WO2012107376A1 - Adhésifs tissulaires à base de triacétals substitués par amino - Google Patents

Adhésifs tissulaires à base de triacétals substitués par amino Download PDF

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Publication number
WO2012107376A1
WO2012107376A1 PCT/EP2012/051915 EP2012051915W WO2012107376A1 WO 2012107376 A1 WO2012107376 A1 WO 2012107376A1 EP 2012051915 W EP2012051915 W EP 2012051915W WO 2012107376 A1 WO2012107376 A1 WO 2012107376A1
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WO
WIPO (PCT)
Prior art keywords
radical
independently
polyols
polyurea system
component
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PCT/EP2012/051915
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German (de)
English (en)
Inventor
Heike Heckroth
Christoph Eggert
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Bayer Materialscience Ag
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Publication of WO2012107376A1 publication Critical patent/WO2012107376A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

  • the present invention relates to a compound for use in a polyurea system, which is particularly intended for sealing, bonding, gluing or covering of cellular tissue. Further objects of the invention are a compound of the invention comprising polyurea system and a metering system for the polyurea system according to the invention.
  • tissue adhesives Various materials used as tissue adhesives are commercially available. These include cyanoacrylates Dermabond ® (octyl-2-cyanoacrylate) and Histoacryl ® Blue (butyl cyanoacrylate). The prerequisite for efficient bonding of cyanoacrylates, however, are dry substrates. With heavy bleeding such adhesives fail.
  • biological adhesives such as BioGlue ® , a mixture of glutaraldehyde and bovine serum albumin, various collagen and gelatine-based systems (FloSeal ® ) and fibrin glue (Tissucol) are available. These systems are primarily used for hemostasis (haemostasis). In addition to the high costs, fibrin sealants are characterized by a relatively low adhesive strength and a rapid degradation, so that they can be used only for minor injuries on non-tensioned tissue. Collagen and gelatin based systems such as FloSeal ® are for hemostasis only.
  • QuikClot ® or QuikClot ACS + TM is available for treatment of traumatic wounds, which is a mineral granulate that is brought into the wound in an emergency, where it leads to coagulation through dehydration. In the case of QuikClot® this is a strongly exothermic reaction leading to burns.
  • QuikClot ACS + TM is a gauze in which the salt is embedded. The system must be firmly pressed onto the wound for hemostasis.
  • WO 2009/106245 A2 discloses the production and use of polyurea systems as tissue adhesives.
  • the systems disclosed herein comprise at least two components. This is an amino-functional aspartic acid ester and an isocyanate-functional prepolymer obtainable by reacting aliphatic polyisocyanates with polyester polyols.
  • the described 2-components Polyurea systems can be used as tissue adhesives for the closure of wounds in human and animal cell aggregates. In this case, a very good adhesive result can be achieved.
  • the polyurea systems are designed to biodegrade within a period of up to 6 months. In order to ensure a good miscibility of the two components of the polyurea system, the viscosity of the components at 23 ° C should be less than 10,000 mPas.
  • a correspondingly low viscosity have prepolymers with NCO functionalities of less than 3. If such prepolymers are used, it is necessary to use an aspartic acid ester with an amino functionality of more than 2 as the second component, since otherwise no polymeric network can be produced. However, this is necessary so that the polyurea system or an existing adhesive seam having the desired mechanical properties such as elasticity and strength. Moreover, when using di Shentechnischeller aspartic ester is disadvantageous that the curing time is up to 24 h, the polyurea system remains sticky even after this time in many cases, so not tack free.
  • WO 2009/106245 A2 The systems known from WO 2009/106245 A2 are also designed to biodegrade within a period of up to 6 months. In many cases, however, it is desirable that degradation takes place in a few days or weeks.
  • the object of the invention was to provide an isocyanate-reactive component for a polyurea system which is readily miscible with a prepolymer, has an amino functionality of more than 2 and can be reacted rapidly with the prepolymer to form a three-dimensional polyurea network ie within a time of a few minutes has sufficient mechanical stability and adhesive strength and tack is free.
  • the hardened system can biodegrade within a period of significantly less than 6 months, making it suitable for use in living organisms.
