 0 to 50%, preferably from 0.001 to 25%, and more preferably from 0.01 to 10% in the weight. The selection of the amount will, of course, depend on the desired monomer and process conditions, and amounts outside those ranges may be acceptable. The initiator can be applied to the tip of the applicator in the form of a preformed initiator film. The initiator can be applied as a solid by vapor deposition, such as by electrodeposition. Additionally, the initiator can be incorporated in the tip of the applicator, for example, during the manufacture of the tip. This can be effected by mixing the initiator with the tip material of the applicator before molding the tip material of the applicator into the desired shape. After application of the initiator on the tip of the applicator, the tip of the applicator may be dried or heated to evaporate or volatilize the liquid medium or to evenly distribute or impregnate the initiator at the tip of the applicator. This can be achieved by drying the tip of the applicator at room temperature or by heating the tip of the applicator in a conventional device such as a conventional oven, vacuum oven, microwave oven, or UV / visible light. Additionally, the container containing the polymerizable and / or crosslinkable material may contain the initiator. For example, the polymerizable and / or crosslinkable material can be stored separately within the applicator container, so that it does not come into contact with the initiator within the container. The applicator container can be lined or coated with the initiator or the initiator can be stored in a separate compartment of the polymerizable and / or crosslinkable material within the applicator container. For example, in the device of Figure 3, the initiator can be coated on the internal surface of the body 200. Within the tip of the applicator, static or dynamic mixers can be provided to ensure a perfect mixing of the polymerizable and / or crosslinkable material with the initiator . Preferred static mixers include internal tortuous paths. The tip of the applicator according to the present invention can also be used in conjunction with systems of polymerizable and / or crosslinkable multi-component material having materials that must remain physically separated from one another before application to avoid chemical reactions between them. Such multicomponent cartridges, for example, are described in U.S. Patent Nos. 3,915,297 to Rausch, 4,493,436, 4,538,920, and 4,801,008 to Rich, all of the disclosures of which are incorporated herein by reference.

Pressure can be applied to the polymerizable and / or crosslinkable material to force the material of the applicator container through the tip of the applicator. When the polymerizable and / or crosslinkable material passes through the tip of the applicator, the material comes in contact with the initiator, thereby initiating the polymerization and / or crosslinking of the material. The shape of the tip of the applicator preferably increases the mixing of the material and the initiator to provide a homogeneous mixture. The shape of the tip of the applicator also facilitates the application of the polymerizing material and / or crosslinker to a suitable substrate. The initiator can co-elute with the polymerizable and / or crosslinkable material, or it can remain at the tip. The material according to the present invention can be applied to a variety of substrates for the purpose of protecting, sealing, and bonding surfaces. Suitable substrates include metals, plastics, rubbers, wood, ceramics, fabrics, cement, paper, living fabrics and the like. For example, the polymerizable and / or crosslinkable material may be useful as tissue adhesives, sealants to prevent bleeding or to cover open wounds, systems for releasing therapeutic agents or other bioactive substances, and other biomedical applications. They find uses in, for example, closing surgically cut or traumatically lacerated tissues; fix fractured bone structures; slow the blood flow of wounds; help repair and re-grow living tissue; provide implantable matrices of bioactive release agents; and provide structural implants. The tip of the applicator according to the present invention provides control over the molecular weight of the polymerized or crosslinked material. For example, the amount of initiator applied to the tip of the applicator can be increased to a degree that could provide a more complete polymerization of a polymerizable and / or crosslinkable material over conventional methods incorporating the polymerization initiator into the polymerizable material and / or crosslinkable before the application thereof. The tip of the applicator according to the present invention also provides control over the hardening time of the material. For example, the amount of initiator applied to the tip of the applicator may vary from tip to tip to provide control over the length of work time for the application of a material. Additionally, applicator tips having different amounts or types of primers may be interchanged to provide different cure times during the application of a particular material or different materials. The applicator tip according to the present invention also provides a prolonged shelf life of the polymerizable and / or crosslinkable material. For example, by providing an increased amount of polymerization initiator on the tip of the applicator, the polymerizable and / or crosslinkable material can be provided with a greater amount of polymerization inhibitors or stabilizers that could decrease the premature polymerization. The tip of applicator according to the present invention also provides a greater ease of application of the polymerizable and / or crosslinkable material by providing improved rheological properties of this material during application to a substrate. For example, the surfactants incorporated in the polymerization initiator on the tip of the applicator can provide the polymerizing material that leaves the tip of the applicator with greater fluidity, and can help the initiator to coelute with the material. The following examples illustrate specific embodiments of the present invention. One skilled in the art will recognize that the reaction parameters, reagents, component / concentration ratios and appropriate device dimensions can be adjusted as necessary to achieve the characteristics of the specific polymerized product. All parts and percentages are by weight unless otherwise indicated.