  • Ri is a C 1 to C 6 alkyl radical or H
  • R 2 is an organic radical containing a secondary amino function
  • R 3, R 4 are each, independently of one another, an organic radical which has no Zereptinoff-active hydrogen
  • R5, R6 are each independently a CFb-COORv radical wherein R7 is an organic radical having no Zerewitinoff active hydrogen, a linear or branched C1 to C4 alkyl, a cyclopentyl, a cyclohexyl radical or Are H,
  • X, Y are each independently of one another a (CH 2 ) p -O radical, where p> 2 ⁇ 4, or a CH 2 radical,
  • n, m are each independently> 1 and ⁇ 6 and
  • the compound of the invention can be easily mixed with a prepolymer, since it has a viscosity of less than 10,000 mPas at 23 ° C. In addition, it has an amino functionality of 3 and thus is capable of rapidly forming a three-dimensional polyurea network with prepolymers. This network is characterized by high elasticity, strength and adhesive strength. In addition, the network is no longer sticky after a short time, i. In addition, it can be broken down under physiological conditions within a period of significantly less than 6 months.
  • a polyurea system is considered degradable under physiological conditions when it dissolves in an isotonic NaCl solution (containing 0.9 weight percent NaCl dissolved in water) at 37 ° C.
  • groups having Zerewitinoff-active hydrogen are OH, NH or SH.
  • R 2 may be a radical of the formula (II)
  • Rs, R 9 are each independently an organic radical which has no Zereptinoff-active hydrogen.
  • Rs may be a linear or branched, saturated, optionally also in the chain with hetero atoms substituted organic radical, in particular a linear or branched, saturated, aliphatic Cl to CIO, preferably C2 to C8 and particularly preferably C2 to C6 hydrocarbon radical.
  • R9 can be a radical of the formula (III)
  • R 1 each independently of one another or at the same time a C 1 to C 10, preferably a C 1 to C 8, particularly preferably a C 2 to C 6 alkyl radical and very particularly preferably a methyl and / or an ethyl radical.
  • Such compounds react particularly fast with a prepolymer to a three-dimensional polyurea system.
  • R5, R5 are each a drb COORv radical in which R7 is an organic radical which has no Zerewitinoff-active hydrogen.
  • R3, R4 and optionally R7 are each independently or simultaneously a Cl to CIO, preferably a Cl to C8, more preferably a C2 to C6 alkyl radical and most preferably a methyl and or an ethyl radical.
  • X and Y are each simultaneously an Orb radical.
  • the indices n and m can each independently or simultaneously be> 1 and ⁇ 6, preferably> 1 and ⁇ 4 and particularly preferably 1 or 2.
  • Another object of the invention is a polyurea system comprising as component A) isocyanate-functional prepolymers obtainable by reacting aliphatic polyisocyanates AI) with polyols A2), in particular a number average molecular weight of>
  • component B) an amino-functional compound according to formula (I), optionally as component C) organic fillers, in particular a viscosity measured according to DIN 53019 at 23 ° C in the range from 10 to 6000 mPas, optionally as component D) reaction products of isocyanate-functional prepolymers according to component A) with amino-functional compounds according to component B) and / or organic fillers according to component C) and optionally as component E) water and / or a tertiary amine.
  • component D) reaction products of isocyanate-functional prepolymers according to component A) with amino-functional compounds according to component B) and / or organic fillers according to component C) and optionally as component E) water and / or a tertiary amine.
  • the polyurea systems according to the invention are obtained by mixing the prepolymers A) with the amino-functional compound B) and optionally the components C), D) and / or E).
  • the ratio of free or blocked amino groups to free NCO groups is preferably 1: 1.5, particularly preferably 1: 1. Water and / or A-min are thereby mixed with component B) or C b).
  • the isocyanate-functional prepolymers A) can be obtained by reacting polyisocyanates AI) with polyols A2), if appropriate with the addition of catalysts and auxiliaries and additives.
  • polyisocyanates AI for example, monomeric aliphatic or cycloaliphatic di- or triisocyanates such as 1,4-butylene diisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4 , 4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 4-isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate), and alkyl 2,6-diisocyanatohe
  • Polyisocyanates AI) of the abovementioned type with exclusively aliphatically or cycloaliphatically bound isocyanate groups or mixtures thereof are preferably used.
  • polyisocyanates AI of the above type having an average NCO functionality of from 1.5 to 2.5, preferably from 1.6 to 2.4, more preferably from 1.7 to 2.3, are very particularly preferred from 1.8 to 2.2 and especially from 2 will be used.
  • the polyols A2) are polyester polyols and / or polyester-polyether polyols and / or polyether polyols. Particularly preferred are polyester-polyether polyols and / or polyether polyols having an ethylene oxide content between 60 and 90 wt .-%.
  • the polyols A2) have a number-average molecular weight of 4000 to 8500 g / mol.
  • Suitable polyetheresterpolyols preferably by polycondensation of polycarboxylic acids, anhydrides of polycarboxylic acids, and esters of polycarboxylic acids with volatile alcohols, preferably Cl to C6 monools, such as methanol, ethanol, propanol or butanol, with molar excess, low molecular weight and / or higher molecular weight Polyol prepared, wherein polyols as the polyol ether fate optionally used in mixtures with other ether weakness clar polyols.
  • Suitable molar excess low molecular weight polyols are, for example, polyols having molecular weights of from 62 to 299 daltons, having 2 to 12 carbon atoms and hydroxyl functionalities of at least 2, which may furthermore be branched or unbranched and whose hydroxyl groups are primary or secondary. These low molecular weight polyols may also have ether groups. Typical representatives are ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol
  • Suitable molar excess higher molecular weight polyols are, for example, polyols having molecular weights of 300 to 3000 daltons, which can be obtained by ring-opening polymerization of epoxides, preferably ethylene and / or propylene oxide, as well as acid-catalyzed, ring-opening polymerization of tetrahydrofuran.
  • epoxides preferably ethylene and / or propylene oxide
  • acid-catalyzed, ring-opening polymerization of tetrahydrofuran for ring-opening polymerization of epoxides, either alkali metal hydroxides or double metal cyanide catalysts can be used.
  • initiators for ring-opening epoxide polymerizations it is possible to use all at least bifunctional molecules from the group of amines and the above-mentioned.
  • low molecular weight polyols are used. Typical representatives are 1, 1, 1-trimethylolpropane, glycerol, o-TDA, ethylenediamine, propylene glycol-1,2, etc., and water, including mixtures thereof. Of course, mixtures can also be used within the group of excess higher molecular weight polyols.
  • the structure of the higher molecular weight polyols as far as it is hydroxyl-terminated polyalkylene oxides of ethylene and / or propylene oxide, can be carried out randomly or in blocks, wherein mixing blocks may be included.
  • Polycarboxylic acids are both aliphatic and aromatic carboxylic acids, which may be both cyclic, linear, branched or unbranched and which may have between 4 and 24 carbon atoms.
  • Examples are succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1, 10-decanedicarboxylic acid, 1, 12-dodecanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid.
  • Succinic acid, glutaric acid, adipic acid are preferred.
  • Particularly preferred are succinic acid, glutaric acid and adipic acid.
  • the group of polycarboxylic acids also hydroxycarboxylic acids, or their internal anhydrides, such. Caprolactone, lactic acid, hydroxybutyric acid, ricinoleic acid, etc. Also included are monocarboxylic acids, in particular those which have more than 10 carbon atoms, such as soybean oil fatty acid, palm oil fatty acid and peanut oil fatty acid, wherein their share of the total, the polyetheresterpolyol constituent reaction mixture 10 wt. % and, in addition, the associated minor functionality is compensated by the concomitant use of at least trifunctional polyols, be it on the side of the low molecular weight or the high molecular weight polyols.
  • monocarboxylic acids in particular those which have more than 10 carbon atoms, such as soybean oil fatty acid, palm oil fatty acid and peanut oil fatty acid, wherein their share of the total, the polyetheresterpolyol constituent reaction mixture 10 wt. % and, in addition, the associated minor functionality is
  • blends of polyether polyols with polyester polyols in any ratios can be used.
  • Polyether polyols are preferably polyalkylene oxide polyethers based on ethylene oxide and optionally propylene oxide. These polyether polyols are preferably based on di- or higher-functional starter molecules, such as di- or higher-functional alcohols or amines.
  • initiators are water (considered as a diol), ethylene glycol, propylene glycol, butylene glycol, glycerol, TMP, sorbitol, pentaerythritol, triethanolamine, ammonia or ethylenediamine.