EXAMPLES Initiators in various percentages by weight were mixed with acetone and stirred for at least 30 minutes to achieve homogeneity. The porous plastic tips of the applicators as shown in Figure 3 were immersed in the initiator solution for several minutes, removed from the solution, and attached to the open end of the flexible butyrate tubes containing the monomeric material in the solution. glass vials as shown in Figure 3. (The butyrate tubes soften upon contact with the acetone, thereby "welding" the tip to the body of the applicator). The applicators were left to dry overnight in an extractor hood. A control tip without initiator was prepared using pure acetone solvent. In a vertical position, the applicator tubes were compressed to break the glass ampules, thereby releasing the monomeric material. The applicators were then inverted, and the monomeric material was forced out of the tip by compressing the applicator tube. When the material starts to come out of the tubes, a thin line of material runs along the back of a person's hand (2-3 inches), and the time to complete the polymerization is recorded. The results are shown in Table 1, and demonstrate the effectiveness of the claimed invention for controlling the polymerization time.

Table 1 Material Initiator Polymerizable Time (% by weight) Hardening (seconds) cyanoacrylate from 2- none > 240 octyl cyanoacrylate from 2- 0.01% Tween 20 45 octyl cyanoacrylate from 2- 0.05% Tween 20 30 octyl cyanoacrylate from 2- 0.15% Tween 20 20 octyl cyanoacrylate from 2- none > 240 isopropoxyethyl Table 1 (continued) Initiator Material Polymerizable Time (% by weight) Hardening (seconds) cyanoacrylate of 2- 2.5% of Tween 20 50 isopropoxyethyl cyanoacrylate of 2- 5.0% of Tween 20 < 40 isopropoxyethyl 2-methylenemalonate of none > 150 dimethyl 2-methylenemalonate 2.5% 50-dimethyl tetrabutylammonium bromide It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention, having described the invention as above, Property is claimed as contained in the following:

Claims (26)

1. An applicator tip for distributing a polymerizable or crosslinkable monomeric material of an applicator, characterized in that it comprises a direct modifier of the crosslinking speed or polymerization for the monomer of such material.

2. The tip of applicator according to claim 1, characterized in that the applicator tip comprises at least one of an absorbent or adsorbent material containing the modifier.

3. The tip of applicator according to claim 1, characterized in that the tip is integrated to an applicator.

4. The tip of applicator according to claim 3, characterized in that the applicator is a syringe, a flexible cylinder, a tube, a pipette or an eye dropper.

5. The tip of applicator according to claim 1, characterized in that the applicator tip comprises more than one part, at least one of such parts comprises the modifier.

6. The tip of applicator according to claim 1, characterized in that the modifier comprises a detergent composition.

7. The tip of applicator according to claim 1, characterized in that the modifier contains at least one member selected from the group consisting of a surfactant and an emulsifier.

8. The applicator tip according to claim 1, characterized in that the modifier is a polysorbate surfactant.

9. A method for preparing an applicator tip for distributing a polymerizable or crosslinkable monomeric material, characterized in that it comprises: applying to at least a portion of a tip of the applicator a polymerization or crosslinking modifier for the monomer of the material.

10. The method according to claim 9, characterized in that the modifier can be applied to the tip by mixing the modifier with the material used to form the tip before forming the tip.

11. The method according to claim 9, characterized in that the modifier is applied by immersing the tip of the applicator in or by spraying the tip of the applicator with a liquid medium containing such a modifier.

12. The method according to claim 11, characterized in that the tip of the applicator is subsequently dried to evaporate or volatilize the liquid medium.

13. The method according to claim 9, characterized in that the material contains at least one member selected from the group consisting of a free radical agent, a stabilizer, a formaldehyde scavenger, a pH modifier, a plasticizer, a modifier of the viscosity, a catalyst and a coolant.

14. The method according to claim 9, characterized in that the material is an adhesive.

15. The method according to claim 13, characterized in that the material is a substituted alkylene.

16. The method in accordance with the claim 15, characterized in that the substituted alkylene is a cyanoacrylate.

17. A method of applying a monomeric polymerizable or crosslinkable material to a substrate, characterized in that it comprises: distributing on said substrate the material through an applicator tip comprising a direct modifier of the polymerization speed or crosslinking for the material.

18. The method according to claim 17, characterized in that the material comes into contact with the modifier during the distribution step to initiate the polymerization or crosslinking of the material.

The method according to claim 17, characterized in that the modifier coelute with the material.

20. A device for distributing a polymerizable or crosslinkable monomeric material of an applicator, characterized in that it comprises a modifier of the speed of polymerization or direct crosslinking to the monomer of the material on a solid support.

21. The device according to claim 20, characterized in that the solid support comprises part of the applicator.

22. The device according to claim 20, characterized in that it comprises a container body and an applicator tip, the tip of the applicator comprises the solid support.

23. A device according to claim 22, characterized in that the material is located in the body of the container in a non-contacting relationship with the tip before distribution of the material.

24. The device according to claim 20, characterized in that the material is encapsulated in a fragile bottle contained within a flexible applicator.

25. The tip of the applicator according to claim 1, characterized in that the polymerizable or crosslinkable monomeric material is a synthetic material.

26. The device according to claim 20, characterized in that the polymerizable or crosslinkable monomeric material is a synthetic material.