  • hydroxyl-containing polycarbonates preferably polycarbonatediols, having number-average molecular weights M n of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol.
  • carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane,
  • the thin-film distillation is used for this purpose.
  • stabilizers such as benzoyl chloride, isophthaloyl chloride, dibutyl phosphate, 3-chloropropionic acid or methyl tosylate may be added during the preparation.
  • the reaction temperature in the preparation of the prepolymers A) is preferably 20 to 120 ° C, and more preferably 60 to 100 ° C.
  • the prepolymers produced have a measured according to DIN EN ISO 11909 average NCO content of 2 to 10 wt .-%, preferably 2.5 to 8 wt .-%.
  • the prepolymers A) can have an average NCO functionality of from 1.5 to 2.5, preferably from 1.6 to 2.4, more preferably from 1.7 to 2.3, completely particularly preferably from 1.8 to 2.2 and in particular from 2.
  • the organic fillers of component C) may preferably be hydroxy-functional compounds, in particular polyether polyols having repeating ethylene oxide units.
  • the fillers of component C) have an average OH functionality of from 1.5 to 3, preferably from 1.8 to 2.2 and particularly preferably from 2.
  • liquid polyethylene glycols such as PEG 200 to PEG 600
  • their mono- or dialkyl ethers such as PEG 500 dimethyl ether
  • liquid polyether and polyester polyols liquid polyesters
  • ultramoll Lixess AG, Leverkusen, DE
  • glycerin and its liquid derivatives e.g. Triacetin (Lanxess AG, Leverkusen, DE).
  • the viscosity of the organic fillers measured according to DIN 53019 at 23 ° C. is preferably 50 to 4000 mPas, more preferably 50 to 2000 mPas.
  • polyethylene glycols are used as organic fillers. These have zugt a number average molecular weight of 100 to 1000 g / mol, particularly preferably from 200 to 400 g / mol.
  • component E) is a tertiary amine of the general formula (IV)
  • the compounds used in component E) may very particularly preferably be tertiary amine selected from the group triethanolamine, tetrakis (2-hydroxyethyl) ethylenediamine, N, N-dimethyl-2- (4-methylpiperazin-1-yl) ethanamine, 2- ⁇ [2- (dimethylamino) ethyl] (methyl) amino ⁇ ethanol, 3,3 ', 3 "- (1,3,5-triazinane-1,3,5-triyl) tris (N , N-dimethyl-propane-1-amine) act.
  • tertiary amine selected from the group triethanolamine, tetrakis (2-hydroxyethyl) ethylenediamine, N, N-dimethyl-2- (4-methylpiperazin-1-yl) ethanamine, 2- ⁇ [2- (dimethylamino) ethyl] (methyl) amino ⁇ ethanol, 3,3 ', 3 "- (1,3,5-triazinan
  • component E) contains 0.2 to 2.0% by weight of water and / or 0.1 to 1.0% by weight of the tertiary amine.
  • polyurea system may also contain pharmacologically active agents such as analgesics with and without anti-inflammatory action, anti-inflammatory drugs, antimicrobial active substances, antimycotics, antiparasitic acting substances.
  • pharmacologically active agents such as analgesics with and without anti-inflammatory action, anti-inflammatory drugs, antimicrobial active substances, antimycotics, antiparasitic acting substances.
  • the polyurea system according to the invention is particularly suitable for sealing, bonding, gluing or covering cell tissue and, in particular, for arresting the escape of blood or tissue fluids or for closing leaks in cell tissue. Most preferably, it may be used for the use or preparation of a means for sealing, bonding, adhering or covering human or animal cell tissue. With its help, fast-curing, strongly adhering to the tissue, transparent, flexible and biocompatible adhesive seams can be produced.
  • Yet another object of the invention is metering system with two chambers for a polyurea system according to the invention, wherein in one chamber, the component A) and in the other chamber, the components B) and optionally the components C), D) and E) of Polyurea system are included.
  • a metering system is particularly suitable for applying the polyurea system as an adhesive to tissue.
  • the structure of the acetal structure was carried out by transacetalization of 2- (4,4-dimethoxybutyl) isoindoline-l, 3-dione with 3-azidopropane-l-ol. Subsequently, the amino function was obtained by hydrazinolysis of the imide and catalytic hydrogenation of the azido function. The final product was prepared by Michael addition of triamine to diethyl maleate.
  • the molecular weights of the prepolymers were determined by gel permeation chromatography (GPC) as follows: Calibration was carried out using polystyrene standards with molecular weights of Mp 1,000,000 to 162. The eluent was tetrahydrofuran p.A. used. The following parameters were observed during the double measurement: Degassing: Online - Degasser; Flow: 1 ml / min; Analysis time: 45 minutes; Detectors: refractometer and UV detector; Injection volume: 100 ⁇ - 200 ⁇ . The calculation of the molecular weight averages Mw; Mn and Mp and the polydispersity Mw / Mn were software-based. Baseline points and evaluation limits were determined in accordance with DIN 55672 Part 1.
  • NCO content Unless otherwise stated, the NCO content was determined volumetrically in accordance with DIN-EN ISO 11909.
  • Viscosity The viscosity was determined according to ISO 3219 at 23 ° C.
  • Residual monomer content The residual monomer content was determined in accordance with DIN ISO 17025.
  • NMR The NMR spectra were generated with a Bruker DRX 700 instrument.
  • HDI Hexamethylene diisocyanate (Bayer MaterialScience AG) All other chemicals and solvents used are from Aldrich.
  • the structure of the acetal structure was carried out by transacetalization of 2- (4,4-dimethoxybutyl) isoindoline-l, 3-dione with 3-azidopropane-l-ol. Subsequently, the amino function was obtained by hydrazinolysis of the imide and catalytic hydrogenation of the azido function. The final product was prepared by Michael addition of triamine to diethyl maleate.
  • the time after which the polyurea system was no longer sticky was measured by sticking tests with a glass rod. For this purpose, the glass rod was brought into contact with the layer of the polyurea system. If this did not stick, the system was considered tack free.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un composé de formule (I) dans laquelle R1 désigne un reste alkyle C1 à C6 ou H, R2 désigne un reste organique contenant une fonction amino secondaire, R3, R4 désignent respectivement indépendamment l'un de l'autre un reste organique qui ne présente pas d'hydrogène selon Zerewitinoff, R5, R6 désignent respectivement indépendamment l'un de l'autre un reste CH2-COOR7, R7 étant un reste organique qui ne présente pas d'hydrogène actif selon Zerewitinoff, un reste alkyle C1 à C4 linéaire ou ramifié, un reste cyclopentyle, un reste cyclohexyle ou H; X, Y désignent respectivement indépendamment l'un de l'autre un reste (CH2)p-O, p ≥ 2 ≤ 4, ou un reste CH2, n, m sont respectivement indépendamment l'un de l'autre ≥ 1 et ≤ 6 et o ≥ 1 et ≤ 10. L'invention concerne également un système polyurée comprenant le composé selon l'invention ainsi qu'un système de dosage pour ledit système polyurée selon l'invention.
PCT/EP2012/051915 2011-02-09 2012-02-06 Adhésifs tissulaires à base de triacétals substitués par amino WO2012107376A1 (fr)

Applications Claiming Priority (2)

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EP11153808.8 2011-02-09
EP11153808 2011-02-09

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WO2012107376A1 true WO2012107376A1 (fr) 2012-08-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2011808A1 (fr) * 2007-07-03 2009-01-07 Bayer MaterialScience AG Colle médicale pour la chirurgie
WO2009106245A2 (fr) 2008-02-28 2009-09-03 Bayer Materialscience Ag Barrières anti-adhérences postopératoires
EP2145634A1 (fr) 2008-07-17 2010-01-20 Bayer MaterialScience AG Colles médicales destinées à arrêter des saignements graves et à étanchéifier des fuites

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2011808A1 (fr) * 2007-07-03 2009-01-07 Bayer MaterialScience AG Colle médicale pour la chirurgie
WO2009106245A2 (fr) 2008-02-28 2009-09-03 Bayer Materialscience Ag Barrières anti-adhérences postopératoires
EP2145634A1 (fr) 2008-07-17 2010-01-20 Bayer MaterialScience AG Colles médicales destinées à arrêter des saignements graves et à étanchéifier des fuites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Römpp Chemie Lexikon", GEORG THIEME VERLAG

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